TWI664244B - Novel compound and composition containing the same - Google Patents

Abstract

The present invention provides a novel compound which is preferably used as a dye of a coloring photosensitive composition excellent in heat resistance and light resistance, and a coloring photosensitive composition using the same. Specifically, it provides a compound of the following general formula (1) And a coloring photosensitive composition comprising a dye (A) containing the compound, a polymerizable compound (B) having an acidic unsaturated bond having an acid value, and a photoradical polymerization initiator ( C) and a monomer (D) having an ethylenically unsaturated bond. The specific content of the general formula (1) is as described in this specification.

Description

Novel compound and composition containing the same

The present invention relates to a dye designed to have a desired hue and improved heat resistance, and a novel compound suitable for the dye. Furthermore, the invention relates to a colored photosensitive composition using the dye, which can be polymerized by energy rays, and a color filter using the colored photosensitive composition.

Compounds with strong absorption of specific light can be used as CD-R (Compact Disc-Recordable), DVD-R (Digital Versatile Disc-Recordable), DVD + R (Digital Versatile Disc + Recordable), recording layer of optical recording media such as BD-R (Blue-ray Disc Recordable), or liquid crystal display (LCD), Optical components of image display devices such as plasma display panels (PDP), electroluminescence displays (ELD), cathode ray tube display devices (CRT), fluorescent display tubes, field emission displays, etc.

Optical filters for image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), cathode ray tube display devices (CRT), fluorescent display tubes, field emission displays, etc. In the light sheet, various compounds that absorb light having a wavelength of 300 to 1100 nm are used as light absorbers.

For these light absorbers, it is required that the light absorption is particularly steep, that is, the half-value width of λmax is small, and it will not lose its function due to light or heat.

Optical filters mainly used in liquid crystal display devices (LCD) include color filters. color The filter usually uses three primary colors of RGB (Red Green Blue, Red Green Blue). However, it is difficult for a single colored material to have a pure RGB hue, and an effort is made to use a plurality of colored materials to approach the pure RGB hue. Therefore, yellow, orange, purple and other colored materials other than RGB must also be used.

The light absorber used in the color filter uses organic and / or inorganic pigments due to its high heat resistance. However, there is a problem that the brightness of the display device is reduced due to the pigment. Previously, the brightness of the light source was increased. And solve the problem. However, with the trend toward lower power consumption, development of color filters using dyes has begun to prevail.

Furthermore, in recent years, a color filter used for a solid-state imaging device has been required to reduce the thickness of a colored pattern from the viewpoint of improving the image quality. In order to reduce the thickness, the dye concentration must be increased in terms of color density. In addition, even when the molar absorption coefficient of the dye is low, a large amount of dye must be added.

However, if the dye concentration is increased, when heat treatment (post-baking) is performed after film formation, color mixing tends to occur between adjacent pixels or between upper and lower layers in a layered structure, so heat resistance is required.

In addition, the light absorber used in the color filter is also susceptible to deterioration due to external light, and light resistance is also required.

Patent Documents 1 to 3 disclose colored resin compositions for color filters containing organic pigments having a specific structure.

However, the compounds used in the coloring composition for color filters described in these documents are not satisfactory in terms of both heat resistance and light resistance.

Prior art literature Patent literature

Patent Document 1: WO2012 / 039286

Patent Document 2: WO2012 / 101946

Patent Document 3: WO2012 / 111400

Therefore, an object of the present invention is to provide a coloring composition such as a coloring photosensitive composition using a novel compound capable of solving the above problems. Another object of the present invention is to provide an optical filter using the colored photosensitive composition, particularly a color filter suitable for image display devices such as a liquid crystal display panel without reducing the brightness.

The inventors have made intensive studies and found that the compound having a specific structure is excellent in heat resistance and light resistance, and also found that the above-mentioned colored photosensitive composition does not reduce the brightness of the optical filter (especially, the color filter). The present invention is suitable for a color filter for an image display device such as a liquid crystal display panel.

The present invention has been completed based on the above findings, and provides a compound represented by the following general formula (1).

(In the formula, A represents a benzene ring, a naphthalene ring, or an anthracene ring, and these rings may be halogenated, cyano, hydroxyl, nitro, 1-12 carbon alkyl, alkoxy, halogenated alkyl, or halogenated. Alkoxy substitution, Y represents cyano or -COOR ⁴ , R ¹ represents hydrogen atom, phenyl, cyano, nitro, halogen atom, alkyl group having 1 to 12 carbon atoms, and alkyl group having 1 to 12 carbon atoms Oxygen, halogenated alkyl having 1 to 12 carbon atoms or halogenated alkoxy having 1 to 12 carbon atoms, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a carbon atom alkyl or aryl group having 6 to 20 carbon atoms of the aralkyl group having 7 to 20, R ² and R ³ in the aryl group and aralkyl group may be substituted with a halogen atom or a nitro group, R ² and R ³ in The methylene group in the alkyl group and the aralkyl group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and R ⁴ represents a hydrogen atom and a carbon number Alkyl group 1 to 12, aryl group 6 to 20 carbon atoms, aralkyl group 7 to 20 carbon atoms or heterocyclic group 2 to 35 carbon atoms, alkyl group and aralkyl group represented by R ⁴ The methylene group can be replaced by -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, X represents a single bond, nitrogen , -NR ⁵ -, an oxygen atom, a sulfur atom, -SO ₂ -, - SO-, a phosphorus atom, -PR ⁶ -, or satisfy the following <1> to <5> a condition of any of the organic groups, R ⁵ And R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and m = an integer of 2 to 6)

<1> m = 2, and X is represented by the following formula (2).

(In the formula, X ¹ represents -NR ^13- , a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a divalent aliphatic group having 3 to 35 carbon atoms, and a divalent carbon atom having 6 to 35. An aromatic ring hydrocarbon group, a divalent heterocyclic group containing 2 to 35 carbon atoms, or a group represented by any of the following (2-1) to (2-3), which is represented by X ¹ The aliphatic hydrocarbon group may be substituted by a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a halogenated alkyl group, or a halogenated alkoxy group. Among the aliphatic hydrocarbon groups represented by X ¹ Methylene may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH- or a combination of these, Z ¹ And Z ² each independently represent a direct bond, -O-, -S-, -SO _2- , -SO-, -NR ¹³ -or -PR ^14- , and R ¹³ and R ¹⁴ each independently represent a hydrogen atom and a carbon atom number An alkyl group of 1 to 8, an aryl group of 6 to 20 carbon atoms, or an aralkyl group of 7 to 20 carbon atoms. The alkyl group, aryl group, and aralkyl group represented by R ¹³ and R ¹⁴ may pass through a halogen atom, Hydroxyl or nitro substitution, methylene in alkyl and aralkyl represented by R ¹³ and R ¹⁴ may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or- CONH-, where (The group represented by the general formula (2) is in the range of 1 to 35 carbon atoms)

(In the formula, R ²¹ represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms, and R ²² represents a carbon number of 1 to Alkyl group of 10, alkoxy group of 1 to 10 carbon atoms, alkenyl group or halogen atom of 2 to 10 carbon atoms, the alkyl group, alkoxy group and alkenyl group represented by R ²¹ and R ²² may pass through a halogen atom (Substituted or unsubstituted, d is an integer from 0 to 5)

(In the formula, R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Arylthio, arylalkenyl having 8 to 20 carbon atoms, aralkyl having 7 to 20 carbon atoms, heterocyclic group or halogen atom having 2 to 20 carbon atoms, represented by R ²³ and R ²⁴ The alkyl, aryl, aryloxy, arylthio, arylalkenyl, aralkyl and heterocyclic groups may be substituted or unsubstituted by halogen atoms. The alkyl groups represented by R ²³ and R ²⁴ and The methylene group in the aralkyl group may be substituted with an unsaturated bond, -O- or -S-, R ²³ may form a ring with each other by adjacent R ²³ , e represents a number from 0 to 4, and f represents a number from 0 to 8. , G represents the number of 0 ~ 4, h represents the number of 0 ~ 4, and the total number of g and h is 2 ~ 4)

<2> m = 3, and X is represented by the following formula (3).

(In the formula, X ² represents a carbon atom substituted with R ²⁵ , an aliphatic hydrocarbon group having a trivalent carbon number of 1 to 35, an alicyclic hydrocarbon group having a trivalent carbon number of 3 to 35, and a trivalent carbon atom. 6 to 35 aromatic ring hydrocarbon group or trivalent heterocyclic group containing 2 to 35 carbon atoms, R ²⁵ represents hydrogen atom, alkyl group having 1 to 8 carbon atoms, and aryl group having 6 to 20 carbon atoms Or an aralkyl group having 7 to 20 carbon atoms, and the aliphatic hydrocarbon group represented by X ² may be a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, and a halogenated alkyl group. Or halogenated alkoxy substitution, the methylene group in the aliphatic hydrocarbon group represented by X ² may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ³ are each independently and the same as the groups represented by Z ¹ and Z ² in the above general formula (2), wherein the above general formula (3 (The bases indicated by) are in the range of 1 to 35 carbon atoms.)

<3> m = 4, and X is represented by the following formula (4).

(In the formula, X ³ represents a carbon atom, an aliphatic hydrocarbon group having a tetravalent carbon number of 1 to 35, an alicyclic hydrocarbon group having a tetravalent carbon number of 3 to 35, and a tetravalent carbon number of 6 to 35. Aromatic cyclic hydrocarbon group or tetravalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ³ may pass through halogen atom, cyano group, hydroxyl group, nitro group, and alkyl group having 1 to 8 carbon atoms. , Alkoxy, halogenated alkyl, or halogenated alkoxy, and the methylene group in the aliphatic hydrocarbon group represented by X ³ may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH- or a combination thereof, Z ¹ to Z ⁴ are independent, and are the same as the bases represented by Z ¹ and Z ² in the general formula (2) (Wherein the group represented by the general formula (4) is in the range of 1 to 35 carbon atoms)

<4> m = 5, and X is represented by the following formula (5).

(In the formula, X ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent aliphatic group having 3 to 35 carbon atoms, and a pentavalent aromatic group containing 6 to 35 carbon atoms. Or a pentavalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ⁴ may pass through a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group Group, halogenated alkyl group or halogenated alkoxy group, and the methylene group in the aliphatic hydrocarbon group represented by X ⁴ may be substituted with -O-, -S-, -CO-, -CO-O-, -O- CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ⁵ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (2) above, wherein, (The group represented by the general formula (5) is in the range of 2 to 50 carbon atoms.)

<5> m = 6, and X is represented by the following formula (6).

(In the formula, X ⁵ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms and an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms. Or a hexavalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ⁵ may pass through a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group Group, halogenated alkyl group or halogenated alkoxy group, and the methylene group in the aliphatic hydrocarbon group represented by X ⁵ may be substituted with -O-, -S-, -CO-, -CO-O-, -O- CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ⁶ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (2) above, wherein, (The group represented by the general formula (6) is in the range of 2 to 50 carbon atoms.)

Moreover, this invention provides the coloring composition containing the compound represented by the said General formula (1).

The present invention also provides a coloring photosensitive composition comprising a dye (A) containing at least one compound represented by the general formula (1), and a polymerizable compound having an acidic ethylenic unsaturated bond having an acid value. (B), a photoradical polymerization initiator (C), and a monomer (D) having an ethylenically unsaturated bond.

Moreover, this invention provides the hardened | cured material of the said coloring photosensitive composition, and the color filter for display devices using the hardened | cured material.

The colored photosensitive composition (colored alkali-developable photosensitive composition) of the present invention containing a compound having a specific structure is one having excellent heat resistance and light resistance. The cured product is suitable for a color filter for a display device.

Hereinafter, the present invention will be described based on a preferred embodiment.

In the compound represented by the general formula (1), m groups may be the same as or different from each other. The value of m is 2 to 6, and in terms of ease of synthesis, 2 to 3 is preferred.

Examples of the halogen atom that can be substituted for A in the general formula (1), the halogen atom represented by R ¹ , or the halogen atom that can be substituted for the alkyl group, aryl group, and aralkyl group represented by R ² and R ³ include the following: : Fluorine, chlorine, bromine, and iodine. Examples of the alkyl group having 1 to 12 carbon atoms which can be substituted for A or the alkyl group having 1 to 12 carbon atoms represented by R ¹ to R ⁶ include methyl and ethyl groups. , Propyl, isopropyl, butyl, second butyl, third butyl, isobutyl, pentyl, isopentyl, third pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl , Cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, 1-octyl, isooctyl, third octyl, adamantyl Examples of the alkoxy group having 1 to 12 carbon atoms which can be substituted for A or the alkoxy group having 1 to 12 carbon atoms represented by R ¹ include methoxy, ethoxy, propoxy, and iso Propoxy, butoxy, second butoxy, third butoxy, isobutoxy, pentoxy, isopentyloxy, third pentoxy, hexyloxy, cyclohexyloxy, cyclo Hexylmethoxy, tetrahydrofuranoxy, tetrahydropiperanyl, etc., as a substitute for A Examples of the halogenated alkyl group having 1 to 12 carbon atoms or the halogenated alkyl group having 1 to 12 carbon atoms represented by R ¹ include: at least one hydrogen atom of the alkyl group having 1 to 12 carbon atoms is replaced with the above Halogen atoms, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, nonafluorobutyl, etc., have 1 to 12 carbon atoms as a substitute for A Examples of the halogenated alkoxy group represented by R ¹ or the halogenated alkoxy group represented by R ^{1 having} 1 to 12 carbon atoms include those in which at least one hydrogen atom of the alkoxy group having 1 to 12 carbon atoms is replaced with the halogen atom. , Such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, nonafluorobutoxy, etc., as R ² ~ R ⁶ The aryl group having 6 to 20 carbon atoms can be exemplified by phenyl, naphthyl, anthracenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, and 4-vinylbenzene. Base, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-thirdbutylphenyl, 4-hexylphenyl, 4- Cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2, 3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3, 5-dimethylphenyl, 2,4-di-third-butylphenyl, 2,5-di-third-butylphenyl, 2,6-di-third-butylphenyl, 2,4 -Di-tertiary pentylphenyl, 2,5-di-tertiary pentylphenyl, 2,5-di-tertiary octylphenyl, 2,4-dicumylphenyl, 4- Cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocene, etc., and the number of carbon atoms represented by R ² to R ⁶ is 7 The aralkyl group of 20 includes benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, 2-phenylpropane-2-yl, benzyl, trityl, styryl, Phenyl, etc., as the heterocyclic group having 3 to 25 carbon atoms represented by R ⁴ include pyridyl, pyrimidinyl, and data Base, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolinyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furyl, benzo Furyl, thienyl, thienyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, Oxazolyl, benzo Oxazolyl, isothiazolyl, iso Oxazolyl, indolyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazol-3-yl, 2,4-dioxy Oxazidin-3-yl and the like.

As the halogen atom, alkyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, aryl group, and aromatic group described in the general formulae (2) to (6) and formulae (2-1) to (2-3) Examples of each of the alkyl groups include the same groups as those described above as examples of the alkyl group, the alkoxy group, the halogenated alkyl group, the halogenated alkoxy group, the aryl group, and the aralkyl group. In addition, among these groups, regarding the number of carbon atoms that is different from the groups listed in this paragraph, examples include those that satisfy a specific number of carbon atoms in the groups listed in this paragraph.

Regarding the substitution positions of the -NR ² R ³ group and -C (R ¹ ) = C (CN) Y group in A, when A is a benzene ring, it is usually a para position, and when A is a naphthalene ring , Usually 1,4 or 1,5, when A is anthracene ring, usually 1,4, 1,5, 1,10 or 9,10.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ¹ in the general formula (2) include methane, ethane, propane, isopropane, butane, second butane, and Tributane, isobutane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, isoheptane, third heptane , 1-methyloctane, isooctane, third octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methyl A divalent group substituted with a group such as cyclohexane by Z ¹ and Z ^2. The methylene group in these groups may be substituted with -O-, -S-, -CO-, -COO-, -OCO- , -SO _2- , -NH-, or a combination of these, the so-called combination of these, for example, -COO-O-, -COO-S-, -O-OCO-, -S- OCO-, -CO-NH-, -NH-CO-, etc., of which, preferably -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH -, -NHCO-O- Substituents, as the divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, 1- Adamantyl, 2-adamantyl, normantyl, 2-methyl Adamantyl, norbornyl Base Base, perhydronaphthyl, perhydroanthryl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [3.1.0] hexyl , Bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2.0] heptyl, bicyclo [3.1.1] heptyl, di Cyclic [2.2.1] heptyl, bicyclic [5.1.0] octyl, bicyclic [4.2.0] octyl, bicyclic [4.1.1] octyl, bicyclic [3.3.0] octyl, di Ring [3.2.1] octyl, bicyclo [2.2.2] octyl, spiro [4,4] nonyl, spiro [4,5] decyl, decalin, tricyclodecyl, tetracyclododecyl Divalent radicals such as alkyl, cedarol, cyclododecyl, etc. substituted with Z ¹ and Z ² , etc. Examples of divalent aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms include: phenylene Divalent radicals such as naphthyl, biphenyl, etc. substituted with Z ¹ and Z ² , etc. Examples of the divalent heterocyclic group containing 2 to 35 carbon atoms include pyridine, pyridine Piperidine , Pyrimidine, da ,three Hexahydrotris , Furan, tetrahydrofuran, benzodihydropiperan, dibenzopyran, thiophene, thiacyclopentane and the like are substituted by Z ¹ and Z ² divalent radicals.

These groups may be further substituted with a halogen atom, a cyano group, a nitro group, or an alkoxy group having 1 to 8 carbon atoms.

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ²¹ in the formula (2-1) include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, and the like. These groups are substituted by the above-mentioned alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl and allyl groups. , 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like, the above-described R ^{22 is} alkyl, alkoxy and The alkenyl group may be substituted by a halogen atom, and the substitution position is not limited.

Examples of the aryloxy group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ in the formula (2-3) include phenoxy, naphthyloxy, 2-methylphenoxy, and 3- Methylphenoxy, 4-methylphenoxy, 4-vinylphenyldioxy, 3-isopropylphenoxy, 4-isopropylphenoxy, 4-butylphenoxy, 4-tert-butylphenoxy, 4-hexylphenoxy, 4-cyclohexylphenoxy, 4-octylphenoxy, 4- (2-ethylhexyl) phenoxy, 2,3- Dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-methylphenoxy, 3,4-dimethylphenoxy , 3,5-dimethylphenoxy, 2,4-di-third-butylphenoxy, 2,5-di-third-butylphenoxy, 2,6-di-third-butyl Phenoxy, 2,4-di-tertiarypentylphenoxy, 2,5-tertiarypentylphenoxy, 4-cyclohexylphenoxy, 2,4,5-trimethylphenoxy Groups such as ferrocenyloxy and the groups substituted with halogen atoms as the arylthio group having 6 to 20 carbon atoms include the following: 6 to 20 carbon atoms which can be substituted with the halogen atom An aryloxy group having an oxygen atom substituted with a sulfur atom, etc., as an aryl group having 8 to 20 carbon atoms Examples of the group include a substitution of an oxygen atom of an aryloxy group having 6 to 20 carbon atoms which can be substituted by the above halogen atom with a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, Examples of alkenyl groups such as 1,3-butadienyl, 2-pentenyl, and 2-octenyl. Examples of the heterocyclic group containing 2 to 20 carbon atoms include pyridine and pyridine. Piperidine , Pyrimidine, da ,three Hexahydrotris , Furan, tetrahydrofuran, benzodihydropyran, dibenzopyran, thiophene, thiol and other groups, and these groups are substituted with halogen atoms.

Examples of the trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms represented by X ² in the general formula (3) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (2). Trivalent radicals substituted with Z ¹ , Z ² and Z ³ , the methylene groups in these radicals may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO -, -SO _2- , -NH-, or a combination of these, the so-called combination of these, for example: -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc. Among them, preferred are -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-,- As the O-CONH-, -NHCO-O- substituted, as the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, the alicyclic ring exemplified in the description of X ¹ in the general formula (2) may be mentioned. A trivalent group substituted by a hydrocarbon group of Z ¹ , Z ² and Z ³ as the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms can be exemplified in the description of X ¹ in the above general formula (2) The exemplified trivalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z ¹ , Z ² and Z ^3. Examples of the trivalent heterocyclic group containing 2 to 35 carbon atoms include the following: X ¹ in the description of the illustrated The heterocyclyl group by Z ^1, Z ² and Z ³ is a trivalent group of substituents.

Examples of the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ³ in the general formula (4) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (2). Tetravalent radicals substituted with Z ¹ , Z ² , Z ³ and Z ^4. The methylene groups in these radicals may be substituted with -O-, -S-, -CO-, -COO-, -OCO- , -SO _2- , -NH-, or a combination of these, the so-called combination of these, for example, -COO-O-, -COO-S-, -O-OCO-, -S- OCO-, -CO-NH-, -NH-CO-, etc., of which, preferably -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH -, -NHCO-O-Substituents, as the alicyclic hydrocarbon group having 3 to 35 carbon atoms having a tetravalent number, the alicyclic hydrocarbon group exemplified in the description of X ¹ in the general formula (2) may be mentioned The tetravalent radicals substituted by Z ¹ , Z ² , Z ³ and Z ^{4 are} exemplified by the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms. In the description of X ¹ in the above general formula (3), The exemplified tetravalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z ¹ , Z ² , Z ³ and Z ⁴ , and as the tetravalent heterocyclic group containing 2 to 35 carbon atoms, the above general formula ( Description 2) of the X ¹ The shown embodiment of the heterocyclic group by Z ^1, Z ^2, Z ³ and Z ⁴ of the substituted tetravalent group.

Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁴ in the general formula (5) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (2). Pentavalent radicals substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ , etc., methylene groups in these radicals may be substituted with -O-, -S-, -CO-, -CO- O-, -O-CO-, -SO _2- , -NH- or a combination of these, the so-called combination of these, for example, -COO-O-, -COO-S-,- O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc. Among them, preferred are -COO-, -O-, -OCO-, -NHCO-, -NH-, Examples of the -CONH-, -O-CONH-, and -NHCO-O- substituted, as the pentavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, include: in the description of X ¹ in the above general formula (2) The exemplified alicyclic hydrocarbon group is a pentavalent group substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ^5. As the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the above-mentioned general The pentavalent group in which the aromatic ring-containing hydrocarbon group exemplified in the description of X ¹ in formula (2) is substituted with Z ¹ , Z ² , Z ³ , Z ^4, and Z ⁵ as the pentavalent carbon number 2 to 35 Examples of the heterocyclic-containing group include: (2) The pentavalent group in which the heterocyclic group exemplified in the description of X ¹ is substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ .

Examples of the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁵ in the general formula (6) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (2). Hexavalent radicals substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ^6. The methylene groups in these radicals may be substituted with -O-, -S-, -CO-,- COO-, -OCO-, -SO _2- , -NH- or a combination of these, the so-called combination of these, for example, means -COO-O-, -COO-S-, -O- OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., of which, preferably -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH Examples of-, -O-CONH-, -NHCO-O- as the alicyclic hydrocarbon group having 3 to 35 carbon atoms having a hexavalent number include the examples exemplified in the description of X ¹ in the above general formula (2) As the hexavalent group in which the alicyclic hydrocarbon group is substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ , as the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the above can be enumerated: A hexavalent group in which the aromatic ring-containing hydrocarbon group exemplified in the description of X ¹ in the general formula (2) is substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ^5, and Z ⁶ as a hexavalent carbon atom Heterocyclic groups containing 2 to 35 can be listed : The above general formula (3) in the description of X ¹ of the embodiment shown in the heterocyclic group by ^{Z 1, Z 2, Z 3} , Z 4, Z 5 and Z ⁶ substituent of hexavalent radical.

In the compound represented by the above general formula (1), A is a benzene ring; R ¹ is a hydrogen atom; R ² and R ³ are alkyl groups having 1 to 12 carbon atoms; R ⁴ is a carbon number of 1 to Alkyl group of 12; when m is 2, X is represented by the general formula (2), and X ¹ in the formula (2) is a group selected from the group 1 below; when m is 3, X is represented by the general formula ( 3) shows that X ² in the formula (3) is a group selected from the following group 2; when m is 4, X is represented by the general formula (4), and X ³ in the formula (4) is selected from The base of group 3; when m is 5, X is represented by the general formula (5), and X ⁴ in the formula (5) is a base selected from group 4 below; when m is 6, X is represented by the general formula ( 6) shows that X ⁵ in the formula (6) is a base selected from the group 5 below, which is preferable because it is easy to obtain or produce raw materials and has high heat resistance.

(In the formula, R ⁵ is the same base as R ⁵ in the general formula (1). When there are two or more bases, they may be the same or different. P represents an integer of 1 to 3, and q represents 0. An integer of ~ 3, r represents an integer of 1 ~ 19).

Specific examples of the compound represented by the general formula (1) include the compounds represented by the following [Chem. 15] to [Chem. 20B], but the present invention is not limited to these compounds.

The compound having at least one structure represented by the general formula (1) of the present invention can be used as a dye in coloring compositions such as the coloring photosensitive composition described below, and can also be used for optical use in displays or optical lenses. Filters, photosensitive materials for silver salt photographs, dyes, coatings, inks, photoreceptors, colorants, thermal recording paper, transfer ribbons, optical recording pigments, solar cells, organic semiconductors, clinical detection reagents, lasers Treatment pigments, stains, etc.

The method for producing the compound represented by the general formula (1) is not particularly limited. For example, when m = 2, A is a benzene ring, Y is a cyano group, and X is represented by * -Z ¹ -X ¹ -Z ^2- *. It can be produced by reacting an aldehyde body with malononitrile under basic conditions like the following reaction formula. That is, when it is convenient for m = 3 ~ 6, it can also be manufactured according to it. As the base, anhydrous piperazine can also be used Etc. instead of triethylamine shown below.

(In the formula, R ¹ , R ² and R ³ are the same as the above-mentioned general formula (1), and Z ¹ , Z ² and X ¹ are the same as the above-mentioned general formula (2)).

The dye (A) of the present invention is sufficient as long as it contains at least one type of the compound represented by the general formula (1), and it may be used alone or in combination. Moreover, a well-known dye can be used other than the compound represented by the said General formula (1). Examples of well-known dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, dibenzopyran dyes, alizarin dyes, acridine dye vat dyes, thiazole dyes, naphthol dyes, Quinoline dye, nitro dye, indamine dye, Dyes, phthalocyanine dyes, cyanine dyes, and the like can also be used in combination.

Here, the "dye" refers to a case where a user dissolves in an organic solvent and uses it by dispersing with a dispersing resin or the like, and is called a "pigment" described below.

In the dye (A) of the present invention, the content of the compound represented by the general formula (1) is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass. When the content of the compound represented by the general formula (1) is less than 50% by mass, the solubility in a solvent may be reduced or the heat resistance may be reduced.

Next, the coloring composition of this invention is demonstrated. The coloring composition of this invention is a thing containing the compound represented by the said General formula (1). In the coloring composition, the above-mentioned dye (A) containing the compound, a polymerizable compound (B) having an ethylenically unsaturated bond having an acid value, a photoradical polymerization initiator (C), and the above-mentioned (B The composition in which the monomer (D) having an ethylenically unsaturated bond other than the) component is an essential component is the colored photosensitive composition of the present invention. Hereinafter, the colored photosensitive composition of the present invention will be described.

In the said coloring photosensitive composition, content of the said dye (A) becomes like this. Preferably it is 0.1-20 mass%, More preferably, it is 0.5-15 mass%. If the content of the dye (A) is less than 0.1% by mass, the colorability will be insufficient, and if it is 20% by mass, the dye (A) may be deposited in the coloring photosensitive composition.

As the polymerizable compound having an acidic unsaturated bond having an acid value as described above, Examples: (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, dicycloheptenedicarboxylic acid, butenoic acid, methacrylic acid, vinylacetic acid, allylacetic acid , Cinnamic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloxyethyl] succinate, mono [2- (meth) acryloxyethyl] phthalate , Ω-carboxy polycaprolactone mono (meth) acrylate, mono (meth) acrylate, hydroxyethyl (meth) acrylate, maleate, (meth) Unsaturation, such as hydroxypropyl acrylate, maleate, dicyclopentadiene, maleate, or a polyfunctional (meth) acrylate with one carboxyl group and two or more (meth) acrylfluorenyl groups Polyacid; phenol and / or cresol novolac epoxy resin, novolac epoxy resin with biphenyl skeleton, naphthalene skeleton, bisphenol A novolac epoxy compound, dicyclopentadiene novolac epoxy compound Novolac-type epoxy compounds, polyphenylmethane-type epoxy resins having polyfunctional epoxy groups, and unsaturated monobasic acids act on the following Hydroxyl-containing polyfunctional acrylates such as epoxy resins of epoxy compounds such as epoxy compounds represented by formula (7) and polybasic acid anhydride, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and succinic anhydride Reactants of dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, etc., that is, polymers such as polyfunctional acrylates with acid values.

(In the formula, X ⁴¹ represents a direct bond, a methylene group, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS-, -SO-, -CO-, -OCO- or a group represented by the above formulae (2-1) to (2-3), the alkylene group may be substituted with a halogen atom, R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group or halogen atom having 2 to 5 carbon atoms, An oxy group and an alkenyl group may be substituted with a halogen atom, and s is an integer of 0 to 10).

These polymerizable compounds may be used singly or in combination of two or more kinds, and may be used in combination with a polymerizable compound having an ethylenically unsaturated bond which does not have an acid value. When two or more types are used, they may be copolymerized in advance and used as a copolymer.

Examples of the polymerizable compound having an ethylenically unsaturated bond that does not have an acid value include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) Glycidyl acrylate, the following compounds No.A1 to No.A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate , Cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, (meth) Lauryl acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, ( Dimethylaminopropyl methacrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, Ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, (meth) Benzyl acrylate Ester, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate Ester, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) Unsaturated monobasic acids such as acrylate, dihydrolinalool di (meth) acrylate, tris [(meth) acrylfluorenylethyl] isocyanurate, (meth) acrylic polyester oligomers, etc. Esters of alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride , Tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-di Carboxylic anhydride, trialkyltetrahydroo Dicarboxylic anhydride-maleic anhydride adducts, dodecenyl succinic anhydride, methylbicycloheptene dicarboxylic anhydride and other unsaturated polybasic acid anhydrides; (meth) acrylamide, methylenebis- (methyl ) Acrylamide, Diethylene triamine tri (meth) acrylamide, xylylene bis (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (methyl ) Unsaturated monoacids such as acrylamide and amines of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, dicyanethylenevinyl, allylcyanide ; Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, benzoic acid, ethylene Unsaturated aromatic compounds such as phenol, vinyl sulfonate, 4-vinylbenzenesulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, olefin Unsaturated amine compounds such as propylamine, N-vinylpyrrolidone, vinylpiperidine; vinyl methyl ether, vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl condensation Vinyl ethers such as glycerol ether; unsaturated fluorene imines such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide; indene such as indene, 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, polymethyl (meth) acrylate, poly (meth) acrylate, poly Macromonomers with mono (meth) acrylfluorene groups at the ends of polymer molecular chains such as siloxane; (meth) acrylonitrile, ethylene, propylene, butene, vinyl chloride, vinyl acetate and other vinyl compounds And macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate with tricyclodecane skeleton, N-phenylmaleimide imine, methacrylic acid Isomethyl-3-ethyloxetane, etc., copolymers with (meth) acrylic acid, and isocyanates having unsaturated bonds with Karenz MOI and AOI manufactured by Showa Denko Corporation A copolymer of (meth) acrylic acid, or vinyl chloride, vinylidene chloride, divinyl succinic acid, diallyl phthalate, triallyl phosphate, Triallyl cyanurate, divinyl sulfide, vinyl imidazole, vinyl Oxazoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinyl monomers containing hydroxyl groups and vinyl carbamate compounds of polyisocyanate compounds, vinyl monomers containing hydroxyl groups, and polyepoxides Compounds such as ethylene-based epoxy compounds, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and other polyfunctional isocyanates such as toluene diisocyanate and hexamethylene diisocyanate.

In order to improve the developability of the photosensitive composition for acid value adjustment, a monofunctional or polyfunctional epoxy compound may be used together with the polymerizable compound having an ethylenically unsaturated bond having an acid value. The polymerizable compound having an acidic unsaturated bond having an acid value is preferably in a range of 5 to 120 mgKOH / g of the solid component, and the amount of the monofunctional or polyfunctional epoxy compound is preferably to satisfy the above. The acid value is selected.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, and isopropyl ether. Butyl glycidyl ether, third butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, cetyl glycidyl ether, 2-ethyl Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether Ether, tolyl glycidyl ether, 2-methyltolyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether Glyceryl ether, methacrylic acid 2 , 3-epoxypropyl ester, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinyl cyclohexane monoxide, 1,2-epoxy-4-vinyl cyclohexane, epoxy Benzene, pinene oxide, methyl phenylene oxide, cyclohexane, propylene oxide, etc.

As the polyfunctional epoxy compound, if one or more members selected from the group consisting of a bisphenol-type epoxy compound and glycidyl ethers are used, a coloring alkali-developing and photosensitive composition having further excellent characteristics can be obtained, so that good. As the bisphenol-type epoxy compound, in addition to the epoxy compound represented by the general formula (7), for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can be used. As the glycidyl ethers, Examples: ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether Ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, Tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tris (glycidyloxymethyl) propane, 1 , 1,1-tris (glycidyloxymethyl) ethane, 1,1,1-tris (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) ) Methane.

In addition to the above, phenolic novolac epoxy compounds, biphenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene phenols can also be used. Novolak epoxy compounds such as varnish epoxy compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carboxylic acid esters, 3,4 -Alicyclic epoxy compounds such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid di Glycidyl esters, such as glycidyl ester, diglycidyl tetrahydrophthalate, glycidyl dimer, etc .; tetraglycidyl diamino diphenylmethane, triglycidyl-p-aminophenol, N, Glycidylamines such as N-diglycidylaniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethyl allantoin, triglycidyl isocyanurate; two Dioxide compounds such as oxidized dicyclopentadiene; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds, etc.

In the coloring photosensitive composition, the content of the polymerizable compound (B) having an ethylenically unsaturated bond having an acid value in the coloring photosensitive composition is preferably 0.1 to 90% by mass, and more preferably 1 to 80% by mass. If the content of the polymerizable compound (B) is less than 0.1%, the developing characteristics become insufficient, and if it exceeds 90%, the strength of the cured film may become insufficient.

The photo-radical polymerization initiator may be a compound capable of starting radical polymerization upon exposure to light, and examples thereof include acetophenone-based compounds, benzophenone-based compounds, benzophenone-based compounds, 9 -Oxysulfur Ketone compounds, such as ketone compounds, oxime compounds, and the like are preferred.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 4'-isopropyl-2-hydroxy- 2-methylphenylacetone, 2-hydroxymethyl-2-methylphenylacetone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminophenethyl Ketone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidebenzylidene, 1-hydroxycyclohexylphenylketone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholinylacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1 , Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl Methyl-1-propane-1-one and the like.

Examples of the benzophenanthrene-based compound include benzophenanthrene and fennelpyrin.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzophenybenzoate, Michelin, 4,4'-bisdiethylaminobenzophenone, 4 , 4'-dichlorobenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide and the like.

Examples of the oxime-based compound include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylideneoxime)], ethyl ketone, 1- [9-ethyl- 6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime), ketone, (2-methylphenyl) [6-nitro -9- [3- (trimethylsilyl) propyl] -9H-carbazol-3-yl]-, 1-O-acetamidoxime), ketone, (9-ethyl-6- Nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetamidooxime, ketone, (9-ethyl-6-nitro-9H-carbazol-3-yl ) [2-methyl-4- (4-morpholinyl) phenyl), O-acetamidooxime, ketone, (3,5-dinitrophenyl) (9-ethyl-6-nitro -9H-carbazol-3-yl) (2-methylphenyl), O-acetamidooxime, ketone, (9-ethyl-6-nitro-9H-carbazol-3-yl) (3-nitrophenyl), O-acetylamoxime, 1,3,5-tris -2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tri [2- (acetamyloxy) -3- [3-[(1E) -1-[(acetamidine (Oxy) iminoethyl] -6-nitro-9H-carbazole-9-yl] propyl]-, 1,2-butanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-acetylamoxime), 1,2-butanedione, 1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl]-, 2 -(O-Ethyl oxime), 1,2-butanedione, 1,1 '-(thiodi-4,1-phenylene) bis-, 2,2-bis (O-acetamido Oxime), 1,2-butanedione, 1- [4- (phenylthio) phenyl]-, 2- [O- (4-methylbenzylidene) oxime], and the like.

As 9-oxysulfur Compounds, 9-oxysulfur 2-methyl 9-oxysulfur 2-ethyl 9-oxysulfur , 2-chloro9-oxysulfur , 2-isopropyl 9-oxysulfur , 2,4-diethyl 9-oxysulfur Wait.

Examples of other photoradical polymerization initiators include 2,4,6-trimethylbenzylidenediphenylphosphine oxide, and bis (cyclopentadienyl) -bis [2,6-difluoro- 3- (pyrrole-1-yl)] titanium and the like.

These photo-radical polymerization initiators can be used by mixing one or more kinds depending on the required performance.

In the coloring photosensitive composition, the content of the photo radical polymerization initiator (C) in the coloring photosensitive composition is preferably 0.1 to 30% by mass, and particularly preferably 0.5 to 10% by mass. If the content of the photopolymerization initiator (C) is less than 0.1% by mass, the curing by exposure may become insufficient. If the content of the photopolymerization initiator (C) is more than 30% by mass, the When the initiator (C) is precipitated in the resin composition.

In the colored photosensitive composition of the present invention, as the monomer (D) having an ethylenically unsaturated bond, the aforementioned polymerizable compound having an ethylenically unsaturated bond having no acid value can be used. As for the content of the monomer (D) having an ethylenically unsaturated bond, it is preferably 10 to 1000% by mass, and more preferably 20 to 100% by mass relative to the polymerizable compound having an ethylenically unsaturated bond having an acid value. 800% by mass.

To the coloring photosensitive composition, an inorganic pigment or an organic pigment may be further added. For example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a dibenzopyran compound, a quinoline compound, or the like may be used. Anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindolin compounds, quinacridone compounds, anthracene compounds, fluorene compounds, hydrazone compounds, diketopyrrolopyrrole Compounds, thioindigo compounds, di Compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigments; carbon black obtained by furnace method, channel method, heating method Or carbon black such as acetylene black, Ketjen black, or lamp black; the carbon black is adjusted and covered by epoxy resin, and the carbon black is dispersed in a solvent in advance to absorb 20 ~ 200 mg / g of resin, acidic or alkaline surface treatment of the above carbon black, average particle diameter of 8nm or more and DBP oil absorption of 90ml / 100g or less, calculated from CO and CO ₂ in volatile matter at 950 ° C The total oxygen content is 9mg or more per 100m ² of surface area of carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon nanohorn, carbon aerogel, fullerene; Aniline Black, Pigment Black 7, Titanium Black; Hydrophobic Resin, Chrome Oxide Green, Milori Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine, Iron Blue, Ultramarine Blue, Sky Blue, Dark Green , Emerald green, lead sulfate, yellow dan, zinc yellow, iron dan (red Iron (III)), cadmium red, synthetic iron black, umber inorganic or organic pigment. These pigments can be used alone or in combination.

As the inorganic pigment or organic pigment, a commercially available pigment can also be used, and examples thereof include pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

The colored photosensitive composition may be dissolved or dispersed in an organic solvent as required, and may be applied by a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, or various printing methods. A known mechanism such as immersion or dipping applies the obtained coating solution to a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc., and hardens it by light irradiation.

Examples of the organic solvent include solvents that can generally dissolve or disperse the above components as necessary, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, and methyl Ketones such as isobutyl ketone, cyclohexanone, 2-heptanone; ether, di Ether solvents such as alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Ester solvents such as isopropyl ester, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, TEXANOL, etc .; cellulosic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; methanol , Ethanol, iso-or-n-propanol, iso-or-n-butanol, pentanol and other alcohol-based solvents; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetic acid Ether (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate and other ether ester solvents; BTX solvents such as benzene, toluene, and xylene; hexane, Aliphatic hydrocarbon solvents such as heptane, octane, cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, Swazol # 310 (Cosmo Songshan Petroleum (stock)), Solvesso # 100 (Exxon Chemical) and other paraffin-based solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, and 1,2-dichloroethane; halogenated chlorobenzene and the like Aromatic hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N- Methylpyrrolidone, dimethylsulfinium, water, etc. These solvents can be used alone or as a mixed solvent of two or more. Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc., are caused by the resist and the photopolymerization initiator in the photosensitive composition. Good compatibility because of good compatibility.

The colored photosensitive composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon dioxide, and aluminum oxide; layered clay minerals, and rice Lolita blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicates, calcium silicates, hydrogen Alumina, platinum, gold, silver, copper, etc.

When a pigment and / or an inorganic compound is used for the coloring photosensitive composition, a dispersant may be added. As the dispersant, any dispersant capable of dispersing and stabilizing colored materials and inorganic compounds may be used. Commercially available dispersants such as BYK series manufactured by BYK-Chemie, etc. may be used. Polymeric dispersants of polyesters, polyethers, polyurethanes with functional groups, functional groups having a nitrogen atom as a basic functional group and a functional group having a nitrogen atom are amines, and / or their quaternary salts, and Those with amine value of 1 ~ 100mgKOH / g.

Further, to the colored photosensitive composition, a thermal polymerization inhibitor such as p-anisole, hydroquinone, catechol, tertiary butyl catechol, and phenothiazine may be added as needed; a plasticizer; ; Next accelerators; fillers; defoaming agents; leveling agents; surface conditioners; phenol-based antioxidants, phosphite-based antioxidants, thioether-based antioxidants and other antioxidants; UV absorbers; dispersion aids; Coagulants; catalysts; effect promoters; cross-linking agents; tackifiers and other commonly used additives.

In addition, by using other organic polymers together with the polymerizable compound having an ethylenically unsaturated bond having an acid value, the properties of the cured product of the colored photosensitive composition can also be improved. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, and styrene- (meth) acrylic acid copolymer. , (Meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS Resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyraldehyde, cellulose ester, polypropylene ammonium, saturated polyester, phenol resin, phenoxy resin, polyamine Polyimide resin, polyamic acid resin, epoxy resin, etc. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred.

In the coloring photosensitive composition, a thermal radical polymerization initiator, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine, and the like may be used in combination.

Examples of the thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), and 2,2'-azobis -2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetamido-1-phenylethane) and other azo-based initiators; benzamidine peroxide, benzene peroxide Peroxide-based starters such as formamidine di-tert-butyl, tert-butyl pervalerate, bis (4-tert-butyl cyclohexyl) peroxydicarbonate, ammonium persulfate, persulfuric acid Persulfates such as sodium and potassium persulfate. These can be used singly or in combination of two or more kinds.

As said chain transfer agent and sensitizer, the compound containing a sulfur atom can be used normally. Examples include: thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine Acid, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) aminomethane] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- ( 3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol , 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole Mercapto compounds such as 2-mercapto-3-hydroxypyridine, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), etc. Disulfide compounds obtained by oxidation of this mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodinated alkyl compounds, trimethylolpropanetriol (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, sebacylthiol, 1,4-dimethylmercaptobenzene Butanediol bisthiopropionate, butanediol bis thioglycolate, ethylene glycol bis thioglycolate, trimethylolpropane Trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol Aliphatic polyfunctional thiol compounds such as tetrathioglycolate, trihydroxyethyltrithiopropionate, the following compound No. Cl, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko Corporation.

As the surfactant, a fluorine surfactant such as a perfluoroalkyl phosphate, a perfluoroalkyl carboxylate, an anionic surfactant such as a higher fatty acid base salt, an alkyl sulfonate, or an alkyl sulfate can be used. , Higher amine hydrohalates, quaternary amine salts and other cationic surfactants, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglyceride and other nonionic interfaces Surfactants such as active agents, amphoteric surfactants, and polysiloxane surfactants can also be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403 and the like having isocyanate groups, methacryl groups, and epoxy groups can be preferably used. Silane coupling agent.

Examples of the melamine compound include (poly) methylol melamine, (poly) methylol glycoluril, and (poly) methylol benzoguanidine Compounds in which all or part (at least 2) of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylolurea are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and they may be the same as or different from each other. In addition, the hydroxymethyl group which is not alkyl etherified may be self-condensed in one molecule, or may be condensed between two molecules, and as a result, an oligomer component is formed. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycol urea, tetrabutoxymethylglycol urea, and the like can be used. Among these, alkyl melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred.

In the coloring photosensitive composition described above, the dye (A), the polymerizable compound (B) having an ethylenically unsaturated bond having an acid value, the photoradical polymerization initiator (C), and the ethylenically unsaturated bond The content of any component (excluding organic solvents) other than the monomer (D) is an appropriate content depending on the purpose of use, and is not limited, but is preferably an ethylenically unsaturated bond with respect to an acidic unsaturated bond 100 parts by mass of the polymerizable compound (B) is 500 parts by mass or less in total.

In addition, as a light source of the active light used for curing the colored photosensitive composition, a light emitting a wavelength of 300 to 450 nm can be used, and for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, and the like can be used.

Furthermore, direct laser writing is useful in terms of not only improving productivity, but also improving imagery and position accuracy. The laser direct writing method uses laser light for an exposure light source. Never use a mask to directly form an image based on digital information from a computer or the like. As the above-mentioned laser light, light with a wavelength of 340 to 430 nm can be preferably used. Argon ion laser, helium neon laser, YAG can also be used. Lasers and semiconductor lasers emit light from the visible to the infrared. When such lasers are used, sensitizing pigments that can be absorbed in the visible to infrared region can be added.

The colored photosensitive composition (or its cured product) can be used for color display of photocurable coatings or varnishes, photocurable adhesives, printed substrates, or color televisions, PC monitors, portable information terminals, and digital cameras. Color filters in liquid crystal display panels, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, and resins for photoforming Ning Adhesive coatings, photoresists for electronics, plating resists, etching resists, both liquid and dry films, solder resists, color filters for various display applications or plasma displays Resists for forming structures in manufacturing steps of panels, electroluminescent display devices, and LCDs, compositions for sealing electrical and electronic parts, solder resists, magnetic recording materials, micro mechanical parts, optical waveguides, and optical switches , Masks for plating, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing three-dimensional objects by stereolithography, materials for holographic imaging, drawings Image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and visible laser direct images The photoresist material used for the system, the photoresist material used for forming the dielectric layer in the successive lamination of the printed circuit board, or the protective film are various uses, and their uses are not particularly limited.

The colored photosensitive composition is used for forming pixels of a color filter, and is particularly useful as a photosensitive composition for forming a color filter for a display device for an image display device such as a liquid crystal display panel.

The color filter for a display device is preferably formed by the following steps: (1) a step of forming a coating film of the colored photosensitive composition on a substrate, and (2) the coating film having a specific pattern shape A step of irradiating the active light with a mask, (3) a step of developing the exposed film using a developing solution, and (4) a step of heating the film after development. Moreover, the said coloring photosensitive composition is also useful as a coloring photosensitive composition of the inkjet system without a development process.

[Example]

Hereinafter, the present invention will be described in more detail with examples and the like, but the present invention is not limited to these examples and the like.

[Examples 1-1 and 1-2] Synthesis of compounds No. 1 and No. 2

Put aldehydes (4 mmol), malononitrile (8 mmol), and anhydrous pipette into the reaction vessel. (0.03 g) and dimethylacetamide (5 g), and these were dissolved and stirred at 80 ° C for 5 hours. 7 g of ethanol was added dropwise, and crystallization was performed. The obtained solid was filtered, washed with ethanol, concentrated, and then purified by silica gel column chromatography (developing solution: toluene) and dried to obtain each yellow solid. ¹ H-NMR (nuclear magnetic resonance) and IR (infrared radiation) were used to confirm that the obtained yellow solid was the target. The absorption wavelength characteristics were measured. The results are shown in [Table 1] and [Table 2].

[Examples 1-3 and 1-4] Synthesis of compounds No. 3 and No. 4

Put aldehydes (4 mmol), ethyl cyanoacetate (8 mmol), and anhydrous pipette into the reaction vessel. (0.03 g) and dimethylacetamide (5 g), and these were dissolved, and stirred at 50 ° C for 5 hours. 7 g of ethanol was added dropwise and crystallized. The obtained solid was filtered and washed with ethanol to obtain each yellow solid. ¹ H-NMR and IR confirmed that the obtained yellow solid was a target substance. The absorption wavelength characteristics were measured. The results are shown in [Table 1] and [Table 2].

[Example 1-5] Synthesis of compound No. 5

Put aldehydes (4 mmol), malononitrile (12 mmol), and anhydrous pipette into the reaction vessel. (0.04g) and dimethylacetamide (5g), and these were dissolved, and it stirred at 50 degreeC for 3 hours. 7 g of ethanol was added dropwise and crystallized. The obtained solid was filtered and washed with ethanol to obtain a yellow solid. ¹ H-NMR and IR confirmed that the obtained yellow solid was a target substance. The absorption wavelength characteristics were measured. The results are shown in [Table 1] and [Table 2].

[Evaluation Examples 1-1 to 1-5] Evaluation of absorption wavelength characteristics

The absorption wavelength characteristics of the compounds No. 1 to No. 5 obtained above and the comparative compounds No. 1 and 2 described above were evaluated in a CHCl ₃ solution. The results are shown in [Table 3].

As is clear from the results of the above [Table 3], the dye (A) of the present invention containing the compound represented by the general formula (1) has an appropriate absorption wavelength.

[Examples 2-1 to 2-5] Preparation of colored photosensitive composition No. 1 to No. 5

<Step 1> Preparation of photosensitive composition No. 1

39.7 g of SPC-1000 (manufactured by Showa Denko) as the component (B), 9.2 g of A-9300-1-CL (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) as the (D) component, and Irgacure as the (C) component 0.8 g of OXE-01 (manufactured by BASF), 28.0 g of PGMEA as a solvent, and 2.31 g of FZ 2122 (manufactured by Dow Corning Toray) as other components were mixed and stirred until insoluble matter disappeared to obtain a photosensitive composition No. .1.

<Step 2> Preparation of dye liquid No. 1 to No. 5

1.90 g of dimethylacetamide was added to 0.10 g of each of the compounds No. 1 to No. 5 obtained in the above as the component (A), and the mixture was stirred and dissolved.

<Step 3> Preparation of colored photosensitive composition No. 1 to No. 5

5.0 g of the photosensitive composition No. 1 obtained in step 1 and 1.0 g of each of the dye liquids No. 1 to No. 5 obtained in step 2 were mixed to obtain the colored photosensitive composition of the present invention, respectively. No.1 ~ No.5.

[Comparative Examples 2-1 and 2-2] Preparation of Comparative Colored Sensitive Light Compositions No. 1 and No. 2

Except that the compound No. 1 of the component (A) in Step 2 of Example 2-1 was changed to Comparative Compounds No. 1 and No. 2, a comparison was obtained by the same method as in Example 2-1. Colored photosensitive compositions No. 1 and No. 2.

[Evaluation Examples 2-1 to 2-5 and Comparative Evaluation Examples 2-1 and 2-2] Evaluation of heat resistance by firing

The colored photosensitive compositions No. 1 to No. 5 and the comparatively colored photosensitive compositions No. 1 and No. 2 obtained above were applied to a glass substrate at 410 rpm × 7 sec, and a hot plate was used. Drying (90 ° C, 90sec). The obtained coating film was exposed with an ultra-high pressure mercury lamp (150 mJ / cm ² ). The exposed coating film was fired at 230 ° C for 30 minutes. The absorbance of the coating film before firing (after exposure) and the absorbance of the coating film after firing at the maximum absorption wavelength (λmax) of the compound (dye) used are measured. The coating film before firing (after exposure) will be measured. The ratio of the absorbance of the coating film after firing at a light absorbance of 100 was evaluated as the relative intensity. In addition, the closer the absorbance of the baked film to 100, the higher the heat resistance. The results are shown in [Table 4].

From the above results, it is clear that the colored photosensitive composition of the present invention has high heat resistance.

[Evaluation Examples 3-1 to 3-5 and Comparative Evaluation Examples 3-1 and 3-2] Evaluation of light resistance

The colored photosensitive compositions No. 1 to No. 5 and the comparatively colored photosensitive compositions No. 1 and No. 2 obtained above were applied to a glass substrate at 410 rpm × 7 sec, and a hot plate was used. Drying (90 ° C, 90sec). The obtained coating film was exposed with an ultra-high pressure mercury lamp (150 mJ / cm ² ). A xenon lamp light resistance tester table type XT-1500L manufactured by Suga Test Instruments was used to perform a light resistance test for 12 hours on the coated film after exposure. The absorbance of the coating film before the light resistance test at the maximum absorption wavelength (λmax) of the compound (dye) used is measured, and the absorbance of the coating film after the light resistance test is measured. The absorbance of the coating film before the light resistance test will be determined. The ratio of the absorbance of the coating film after the light resistance test at 100 was evaluated as the relative intensity. In addition, the closer the absorbance of the coating film after the light resistance test is to 100, the higher the light resistance. The evaluation results are shown in [Table 5].

From the above results, it is clear that the colored photosensitive composition of the present invention has high light resistance.

From the above results, it is clear that the dye using the novel compound of the present invention has absorption in an appropriate wavelength region, and the photosensitive composition using the dye and its cured product have high heat resistance and light resistance. Therefore, the novel compound and colored photosensitive composition of the present invention are useful for a color filter for a display device and a liquid crystal display panel using the same.

Claims (5)

A compound represented by the following general formula (1), the following [Chemical 15], the following [Chemical 16], the following [Chemical 20A], or the following [Chemical 28], (In the formula, A represents a benzene ring, a naphthalene ring, or an anthracene ring, and these rings may be halogenated, cyano, hydroxyl, nitro, 1-12 carbon alkyl, alkoxy, halogenated alkyl, or halogenated. Alkoxy substituted, Y represents cyano or -COOR ⁴ , R ¹ represents hydrogen atom, phenyl, cyano, nitro, halogen atom, alkyl group having 1 to 12 carbon atoms, and alkyl group having 1 to 12 carbon atoms Oxygen, halogenated alkyl having 1 to 12 carbon atoms or halogenated alkoxy having 1 to 12 carbon atoms, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a carbon atom alkyl or aryl group having 6 to 20 carbon atoms of the aralkyl group having 7 to 20, R ² and R ³ in the aryl group and aralkyl group may be substituted with a halogen atom or a nitro group, R ² and R ³ in The methylene group in the alkyl group and the aralkyl group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and R ⁴ represents a hydrogen atom and a carbon number Alkyl group 1 to 12, aryl group 6 to 20 carbon atoms, aralkyl group 7 to 20 carbon atoms or heterocyclic group 2 to 35 carbon atoms, alkyl group and aralkyl group represented by R ⁴ The methylene group can be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, X represents a single bond, a nitrogen atom , -NR ^5- , oxygen atom, sulfur atom, -SO _2- , -SO-, phosphorus atom, -PR ⁶ -or an organic group satisfying any one of the following conditions <1> to <5>, R ⁵ And R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, m = an integer of 2 to 6) <1 > m = 2, and X is represented by the following formula (2), * -Z ¹ -X ¹ -Z ^2- * (2) (wherein X ¹ represents -NR ^13- , and the number of carbon atoms is 1) ~ 35 aliphatic hydrocarbon group, divalent alicyclic hydrocarbon group of 3 to 35 carbon atoms, bivalent carbon atom of 6 to 35 aromatic ring group, bivalent carbon atom of 2 to 35 heterocyclic group Or a base represented by any of the following (2-1) to (2-3), and the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms is ethane, propane, isopropane, butane Alkane, second butane, third butane, isobutane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, Isoheptane, third heptane, 1-methyloctane, isooctane, third octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethyl cyclobutane group, 4-methylcyclohexane by the group Z ¹ Z ² of the divalent substituted, X ¹ represents an aliphatic hydrocarbon group may be of a cyano group, a nitro group, an alkyl group having 1 to 8 carbon atoms, the alkoxy group, halogenated alkyl group or a halogenated alkoxy group, X represents ^an aliphatic hydrocarbon group of the methylene groups may be substituted with -CO -, - CO-O-, or from a combination of such groups, Z ¹ and Z ² each independently represents a direct bond, -O -, - S-, -SO _2- , -SO-, -NR ¹³ -or -PR ^14- , R ¹³ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ¹⁴ represents hydrogen Atom, alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms or aralkyl group having 7 to 20 carbon atoms, alkyl group, aryl group, and aralkyl group represented by R ¹³ and R ¹⁴ It may be substituted by halogen atom, hydroxyl group or nitro group, and the methylene group in the alkyl group and aralkyl group represented by R ¹³ and R ¹⁴ may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, wherein the group represented by the general formula (2) is in a range of 1 to 35 carbon atoms) (In the formula, R ²¹ represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms, and R ²² represents a carbon number of 1 to Alkyl group of 10, alkoxy group of 1 to 10 carbon atoms, alkenyl group or halogen atom of 2 to 10 carbon atoms, the alkyl group, alkoxy group and alkenyl group represented by R ²¹ and R ²² may pass through a halogen atom (Substituted or unsubstituted, d is an integer from 0 to 5) (In the formula, R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Arylthio, arylalkenyl having 8 to 20 carbon atoms, aralkyl having 7 to 20 carbon atoms, heterocyclic group or halogen atom having 2 to 20 carbon atoms, represented by R ²³ and R ²⁴ The alkyl, aryl, aryloxy, arylthio, arylalkenyl, aralkyl and heterocyclic groups may be substituted or unsubstituted by halogen atoms. The alkyl groups represented by R ²³ and R ²⁴ and The methylene group in the aralkyl group may be substituted with an unsaturated bond, -O- or -S-, R ²³ may form a ring with each other by adjacent R ²³ , e represents a number from 0 to 4, and f represents a number from 0 to 8. , G is a number from 0 to 4, h is a number from 0 to 4, and the total number of g and h is 2 to 4) <2> m = 3, and X is represented by the following formula (3), (In the formula, X ² represents a carbon atom substituted with R ²⁵ , an aliphatic hydrocarbon group having a trivalent carbon number of 1 to 35, an alicyclic hydrocarbon group having a trivalent carbon number of 3 to 35, and a trivalent carbon atom. 6 to 35 aromatic ring hydrocarbon group or trivalent heterocyclic group containing 2 to 35 carbon atoms, R ²⁵ represents hydrogen atom, alkyl group having 1 to 8 carbon atoms, and aryl group having 6 to 20 carbon atoms Or an aralkyl group having 7 to 20 carbon atoms, and the aliphatic hydrocarbon group represented by X ² may be a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, and a halogenated alkyl group. Or halogenated alkoxy substitution, the methylene group in the aliphatic hydrocarbon group represented by X ² may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ³ are each independently and the same as the groups represented by Z ¹ and Z ² in the above general formula (2), wherein the above general formula (3 The group represented by) is in the range of 1 to 35 carbon atoms) <3> m = 4, and X is represented by the following formula (4), (In the formula, X ³ represents a carbon atom, an aliphatic hydrocarbon group having a tetravalent carbon number of 1 to 35, an alicyclic hydrocarbon group having a tetravalent carbon number of 3 to 35, and a tetravalent carbon number of 6 to 35. Aromatic cyclic hydrocarbon group or tetravalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ³ may pass through halogen atom, cyano group, hydroxyl group, nitro group, and alkyl group having 1 to 8 carbon atoms. , Alkoxy, halogenated alkyl, or halogenated alkoxy, and the methylene group in the aliphatic hydrocarbon group represented by X ³ may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH- or a combination thereof, Z ¹ to Z ⁴ are independent, and are the same as the bases represented by Z ¹ and Z ² in the general formula (2) (Wherein the group represented by the general formula (4) is in the range of 1 to 35 carbon atoms) <4> m = 5, and X is represented by the following formula (5), (In the formula, X ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent aliphatic group having 3 to 35 carbon atoms, and a pentavalent aromatic group containing 6 to 35 carbon atoms. Or a pentavalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ⁴ may pass through a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group Group, halogenated alkyl group or halogenated alkoxy group, and the methylene group in the aliphatic hydrocarbon group represented by X ⁴ may be substituted with -O-, -S-, -CO-, -CO-O-, -O- CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ⁵ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (2) above, wherein, The group represented by the above general formula (5) is in the range of 2 to 50 carbon atoms) <5> m = 6, and X is represented by the following formula (6), (In the formula, X ⁵ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms and an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms. Or a hexavalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ⁵ may pass through a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group Group, halogenated alkyl group or halogenated alkoxy group, and the methylene group in the aliphatic hydrocarbon group represented by X ⁵ may be substituted with -O-, -S-, -CO-, -CO-O-, -O- CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ⁶ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (2) above, wherein, The group represented by the above general formula (6) is in the range of 2 to 50 carbon atoms); [Chemical 16] [化 20A] A coloring composition containing a compound as claimed in claim 1. A coloring photosensitive composition comprising: a dye (A) containing at least one compound represented by the following general formula (1); a polymerizable compound (B) having an acidic unsaturated bond having an acid value; Photo radical polymerization initiator (C) and monomer (D) having ethylenically unsaturated bonds, (In the formula, A represents a benzene ring, a naphthalene ring, or an anthracene ring, and these rings may be halogenated, cyano, hydroxyl, nitro, 1-12 carbon alkyl, alkoxy, halogenated alkyl, or halogenated. Alkoxy substituted, Y represents cyano or -COOR ⁴ , R ¹ represents hydrogen atom, phenyl, cyano, nitro, halogen atom, alkyl group having 1 to 12 carbon atoms, and alkyl group having 1 to 12 carbon atoms Oxygen, halogenated alkyl having 1 to 12 carbon atoms or halogenated alkoxy having 1 to 12 carbon atoms, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a carbon atom alkyl or aryl group having 6 to 20 carbon atoms of the aralkyl group having 7 to 20, R ² and R ³ in the aryl group and aralkyl group may be substituted with a halogen atom or a nitro group, R ² and R ³ in The methylene group in the alkyl group and the aralkyl group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, and R ⁴ represents a hydrogen atom and a carbon number Alkyl group 1 to 12, aryl group 6 to 20 carbon atoms, aralkyl group 7 to 20 carbon atoms or heterocyclic group 2 to 35 carbon atoms, alkyl group and aralkyl group represented by R ⁴ The methylene group can be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, X represents a single bond, a nitrogen atom , -NR ^5- , oxygen atom, sulfur atom, -SO _2- , -SO-, phosphorus atom, -PR ⁶ -or an organic group satisfying any one of the following conditions <1> to <5>, R ⁵ And R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, m = an integer of 2 to 6) <1 > m = 2, and X is represented by the following formula (2), * -Z ¹ -X ¹ -Z ^2- * (2) (wherein X ¹ represents -NR ^13- , and the number of carbon atoms is 1) ~ 35 aliphatic hydrocarbon group, divalent alicyclic hydrocarbon group of 3 to 35 carbon atoms, bivalent carbon atom of 6 to 35 aromatic ring group, bivalent carbon atom of 2 to 35 heterocyclic group Base or any one of the following (2-1) to (2-3), and the aliphatic hydrocarbon group represented by X ¹ may pass through a halogen atom, a cyano group, a hydroxyl group, a nitro group, and a carbon number. 1 to 8 alkyl, alkoxy, haloalkyl or haloalkoxy substitutions, the methylene group in the aliphatic hydrocarbon group represented by X ¹ may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH- or a combination of these, Z ¹ and Z ² each independently represent a direct bond, -O-, -S-, -SO _{2 -, - SO -, -} NR 13 - or -PR ¹⁴ -, R ¹³ and R ¹⁴ each Li represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, the carbon atoms, an aryl group or having 6 to 20 carbon atoms of the aralkyl group having 7 to 20, R ¹³ and R ¹⁴ represented by the alkyl group, an aryl group, and The aralkyl group may be substituted with a halogen atom, a hydroxyl group, or a nitro group, and the alkyl group represented by R ¹³ and R ¹⁴ and the methylene group in the aralkyl group may be substituted with -COO-, -O-, -OCO-,- NHCO-, -NH-, or -CONH-, where the group represented by the above general formula (2) is in the range of 1 to 35 carbon atoms) (In the formula, R ²¹ represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms, and R ²² represents a carbon number of 1 to Alkyl group of 10, alkoxy group of 1 to 10 carbon atoms, alkenyl group or halogen atom of 2 to 10 carbon atoms, the alkyl group, alkoxy group and alkenyl group represented by R ²¹ and R ²² may pass through a halogen atom (Substituted or unsubstituted, d is an integer from 0 to 5) (In the formula, R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Arylthio, arylalkenyl having 8 to 20 carbon atoms, aralkyl having 7 to 20 carbon atoms, heterocyclic group or halogen atom having 2 to 20 carbon atoms, represented by R ²³ and R ²⁴ The alkyl, aryl, aryloxy, arylthio, arylalkenyl, aralkyl and heterocyclic groups may be substituted or unsubstituted by halogen atoms. The alkyl groups represented by R ²³ and R ²⁴ and The methylene group in the aralkyl group may be substituted with an unsaturated bond, -O- or -S-, R ²³ may form a ring with each other by adjacent R ²³ , e represents a number from 0 to 4, and f represents a number from 0 to 8. , G is a number from 0 to 4, h is a number from 0 to 4, and the total number of g and h is 2 to 4) <2> m = 3, and X is represented by the following formula (3), (In the formula, X ² represents a carbon atom substituted with R ²⁵ , an aliphatic hydrocarbon group having a trivalent carbon number of 1 to 35, an alicyclic hydrocarbon group having a trivalent carbon number of 3 to 35, and a trivalent carbon atom. 6 to 35 aromatic ring hydrocarbon group or trivalent heterocyclic group containing 2 to 35 carbon atoms, R ²⁵ represents hydrogen atom, alkyl group having 1 to 8 carbon atoms, and aryl group having 6 to 20 carbon atoms Or an aralkyl group having 7 to 20 carbon atoms, and the aliphatic hydrocarbon group represented by X ² may be a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, and a halogenated alkyl group. Or halogenated alkoxy substitution, the methylene group in the aliphatic hydrocarbon group represented by X ² may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ³ are each independently and the same as the groups represented by Z ¹ and Z ² in the above general formula (2), wherein the above general formula (3 The group represented by) is in the range of 1 to 35 carbon atoms) <3> m = 4, and X is represented by the following formula (4), (In the formula, X ³ represents a carbon atom, an aliphatic hydrocarbon group having a tetravalent carbon number of 1 to 35, an alicyclic hydrocarbon group having a tetravalent carbon number of 3 to 35, and a tetravalent carbon number of 6 to 35. Aromatic cyclic hydrocarbon group or tetravalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ³ may pass through halogen atom, cyano group, hydroxyl group, nitro group, and alkyl group having 1 to 8 carbon atoms. , Alkoxy, halogenated alkyl, or halogenated alkoxy, and the methylene group in the aliphatic hydrocarbon group represented by X ³ may be substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH- or a combination thereof, Z ¹ to Z ⁴ are independent, and are the same as the bases represented by Z ¹ and Z ² in the general formula (2) (Wherein the group represented by the general formula (4) is in the range of 1 to 35 carbon atoms) <4> m = 5, and X is represented by the following formula (5), (In the formula, X ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent aliphatic group having 3 to 35 carbon atoms, and a pentavalent aromatic group containing 6 to 35 carbon atoms. Or a pentavalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ⁴ may pass through a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group Group, halogenated alkyl group or halogenated alkoxy group, and the methylene group in the aliphatic hydrocarbon group represented by X ⁴ may be substituted with -O-, -S-, -CO-, -CO-O-, -O- CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ⁵ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (2) above, wherein, The group represented by the above general formula (5) is in the range of 2 to 50 carbon atoms) <5> m = 6, and X is represented by the following formula (6), (In the formula, X ⁵ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms and an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms. Or a hexavalent heterocyclic group containing 2 to 35 carbon atoms, and the aliphatic hydrocarbon group represented by X ⁵ may pass through a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group Group, halogenated alkyl group or halogenated alkoxy group, and the methylene group in the aliphatic hydrocarbon group represented by X ⁵ may be substituted with -O-, -S-, -CO-, -CO-O-, -O- CO-, -SO _2- , -NH-, or a combination of these groups, Z ¹ to Z ⁶ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (2) above, wherein, The group represented by the general formula (6) is in a range of 2 to 50 carbon atoms). A cured product, which is a cured product of the colored photosensitive composition according to claim 3. A color filter for a display device, which is formed using a hardened material as claimed in claim 4.