JP5393766B2 - Colored photosensitive composition, color filter, method for producing color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a colored photosensitive composition containing a dye as a colorant, a color filter, a method for producing a color filter, and a liquid crystal display device.

  As one of methods for producing a color filter used in a liquid crystal display 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 photosensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat because it contains a pigment, and is patterned by a photolithographic method, so that the positional accuracy is sufficiently ensured, and for the production of color filters used in liquid crystal display devices and the like. This is the preferred method.

  As a colorant used for producing a color filter, not only pigments but also coloring compounds other than pigments such as dyes are widely studied. Among these, as dyes, compounds having a wide variety of dye bases such as pyromethene dyes, pyrimidineazo dyes, pyrazole azo dyes, xanthene dyes are known (see, for example, Patent Documents 1 to 3).

Use of a dye as a colorant is useful in that the hue and brightness of a display image when an image is displayed can be increased by the color purity of the dye itself and the vividness of the hue.
Further, it is disclosed that when a specific anthraquinone compound is used as a dye, a color filter excellent in contrast or the like can be obtained (see, for example, Patent Document 4).

  Also, a colored photosensitive composition containing an organic solvent-soluble dye, an alkali-soluble binder, a polyfunctional thiol compound and the like has been proposed, and it is known that a rectangular pattern can be obtained with high sensitivity (see, for example, Patent Document 5). In addition, a colored photosensitive composition using a colorant such as a dye and a low molecular weight binder having an unsaturated group has improved solvent resistance (see, for example, Patent Document 6). It has been known.

JP 2008-292970 A JP 2007-039478 A Japanese Patent No. 3387541 JP 2001-108815 A JP 2006-71890 A JP 2009-169231 A

  However, when a dye is used in a color filter for a liquid crystal display device to improve contrast and color reproducibility, a color filter with good electrical characteristics is required from the viewpoint of preventing the occurrence of crosstalk. There has been a long-awaited coloring photosensitive composition that can provide a good coloring pattern.

  The present invention has been made in view of the above prior art. That is, the present invention provides a color filter having a colored film with high sensitivity, high contrast, and high adhesion to the substrate, and the specific resistance of the liquid crystal when the obtained color filter is used in a liquid crystal display device. It is an object of the present invention to provide a colored photosensitive composition from which a good color filter can be obtained, and further, a color filter using the colored photosensitive composition, a method for producing the same, and an electrical property using the color filter. It is an object of the present invention to provide a liquid crystal display device that is good and has good image quality.

Specific means for achieving the above object are as follows.
<1> (A) a dye that is a metal complex compound in which a structure represented by the following general formula (I) is coordinated to a metal atom or a metal compound, (B) a polyfunctional thiol compound, and (C) photopolymerization initiation The coloring photosensitive composition containing an agent and (D) polymeric compound.

In the general formula (I), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.

<2> The colored photosensitive composition according to <1>, wherein the (A) dye is a complex compound represented by the following general formula (I-3).

In General Formula (I-3), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, or an alkyl. Represents a group, an aryl group, or a heterocyclic group. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom. Or a sulfur atom. Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), oxygen. Represents an atom, sulfur atom, or carbon atom.
X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed.

<3> The colored photosensitive composition according to <1> or <2>, further comprising (E) an anthraquinone compound having an anthracene-9,10-dione skeleton.

<4> The colored photosensitivity according to any one of <1> to <3>, wherein the (B) polyfunctional thiol compound is a compound having two or more groups represented by the following general formula (2). Composition.

In general formula (2), R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —.

<5> The colored photosensitive composition according to any one of <1> to <4>, wherein the (B) polyfunctional thiol compound is a compound represented by the following general formula (1).

In general formula (1), R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —. L represents an n-valent linking group, and n represents an integer of 2 to 6.

<6> Any of <1> to <5>, wherein the content of the (B) polyfunctional thiol compound is 0.1 to 20% on a mass basis with respect to the total solid content of the colored photosensitive composition. The colored photosensitive composition of Claim 1.

<7> Any one of <1> to <6>, wherein the content of the (A) dye is 0.1 to 30% on a mass basis with respect to the total solid content of the colored photosensitive composition. The colored photosensitive composition described in 1.

<8> The colored photosensitive composition according to any one of <1> to <7>, wherein the (C) photopolymerization initiator is a compound having an oxime structure.

<9> The colored photosensitive composition according to any one of <1> to <8>, wherein the (C) photopolymerization initiator is an oxime compound represented by the following general formula (III).

In general formula (III), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, -CONRR ', or represents -CN, each ^{R 2} and ^{R 3} independently, -R, -OR, -COR, -SR , or -NRR' represents a. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more of carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. A ring may be formed.

<10> The colored photosensitive composition according to any one of <1> to <8>, wherein the (C) photopolymerization initiator is an oxime compound represented by the following general formula (II).

In the general formula (II), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0-5. X ²² represents a monovalent substituent, and when n is an integer of 2 to 4, a plurality of X ²² may be the same or different.

<11> A color filter using the colored photosensitive composition according to any one of <1> to <10>.

<12> A colored layer forming step of forming a colored layer by applying the colored photosensitive composition according to any one of <1> to <10> on a support;
An exposure step of pattern-like exposure to the colored layer to form a latent image;
A developing step of developing a colored layer on which the latent image is formed to form a pattern;
The manufacturing method of the color filter which has this.

<13> A liquid crystal display device comprising the color filter according to <11>.

  According to the present invention, a color filter having a colored film with high sensitivity, high contrast, and high adhesion to a substrate can be obtained, and the specific resistance of liquid crystal when the obtained color filter is used in a liquid crystal display device. It is possible to provide a colored photosensitive composition from which a color filter having a good color can be obtained. Furthermore, a color filter using the colored photosensitive composition, a method for producing the same, and a liquid crystal display device with good electrical characteristics and good image quality can be provided using the color filter.

  Hereinafter, the colored photosensitive composition of the present invention will be described in detail, and the color filter of the present invention using the same, a manufacturing method thereof, and a liquid crystal display device will be described in detail.

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises (A) a dye which is a metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound, and (B) a polyfunctional thiol compound. And (C) a photopolymerization initiator and (D) a polymerizable compound.
The colored photosensitive composition of this invention can be further comprised using binders, such as alkali-soluble resin, an organic solvent, and various additives as needed.

Hereinafter, each component which comprises the coloring photosensitive composition of this invention is demonstrated in detail. In the following, the colored photosensitive composition of the present invention may be simply referred to as “colored composition of the present invention” or “colored composition”.
In addition, in this specification, the numerical range shown using "-" represents the range below the upper limit value more than the lower limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, the alkyl group is a general term for linear, branched or cyclic alkyl groups unless otherwise specified.
In the present invention, the total solid content of the colored photosensitive composition is a total measurement of components obtained by removing the solvent from the entire colored photosensitive composition.

<(A) Dye that is a metal complex compound in which the structure represented by formula (I) is coordinated to a metal atom or a metal compound>
The colored photosensitive composition of the present invention is a dye which is a metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound (hereinafter referred to as “dipyrromethene metal complex compound” as appropriate). 1 or more types are included. The colored photosensitive composition of the present invention may contain two or more dipyrromethene metal complex compounds.
Hereinafter, the metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound will be described.

In general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, halogen, An atom, an alkyl group, an aryl group, or a heterocyclic group is represented.

In the general formula (I), the monovalent substituents represented by R ^{1 to} R ⁶ are each independently a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having a carbon number of 1 to 48, more preferably a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 2 carbon atoms) 48, more preferably an alkenyl group having 2 to 18 carbon atoms, for example, vinyl group, allyl group, 3-buten-1-yl group), aryl group (preferably An aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 hetero atoms. A cyclic group, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole-1 -Yl group), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t -Hexyldimethylsilyl group),

Hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group , Isopropoxy group, t-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group), aryloxy group (preferably having 6 to 48 carbon atoms, more preferably An aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group or a 1-naphthoxy group), a heterocyclic oxy group (preferably having a carbon number of 1 to 32, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, For example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably Or a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably having 2 carbon atoms). To 48, more preferably an acyloxy group having 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having a carbon number of 2 to 48, more preferably An alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group,

Further, in the case of a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group) or an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms). For example, 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 an N, N-dimethylcarbamoyloxy group, N-butyl group). Rucarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms) A group such as N, N-diethyl Rufamoyloxy group, N-propylsulfamoyloxy group), alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, A hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, for example, a phenylsulfonyloxy group), an acyl group (Preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (Preferably 2 to 48 carbon atoms, more Preferably, it is an alkoxycarbonyl group having 2 to 24 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl. Group),

An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably carbon A carbamoyl group of 1 to 24, for example, carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group Group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, for example, amino group, methyl Amino group, N, N-dibutylamino group, tetradecylamino group, 2- A tilhexylamino group, a cyclohexylamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24, for example, an anilino group or an N-methylanilino group), a heterocyclic amino group (preferably A heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 4-pyridylamino group, a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). For example, an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a ureido group, N, N-dimethylureido group, N-phenylureido group),

An imide group (preferably an imide group having 36 or less carbon atoms, more preferably an imide group having 24 or less carbon atoms, for example, an N-succinimide group or an N-phthalimide group), an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably Is an alkoxycarbonylamino group having 2 to 24 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (Preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonylamino group), a sulfonamide group (preferably having 1 to 48 carbon atoms, more preferably a carbon number). 1-24 A honamide group such as methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably carbon A sulfamoylamino group having 1 to 24, for example, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably having 1 to 32 carbon atoms, More preferably, it is an azo group having 1 to 24 carbon atoms, such as a phenylazo group or 3-pyrazolylazo group), an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, , Methylthio group, ethylthio group, octylthio group, cyclohexylthio group), aryl O group (preferably having a carbon number of 6 to 48, more preferably an arylthio group having 6 to 24 carbon atoms, e.g., phenylthio group),

Heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group ), An alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), an arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 carbon atoms, such as a phenylsulfinyl group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group; Ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropyls A sulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, a cyclohexylsulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, , Phenylsulfonyl group, 1-naphthylsulfonyl group), sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N -Ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group of 1 to 24, for example, A nonoxyphosphonyl 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, A phynoylamino group, a dioctyloxyphosphinoylamino group).

  When the monovalent substituent described above is a further substitutable group, it may be further substituted with any of the above-described groups (hereinafter referred to as substituent R). In addition, when it has two or more substituents R, those substituents R may be the same or different.

In the general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5, 6 or 7 members. The ring may be formed. In addition, as a ring formed, there exists a saturated ring or an unsaturated ring. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
When the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they may be substituted with any of the above-mentioned substituents R and substituted with two or more substituents. The substituents may be the same or different.
In addition, it is preferable that R ¹ and R ⁶ do not form a ring.
In the general formula (I), when R ⁷ is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges are examples of the monovalent substituents of R ^{1 to} R ⁶ described above. It is the same as the preferable range of the halogen atom, alkyl group, aryl group, or heterocyclic group mentioned as above.

In general formula (I), R ¹ and R ⁶ are each independently an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, or a sulfonamide group. Preferred are carbonamido group, ureido group, alkoxycarbonylamino group and sulfonamido group, more preferred are carbonamido group, ureido group, alkoxycarbonylamino group and sulfonamido group, and particularly preferred are carbonamido group and ureido group. .

In the general formula (I), as R ² and R ⁵ , among the above, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, A carbamoylsulfonyl group is preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are more preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, An imide group and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In general formula (I), as R ³ and R ⁴ , among the above, each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. And more preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

In general formula (I), the alkyl group represented by R ³ and R ⁴ is preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and more specifically. For example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl More preferably a branched chain having 1 to 12 carbon atoms or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and more preferably a secondary or tertiary substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Ri, more specifically, for example, isopropyl, cyclopropyl, i- butyl, t- butyl group, a cyclobutyl group, a cyclohexyl group.

In the general formula (I), the aryl group represented by R ³ and R ⁴ is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, more preferably a substituted or unsubstituted phenyl group. It is a group.
When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 3 -Pyridyl group, substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1 -Imidazolyl group, substituted or unsubstituted 1-pyrazolyl group, substituted or unsubstituted benzotriazol-1-yl group, more preferably substituted or unsubstituted 2-thienyl group, substituted or unsubstituted 4- Examples include a pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, and a substituted or unsubstituted 1-pyridyl group.

Next, the metal atom or metal compound that forms the dipyrromethene metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. Examples of the metal or metal compound include ZnCl, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, as well as AlCl ₃ , InCl ₃ , and FeCl. ₃ , metal chlorides such as TiCl ₂ , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, as a metal or a metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, and the like from the viewpoint of stability of the complex, spectral characteristics, heat resistance, light resistance, manufacturing suitability, and the like. Ni, Co, TiO, B, or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO is most preferred. Among these, Zn is particularly preferable.

In the metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound, preferred embodiments are shown below.
That is, in general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone Represented by an amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, Atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxy Sil group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group , An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, Aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group An alkoxycarbonylamino group, Ruhon'amido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, represented by a sulfamoyl group, or a phosphinoylamino group, R ⁷ is a hydrogen atom, a halogen atom, an alkyl group , An aryl group, or a heterocyclic group, and the metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO Is mentioned.

The more preferable aspect of a dipyrromethene metal complex compound is shown below.
That is, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, Amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide Group, alkylsulfonyl group, arylsulfonyl group, or sulfa Represented by a moyl group, and R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, It is represented by a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ⁷ is a hydrogen atom or a halogen atom. , An alkyl group, an aryl group, or a heterocyclic group, and a metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.

  Preferred embodiments of the metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound include the following general formulas (I-1), (I-2), and (I-3) It is a complex compound represented by these.

In the general formula (I-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, and X ² represents a group necessary for neutralizing the charge of Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.

R < ¹ > -R < ⁶ > in general formula (I-1) is respectively synonymous with R < ¹ > -R < ⁶ > in general formula (I), and its preferable aspect is also the same.
Ma in the general formula (I-1) represents a metal atom or a metal compound, and the metal atom or metal compound in the “complex in which the compound represented by the general formula (I) is coordinated to the metal atom or metal compound” The preferred range is also the same.
Formula (I-1) ^{R 7} in has the same meaning as ^{R 7} in formula (I), preferable embodiments thereof are also the same.

X ¹ in the general formula (I-1) may be any group as long as it is a group capable of binding to Ma, such as water, alcohols (for example, methanol, ethanol, propanol), and further “metal chelate” [1 ] Groups derived from the compounds described in Takeichi Sakaguchi and Keihei Ueno (1995 Nanedou), [2] (1996), [3] (1997), and the like. Among these, water, carboxylic acid compounds, alcohols, amine compounds, and amide compounds are preferable in terms of production, and water, carboxylic acid compounds, and amide compounds are more preferable.

X ^{2 in the} general formula (I-1) represents a group necessary for neutralizing the charge of Ma. For example, a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, R—CONHCO— R (R is each independently an alkyl group, aryl group, heterocyclic group), R-CONHSO ₂ -R (R is each independently an alkyl group, aryl group, heterocyclic group), etc. Among these, in terms of production, a halogen atom, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, R—CONHCO—R, and R—CONHSO ₂ —R are preferable, and a hydroxyl group, a carboxylic acid group, and R—CONHCO—R are more preferable. preferable.

X ¹ and X ² in formula (I-1) may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma. The 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings are heterocycles having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, which may be composed of only carbon and hydrogen atoms. There may be.

In the general formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently Represents a hydrogen atom or a monovalent substituent. R ⁷ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound.

R < ¹ > -R < ⁶ > in general formula (I-2) is respectively synonymous with R < ¹ > -R < ⁶ > in general formula (I), and its preferable aspect is also the same.
The monovalent substituent represented by R ^{8 to} R ¹³ in the general formula (I-2) is a monovalent substituent represented by R ^{1 to} R ⁶ of the compound represented by the general formula (I). And their preferred embodiments are also the same. When the monovalent substituent represented by R ^{8 to} R ¹³ of the compound represented by the general formula (I-2) is a further substitutable group, it is substituted with any of the substituents R described above. In the case where it is substituted with two or more substituents, these substituents R may be the same or different.

Formula (I-2) ^{R 7} in has the same meaning as ^{R 7} in formula (I), preferable embodiments thereof are also the same.
R ¹⁴ in the general formula (I-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a preferable range of R ^{14 is} the same as the preferable range of R ⁷ . When R ¹⁴ is a further substitutable group, it may be substituted with any of the aforementioned substituents R, and when it is substituted with two or more substituents, those substituents are They may be the same or different.

  Ma in the general formula (I-2) represents a metal or a metal compound, and a metal atom or a metal compound in the “complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound” It is synonymous and the preferable range is also the same.

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ in general formula (I-2) are each independently bonded to each other to form a 5-membered, 6-membered, or 7-membered compound. A membered saturated ring or an unsaturated ring may be formed. The saturated ring or unsaturated ring formed is synonymous with the saturated or unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ^6. The preferred examples are also the same.
Moreover, it is preferable that R < ¹ > and R < ⁸ > or R < ¹³ > in general formula (I-2) do not form a ring, and that R < ⁶ > and R < ⁸ > or R < ¹³ > form a ring. Preferably not.

In the general formula (I-3), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, Represents an alkyl group, an aryl group, or a heterocyclic group; R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom. Or a sulfur atom. Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), oxygen. Represents an atom, sulfur atom, or carbon atom.
X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed.

R < ² > -R < ⁵ > and R < ⁷ > in general formula (I-3) are respectively synonymous with R < ² > -R < ⁵ > and R < ⁷ > in general formula (I), and its preferable aspect is also the same.
Ma in the general formula (I-3) represents a metal or a metal compound, and has the same meaning as the metal atom or the metal compound in the complex in which the compound represented by the general formula (I) is coordinated to the metal atom or the metal compound. The preferred range is also the same.

In General Formula (I-3), R ⁸ and R ⁹ are each independently an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms). For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl Group), an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably a carbon number). An aryl group having 6 to 36, more preferably 6 to 18, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 2 heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, Triazol-1-yl group), an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy group, 2 -Ethylhexyloxy group, dodecyloxy group, cyclohexyloxy group), aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18, for example, phenoxy group, naphthyloxy group), alkylamino A group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as Ruamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, t-butylamino group, t-octylamino group, cyclohexylamino group, N, N-diethylamino Group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl-N-ethylamino group), arylamino group (preferably C6-C36, more preferably 6-18 aryl) Amino group, for example, phenylamino group, naphthylamino group, N, N-diphenylamino group, N-ethyl-N-phenylamino group), or heterocyclic amino group (preferably having 1 to 24 carbon atoms, more preferably 1-12 heterocyclic amino groups such as 2-aminopyrrole group, 3-aminopyrazole group, 2-aminopyridine Down group, a 3-aminopyridine group).

In general formula (I-3), the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R ⁸ and R ⁹ is In the case of a further substitutable group, it may be substituted with any of the above substituents R, and when substituted with two or more substituents, these substituents are the same. Or different.

In General Formula (I-3), X ³ and X ⁴ each independently represent NR ^a , an oxygen atom, or a sulfur atom. R ^a is a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. , Butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 24 carbon atoms, More preferably, it is an alkenyl group having 2 to 12, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms). A phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, Enyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), acyl group ( Preferably it is a C1-C24, more preferably C2-C18 acyl group, for example, an acetyl group, a pivaloyl group, a 2-ethylhexyl group, a benzoyl group, a cyclohexanoyl group), an alkylsulfonyl group (preferably a carbon number of 1 To 24, more preferably an alkylsulfonyl group having 1 to 18, for example, methylsulfonyl group, ethylsulfonyl group, isopropylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably 6). To 18 arylsulfonyl groups such as phenylsulfonyl group, It represents a Chirusuruhoniru group). Further, when R ^a can be substituted, it may be further substituted with a substituent, and when it is substituted with a plurality of substituents, these substituents may be the same or different.
X ³ and X ⁴ are preferably each independently an oxygen atom or a sulfur atom, and particularly preferably both X ³ and X ⁴ are oxygen atoms.

In General Formula (I-3), Y ¹ and Y ² each independently represent NR ^b , a sulfur atom, or a carbon atom, and R ^b has the same meaning as R ^a in X ³ .
Y ¹ and Y ² are preferably each independently NR ^b (R ^b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ² are particularly preferably both NH.

In general formula (I-3), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ , and carbon atom, a 5-membered ring (eg, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole) , Furan, thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline) Or a 7-membered ring (eg, cycloheptane, hexamethyleneimine).

In General Formula (I-3), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. 5-membered to be formed, 6-membered, and 7-membered ring, the ring one bond in the ring formed by said R ⁸ and Y ¹ and the carbon atom is changed to the double bond.

In the general formula (I-3), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are further substitutable rings May be substituted with the group described in any one of the substituents R, and when substituted with two or more substituents R, the substituents R may be the same or different. May be.

In General Formula (I-3), X ⁵ represents a group capable of binding to Ma, and examples thereof include the same groups as X ² in General Formula (I-1). X ⁵ preferably has 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and is bonded to a metal (Ma) with a hetero atom (eg, O, N, or S). Is preferred.
a represents 0, 1, or 2. When a is 2, two X ⁵ may be the same as or different from each other.

Preferred embodiments of the compound represented by formula (I-3) are shown below. That is, R ^{2 to} R ⁵ , R ⁷ and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are Each independently NR ^a (R ^a is a hydrogen atom, alkyl group, heterocyclic group) or an oxygen atom; Y ¹ and Y ² are each independently NR ^b (R ^b is a hydrogen atom or alkyl group), A nitrogen atom or a carbon atom, X ⁵ is an oxygen atom or a group bonded via a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, or an alkoxy group. Or R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring. A is an embodiment represented by 0 or 1.

The more preferable aspect of a compound represented by general formula (I-3) is shown below. That is, R ^{2 to} R ⁵ , R ⁷ and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are oxygen atoms. Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is an oxygen atom or a group bonded through a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, Represents an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, and R ⁹ and Y ² are bonded to each other. A 5- or 6-membered ring is formed, and a is an embodiment represented by 0 or 1.

Further preferred embodiments of the compound represented by formula (I-3) are shown below. That is, R ² and R ⁵ are each independently an optionally substituted aryloxycarbonyl group having 7 to 32 carbon atoms, R ³ and R ⁴ are each independently a phenyl group, and R ⁷ Is a hydrogen atom, R ⁸ and R ⁹ are each independently a substituted phenyl group having 6 to 36 carbon atoms or an alkyl group having 1 to 36 carbon atoms, Ma is Zn, and X ³ and X ⁴ are each In this embodiment, they are each independently an oxygen atom, Y ¹ and Y ² are each independently NH, and X ⁵ is —OC (O) CH ₃ or the following group.

  The general formulas (I-1), (I-2) and (I) are preferred embodiments of dyes in which the structure represented by the general formula (I) is a metal complex compound coordinated to a metal atom or a metal compound. Among the complex compounds represented by -3), the complex compound represented by the general formula (I-3) is a particularly preferred embodiment.

Hereinafter, specific examples of the dye which is a metal complex compound in which the structure represented by the general formula (I) used in the present invention is coordinated to a metal atom or a metal compound will be shown. However, the present invention is not limited to these.
In the following exemplary compounds 43 to 45, a / b and a / b / c represent mass ratios of the respective constituent components.

  Among the exemplary compounds of these dipyrromethene metal complex compounds, exemplary compounds (46) to (50) are also exemplary compounds of general formula (I-1), and exemplary compound (51) is an exemplary compound of general formula (I-2). Exemplified compounds (1) to (45) are also exemplified compounds of general formula (I-3).

  In addition to the above exemplary compounds, exemplary compounds (Ia-3) to (Ia-83), (Ia-1) to (IIa-20), (I-1) to (Ia) described in JP-A-2008-292970 (I-36) (II-1) to (II-11) and (III-1) to (III-103), Exemplified compounds (I-1) to (I-35) described in Japanese Patent No. 3324279 Exemplified compounds (I-1) to (I-13) described in Japanese Patent No. 3279035, Exemplified compounds (2-1) to (2-32) and (3-1) described in JP-A-11-256057 To (3-32), (4-1) to (4-26), and (5-1) to (5-26), exemplified compounds described in JP-A-2005-77953 (I-1) to ( I-6), and (VII-1) to (VII-8), described in JP-A-11-352686. Compounds (1-1) to (1-45), Exemplified compounds (1-1) to (1-50) described in JP-A No. 2000-19729, and Exemplified compounds described in JP-A No. 11-352585 ( 1-1) to (1-45) are also examples of dyes (dipyrromethene metal complex compounds) that are metal complex compounds in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound. .

  The content of the dye which is a metal complex compound in which the structure represented by the general formula (I) used in the present invention is coordinated to a metal atom or a metal compound is based on the total solid content of the colored photosensitive composition. And it is preferable that it is 0.1 to 30% on a mass basis, and it is more preferable that it is 0.5 to 20%. By setting it within this range, a good color density (for example, a color density suitable for liquid crystal display) can be obtained, and if it is 50% by mass or less, it is advantageous in that the patterning of pixels becomes good.

(Other dyes)
The colored photosensitive composition of the present invention may further contain a known dye other than the above-described dipyrromethene metal complex compound.
Other dyes that may be included in the colored photosensitive composition of the present invention include pyrazole azo dyes, anilinoazo dyes, triphenylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, Pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, squarylium dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, etc. .
Specific examples of other dyes that may be included in the colored photosensitive composition of the present invention include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, No. 6-11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10- No. 123316, JP-A-11-302283, JP-A-7-286107, JP-A 2001-4823, JP-A-8-15522, JP-A-8- No. 9771, No. 8-146215, No. 11-343437, No. 8-62416, No. 2002-14220, No. 2002-14221, No. 2002-14222 JP, 2002-14223, JP 8-302224, JP 8-73758, JP 8-179120, JP 8-151531, JP 6-230210, etc. And dyes described in the above.

<(E) Anthraquinone compound>
Other dyes that may be included in the colored photosensitive composition of the present invention are preferably (E) at least one dye of an anthraquinone compound having an anthracene-9,10-dione skeleton.
When the colored photosensitive composition of the present invention contains the anthraquinone compound, the reason is not clear, but when the colored photosensitive composition is applied to a color filter, the contrast can be effectively increased. .

  The (E) anthraquinone compound having an anthracene-9,10-dione skeleton in the present invention (hereinafter simply referred to as “anthraquinone compound”) is a compound having an absorption maximum at 400 to 700 nm, and preferably in the present invention, An anthraquinone compound having an absorption maximum at 500 to 700 nm, particularly preferably an absorption maximum at 550 to 700 nm. The anthraquinone compound having such an absorption maximum is not particularly limited in structure, and is excellent in contrast improvement effect when the colored photosensitive composition is applied to a color filter.

Among the anthraquinone compounds in the present invention, a diaminoanthraquinone compound represented by the following general formula (IX) is preferable.
Among these diaminoanthraquinone compounds, a compound represented by the following general formula (X) is more preferable from the viewpoint of absorption characteristics, and a compound represented by the following general formula (XI) is more preferable from the viewpoint of thermal stability. Furthermore, from the viewpoint of achieving both absorption characteristics and thermal stability, compounds represented by the following general formula (XII) or the following general formula (XIII) are particularly preferred.

  First, the aminoanthraquinone compound represented by the following general formula (IX) will be described.

In the general formula (IX), R ^11a and R ^12a each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, but R ^11a and R ^12a represent a hydrogen atom at the same time. Absent.

The alkyl group represented by R ^11a and R ^12a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Group, iso-propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

The aryl group represented by R ^11a and R ^12a is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, o -Methylphenyl group, p-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenylbiphenyl group, 2,6-dibromophenyl group, naphthyl group, anthranyl group, phenanthryl group and the like.

The heterocyclic group represented by R ^11a and R ^12a is preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom, or Contains sulfur atoms. Examples of the heterocyclic group include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, naphthothiazolyl, benzoxazolyl, carbazolyl, azepinyl Etc.

Moreover, the alkyl group, aryl group, and heterocyclic group represented by R ^11a and R ^12a may further have a substituent.
The substituent in the case of having a substituent is, for example, an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as a methyl group. , Ethyl group, iso-propyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably. The alkenyl group has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group. ), An alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms). For example, a propargyl group, a 3-pentynyl group, etc.), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, For example, a phenyl group, a p-methylphenyl group, a biphenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, etc.), an amino group (preferably having 0 to 30 carbon atoms, more preferably having 0 to 20 carbon atoms, particularly preferably Is an amino group having 0 to 10 carbon atoms and includes an alkylamino group, an arylamino group, or a heterocyclic amino group, and specific examples include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, A dibenzylamino group, a diphenylamino group, a ditolylamino group, etc.), an alkoxy group (preferably carbon An alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, and a 2-ethylhexyloxy group. ), An aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, 2-naphthyloxy groups, etc.), aromatic heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, and particularly preferably having 1 to 12 carbon atoms). An oxy group, and examples thereof include a pyridyloxy group, a pyrazyloxy group, a pyrimidyloxy group, and a quinolyloxy group).

Acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group. An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, etc. An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonyl group. An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably carbon An acyloxy group having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2 to 30 carbon atoms, more preferably a carbon number). An acylamino group having 2 to 20, particularly preferably 2 to 10 carbon atoms, such as an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably An alkoxycarbonylamino group having 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably Is an aryloxycarbon having 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms. An amino group such as a phenyloxycarbonylamino group), a sulfonylamino group (preferably a sulfonylamino group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). A methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 12 carbon atoms). Sulfamoyl groups such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably carbon A carbamoyl group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, For example, carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like can be mentioned. ), An alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group). An arylthio group (preferably an arylthio group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group).

An aromatic heterocyclic thio group (preferably an aromatic heterocyclic thio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a pyridylthio group, 2-benz Imidazolylthio group, 2-benzoxazolylthio group, 2-benzthiazolylthio group, etc.), sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably A sulfonyl group having 1 to 12 carbon atoms, for example, a mesyl group, a tosyl group, etc.), a sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably carbon number). 1 to 12 sulfinyl groups such as methanesulfinyl group and benzenesulfinyl group), ureido group (preferably having 1 to 3 carbon atoms). More preferably, it is a ureido group having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a ureido group, a methylureido group, and a phenylureido group.), A phosphoric acid amide group (preferably A phosphoric acid amide group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenylphosphoric acid amide). Group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (Preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Specific examples include, for example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, and a benzimidazolyl group. A benzthiazolyl group, a carbazolyl group, an azepinyl group, etc.), a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include a trimethylsilyl group and a triphenylsilyl group. These substituents may be further substituted.

In the general formula (IX), n ¹¹ represents an integer of 1 to 4, and when n ¹¹ is an integer of 2 to 4, the plurality of NR ^11a R ^12a may be the same or different.

  Next, the diaminoanthraquinone compound represented by the general formula (X) will be described.

In the general formula (X), R ^21a and R ^22a each independently represents an alkyl group or an aryl group.

The alkyl group represented by R ^21a and R ^22a is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. For example, methyl, ethyl, Examples include iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

The aryl group represented by R ^21a and R ^22a is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. For example, phenyl, o- Examples thereof include methylphenyl, p-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenylbiphenyl, 2,6-dibromophenyl, naphthyl, anthranyl, phenanthryl and the like.

The alkyl group or aryl group represented by R ^21a and R ^22a may further have a substituent. Examples of further substituents include R ^11a in the general formula (IX), Examples described above are further exemplified as further substituents for the alkyl group, aryl group and heterocyclic group represented by R ^12a . Among them, examples of the substituent are preferably an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, and a sulfonylamino group. Sulfamoyl group, sulfonyl group, ureido group, hydroxy group, halogen atom, sulfo group, carboxyl group and the like. These details and preferred embodiments are as described above.

  Next, the diaminoanthraquinone compound represented by the general formula (XI) will be described.

In the general formula (XI), R ^31a , R ^32a , R ^33a , and R ^34a each independently represent an alkyl group or a halogen atom.

The alkyl group represented by R ^31a , R ^32a , R ^33a , and R ^34a is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 2 carbon atoms. Examples include methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

Examples of the halogen atom represented by R ^31a , R ^32a , R ^33a , and R ^34a include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.

In the general formula (XI), R ^35a and R ^36a each independently represents an alkyl group, an alkoxy group, an aryloxy group, a sulfo group or a salt thereof, an aminosulfonyl group, an alkoxysulfonyl group, or a phenoxysulfonyl group.

The alkyl group represented by R ^35a and R ^36a has the same meaning as the alkyl group represented by R ^31a , R ^32a , R ^33a and R ^34a , and the preferred embodiment is also the same.

The alkoxy group represented by R ^35a and R ^36a is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. , Butoxy, 2-ethylhexyloxy and the like.

The aryloxy group represented by R ^35a and R ^36a is preferably an aryloxy group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples include oxy, 1-naphthyloxy, 2-naphthyloxy and the like.

The sulfo group represented by R ^35a and R ^36a and a salt thereof are preferably a sulfonic acid group and a group derived from a sulfonic acid salt. The sulfonate is preferably a quaternary ammonium salt or an amine salt, and particularly preferably a sulfonate having 4 to 30 carbon atoms (preferably 10 to 30, more preferably 15 to 30).

The aminosulfonyl group represented by R ^35a and R ^36a is preferably an aminosulfonyl group having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 15 carbon atoms. Ethylaminosulfonyl group, propylaminosulfonyl group, isopropylaminosulfonyl group, butylaminosulfonyl group, isobutylaminosulfonyl group, sec-butylaminosulfonyl group, pentylaminosulfonyl group, isopentylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylamino Examples include a sulfonyl group, 2-ethylhexylaminosulfonyl group, decylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group and the like. Phonyl group, diethylaminosulfonyl group, dipropylaminosulfonyl group, diisopropylaminosulfonyl group, dibutylaminosulfonyl group, disec-butylaminosulfonyl group, disec-propylaminosulfonyl group, dihexylaminosulfonyl group, methylethylaminosulfonyl group, Examples thereof include a methylbutylaminosulfonyl group, an ethylbutylaminosulfonyl group, and a phenylmethylaminosulfonyl group. Among these, a dialkylaminosulfonyl group having 4 to 15 carbon atoms in the alkyl moiety is particularly preferable.

The alkoxysulfonyl group represented by R ^35a and R ^36a is preferably an alkoxysulfonyl group having 1 to 30 carbon atoms, more preferably 2 to 20, still more preferably 2 to 15 and particularly preferably 4 to 15 carbon atoms. Examples include butylsulfonyl group, hexanesulfonyl group, decylsulfonyl group, dodecylsulfonyl group and the like.

The phenoxysulfonyl group represented by R ^35a and R ^36a is preferably a phenoxysulfonyl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms. Specific examples include a phenoxysulfonyl group, And a tolylsulfonyl group.

R ^35a and R ^36a may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic ring represented by R ^11a and R ^12a in the general formula (IX). Examples described above as the substituent of the group are given.

In the general formula (XI), n ³¹ and n ³² each independently represent an integer of 0 to 2, and when n = 2, a plurality of R ^35a and / or R ^36a may be the same or different. Good.

  Among the above, compounds selected from diaminoanthraquinone compounds represented by the following general formula (XII) or the following general formula (XIII) are preferable.

[Diaminoanthraquinone compound represented by the general formula (XII)]

In the general formula (XII), R ^41a , R ^42a , R ^43a , and R ^44a each independently represent an alkyl group or a halogen atom, and R ^31a , R ^32a , R in the general formula (XI) It is synonymous with the alkyl group and halogen atom in ^33a , ^R34a , and its preferable aspect is also the same.

R ^45a , R ^46a , R ^47a and R ^48a in the general formula (XII) each independently represents an alkyl group, a sulfo group or a salt thereof, or an aminosulfonyl group. One of R ^45a and R ^47a and one of R ^46a and R ^48a represent a sulfo group or a salt thereof, or an aminosulfonyl group. R ^45a , R ^46a , R ^47a , and R ^48a have the same ^meanings as the alkyl group, sulfo group or salt thereof, and aminosulfonyl group represented by R ^35a and R ^36a in the general formula (XI). Is the same.

[Diaminoanthraquinone compound represented by the general formula (XIII)]

In the general formula (XIII), R ^51a , R ^52a , R ^53a , and R ^54a each independently represents an alkyl group or a halogen atom, and R ^31a , R ^32a , R ^{33a in the} general formula (XI) , R ^{34a have} the same meaning as the alkyl group and halogen atom, and the preferred embodiments are also the same.

In the general formula (XIII), R ^55a and R ^56a each independently represent a hydrogen atom or an alkyl group, and the alkyl group represents R ^31a , R ^32a , R ^33a , R ^{34a in the} general formula (XI). And the preferred embodiments are also the same.
R ^57a and R ^58a each independently represent a hydrogen atom or an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is a methyl group.

In the general formula (XIII), L ^51a and L ^52a each independently represent a divalent linking group, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, —O—, —S. _{-, - NR -, - SO} 2 -, - CO-, or a divalent linking group is preferably formed by combining a plurality of these. L ^51a and L ^52a are more preferably an alkylene group having 1 to 10 carbon atoms, a phenylene group having 6 to 12 carbon atoms, a sulfonylamino group, or a divalent linking group formed by combining a plurality of these, and particularly preferable. Is a C1-C10 alkylene group, a sulfonylamino group, or a divalent linking group formed by combining a plurality of these.

The divalent linking group formed by combining the alkylene group having 1 to 10 carbon atoms or —O— or the like may be unsubstituted or substituted, and examples thereof include ethylene, propylene, butylene groups, Examples thereof include an ethyleneoxy group, a propyleneoxy group, an ethyleneaminosulfonyl group, a propyleneaminosulfonyl group, a butyleneaminosulfonyl group, a pentyleneaminosulfonyl group, and a 1-methylethylenesulfonyl group. Among these, an alkyleneaminosulfonyl group having 2 to 10 carbon atoms (eg, ethyleneaminosulfonyl group, propyleneaminosulfonyl group, butyleneaminosulfonyl group, pentyleneaminosulfonyl group) is preferable.
The divalent linking group formed by combining the arylene group having 6 to 20 carbon atoms or —O— and the like may be unsubstituted or substituted, and examples thereof include phenylene, biphenylene, and phenyleneaminosulfonyl. Among them, an aryleneaminosulfonyl group having 6 to 12 carbon atoms (e.g., a phenyleneaminosulfonyl group) is preferable.
Moreover, R of -NR- represents a hydrogen atom or a C1-C10 alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, an isobutyl group, a sec-butyl group, and a 2-ethylhexyl group.

In the general formula (XIII), L ^53a and L ^54a each independently represent an oxygen atom or a —NH— group.

Among the above, a preferable anthraquinone compound in the present invention is a compound selected from the diaminoanthraquinone compounds represented by the general formula (XII) or the general formula (XIII), and the following cases are particularly preferable. That is,
In the general formula (XII), R ^41a , R ^42a , R ^43a , and R ^44a are each independently a methyl group, an ethyl group, or a bromine atom, and R ^45a , and R ^46a are each independently And an aminosulfonyl group having 2 to 15 carbon atoms, and R ^47a and R ^48a are preferably methyl groups,
In the general formula (XIII), R ^51a , R ^52a , R ^53a , and R ^54a are each independently a methyl group, an ethyl group, or a bromine atom, and R ^55a and R ^56a are each Independently a hydrogen atom or a methyl group, R ^57a and R ^58a are each independently a hydrogen atom or a methyl group, and L ^51a and L ^52a are each independently an alkyleneamino group having 1 to 10 carbon atoms. It is preferably a sulfonyl group, an aralkyleneaminosulfonyl group having 7 to 12 carbon atoms, or an alkyleneoxy group having 2 to 10 carbon atoms, and L ^53a and L ^54a are oxygen atoms.
In this case, when the following dye compound is used in combination with a dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, the effect of the present invention is more effective. It is preferable in that it is played.

  Hereinafter, the specific example of the anthraquinone compound in this invention is shown. However, the present invention is not limited to these.

  The content of the anthraquinone compound with respect to the dipyrromethene metal complex compound is preferably 200% by mass or less, more preferably 1% by mass to 200% by mass, and more preferably 10% by mass to 150% by mass. The range is more preferable. When the ratio of the anthraquinone compound is within this range, the hue of the colored image is good and the contrast can be more effectively enhanced while maintaining fastness.

  The dye other than the dipyrromethene metal complex compound contained in the colored photosensitive composition of the present invention is 1% by mass to 200% by mass, preferably 10% by mass to 150% by mass with respect to the dipyrromethene metal complex compound. Is preferred.

(Pigment)
A pigment may be used in combination with the dipyrromethene metal complex compound in the colored photosensitive composition of the present invention.
As the pigment, a pigment having an average primary particle size of 10 nm or more and 30 nm or less is preferable. A colored photosensitive composition having excellent hue and contrast can be obtained when it is in the above embodiment.

Conventionally known various inorganic pigments or organic pigments can be used as the pigment, but organic pigments are preferably used from the viewpoint of reliability. In the present invention, examples of the organic pigment include organic pigments described in paragraph [0093] of JP2009-256572A.
In particular,
C. I. Pigment Red 177, 224, 242, 254, 255, 264,
C. I. Pigment Yellow 138, 139, 150, 180, 185,
C. I. Pigment Orange 36, 38, 71,
C. I. Pigment Green 7, 36, 58,
C. I. Pigment Blue 15: 6,
C. I. Pigment Violet 23
Is preferable from the viewpoint of color reproducibility, but the present invention is not limited thereto. These organic pigments can be used alone or in various combinations in order to increase color purity.

  When a pigment is used, the content of the pigment in the colored photosensitive composition of the present invention is preferably 0.5 to 50% by mass, and 1 to 30% by mass with respect to the total solid content of the composition. Is more preferable. When the pigment content is within the above range, it is effective to ensure excellent color characteristics.

<(B) Polyfunctional thiol compound>
The colored photosensitive composition of the present invention contains a polyfunctional thiol compound.
The colored photosensitive composition of the present invention contains a polyfunctional thiol compound to increase sensitivity and suppress ion elution caused by a coloring material such as a dye, so that the colored photosensitive composition of the present invention can be used for producing a color filter of a liquid crystal display device. When the composition is used, it is possible to prevent deterioration of image quality such as crosstalk and display a clear image with high image quality. In addition, since the color filter using the colored photosensitive composition of the present invention can have an appropriate taper in the pattern shape, there is no disconnection of the transparent electrode even when the transparent electrode is provided, and the colored pixel in pattern development. No protrusion is generated, and the linearity of the pattern is good. By providing a color filter using the colored photosensitive composition of the present invention, a high-quality liquid crystal display device can be obtained.

  In the present invention, the “polyfunctional thiol compound” means a compound having two or more thiol groups in the molecule. As the polyfunctional thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1500 is preferable, and 150 to 1000 is more preferable. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, and more preferably 2 to 6 thiol groups. Moreover, it is preferable that these polyfunctional thiol compounds are a system that is used auxiliary when a polymerizable compound described later is polymerized. Specifically, the addition amount of the polyfunctional thiol compound is set to 0.01 to 20% by mass with respect to the total solid content of the composition, or from the addition amount of the polymerizable compound described later contained simultaneously. It is preferable that the addition amount be as small as possible.

  In the present invention, the (B) polyfunctional thiol compound is preferably a compound having two or more groups represented by the following general formula (2).

In General Formula (2), R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —.

(B) As a polyfunctional thiol compound, the compound which has 2 or more and 6 or less groups represented by General formula (2) is preferable, and the compound which has 2 or more and 4 or less is more preferable.
The alkyl group in R in the general formula (2) is a linear, branched, or cyclic alkyl group, and the carbon number is preferably 1 to 16, more preferably 1 to 10. . Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and 2-ethylhexyl group. And a methyl group, an ethyl group, a propyl group, and an i-propyl group are preferable.
R is particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or an i-propyl group, and most preferably a methyl group or an ethyl group.

  In the present invention, the (B) polyfunctional thiol compound is particularly preferably a compound represented by the following general formula (1) having a plurality of the general formula (2).

In general formula (1), R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —. L represents an n-valent linking group, and n represents an integer of 2 to 6.

The alkyl group in R in General formula (1) is synonymous with R in the said General formula (1), and its preferable range is also the same. n is preferably from 2 to 4.
As L which is an n-valent linking group in the general formula (1), for example, a divalent linking group such as — (CH ₂ ) m— (m is 2 to 6), a trimethylolpropane residue, — (CH ₂ ) A trivalent linking group such as an isocyanur ring having three p- (p is 2 to 6), a tetravalent linking group such as a pentaerythritol residue, and a hexavalent linking group such as a dipentaerythritol residue. Is mentioned.

  (B) Specific examples of the polyfunctional thiol compound include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). Nate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine -2, 4, 6 (1H, 3 , 5H) - trione, and the like Suitable polyfunctional thiol compound.

  The content of the polyfunctional thiol compound is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total solid content in the colored photosensitive composition. When the content of the polyfunctional thiol compound is within this range, the sensitivity of the colored photosensitive composition is good, the storage stability is good, the adhesion between the substrate and the pixel in the obtained color filter is good, and the pattern defect is Therefore, it is possible to provide a colored photosensitive composition having good electrical characteristics when used in a liquid crystal display device.

<(C) Photopolymerization initiator>
The colored photosensitive composition of the present invention 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, cost, and the like.
The photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound. A compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable. In addition, a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.

Specifically, for example, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide), benzophenone compounds, acetophenone compounds, and derivatives thereof.
Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.

  Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, WO 2005/080337, WO 2006/018933, JP The compounds described in JP 2007-210991 A, JP 2007-231000 A, JP 2007-2699779 A, JP 2009-191061 A, and International Publication No. 2009/131189 can be used.

  Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  In the present invention, a compound represented by the following general formula (III) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

In the general formula (III), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, —CONRR 'Or -CN, and R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.

In the general formula (III), examples of the halogen atom in the case where X ¹ , X ² , and X ³ represent a halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X ³ are Examples of the alkyl group in the case of representing an alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2 -Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl , Monofluoromethyl, difluoromethyl Trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2'-yl) ethenyl and the like.
Especially, it is preferable that all of X < ¹ >, X < ² > and X < ³ > represent a hydrogen atom, or X < ¹ > represents an alkyl group and X < ² > and X < ³ > both represent a hydrogen atom.

In the general formula (III), examples of the alkyl group represented by R and R ′ include methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, Vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl , Perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R ² and R ^{3 including} R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—. Br is a particularly preferred embodiment.

(C) Among the photopolymerization initiators, in the general formula (III), X ¹ , X ² and X ³ are all hydrogen atoms; R ¹ is an alkyl group, particularly a methyl group; Those in which R ² is an alkyl group, particularly a methyl group; those in which R ³ is an alkyl group, particularly an ethyl group, are particularly suitable as a photopolymerization initiator.

  Accordingly, preferred specific examples of the photopolymerization initiator represented by the general formula (III) include compounds A to G exemplified below. However, the present invention is not limited by the following compounds.

  The photopolymerization initiator represented by the general formula (III) can be synthesized, for example, by the method described in JP-A-2005-220097.

The compound represented by the general formula (III) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  In the present invention, a compound represented by the following general formula (II) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

In the general formula (II), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0-5. X ²² represents a monovalent substituent, and when n is an integer of 2 to 4, a plurality of X ²² may be the same or different.

The monovalent substituent represented by R ²² is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ²² include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkylsulfonyl group that may have a substituent, Examples include an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or a trifluoromethyl group. , Etc.

  The aryl group that may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.

R ²² is more preferably an unsubstituted or substituted acyl group from the viewpoint of high sensitivity, specifically, an unsubstituted or substituted acetyl group, an unsubstituted or substituted group. A propionyl group having an unsubstituted or substituted or substituted benzoyl group, an unsubstituted or substituted toluyl group is preferred.
Examples of the substituent include groups represented by the following structural formula, and among these, any of (d-1), (d-4), and (d-5) is preferable.

Examples of the divalent linking group represented by A ^22, alkylene having 1 to 12 carbon atoms which may have a substituent, may cyclohexylene which may have a substituent and may have a substituent Alkynylene is mentioned.
Examples of the substituent that can be introduced into these groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Examples include aryloxy groups such as a tolyloxy group, alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.

Among these, A ²² is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Alkylene group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, An alkylene group substituted with a styryl group) is preferred.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, Ar is phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m. -, P-cumenyl group, mesityl group, etc. are mentioned. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy such as methoxy group, ethoxy group and tert-butoxy group. Groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acetoxy groups, propionyloxy groups, acyloxy groups such as benzoyloxy groups, acetyl groups, Benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylamino group, cyclohexylamino group and other alkylamino groups, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino groups, Fe Arylamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group, a hydroxy group, a carboxy group, and the like.

In general formula (III), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

The monovalent substituent represented by X ^22, optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, a substituted group An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, and a substituent And an arylthiooxy group, a halogen atom, an amino group which may have a substituent, an amide group which may have a substituent on N, and the like.

Examples of the alkyl group which may have a substituent represented by X ^22, preferably an alkyl group having 1 to 30 carbon atoms, e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, Examples thereof include a halogenated alkyl group, a 2-ethylhexyl group, a phenacyl group and the like which may have a substituent such as a cyclohexyl group and a trifluoromethyl group.

The aryl group which may have a substituent represented by X ^22, preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a biphenyl group, 1-naphthyl, 2-naphthyl, terphenyl Groups, quarterphenyl groups, o-, m-, and p-tolyl groups, xylyl groups, and the like.

The alkenyl group which may have a substituent represented by X ²² is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The alkynyl group which may have a substituent represented by X ²² is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The alkoxy group optionally having a substituent represented by X ^22, preferably an alkoxy group having 1 to 30 carbon atoms, such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, a butoxy group, benzyl An oxy group etc. are mentioned.

The aryloxy group which may have a substituent represented by X ^22, preferably an aryloxy group having 6 to 30 carbon atoms, for example, a phenyl group, 1-naphthyloxy group, 2-naphthyloxy group, Examples include 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, and the like.

The alkyl thio group optionally having a substituent represented by X ^22, preferably a thioalkoxy group having 1 to 30 carbon atoms, such as methyl thio group, ethyl thio group, propyl thio group, isopropylthio Oxy group, butylthiooxy group, isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthio Examples thereof include an oxy group, 2-ethylhexylthiooxy group, decylthiooxy group, dodecylthiooxy group, octadecylthiooxy group, and benzylthiooxy group.

As good arylthio group optionally having a substituent represented by X ^22, preferably arylthio group having 6 to 30 carbon atoms, e.g., phenylthio group, 1-naphthyl thio group, 2- Naphthylthiooxy group, 2-chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthio Oxy group, 3-cyanophenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group Group, 4-methylsulfanylphenylthiooxy group, 4-phenyls Rufanylphenylthiooxy group and the like.

Examples of the halogen atom represented by X ²² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group. Etc.

  Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.

Among these, X ²² has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio which may have a substituent Oxy group, arylthiooxy group which may have a substituent, halogenated alkyl group which may have a substituent, amino group which may have a substituent, or a substituent on N A good amide group is preferable, and an alkyl group which may have a substituent is more preferable.

Moreover, although n in general formula (III) represents the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of a synthesis | combination, and the integer of 0-2 is more preferable.
In formula (III), if X ²² there are a plurality, the plurality of X ²² may be the same,
May be different.

  Specific examples of the oxime photopolymerization initiator represented by the general formula (III) are shown below.

The compound represented by the general formula (III) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

Specific examples of organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan”.
42, 2924 (1969), U.S. Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-32070, Japanese Unexamined Patent Publication No. 60-. No. 239736, JP-A 61-169835, JP-A 61-169837, JP-A 62-58241, JP-A 62-212401, JP-A 63-70243, No. 63-298339, M.K. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and particularly, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5'-tetraphenyl Imidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

A photoinitiator can be used 1 type or in combination of 2 or more types. When using 2 or more types, multiple types of compounds represented by general formula (III) may be used, and multiple types of compounds represented by general formula (II) may be used. In addition, at least one of the compounds represented by the general formulas (II) and (III) may be used. In addition, at least one compound represented by the general formulas (II) and (III) and an oxime compound other than the compounds represented by the general formulas (II) and (III) or photopolymerization other than the oxime compound are started. An agent may be used. Moreover, you may use a sensitizer together.

  The total content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to the total solid content in the colored photosensitive composition. More preferably, 1% by mass to 5% by mass is most preferable. When the content of the photopolymerization initiator is within this range, the sensitivity at the time of exposure is high, and the color characteristics are also good.

(Sensitizer)
A sensitizer can also be added to the colored photosensitive composition of the present invention. Typical sensitizers used in the present invention include those disclosed in Crivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically pyrene, perylene, Acridine, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like can be mentioned. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.

<(D) Polymerizable compound>
The colored photosensitive composition of the present invention contains at least one polymerizable compound.
The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition, as disclosed in JP-A-2006-23696. Examples include the components described in paragraph numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

In addition, a urethane-added polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. JP-A-51-37193, JP-B-2-32293, JP-B-2-16765 And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK Oligo UA-7200 (above, Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M -402, TO-1382, TO-2349 (manufactured by Toagosei Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), V # 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) are preferred examples. Can be mentioned.
These polymerizable compounds can be used alone or in combination of two or more.

  The content of the polymerizable compound in the total solid content of the colored photosensitive composition (total content in the case of 2 or more types) is preferably 10% by mass to 80% by mass, and more preferably 15% by mass to 75% by mass. Preferably, 20% by mass to 60% by mass is particularly preferable.

If necessary, the colored photosensitive composition of the present invention may further contain an alkali-soluble binder, a chain transfer agent, a polymerization inhibitor, an organic solvent, a surfactant, an adhesion improver, a crosslinking agent, a development accelerator, and other additives. Can be contained.
Below, these components are demonstrated.

(Alkali-soluble binder)
The alkali-soluble binder 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 binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to those described above, the alkali-soluble binder includes, for example, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the above-mentioned polymer containing a polymerizable group include: Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Manufactured by Diamond Shamrock Co. Ltd.), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

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

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the Photomer 6173, and the KS resist-106. Cyclomer P series and the like are preferable.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable. It can be used alone or in combination of two or more.

(Chain transfer agent)
A chain transfer agent may be added to the colored photosensitive composition of the present invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2- Examples include mercapto compounds having a heterocyclic ring such as mercaptobenzimidazole and N-phenylmercaptobenzimidazole.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01 to 15% by mass with respect to the total solid content of the colored photosensitive composition of the present invention, from the viewpoint of reducing sensitivity variation. 1-10 mass% is more preferable, and 0.5-5 mass% is especially preferable.

(Polymerization inhibitor)
The colored photosensitive composition of the present invention may contain a polymerization inhibitor.
A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to a polymerization initiating species such as a radical generated in a colored photosensitive composition by light or heat. , Electron donation) and the like to deactivate the polymerization initiating species and to prevent unintentional initiation of polymerization. The polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A can be used.
Among these, p-methoxyphenol is preferably exemplified as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored photosensitive composition of the present invention is preferably from 0.0001 to 5% by mass, more preferably from 0.001 to 5% by mass, based on the total mass of the polymerizable compound. 001 to 1% by mass is particularly preferable.

(Organic solvent)
The colored photosensitive composition of the present invention can contain an organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each coexisting component and the coating property when it is a colored photosensitive composition. In view of safety, it is preferably selected.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propylpyruvate, a DOO methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether. , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate Etc. The.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-mentioned components, and the solubility and the improvement of the coating surface state when an alkali-soluble binder is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the colored photosensitive composition is preferably such that the total solid concentration in the colored photosensitive composition is 10% by mass to 80% by mass, and the amount is 15% by mass to 60% by mass. Is more preferable.

(Surfactant)
The colored photosensitive composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (made by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula (W) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

(In the formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following formula (W-2). R ⁵ in formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used alone or in combination of two or more.
The addition amount of the surfactant in the colored photosensitive composition of the present invention is preferably 0.01 to 2.0% by mass, particularly 0.02 to 1.0% by mass in the total solid content of the colored photosensitive composition. preferable. Within this range, the coatability and the uniformity of the cured film are good.

(Adhesion improver)
The colored photosensitive composition of the present invention may contain an adhesion improving agent.
The adhesion improver improves the adhesion between an inorganic substance serving as a support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored photosensitive composition layer. A compound. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored photosensitive composition of the present invention is preferably 0.1 to 20% by mass, and more preferably 0.2 to 5% by mass with respect to the total solid content of the colored photosensitive composition. .

(Crosslinking agent)
A supplementary crosslinking agent may be used in the colored photosensitive composition of the present invention to further increase the hardness of the colored layer obtained by curing the colored photosensitive composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.

(Development accelerator)
A development accelerator can also be added in order to promote the alkali solubility of the non-exposed region when the colored photosensitive composition layer is exposed and to further improve the developability of the colored photosensitive composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
If necessary, the colored photosensitive composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored photosensitive composition of the present invention can contain the light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of the publication. .

(Preparation method of colored photosensitive composition)
The colored photosensitive composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored photosensitive composition, the components constituting the colored photosensitive composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a colored photosensitive composition.
The colored photosensitive composition prepared as described above can preferably be used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm.

  Since the colored photosensitive composition of the present invention can form a colored cured film excellent in hue and contrast, it is used for forming colored pixels such as color filters used in liquid crystal display devices, and also for printing inks and inkjet inks. And can be suitably used as a production application for paints and the like.

(Color filter and manufacturing method thereof)
The color filter of the present invention is configured by providing a substrate and a colored region made of the colored photosensitive composition of the present invention on the substrate. The colored region on the substrate is composed of colored layers such as red (R), green (G), and blue (B) that form each pixel of the color filter.

The method for producing a color filter of the present invention includes a colored layer forming step (A) in which a colored layer (colored photosensitive composition layer) is formed by applying the above-described colored photosensitive composition on a support, and a step ( An exposure step (B) for forming a latent image by performing pattern-like exposure on the colored layer formed in A), and a developing step for developing the colored layer on which the latent image is formed to form a pattern (C).
Moreover, in the manufacturing method of the color filter of this invention, the aspect which further provided the process (D) which heat-processes with respect to the coloring pattern obtained at the process (C) is preferable.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored photosensitive composition of the present invention is applied onto a support by spin coating, slit coating, cast coating, roll coating, bar coating, ink jet or the like coating method. Is applied to form a colored layer, and then the colored layer is dried by heating (pre-baking) or vacuum drying.

  Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, silicon substrate, and resin substrate used in liquid crystal display devices. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
Moreover, the thickness of the colored layer formed with a colored photosensitive composition is suitably selected according to the objective. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, and the range of 1.0 μm to 4.0 μm is more preferable. In addition, the thickness of a colored layer is a film thickness after drying.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, pattern-like exposure is performed on the colored layer formed on the support. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .

  In addition, as other exposure light sources, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.

~ Exposure process using laser light source ~
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of ^{productivity,} preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable.

  There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. In addition, devices other than those described above are also preferably used.

-Step (C)-
Subsequently, the colored layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

  In the method for producing a color filter of the present invention, it is particularly preferable to perform post-exposure by ultraviolet irradiation on a colored pattern (pixel) formed using a colored photosensitive composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having a plurality of hue pixels, the above-described step (A), step (B), step (C), and step (D) may be repeated according to the desired number of colors.
In addition, whenever formation, exposure, and development of a single color layer are completed (for each color), the step (D) may be performed, or formation, exposure, and formation of all colored layers having a desired number of colors. After the development is completed, the step (D) may be performed collectively.

  The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast since the colored photosensitive composition of the present invention is used. When used in a liquid crystal display device or the like, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the above-described color filter of the present invention. For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can. The color filter of the present invention can also be used for a COA (Color-filter On Array) system.

  When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

[Example 1]
-Preparation of colored photosensitive composition-
The following components were mixed and dissolved to prepare a colored photosensitive composition.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 33.1 g
Organic solvent 2 (ethyl 3-ethoxypropionate) 25.2g
Alkali-soluble binder 1 (addition of cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate and methacrylic acid (30/30/40 [molar ratio], 45% propylene glycol monomethyl ether solution) 5.8 g
Alkali-soluble binder 2 (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 1.1 g
Polymerizable compound 1: Nippon Kayaku Co., Ltd., KAYARAD DPHA 2.8 g
Polymerizable compound 2: manufactured by Toagosei Co., Ltd., Aronix TO-2349 2.8 g
・ Polymerization inhibitor (p-methoxyphenol) 0.003g
Photopolymerization initiator (oxime compound 1) (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone) 0.39 g
・ Polyfunctional thiol compound 1 0.2g
-Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2g
・ Fluorine-based surfactant (Megafac F-554 manufactured by DIC) 0.01g
Blue pigment dispersion (Pigment Blue 15: 6 dispersion (solid content concentration 16.8%, pigment concentration 9.9%)) 27.0 g
・ Dye (A-1) 1.1g
・ Dye (B-1) 0.4g

The blue pigment dispersion was prepared as follows.
C. I. 12.8 parts of Pigment Blue 15: 6 and 7.2 parts of a dispersant (Solsperse 5500 manufactured by Nippon Lubrizol Co., Ltd.) are mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently mixed using a bead mill. A blue pigment dispersion was prepared by dispersing.

Below, each component used by preparation of the coloring photosensitive composition of Example 1 is shown with each component used in Examples 2-37 and Comparative Examples 1-7.
The dye (A-1) and the dye (A-2) are dyes that are dipyrromethene metal complex compounds, and the dye (B-1) and the dye (B-2) are anthraquinone compounds (anthracene-9,10-dione). Compound having a skeleton). Dye (A-3), (A-4), and dye (A-5) are dyes which are not a dipyrromethene metal complex compound and an anthraquinone compound.

Moreover, the polyfunctional thiol compound used in Examples 1-37 and Comparative Examples 1-7 is as follows.
Polyfunctional thiol compound 1: 1,4-bis (3-mercaptobutyryloxy) butane Multifunctional thiol compound 2: 1,4-bis (3-mercaptobutyloxy) butane Polyfunctional thiol compound 3: 1, 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione)
Polyfunctional thiol compound 4: trimethylolpropane tris (3-mercaptopropionate, polyfunctional thiol compound 5: pentaerythritol tetrakis (3-mercaptopropionate, polyfunctional thiol compound 6: dipentaerythritol hexakis (3- Mercaptopropionate

-Formation of colored photosensitive composition layer (colored layer)-
After applying the colored photosensitive composition prepared above on a glass (# 1737; made by Corning) substrate by spin coating, the volatile components are volatilized by drying at room temperature for 30 minutes to form the colored layer A. Formed. The colored layer A was irradiated with i rays (wavelength 365 nm) to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm ² . Next, the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. And dried with a spray to obtain a fine line pattern image. The obtained fine line pattern image was post-baked at 230 ° C. for 20 minutes to obtain a colored layer B having a thickness of 2 μm.

-Evaluation-
The sensitivity of the colored layer obtained above, the specific resistance of the liquid crystal, the spectral characteristics, the contrast, and the adhesion were evaluated by the following methods. The evaluation results are shown in Table 2 below.

(1) Sensitivity The colored layer A after coating and drying obtained above was irradiated with an irradiation light amount of 40 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm using an i-line reduction projection exposure apparatus. After the irradiation, development was performed at 26 ° C. for 45 seconds using a developer (an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%)). Subsequently, after rinsing with running water for 20 seconds, the film was dried by spraying to obtain a fine line pattern image. An image of a fine line pattern was taken from the obtained image with an optical microscope at a magnification of 200 times.
At this time, the width of the fine line was measured from the obtained image. Since the width of the fine line becomes thicker as the sensitivity is higher, the width of the fine line width from the mask width is defined as the line width sensitivity. Larger numbers are preferred because of higher sensitivity.

(2) Specific resistance of liquid crystal The colored layer B obtained above was scraped off from the substrate, and 9.0 mg of the scraped material was added to 2.00 g of liquid crystal material ZLI-4792 (Merck) and heated at 120 ° C. for 5 hours. did. Then, it filtered and the specific resistance of liquid crystal material was measured with the liquid crystal specific resistance measuring apparatus (model number ADVANTEST R8340 ULTRA HIGHT RESISTANCE ME Co., Ltd. product made by Advantest). Since the specific resistance of the liquid crystal material decreases due to the elution of metal ions, the elution of metal ions can be evaluated by the degree of the specific resistance.
<Evaluation criteria>
A: Specific resistance ≧ 5.0 × 10 ¹¹ MΩ, and no seizure failure was observed when the panel was assembled in a liquid crystal display device.
○: Specific resistance ≧ 1.0 × 10 ¹¹ MΩ, and when incorporated in a liquid crystal display device as a panel, almost no seizure failure was observed, and there was no problem in performance.
×: Specific resistance <1.0 × 10 ¹¹ MΩ, and a seizure failure occurred when a panel was assembled in a liquid crystal display device.

(3) Spectral characteristics The transmission spectrum of the colored layer B obtained above was measured using a microspectrophotometer OSP-SP200 (trade name) manufactured by Olympus Corporation. From the obtained transmission spectrum, the chromaticity coordinate x value, y value, and Y value in the CIE 1931 color system were determined.
The spectral characteristics can be said to have excellent spectral characteristics when the Y value at (x, y) = (0.138, 0.085) is high. It can be said that the larger the Y value, the better the spectral characteristics.

(4) Contrast In addition, when the obtained substrate having each colored layer B is sandwiched between two polarizing films, the luminance values when the polarizing axes of the two polarizing films are parallel and perpendicular are colored. Measured using a luminance meter (Topcon Co., Ltd., model number: BM-5A), and obtained by dividing the luminance when the polarization axes of the two polarizing films were parallel by the luminance when vertical. The value was determined as contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.

(5) Adhesiveness About the colored layer A obtained above, a mask having a mask width of 5, 10, 15, 20, and 25 μm on the colored layer A at a wavelength of 365 nm using an i-line reduction projection exposure apparatus. And irradiated with an exposure amount of 40 mJ / cm ² . After irradiation, the developer was used and developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, the film was dried by spraying to obtain a fine line pattern image. Image formation was observed by an ordinary method using an optical microscope and SEM photograph observation. The pattern dimension of the thinnest fine line pattern remaining on the substrate was used as the evaluation of adhesion.
It can be said that the thinner the fine wire remains, the better the adhesion.

[Examples 2 to 6]
In Example 1, the polyfunctional thiol compound 1 was changed to the polyfunctional thiol compounds 2 to 6 as shown in Table 1, and other than that, the colored photosensitive composition was prepared in the same manner as in Example 1. Then, a colored layer was formed and evaluated. The evaluation results are collectively shown in Table 2.

[Examples 7 to 8]
In Example 1, the dye (A-1) and the dye (B-1) were changed as shown in Table 1, and other than that, a colored photosensitive composition was prepared in the same manner as in Example 1. A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.

Example 9
In Example 1, colored photosensitivity was obtained in the same manner as in Example 1 except that the photopolymerization initiator (oxime compound 1) was changed to 4,4′-bis (diethylamino) benzophenone (photopolymerization initiator 1). A composition was prepared to form a colored layer and evaluated. The evaluation results are shown in Table 2 below.

Example 10
In Example 1, the dye (B-1) was replaced with the dye (A-1) (that is, the total amount of the dye (A-1) and the dye (B-1) in Example 1 was changed to the dye (A- Except for 1), a colored photosensitive composition was prepared in the same manner as in Example 1 to form a colored layer and evaluated. The evaluation results are shown in Table 2 below.

Example 11
In Example 1, a colored photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator (oxime compound 1) was changed to an oxime initiator having the following structure (oxime compound 2). A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.

Example 12
In Example 1, a colored photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator (oxime compound 1) was changed to an oxime initiator having the following structure (oxime compound 3). A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.

Example 13
In Example 1, a colored photosensitive composition was prepared in the same manner as in Example 1 except that the photopolymerization initiator (oxime compound 1) was changed to an oxime initiator having the following structure (oxime compound 4). A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.

[Comparative Example 1]
In Example 1, except that the polyfunctional thiol compound 1 was not added, a colored photosensitive composition was prepared and a colored layer was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

[Comparative Example 2]
In Example 7, a colored photosensitive composition was prepared and a colored layer was formed and evaluated in the same manner as in Example 1 except that the polyfunctional thiol compound 1 was not added. The evaluation results are shown in Table 2 below.

[Comparative Example 3]
In Example 8, a colored photosensitive composition was prepared and a colored layer was formed and evaluated in the same manner as in Example 1 except that the polyfunctional thiol compound 1 was not added. The evaluation results are shown in Table 2 below.

[Comparative Example 4]
In Example 1, except that polyfunctional thiol compound 1 was changed to monofunctional thiol compound 1: mercaptobenzimidazole, a colored photosensitive composition was prepared and a colored layer was formed in the same manner as in Example 1. Evaluation was performed. The evaluation results are shown in Table 2 below.

[Comparative Example 5]
In Example 10, a colored photosensitive composition was prepared in the same manner as in Example 1 except that the dye (A-1) was changed to the dye (A-3), and a colored layer was formed and evaluated. Was done. The evaluation results are shown in Table 2 below.

[Comparative Example 6]
In Example 10, a colored photosensitive composition was prepared in the same manner as in Example 1 except that the dye (A-1) was changed to the dye (A-4), and a colored layer was formed and evaluated. Was done. The evaluation results are shown in Table 2 below.

[Comparative Example 7]
A colored photosensitive composition was prepared in the same manner as in Example 1 except that the dye (A-1) was changed to the dye (A-5) in Example 1, and a colored layer was formed and evaluated. Was done. The evaluation results are shown in Table 2 below.

Table 2 shows the following.
The colored photosensitive composition using the dipyrromethene metal complex compound and the polyfunctional thiol compound of Examples 1 to 13 is excellent in sensitivity and spectral characteristics (Y value), has high contrast, excellent adhesion, and specific resistance of liquid crystal. The liquid crystal display devices obtained using the colored photosensitive compositions of Examples 1 to 13 did not cause burn-in. On the other hand, in Comparative Examples 1-3 which does not use a polyfunctional thiol, the sensitivity was low and the adhesiveness was also low. In Comparative Example 4 using a monofunctional thiol compound instead of a polyfunctional thiol compound, the sensitivity is insufficient, and in Comparative Examples 5 to 7 using a dye whose dye is not a dipyrromethene metal complex compound, all the performances deteriorated. .
In Example 9 in which no oxime initiator was used as a photopolymerization initiator, the sensitivity was slightly lowered, and in Example 10 in which no anthraquinone compound was used, the contrast was slightly low.

Example 14
The following components were mixed and dissolved to prepare a colored photosensitive composition, and a colored layer was formed in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 6.4g
・ Organic solvent 3 (diethylene glycol ethyl methyl ether) 25.2 g
・ Alkaline soluble binder 1 1.3g
・ Alkali-soluble binder 2 3.4g
・ Polymerizable compound 1 4.2 g
・ Polymerizable compound 2 1.4 g
・ Polymerization inhibitor (p-methoxyphenol) 0.003g
-Photopolymerization initiator (oxime compound 1) 0.39 g
Photopolymerization initiator 2 (1,3-dihydro-1-phenyl-2H-benzimidazol-2-thione) 0.11 g
・ Polyfunctional thiol compound 1 0.27g
-Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.16 g
-Fluorosurfactant (manufactured by DIC MegaFuck F-554, 0.2% propylene glycol monomethyl ether acetate solution) 5.36 g
Blue pigment dispersion (same as the blue pigment dispersion used in Example 1,
Pigment Blue 15: 6 dispersion (solid concentration 16.8% by mass, pigment concentration 9.9%) 22.0 g
-Dye solution 1 4.7g
・ Dye Solution 2 25.1g

The dye solution 1 was prepared by mixing and dissolving the following components to prepare a dye solution.
Organic solvent 1: Propylene glycol monomethyl ether acetate 4.23g
・ Dye (B-1) 0.47g
In addition, dye solution 2 was prepared by mixing and dissolving the following components to prepare a dye solution.
Organic solvent 1: propylene glycol monomethyl ether acetate 23.94g
・ Dye (A-1) 0.04g
・ Dye (A-6) 1.22 g

The dyes (A-6) to (A-10) used in the preparation of the colored photosensitive compositions of Examples 14 to 37 are shown below.
Dyes (A-6) to (A-10) are dyes that are dipyrromethene metal complex compounds.

[Examples 15 to 32]
In the preparation of the dye solution 2 of Example 14, the components used for the preparation of the dye solution 2 were changed as shown in Table 3, and other than that, a colored photosensitive composition was prepared in the same manner as in Example 14, A colored layer was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

[Examples 33 to 37]
In Example 14, the diethylene glycol ethyl methyl ether of the organic solvent 3 was changed to the solvent described in Table 4, and a colored photosensitive composition was prepared in the same manner as in Example 14 to form a colored layer. Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

  Table 5 shows the following. Colored photosensitive compositions of Examples 14 to 32 using dipyrromethene metal complex compounds having different structures, Examples 14 to 18 using two kinds of dipyrromethene metal complex compounds, and colored photosensitive compositions of Examples 26 to 28, In addition, in Examples 33 to 37 in which the organic solvent is changed, when used in combination with the polyfunctional thiol compound, the sensitivity and spectral characteristics (Y value) are excellent, the contrast is high, the adhesion is excellent, and the specific resistance of the liquid crystal is high. It was a big one. Further, the liquid crystal display devices obtained by using the colored photosensitive compositions of Examples 14 to 37 of the present invention did not cause burn-in.

Example 38
The following components were mixed and dissolved to prepare a colored photosensitive composition, and a colored layer was formed in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 7.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 6.6 g
・ Organic solvent 3 (diethylene glycol ethyl methyl ether) 25.2 g
・ Alkali-soluble binder 1 1.0g
・ Alkali-soluble binder 2 2.7g
・ Polymerizable compound 1 4.8 g
・ Polymerizable compound 2 1.6 g
・ Polymerization inhibitor (p-methoxyphenol) 0.003g
-Photopolymerization initiator (oxime compound 1) 0.39 g
Photopolymerization initiator 2 (1,3-dihydro-1-phenyl-2H-benzimidazol-2-thione) 0.11 g
・ Polyfunctional thiol compound 1 0.27g
-Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.16 g
-Fluorosurfactant (manufactured by DIC MegaFuck F-554, 0.2% propylene glycol monomethyl ether acetate solution) 5.36 g
Blue pigment dispersion (same as the blue pigment dispersion used in Example 1, Pigment Blue 15: 6 dispersion (solid content concentration 16.8% by mass, pigment concentration 9.9%)) 22.0 g
-Dye solution 1 4.7g
・ Dye Solution 2 25.1g

[Examples 39 to 43]
In Example 38, the photopolymerization initiator (oxime compound 1), photopolymerization initiator 2, and polyfunctional thiol compound were added as shown in Table 6 except that the amount of colored photosensitivity was the same as in Example 38. The composition was prepared to form a colored layer and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 7.

  Table 7 shows the following. Colored photosensitive composition of Example 38 in which the addition amount of the polymerizable compound was changed, Colored photosensitive composition in Examples 39 to 40 in which the amount of the polyfunctional thiol compound was changed, Photopolymerization initiator 1, Photopolymerization initiator In any of the colored photosensitive compositions of Examples 41 to 43 in which the addition amount of 2 was changed, when used in combination with the polyfunctional thiol compound, the sensitivity and spectral characteristics (Y value) were excellent, the contrast was high, and the adhesion was high. It was excellent and the specific resistance of the liquid crystal was large. Further, the liquid crystal display devices obtained using the colored photosensitive compositions of Examples 38 to 43 of the present invention did not cause burn-in.

Claims (13)

(A) a dye that is a metal complex compound in which a structure represented by the following general formula (I) is coordinated to a metal atom or a metal compound, (B) a polyfunctional thiol compound, (C) a photopolymerization initiator, (D) A colored photosensitive composition containing a polymerizable compound.

In the general formula (I), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents. The colored photosensitive composition according to claim 1, wherein the (A) dye is a complex compound represented by the following general formula (I-3).

In General Formula (I-3), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, or an alkyl. Represents a group, an aryl group, or a heterocyclic group. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom. Or a sulfur atom. Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), oxygen. Represents an atom, sulfur atom, or carbon atom.
X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed.
  The colored photosensitive composition according to claim 1 or 2, further comprising (E) an anthraquinone compound having an anthracene-9,10-dione skeleton. The colored photosensitive composition according to any one of claims 1 to 3, wherein the (B) polyfunctional thiol compound is a compound having two or more groups represented by the following general formula (2).

In general formula (2), R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —. The colored photosensitive composition according to any one of claims 1 to 4, wherein the (B) polyfunctional thiol compound is a compound represented by the following general formula (1).

In general formula (1), R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —. L represents an n-valent linking group, and n represents an integer of 2 to 6.   The content of the (B) polyfunctional thiol compound is 0.1 to 20% on a mass basis with respect to the total solid content of the colored photosensitive composition. The colored photosensitive composition described in 1.   The content of the (A) dye is 0.1 to 30% on a mass basis with respect to the total solid content of the colored photosensitive composition. Colored photosensitive composition.   The colored photosensitive composition according to any one of claims 1 to 7, wherein the (C) photopolymerization initiator is a compound having an oxime structure. The colored photosensitive composition according to any one of claims 1 to 8, wherein the (C) photopolymerization initiator is an oxime compound represented by the following general formula (III).

In general formula (III), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, -CONRR ', or represents -CN, ^{R 2} and ^{R 3} are each independently, -R, -OR, -COR, -SR, or -NRR' represents a. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more of carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. A ring may be formed. The colored photosensitive composition according to any one of claims 1 to 8, wherein the (C) photopolymerization initiator is an oxime compound represented by the following general formula (II).

In the general formula (II), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0-5. X ²² represents a monovalent substituent, and when n is an integer of 2 to 4, a plurality of X ²² may be the same or different.   The color filter which uses the colored photosensitive composition of any one of Claims 1-10. A colored layer forming step of forming a colored layer by applying the colored photosensitive composition according to any one of claims 1 to 10 on a support;
An exposure step of pattern-like exposure to the colored layer to form a latent image;
A developing step of developing a colored layer on which the latent image is formed to form a pattern;
The manufacturing method of the color filter which has this.   A liquid crystal display device comprising the color filter according to claim 11.