TWI665264B - Novel compound and composition containing the same - Google Patents

Abstract

The present invention provides a novel compound which is preferably used as a pigment of a color-sensitive photosensitive composition (colored alkali-developing sexy photosensitive composition) excellent in heat resistance, and a color-sensitive photosensitive composition using the novel compound. The compound is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and is a compound having 1 to 10 substituents represented by the following general formula (1) in a molecule, and it is preferable to provide a compound A coloring photosensitive composition using a cyanostyrene compound, a triarylmethane compound or a cyanine compound together with a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator . 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 an organic pigment compound having a phenolic antioxidant structure and a composition containing the same. Furthermore, the present invention relates to a colored photosensitive composition using the composition, 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, when the molar absorption coefficient of the dye is low, it is necessary to add a large amount of the dye.

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.

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

In addition, Patent Documents 4 and 5 disclose coloring compositions for color filters containing a pigment and an antioxidant.

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

Prior art literature Patent literature

Patent Document 1: WO2012 / 039286

Patent Document 2: WO2012 / 101946

Patent Document 3: WO2012 / 111400

Patent Document 4: Japanese Patent Laid-Open No. 2010-008650

Patent Document 5: Japanese Patent Laid-Open No. 2011-141356

Therefore, an object of the present invention is to provide a colored photosensitive composition (colored alkali-developable photosensitive composition) excellent in heat resistance. Another object of the present invention is to provide an optical filter using the above-mentioned coloring photosensitive composition (colored alkali-developing sexy light-sensitive composition), and particularly suitable for image display such as a liquid crystal display panel without reducing brightness. Device color filters.

The inventors have conducted intensive studies and found that a compound having a specific structure is excellent in heat resistance, and also found that a coloring photosensitive composition (colored alkali-developable photosensitive composition) using the compound does not make an optical filter (especially Is a color filter), which is suitable for a color filter for an image display device such as a liquid crystal display panel, and the present invention has been completed.

The present invention has been completed based on the above-mentioned findings, and provides a compound which is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and has 1 to 10 molecules represented by the following general formula (1) in a molecule. Of substituents.

(Wherein R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, and a carbon number 6 to 20 aryl groups, 7 to 20 carbon atoms aralkyl groups, 2 to 20 carbon atoms heterocyclic groups or -OR ¹ , among R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ At least one of them is represented by -OR ^1. R ¹ represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a carbon atom. Heterocyclic group or trialkylsilyl group of 2-20, alkyl group, aryl group, aralkyl group or heterocyclic group group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ The group may have a substituent or be unsubstituted, and the methylene group in the alkyl group or aralkyl group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ may be substituted with a carbon-carbon double bond. , -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO- O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR ² -,> P = O, -SS- or -SO _2- , (R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms)

The present invention also provides a composition containing the above-mentioned compound, which is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near-infrared, and has 1 to 10 molecules of the following general formula (1) in the molecule. Represents a substituent.

The present invention also provides a coloring photosensitive composition, which further contains a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator in the composition.

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. The cured product is suitable for color filters for display devices.

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

First, the above compound will be described. The compound is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared and having at least one structure represented by the general formula (1) in the molecule.

The organic pigment having an absorption maximum value in the wavelength region from ultraviolet to near infrared is not particularly limited as long as it is a compound having an absorption maximum value in the wavelength region from ultraviolet to near infrared, that is, 380 to 1200 nm. Examples include: cyanide Styrene compounds, azo compounds, anthraquinone compounds, indigo compounds, triarylmethane compounds, dibenzopyran compounds, alizarin compounds, acridine compounds, fluorene compounds, thiazole compounds, naphthol compounds, quinoline compounds , Nitro compounds, indamine compounds, Compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanovinyl compounds, dicyanostyrene compounds, carbonium compounds, rose red compounds, pyrene compounds, polyene naphthalene compounds, coumarins Compounds, quaternary compounds, ketonium compounds, spiropyran compounds, spiro compounds Compounds, merocyanine compounds, oxygen compounds, styryl compounds, pyranium compounds, rhodanine compounds, Azolinone compounds, phthalimide compounds, naphthalene imine compounds, Compounds, naphthoquinone compounds, anthraquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyrrole methylene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, Acridine compound, acridine Dyes, such as compounds, methylimine compounds, aniline compounds, quinophthalone compounds, quinone imine compounds, oligomeric benzene compounds, iridium complex compounds, and osmium complex compounds, etc., may be used in combination of a plurality of types.

The method for introducing the structure represented by the general formula (1) into the organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared is not particularly limited, and a method using a known reaction can be exemplified, and examples thereof include: Application of reaction methods such as esterification and amidine.

The organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared has a structure in which 1 to 10 substituents represented by the general formula (1) are bonded. Instead of being based on a plurality of cases, they may be the same as or different from each other. The number of substituents is preferably 2 to 6 in terms of ease of synthesis.

Examples of the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and R ⁰⁵ in the general formula (1) include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ include methyl, ethyl, 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, nonyl, isononyl, decyl, undecyl , Dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, adamantyl, 1-adamantane Base, 2-adamantyl, 2-methyl-1-adamantyl, 2-methyl-2-adamantyl, 2-ethyl-1-adamantyl, 2-ethyl-2-adamantane Base, 2-drop Base, 2-drop Examples of the methyl group include a aryl group having 6 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , R ⁰⁵ and R ^1. Examples include phenyl, naphthyl, anthracenyl, 2- Methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4 -Isobutylphenyl, 4-thirdbutylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4- Stearyl phenyl, 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-third-pentylphenyl, 2,5-di-third-pentylphenyl, 2,5-di-third-octylphenyl, 2,4-diiso Propylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl, etc., as R ⁰¹ , R ^02, R ^03, R ^04, and R ⁰⁵ and the number of carbon atoms represented by R ¹ to 20 7 of the arylalkyl group include: benzyl, fluorenyl, indenyl, 9-fluorenyl group, 2-phenyl Propane-2- Group, benzyl, trityl, styryl, phenallyl, etc., as the number of carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ Examples of heterocyclic-containing groups include: pyridyl, pyrimidinyl, 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 The triazyl-3-yl group represented by R ¹ includes trimethylsilyl, triethylsilane, ethyldimethylsilane, and the like.

Examples of the substituent that substitutes the alkyl group, aryl group, aralkyl group, and heterocyclic group-containing group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , R ^05, and R ¹ include vinyl, olefin, and the like. Ethylenically unsaturated groups such as propyl, acrylic, methacrylic groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; ethylfluorenyl, 2-chloroethylfluorenyl, propionyl, octyl, propenyl, and methyl Allyl acryl, phenylcarbonyl (benzyl), phthalyl, 4-trifluoromethylbenzyl, trimethylethylamyl, o-hydroxybenzyl, oxalyl , Stearyl fluorenyl, methoxycarbonyl, ethoxycarbonyl, tertiary butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl and the like Oxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, aniline, Chlorophenylamino, toluidine, methoxyaniline, N-methyl-aniline, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxy Carbonylamino, ethylamino, benzene Amidinoamino, methylamidoamino, trimethylethylamidoamino, laurylamino, aminocarbamoylamino, N, N-dimethylaminocarbonylamino, N, N-di Ethylaminocarbonylamino, morpholinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-formyl -Methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfoamido, methylsulfoamido, butylsulfoamido, Substituted amine groups such as phenylsulfonylamino; sulfonamido, sulfonamido, carboxyl, cyano, sulfo, hydroxyl, nitro, thiol, sulfenimide, carbamoyl, and sulfonamido , Phosphonate, phosphate or carboxyl, sulfo, phosphonate, phosphate, etc.

The methylene group in the alkyl group or aralkyl group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ may be substituted with a carbon-carbon double bond, -O-, -S- , -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO- S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR ² -,> P = O, -SS- or -SO _2- , the position and number of substitutions are arbitrary.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include alkyl groups having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ . Among the exemplifiers, groups satisfying a specific number of carbon atoms, and the like.

In the structure represented by the general formula (1), at least one of R ⁰² or R ⁰⁴ is preferably an alkyl group having 1 to 40 carbon atoms and 6 to 20 carbon atoms in terms of heat resistance. For aryl, aralkyl with 7 to 20 carbon atoms or heterocyclic containing group with 2 to 20 carbon atoms, R ⁰³ is -OR ¹ , especially R ¹ is a hydrogen atom or 2 to 9 carbon atoms Among the alkoxycarbonyl groups, R ¹ is preferably a hydrogen atom or an alkoxycarbonyl group having 2 to 9 carbon atoms, and at least one of R ⁰² or R ⁰⁴ is an alkyl group having 1 to 40 carbon atoms, Aryl groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms or heterocyclic groups with 2 to 20 carbon atoms, especially R ¹ is a hydrogen atom or 2 to 9 carbon atoms An alkoxycarbonyl group, and at least one of R ⁰² or R ⁰⁴ is an alkyl group having 1 to 10 carbon atoms.

Examples of the alkoxycarbonyl group having 2 to 9 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, and a second butoxy group. Carbonyl, third butoxycarbonyl, isobutoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, third pentoxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, cyclohexylmethoxy Carbonyl, tetrahydrofuranyloxycarbonyl, tetrahydropyranyloxycarbonyl and the like.

Among the above-mentioned organic pigments having an absorption maximum in a wavelength region from ultraviolet to near infrared, in terms of ease of synthesis and molecular design, cyanostyrene compounds, triarylmethane compounds, and flowers are preferred. Cyan compounds.

Among the cyanostyrene compounds, in terms of ease of synthesis and molecular design, those represented by the following general formula (2) are preferred.

(In the formula, A represents a benzene ring, a naphthalene ring, or an anthracene ring, and these rings may be substituted by a substituent represented by the general formula (1), a halogen atom, a cyano group, a hydroxy group, a nitro group, and 1 to 8 carbon atoms Alkyl group, alkoxy group having 1 to 8 carbon atoms, halogenated alkyl group having 1 to 8 carbon atoms or halogenated alkoxy group having 1 to 8 carbon atoms is substituted or unsubstituted, R ⁵ represents a hydrogen atom, a phenyl group , Cyano, nitro, halogen atom, alkyl group with 1 to 8 carbon atoms, alkoxy group with 1 to 8 carbon atoms, halogenated alkyl group with 1 to 8 carbon atoms, or halogenation with 1 to 8 carbon atoms Alkoxy, Y represents a cyano group or -COOR ⁸ , R ⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a substituent represented by the general formula (1), and an alkyl group represented by R ⁸ Methylene may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, X is a single bond, nitrogen atom, -NR ^9- , oxygen atom, sulfur atom, A phosphorus atom, -PR ¹⁰ -or an organic group that satisfies any of the following conditions <1> to <5>, and any of R ⁸ , A, R ⁶ or R ⁷ when Y is represented by -COOR ⁸ one or more ^{bond, R 6, R 7, R} 9 and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, the carbon atoms An aryl group of 6 to 20 carbon atoms, an aralkyl group having 7 to 20 or of the general formula (1) represented by the substituent group, R ^6, R ^7, represented by R ⁹ and R ¹⁰ the alkyl group, an aryl group, and The aralkyl group may be substituted by a substituent, a halogen atom, a hydroxyl group, or a nitro group represented by the general formula (1), an alkyl group represented by R ⁶ , R ⁷ , R ^9, and R ¹⁰ and a methylene group of the aralkyl group. The group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-, m is an integer of 1 to 6, and the molecule has at least one of the above formula (1) Substituents)

<1> m = 2, and X is represented by the following general formula (3).

(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 or a divalent heterocyclic group having 2 to 35 carbon atoms or a substituent represented by any of the following (3-1) to (3-3), a fat represented by X ¹ The methylene group in the hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination of these, and Z ¹ and Z ² are independent of each other Represents a direct bond, -O-, -S-, -SO _2- , -SO-, -NR ^13- , -PR ^14- , R ¹³ and R ¹⁴ each independently represent a hydrogen atom and an alkane having 1 to 8 carbon atoms Group, aryl group having 6 to 20 carbon atoms or aralkyl group having 7 to 20 carbon atoms, and the alkyl group, aryl group, and aralkyl group represented by R ¹³ and R ¹⁴ may be substituted with a halogen atom, a hydroxyl group, or a nitro group , The methylene group in the alkyl group and the 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 (3) is in the range of 1 to 35 carbon atoms.)

(Wherein 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 having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, R ²² Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group or halogen atom having 2 to 10 carbon atoms, and an alkyl group, alkoxy group, and R ²¹ and R ²² Alkenyl can be substituted by halogen atom or unsubstituted, d is an integer from 0 to 5)

[Chemical 6]

(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 general formula (4).

(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 methylene group in the aliphatic hydrocarbon group represented by X ² may be substituted with -O-, -S-, -CO-, -COO-, -OCO-,- NH- or a combination of these groups, Z ¹ to Z ³ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (3), wherein (The group is in the range of 1 to 35 carbon atoms)

<3> m = 4, and X is represented by the following general formula (5).

(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 methylene group in the aliphatic hydrocarbon group represented by X ³ may be substituted with -O-, -S-, -CO-,- COO-, -OCO-, -NH-, or a combination of these groups, Z ¹ to Z ⁴ are each independent, and are the same as the groups represented by Z ¹ and Z ² in the above general formula (3), wherein the above (The group represented by the general formula (5) is in the range of 1 to 35 carbon atoms.)

<4> m = 5, and X is represented by the following general formula (6).

(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 methylene group in the aliphatic hydrocarbon group represented by X ⁴ may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a combination of these groups, Z ¹ to Z ⁵ are independently independent, and are the same as the groups represented by Z ¹ and Z ² in the general formula (3), wherein the general formula ( 6) The indicated base is in the range of 2 to 35 carbon atoms)

<5> m = 6, and X is represented by the following general formula (7).

(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 methylene group in the aliphatic hydrocarbon group represented by X ⁵ may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, -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 (3), wherein the general formula ( 7) The indicated base is in the range of 2 to 35 carbon atoms)

The halogen atom represented by the benzene ring, naphthalene ring, and anthracene which can be substituted by A in the general formula (2), the halogen atom represented by R ⁵ , and the substituent represented by R ⁶ , R ⁷ , R ^9, and R ¹⁰ Examples of the halogen atom of the alkyl group, the aryl group, and the aralkyl group include the groups exemplified as the halogen atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and R ⁰⁵ , and the benzene represented by A in place of A. Examples of the alkyl group having 1 to 8 carbon atoms of the ring, naphthalene ring and anthracene and the alkyl group having 1 to 8 carbon atoms represented by R ⁵ to R ¹⁰ include R ⁰¹ , R ⁰² , R ⁰³ , R Among the groups exemplified by the alkyl groups having 1 to 40 carbon atoms represented by ⁰⁴ and R ⁰⁵ and R ^1, those satisfying a specific carbon number, etc., can be substituted for the carbon atoms of the benzene ring, naphthalene ring and anthracene represented by A Examples of the alkoxy group having 1 to 8 and the alkoxy group having 1 to 8 carbon atoms represented by R ⁵ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and Dibutoxy, third butoxy, isobutoxy, pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy, tetrahydrofuranoxy, Tetrahydropyranyl, etc., as a substitute for A Benzene ring carbon atoms are shown, the number of carbon atoms of the naphthalene ring and an anthracene halogenated alkyl group and R ⁵ 1 ~ 8 of the halogenated alkyl group represented by the 1-8, include: the above carbon atoms of alkyl group having 1 to 8 Where at least one hydrogen atom is replaced with the above-mentioned halogen atom, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, fluoromethyl, trifluoromethyl, nonafluorobutyl, etc. Examples of the halogenated alkoxy group having 1 to 8 carbon atoms represented by benzene ring, naphthalene ring and anthracene represented by A and the halogenated alkoxy group having 1 to 8 carbon atoms represented by R ⁵ include the above-mentioned carbon number 1 Those in which at least one hydrogen atom of the alkoxy group of ~ 8 is substituted with the above halogen atom, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, fluoromethoxy, trifluoro Methoxy, nonafluorobutoxy, etc., as the aryl group having 6 to 20 carbon atoms represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ include R ⁰¹ , R ⁰² , R ⁰³ , R Examples of aryl groups having 6 to 20 carbon atoms represented by ⁰⁴ and R ⁰⁵ and R ¹ are aralkyl groups having 7 to 20 carbon atoms represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ , include: as ^{R 01, R 02, R 03} , R 04 and R ⁰⁵ And it illustrated the number of carbon atoms represented by R ¹ of the aralkyl group having 7 to 20 of the group.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ¹ in the general formula (3) 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 the aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -OCO- , -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 -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH-, or -NHCO- As the O-substituent, examples of the divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by X ¹ include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, 1- Adamantyl, 2-adamantyl, normantyl , 2-methyladamantyl, 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 and the like substituted with Z ¹ and Z ² , etc., as the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X ¹ . Examples: Divalent radicals such as phenyl, naphthyl, biphenyl substituted with Z ¹ and Z ² , etc., as the divalent heterocyclic group containing 2 to 35 carbon atoms represented by X ¹ , but List: 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 alkyl group having 1 to 8 carbon atoms represented by R ¹³ and R ¹⁴ include carbon atoms having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ . Among the groups exemplified by the alkyl group, a group satisfying a specific carbon number. Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and Examples of the aryl group having 6 to 20 carbon atoms represented by R ⁰⁵ and R ¹ are examples of the aralkyl group having 7 to 20 carbon atoms represented by R ¹³ and R ^14. Examples include R ⁰¹ and R. Examples of ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and aralkyl groups having 7 to 20 carbon atoms represented by R ¹ may be substituted for alkyl groups, aryl groups, and aralkyl groups represented by R ¹³ and R ¹⁴ Examples of the halogen atom of the group include the groups exemplified as the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and R ⁰⁵ .

Among the substituents represented by the above (3-1), the phenyl group represented by R ²¹ and the cycloalkyl group having 3 to 10 carbon atoms, the alkyl group having 1 to 10 carbon atoms, and R ²² may be substituted. The alkyl group having 1 to 10 carbon atoms can be exemplified by the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , R ^05, and R ¹ . Specific carbon number groups and the like can be substituted for the phenyl group represented by R ²¹ and the cycloalkyl group having 3 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, and the carbon number represented by R ²² 1 Examples of the alkoxy group of ~ 10 include alkoxy groups having 1 to 8 carbon atoms and alkoxy groups having 1 to 8 carbon atoms represented by R ⁵ which can be substituted for the benzene ring, naphthalene ring and anthracene represented by A. Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ²¹ include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, and the like. The group substituted with the above-mentioned alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and the like. Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ²² include vinyl, Allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3- Dienyl, 2-pentenyl, 2-octenyl and the like, the halogen atom represented by R ^22, and a substituted alkyl group represented by the R ²¹ and R ^22, alkoxy and alkenyl group of a halogen atom, Examples thereof include those exemplified as the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and R ⁰⁵ .

In addition, there are no restrictions on the substitution position of the halogen atom of the alkyl group, alkoxy group, and alkenyl group represented by R ²² .

Among the substituents represented by the above (3-3), examples of the alkyl group having 1 to 10 carbon atoms represented by R ²³ and R ²⁴ include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R Among the groups exemplified by the alkyl groups having 1 to 40 carbon atoms represented by ⁰⁵ and R ¹ that satisfy a specific carbon number, etc., as the aryl groups having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ are listed : as ^{R 01, R 02, R 03} , R 04 , and R ⁰⁵ and the number of carbon atoms represented by R ¹ of an aryl group having 6 to 20 of the group shown the embodiment, the number as R ²³ and R ²⁴ represented by the carbon atom 6 Examples of aryloxy groups to 20 include phenoxy, naphthyloxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, and 4-vinylphenyldioxy. Base, 3-isopropylphenoxy, 4-isopropylphenoxy, 4-butylphenoxy, 4-tert-butylphenoxy, 4-hexylphenoxy, 4-cyclohexylbenzene Oxy, 4-octylphenoxy, 4- (2-ethylhexyl) phenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5- Dimethylphenoxy, 2,6- and methylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,4-di-third butyl Phenoxy, 2,5-di-tert-butylphenoxy Group, 2,6-di-tertiary-butylphenoxy, 2,4-di-tertiary-pentylphenoxy, 2,5-tertiary-pentylphenoxy, 4-cyclohexylphenoxy, Groups such as 2,4,5-trimethylphenoxy, ferrocenyloxy, and the like, which are substituted with halogen atoms, are aromatic groups having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ Examples of the sulfur group include a group in which an oxygen atom of an aryloxy group having 6 to 20 carbon atoms which can be substituted by the above halogen atom is replaced with a sulfur atom, and the like, and the number of carbon atoms represented by R ²³ and R ²⁴ is 8 to 20 Examples of the arylalkenyl group include: an oxygen atom of an aryloxy group having 6 to 20 carbon atoms which may be substituted by the halogen atom described above is substituted by vinyl, allyl, 1-propenyl, isopropenyl, 2- Alkenyl groups such as butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc., are aralkyl groups having 7 to 20 carbon atoms represented by R ²³ and R ²⁴ Examples include the groups exemplified as the aralkyl group having 7 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ .

Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R ²³ and R ²⁴ 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 halogen atom that can be substituted for the alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, aralkyl group, and heterocyclic group-containing halogen atom represented by R ¹³ and R ¹⁴ include R ⁰¹ , The radicals exemplified by halogen atoms represented by R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ .

Examples of the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ² in the general formula (4) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). Trivalent groups substituted with Z ¹ , Z ² and Z ³ , etc., the methylene group in the aliphatic hydrocarbon group 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-, -O As the -CONH- or -NHCO-O-substituent, as the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by X ² , the following may be mentioned in the description of X ¹ in the general formula (3). Exemplified alicyclic hydrocarbon groups are trivalent groups substituted with Z ¹ , Z ² and Z ³ , etc. As the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X ² , the above-mentioned general formula can be given: (3) The trivalent radicals such as the aromatic ring-containing hydrocarbon groups exemplified in the description of X ¹ in Z ¹ , Z ² and Z ^{3 are} used as the trivalent carbon atoms of 2 to 35 represented by X ² Examples of heterocyclic groups : A trivalent group in which the heterocyclic group-containing group exemplified in the description of X ¹ in the general formula (3) is substituted with Z ¹ , Z ^2, and Z ³ , and the like.

Examples of the alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms, or the aralkyl group having 7 to 20 carbon atoms represented by R ^{25 include} those represented by R ¹³ and R ¹⁴ An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms is the same.

Examples of the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ³ in the general formula (5) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). Tetravalent radicals substituted with Z ¹ , Z ² , Z ³ and Z ⁴ etc., the methylene group in the aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -OCO -, -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, preferably -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH-, or -NHCO As the -O-substituent, examples of the alicyclic hydrocarbon group having 3 to 35 carbon atoms having a tetravalent number represented by X ³ include the alicyclic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). The trivalent radicals substituted with Z ¹ , Z ² , Z ³ and Z ⁴ , etc., as the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms having a tetravalent value represented by X ³ include the above-mentioned general formula (3) The tetravalent radicals such as the aromatic ring-containing hydrocarbon radicals exemplified in the description of X ¹ in which Z ¹ , Z ² , Z ³ and Z ^{4 are} substituted, are the tetravalent carbon atoms of 2 to 35 represented by X ³ Heterocyclic radicals, Examples include tetravalent radicals in which the heterocyclic group-containing group exemplified in the description of X ¹ in the general formula (3) is substituted with Z ¹ , Z ² , Z ^3, and Z ⁴ .

Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁴ in the general formula (6) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). Pentavalent radicals substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ , etc., the methylene group in the aliphatic hydrocarbon group 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-, As the -CONH-, -O-CONH-, or -NHCO-O-substituent, as the alicyclic hydrocarbon group having 3 to 35 carbon atoms having a pentavalent value represented by X ⁴ , examples thereof include: The pentavalent radical of the alicyclic hydrocarbon group exemplified in the description of X ¹ substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ , etc., as the pentavalent carbon number represented by X ⁴ is 6 to 35 Examples of the aromatic ring-containing hydrocarbon group include a pentavalent group in which the aromatic ring-containing hydrocarbon group exemplified in the description of X ¹ in the above general formula (3) is substituted with Z ¹ , Z ² , Z ³ , Z ^4, and Z ⁵ Etc. as the pentavalent carbon represented by X ⁴ Examples of the heterocyclic group containing 2 to 35 atoms include the heterocyclic group exemplified in the description of X ¹ in the general formula (12) via Z ¹ , Z ² , Z ³ , Z ⁴ and Z. ^{5 is} substituted by a pentavalent base.

Examples of the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁵ in the general formula (7) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). Hexavalent groups substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ , etc., the methylene group in the aliphatic hydrocarbon group 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, -COO-, -O-, -OCO-, -NHCO-, -NH-,- As a substitute for CONH-, -O-CONH-, or -NHCO-O-, as the alicyclic hydrocarbon group having 3 to 35 carbon atoms of hexavalent represented by X ⁵ , X in the general formula (3) may be mentioned. lipid illustrated the illustrative ^1. cyclic hydrocarbon via ^{Z 1, Z 2, Z 3} , Z 4, Z 5 and Z substituent of ⁶ pentavalent group and the like, the number of hexavalent of carbon atoms as X ⁵ is represented by the 6 Examples of the aromatic ring-containing hydrocarbon group of ~ 35 include the aromatic ring-containing hydrocarbon groups exemplified in the description of X ¹ in the above general formula (3), which are substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ the hexavalent group, as X ⁵ Suo Hexavalent of carbon atoms of 2 to 35 illustrate the of the heterocyclic group include: the above general formula (3) in the description of X ¹ as exemplified by the heterocyclic group of Z ^1, Z ^2, Z ³ , Z ⁴ , Z ⁵ and Z ⁶ substituted hexavalent radicals and the like.

In the compound represented by the general formula (2), A is a benzene ring; R ⁵ is a hydrogen atom; R ⁶ , R ⁷ or R ⁸ has a substituent represented by the general formula (1); m is 2 When X is represented by the above general formula (3), X ¹ in formula (3) is a group selected from the group 1 below; when m is 3, X is represented by the above general formula (4), formula (4) In the formula, X ² is a group selected from the group 2 below; when m is 4, X is represented by the above general formula (5), and X ³ in the formula (5) is a group selected from the group 3; m is 5 When X is represented by the above general formula (6), X ⁴ in formula (6) is a group selected from the group 4 below; when m is 6, X is represented by the above general formula (7), formula (7) X ^{5 in the above} is a base selected from the following group 5 because it is easy to obtain or manufacture raw materials and has high heat resistance, so it is preferable.

[Chemical 11]

(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 0-19).

[Chemical 12]

[Chemical 15]

Specific examples of the compound represented by the general formula (1) include the compounds represented by the following [Chem. 16] to [Chem. 18], but the present invention is not limited to these compounds.

[Chemical 17]

[化 18B]

Among the above triarylmethane compounds, in terms of ease of synthesis and molecular design, it is preferably represented by the following general formula (8).

[Chemical 19]

(Wherein R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ^41, and R ⁴² each independently represent a hydrogen atom, a halogen atom, and a cyano group , Nitro, hydroxyl, alkyl having 1 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, aralkyl having 7 to 20 carbon atoms or -X ¹¹ -Y ¹¹ , X ¹¹ represents an oxygen atom or Sulfur atom, Y ¹¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, R ³¹ to R ⁴² and an alkyl group represented by Y ¹¹ , Aryl or aralkyl may be substituted or unsubstituted by halogen atom, R ³² and R ⁴³ , R ³³ and R ⁴⁴ , R ³⁶ and R ⁴⁵ , R ³⁷ and R ⁴⁶ , R ⁴⁰ and R ⁴⁷ , R ⁴¹ and R ⁴⁸ , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , R ³⁹ and R ^40, and R ⁴¹ and R ⁴² can be connected to form a 6-membered ring, R ³¹ and R ⁴² , R ³⁴ and R ³⁵ and R ³⁸ and R ³⁹ can form a ring through a single bond, an oxygen atom, a sulfur atom, a selenium atom, CR ⁴⁹ R ⁵⁰ , CO, NR ⁵¹ , PR ⁵² or SO ₂ , and R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and the alkyl group represented by R ⁴³ to R ⁴⁸ may be Substituted or unsubstituted with a hydroxyl group, a halogen atom, a cyano group, or a nitro group. The phenyl and benzyl groups represented by R ⁴³ to R ⁴⁸ may be substituted with an alkyl group, a halogen atom, a cyano group, or a vinyl group. Substituted or unsubstituted, R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , and R ⁴⁷ and R ⁴⁸ may be linked to form a 3- to 6-membered ring, An ^q- represents a q-valent anion, q represents 1 or 2, p Represents a coefficient that keeps charges neutral, and has at least one substituent represented by the general formula (1) in the molecule).

In the above general formula (8), examples of the halogen atom represented by the R ³¹ ~ R ^42, R ³¹ ~ may be a substituted alkyl group represented by the R ^42, and Y ^11, an aryl group or aralkyl group of a halogen atom, may be substituted with R Examples of the halogen atom of the alkyl group, phenyl group, and benzyl group represented by ⁴³ to R ⁴⁸ include the groups exemplified as the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and R ⁰⁵ .

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ³¹ to R ⁴⁸ and Y ¹¹ and the alkyl group having 1 to 4 carbon atoms that can replace phenyl and benzyl represented by R ⁴³ to R ⁴⁸ include the following: : As a group satisfying a specific carbon number among the groups exemplified by the alkyl group having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ , as R ³¹ to R Examples of the aryl group having 6 to 12 carbon atoms represented by ⁴² and Y ¹¹ include the aryl group having 6 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ . Among the exemplified groups that satisfy a specific carbon number, examples of the aralkyl group having 7 to 20 carbon atoms represented by R ³¹ to R ⁴² and Y ¹¹ include R ⁰¹ , R ⁰² , R ⁰³ , Examples of R ⁰⁴ and R ⁰⁵ and the aralkyl group having 7 to 20 carbon atoms represented by R ¹ are R ³² and R ⁴³ , R ³³ and R ⁴⁴ , R ³⁶ and R ⁴⁵ , R ³⁷ and R ⁴⁶ , R ⁴⁰ and R ⁴⁷ , R ⁴¹ and R ⁴⁸ , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ³⁸ , R ³⁹ and R ^40, and R ⁴¹ and R ^{42 are} connected The 6-membered ring that can be formed includes: piperidine ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, A pyridine ring, etc., as R ³¹ and R ⁴² , R ³⁴ and R ³⁵ and R ³⁸ and R ³⁹ via a single bond, oxygen atom, sulfur atom, selenium atom, CR ⁴⁹ R ⁵⁰ , CO, NR ⁵¹ , PR ⁵² or SO ₂ Rings that can be formed by connection, examples include dihydroanthracene ring, acridine ring, dibenzopyran ring, and sulfur Rings and the like, as the heterocyclic ring of 3 to 6 members which can be formed by linking R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , and R ⁴⁷ and R ⁴⁸ , examples include piperidine ring and piperidine Ring, pyrrolidine ring, morpholine ring, thiomorpholine ring, pyridine ring, pyridine Ring, pyrimidine ring, quinoline ring, isoquinoline ring, imidazole ring, Azole ring, imidazolidine ring, pyrazidine ring, iso Azodinidine ring, isotetrahydrothiazole ring, etc. These rings may be condensed with other rings or substituted.

As the anion represented by An ^q- in the general formula (8), for example, as a monovalent one, a chloride ion, a bromide ion, an iodide ion, a fluoride ion, and other halide ions; and perchlorate Ions, chlorate ions, thiocyanate ions, hexafluorophosphate ions, hexafluoroantimonate ions, tetrafluoroborate ions and other inorganic anions; methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion , Toluenesulfonate ion, triflate ion, naphthalenesulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzenesulfonate ion, 2-amino- 5-nitrobenzenesulfonate ion, phthalocyaninesulfonate ion, sulfonate ion with polymerizable substituent, Japanese Patent Laid-Open No. 10-235999, Japanese Patent Laid-Open No. 10-337959, Japanese Patent Laid-Open No. 11-102088, Japan Patent Laid-Open No. 2000-108510, Japanese Patent Laid-Open No. 2000-168223, Japanese Patent Laid-Open No. 2001-209969, Japanese Patent Laid-Open No. 2001-322354, Japanese Patent Laid-Open No. 2006-248180, Japanese Patent Laid-Open No. 2006-297907, Japanese Patent Laid-Open No. Kaiping No. 8-253705, special Organic sulfonic acid anions such as sulfonate ions described in JP 2004-503379, Japanese Patent Laid-Open No. 2005-336150, and International Publication 2006/28006; octyl phosphate ions, dodecyl phosphate ions , Octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylenebis (4,6-di-third-butylphenyl) sulfonate ion, etc. Organic phosphate anion, bistrifluoromethanesulfonylsulfonium imine ion, bisperfluorobutanesulfonylsulfonium imine ion, perfluoro 4-ethylcyclohexanesulfonate ion, tetrakis (pentafluorophenyl) borate Examples of the divalent group include ions, tris (fluoroalkylsulfonyl) carboxylate anions, and the like; benzenedisulfonate ions, naphthalenedisulfonate ions, and the like. Also, if necessary, a quenching anion having a function of deactivating (quenching) an active molecule in an excited state or an anionic group such as a carboxyl group, a phosphonic acid group, or a sulfonic acid group in a cyclopentadienyl ring may be used. Anions of metallocene compounds such as ferrocene and ruthenium. In addition, p is selected so that the charge in the entire molecule becomes neutral.

In the general formula (8), the anion represented by An ^q- may have 1 to 10 substituents represented by the general formula (1). Examples of such anions include the following [Chem. 19A] Represents an anion, but the present invention is not limited by these anions.

Examples of the quenching anion include, for example, Japanese Patent Laid-Open No. 60-234892, Japanese Patent Laid-Open No. 5-43814, Japanese Patent Laid-Open No. 5-305770, and Japanese Patent Laid-Open No. 6-239028. Publication No. 9-309886, Japanese Patent Publication No. 9-323478, Japanese Patent Publication No. 10-45767, Japanese Patent Publication No. 11-208118, Japanese Patent Publication No. 2000-168237 Publication No. 2002-201373, Japanese Patent Publication No. 2002-206061, Japanese Patent Publication No. 2005-297407, Japanese Patent Publication No. 7-96334, International Publication No. 98/29257 Etc. described anions.

As the anion represented by An ^q- in the general formula (I), in terms of heat resistance, a monovalent organic sulfonic acid anion, a bistrifluoromethanesulfonylsulfonium imine ion, and a diquat Fluorobutanesulfonium sulfonium imine ion, perfluoro 4-ethylcyclohexanesulfonate ion, benzene disulfonate ion, naphthalene disulfonate ion, and further preferably bistrifluoromethanesulfonyl sulfonium imine ion .

Specific examples of the compound represented by the general formula (8) include the compounds represented by the following [Chem 20A] and [Chem 20B], but the present invention is not limited to these compounds.

Among the above cyanine compounds, in terms of ease of synthesis and molecular design, it is preferably represented by any one of the following general formulae (9) to (12).

[Chemical 21]

(In the formula, D represents a base selected from (a) to (m) of the following group I, D 'represents a base selected from (a') to (m ') of the following group II, and Q represents a constitution A methine chain having 1 to 9 carbon atoms, and a linking group of a ring structure may also be included in the chain. The hydrogen atom in the methine chain may pass through a hydroxyl group, a halogen atom, a cyano group, -NR ⁵¹ R ⁵² , The aryl group having 6 to 12 carbon atoms, the aralkyl group having 7 to 12 carbon atoms or the alkyl group having 1 to 8 carbon atoms are substituted. The -NR ⁵¹ R ⁵² , aryl group, aralkyl group, and alkyl group may be further substituted. Substituted by hydroxyl, halogen atom, cyano or -NR ⁵¹ R ⁵² , -NR ⁵¹ R ⁵² , aryl, aralkyl and methylene in alkyl group may be substituted with -O-, -S-, -CO -, -COO-, -OCO-, -SO _2- , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-, R ⁵¹ and R ⁵² represent 6 to 6 carbon atoms An aryl group of 12, an aralkyl group of 7 to 12 carbon atoms, or an alkyl group of 1 to 8 carbon atoms, An ^q- represents a q-valent anion, q represents 1 or 2, and p represents a factor that maintains charge as neutral And has at least one substituent represented by the general formula (1) in the molecule).

(In the formula, D represents a base selected from (a) to (m) of group I described below, and D 'represents a base selected from (a') to (m ') of group II described below).

[Chemical 23]

(In the formula, ring G and ring G ′ represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring, and R ⁵³ and R ^{53 ′} represent a hydroxyl group, a halogen atom, a nitro group, a cyano group, —SO ₃ H, a carboxyl group, and an amine group. , Amido, ferrocene, aryl having 6 to 30 carbon atoms, aralkyl having 7 to 30 carbon atoms or alkyl having 1 to 8 carbon atoms, represented by R ⁵³ and R ^{53 ′} Aryl, aralkyl, and alkyl groups may be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amine group, a fluorenylamino group, or a ferrocene group, and R ⁵³ and R ^{53 '} represent Aryl, aralkyl and methylene in alkyl can be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -SO _2- , -NH-, -CONH -, -NHCO-, -N = CH- or -CH = CH-, R ⁵⁴ ~ R ⁶¹ and R ^{54 '} ~ R ^61' represent the same base or hydrogen atom as R ⁵³ and R ^{53 '} , X ¹² , X ^{12 '} , X ¹³ and X ^13' represent an oxygen atom, a sulfur atom, a selenium atom, -CR ⁶² R ^63- , a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, -NH- or -NY ¹³ -, R ⁶² and R ⁶³ represent the same base or hydrogen atom as R ⁵³ and R ^{53 ′} , and Y ¹² , Y ^{12 ′} and Y ¹³ represent an alkyl group having 1 to 20 carbon atoms and an aromatic group having 6 to 30 carbon atoms Or aralkyl group having 7 to 30 carbon atoms, Y ¹² , Y ^{12 '} And the alkyl group, aryl group, and aralkyl group represented by Y ¹³ may be substituted by a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an amine group, a fluorenylamino group, a ferrocene group, -SO ₃ H, or a nitro group Substitution, the methylene group in the alkyl group, aryl group, and aralkyl group represented by Y ¹² , Y ^{12 ′,} and Y ¹³ may be substituted with -O-, -S-, -CO-, -COO-, -OCO -, -SO _2- , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-, r and r 'represent 0 or in (a) ~ (e), (g) ~ (j), (l), (m), (a ') ~ (e'), (g ') ~ (j'), (l '), and (m') substitutable numbers).

In the above general formula (9), Q may be a methine chain having 1 to 9 carbon atoms, and may include a linking group having a ring structure in the chain. The following (Q-1) to (Q-11) Gene production indicated by any of the above) is easy and therefore preferable. The number of carbon atoms in a methine chain having 1 to 9 carbon atoms does not include a linking group representing a methine chain and a ring structure in the chain, and further replacing the linking group (e.g., Carbon atoms of the following R ⁶² to R ⁶⁷ , Z ′) (for example, carbon atoms at both ends of the linking group (Q-1)).

[化 23A]

(Wherein R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and Z 'each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, -NRR', and an aromatic group having 6 to 12 carbon atoms. Group, aralkyl group having 7 to 12 carbon atoms or alkyl group having 1 to 8 carbon atoms, -NRR ', aryl group, aralkyl group, and alkyl group represented by R ⁶² to R ⁶⁷ and Z' may pass through a hydroxyl group , Halogen atom, cyano or -NRR ', and can also be replaced by -O-, -S-, -CO-, -COO-, -OCO-, -SO _2- , -NH-, -CONH-, -NHCO -, -N = CH- or -CH = CH- is cut off, R and R 'represent an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or an alkane having 1 to 8 carbon atoms base).

Examples of the halogen atom represented by R ⁶² to R ⁶⁷ and Z ′ include the groups exemplified as the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and R ⁰⁵ .

Examples of the aryl group having 6 to 12 carbon atoms represented by R ⁶² to R ⁶⁷ , Z ′, R, and R ′ include the following: R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , R ^05, and R ¹ Among the groups exemplified by the aryl group having 6 to 20 carbon atoms, a group satisfying a specific carbon number, etc., is the number of carbon atoms represented by R ⁶² to R ⁶⁷ , Z ′, R, and R ′ described above, 7 to 12 Examples of the aralkyl group include a group satisfying a specific carbon number among the groups exemplified by the aryl group having 6 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05, and R ¹ . .

In the general formula (9), as the anion represented by An ^q-, include: An ^q- in the general formula (. 8) in the represented embodiment of the anions of the group shown.

As the two Ds in the general formula (10) and the D and D 'in the general formulas (11) and (12), one nonionic group and one are selected so that the charge of the compound becomes neutral. Cationic group.

As the halogen atom represented by R ⁵³ to R ⁶³ and R ^{53 ′} to R ^{63 ′} in the general formulae (10) to (12), the aryl group, aralkyl group, and aryl group represented by R ⁵³ and R ^{53 ′} may be substituted. Examples of the halogen atom of the alkyl group and the halogen atom capable of replacing the alkyl group, the aryl group, and the aralkyl group represented by Y ¹² , Y ^{12 ′,} and Y ¹³ include R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and The radicals exemplified for the halogen atom represented by R ⁰⁵ .

Examples of the aryl group having 6 to 30 carbon atoms represented by R ⁵³ to R ⁶³ and R ^{53 ′} to R ^{63 ′} and Y ¹² , Y ^{12 ′,} and Y ¹³ include a phenyl group, a naphthyl group, and a 2-methyl group. Phenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isopropyl Butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearyl Phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethyl Phenyl, 3,5-dimethylphenyl, 2,4-di-third-butylphenyl, 2,5-di-third-butylphenyl, 2,6-di-third-butyl Phenyl, 2,4-di-third-pentylphenyl, 2,5-di-third-pentylphenyl, 2,5-di-third-octylphenyl, 2,4-dicumyl Phenyl, 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl, etc., as R ⁵³ ~ R ⁶³ and R ^{53 '} -~ R ^63' and aralkyl groups having 7 to 30 carbon atoms represented by Y ¹² , Y ^{12 '} and Y ¹³ include benzyl, phenethyl, and 2-phenylpropane-2- , Diphenylmethyl, triphenyl As R ⁵³ ~ R ⁶³ R ^53, and the number ^'~ R ^63' represents the carbon atom of the methyl group, a styryl group, an allyl benzene, methyl ferrocene, propyl ferrocene group having 1 to 8 Examples of the alkyl group and the alkyl group having 1 to 20 carbon atoms represented by Y ¹² , Y ^{12 ′,} and Y ¹³ include the following: R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , R ^05, and R ¹ Among the groups exemplified by the alkyl group having 1 to 40 carbon atoms, a group satisfying a specific carbon number, and the like.

Examples of the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X ¹² , X ^{12 ′} , X ¹³ and X ^{13 ′} in the general formulae (10) to (12) include: Propane-1,1-diyl, cyclobutane-1,1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1 , 1-diyl, cyclobutane-1,1-diyl, cyclohexane-1,1-diyl, etc.

Specific examples of the compounds represented by the general formulae (9) to (12) include the compounds represented by the following [Chem. 24], but the present invention is not limited to these compounds.

The compound of the present invention is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and has at least one structure represented by the above-mentioned general formula (1) in the molecule. The method for producing the compound is not particularly limited. For example, a method obtained by making a wavelength from ultraviolet to near-infrared by a known method can be mentioned. The cyanostyrene compound, triarylmethane compound, and cyanine compound having an organic pigment having a maximum absorption value in the region are mixed with arsine chloride, Bocation reagent, alkyl halide compound, silyl chloride compound, allyl An ether compound or the like is reacted to introduce a structure represented by the general formula (1).

The compound of the present invention is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and has at least one structure represented by the above general formula (1) in the molecule. The compound can be used as a dye in the following In addition to the coloring photosensitive composition described, it can also be used in optical filters used in displays or optical lenses, photosensitive materials for silver salt photographs, dyes, paints, inks, photoreceptors, colorants, thermal recording paper, conversion Printing ribbons, optical recording pigments, solar cells, organic semiconductors, clinical detection reagents, laser treatment pigments, dyeing, etc.

In addition to being used as an antioxidant in a photocurable composition, a thermosetting composition or a polymerizable composition, it can also be used as a color developer in a heat-sensitive material.

The compound of the present invention is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and has at least one structure represented by the general formula (1) in the molecule, and the compound is in the general formula (1) When R ¹ is not a hydrogen atom, it can also be used as a latent additive.

The so-called latent additive is inert in the pre-baking step at normal temperature or below 150 ° C, and is heated at 100 ~ 250 ° C or heated at 80 ~ 200 ° C in the presence of an acid / base catalyst, so that Specific examples include: latent resin additives such as latent antioxidants and latent ultraviolet absorbers; latent colorants for thermal paper; latent storage stabilizers for thermal paper; and latent resin additives. Sex hardener and so on.

Next, a composition containing the compound of the present invention will be described. The compound of the present invention is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and has at least one of the above-mentioned general formula (1) in the molecule. Structurer.

The composition containing the compound of the present invention can be used as a coloring photosensitive composition as well as a polymerizable composition. The compound of the present invention is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and Those having at least one structure represented by the general formula (1) in the molecule.

When used as the coloring photosensitive composition, the content of the compound of the present invention is preferably from 0.01 to 50% by mass, more preferably from 0.1 to 30% by mass. The compound of the present invention is in a wavelength region from ultraviolet to near infrared. An organic pigment having an absorption maximum and having at least one structure represented by the general formula (1) in the molecule.

The said coloring photosensitive composition is hardened | cured by light irradiation, It can be any of photocationic hardening, photoanion hardening, and photoradical hardening, but it is preferable that it is photoradical hardening.

When the colored photosensitive composition is photoradically curable, in addition to the compound of the present invention as an essential component, the colored photosensitive composition is also a polymerizable compound having an ethylenically unsaturated bond having an acid value and A photoradical polymerization initiator is an essential component. The compound of the present invention is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and having at least one structure represented by the above general formula (1) in a molecule. . Hereinafter, this colored photosensitive composition is also referred to as a colored photosensitive composition of the present invention.

Examples of the polymerizable compound having an ethylenically unsaturated bond having an acid value include (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, and dicycloheptene. Dicarboxylic acid, butenoic acid, methacrylic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloxyethyl] ester, o-benzene Mono (meth) acrylic acid such as mono [2- (meth) acryloxyethyl] dicarboxylate, ω-carboxy polycaprolactone mono (meth) acrylate, and polymers having carboxyl and hydroxyl groups at both ends Ester, hydroxyethyl (meth) acrylate. Maleate, hydroxypropyl (meth) acrylate. Maleate, dicyclopentadiene. Unsaturated polybasic acids such as maleate or polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acryl groups; phenol and / or cresol novolac Novolac epoxy compounds such as varnish epoxy resins, novolac epoxy resins having biphenyl skeleton, naphthalene skeleton, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, etc. A functional epoxy-type polyphenylmethane type epoxy resin, an unsaturated monobasic acid acting on the epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (13), and a polybasic acid anhydride acting The reactants of hydroxyl-containing polyfunctional acrylates such as resins, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dibasic acid anhydrides such as succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride, have an acid value. Polyfunctional acrylate and other polymers.

(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 the substituents represented by the above (3-1) to (3-3), the alkylene group may be substituted by a halogen atom, R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ 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.

[Chemical 26]

In order to adjust the acid value to improve the developability of the colored photosensitive composition of the present invention, 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 Esters, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, third butyl glycidyl ether, pentyl Glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, ten Trialkyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, cetyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl Glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, tolyl glycidyl ether, 2-methyltolyl glycidyl ether Ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, cyclic Oxidized soybean oil, epoxidized linseed oil, butyric acid Oleyl ester, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, phenylene oxide, pinene oxide, methyl phenylene oxide, epoxycyclohexane, Propylene oxide, etc.

As the polyfunctional epoxy compound, it is preferable to use one or more members selected from the group consisting of a bisphenol-type epoxy compound and glycidyl ethers, since a coloring photosensitive composition having further excellent characteristics can be obtained. As the bisphenol-type epoxy compound, in addition to the epoxy compound represented by the general formula (13), for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can be used. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1, 8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, tris Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tris (glycidyl Oxymethyl) propane, 1,1,1-tris (glycidyloxymethyl) ethane, 1,1,1-tris (glycidyloxymethyl) methane, 1,1,1,1- Tetrakis (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 of the present invention, the content of the polymerizable compound having an ethylenically unsaturated bond having an acid value is preferably 1 to 95% by mass in the coloring photosensitive composition of the present invention, particularly preferably 10 to 80% by mass.

When the polymerizable compound having an ethylenically unsaturated bond having no acid value is used, the content thereof is preferably 100 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond having an acid value. It is set to 10 to 1000 parts by mass.

The photo-radical polymerization initiator may be a compound capable of starting radical polymerization upon exposure to light. Examples of the initiator include acetophenone-based compounds, benzophenone-based compounds, benzophenone-based compounds, and oximes. Compounds, 9-oxysulfur Ketone 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-azidobenzene Methyleneacetophenone, 1-hydroxycyclohexylphenyl ketone, 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-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)], and ethyl ketone, 1- [9- Ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (0-acetamidooxime), ketone, (2-methylphenyl) [ 6-nitro-9- [3- (trimethylsilyl) propyl] -9H-carbazol-3-yl]-, 1-O-acetamidooxime), ketone, (9-ethyl -6-nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetamoxime, ketone, (9-ethyl-6-nitro-9H-carbazole- 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-acetamoxime, ketone, (9-ethyl-6-nitro-9H-carbazole-3 -Yl) (3-nitrophenyl), O-acetamoxime, 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- [0- (4-methylbenzylidene) oxime], and the like.

As the above 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.

As long as the above photoradical polymerization initiators are polymerizable with respect to radical polymerizable organic substances (the above-mentioned polymerizable compounds having an ethylenically unsaturated bond having an acid value, and the polymerizable compounds having an ethylenic unsaturated bond without an acid value) Compound, monofunctional or polyfunctional epoxy compound), the stoichiometric amount is sufficient, but it is preferably 0.05 to 10 parts by mass relative to the radically polymerizable organic substance, and more preferably 0.1 to 10 Parts by mass. If it is higher than this range, a cured material having sufficient strength may not be obtained, and if it is lower than this range, the resin may not be sufficiently cured.

In the coloring photosensitive composition of the present invention, the content of the photo-radical polymerization initiator in the coloring photosensitive composition of the present invention is preferably from 0.1 to 30% by mass, particularly preferably from 0.5 to 10% by mass. If the content of the photopolymerization initiator is less than 0.1% by mass, the curing by exposure may become insufficient. If the content of the photopolymerization initiator is more than 30% by mass, the photopolymerization initiator may be contained in the colored photosensitive composition. When the initiator is precipitated.

The colored photosensitive composition of the present invention can be dissolved or dispersed in an organic solvent as needed, and a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, Various known mechanisms such as printing and dipping apply the obtained coating liquid to a support substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc., and harden 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. Compatibility is good, so it is preferred.

A coloring agent may be further added to the colored photosensitive composition of the present invention, and examples of the coloring agent include dyes and pigments.

The dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm. Examples include azo compounds, anthraquinone compounds, indigo compounds, triarylmethane compounds, dibenzopyran compounds, and alizarin. Compounds, acridine compounds, fluorene compounds, thiazole compounds, naphthol compounds, quinoline compounds, nitro compounds, indamine compounds, Compounds, phthalocyanine compounds, cyanine compounds, diimmonium compounds, cyanovinyl compounds, dicyanostyrene compounds, rose red compounds, pyrene compounds, polyene naphthalene compounds, coumarin compounds, squamoic acid Onium compound, ketonium compound, spiropyran compound, spiro Compounds, merocyanine compounds, oxygen compounds, styryl compounds, pyranium compounds, rhodanine compounds, Azolinone compounds, phthalimide compounds, Compounds, naphthoquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyrrole methylene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, Acridine Dyes, such as compounds, methylimine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinone imine compounds, iridium complex compounds, osmium complex compounds, etc., may be used in combination of a plurality of types.

As the pigment, an inorganic pigment or an organic pigment can be used, and for example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a dibenzopyran compound, a quinoline compound, an anthraquinone compound, and a coumarin can be used. Compounds, phthalocyanine compounds, isoindolinone compounds, isoindolin compounds, quinacridone compounds, anthracene compounds, fluorene compounds, fluorene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, two 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.

In the colored photosensitive composition of the present invention, the content of the colorant in the colored photosensitive composition of the present invention is preferably from 0 to 99% by mass, particularly preferably from 0 to 80% by mass.

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 pigment or inorganic compound can be dispersed and stabilized. Any commercially available dispersant can be used, such as BYK series manufactured by BYK-Chemie. Polymeric dispersants of functional polyesters, polyethers, polyurethanes, having nitrogen atoms as basic functional groups, and A functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and the amine value is 1 to 100 mgKOH / g.

In the coloring photosensitive composition of the present invention, thermal polymerization inhibitors such as p-anisole, hydroquinone, catechol, third 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 of the present invention can 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, amino formic acid Ester resin, polycarbonate polyvinyl butyral, cellulose ester, polypropylene ammonium, saturated polyester, phenol resin, phenoxy resin, polyamidamine imine resin, polyamino acid resin, epoxy resin, etc. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable.

In the colored photosensitive composition of the present invention, a thermal radical polymerization initiator, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, 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 Sodium, persulfate Potassium and other persulfates. 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 dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate Ester, trimethylolpropane trithiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate Aliphatic polyfunctional thiol compounds such as esters, the following compound No. C1, trimercaptopropionic acid isocyanurate tri (2-hydroxyethyl) ester, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko Corporation.

[Chemical 30]

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 addition, as the light source of the active light used when the colored photosensitive composition of the present invention is cured, a light emitting light having a wavelength of 300 to 450 nm can be used, and for example, ultra-high pressure water can be used. Silver, mercury vapor arc, carbon arc, xenon arc, etc.

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 using such lasers, sensitizing pigments that can be absorbed in the visible to infrared region can be added.

The coloring photosensitive composition (or its cured product) of the present invention can be used in colors such as 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 for display, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, photoforming Use resin, gel coating, photoresist for electronics, electroplating resist, etching resist, liquid and dry film, solder resist, color filters for various display applications or In the manufacturing steps of plasma display panels, electroluminescent display devices, and LCDs, resists are used to form structures, compositions used to encapsulate electrical and electronic parts, solder resists, magnetic recording materials, micromechanical parts, and optical waveguides. Roads, optical switches, masks for plating, etching masks, color test systems, glass fiber cable coatings, templates for screen printing, materials used to make three-dimensional objects by stereolithography, Holographic recording materials, 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, The photoresist material used in UV and visible laser direct image systems, the photoresist material used in the formation of the dielectric layer in the successive lamination of printed circuit boards, or the protective film are various uses, and their uses are not particularly limited.

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

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. The coloring photosensitive composition of the present invention is also useful as a coloring photosensitive composition in an inkjet system without a development step.

[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.

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

<Step 1> Synthesis of Compound 4

In the above scheme, 1 equivalent of compound 3 and 2.42 g of pyridine were mixed, 2.5 equivalent of compound 2 and 2.42 g of 4-dimethylaminopyridine were added, and stirred in an ice bath for 30 minutes, and EDC hydrochloride (1 4.5 equivalent of-(3-Dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride), under nitrogen atmosphere at room temperature Stir for 5 hours. After oil-water separation was performed with ethyl acetate / water, the mixture was washed with water and dried, and the solvent was distilled off to obtain compound 4.

<Step 2> Synthesis of Compound No. 1

Mix 1 equivalent of compound 4 obtained in step 1 and 2.05 g of pyridine, add 0.1 equivalent of 4-dimethylaminopyridine and stir, then add 12 equivalents of third butyl dicarbonate dropwise below 10 ° C, Stir at room temperature for 20 hours. After oil-water separation was performed with ethyl acetate / water, the mixture was washed with water, dried, and the solvent was distilled off. Purification was performed by column chromatography (ethyl acetate: hexane = 1: 1), and crystallization was performed from methanol to obtain Compound No. 1 in a yield of 24%. ¹ H-NMR (nuclear magnetic resonance) and IR (infrared radiation) were used to confirm that the obtained compound was a target. The absorption wavelength characteristics were measured. The results are shown in [Table 1] and [Table 2].

[Example 1-2] Synthesis of compound No. 2

[Chem 31B]

<Step 1> Synthesis of Compound 6

In the above scheme, 1 equivalent of compound 5 and 3.12 g of pyridine were mixed, 0.1 equivalent of 4-dimethylaminopyridine was added and stirred, and 3 equivalents of the third butyl oxide was added dropwise at 10 ° C or lower. Stir at room temperature for 3 hours. After oil-water separation was performed with ethyl acetate / water, the mixture was washed with water, dried, and the solvent was distilled off to obtain compound 6.

<Step 2> Synthesis of Compound No. 2

1 equivalent of compound 7 is mixed with 10 g of ethyl acetate and 10 g of water. After 1 equivalent of compound 6 obtained in step 1 is added and stirred, the ethyl acetate layer is separated and dried, and concentrated until the theoretical yield is reached. 5 times. The concentrated ethyl acetate solution was dispersed in hexane and crystallized to obtain Compound No. 2 in a yield of 70%. The obtained compound was confirmed to be the target by ¹ H-NMR and IR. The absorption wavelength characteristics were measured. The results are shown in [Table 1] and [Table 2].

[Chem 31C]

[Example 1-3] Synthesis of compound No. 3

<Step 1> Synthesis of Compound 9

In the above scheme, 1 equivalent of compound 8, 2 g of sodium hydroxide, 2 g of water, and 2 g of toluene were mixed and stirred at room temperature. Thereafter, 2 mL of a 1N hydrochloric acid aqueous solution was added under ice-cooling to prepare an acidic solution, and oil-water separation was performed to obtain a toluene solution containing Compound 9.

<Step 2> Synthesis of Compound No. 3

To a toluene solution containing 1 equivalent of compound 9 obtained in step 1 was added 4 g of chloroform and 1 eq of compound 6 and stirred. After oil-water separation, it was dispersed in hexane and crystallized to obtain a compound at a yield of 80%. No.3. The obtained compound was confirmed to be the target by ¹ H-NMR and IR. The absorption wavelength characteristics were measured. The results are shown in [Table 1] and [Table 2].

[Examples 2-2 to 2-3] Preparation of colored photosensitive composition No. 1 to No. 3

<Step 1> Preparation of photosensitive composition No. 1

30.3 g of ACA Z250 (made by Daicel-Cytec) as a polymerizable compound component having an ethylenically unsaturated bond having an acid value, and ARONIX M as a polymerizable compound component having an ethylenically unsaturated bond having no acid value -450 (manufactured by Toa Synthesis) 11.04 g, Irgacure 907 (manufactured by BASF) 1.93 g as a photoradical polymerization initiator component, 36.60 g of PGMEA as a solvent, 20.08 g of cyclohexanone, and FZ2122 as other components (Manufactured by Dow Corning Toray) 0.01 g was mixed and stirred until insoluble matter disappeared to obtain a photosensitive composition No. 1.

<Step 2> Preparation of dye solution No. 1 to No. 3

To 0.10 g of the compounds No. 1 to No. 3 obtained above, 1.90 g of dimethylacetamide was added and stirred to dissolve them to prepare dye solutions No. 1 to No. 3, respectively.

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

5.0 g of the photosensitive composition No. 1 obtained in step 1 and 1.0 g of the dye liquid No. 1 to No. 3 obtained in step 2 are separately mixed and stirred until they become uniform, thereby obtaining the present invention. The colored photosensitive compositions No. 1 to No. 3.

[Comparative Examples 1-1 to 1-3] Preparation of Comparative Colored Sensitive Light Compositions No. 1 to No. 3

Except that the compound No. 1 in step 2 of Example 2 was changed to any one of the following comparative compounds No. 1 to No. 3, a comparison was obtained by the same method as in Example 2-1. Colored photosensitive compositions No. 1 to No. 3.

[Chemical 32]

[Comparative Examples 2-1 to 2-3] Preparation of Comparative Colored Sensitive Light Compositions No. 1A to No. 3A

The comparative coloring photosensitive composition No. 1A was obtained in the same manner as in Example 2-1, except that the following compound α was added as an antioxidant to the comparative coloring photosensitive composition No. 1 to No. 3. ~ No.3A.

[Evaluation Examples 1-1 to 1-3 and Comparative Evaluation Examples 1-1 to 1-3] Evaluation of heat resistance by firing

The colored photosensitive compositions No. 1 to No. 3 and the comparatively colored photosensitive compositions No. 1 to No. 3 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 (150 mJ / cm ² ) using an ultra-high pressure mercury lamp. The exposed coating film was fired at 230 ° C for 30 minutes. The absorbance of the coating film before baking (after exposure) and the baking film after baking at the maximum absorption wavelength (λmax) of the compound used were measured, and the absorbance of the coating film before baking (after exposure) was measured. The relative strength at 100 was evaluated. In addition, the closer the absorbance of the baked film to 100, the higher the heat resistance. The color difference (ΔE _{ab *} ) before and after the firing was _examined . The results are shown in [Table 3].

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

[Evaluation Examples 2-1 to 2-3 and Comparative Evaluation Examples 2-1 to 2-3] Evaluation of Antioxidant Function

First, except that the comparative compound No. 1 was added to the colored photosensitive composition No. 1 to No. 3, the colored photosensitive composition No. 1A to No. 1 were obtained by the same method as in Example 2-1. 3A.

The coloring photosensitive compositions No. 1A to No. 3A obtained in the above and the comparative coloring photosensitive compositions No. 1A to No. 3A obtained in Comparative Examples 2-1 to 2-3 were placed at 410 rpm x 7 sec. They were each coated on a glass substrate under conditions and dried with a hot plate (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 baking (after exposure) and the baking film after baking at the maximum absorption wavelength (λmax) of the compound used were measured, and the absorbance of the coating film before baking (after exposure) was measured. The relative strength at 100 was evaluated. The color difference (ΔE _{ab *} ) before and after the firing was _examined . The results are shown in [Table 4].

From the above results, it is clear that the colored photosensitive composition to which the compound of the present invention was added to the previous pigment has higher heat resistance than the comparative colored photosensitive composition to which the antioxidant was added to the previous pigment. Therefore, it indicates that the compound of the present invention has a higher antioxidant function.

From the above results, it is clear that the colored photosensitive composition using the novel compound of the present invention and the cured product thereof have high heat resistance. Therefore, the dye and coloring 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 (7)

A compound which is an organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared, and has 1 to 10 substituents represented by the following general formula (1) in a molecule, (Wherein R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, and a carbon number 6 to 20 aryl groups, 7 to 20 carbon atoms aralkyl groups, 2 to 20 carbon atoms heterocyclic groups or -OR ¹ , among R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ At least one of them is represented by -OR ¹ , R ¹ represents a hydrogen atom or an alkoxycarbonyl group having 2 to 9 carbon atoms, and an alkyl group or an aryl group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^04, and R ⁰⁵ , Aralkyl or heterocyclic group and alkoxycarbonyl represented by R ¹ may have a substituent or unsubstituted, and alkyl or aromatic represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ The methylene group in the alkyl group and the alkoxycarbonyl group represented by R ¹ may be substituted with a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O- , -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-,- NH-CO-O-, -NR ² -,> P = O, -SS-, or -SO _2- , and R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). The compound according to claim 1, wherein in the general formula (1), at least one of R ⁰² or R ⁰⁴ is an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms An aralkyl group of ~ 20 or a heterocyclic group containing 2 to 20 carbon atoms, and R ⁰³ is represented by -OR ¹ . The compound according to claim 1 or 2, wherein the organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared is a cyanostyrene compound. The compound according to claim 1 or 2, wherein the organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared is a triarylmethane compound. The compound according to claim 1 or 2, wherein the organic pigment having an absorption maximum in a wavelength region from ultraviolet to near infrared is a cyanine compound. A composition comprising a compound according to any one of claims 1 to 5. A coloring photosensitive composition, characterized in that the composition as claimed in claim 6 further contains a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator.