KR20150112807A - Colored curable composition, cured film, color filter, method for manufacturing color filter, solid-state imaging device and image display device - Google Patents

Abstract

일반식(1)에 있어서, R¹∼R⁶은 각각 독립적으로 수소원자, 하기 일반식(2A), 일반식(2B), 일반식(2C) 및 일반식(2D) 중 어느 하나로 나타내어지는 반응성기를 갖는 기, 탄소수 1∼12의 알킬기 또는 탄소수 6∼20의 아릴기를 나타내고, R¹∼R⁶ 중 적어도 1개는 하기 일반식(2A), 일반식(2B), 일반식(2C) 및 일반식(2D) 중 어느 하나로 나타내어지는 반응성기를 갖는다; R⁷∼R²⁰은 각각 독립적으로 수소원자, 할로겐원자 또는 탄소수 1∼7의 알킬기를 나타내고, X^-는 음이온을 나타내거나, X^-는 존재하지 않고 R¹∼R²⁰ 중 적어도 1개가 음이온을 포함한다.

A color filter, a method of manufacturing a color filter, a solid-state image pickup device, and a liquid crystal display device.
A colored curable composition containing a xanthene dye, a triarylmethane dye represented by the general formula (1) and a polymerizable compound;

In the general formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, a reactive group represented by any one of the following general formulas (2A), (2B), (2C) At least one of R ¹ to R ⁶ is a group represented by the following general formula (2A), general formula (2B), general formula (2C) and general formula Has a reactive group represented by any one of the formulas (2D); R ⁷ to R ²⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 7 carbon atoms, X ^- represents an anion, X ^- does not exist and at least one of R ¹ to R ²⁰ contains an anion do.

Description

TECHNICAL FIELD [0001] The present invention relates to a color curable composition, a cured film, a color filter, a method of manufacturing a color filter, a solid-state image capturing device, and an image display device.

The present invention relates to a colored curable composition comprising a dye as a coloring compound, a cured film, a color filter, a method for producing a color filter, a solid-state image pickup device and an image display device.

BACKGROUND ART As a method for manufacturing a color filter used for a liquid crystal display device or a solid-state image pickup device, a pigment dispersion method is widely used. As a pigment dispersion method, there is a method of producing a color filter by a photolithography method using a colored curable composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light or heat because it contains a pigment, and is patterned by a photolithography method. Therefore, positional accuracy is sufficiently ensured, and a color display (a liquid crystal display) used for a liquid crystal display, an organic electroluminescent And is considered to be a suitable method for fabricating a color filter for a color filter.

Coloring compounds other than pigments such as dyes as well as pigments have been extensively studied as coloring compounds used in the production of color filters. Among them, as a dye, there are known compounds having a variety of dye pigments such as pyromethene dye, pyrimidine dye, pyrazole dye, xanthene dye and triarylmethane dye (see, for example, Patent Document 1 ~ 5). Among them, Patent Documents 1 to 3 disclose that high sharpness, heat resistance and fastness can be obtained by using a triarylmethane-based dye.

Japanese Patent Application Laid-Open No. 2013-144724 Japanese Patent Application Laid-Open Publication No. 20-20494 Japanese Patent Application Laid-Open No. 2008-292970 Japanese Patent Application Laid-Open No. 2007-039478 Japanese Patent No. 3387541 (Japanese Patent Application Laid-Open No. 6-230210)

The use of a dye as a coloring compound is believed to be useful in that it can increase the hue and brightness of a display image when an image is displayed due to the color purity of the dye itself or the sharpness of its color. However, there is also room for improvement in the production of color filters using dyes, and in particular, improvements in heat resistance are required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described conventional techniques, and it is an object of the present invention to provide a colored curable composition excellent in heat resistance. The present invention also provides a color filter capable of displaying an image with high brightness and high contrast using the colored curable composition of the present invention, a method of manufacturing the same, and a solid-state image pickup device and an image display And to provide a device.

Under these circumstances, the present inventors have intensively studied and found that a colored curable composition having excellent heat resistance can be obtained by using a composition containing a xanthene dye and a triarylmethane dye having a specific reactive group, and to complete the present invention It came.

Specifically, the above-mentioned problem is solved by the following means <1>, preferably by means <2> - <16>.

<1> A colored curable composition containing a xanthene dye, a triarylmethane dye represented by the following formula (1) and a polymerizable compound;

In the general formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, a reactive group represented by any one of the following general formulas (2A), (2B), (2C) At least one of R ¹ to R ⁶ is a group represented by the following general formula (2A), general formula (2B), general formula (2C) and general formula Has a reactive group represented by any one of the formulas (2D); R ⁷ to R ²⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 7 carbon atoms, X ^- represents an anion, X ^- does not exist and at least one of R ¹ to R ²⁰ contains an anion do;

In the general formulas (2A) to (2D), R ^1a represents a hydrogen atom or a methyl group, R ^2a and R ^3a each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents an oxygen atom or -NR-, L ^{1 to} L ⁴ each independently represent a single bond or a divalent organic group; -NR-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

(2) In the general formula (3), R ²¹ and R ²³ each independently represent an alkyl group having 1 to 6 carbon atoms, R ²² and R ²⁴ each independently represent an aryl group having 6 to 10 carbon atoms, R ²⁶ and R Lt; ²⁷ &gt; represents a hydrogen atom.

&Lt; 3 > The colored curable composition according to < 1 >, wherein the xanthene dye is represented by the following formula (3b)

(3b)

In the general formula (3b), R ⁵⁰ and R ⁵¹ each independently represent an alkyl group having 1 to 6 carbon atoms, R ⁵² and R ⁵³ each independently represent an aryl group having 6 to 10 carbon atoms, and R ⁵⁴ and R ⁵⁵ represent hydrogen Represents an atom; R ⁵⁶ to R ⁶⁰ each independently represent a hydrogen atom or a substituent; a represents 0 or 1, and when a represents 0, any one of R ⁵⁰ to R ⁶⁰ includes an anion; X ^- represents an anion.

 <4> The colored curable composition according to any one of <1> to <3>, wherein the xanthene dye contains a cation and an anion in the same molecule.

<5> The colored curable composition according to any one of <1> to <4>, wherein X ^- in the general formula (1) is an anion represented by any one of the following formulas (AN-1) to (AN-3)

The formula (AN-1)

In formula (AN-1), A ¹ represents a single bond or a divalent linking group, A ² represents a polymerizable group, a fluorine atom or an alkyl group having 1 to 10 carbon atoms and having a fluorine atom; A ³ represents a fluorine atom or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms;

Expression (AN-2)

In the formula (AN-2), A ⁴ represents a single bond or a divalent linking group, and A ⁵ represents a polymerizable group;

Expression (AN-3)

In the formula (AN-3), X ³ , X ⁴ and X ⁵ each independently represent an alkyl group having a polymerizable group, a fluorine atom or a fluorine atom having 1 to 10 carbon atoms.

<6> The colored curable composition according to any one of <1> to <5>, wherein X ^- in the general formula (1) is an anion selected from the following compounds.

<7> The colored curable composition according to any one of <1> to <5>, wherein X ^- in the general formula (1) is an anion having a polymerizable group.

<8> The colored curable composition according to any one of <1> to <7>, which further contains a phthalocyanine pigment.

<9> The colored curable composition according to any one of <1> to <8>, further comprising an alkali-soluble resin and a photopolymerization initiator.

<10> The colored curable composition according to any one of <1> to <9>, which is used for forming a colored layer of a color filter.

<11> A cured film obtained by curing the colored curable composition according to any one of <1> to <10>.

<12> A color filter having a cured film according to <11>.

<13> A color filter using the color-curable composition according to any one of <1> to <10>.

&Lt; 14 > A process for producing a colored curable composition, comprising the steps of: applying a colored curable composition according to any one of < 1 > to < 10 > onto a substrate to form and curing the colored curable composition layer to form a colored layer; A step of patterning the photoresist layer by a process, exposure and development to obtain a resist pattern, or a step of dry-etching the colored layer using the resist pattern as an etching mask.

<15> A solid-state image pickup element having a color filter obtained by a color filter according to <12> or <13> or a method of manufacturing a color filter according to <14>.

<16> An image display device having a color filter obtained by the method according to <12> or <13> or the method of manufacturing a color filter described in <14>.

(Effects of the Invention)

According to the present invention, it is possible to provide a colored curable composition having excellent heat resistance. It is also possible to provide a color filter using the above-mentioned colored curable composition, a method of manufacturing a color filter, a solid-state image pickup device, and an image display device.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, the term &quot; ~ &quot; is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

In the present specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the colored curable composition.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term &quot; radiation &quot; in the present specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray. In the present invention, light means an actinic ray or radiation.

"Exposure" in the present specification includes not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle beams such as electron beams and ion beams, .

In the present specification, the term "(meth) acrylate" refers to both or any one of acrylate and methacrylate, "(meth) acrylic" refers to both acrylate and methacrylate, Methacryloyl "means either or both of acryloyl and methacryloyl.

In the present specification, the terms "monomer" and "monomer" are synonyms.

Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less.

In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, Ph represents a phenyl group, and AC represents an acetyl group.

In this specification, the term &quot; process &quot; is included in this term as well as an independent process, even if the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

The weight average molecular weight in the present invention refers to a value measured by gel permeation chromatography (GPC) unless otherwise specified. The obtained polymer was isolated by removing the solvent, and the obtained solid content was diluted with tetrahydrofuran to 0.1% by mass and subjected to gel permeation chromatography (GPC) using TSKgel Super Multipore HZ-H [manufactured by Tosoh Corporation] with HLC-8020GPC , 4.6 mm ID x 15 cm] connected in series can be measured using a column. The conditions can be performed using an RI detector with a sample concentration of 0.35 mass%, a flow rate of 0.35 ml / min, a sample injection amount of 10 μl, and a measurement temperature of 40 ° C.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the composition. The solid content in the present invention is the solid content at 25 占 폚.

&Lt; Coloring curable composition >

The colored curable composition of the present invention (hereinafter also referred to as the composition of the present invention) is characterized by containing a xanthene dye, a triarylmethane dye represented by the general formula (1), and a polymerizable compound.

By such a constitution, a colored curable composition having excellent heat resistance can be provided. Although this mechanism is an estimation, it is considered that the triarylmethane dye represented by the general formula (1) has a structure represented by any one of the general formula (2A), the general formula (2B), the general formula (2C) By having a reactive group, the triarylmethane dyes represented by the general formula (1) can react with each other by radicals or heat. In addition, the triarylmethane dye represented by the general formula (1) can be reacted with a curing agent such as a polymerizable compound, an alkali-soluble resin or an epoxy compound contained in the composition of the present invention. When this reaction occurs, the triarylmethane dye is easily immobilized in the cured film, and the reaction with the cyanide in the composition is inhibited. As a result, heat resistance is improved.

Further, by using the xanthene dye and the triarylmethane dye represented by the general formula (1) in combination, the energy from the excited state of the triarylmethane dye represented by the general formula (1) shifts to the xanthene dye, Light resistance and brightness can be improved because the relaxation of the aryl methane dye is promoted and the absorption waveform is optimized when the composition of the present invention is used as a film (filter).

In addition, the sputtering process resistance (for example, ITO (Indium Tin Oxide) resistance) can be improved. In addition, light resistance, solvent resistance, electrical characteristics, contrast, spectral characteristics, line width sensitivity and the like can be improved.

&Quot; Triarylmethane dye represented by the general formula (1) &quot;

In the general formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, a reactive group represented by any one of the following general formulas (2A), (2B), (2C) At least one of R ¹ to R ⁶ is a group represented by the following general formula (2A), general formula (2B), general formula (2C) and general formula And a reactive group represented by any one of the formulas (2D). R ⁷ to R ²⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 7 carbon atoms, X ^- represents an anion, X ^- does not exist and at least one of R ¹ to R ²⁰ contains an anion do;

In the general formulas (2A) to (2D), R ^1a represents a hydrogen atom or a methyl group, R ^2a and R ^3a each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents an oxygen atom or -NR-, L ^{1 to} L ⁴ each independently represent a single bond or a divalent organic group; -NR-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

When R ¹ to R ⁶ represent an alkyl group having 1 to 12 carbon atoms, the alkyl group having 1 to 12 carbon atoms may be any of linear, branched or cyclic, but is preferably a linear or branched. The number of carbon atoms of the alkyl group having 1 to 12 carbon atoms is preferably 1 to 9, more preferably 1 to 3. The alkyl group having 1 to 12 carbon atoms may have a substituent. Examples of the substituent which may have an alkyl group having 1 to 12 carbon atoms include a substituent group defined in Substituent Group A described later, and for example, a phenyl group is preferable. When the alkyl group having 1 to 12 carbon atoms has a substituent, it may further have a substituent. Examples of the substituent which may further contain an alkyl group having 1 to 12 carbon atoms include a substituent group defined in Substituent Group A described later.

Specific examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a benzyl group and an ethoxycarbonylmethyl group. Group or a benzyl group is preferable.

<Substituent group A>

The substituent group A may be a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, preferably a chlorine atom, a fluorine atom and more preferably a fluorine atom), an alkyl group (preferably having 1 to 48 carbon atoms, Branched or cyclic alkyl group having 1 to 24 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, Cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), an alkenyl group (preferably a methyl group, an ethyl group, Is preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably having a carbon number of 6 to 48, Preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, and examples thereof include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, A 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group or a benzotriazol-1-yl group), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably a silyl group having 3 to 18 carbon atoms (E.g., trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl, cyano, nitro, alkoxy Is an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, Cycloalkyloxy group such as cyclopentyloxy group and cyclohexyloxy group), an aryloxy group (preferably having 6 to 48 carbon atoms, An aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group and a 1-naphthoxy group), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, (Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a silyloxy group having 1 to 18 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group) (For example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably an acyloxy group having 2 to 24 carbon atoms (For example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, And examples thereof include an ethoxycarbonyloxy group, t-butoxycar A cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably an aryl group having 7 to 24 carbon atoms, An oxycarbonyloxy group such as a phenoxycarbonyloxy group), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group and N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 32 carbon atoms Preferably a C 1-24 sulfamoyloxy group, for example, N, N-diethylsulfamoyloxy or N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably Is an alkylsulfonyloxy group having 1 to 24 carbon atoms, and examples Methyl sulfonyloxy group g, hexadecyl sulfonate group, a cyclohexyl-sulfonyloxy group),

An arylsulfonyloxy group (preferably having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, (For example, a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, a cyclohexanoyl group), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably An alkoxycarbonyl group having 2 to 24 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, , An aryloxycarbonyl group (preferably an aryloxycarbonyl group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24, such as a phenoxycarbonyl group), a carbamoyl group More preferably a carbamoyl group having 1 to 24 carbon atoms, such as a carbamoyl group, an N, N-diethylcarbamoyl group, an N-ethyl-N-octylcarbamoyl group, An N-phenylcarbamoyl group, an N-methylcarbamoyl group, an N, N-dicyclohexylcarbamoyl group), an amino group (preferably having a carbon number of not more than 32, Preferably an amino group having 24 or less carbon atoms, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group or a cyclohexylamino group), an anilino group An anilino group, an N-methylanilino group), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, And, for example, a 4-pyridylamino group), a carbonamido group Preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetamide group, a benzamide group, a tetradecanamide group, a pivaloylamide group and a cyclohexanamide group) (Preferably an ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethyl ureido group, N-phenylureido group) (For example, an N-succinimide group, an N-phthalimide group), an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably an amino group Is an alkoxycarbonylamino group having 2 to 24 carbon atoms and includes, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group ), (Preferably an aryloxycarbonylamino group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24, such as a phenoxycarbonylamino group), a sulfonamide group (preferably having a carbon number of 1 to 20, A sulfonamido group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group or a cyclohexanesulfonamide group), a sulfamoylamino group (Preferably a C 1-48, more preferably a C 1-24 sulfamoylamino group, for example, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group) (Preferably having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms, such as phenyl azo group and 3-pyrazolyl azo group)

An alkylthio group (preferably having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, such as methylthio group, ethylthio group, octylthio group or cyclohexylthio group) (Preferably an arylthio group having from 6 to 48 carbon atoms, and more preferably from 6 to 24 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably 1 to 4 carbon atoms (For example, 2-benzothiazolylthio, 2-pyridylthio group, 1-phenyltetazolylthio group), an alkylsulfinyl group (preferably having 1 to 32 carbon atoms, more preferably 1 to 20 carbon atoms, Is an alkylsulfinyl group having 1 to 24 carbon atoms, such as a dodecanesulfinyl group), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably a carbon number 6 to 24, such as phenyl Sulfinyl group), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably Preferably an alkylsulfonyl group having 1 to 24 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably a carbon number of 6 to 24, such as phenylsulfonyl group and 1-naphthylsulfonyl group), an arylsulfonyl group A sulfamoyl group (preferably a sulfamoyl group having not more than 32 carbon atoms, more preferably not more than 24 carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl- (Preferably an alkyl group having 1 to 32 carbon atoms, more preferably a carbon number &lt; RTI ID = 0.0 &gt; A phosphonyl group having 1 to 24 carbon atoms, such as a phenoxyphosphonyl group, an octyloxyphosphonyl group , A phenylphosphonyl group), a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group, dioctyloxyphosphino An amino group).

When R ¹ to R ⁶ represent an aryl group having ⁶ to 20 carbon atoms, the number of carbon atoms of the aryl group having 6 to 20 carbon atoms is preferably 6 to 12, and more preferably 6 to 9. The aryl group having 6 to 20 carbon atoms may have a substituent. Examples of the substituent which the aryl group having 6 to 20 carbon atoms may have include a substituent group defined in the above substituent group A, and for example, a methyl group or an alkoxy group is preferable.

Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 2-methylphenyl group, a 2,4,6-trimethylphenyl group, a 2-ethoxycarbonylphenyl group and a 4-methoxy- , A 2-methylphenyl group or a 2,4,6-trimethylphenyl group is preferable.

R ¹ ~R at least one of the ^six is represented by the general formula (2A), the general formula (2B), the general formula (2C) and the general formula (2D) of having a reactive group represented by any one, any one of R ¹ ~R ⁶¹ Or two of them preferably have any one of the above reactive groups.

In formula (2A), R ^1a represents a hydrogen atom or a methyl group.

In the general formula (2A), Y represents an oxygen atom or -NR-, and an oxygen atom is preferable. In -NR-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an oxygen atom. The alkyl group having 1 to 4 carbon atoms may be linear or branched. In the case of -NR-, when R represents an alkyl group having 1 to 4 carbon atoms, the number of carbon atoms in the alkyl group is preferably 1 or 2.

In formula (2A), L ¹ represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group, an arylene group, -O-, -CO-, -S-, -NR ^A -, or a group formed by combining these groups, and an alkylene group is preferable. In the -NR ^A -, R ^A represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkylene group may be any of linear, branched or cyclic. The arylene group may be a monocyclic ring or a condensed ring. L ¹ is preferably a single bond or an alkylene group having 1 to 8 carbon atoms.

In the general formula (2B), L ² represents a single bond or a divalent organic group. The bivalent organic group is synonymous with L ¹ in formula (2A), and the preferred range is also the same. L ² is preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

In the general formula (2C), R ^2a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear or branched. In the general formula (2C), L ³ represents a single bond or a divalent organic group. The bivalent organic group is synonymous with L ¹ in formula (2A), and the preferred range is also the same. L ³ is preferably a single bond.

In the general formula (2D), R ^3a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear or branched. R ^3a preferably represents a hydrogen atom. When R ^3a represents an alkyl group having 1 to 4 carbon atoms, the alkyl group preferably has 1 or 2 carbon atoms. In the general formula (2D), L ⁴ represents a single bond or a divalent organic group. The bivalent organic group is synonymous with L ¹ in formula (2A), and the preferred range is also the same. L ⁴ is preferably a single bond.

Specific examples of the reactive group represented by any one of the general formulas (2A), (2B), (2C) and (2D) include (meth) acryloyl groups, (meth) acrylamide groups, styryl groups , An oxetanyl group, and an epoxy group.

In the general formula (1), R ⁷ to R ²⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 7 carbon atoms. The halogen atom is preferably a chlorine atom. The alkyl group having 1 to 7 carbon atoms may be linear or branched, but is preferably straight-chain. The alkyl group having 1 to 7 carbon atoms preferably has 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

R ⁷ is preferably a hydrogen atom. R ⁸ is preferably a hydrogen atom or a methyl group. R ⁹ is preferably a hydrogen atom. R ¹⁰ is preferably a hydrogen atom or a methyl group. R ¹¹ is preferably a hydrogen atom. R ¹² is preferably a hydrogen atom or a methyl group. R ¹³ is preferably a hydrogen atom. R ¹⁴ is preferably a hydrogen atom or a methyl group. R ¹⁵ to R ²⁰ are preferably hydrogen atoms.

In the formula (1), X ^- represents an anion, or, X ^- is at least one of R ¹ ~R ²⁰ is not present the dog comprises an anion, X ^- preferably represents an anion. In the composition of the present invention, xanthene dyes to be described later are preferably of the so-called intramolecular salt type in which cations and anions are contained in the same molecule. Although the mechanism below is presumed, this configuration makes it easier for the cation skeleton of the triarylmethane dye to interact with the anion portion of the xanthene dye. As a result, the apparent molecular weight of the dye in the composition of the present invention (the molecular weight of the sum of the anion moiety of the xanthan dyestuff and the cationic skeleton of the triarylmethane dye) increases, and the dissolution in the solvent is more effectively suppressed , And as a result, it is considered that the solvent resistance is further improved.

The anion X &lt; ^- &gt; is included depending on the valence of the cations contained in the triarylmethane dye represented by the general formula (1). The cation is usually monovalent or divalent, and monovalent is preferred.

The fact that at least one of R ¹ to R ²⁰ contains an anion means that the molecule has an anion X ^- in the molecule of the triarylmethane dye represented by the general formula (1), and an anion moiety and a cation moiety Is present in the triarylmethane dye represented by the general formula (1). When X ^- is absent and at least one of R ¹ to R ²⁰ contains an anion, it is preferable that R ¹⁹ includes an anion.

When X ^- represents an anion, it means that anion X exists outside the molecule of the triarylmethane dye represented by the general formula (1).

The anion X &lt; ^- &gt; is not particularly limited, but a low nucleophilic anion is preferable. The low nucleophilic anion indicates an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is decomposed.

(When X ^- represents anion)

The anion X ^- of the first embodiment is an anion X ^- without a cation of a triarylmethane dye represented by the general formula (1) bonded through a covalent bond, and if there exists another molecule.

Examples of the anion X ^{- in} this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion and the like, and a low nucleophilic anion, and a low nucleophilic anion is preferable.

The lower nucleophilic anion may be an organic anion, an inorganic anion, or an organic anion. Examples of the anions used in the present invention include the known low nucleophilic anions described in paragraph No. 0075 of Japanese Patent Application Laid-Open No. 2007-310315, the anions described in paragraphs 0016 to 0027 of Japanese Patent Application Laid-Open Publication No. 2012-173399, And anion moieties described in paragraphs 0025 to 0033 of publication No. 2013-037316, the contents of which are incorporated herein by reference.

The anion X ^- is preferably a methide, a sulfonylimide or a sulfonate anion having an electron-withdrawing group, and more preferably a bis (sulfonyl) imide anion or a tris (sulfonyl) methide anion. By using such anions, the usability and heat resistance can be further improved.

Further, the anion X ^- as is also preferred anion having a polymerizable group (e.g., such as a styryl group, a (meth) acryloyl group). By using such anions, the voltage holding ratio can be further improved.

It is preferable that the anion X ^- is represented by the following formulas (AN-1) to (AN-3).

The formula (AN-1)

(In the formula (AN-1), A ¹ represents a single bond or a divalent linking group, A ² represents a polymerizable group, a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, A ³ represents a fluorine atom or fluorine Represents an alkyl group having 1 to 10 carbon atoms.

When A ¹ represents a divalent connecting group, examples of the divalent organic group include an alkylene group, an arylene group, -O-, -CO-, -S-, or a combination thereof, and the alkyl group having 1 to 6 carbon atoms Rhenylene is preferred.

When A ² represents a polymerizable group, the polymerizable group is preferably a styryl group, a (meth) acryloyl group, an epoxy group or an oxetanyl group, and more preferably a styryl group and a (meth) acryloyl group.

When A ² and A ³ represent an alkyl group having 1 to 10 carbon atoms having a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms is more preferable, a perfluoroalkyl group having 1 to 4 carbon atoms is more preferable, A methyl group is particularly preferred.

Particularly, it is preferable that A ² in the formula (AN-1) represents a polymerizable group and A ³ represents an alkyl group having 1 to 10 carbon atoms having a fluorine atom.

Expression (AN-2)

(In the formula (AN-2), A ⁴ represents a single bond or a divalent linking group, and A ⁵ represents a polymerizable group.)

A ⁴ is synonymous with A ¹ in formula (AN-1). A ⁵ is A ² and accept the formula (AN-1), it is preferable that the polymerizable group.

Expression (AN-3)

(In the formula (AN-3), X ³ , X ⁴ and X ⁵ each independently represent an alkyl group having a polymerizable group, a fluorine atom or a fluorine atom having 1 to 10 carbon atoms.)

X ³ , X ⁴ and X ⁵ each independently represent a bond with A ² in formula (AN-1), and each of X ³ , X ⁴ and X ⁵ independently represents an alkyl group having 1 to 10 carbon atoms desirable. It is also preferable that any one of X ³ , X ⁴ and X ⁵ represents a polymerizable group and the other two represent an alkyl group having a fluorine atom of 1 to 10 carbon atoms.

The triarylmethane dye represented by the general formula (1) may contain only one kind of anion X &lt; ^- &gt; or two or more kinds of the anion X &lt; ^{- &} gt ;.

Specific examples of the anion X &lt; ^- &gt; are shown below, but the present invention is not limited thereto. It is also possible to consider the description of paragraph No. 0075 of Japanese Patent Application Laid-Open No. 2007-310315, the contents of which are incorporated herein by reference.

In the first embodiment, the anion X &lt; ^- &gt; The anion in this case is exemplified by a repeating unit including an anion moiety when at least one of R ¹ to R ²⁰ does not contain X ^- , which will be described later, contains an anion.

(When X ^- is absent and at least one of R ¹ to R ²⁰ contains an anion)

The anion X ^- is a case is within the same molecule and a triarylmethane dye represented by formula ⁽¹⁾ according to a second embodiment of the form X is an anion. Specifically, there is a case where cations and anions are bonded through a covalent bond in one molecule of a triarylmethane dye represented by the general formula (1).

In this case, the anion X ^- as _{^{-SO 3 -, -COO -, -PO}} 4 -, and to a group containing a structure represented by formula (A1) group containing a structure represented by formula (A2) And the like.

In formula (A1)

(In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ - or -CO-.)

In the general formula (A1), at least one of R ¹ and R _² -SO ² -, and more preferably represents a, both of R ¹ and R _² -SO ² - and more preferably it is indicating.

The group having a structure represented by the general formula (A1) preferably has a fluorine-substituted alkyl group at one end of R ¹ and R ^{2 in} the general formula (A1), and one of R ¹ and R ² is a fluorine- And more preferably bonded to an alkyl group. The number of carbon atoms of the fluorine-substituted alkyl group is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 1 to 3, still more preferably 1 or 2, These alkyl groups are more preferably perfluoroalkyl groups. As specific examples of the fluorine-substituted alkyl group, a trifluoromethyl group is preferable.

In general formula (A2)

(In the formula (A2), R ³ represents -SO ₂ - or -CO-, and R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN.)

In the general formula (A2), R 1 ~R ³ with at least one -SO ₂ ^5- preferable that a and at least two of R ³ ~R ⁵ -SO ₂ - and more preferably indicating.

The group containing the structure represented by formula (A2) preferably has a fluorine-substituted alkyl group at the terminal of at least any one of R ³ to R ⁵ in formula (A2), and at least either of R ³ to R ⁵ And it is more preferable that one of them is directly bonded to a fluorine-substituted alkyl group. In particular, R ³ ~R desirable to have a fluorine-substituted alkyl group of at least two of the terminal ^5, and, R ³ is ~R more preferably coupled with at least two fluorine-substituted alkyl group of ⁵ directly. The fluorine-substituted alkyl group is the same as that described in the group including the structure represented by formula (A1), and the preferable range is also the same.

The triarylmethane dyes represented by the general formula (1) exist in a noncircularized state as follows. For example, in the triarylmethane dye represented by the general formula (1), the following structures are synonymous, and any of them is included in the present invention. The cation site may be located at any position in the molecule.

Specific examples of the triarylmethane dye represented by the general formula (1) include, but are not limited to, the following compounds.

The triarylmethane dye represented by the general formula (1) may be a low molecular weight (for example, a molecular weight of less than 2,000), a high molecular weight (for example, a molecular weight of 2,000 or more)

The molecular weight of the triarylmethane dye represented by the general formula (1) is preferably 700 to 2,000, more preferably 800 to 1,200.

The content of the triarylmethane dye represented by the general formula (1) is preferably 1 to 40 mass%, more preferably 5 to 20 mass%, based on the total solid content in the composition of the present invention. By setting this range, it is possible to further improve heat resistance, solvent resistance, and voltage holding ratio.

The triarylmethane dye represented by the general formula (1) may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount satisfies the above range.

<Xanthan Dye>

The compositions of the present invention contain xanthene dyes. The composition of the present invention can improve light resistance, brightness (contrast) and the like by containing a xanthene dye together with a triarylmethane dye represented by the above general formula (1).

The xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule.

As described above, the xanthene dye is preferably a salt in which the cation and the anion are present in the same molecule, i.e., intramolecularly. With such a constitution, the solvent resistance can be further improved.

As the xanthene dye, a dye containing a compound represented by the following general formula (3) (hereinafter sometimes referred to as "compound (3)") is also preferable. The compound (3) may be a tautomer thereof. The xanthene dye is preferably dissolved in an organic solvent.

In general formula (3)

In the general formula (3), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ²¹ and R ²² are bonded to each other to form a ring Or R ²³ and R ²⁴ may be bonded to each other to form a ring containing a nitrogen atom; R ²⁵ is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 28, -SO 3 R 8 or -SO ₂ NR ²⁹ R ³⁰ ; R ²⁶ and R ²⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is 2 or more, plural R ^{25 s} may be the same or different; a represents 0 or 1, and when a represents 0, any one group of the xanthene dye structure contains an anion. X ^- represents an anion; Z ⁺ represents N ⁺ (R ³¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^{31 s} may be the same or different; R ²⁸ represents an alkyl group having 1 to 20 carbon atoms. R ²⁹ and R ³⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R ²⁹ and R ³⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. R ³¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

When R ²¹ to R ²⁴ represent an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms may be any of linear, branched or cyclic. The number of carbon atoms of the alkyl group having 1 to 20 carbon atoms is preferably 1 to 6, more preferably 1 to 3. Specific examples of the alkyl group having 1 to 20 carbon atoms in R ²¹ to R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, A straight chain alkyl group such as a decyl group or an icosyl group; A branched chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

Of these, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl and 2-ethylhexyl groups are preferable, and a propyl group, an isopropyl group, And a 2-ethylhexyl group is more preferred.

When R ²¹ to R ²⁴ represent an aryl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms preferably has an alkyl group as a substituent. Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group and a butylphenyl group. Among them, a toluyl group, a xylyl group, a mesyl group and a propylphenyl group are preferable, and a toluyl group and a xylyl group are particularly preferable, and a 2,6-disubstituted xylyl group is more preferable.

The aryl group having 6 to 10 carbon atoms may have a substituent other than the alkyl group. As a substituent other than an alkyl group, a halogen ^{atom, -R 28, -OH, -OR 28} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 28, -SR ²⁸ , -SO ₂ R ²⁸ , -SO ₃ R ²⁸ or -SO ₂ NR ²⁹ R ³⁰ . Among these, as the substituent -SO ₃ ^- Z ⁺ is more preferable, and -SO ₂ NR ²⁹ R ³⁰ a ^{_{-, -SO 3 H, -SO 3}} - Z + and -SO ₂ NR ²⁹ R ³⁰ are preferred, SO ₃ . In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ³¹ ) ₄ . Since R ²¹ to R ²⁴ have such a structure, a color filter having less occurrence of foreign matter and excellent in heat resistance can be formed by using the composition of the present invention including the compound (3).

Examples of the ring containing a nitrogen atom formed by bonding R ²¹ and R ²² to each other and the nitrogen atom formed by bonding R ²³ and R ²⁴ to each other include the following.

In view of the compound stability, the following structures are preferable among them.

Formula (3) in, R ²⁵ is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 28, -SO ₃ R ⁸ or -SO ₂ represents _{^{NR 29 R 30, -SO 3 -}} , -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 28, -CO 2 NHR 29, -SO ₃ H, -SO ₂ R ²⁸ or SO ₂ NHR ²⁹ , and -SO ₃ ^- is more preferable. -SO ₂ NR ²⁹ R ³⁰ is preferably -SO ₂ NHR ²⁹ .

R ²⁸ represents an alkyl group having 1 to 20 carbon atoms. Each of R ²⁹ and R ³⁰ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms in R ²⁸ to R ³⁰ is synonymous with the case where R ²¹ to R ²⁴ represent an alkyl group having 1 to 20 carbon atoms, and the preferable range is also the same.

Specific examples of -OR ²⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy Methoxy group, ethoxy group, propoxy group and butoxy group are more preferable.

Specific examples of -CO ₂ R ²⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group, and examples of the methoxycarbonyl group, ethoxycarbonyl group, More preferred is a foxy carbonyl group.

Specific examples of -SR ²⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.

Specific examples of -SO ₂ R ²⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.

Specific examples of -SO ₃ R ²⁸ include a methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, and eicosyloxysulfonyl group.

In -SO ₂ NR ²⁹ R ³⁰ , R ²⁹ and R ³⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

Specific examples of -SO ₂ NR ²⁹ R ³⁰ include a sulfamoyl group; N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, an N- (1,3-dimethylbutyl) sulfamoyl group, (1-methylpentyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group such as N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) N-1 substituted sulfamoyl group; N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

Of these, N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-pentylsulfamoyl and N- -Ethylhexyl) sulfamoyl group is preferable and an N-methylsulfamoyl group, an N-ethylsulfamoyl group, an N-propylsulfamoyl group, an N-butylsulfamoyl group, and N- (2-ethylhexyl) sulfamoyl group Is more preferable.

The alkyl group having 1 to 20 carbon atoms in R ²⁹ and R ³⁰ may have a substituent. Examples of the substituent include a hydroxy group and a halogen atom.

In the general formula (3), m is preferably from 1 to 4, more preferably 1 or 2.

R ²⁶ and R ²⁷ are preferably a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms for R ²⁶ and R ²⁷ include those having 1 to 6 carbon atoms in the alkyl group having 1 to 20 carbon atoms represented by R ²¹ to R ²⁴ .

Z ⁺ is N ⁺ (R ³¹ ) ₄ , Na ⁺ or K ⁺ , and N ⁺ (R ³¹ ) ₄ is preferable. As N ⁺ (R ³¹ ) ₄ , it is preferable that at least two of the four R ^{31 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, that the total number of carbon atoms of R 4 is ³¹ 20 to 80 is preferred and more preferably, 20 to 60. When N ⁺ (R ³¹ ) ₄ is present in the compound (3), at least two of the four R ^{31 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms, and the composition of the present invention comprising the compound (3) It is possible to form a small color filter.

When R ³¹ represents an alkyl group having 1 to 20 carbon atoms, R ²¹ to R ²⁴ are synonymous with an alkyl group having 1 to 20 carbon atoms, and preferable ranges are also the same.

In the general formula (3), a represents 0 or 1, and 0 is preferable. By such a constitution, the amount of the ion component present in the compound (3) is reduced, so that the electric characteristics can be improved.

When a in general formula (3) represents 0, any one group of the xanthene dye structure has an anion, and any one of R ²¹ to R ²⁷ preferably contains an anion, and when R ²⁵ includes an anion Is more preferable.

When a in general formula (3) represents 1, any one of R ²¹ to R ²⁷ may or may not contain an anion depending on the valency of the cation of the xanthene dye represented by the general formula (3) .

X ^- in the general formula (3) represents an anion and is included depending on the valence of the cation included in the xanthene dye represented by the general formula (3), and is usually monovalent or divalent, preferably monovalent.

When the anion is monovalent, it is synonymous with the case that X ^- described in the triarylmethane dye represented by the above-mentioned general formula (1) represents an anion. When the anion is bivalent, for example, naphthalene disulfonic acid can be mentioned.

Particularly, in the general formula (3), R ²¹ and R ²³ represent an alkyl group having 1 to 6 carbon atoms, R ²² and R ²⁴ represent an aryl group having 6 to 10 carbon atoms, and R ²⁶ and R ²⁷ represent a hydrogen atom desirable. By such a constitution, the molecular weight of the compound (3) becomes comparatively large, so that the performance as an acid is suppressed, and it becomes difficult to conduct electricity, and the electric characteristics can be further improved. In addition, the luminance (contrast) and the like can be further improved.

Further, the xanthene dyes represented by the general formula (3) exist in the form of non-gaseous cations as follows, and the following structures are synonymous, and any of them is included in the present invention. The cation moiety may be at any position in the molecule, but is preferably located on the nitrogen atom. The same applies to the compound represented by the general formula (3a) and the compound represented by the general formula (3b) described below.

Also, as the compound (3), a compound represented by the following formula (3a) (hereinafter also referred to as "compound (3a)") is also preferable. The compound (3a) may be a tautomer thereof.

In general formula (3a)

(Wherein R ⁴¹ and R ⁴² each independently represent a monovalent alkyl group having 1 to 10 carbon atoms, R ⁴³ and R ⁴⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms A sulfanyl group or an alkylsulfonyl group having 1 to 4 carbon atoms, and R ⁴¹ and R ⁴ may combine with each other to form a ring containing a nitrogen atom, and R ⁴² and R ⁴⁴ may be bonded to each other to form a P and q each independently represent an integer of 0 to 5. When p represents an integer of 2 or more, plural R ^43s may be the same or different, and when q represents an integer of 2 or more, plural the R ⁴⁴ may be the same or different.)

Examples of the alkyl group having 1 to 10 carbon atoms in R ⁴¹ and R ⁴² include an alkyl group having 1 to 10 carbon atoms in the alkyl group having 1 to 20 carbon atoms described for R ²⁸ , and examples thereof include a methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group is preferable.

R ⁴¹ and R ⁴² may have a substituent and examples of the substituent include an aryl group having 6 to 10 carbon atoms. The aryl group having 6 to 10 carbon atoms is the same as the aryl group having 6 to 10 carbon atoms described for R &lt; ^{21 &} gt ;.

R ⁴¹ and R ⁴² are each independently preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms for R ⁴³ and R ⁴⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl and tert- Ethyl group and propyl group are preferable.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R ⁴³ and R ⁴⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ⁴³ and R ⁴⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

p and q are preferably an integer of 0 to 2, and 0 or 1 is preferable.

As the xanthene dye, a dye containing a compound represented by the following general formula (3b) (hereinafter sometimes referred to as &quot; compound (3b) &quot;) is also preferable. The compound (3b) may be a tautomer thereof.

(3b)

In the general formula (3b), R ⁵⁰ and R ⁵¹ each independently represent an alkyl group having 1 to 6 carbon atoms, R ⁵² and R ⁵³ each independently represent an aryl group having 6 to 10 carbon atoms, and R ⁵⁴ and R ⁵⁵ represent hydrogen Represents an atom; R ⁵⁶ to R ⁶⁰ each independently represent a hydrogen atom or a substituent; a represents 0 or 1, and when a represents 0, any one of R ⁵⁰ to R ⁶⁰ includes an anion; X ^- represents an anion.

It is more preferable that each of R ⁵⁰ and R ⁵¹ is independently an alkyl group having 1 to 3 carbon atoms.

R ⁵² and R ⁵³ are synonymous with the case where R ²¹ to R ²⁴ in the general formula (3) represent an aryl group having 6 to 10 carbon atoms, and preferable ranges are also the same.

It is preferable that R ⁵⁶ to R ⁵⁹ represent a hydrogen atom. R ⁶⁰ is preferably a substituent, and the substituent is preferably an aryl group. The carbon number of the aryl group is preferably from 1 to 12, more preferably from 1 to 8. R ⁶⁰ may further have a substituent, and examples of the substituent include the groups described for R ²⁵ in the general formula (3).

In the general formula (3b), a is 0 or 1, if A is a represent 0, R ⁵⁰ ~R ⁶⁰ include any of a group and the anion, it is preferred that R ⁶⁰ comprises an anion.

In the general formula (3b), X ^- represents an anion, X in the general formula ⁽³⁾ with a consent Also, the preferable range is the same.

Specific examples of the compound (3) include compounds represented by the formulas (1-1) to (1-43), but are not limited thereto. In the following structures, R preferably represents an alkyl group having 1 to 20 carbon atoms, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, further preferably a 2-ethylhexyl group.

Specific examples of the xanthene dye include CI ated Sed Red 51 (hereinafter, the description of CI ated Sed Red will be omitted, and the description will be made only of the number, and the other is the same), 52, 87, 92, 94, 289, 388, CI at seed violet 9,30,102, CI basic red 1 (rhodamine 6G), 2,3,4,8, CI basic red 10 (rhodamine B), 11, CI basic violet 10,11,25 , CI Solvent Red 218, CI Modern Red 27, CI Reactive Red 36 (Rose Bengal B), Sulfolodamine G, the xanthene dyes disclosed in Japanese Patent Application Laid-Open No. 2010-32999, and the cyanide dyes described in Japanese Patent No. 4492760 And xanthan dyes.

Among the above exemplified compounds, the sulfonamides of C. I. at. Seed red 289, the quaternary ammonium salts of C. I. at. Seed red 289, the sulfonamides of C. I. at. Seed violet 102 or the quaternary ammonium salt of C. I. at. Seed violet 102 are preferred. Examples of such compounds include Exemplary Compounds (1-1) to (1-8), Exemplary Compounds (1-11), Exemplary Compounds (1-12), and the like.

In addition, any one of the exemplified compounds (1-24) to (1-33) is preferable in view of excellent solubility in an organic solvent.

Examples of the xanthene dyes include commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Chemical Industry Co., Ltd., "Rhodamin 6G" manufactured by Daoka Chemical Industry Co., Ltd.) May be used. Further, a commercially available xanthene dye can be used as a starting material and synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

The content of the xanthene dye is preferably 1 to 40 mass%, more preferably 5 to 20 mass%, based on the total solid content in the composition of the present invention.

The content of the compound (3) relative to the total mass of the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass. The upper limit of the content of the compound (3) relative to the total mass of the xanthene dye is usually 100 mass% or less.

The xanthene dyes may be used alone or in combination of two or more. When two or more species are used in combination, it is preferable that the total amount satisfies the above range.

&Lt; Other coloring compounds >

The composition of the present invention may contain dyes, pigments and dispersions thereof other than the xanthene dyes and the triarylmethane dyes represented by the general formula (1), and preferably include pigments. These are preferably not more than 1% by mass of the coloring material.

As the dye, any structure may be used as long as it does not affect the color of a colored image. Examples of the dye include azo dyes (for example, Solvent Yellow 162), anthraquinone dyes (for example, those described in JP 2001-10881 A Anthraquinone compounds), phthalocyanine compounds (for example, phthalocyanine compounds described in U.S. Patent Application 2008/00796044 A1), xanthene compounds (for example, CI Acid Red 289), triarylmethane compounds For example, CI Acid Blue 7, CI Acid Blue 83, CI Acid Blue 90, CI Solvent Blue 90, Blue 38), CI Acid Violet 17, CI Acid Violet 49, CI Acid Green 3, and methine dyes. .

Examples of pigments include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, Aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, Pigment Violet 29, Pigment Orange 43, or Pigment Red 194, and Pigment Violet 19 Pigment Red 202, Pigment Red 202, Pigment Red 202, Pigment Red 207, or Pigment Red 209, Pigment Red 206, Pigment Orange 48, Quinacridone quinone compound pigments such as CI Pigment Orange 49, anthraquinone compound pigments such as Pigment Yellow 147, anthrone compound pigments such as Pigment Red 168, Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Benzimidazolone compounds such as Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185 Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, and Pigment Brown 23, Pigment Yellow 13, Pigment Yellow 83, Or Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Azo compound pigments such as Red 247, indanthrone compound pigments such as Pigment Blue 60, Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment Blue 15, Pigment Blue 56, or a triarylcarbonium compound pigment such as Pigment Blue 61, Pigment Violet 23, or Pigment Violet 37 and aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Orange 73, and the like; thioindigo compound pigments such as Pigment Red 88; pigments such as Pigment Yellow 139 and Pigment Orange 66, Pigment Yellow 109, Pigment Orange 61, etc. A pyranthrone compound pigment such as an isoindolinone compound pigment, Pigment Orange 40, or Pigment Red 216, It may be mentioned isobutyl biolran anthrone compound pigments, such as the olret 31.

The composition of the present invention preferably contains a phthalocyanine pigment. The composition of the present invention contains a phthalocyanine pigment to further improve the light resistance.

The composition of the present invention preferably contains a green to cyan coloring material, and is preferably selected from the group consisting of Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, Phthalocyanine compound pigments such as Blue 15 and Pigment Blue 15: 6, triarylcarbonium compound pigments such as Pigment Blue 56 and Pigment Blue 61, Pigment Violet 23, and Pigment Violet 37 , Pigment Red 177, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Orange 73 Pigment, thioindigo compound pigments such as Pigment Red 88, pigment isoindoline compounds such as Pigment Yellow 139 and Pigment Orange 66, pigments Yellow 109, or Pigment Orange 61, pyranthrone compound pigments such as Pigment Orange 40 or Pigment Red 216, or isoviolanthrone compound pigments such as Pigment Violet 31 are preferred.

When the dye or pigment is formulated as a dispersion, it can be adjusted according to the description of JP-A-9-197118 and JP-A-2000-239544, the contents of which are incorporated herein by reference.

The content of the phthalocyanine pigment is preferably 0.5% by mass to 70% by mass, more preferably 0.5% by mass to 20% by mass, and more preferably 0.5% by mass to 10% by mass, based on the total solid content of the coloring and curing composition of the present invention More preferable.

The total content of the dyes or pigments other than the xanthene dyes, the triarylmethane dyes represented by the general formula (1) and the phthalocyanine pigments can be used within a range not impairing the effects of the present invention, It may be 30 mass% or less, 20 mass% or less, and 10 mass% or less, based on the total solid content of the color-curable composition. The lower limit of the total content of other dyes or pigments is generally 0.5% by mass or more.

Further, it is preferable to add it to the composition of the present invention such that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.

The other coloring agents may be used alone or in combination of two or more. When two or more species are used in combination, it is preferable that the total amount satisfies the above range.

The composition of the present invention includes a curable compound in addition to a triarylmethane dye and a xanthene dye represented by the general formula (1). As the curable compound, a polymerizable compound or an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group) is exemplified and appropriately selected according to the application and the production method. In addition, the composition of the present invention preferably contains a photopolymerization initiator.

For example, when a colored layer is formed by a photoresist, the composition of the present invention comprises a triarylmethane dye represented by the general formula (1), a xanthene dye, a polymerizable compound as a curable compound, an alkali soluble resin, It is preferable to include a photopolymerization initiator. It may also contain a surfactant.

When the colored layer is formed by dry etching, it preferably contains a triarylmethane dye represented by the general formula (1), a xanthene dye, a polymerizable compound as a curable compound, a solvent, and a photopolymerization initiator. It may also contain a surfactant.

The details of these will be described below.

<< Curing compound >>

The coloring composition of the present invention contains a curable compound. The curable compound preferably contains at least a polymerizable compound.

<<< Polymerizable compound >>>

The colored curable composition of the present invention preferably contains at least one polymerizable compound. As the polymerizable compound, for example, an addition polymerizable compound having at least one ethylenically unsaturated double bond can be mentioned.

Specifically, it is selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds. Such a group of compounds is well known in the industrial field of the present invention and can be used in the present invention without particular limitation. These may be, for example, any of a monomer, a prepolymer, that is, a chemical form such as a dimer, a trimer and an oligomer, or a mixture thereof and a (co) polymer thereof. As specific examples of the polymerizable compound, reference may be made to paragraphs 0042 to 0049 of JP-A-2013-182215, the contents of which are incorporated herein by reference.

Commercially available products may be used as the polymerizable compound. For example, Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) can be mentioned.

The content of the polymerizable compound relative to the total solid content of the composition of the present invention is preferably from 10% by mass to 80% by mass, more preferably from 15% by mass to 75% by mass, and still more preferably from 20% by mass to 20% by mass, from the viewpoint of obtaining the effect of the present invention more effectively. And particularly preferably 60% by mass to 60% by mass.

The polymerizable compound may be used alone or in combination of two or more. When two or more kinds of polymerizable compounds are used in combination, the total amount is preferably in the above range.

<< Photopolymerization initiator >>

The composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, and cost.

Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a ropin dimer, a benzophenone compound, an acetophenone compound And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of Japanese Patent Application Laid-Open No. 2004-295116. Among them, an oxime compound or a nonimidazole-based compound is preferable because of the fact that the polymerization reaction is quick.

The oxime-based compound (hereinafter, also referred to as "oxime-based photopolymerization initiator") is not particularly limited, and examples thereof include oxime-based compounds such as oximes described in JP-A 2000-80068, WO 02/100903 A1, JP 2001-233842, Based compounds.

As a specific example of the oxime-based compound, the description of paragraph 0053 of Japanese Patent Application Laid-Open No. 2013-182215 may be taken into consideration, and the content of the oxime-based compound is incorporated herein.

As the oxime compound, TR-PBG-304 (manufactured by Sangho Power Electronics Co., Ltd.), Adeka Crus NCI-831, Adeka Crus NCI-930 (manufactured by ADEKA) can be used.

From the viewpoints of sensitivity, stability with time, and coloration upon post heating, compounds represented by the following general formula (1) are more preferable as the oxime compounds.

(In the general formula (1), R and X each represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents an integer of 1 to 5.)

As R, an acyl group is preferable from the viewpoint of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

Examples of A include an alkylene group substituted with an unsubstituted alkylene group, an alkyl group (e.g., methyl group, ethyl group, tert-butyl group or dodecyl group), an alkenyl group (For example, a vinyl group, an allyl group), an aryl group (for example, a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, Alkylene group is preferred.

As Ar, a substituted or unsubstituted phenyl group is preferable in view of increasing the sensitivity and inhibiting coloration due to the heating time. In the case of the substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a substituent An aryloxy group which may have a substituent, an alkyloxy group which may have a substituent, an aryloxy group which may have a substituent, and an amino group which may have a substituent are preferable. In the general formula (1), n is preferably an integer of 1 to 2.

As a specific example of the imidazole-based compound, reference may be made to the description in paragraphs 0061 to 0067 of JP-A-2013-182213, the contents of which are incorporated herein by reference.

The composition of the present invention may contain, in addition to the above-mentioned photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP 2004-295116 A.

When the composition of the present invention has a photopolymerization initiator, the content of the photopolymerization initiator relative to the total solid content of the composition of the present invention is preferably 3% by mass to 20% by mass, more preferably 4% More preferably 19 mass%, and particularly preferably 5 mass% to 18 mass%.

The photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds of polymerizable compounds are used in combination, the total amount is preferably in the above range.

<< Organic solvents >>

The composition of the present invention may contain at least one organic solvent.

The organic solvent is not particularly limited so far as it can satisfy the solubility of the respective constituent components and the coating property of the composition, and is preferably selected in consideration of the solubility, the coatability, and the safety of the binder.

As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons are used. Specifically, those described in paragraphs 0161 to 0162 of JP-A-2012-032754 are exemplified.

These organic solvents are preferably mixed with two or more kinds from the viewpoints of the solubility of each of the above-mentioned components and the solubility of the alkali-soluble polymer, and the improvement of the shape of the coated surface. In this case, particularly preferable examples thereof include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, , Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate, and propylene glycol monomethyl ether acetate.

When the composition of the present invention contains an organic solvent, the content of the organic solvent in the composition of the present invention is preferably such that the total solid content concentration in the composition of the present invention is 10% by mass to 80% by mass, more preferably 15% To 60 mass% is more preferable.

The organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total amount is preferably in the above range.

<< Alkali-soluble resin >>

The composition of the present invention may contain an alkali-soluble resin. The alkali-soluble resin is not particularly limited, except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability and the like.

The alkali-soluble resin is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed with a weakly alkaline aqueous solution. Examples of such linear organic polymer include polymers having a carboxylic acid in the side chain, such as those disclosed in Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication 54 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, and acrylic acid copolymers as described in the respective publications of Japanese Patent Application Laid-Open No. 25957, Japanese Patent Application Laid-open No. 59-53836, Maleic acid copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

As the alkali-soluble resin in the present invention, the description of paragraphs 0079 to 0082 of JP-A-2013-182215 may be taken into consideration, and the content thereof is incorporated herein by reference.

A copolymer of maleimide and ethylene oxide represented by the structural formulas b1 and b2 may also be preferably used.

In the general formula (b1), R ¹ represents a hydrogen atom, an aryl group, or an alkyl group.

Examples of the alkyl group when R ¹ represents an alkyl group include a straight chain alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain having 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, , a t-butyl group, and a cyclohexyl group.

The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxy group, and an amino group.

Examples of the aryl group when R ¹ represents an aryl group include an aryl group of a monocyclic structure, an aryl group of a polycyclic structure, an aryl group of a cyclic structure, and a heteroaryl group containing a hetero atom. More specifically, examples include a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, and a furyl group.

Examples of the substituent which can be introduced into the aryl group include an alkyl group such as a methyl group, ethyl group, t-butyl group and cyclohexyl group, an alkoxy group such as methoxy group, a carboxyl group, a hydroxy group, an amino group, a nitro group, Mosquitoes, and the like.

In the general formula (b2), R ² represents a hydrogen atom or a methyl group. R ³ is an alkylene group having 2 or 3 carbon atoms, R ⁴ is a hydrogen atom, an aryl group or an alkyl group, and m is an integer of 1 to 15.

When R ⁴ represents an alkyl group, examples of the alkyl group include a straight chain alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, , a t-butyl group, a cyclohexyl group, and a 2-ethylhexyl group.

The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, and an alkoxy group.

Examples of the aryl group when R ⁴ represents an aryl group include an aryl group of a monocyclic structure, an aryl group of a polycyclic structure, an aryl group of a cyclic structure, and a heteroaryl group containing a hetero atom. More specifically, examples thereof include a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a benzoimidazolyl group, an indolyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group and a furyl group.

Examples of the substituent which can be introduced into the aryl group include an alkyl group such as a nonyl group, a methyl group, an ethyl group, a t-butyl group and a cyclohexyl group, an alkoxy group such as a methoxy group, a carboxyl group, a hydroxy group, A bromo group, and the like.

The alkali-soluble resin may also have a polymerizable group in the side chain to improve the crosslinking efficiency. For example, a polymer containing an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in its side chain is also useful. Examples of the above-mentioned polymer containing a polymerizable group include commercial products such as KS Res 106 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) and Sycolmer P series (manufactured by Daicel Chemical Industries, Ltd.). Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured coating.

Of these various alkali-soluble resins, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins and acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and from the viewpoint of development control, Resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

Among them, a copolymer having a repeating unit and an acidic group represented by the following general formula (2) is preferable, and more preferably a copolymer having a structural unit represented by the general formula (3) in addition to the general formula (2) Copolymers can be mentioned as preferred examples.

Wherein in the formula (2), R ²⁰ is a hydrogen atom or a methyl group, R ^21, R ^22, R ^23, R ^24, and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or Lt; / RTI &gt;

In the general formula (3), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group having 3 to 20 carbon atoms which contains an unsaturated double bond as a partial structure, and both of R ¹² and R ¹³ are not hydrogen atoms. When at least one of R ¹² and R ¹³ is a carbonyl group having 3 to 20 carbon atoms and contains an unsaturated double bond as a partial structure, the carbonyl group may further include a carboxyl group as a partial structure.

Examples of the acrylic resin include copolymers comprising monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide and the like, and KS resists 106 commercially sold by Osaka Yuki Kagaku (Trade name, product of Kagaku Kogyo Co., Ltd.), and Cychromer P series (product of Daicel Chemical Industries, Ltd.). Copolymers of benzyl methacrylate / methacrylic acid (85/15 [mass ratio]) are also preferable.

The alkali-soluble resin may also contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).

In general formula (X)

(In the formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, R ³ represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring, And n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group of R ² is preferably 2 to 3. The alkyl group of R ³ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (isopropyl) group.

The alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 x 10 ⁵ from the viewpoint of developability and liquid viscosity, more preferably a polymer of 2000 to 1 x 10 ⁵ , And particularly preferably from 5,000 to 5 x 10 &lt; ⁴ &gt;

When the composition of the present invention contains an alkali-soluble resin, the amount of the alkali-soluble resin relative to the total solid content of the composition of the present invention is preferably from 10 to 80 mass%, more preferably from 20 to 60 mass%. The acid value of the binder is preferably 10 to 1000 mg / KOH, more preferably 50 to 300 mg / KOH, and further preferably 50 to 200 mg / KOH.

The alkali-soluble resin may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total amount is preferably in the above range.

<< Cross-linking agent >>

The present invention may contain a crosslinking agent. By containing a crosslinking agent, the hardness of the cured film obtained by curing the composition of the present invention can be further increased.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples of the crosslinking agent include (a) an epoxy resin, (b) at least one substituent selected from methylol group, alkoxymethyl group and acyloxymethyl group A phenol compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a naphthol compound or a hydroxyanthracene compound . Among them, a polyfunctional epoxy resin is preferable.

For details of specific examples of the crosslinking agent and the like, reference can be made to the description of paragraphs 0134 to 0147 of Japanese Patent Application Laid-Open No. 2004-295116.

When the colored curable composition has a cross-linking agent, the amount of the cross-linking agent relative to the total solid content of the composition of the present invention is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 15 to 30 mass%.

The crosslinking agent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total amount is preferably in the above range.

<< Surfactant >>

The composition of the present invention may contain a surfactant. The surfactant may be a nonionic, cationic or anionic surfactant, but a surfactant having an ethylene oxide structure and a fluorine-containing surfactant are preferred. In particular, a surfactant having an ethylene oxide structure with an HLB value in the range of 9.2 to 15.5 or a fluorinated surfactant disclosed in JP-A-2-54202 is preferable.

As a commercial product, Megapac F781-F (manufactured by DIC) can be used.

When the composition of the present invention contains a surfactant, the amount of the surfactant relative to the total solid content of the composition of the present invention is preferably 0.0001 to 5 mass%, more preferably 0.001 to 3 mass%, and most preferably 0.01 to 1 mass% % By mass is more preferable.

The surfactant may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total amount is preferably in the above range.

<< Dye Stabilizer >>

In the composition of the present invention, it is preferable to add a dye stabilizer separately from the triarylmethane dye represented by the general formula (1). As the stabilizer, for example, a surfactant such as a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a silicon surfactant, and a fluorine surfactant can be used. A polymer surfactant (polymer dispersant) is preferable because it can uniformly and finely disperse in the surfactant.

Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (Partial) amine salts, (partial) ammonium salts or (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; A (co) polymer of a hydroxyl group-containing unsaturated carboxylic acid ester such as a hydroxyl group-containing polyacrylic acid ester or a knit thereof; A polymer of a sulfonic acid or phosphoric acid having a crosslinkable group, and the like.

As the crosslinkable group, known polymerizable groups which can be crosslinked by radicals, acids and heat can be used. (Meth) acrylic group, a styrene group and a vinyl group are preferable, and a (meth) acrylic group and a styrene group are more preferable, although a (meth) acrylic group, a styrene group, a vinyl group, a cyclic ether group and a methylol group can be exemplified Do.

When the composition of the present invention contains a dye stabilizer, the amount of the dye stabilizer relative to the total solid content of the composition of the present invention is preferably from 1 to 10% by mass, more preferably from 1 to 7% by mass, still more preferably from 3 to 5% % Is more preferable.

The dye stabilizer may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total amount is preferably in the above range.

<< Antioxidants >>

The composition of the present invention may contain an antioxidant. The antioxidant is not particularly limited, and examples thereof include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, a singlet oxygen ketcher, and the like.

Examples of the radical scavenger include phenol-based antioxidants and hindered amine-based antioxidants. Examples of the phenol antioxidant include a hydroxyphenylpropionate compound, a hydroxybenzyl compound, a thiobisphenol compound, a thiomethylphenol compound, and an alkanediphenol compound. Among them, a hydroxyphenylpropionate-based compound is preferable from the viewpoint of stability of color characteristics.

The release of peroxide is a compound which decomposes peroxide generated by exposure to light or the like into a harmless substance so as not to generate new radicals. Examples thereof include phosphorus antioxidants and sulfur-based antioxidants. Among them, a sulfur-based antioxidant is preferable from the viewpoint of stability of color characteristics.

Examples of the ultraviolet absorber include salicylic acid ester antioxidants and benzophenone antioxidants.

The singlet oxygen ketcher is a compound capable of deactivating singlet oxygen by energy transfer from singlet oxygen, and includes, for example, ethylenic compounds such as tetramethylethylene and cyclopentene, diethylamine, triethylamine, Amines such as 1,4-diazabicyclooctane (DABCO) and N-ethylimidazole, condensed polycyclic aromatic compounds such as naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene and diphenylanthracene which may be substituted; Aromatic compounds such as 1,3-diphenylisobenzofuran, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene and pentaphenylcyclopentadiene, as well as Harry H. wasserman, "Singlet Oxygen", " 14, The Benjamin Cuylings Publishing Co., Inc. (1978), and CMC, high-performance chemicals for photographic color photographic materials, published by Nippon Kayaku Co., Ltd., Chapter 5, Academic Press (1979), Nicholas J.Turro, "Modern Molecular Photochemistry" , Chapter 7 (2002), compounds exemplified as monooxygen quenchers.

In addition to these, metal complexes containing a compound having a sulfur atom as a ligand can be mentioned. Examples of such compounds include transition metal chelate compounds such as nickel complexes, cobalt complexes, copper complexes, manganese complexes and platinum complexes having bistite-a-diketone, bisphenol dithiol, and thiobisphenol as ligands.

Examples of the sulfur-based antioxidant include a thiopropionate compound and a mercaptobenzimidazole-based compound. Among them, a thiopropionate compound is preferable from the viewpoint of stability of color characteristics.

In the present invention, the antioxidants may be used alone or in combination of two or more.

When the composition of the present invention has an antioxidant, the content of the antioxidant is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total mass of the colorant in the composition of the present invention. In this case, if the content of the antioxidant is too small, a desired effect may not be obtained. On the other hand, if the content is too large, the curing property may deteriorate.

<< Hardener >>

The composition of the present invention may contain a curing agent.

The curing agent is at least one compound selected from the group consisting of an aromatic amine compound, a tertiary amine compound, an amine salt, a phosphonium salt, an amidine salt, an amide compound, a thiol compound, a block isocyanate compound and an imidazole ring containing compound.

By containing the curing agent in which the colored curable composition is selected from the specific group of compounds, low-temperature curing of the colored pattern can be realized. In addition, the storage stability of the colored curable composition may be improved.

The composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound as a thiol compound. The polyfunctional thiol compound is preferably a secondary alkane thiol, particularly preferably a compound having a structure represented by the following general formula (T1).

The general formula (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group having a valency of 2 to 4.)

In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and L is an alkylene group having 2 to 12 carbon atoms in particular. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and compounds represented by the formula (T2) are particularly preferable.

When the composition of the present invention has a curing agent, the amount of the curing agent to be blended is preferably from 1 to 20 mass%, more preferably from 3 to 15 mass%, and even more preferably from 5 to 10 mass%, of the total solid content in the composition.

The curing agent may be one type or two or more kinds. When the amount of the curing agent is two or more, the total amount is preferably in the above range.

<< Reduction agent >>

The composition of the present invention may contain a compound that is more likely to be reduced than the dye as a reduction inhibitor of the dye for the purpose of suppressing dye reduction fading during ITO sputtering after pixel formation. Specifically, a quinone compound is preferable, and a quinone compound having a molecular weight of about 100 to 800 or less is preferable.

When the color-curable composition has a reduction inhibitor, the amount of the reduction inhibitor to be blended is preferably from 1 to 20 mass%, more preferably from 3 to 15 mass%, and even more preferably from 3 to 10 mass%, of the total solid content in the composition.

The reducing agent may be one kind or two or more kinds. When the amount of the reducing agent is two or more, the total amount is preferably in the above range.

<< Other Ingredients >>

The composition of the present invention may also contain various additives such as a filler, an ultraviolet absorber, an anti-aggregation agent, a sensitizer, a light stabilizer and the like, if necessary.

&Lt; Preparation method of colored curable composition >

The colored curable composition of the present invention is prepared by mixing the respective components described above and optional components as required.

Further, at the time of preparing the colored curable composition, each component constituting the colored curable composition may be blended at one time, or each component may be dissolved and dispersed in a solvent and then blended sequentially. In addition, the order of injection and the working conditions at the time of compounding are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition. If necessary, each component may be appropriately mixed with two or more solutions and dispersions, and these components may be mixed at the time of use (upon application) .

The colored curable composition prepared as described above can be used for filtration after being filtered using a filter having a pore diameter of preferably 0.01 to 3.0 탆, more preferably a pore diameter of 0.05 to 0.5 탆 .

Since the colored curable composition of the present invention can form a cured film having excellent color and contrast, it is possible to form colored pixels such as a color filter used for a liquid crystal display (LCD) or a solid-state image pickup device (CCD, CMOS, And can be suitably used for production of printing ink, inkjet ink, and paint. Particularly, it is suitable for the purpose of forming a colored pixel for a liquid crystal display device.

The present invention also relates to a colored cured film obtained by curing the above-mentioned colored curable composition.

&Lt; Color filter and manufacturing method thereof &

The color filter of the present invention is constituted by forming a substrate and a colored region containing the colored curable composition of the present invention on the substrate. The colored regions on the substrate are composed of coloring films such as red (R), green (G), and blue (B), which constitute each pixel of the color filter.

The color filter of the present invention uses the above-mentioned colored curable composition. The color filter of the present invention may be formed by any method that can form a cured colored region (coloring pattern) by applying the colored curable composition of the present invention on a substrate. The present invention also relates to a color filter having a colored cured film formed by curing the above-mentioned colored curable composition.

When the color-curable composition of the present invention is used to produce a color filter for a solid-state imaging device, the manufacturing method described in paragraphs 0359 to 0371 of Japanese Patent Application Laid-Open No. 252065/1987 may be employed.

A method of manufacturing a color filter of the present invention includes the steps of: (A) forming a colored layer (also referred to as a colored curable composition layer) by applying the above-mentioned colored curable composition on a substrate; And a curing step (B).

In the curing step, it is preferable to form a colored region (coloring pattern) by exposing in a pattern shape (preferably through a mask) and removing the unexposed portion with a developing solution. Through these steps, a coloring pattern composed of pixels of each color (three colors or four colors) is formed, and a color filter can be obtained. In the method for producing a color filter according to the present invention, the step (C) of irradiating ultraviolet rays to the colored pattern formed in the step (B) and the step (C) of heating the colored pattern irradiated with ultraviolet rays in the step It is preferable that the step (D) is further provided.

The method for producing a color filter of the present invention comprises the steps of forming a colored curable composition layer by applying the composition of the present invention described above on a support, forming a photoresist on the colored curable composition layer, And a step of patterning the photoresist layer to obtain a resist pattern.

By such a method, a color filter used in a liquid crystal display element or a solid-state image pickup element can be manufactured with low difficulty in process, high quality and low cost.

Hereinafter, the method of manufacturing the color filter of the present invention will be described in more detail.

- Process (A) -

In the method for producing a color filter of the present invention, first, the above-mentioned colored curable composition of the present invention is directly applied onto a substrate or through another layer by a desired coating method to form a coating film (colored curable composition layer) And then, preliminarily curing (prebaking) is carried out as necessary to dry the colored curable composition layer.

Examples of the substrate include a non-alkali glass, sodium glass, Pyrex (registered trademark) glass, quartz glass, and a photoelectric conversion element substrate used for a solid-state image pickup device, For example, a silicon substrate or a plastic substrate. A black matrix for isolating each pixel may be formed on the substrate, or a transparent resin layer may be formed for facilitating adhesion. In addition, a foundation layer may be formed on the substrate for improving adhesion with the upper layer, preventing diffusion of the material, or planarizing the surface, if necessary.

It is also preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface.

(Hereinafter referred to as &quot; TFT type liquid crystal driving substrate &quot;) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used as the substrate, , A colored pattern can be formed by using the colored curable composition of the present invention to produce a color filter.

Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition or the like, if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of a TFT type liquid crystal driving substrate can be used.

The colored curable compositions of the present invention are applied to the substrate either directly or through another layer. The application is preferably carried out by a coating method such as spin coating, slit coating, flexible coating, roll coating, bar coating, or ink jet coating.

The method of applying the colored curable composition of the present invention to the substrate in the coating step is not particularly limited, but a method using a slit nozzle such as a slit-and-spin coating method or a spinless coating method (hereinafter referred to as a slit nozzle coating method) ) Is preferable.

In the slit nozzle spin coating method, the slit-and-spine coating method and the spin-less coating method have different conditions depending on the size of the application substrate. For example, a fifth-generation glass substrate (1100 mm x 1250 mm) is coated by a spinless coating method , The discharge amount of the colored curable composition from the slit nozzle is usually 500 to 1000 microliters / second, preferably 800 to 1,500 microliters / second, and the coating speed is usually 50 mm / Second to 300 mm / second, preferably 100 mm / second to 200 mm / second.

The solid content of the colored curable composition used in the application step is usually 10% to 20%, preferably 13% to 18%.

When a coating film of the coloring and curing composition of the present invention is formed on a substrate, the thickness of the coating film (after the pre-baking treatment) is generally 0.3 m to 5.0 m, preferably 0.5 m to 4.0 m, Is 0.5 mu m to 3.0 mu m.

In the case of a color filter for a solid-state imaging device, the thickness of the coating film (after the pre-baking treatment) is preferably in the range of 0.5 mu m to 5.0 mu m.

In the coating step, a prebaking treatment is usually carried out after application. If necessary, a vacuum treatment may be performed before prebaking. Vacuum drying conditions are usually about 0.1 torr to 1.0 torr, preferably about 0.2 torr to 0.5 torr.

The prebaking treatment can be carried out in a temperature range of 50 ° C to 140 ° C, preferably 70 ° C to 110 ° C, for 10 seconds to 300 seconds using a hot plate, an oven or the like. The pre-baking treatment may be combined with a high-frequency treatment. High frequency processing can be used alone.

Examples of the prebaking conditions include heating at 70 to 130 캜 for about 0.5 to 15 minutes using a hot plate or an oven.

The thickness of the colored curable composition layer formed by the colored curable composition is appropriately selected according to the purpose. In the case of a color filter for a liquid crystal display device, the thickness is preferably in the range of 0.2 탆 to 5.0 탆, more preferably in the range of 1.0 탆 to 4.0 탆, and most preferably in the range of 1.5 탆 to 3.5 탆. In the case of the color filter for a solid-state imaging device, the range is preferably 0.2 to 5.0 m, more preferably 0.3 to 2.5 m, and most preferably 0.3 to 1.5 m.

The thickness of the layer of the color-curable composition is the thickness of the layer after pre-baking.

- Process (B) -

Subsequently, in the manufacturing method of the color filter of the present invention, the film (the colored curable composition layer) formed of the colored curable composition formed as described above on the substrate is exposed through, for example, a photomask. As the light or radiation applicable to the exposure, g rays, h rays, i rays, j rays, KrF rays, and ArF rays are preferable, and i rays are particularly preferable. When i-line is used for the irradiation light, it is preferable to irradiate at an exposure amount of 100 mJ / cm 2 to 10,000 mJ / cm 2.

As other exposure light beams, various visible and non-visible laser light sources such as ultrahigh pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps and metal halides, fluorescent lamps, tungsten lamps, have.

Exposure process using laser light source

In an exposure method using a laser light source, an ultraviolet laser is used as a light source.

The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 300 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm conforms to the photosensitive wavelength of the resist . Concretely, a third harmonic (355 nm) of a Nd: YAG laser of a relatively large and relatively inexpensive solid-state laser, XeCl (308 nm) and XeF (353 nm) of an excimer laser can be suitably used.

The exposed amount of the pinhole (pattern) is in the range of 1 mJ / cm 2 to 100 mJ / cm 2, more preferably in the range of 1 mJ / cm 2 to 50 mJ / cm 2. When the exposure dose is within this range, it is preferable from the viewpoint of productivity of pattern formation.

The exposure apparatus is not particularly limited, and examples of the commercially available apparatus include a commercially available system such as Callisto (manufactured by V Technology Corporation), EGIS (manufactured by V Technology Corporation), and DF2200G (manufactured by Dainippon Screen Corporation). Apparatuses other than those described above are also suitably used.

When a color filter for a liquid crystal display device is manufactured, exposure using h-line or i-line is preferably used by a proximity photolithography machine or a mirror projection exposure machine. In manufacturing a color filter for a solid-state imaging device, it is preferable to use i-line mainly by a stepper aligner. Further, when manufacturing a color filter using a TFT type liquid crystal driving substrate, a photomask used is formed with a pattern for forming a through hole or a U-shaped concave portion in addition to a pattern for forming a pixel (coloring pattern) Is used.

The colored curable composition layer thus exposed can be heated.

In addition, the exposure can be performed while flowing nitrogen gas into the chamber so as to suppress oxidation and discoloration of the coloring material in the colored curable composition layer.

Subsequently, development is performed on the colored curable composition layer after exposure with a developing solution. Accordingly, a coloring pattern (resist pattern) of a negative or positive type can be formed. In the developing step, the uncured portion of the coated film after exposure is eluted into the developing solution so that only the hardened powder remains on the substrate.

Any developer may be used as long as it dissolves the coating film (colored curable composition layer) of the colored curable composition in the uncured portion and does not dissolve the cured portion. For example, a combination of various organic solvents or an alkaline aqueous solution can be used.

As the organic solvent to be used for the development, the above-mentioned solvents that can be used when preparing the colored curable composition of the present invention can be mentioned.

The alkaline aqueous solution includes, for example, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, , Ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] And an alkaline aqueous solution obtained by dissolving an alkaline compound such as 7-undecene in a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. When the developer is an alkaline aqueous solution, it is preferable to adjust the alkali concentration so that the pH is preferably from 11 to 13, more preferably from 11.5 to 12.5.

To the alkaline aqueous solution, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added.

The developing temperature is usually 20 to 30 占 폚, and the developing time is 20 to 90 seconds.

The phenomenon may be a dip method, a shower method, a spray method, or the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined. It is also possible to wet the surface to be developed with water or the like before coming into contact with the developing solution to prevent uneven development. Further, the substrate may be inclined and developed.

When a color filter for a solid-state imaging device is manufactured, a paddle phenomenon is also used.

After the developing treatment, the drying is performed through a rinsing treatment in which excess developer is removed by cleaning, and then heat treatment (post baking) is performed in order to complete the curing.

The rinse treatment is usually carried out with pure water, but pure water is used in the final rinse for the purpose of saving the liquid, and pure water used at the beginning of the rinse is used, or the substrate is tilted or the ultrasonic irradiation is used in combination It is also good.

After rinsing, removing water and drying, heat treatment is generally performed at a temperature of about 200 to 250 캜. In this heating treatment (post baking), the coated film after development can be carried out continuously or batchwise using heating means such as a hot plate, a convection oven (hot air circulation type drier), a high frequency heater or the like so as to satisfy the above conditions.

Each of the above steps can be repeated for each color in accordance with the desired number of colors to produce a color filter in which colored cured films (colored patterns) of a plurality of colors are formed.

The color filter of the present invention can be suitably used for a solid-state image pickup device or a liquid crystal display device because of its high contrast, small color density unevenness, and good color characteristics.

- Process (C) -

In the method of manufacturing a color filter according to the present invention, a colored pattern (pixel) formed by using a colored curable composition may be subjected to post exposure by ultraviolet irradiation.

- Process (D) -

It is preferable to perform heat treatment on the colored pattern on which the post exposure is performed by the ultraviolet ray irradiation as described above. The coloring pattern formed can be further cured by heat treatment (so-called post-baking treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.

The temperature during the heat treatment is preferably 100 占 폚 to 300 占 폚, and more preferably 150 占 폚 to 250 占 폚. The heating time is preferably about 10 minutes to 120 minutes.

The coloring pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of colors, the above-mentioned steps (A), (B) and (C) and (D) may be repeated according to the desired number of colors.

Further, the step (C) and / or the step (D) may be performed every time the formation of the monochromatic colored curable composition layer, the exposure and the development are completed (per one color), and all the colored curable compositions (C) and / or the step (D) may be performed collectively after the formation of the layer, the exposure, and the development are completed.

The colored curable composition of the present invention can also be applied to a method of manufacturing a color filter including a dry etching process. As one example of such a manufacturing method, there is a method of forming a colored layer using a colored curable composition of the present invention, a step of forming a colored layer, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development, And a step of dry-etching the colored layer using the resist pattern as an etching mask.

When the colored curable composition of the present invention is used in a process for producing a color filter including a dry etching process, the photo-curable composition may be a thermosetting composition. In the case of a thermosetting composition, a thermosetting agent can be used, and as the thermosetting agent, a compound having two or more epoxy groups in one molecule is preferable.

The color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention is excellent in color and contrast because the colored curable composition of the present invention is used.

The color filter of the present invention can be used for a liquid crystal display element or a solid-state image pickup element, and is particularly suitable for use in a liquid crystal display apparatus. When used in a liquid crystal display device, images can be displayed with excellent spectral characteristics and contrast while achieving good hue by using a dye as a coloring agent.

The use of the colored curable composition of the present invention has mainly been described above mainly for the purpose of forming a coloring pattern of a color filter, but it can also be applied to the formation of a black matrix for isolating colored patterns (pixels) constituting a color filter.

The black matrix on the substrate can be formed by using a colored curable composition containing a working pigment of a black pigment such as carbon black or titanium black, through each step of coating, exposure, and development, and then post baking if necessary have.

[Image display device]

The color filter of the present invention can be used in an image display apparatus such as a liquid crystal display apparatus and an organic EL display apparatus, and is particularly suitable for use in a liquid crystal display apparatus. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with good display tones and excellent display characteristics.

It is preferable that the image display device of the present invention has at least three color filters of red, green, and blue, and the blue color filter uses the above-mentioned colored curable composition.

The definition of a liquid crystal display device and the details of each display device are described in, for example, "Electronic Display Device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 Issued)", "Display Device (Ibuki Sumi Architect, Quot ;, published in 1989). The liquid crystal display device is described in, for example, &quot; Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Sakai Corporation in 1994). The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various liquid crystal display devices described in the &quot; next generation liquid crystal display technology &quot;.

The color filter of the present invention is particularly effective for a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, &quot; Color TFT liquid crystal display (Kyoritsu Shotpan Co., Ltd., 1996) &quot;. The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

Further, the color filter of the present invention can be provided in a bright and high-definition color-filter on array (COA) method.

When the color filter of the present invention is used in a liquid crystal display element, high contrast can be realized when combined with a conventional three-wavelength tube of a cold cathode tube. In addition, a red LED, a green LED, and a blue LED light source It is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.

[Solid-state image pickup device]

The colored curable composition of the present invention can also be preferably used as a solid-state imaging device. The configuration of the solid-state image pickup device is a configuration provided with a color filter manufactured using the colored curable composition of the present invention, and is not particularly limited as far as it functions as a solid-state image pickup device. .

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode composed of polysilicon or the like on the support, and a photodiode light- Shielding film formed on the light-shielding film and covering the entire surface of the light-shielding film and the photodiode light-receiving portion, and having a color filter for a solid-state image pickup device according to the present invention on the device protective film to be.

Further, even in a configuration having the light-converging means (for example, a microlens or the like hereinafter) on the device protective layer and under the color filter (near the support) or a configuration having the light- good.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the contents of processing, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise stated, "%" and "parts" are on a mass basis.

<Synthesis Example>

<< Synthesis Example of Triarylmethane Dye >>

The intermediate of the triarylmethane dye and the triarylmethane dye used in the present invention can be synthesized using the synthesis method described in JP-A-2008-201694 and WO2009 / 107734.

<< Synthesis Example of Triarylmethane Dye C-2 >>

A triarylmethane dye C-2 was synthesized according to the following synthesis route.

Compound A was obtained by reacting N-hydroxyethylnaphthylamine (19 parts by mass), methacrylic chloride (20 parts by mass) and triethylamine (20 parts by mass) in acetonitrile (200 parts by mass). Compound A and methyl-substituted bisdiethylaminobenzophenone were reacted at 90 占 폚 in the presence of phosphorus oxychloride to synthesize a triarylmethane dye. After mixing with a bistrifluoromethane sulfonylimide lithium salt in a methanol solvent, And purified by silica gel chromatography to obtain a triarylmethane dye C-2 (14 parts by mass). The molar extinction coefficient of triarylmethane dye C-2 in ethyl acetate was 86,000 and the maximum absorption wavelength was 625 nm.

<< Synthesis Example of Triarylmethane Dye C-3 >>

A triarylmethane dye C-3 was synthesized according to the following synthesis route.

(14 parts by mass), epoxycyclohexane (12 parts by mass) and hexafluoroisopropanol (100 parts by mass) were reacted at 90 占 폚 for 6 hours. The reaction solution was concentrated, and the precipitated crystals were collected by filtration and washed with hexane to obtain a compound B. Subsequently, compound B and methacrylic chloride were esterified in the presence of triethylamine to obtain compound C.

A triarylmethane dye was synthesized by reacting Compound C and bisdiethylaminobenzophenone in the presence of phosphorus oxychloride at 90 占 폚. The triarylmethane dye was mixed with a bistrifluoromethane sulfonylimide lithium salt in a methanol solvent, The crude product was purified by chromatography to obtain a triarylmethane dye C-3 (20 parts by mass). The molar extinction coefficient of triarylmethane dye C-3 in ethyl acetate was 96,000 and the maximum absorption wavelength was 600 nm.

<< Synthesis Example of Triarylmethane Dye C-6 >>

Synthesis was conducted in the same manner as the triarylmethane dye C-2 and the triarylmethane dye C-3 to obtain a triarylmethane dye C-6.

The molar extinction coefficient of triarylmethane dye C-6 in ethyl acetate was 92,000 and the maximum absorption wavelength was 602 nm.

<< Synthesis Example of Triarylmethane Dye C-9 >>

The following compounds D and E were synthesized in the same manner as the triarylmethane dye C-2 and the triarylmethane dye C-3 to obtain a triarylmethane dye C-9.

The molar extinction coefficient of the triarylmethane dye C-9 in ethyl acetate was 90,000 and the maximum absorption wavelength was 615 nm.

<Synthesis Example of Xanthan Dye>

The intermediate and the xanthene dyes of the xanthene dyes used in the present invention can be synthesized using the synthesis method described in JP-A-2013-144724 and JP-A-2013-116955.

<< Synthesis Example of Xanthene Dyes 1-1 >>

Atced Red 289 was acid halide-converted using phosphorus oxychloride and then reacted with butylamine to obtain a xanthene dye 1-1. The molar extinction coefficient of the obtained xanthan dyestuff 1-1 in methanol was 67,000 and the maximum absorption wavelength was 562 nm.

<< Synthesis Example of Xanthene Dyes 1-32 >>

The xanthene dyes 1-32 were obtained by introducing propyl groups using propyl bromide in the presence of sodium hydride for xanthene dye A. The molar extinction coefficient of xanthene dyes 1-32 in methanol was 68,000 and the maximum absorption wavelength was 567 nm.

<< Synthesis Example of Xanthene Dyes 1-39 >>

The xanthene dyes B 1-39 were obtained by mixing the bistrifluoromethanesulfonylimide lithium salt in methanol with respect to the xanthene dye B. The molar extinction coefficient of xanthene dye 1-39 in methanol was 66,000 and the maximum absorption wavelength was 570 nm.

<Fabrication of colored film>

<< Preparation of colored curable composition (coating liquid) >>

The components in the following composition were mixed to prepare a colored curable composition.

Triarylmethane dye C-3 5.0 parts by mass

Xanthene dye 1-32 4.0 parts by mass

C. I. Pigment Blue 15: 6 dispersion 1.0 part by mass

12.8 parts by mass (T-1) shown below

21.2 parts by mass (in terms of solid content: 8.5 parts by mass) shown below in (U-1)

3.0 parts by mass of the following (V-3)

??? 120.4 parts by mass of the following (X-1)

24.2 parts by mass of the following (X-2)

??? 0.006 parts by mass of the following (Z-1)

(T-1) Photopolymerizable compound: KAYARAD DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

(Solid content: 40.0% by mass), an acid value (U-1), an alkali-soluble resin: a solution of benzyl methacrylate / methacrylic acid [85/15 (mass ratio)] (weight average molecular weight: 12,000) in propylene glycol monomethyl ether acetate 100 mg KOH / g)]

(V-3) Photopolymerization initiator: Oxime compound of the following structure (Et represents ethyl group and Ac represents acetyl group)

(X-1) Solvent: Propylene glycol monomethyl ether acetate

(X-2) Solvent: ethyl 3-ethoxypropionate

(Z-1) Surfactant: Megapack F781-F [manufactured by DIC Corporation]

&Lt; Comparative Example 1 &

A coloring curable composition of Example 1 was prepared in the same manner as in Example 1 except that C. I. Basic Blue 7 (B.B.7) (Tokyo Kasei Kogyo Co., Ltd.) was used instead of triarylmethane dye C-3.

C. I. Basic Blue 7

&Lt; Comparative Example 2 &

The procedure of Example 4 was repeated except that the xanthene dyestuff 1-32 was not added to the color-curable composition of Example 4.

&Lt; Comparative Example 3 &

A coloring curable composition of Example 1 was prepared in the same manner as in Example 1 except that the comparative dye having the following structure was used in place of the triarylmethane dye C-3.

Comparative dye

(Colored layer A)

The colored curable composition prepared above was coated on a glass (made by Corning Incorporated) substrate by a spin coat method and dried at room temperature for 30 minutes to volatilize the volatile components to obtain a colored layer. This colored layer was irradiated with i-line (wavelength 365 nm) of the front exposure without a photomask interposed therebetween to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source and irradiated after being made into parallel light. At this time, the irradiation light amount was set to 40 mJ / cm 2. Subsequently, the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration: 2.4 mass%) at 26 DEG C for 45 seconds, rinsed with flowing water for 20 seconds, and then dried by spraying. The dried film was baked in a clean oven at 230 占 폚 for 20 minutes to obtain a colored layer A.

(Colored layer B)

In the production procedure of the colored layer A, a colored layer B was obtained in the same manufacturing procedure as that of the colored layer A except that a photomask of 20 mu m L & S pattern was used for exposure of the colored layer.

(1) Line width sensitivity

The width of the pixel-forming layer obtained from the colored layer B was measured with a microscopic image measuring system (CP-30, manufactured by AROSE ENGINEERING CO., LTD.). The thicker the width of the fine line width from the mask width was called the line width sensitivity because the width of the fine line becomes thicker as the sensitivity becomes higher.

(2) Liquid resistivity (electrical property)

The coloring layer A obtained above was scraped from the substrate, and 9.0 mg of the scraped product was added to 2.00 g of liquid crystal material ZLI-4792 (Merck Co.), and the mixture was heated at 120 캜 for 5 hours. Thereafter, the resultant was filtered, and the resistivity of the liquid crystal material was measured by a liquid resistivity measuring apparatus (Model ADVANTEST R8340 ULTRA HIGH RESISTANCE ME Co., Ltd. Advan Test Co., Ltd.).

<Evaluation Criteria>

4: Resistivity was 1.0 × 10 ¹² MΩ or more, and when attached to a liquid crystal display device, it was not confirmed to stick to the panel.

3: Resistivity was less than 1.0 x 10 ¹² M ?, and when the panel was mounted on a liquid crystal display device, it was not confirmed to stick to the panel.

2: Resistivity was less than 1.0 x 10 &lt; ¹¹ &gt; M [Omega], and when attached to a liquid crystal display device and made into a panel,

1: Resistivity was less than 1.0 x 10 &lt; 10 ^&gt; M &lt; M &gt;, which was a level that could not withstand practical use due to adhesion when attached to a liquid crystal display device and made into a panel.

(3) Spectral characteristics

The transmission spectrum of the colored layer A obtained above was measured using a photometric system (MCPD-3700, manufactured by Otsuka Denshi Co., Ltd.). From the obtained transmission spectrum, the chromaticity (C light source) and the luminance Y in the CIE 1931 colorimetric system were determined.

(4) Heat resistance

The transmission spectrum of the colored layer A obtained above and the color difference DELTA E * ab of the transmission spectrum when the colored layer A was fired at 230 DEG C for 60 minutes were calculated. The value of? E * ab indicates that heat resistance is good when the value is smaller. Also, the value of ΔE * ab is a value obtained from the following color difference formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system (Japanese Society for Color Science Handbook (1985) p.266).

ΔE * ab = {(ΔL * ) 2 + (Δa *) 2 + (Δb *) 2} 1/2

(5) ITO resistance

The coloring layer A obtained above was applied to a substrate having a film thickness of ITO (indium tin oxide) of 1500 Å in an atmosphere of an oxygen flow rate of 2 sccm, an Ar flow rate of 84 sccm, and a sputter temperature of 230 ° C. by using a sputtering device (ALBACCO Co., Ltd. SIH- DC sputtering was performed. The color difference DELTA E * ab of the transmission spectrum when the sputtered ITO-attached colored layer A and the ITO-attached colored layer A were further fired at 230 DEG C for 60 minutes was calculated.

(6) Contrast

The colored layer A obtained above was sandwiched between two polarizing films, and the values of luminance in the case where the polarization axes of the two polarizing films were parallel to each other and in the case of the vertical direction were measured using an color luminance meter (manufactured by Topcon Co., : BM-5A], and a value obtained by dividing the luminance when the polarization axes of two polarizing films were parallel and the luminance when the polarization axes of the two polarizing films were vertical was obtained as a contrast.

(7) Light fastness

The transmittance spectrum of the colored layer A obtained above and the color difference ΔE of the transmission spectrum of the colored layer A after irradiating the colored layer A with illuminance of 390 W / m 2 for 48 hours with a xenon fade meter (XL-75, manufactured by Suga Shikeki Co.) * calculated ab.

(8) Solvent resistance (chromaticity difference)

The colored layer A obtained above was immersed in NMP (N-methylpyrrolidone) at 25 占 폚 for 10 minutes, and the UV-Vis spectrum before and after immersion was measured to calculate an index? Eab of color change. Further, when the value of DELTA Eab is 4 or less, the color change is small, and the excellent solvent resistance is obtained.

From the results of the above table, it was found that the color-curable composition used in Examples had excellent heat resistance. In addition, it was found that excellent in both line width sensitivity, liquid crystal resistivity, spectroscopic characteristics, ITO resistance, contrast, light resistance and solvent resistance.

Further, it was found that the light resistance can be further improved by further containing a phthalocyanine pigment in addition to the xanthene dye and the triarylmethane dye represented by the following general formula (1).

On the other hand, it was found that the color-curable composition of Comparative Example 1 using a triarylmethane dye having no reactive group did not have sufficient heat resistance. It was also found that the ITO resistance and the solvent resistance were not sufficient.

It was found that the heat resistance was not sufficient in Comparative Example 2 using the color-curable composition containing no xanthene dye. It was also found that the ITO resistance, contrast, and light resistance were not sufficient.

It was found that the color-curing composition of Comparative Example 3 in which the triarylmethane dye was not blended had insufficient heat resistance. Further, it was found that the liquid crystal resistivity, ITO resistance and solvent resistance were not sufficient.

Claims (16)

A cyanate dye, a triarylmethane dye represented by the following general formula (1), and a polymerizable compound.

[In the general formula (1), R ¹ to R ⁶ each independently represents a hydrogen atom, a group represented by any one of the following general formulas (2A), (2B), (2C) At least one of R ¹ to R ⁶ represents a group having a reactive group, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and at least one of R ¹ to R ⁶ is a group represented by the following general formula (2A), general formula (2B) Has a reactive group represented by any one of the general formula (2D); R ⁷ to R ²⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 7 carbon atoms, X ^- represents an anion, X ^- does not exist and at least one of R ¹ to R ²⁰ contains an anion do.]

Wherein R ^1a represents a hydrogen atom or a methyl group, R ^2a and R ^3a each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y represents an oxygen atom (for example, Or -NR-, L ^{1 to} L ⁴ each independently represent a single bond or a divalent organic group; -NR-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.] The method according to claim 1,
Wherein R ²¹ and R ²³ each independently represent an alkyl group having 1 to 6 carbon atoms, R ²² and R ²⁴ each independently represent an aryl group having 6 to 10 carbon atoms, and R ²⁶ and R ²⁷ , Lt; / RTI &gt; represents a hydrogen atom. In the first aspect,
Wherein the xanthene dye is represented by the following general formula (3b).
(3b)

(In the general formula (3b), R ⁵⁰ and R ⁵¹ each independently represent an alkyl group having 1 to 6 carbon atoms, R ⁵² and R ⁵³ each independently represent an aryl group having 6 to 10 carbon atoms, and R ⁵⁴ and R ⁵⁵ Represents a hydrogen atom; R ⁵⁶ to R ⁶⁰ each independently represent a hydrogen atom or a substituent; a represents 0 or 1, and when a represents 0, any one of R ⁵⁰ to R ⁶⁰ includes an anion; X ^- represents an anion.] 3. The method according to claim 1 or 2,
Wherein the xanthene dye contains a cation and an anion in the same molecule. 3. The method according to claim 1 or 2,
X &lt; ^- &gt; in the general formula (1) is an anion represented by any one of the following formulas (AN-1) to (AN-3).
The formula (AN-1)

[In the formula (AN-1), A ¹ represents a single bond or a divalent linking group; A ² represents an alkyl group having 1 to 10 carbon atoms having a polymerizable group, a fluorine atom or a fluorine atom; A ³ represents a fluorine atom or a fluorine atom-containing alkyl group having 1 to 10 carbon atoms.]
Expression (AN-2)

[In the formula (AN-2), A ⁴ represents a single bond or a divalent linking group, and A ⁵ represents a polymerizable group.]
Expression (AN-3)

X ³ , X ⁴ and X ⁵ each independently represent an alkyl group having a polymerizable group, a fluorine atom or a fluorine atom having 1 to 10 carbon atoms. 3. The method according to claim 1 or 2,
X &lt; ^- &gt; in the general formula (1) is an anion selected from the following compounds.

3. The method according to claim 1 or 2,
A colored curable composition characterized in that X &lt; ^- &gt; in the general formula (1) is an anion having a polymerizable group. 3. The method according to claim 1 or 2,
Wherein the pigment further contains a phthalocyanine pigment. 3. The method according to claim 1 or 2,
An alkali-soluble resin, and a photopolymerization initiator. 3. The method according to claim 1 or 2,
Wherein the colored curable composition is used for forming a coloring layer of a color filter. A cured film characterized by curing the colored curable composition according to any one of claims 1 to 3. A color filter having the cured film according to claim 11. A color filter comprising the color-curable composition according to any one of claims 1 to 3. A process for producing a colored curable composition, comprising the steps of: applying the colored curable composition according to claim 1 or 2 on a substrate to form a colored curable composition layer and curing to form a colored layer; forming a photoresist layer on the colored layer; A step of patterning the photoresist layer to obtain a resist pattern, or a step of dry-etching the colored layer using the resist pattern as an etching mask. A solid-state imaging device comprising the color filter according to claim 12 or 13. An image display apparatus having the color filter according to claim 12 or 13.