KR20210156873A - Novel compound and composition containing novel compound - Google Patents

Abstract

The present invention provides a novel compound suitable as a dye for a colored photosensitive composition excellent in heat resistance (a colored alkali developable photosensitive composition) and a colored photosensitive composition using the novel compound. Specifically, the absorption maximum in the ultraviolet to near-infrared wavelength region is provided. It is an organic dye having a compound having 1 to 10 substituents represented by the following general formula (1) in the molecule, preferably a cyanostyrene compound, a triarylmethane compound or a cyanine compound, and an ethylenic property having an acid value with the novel compound It is to provide the colored photosensitive composition which used together the polymeric compound which has an unsaturated bond, and a radical photopolymerization initiator. The specific content of the general formula (1) is as described herein.

Description

A novel compound and a composition containing the compound {NOVEL COMPOUND AND COMPOSITION CONTAINING NOVEL COMPOUND}

The present invention relates to an organic dye compound having a phenolic antioxidant structure, and to a composition containing the compound. Moreover, it is related with the coloring photosensitive composition which can be polymerized by an energy ray using the said composition, and the color filter using the said coloring photosensitive composition.

A compound having high intensity absorption with respect to a specific light is a recording layer of an optical recording medium such as CD-R, DVD-R, DVD+R, BD-R, liquid crystal display device (LCD), plasma display panel (PDP), etc. , an electroluminescence display (ELD), a cathode tube display device (CRT), a fluorescence display tube, is used as an optical element of an image display device such as an electroluminescence display.

In optical filters for image display devices such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescent display (ELD), cathode tube display (CRT), fluorescent display tube, and field emission display, 300 to 1100 nm Various compounds that absorb wavelength light are used as light absorbers.

These light absorbers are required to have particularly rapid light absorption, that is, to have a small half width of ?max, and to not lose their function due to light, heat, or the like.

Optical filters mainly used in liquid crystal displays (LCDs) include color filters. Although the three primary colors of RGB have been generally used in color filters, it is difficult to have pure RGB colors with a single color material, and efforts have been made to approximate the pure RGB colors by using a plurality of color materials. Therefore, not RGB but color materials such as yellow, orange, and purple are also required.

Organic and/or inorganic pigments have been used for light absorbers used in color filters due to their high heat resistance, but since they are pigments, there is a problem that the luminance as a display device is lowered, and this problem has been solved by increasing the luminance of the light source. However, with the trend of lowering power consumption, development of color filters using dyes is vigorous.

Moreover, in recent years, in the color filter used for a solid-state image sensor, thinning of a coloring pattern is requested|required from a viewpoint of image quality improvement, In order to thin it, it is necessary to raise the dye density|concentration in terms of color density. In addition, it is necessary to add a large amount of dye even when the molar extinction coefficient of the dye is low.

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

Patent Documents 1 to 3 disclose a colored resin composition for color filters containing an organic dye having a specific structure.

Moreover, the coloring composition for color filters containing a pigment|dye and antioxidant is disclosed by patent document 4 and 5.

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

WO2012/039286 WO2012/101946 WO2012/111400 Japanese Patent Laid-Open No. 2010-008650 Japanese Patent Laid-Open No. 2011-141356

Therefore, the objective of this invention is providing the coloring photosensitive composition (coloring alkali developable photosensitive composition) excellent in heat resistance. Another object of the present invention is to provide an optical filter using the colored photosensitive composition (colored alkali developable photosensitive composition), particularly a color filter suitable for an image display device such as a liquid crystal display panel without lowering the luminance.

As a result of repeated intensive studies, the present inventors found that a compound having a specific structure is excellent in heat resistance, and a colored photosensitive composition (colored alkali developable photosensitive composition) using this compound lowers the luminance of an optical filter (especially a color filter) Without having to do it, it discovered that it was suitable for color filters for image display apparatuses, such as a liquid crystal display panel, and arrived at this invention.

The present invention has been made based on the above knowledge, and is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region, and provides a compound having 1 to 10 substituents represented by the following general formula (1) in the molecule will do

( ^{Wherein, R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ are each independently 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, 6 carbon atoms represents an aryl group having ~20, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or -OR ¹ ,

At least one of R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05 is represented by -OR 1} ,

R ¹ is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or trialkylsilyl represents the flag,

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the alkyl group, aryl group, arylalkyl group or heterocyclic-containing group represented by R ^{1 have a substituent or are unsubstituted;}

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ In ^{the alkyl or arylalkyl group represented by R 1} , the methylene group is 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 - may be substituted,

R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

Furthermore, the present invention is to provide a composition containing a compound having 1 to 10 substituents represented by the following general formula (1) in the molecule, which is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength range described above.

Moreover, this invention provides the coloring photosensitive composition containing the polymeric compound which has an ethylenically unsaturated bond which has an acid value, and a radical photopolymerization initiator in the said composition further.

The coloring photosensitive composition (coloring alkali developable photosensitive composition) of this invention containing the compound which has a specific structure is excellent in heat resistance. Moreover, the hardened|cured material is suitable for the color filter for display devices.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on preferable embodiment.

First, a compound that is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region and has at least one structure represented by the general formula (1) in its molecule will be described.

The organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region is not particularly limited as long as it is a compound having an absorption maximum in the ultraviolet to near-infrared wavelength region, that is, 380 to 1200 nm. For example, a cyanostyrene compound, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazole compound, naphthol compound, quinoline compound, nitro compound, indamine compound, oxazine Compound, phthalocyanine compound, cyanine compound, dimonium compound, cyanoethenyl compound, dicyanostyrene compound, carbonium compound, rhodamine compound, perylene compound, polyennaphtholactam compound, coumarin compound, squarylium compound, chromium Conium compound, spiropyran compound, spirooxazine compound, merocyanine compound, oxonol compound, styryl compound, pyrylium compound, rhodanine compound, oxazolone compound, phthalimide compound, naphthalimide compound, cinnoline compound, naphthoquinone compound, anthraquinone compound, azaanthraquinone compound, porphyrin compound, azaporphyrin compound, pyromethene compound, quinacridone compound, diketopyrrolopyrrole compound, indigo compound, acridine compound, azine compound, azo Dyes, such as a methine compound, an aniline compound, a quinophthalone compound, a quinoneimine compound, an oligophenylene compound, an iridium complex compound, and a europium complex compound, These may be mixed and used.

The method for introducing the structure represented by the general formula (1) into the organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region is not particularly limited, and a method to which a known reaction is applied can be mentioned, for example, Methods using reactions, such as esterification and amidation, are mentioned.

The organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region has a structure in which 1 to 10 substituents represented by the general formula (1) are bonded. When there are a plurality of substituents, they may be the same as or different from each other. The number of substituents is preferably 2 to 6 in view of the 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.

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and an alkyl group having 1 to 40 carbon atoms represented by R ¹ include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso -Butyl, amyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert -Heptyl, 1-octyl, iso-octyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Adamantyl, 1-adamantyl, 2-adamantyl, 2-methyl-1-adamantyl, 2-methyl-2-adamantyl, 2-ethyl-1-adamantyl, 2-ethyl- 2-adamantyl, 2-norbornyl, 2-norbornylmethyl, and the like;

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the aryl group having 6 to 20 carbon atoms represented by R ¹ include phenyl, naphthyl, anthracenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4 -Vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4- Octylphenyl, 4-(2-ethylhexyl)phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4 -Dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di- tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl, and the like,

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl group, 2-phenylpropane -2-yl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl;

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the heterocyclic group containing 2 to 20 carbon atoms represented by R ¹ include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, Triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl , benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimida Jolidin-3-yl, 2,4-dioxazolidin-3-yl, etc. are mentioned,

Trimethylsilane, triethylsilane, ethyldimethylsilane, etc. are mentioned as a trialkylsilyl group represented by R<^1>.

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05 and R 1 As} a substituent for substituting the alkyl group, aryl group, arylalkyl group and heterocyclic-containing group represented by R 1 , ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacryl ; halogen atoms such as fluorine, chlorine, bromine and iodine; Acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, jade acyl groups such as saloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and carbamoyl; acyloxy groups such as acetyloxy and benzoyloxy; Amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, Diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino , N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n -octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenyl substituted amino groups such as sulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphoric acid group or carboxyl group, sulfo group, phosphonic acid group, A salt of a phosphoric acid group, etc. are mentioned.

In addition, R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05 In} addition ^{, the methylene group in the alkyl group or arylalkyl group represented by R 1} is 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 - may be substituted, and the position and number of substitution are arbitrary.

The alkyl group having 1 to 8 carbon atoms represented by R ^{2 includes R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and a predetermined carbon atom among those exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ^{1 .} and groups satisfying the number.

Among the structures represented by 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, an arylalkyl group having 7 to 20 carbon atoms, or carbon It is a heterocyclic-containing group having 2 to 20 atoms, R ⁰³ is -OR ¹ , in particular R ¹ is a hydrogen atom or an alkoxycarbonyl group having 2 to 9 carbon atoms, especially R ¹ is a hydrogen atom or a carbon atom 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, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. In terms of heat resistance, it is a heterocyclic ring-containing group of 2 to 20, particularly that R ¹ is 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 10 carbon atoms. desirable.

On the other hand, examples of the alkoxycarbonyl group having 2 to 9 carbon atoms include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, s-butyloxycarbonyl, and t-butyloxycarbonyl. Bornyl, isobutyloxycarbonyl, pentyloxycarbonyl, isoamyloxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, cyclohexylmethyloxycarbonyl, tetrahydrofuranyl Oxycarbonyl, tetrahydropyranyloxycarbonyl, etc. are mentioned.

Among those exemplified as organic dyes having absorption maxima in the ultraviolet to near-infrared wavelength range, cyanostyrene compounds, triarylmethane compounds, and cyanine compounds are preferable in terms of easiness of synthesis and molecular design.

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

(wherein A represents a benzene ring, a naphthalene ring or an anthracene ring, these rings are a substituent represented by the general formula (1), a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, a carbon atom substituted or unsubstituted with an alkoxy group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or a halogenated alkoxy group having 1 to 8 carbon atoms;

R ⁵ is a hydrogen atom, a phenyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or 1 carbon atom represents a halogenated alkoxy group of ~8,

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),

Among the alkyl groups represented by R ⁸ , the methylene group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-;

X is a single bond, a nitrogen atom, -NR ⁹ -, an oxygen atom, a sulfur atom, a phosphorus atom, -PR ¹⁰ -, or an organic group satisfying any one of the following conditions <1> to <5>, and Y is - It is bonded to any one or more ^{of R 8} , A, R ⁶ or R ⁷ when represented by ^{COOR 8,}

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or the above general formula (1) represents a substituent represented by,

The ^{alkyl group, aryl group and arylalkyl group represented by R 6} , R ⁷ , R ⁹ and R ¹⁰ may be substituted with a substituent, a halogen atom, a hydroxyl group or a nitro group represented by the general formula (1) above,

Among the alkyl and arylalkyl groups represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ , the methylene group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-;

m is an integer from 1 to 6,

It has at least one substituent represented by the said General formula (1) in a molecule|numerator.)

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

(Wherein, X ¹ is -NR ¹³ -, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and a divalent aromatic ring having 6 to 35 carbon atoms. represents a hydrocarbon group or a divalent heterocyclic group having 2 to 35 carbon atoms, or a substituent represented by any one of the following (3-1) to (3-3),

Among the aliphatic hydrocarbon groups represented by X ¹ , the methylene group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group combining these;

Z ¹ And Z ² Each independently represents a direct bond, -O-, -S-, -SO ₂ -, -SO-, -NR ¹³ -, -PR ¹⁴ -,

R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

The ^{alkyl group, aryl group and arylalkyl group represented by R 13} and R ¹⁴ may be substituted with a halogen atom, a hydroxyl group or a nitro group,

Among the alkyl and arylalkyl groups represented by R ¹³ and R ¹⁴ , the methylene group may be substituted with -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-.

However, the group represented by the said General formula (3) exists in the range of C1-C35.)

(wherein R ²¹ represents a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 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 having 2 to 10 carbon atoms or a halogen atom,

The alkyl group, alkoxy group and alkenyl group represented by ^{R 21} and R ^{22 are unsubstituted or substituted with a halogen atom,}

d is an integer from 0 to 5.)

(Wherein, R ²³ and R ²⁴ are each independently 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 aryl having 6 to 20 carbon atoms. represents a thio group, an arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom;

The alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocyclic-containing group represented by ^{R 23} and R ^{24 are unsubstituted or substituted with a halogen atom;}

Among the alkyl group and the arylalkyl group represented by R ²³ and R ²⁴ , the methylene group may be substituted with an unsaturated bond, -O- or -S-;

R ²³ may form a ring between adjacent R ^{23 ,}

e represents the number of 0-4, f represents the number of 0-8, g represents the number of 0-4, h represents the number of 0-4, and the sum of the numbers of g and h is 2~ It is 4.)

<2> m=3, and X is represented by the following general formula (4).

(Wherein, X ² is ^{a carbon atom substituted with R 25} , a trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and a trivalent carbon atom of 6 to 35 carbon atoms represents an aromatic ring-containing hydrocarbon group or a trivalent heterocyclic ring-containing group having 2 to 35 carbon atoms;

R ²⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

Among the aliphatic hydrocarbon groups represented by X ² , the methylene group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group combining these;

Z ¹ to Z ³ are each independently the same as the groups represented by ^{Z 1} and Z ² in the general formula (3).

However, the group represented by the said General formula (4) exists in the range of C1-C35.)

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

(wherein, X ³ is a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and a tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms. or a tetravalent heterocyclic-containing group having 2 to 35 carbon atoms,

Among the aliphatic hydrocarbon groups represented by X ³ , the methylene group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group combining these;

Z ¹ to Z ⁴ are each independently the same as the groups represented by ^{Z 1} and Z ² in the general formula (3).

However, the group represented by the said General formula (5) exists in the range of C1-C35.)

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

(wherein X ⁴ is a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, a pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a pentavalent Represents a heterocyclic-containing group having 2 to 35 carbon atoms,

Among the aliphatic hydrocarbon groups represented by X ⁴ , the methylene group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group combining these;

Z ¹ to Z ⁵ are each independently the same as the groups represented by ^{Z 1} and Z ² in the general formula (3).

However, the group represented by the said General formula (6) exists in the range of C2-C35.)

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

(Wherein, X ⁵ is a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, a hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a hexavalent Represents a heterocyclic-containing group having 2 to 35 carbon atoms,

Among the aliphatic hydrocarbon groups represented by X ⁵ , the methylene group may be substituted with -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group combining these;

Z ¹ to Z ⁶ are each independently the same as the groups represented by ^{Z 1} and Z ² in the general formula (3).

However, the group represented by the said General formula (7) exists in the range of C2-C35.)

A halogen atom optionally substituted for the benzene ring, naphthalene ring and anthracene represented by A in the general formula (2), a halogen atom represented by ^{R 5} , and an alkyl group represented by ^{R 6} , R ⁷ , R ⁹ and R ^{10 , aryl} Examples of the halogen atom optionally substituted for the group and the arylalkyl group 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 which may be substituted for the benzene ring, naphthalene ring and anthracene represented by A, 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 ⁰⁴ and R ⁰⁵ and a group satisfying a predetermined number of carbon atoms among the groups exemplified as an alkyl group having 1 to 40 carbon atoms represented by R ^{1 ;}

Examples of the alkoxy group having 1 to 8 carbon atoms which may be substituted for the benzene ring, naphthalene ring and anthracene represented by A and the alkoxy group having ^{1 to 8 carbon atoms represented by R 5} include methoxy, ethoxy, propyloxy, isopropyloxy , butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, Tetrahydropyranyloxy, etc. are mentioned,

Examples of the halogenated alkyl group having 1 to 8 carbon atoms which may be substituted for the benzene ring, naphthalene ring and anthracene represented by A and the halogenated alkyl ^{group having 1 to 8 carbon atoms represented by R 5} include the above-mentioned alkyl groups having 1 to 8 carbon atoms. At least one hydrogen atom is substituted with the above-mentioned halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, fluoromethyl, trifluoromethyl, nonafluorobutyl, etc. can be heard,

As the halogenated alkoxy group having 1 to 8 carbon atoms which may be substituted for the benzene ring, naphthalene ring and anthracene represented by A, and the halogenated alkoxy group having 1 to 8 carbon atoms represented by ^{R 5 ,} those in which at least one hydrogen atom in the alkoxy group is substituted by the above-mentioned halogen atoms, for example, chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, fluoromethyloxy, trifluoromethyl oxy, nonafluorobutyloxy, and the like;

Examples of 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 ⁰⁴ and R ⁰⁵ and an aryl group having 6 to 20 carbon atoms represented by R ^{1 .} The group exemplified as the group is exemplified,

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by ^{R 6} , R ⁷ , R ⁹ and R ^{10 include R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ . The group illustrated as an arylalkyl group is mentioned.

^{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, iso-propane, butane, sec-butane, tert-butane, iso-butane, and hexane. , 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane, tert-octane, cyclopropane, cyclobutane, and a divalent group in which a group such as cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, and 4-methylcyclohexane ^{is substituted with Z 1 and Z 2} , and among the aliphatic hydrocarbon groups, a methylene group is -O-; -S-, -CO-, -COO-, -OCO-, -NH- or a group combining these may be substituted, Here, the group combining these is, for example, -COO-O-, -COO-S- , -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc. are shown, and among them, -COO-, -O-, -OCO-, -NHCO-, -NH-, It is preferably substituted with -CONH-, -O-CONH- or -NHCO-O-,

Examples of the divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by X ¹ include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2-adamantyl, and noadamantyl. , 2-methyladamantyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthracenyl, 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, bicyclo[2.2.1]heptyl, bicyclo[5.1.0]octyl, bicyclo[4.2.0]octyl, bicyclo[4.1.1]octyl, bicyclo[3.3.0]octyl , bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl, spiro [4,4] nonanyl, spiro [4,5] decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, and a divalent group in which a group such as cedrol or cyclododecanyl ^{is substituted with Z 1 and Z 2 ;}

Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X ^{1 include a divalent group in which groups such as phenyl, naphthyl, and biphenyl are substituted with Z 1} and Z ² , and the like.

Examples of the divalent heterocyclic ring-containing group having 2 to 35 carbon atoms represented by X ¹ include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chloro. However, a divalent group in which a group such as xanthene, thiophene, or thiolane ^{is substituted with Z 1} and Z ^{2 may be mentioned.}

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

As the alkyl group having 1 to 8 carbon atoms represented by ^{R 13} and R ^{14 , R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ are selected from among the exemplified alkyl groups having 1 to 40 carbon atoms represented by R ^{1 .} and a group satisfying the number of carbon atoms of

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include the groups exemplified as 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 .} can,

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include the groups exemplified as the arylalkyl group having 7 to 20 carbon atoms represented ^{by R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^{1 .} can be heard,

Examples of the halogen atom optionally substituted for the alkyl group, aryl group and arylalkyl group represented by R ¹³ and R ¹⁴ include the groups exemplified as the halogen atom represented ^{by R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05 .}

In the substituent represented by (3-1) above, an ^{alkyl group having 1 to 10 carbon atoms which may be substituted for the phenyl group represented by R 21} and a cycloalkyl group having 3 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms represented by ^{R 22 .} Examples of the alkyl group include groups satisfying a predetermined number of carbon atoms among the groups exemplified as 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 ,}

Examples of the alkoxy group having 1 to 10 carbon atoms which may be substituted for the phenyl group and the cycloalkyl group having 3 to 10 carbon atoms represented by R ^{21 and the alkoxy group having 1 to 10 carbon atoms represented by R 22} include the benzene ring represented by A, naphthalene and the groups exemplified as the alkoxy group having 1 to 8 carbon atoms which may be substituted for the ring and anthracene and the alkoxy group having ^{1 to 8 carbon atoms represented by R 5 are exemplified;}

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ²¹ include cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, and the like, and these groups are an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. and a group substituted with an alkoxy group;

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-butadienyl, 2-pentenyl, and 2-octenyl. and the like,

The ^{halogen atom represented by R 22} and the halogen atom which may be substituted with the alkyl, alkoxy group and alkenyl group represented by ^{R 21} and R ^{22 include the halogen atoms represented by R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ . can be lifted

In addition, the substitution position of the halogen atom which may substitute the alkyl group, alkoxy group, and alkenyl group represented by ^{R 22 is not restrict|limited.}

In the substituent represented by (3-3) above, the alkyl group having 1 to 10 carbon atoms represented by ^{R 23} and R ^{24 includes R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the number of carbon atoms represented by R ^{1 .} Among the groups exemplified as the alkyl group of 1 to 40, a group satisfying a predetermined number of carbon atoms, etc. are mentioned;

Examples of the aryl group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ include the groups exemplified as 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 , etc.} can be heard,

Examples of the aryloxy group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyloxy, 3-iso- Propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4- (2- ethylhexyl)phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethylphenyloxy, 3.4-dimethylphenyloxy, 3.5-dimethylphenyloxy, 2, 4-ditert-butylphenyloxy, 2,5-ditert-butylphenyloxy, 2,6-ditert-butylphenyloxy, 2.4-ditert-pentylphenyloxy, 2,5-tert-amylphenyloxy, groups, such as 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, and ferrocenyloxy, and groups in which these groups are substituted with halogen atoms;

Examples of the arylthio group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ include groups in which an oxygen atom in an aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom is substituted with a sulfur atom;

As ^{the arylalkenyl group having 8 to 20 carbon atoms represented by R 23} and R ²⁴ , the oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted with the above halogen atom is vinyl, allyl, 1-propenyl, iso and groups substituted with alkenyl groups such as propenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, and 2-octenyl;

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ²³ and R ^{24 include R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the groups exemplified as the arylalkyl group having 7 to 20 carbon atoms represented by R ^{1 .} and the like.

Examples ^{of the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R 23} and R ²⁴ include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, groups, such as chroman, xanthene, thiophene, and thiofuran, and groups in which these groups are substituted with halogen atoms; and the like.

Examples of the halogen atom optionally substituted with the alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocyclic-containing group represented by R ¹³ and R ^{14 include R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and Examples of the halogen atom represented by R ^{05 include groups exemplified.}

As the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by ^{X 2} in the general formula (4), the aliphatic hydrocarbon groups exemplified in the description ^{of X 1 in the general formula (3) are Z 1} , Z ² and Z ^{and a} trivalent group substituted with 3, and among the aliphatic hydrocarbon groups, a methylene group is -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO ₂ -, -NH - or a group combining these may be substituted, wherein the group combining these is, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among which -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O- Preferably, as the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by ^{X 2} , the alicyclic hydrocarbon group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² and Z ³ . and a substituted trivalent group;

As the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by ^{X 2} , the aromatic ring-containing hydrocarbon group exemplified in the description ^{of X 1} in the general formula (3) is substituted with ^{Z 1} , Z ² and Z ^{3 .} and trivalent groups,

The trivalent heterocycle-containing group having 2 to 35 carbon atoms represented by ^{X 2} is a trivalent group in which the heterocyclic 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.

In addition, the alkyl group of the carbon atoms 1-8 represented by R ^25, carbon atoms in the 6-20 aryl group or a carbon atom number of 7 to 20 of the arylalkyl group is R ¹³ and the number of carbon atoms represented by the R ¹⁴ alkyl of 1 to 8 , the same group as an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms.

As the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by ^{X 3} in the general formula (5), the aliphatic hydrocarbon groups exemplified in the description ^{of X 1 in the general formula (3) are Z 1} , Z ² , Z and a ^{tetravalent group substituted with 3 and Z 4} , and among the aliphatic hydrocarbon groups, the methylene group is -O-, -S-, -CO-, -COO-, -OCO-, -NH-, or a group comprising a combination thereof. It may be substituted, and the group combining these is, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO- and the like, and among them, those substituted with -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O- are preferable,

As the tetravalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by ^{X 3} , the alicyclic hydrocarbon 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 .} and trivalent groups that have been

As the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by ^{X 3} , the aromatic ring-containing hydrocarbon group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² , Z ³ and Z ^{4 .} and a tetravalent group substituted with

As the tetravalent heterocycle-containing group having 2 to 35 carbon atoms represented by ^{X 3} , the heterocyclic 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 .} and tetravalent groups.

As the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by ^{X 4} in the general formula (6), the aliphatic hydrocarbon groups exemplified in the description ^{of X 1 in the general formula (3) are Z 1} , Z ² , Z and a ^{pentavalent group substituted with 3} , Z ^{4 and Z 5} . Among the aliphatic hydrocarbon groups, a methylene group is -O-, -S-, -CO-, -CO-O-, -O-CO-, - You may be substituted with SO ₂ -, -NH- or a group combining these, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO- , -CO-NH-, -NH-CO-, etc. are represented, among them -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO It is preferably substituted with -O-,

As the pentavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by ^{X 4} , the alicyclic hydrocarbon group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² , Z ³ , Z ⁴ and Z and the like group optionally substituted by a pentavalent ^5,

As the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by ^{X 4} , the aromatic ring-containing hydrocarbon group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² , Z ³ , Z ^{4 .} and a ^{pentavalent group substituted with Z 5} , and the like.

As the pentavalent heterocycle-containing group having 2 to 35 carbon atoms represented by ^{X 4} , the heterocyclic-containing groups exemplified in the description as ^{X 1 in the general formula (12) are Z 1} , Z ² , Z ³ , Z ⁴ and Z ^The pentavalent group substituted by 5, etc. are mentioned.

As the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by ^{X 5} in the general formula (7), the aliphatic hydrocarbon group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² , Z and a ^{hexavalent group substituted with 3} , Z ⁴ , Z ^{5 and Z 6} , and among the aliphatic hydrocarbon groups, a methylene group is -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH- or a group combining these may be substituted, and the group combining these is, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc. are represented, among them -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO- It is preferably substituted with O-,

As the hexavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by ^{X 5} , the alicyclic hydrocarbon group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² , Z ³ , Z ⁴ , Z and a pentavalent group substituted with ^{5 and Z 6 ,}

As the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by ^{X 5} , the aromatic ring-containing hydrocarbon group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² , Z ³ , Z ^{4 .} and a ^{hexavalent group substituted with Z 5} and Z ⁶ , and the like;

As the hexavalent heterocyclic-containing group having 2 to 35 carbon atoms represented by ^{X 5} , the heterocyclic-containing group exemplified in the description ^{of X 1 in the general formula (3) is Z 1} , Z ² , Z ³ , Z ⁴ , Z and a hexavalent group substituted with ^{5 and Z 6 .}

Among the compounds represented by the general formula (2), A is a benzene ring; R ⁵ is a hydrogen atom; R ⁶ , R ⁷ or R ⁸ having a substituent represented by the general formula (1); When m is 2, X is represented by the above general formula (3), and X ¹ in the formula (3) is a group selected from the following group 1; When m is 3, X is represented by the general formula (4), and X ² in the formula (4) is a group selected from the following group 2; When m is 4, X is represented by the general formula (5), and X ³ in the formula (5) is a group selected from group 3; When m is 5, X is represented by the above general formula (6), and X ⁴ in the formula (6) is a group selected from the following group 4; When m is 6, X is represented by the general formula (7), and X ⁵ in the formula (7) is a group selected from the following group 5, which is preferable because raw materials are easy to obtain or manufacture and has high heat resistance.

(R ⁵ in the formula are the same groups as R ⁵ in the general formula (1), when there is more than one in the group, may be the same or be different, p is an integer of 1 ~ 3, q is from 0 to 3 represents an integer, and r represents an integer from 0 to 19.)

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

Among the triarylmethane compounds, those represented by the following general formula (8) are preferable in terms of easiness of synthesis and molecular design.

(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 are each independently a hydrogen atom, a halogen atom, or a cyano group , a nitro group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or -X ¹¹ -Y ¹¹ ;

X ¹¹ represents an oxygen atom or a sulfur atom,

Y ¹¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

The alkyl group, aryl group or arylalkyl group represented by ^{R 31} to R ⁴² and Y ^{11 is unsubstituted or substituted with a 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 may be linked to form a 6-membered ring;

R ³¹ and R ⁴² , R ³⁴ and R ^{35 ,} and R ³⁸ and R ³⁹ are linked 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 to form a ring may form,

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,

The ^{alkyl group represented by R 43} to R ⁴⁸ is unsubstituted or substituted with a hydroxyl group, a halogen atom, a cyano group or a nitro group,

The ^{phenyl group and the benzyl group represented by R 43} to R ⁴⁸ are unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group or a vinyl group,

R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , and R ⁴⁷ and R ⁴⁸ may be connected to form a 3-6 membered ring,

An ^q- represents an anion having a q valence, q represents 1 or 2, p represents a coefficient for maintaining a neutral charge,

It has at least one substituent represented by the said General formula (1) in a molecule|numerator.)

In the formula (8), ^{a halogen atom represented by R 31} to R ⁴² , an alkyl group represented by R ³¹ to R ⁴² and Y ¹¹ , a halogen atom optionally substituted with an aryl group or an arylalkyl group, an alkyl group represented by R ⁴³ to R ⁴⁸ , The groups exemplified as the halogen atom represented ^{by R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ are exemplified as the halogen atom optionally substituted for the phenyl group and the benzyl group.

Examples of the alkyl group having 1 to 8 carbon atoms represented by ^{R 31} to R ⁴⁸ and Y ¹¹ and the phenyl group and the benzyl group represented by ^{R 43} to R ^{48 include R 01} , R ⁰² , and groups satisfying a predetermined number of carbon atoms among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ⁰³ , R ⁰⁴ and R ^{05 and R 1 ;}

Examples of the aryl group having 6 to 12 carbon atoms represented by R ³¹ to R ⁴² and Y ^{11 include R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and an aryl group having 6 to 20 carbon atoms represented by R ^{1 .} and a group satisfying a predetermined number of carbon atoms in one group, and the like.

Examples of the arylalkyl group having 7 to 20 carbon atoms represented by ^{R 31} to R ⁴² and Y ^{11 include R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and an arylalkyl group having 7 to 20 carbon atoms represented by R ^{1 .} Examples include groups,

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 may be connected to each other to form a 6-membered ring, which may include a piperidine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, and a julolidine ring,

R ³¹ and R ⁴² , R ³⁴ and R ^{35 ,} and R ³⁸ and R ³⁹ are connected 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 to form Examples of the ring that may be included include a dihydroanthracene ring, an acridine ring, a xanthene ring, a thioxanthene ring, and the like,

R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , and R ⁴⁷ and R ⁴⁸ may be linked to form a 3-6 membered heterocyclic ring, including a piperidine ring, a piperazine ring, a pyrrolidine ring, a morpholine ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, isoxazolidine ring, isothiazolidine ring, etc. and these rings may be condensed or substituted with other rings.

^{Examples of the anion represented by An q-} in the general formula (8) include halide ions such as chloride ions, bromide ions, iodide ions and fluoride ions as monovalent ones; inorganic anions such as perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, and tetrafluoroborate ion; Methanesulfonic acid ion, dodecylsulfonic acid ion, benzenesulfonic acid ion, toluenesulfonic acid ion, trifluoromethanesulfonic acid ion, naphthalenesulfonic acid ion, diphenylamine-4-sulfonic acid ion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid ion, 2-amino-5-nitrobenzenesulfonic acid ion, phthalocyaninesulfonic acid ion, sulfonic acid ion having a polymerizable substituent, Japanese Patent Application Laid-Open No. Hei 10-235999, Japanese Patent Application Laid-Open No. Hei 10-337959, Japanese Patent Laid-Open No. Hei 11- 102088, Japanese Patent Application Laid-Open No. 2000-108510, Japanese Patent Application Laid-Open No. 2000-168223, Japanese Patent Application Laid-Open No. 2001-209969, Japanese Patent Application Laid-Open No. 2001-322354, Japanese Patent Application Laid-Open No. 2006-248180, Japanese Patent Application Laid-Open No. 2006-297907, organic sulfonic acid-based anions such as sulfonic acid ions described in Japanese Patent Application Laid-Open No. 8-253705, Japanese Patent Application Laid-Open No. 2004-503379, Japanese Patent Application Laid-Open No. 2005-336150, and International Publication No. 2006/28006; Organophosphoric acids such as octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, and 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphonate ion Anion, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonic acid ion, tetrakis(pentafluorophenyl)borate ion, tris(fluoro A roalkylsulfonyl) carbanion etc. are mentioned, As a bivalent thing, a benzene disulfonic acid ion, a naphthalene disulfonic acid ion, etc. are mentioned, for example. In addition, a quencher anion having a function of de-excitation (quenching) an active molecule in an excited state, or a carboxyl group, phosphonic acid group, or sulfonic acid group on the cyclopentadienyl ring Metallocene compound anions, such as ferrocene and ruthenocene, which have anionic groups, such as a group, can also be used as needed. Also p is chosen such that the charge is neutral throughout the molecule.

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 an anion represented by the following formula, The invention is not limited to these anions.

As the above-mentioned secondary anion, for example, Japanese Patent Application Laid-Open No. 60-234892, Japanese Unexamined Patent Publication No. Hei 5-43814, Japanese Unexamined Patent Publication No. 5-305770, Japanese Patent Application Laid-Open No. Hei 6-239028, Japanese Unexamined Patent Publication No. Hei 9-309886, Japanese Unexamined Patent Publication No. Hei 9-323478, Japanese Unexamined Patent Publication No. 10-45767, Japanese Unexamined Patent Publication No. Hei 11-208118, Japanese Unexamined Patent Publication No. 2000-168237, Japanese Unexamined Patent Publication No. 2002-201373, Japanese Unexamined Patent Publication No. 2002-206061, Japanese Unexamined Patent Publication No. 2005-297407, Japanese Patent Publication No. 7-96334 , an anion as described in International Publication No. 98/29257 and the like.

^{Examples of the anion represented by An q-} in the general formula (I) include a monovalent organic sulfonic acid anion, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, and perfluoro-4- Ethylcyclohexanesulfonic acid ion, benzenedisulfonic acid ion, and naphthalenedisulfonic acid ion are preferable in terms of heat resistance, and bistrifluoromethylsulfonylimide ion is more preferable.

Specific examples of the compound represented by the general formula (8) include compounds represented by the following formula, but the present invention is not limited to these compounds.

Among the cyanine compounds, those represented by any of the following general formulas (9) to (12) are preferable from the viewpoint of easiness of synthesis and molecular design.

(Wherein, D represents a group selected from (a) to (m) in the following group I, and D' represents a group selected from (a') to (m') in the following group II,

Q constitutes a methine chain having 1 to 9 carbon atoms, and represents a linking group which may include a ring structure in the chain, and a hydrogen atom in the methine chain is a hydroxyl group, a halogen atom, a cyano group, -NR ⁵¹ R ⁵² , may be substituted with an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, said -NR ⁵¹ R ⁵² , an aryl group, an arylalkyl group, and an alkyl group may also be substituted with a hydroxyl group, a halogen atom, a cyano group or -NR ⁵¹ R ^{52 , -NR 51} R ⁵² , an aryl group, an arylalkyl group, and a methylene group among the alkyl groups are -O-, -S-, -CO-, - may be substituted with COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N=CH- or -CH=CH-;

R ⁵¹ and R ⁵² represent an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms,

An ^q- represents an anion of q valence, q represents 1 or 2, p represents a coefficient for keeping the charge neutral,

It has at least one substituent represented by the said General formula (1) in a molecule|numerator.)

(Wherein, D represents a group selected from (a) to (m) in the following group I, and D' represents a group selected from (a') to (m') in the following group II.)

(In the formula, ring G and ring G' represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,

R ⁵³ and R ^53' are a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amide group, a ferrocenyl group, an aryl group having 6 to 30 carbon atoms, 7 to 30 carbon atoms represents an arylalkyl group or an alkyl group having 1 to 8 carbon atoms,

The ^{aryl group, arylalkyl group and alkyl group represented by R 53} and R ^{53' may} be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amide group or a ferrocenyl group,

Among the aryl groups, arylalkyl groups and alkyl groups represented by R ⁵³ and R ^53' , the methylene group is -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH- , -NHCO-, -N=CH- or -CH=CH- may be substituted, and R ⁵⁴ to R ⁶¹ and R ^54' to R ^61' represent the same group or hydrogen atom as ^{R 53} and R ^53'. ,

X ¹² , X ^12' , X ¹³ and X ^13' are 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 group as R 53} and R ^53' or a hydrogen atom,

Y ¹² , Y ^12' and Y ¹³ represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms,

Y ¹² , Y ^12' and Y ^{13 The} alkyl group, aryl group and arylalkyl group are substituted with a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, an amino group, an amide group, a ferrocenyl group, -SO ₃ H or a nitro group, or not is a substitution,

Among the alkyl, aryl and arylalkyl groups represented by Y ¹² , Y ^{12 '} and Y ¹³ , the methylene group is -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N=CH- or -CH=CH- may be substituted,

r and r' are 0 or (a)-(e), (g)-(j), (l), (m), (a')-(e'), (g')-(j') , (l') and (m') represent substitutable numbers.)

In the general formula (9), Q constitutes a methine chain having 1 to 9 carbon atoms, and as a linking group that may include a ring structure in the chain, a group represented by any of the following (Q-1) to (Q-11) , which is preferable because it is easy to manufacture. The number of carbon atoms in the methine chain having 1 to 9 carbon atoms represents a methine chain and a linking group that may include a ring structure in the chain, and a group further substituted for the linking group (for example, the following R ⁶² to R ⁶⁷ , Z ') (eg, the carbon atom at both ends in the linking group (Q-1)).

( ^{Wherein, R 62} , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and Z' are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, -NRR', an aryl having 6 to 12 carbon atoms. Represents a group, an arylalkyl group having 7 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms,

-NRR', an aryl group, an arylalkyl group and an alkyl group represented by R ⁶² to R ⁶⁷ and Z' may be substituted with a hydroxyl group, a halogen atom, a cyano group or -NRR', -O-, -S-, -CO- , -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N=CH- or -CH=CH- may be interrupted,

R and R' represent an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or alkyl having 1 to 8 carbon atoms.)

Examples of the ^{halogen atom represented by R 62} to R ⁶⁷ and Z' include 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′ above include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and 6 carbon atoms represented by R ^{1 .} Among the groups exemplified as the aryl group of ~20, a group satisfying a predetermined number of carbon atoms, etc. are mentioned;

Examples of ^{the arylalkyl group having 7 to 12 carbon atoms represented by R 62} to R ⁶⁷ , Z′, R and R′ above include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the number of carbon atoms represented by R ^{1 .} Among the groups exemplified as the 6 to 20 aryl group, a group satisfying a predetermined number of carbon atoms and the like are exemplified.

^{Examples of the anion represented by An q-} in the general formula (9) include groups exemplified as the anion represented by ^{An q-} in the general formula (8).

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

In the general formulas (10) to (12), halogen atoms represented ^{by R 53} to R ⁶³ and R ^53′ to R ^{63′ , aryl groups represented by R 53} and R ^53′ , arylalkyl groups and halogen optionally substituted with alkyl groups The atoms and the halogen atoms which may be substituted for the alkyl, aryl and arylalkyl groups represented by ^{Y 12} , Y ^{12 '} and Y ¹³ include the groups exemplified as the halogen atoms represented ^{by R 01} , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05 .} can be heard

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 includes phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4- Methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl , 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-Dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4 -di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'- biphenyl)-4-yl, 2,4,5-trimethylphenyl, ferrocenyl, and the like;

Examples of the arylalkyl group having 7 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 benzyl, phenethyl, 2-phenylpropan-2-yl,} diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl, and the like;

Examples of the alkyl group having 1 to 8 carbon atoms represented by ^{R 53} to R ⁶³ and R ^53′ to R ^63′ and the alkyl group having 1 to 20 carbon atoms represented by ^{Y 12} , Y ^12′ and Y ^{13 include R 01} , R ⁰² , R ⁰³ , R ^{04 ,} and R ⁰⁵ and a group satisfying a predetermined number of carbon atoms among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ^{1 .}

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 formulas (10) to (12) is cyclopropane-1,1 -diyl, cyclobutane-1,1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, cyclo Hexane-1, 1-diyl, etc. are mentioned.

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

The organic dye of the present invention has an absorption maximum in the ultraviolet to near-infrared wavelength region, and the method for producing a compound having at least one structure represented by the general formula (1) in its molecule is not particularly limited, but for example, from ultraviolet to near-infrared. A cyanostyrene compound, a triarylmethane compound, and a cyanine compound are prepared by a known method as an organic dye having an absorption maximum in a wavelength region other than that, and then, an acid chloride, a Boc reagent, an alkyl halide compound, a silyl chloride compound, and allyl The method obtained by making an ether compound etc. react and introduce|transducing the structure represented by the said General formula (1) is mentioned.

The organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region of the present invention, the compound having at least one structure represented by the general formula (1) in the molecule is used as a dye in the coloring photosensitive composition described below, Optical filters used in displays and optical lenses, silver dye photosensitive materials, dyes, paints, inks, electrophotographic photoconductors, toners, thermal recording papers, transfer ribbons, optical recording dyes, It is used in solar cells, organic semiconductors, clinical test reagents, laser treatment dyes, dyes, etc.

In addition to being used as an antioxidant in a photocurable composition, a heat-changeable composition or a polymerizable composition, it is also used in a heat-sensitive material as a developing agent.

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

The latent additive is inactive in the pre-bake process at room temperature or 150 ° C. or less, and the protective group is released and becomes active by heating at 100 to 250 ° C or by heating at 80 to 200 ° C in the presence of an acid/base catalyst As a thing, specifically, latent resin additives, such as a latent antioxidant and a latent ultraviolet absorber; latent color developer for thermal paper; latent preservation stabilizer for thermal paper; A latent hardener etc. are mentioned.

Next, the composition containing the compound which is an organic dye which has an absorption maximum in the ultraviolet to near-infrared wavelength region of this invention, and has at least one structure represented by the said General formula (1) in a molecule|numerator is demonstrated.

In addition to being used as a colored photosensitive composition, the composition comprising an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region of the present invention and having at least one structure represented by the general formula (1) in its molecule is polymerizable. It is also used as a composition.

When used as the said colored photosensitive composition, it is an organic dye which has an absorption maxima in the ultraviolet to near-infrared wavelength region of this invention, Content of the compound which has at least one structure represented by the said General formula (1) in a molecule|numerator is 0.01-50 mass % is preferable, and 0.1-30 mass % is more preferable.

The said coloring photosensitive composition is what hardens|cures by light irradiation, Although any of photocation sclerosis|hardenability, photoanion sclerosis|hardenability, or photoradical sclerosis|hardenability may be sufficient, it is preferable that it is photoradical sclerosis|hardenability.

When the colored photosensitive composition is photo-radical curable, the colored photosensitive composition is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region of the present invention, in addition to the compound having at least one structure represented by the general formula (1) in the molecule , a polymerizable compound having an ethylenically unsaturated bond having an acid value, and an optical radical polymerization initiator as essential components. Hereinafter, this coloring photosensitive composition is also called the coloring photosensitive composition of this 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, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, Allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth) Polymer mono (meth) acrylate, hydroxyethyl (meth) acrylate/maleate, hydroxypropyl (meth) acrylate/maleate, dicyclopentadiene/ unsaturated polybasic acids such as maleate or polyfunctional (meth)acrylate having one carboxyl group and two or more (meth)acryloyl groups; Novolak epoxy compounds, such as phenol and/or cresol novolak epoxy resins, novolac epoxy resins having a biphenyl skeleton and naphthalene skeleton, bisphenol A novolak epoxy compounds, and dicyclopentadien novolac epoxy compounds, polyfunctional Polyphenylmethane type epoxy resin having an epoxy group, a resin obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (13), and also reacting a polybasic acid anhydride, pentaerythritol triacrylate, Polymers, such as polyfunctional acrylate which have an acid value which is a reaction product of hydroxyl-containing polyfunctional acrylates, such as dipentaerythritol pentaacrylate, and dibasic acid anhydride, such as succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride, are mentioned.

(wherein X ⁴¹ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS -, -SO-, -CO-, -OCO- or a substituent represented by the above (3-1) to (3-3), wherein the alkylidene group may be substituted with 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 having 2 to 5 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and the alkenyl group may be substituted with a halogen atom, and s is an integer of 0 to 10.)

These polymeric compounds can be used individually or in mixture of 2 or more types, and can be used in combination with the polymeric compound which has an ethylenically unsaturated bond which does not have an acid value. When using 2 or more types in mixture, you may copolymerize them beforehand and may use them as a copolymer.

Examples of the polymerizable compound having an ethylenically unsaturated bond having no acid value include (meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid glycidyl; The following compounds No. A1 to No. A4, (meth) methyl acrylate, (meth) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylate-t-butyl, (meth) cyclohexyl acrylate, (meth) acrylic acid n -Octyl, (meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate ) dimethylaminoethyl acrylate, (meth)acrylic acid aminopropyl, (meth)acrylic acid dimethylaminopropyl, (meth)acrylic acid ethoxyethyl, (meth)acrylic acid poly(ethoxy)ethyl, (meth)acrylic acid butoxyethoxyethyl, (meth)acrylate ethylhexyl, (meth)acrylate phenoxyethyl, (meth)acrylic acid tetrahydrofuryl, (meth)acrylic acid vinyl, (meth)acrylate allyl, (meth)acrylate benzyl, 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, trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester ( esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as meth)acrylate oligomers; 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-dioxotetrahydrofuryl)-3-methyl-3 -Acid anhydrides of unsaturated polybasic acids, such as cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride- maleic anhydride adduct, dodecenyl succinic anhydride, and methyl hymic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl ( amides of unsaturated monobasic acids and polyvalent amines such as meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid unsaturated aromatic compounds such as vinyl benzyl methyl ether and vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indene, such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane; Other vinyl compounds such as (meth)acrylonitrile, ethylene, propylene, butylene, vinyl chloride, and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, tricyclodecane skeleton mono Copolymers of (meth)acrylic acid, such as methacrylate, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, and Showa Denko Co., Ltd. products such as Karenz MOI and AOI A copolymer of (meth)acrylic acid reacted with an isocyanate compound having an unsaturated bond, vinyl chloride, vinylidene chloride, divinyl succinic acid, diallyl pralate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl Imidazole, vinyloxazoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinylurethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, vinylepoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds, pentaerythritoltriacrylic The reaction product of polyfunctional isocyanates, such as hydroxyl-containing polyfunctional acrylates, such as a rate and dipentaerythritol pentaacrylate, and tolylene diisocyanate, and hexamethylene diisocyanate, etc. are mentioned.

In order to improve the developability of the coloring photosensitive composition of this invention by adjusting an acid value, with the polymeric compound which has an ethylenically unsaturated bond which has the said acid value, a monofunctional or polyfunctional epoxy compound can be used further. The polymerizable compound having an ethylenically unsaturated bond having the above acid value preferably has an acid value of 5 to 120 mgKOH/g of solid content, and the amount of monofunctional or polyfunctional epoxy compound used is selected to satisfy the acid value it is preferable

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl. Ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether Dil ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether Dil ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl Glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3- Epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclo Hexene oxide, propylene oxide, etc. are mentioned.

As said polyfunctional epoxy compound, when 1 or more types chosen from the group which consists of a bisphenol-type epoxy compound and glycidyl ethers are used, since the coloring photosensitive composition with further favorable characteristics can be obtained, it is preferable. As said bisphenol-type epoxy compound, besides being able to use the epoxy compound represented by the said General formula (13), bisphenol-type epoxy compounds, such as a hydrogenated bisphenol-type epoxy compound, can also be used, for example. 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, triethylene Glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyl) Oxymethyl) propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, 1,1,1,1-tetra(glycidyl) oxymethyl)methane.

In addition, novolak-type epoxy compounds, such as a phenol novolak-type epoxy compound, a biphenyl novolak-type epoxy compound, a cresol novolak-type epoxy compound, a bisphenol A novolak-type epoxy compound, and a dicyclopentadien novolak-type epoxy compound; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1- alicyclic epoxy compounds such as epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and dimer acid glycidyl ester; glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, and N,N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds, such as dicyclopentadiene dioxide; A naphthalene type epoxy compound, a triphenylmethane type epoxy compound, a dicyclopentadiene type epoxy compound, etc. can also be used.

In the coloring photosensitive composition of this invention, as for content of the polymeric compound which has an ethylenically unsaturated bond which has the said acid value, 1-95 mass %, especially 10-80 mass % in the coloring photosensitive composition of this invention is preferable.

Moreover, when using the polymeric compound which has an ethylenically unsaturated bond which does not have the said acid value, it is preferable that the content shall be 10-1000 mass parts with respect to 100 mass parts of polymeric compounds which have an ethylenically unsaturated bond which has the said acid value. .

The radical photopolymerization initiator may be a compound capable of initiating radical polymerization upon exposure to light, for example, an acetophenone-based compound, a benzyl-based compound, a benzophenone-based compound, an oxime-based compound, a thioxanthone-based compound, etc. of ketone compounds and the like can be exemplified as preferable ones.

As the acetophenone-based compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiope Non, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tashaributyldichloroacetophenone , p-Tashaributyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopro Panone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-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-propan-1-one, etc. are mentioned. .

Examples of the benzyl-based compound include benzyl, anisyl, and the like.

Examples of the benzophenone-based compound include benzophenone, o-benzoyl methyl benzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4 -benzoyl-4'-methyldiphenyl sulfide, etc. are mentioned.

Examples of the oxime-based compound include 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methyl) Benzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), methanone,(2-methylphenyl)[6-nitro-9-[3-(trimethylsilyl)propyl]-9H- Carbazol-3-yl]-,1-O-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetyloxime, meta Non, (9-ethyl-6-nitro-9H-carbazol-3-yl) [2-methyl-4- (4-morpholinyl) phenyl), O-acetyloxime, methanone, (3,5- Dinitrophenyl) (9-ethyl-6-nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetyloxime, methanone, (9-ethyl-6-nitro-9H-carbazole- 3-yl) (3-nitrophenyl), O-acetyloxime, 1,3,5-triazine-2,4,6(1H,3H,5H)-trione,1,3,5-tris[2 -(Acetyloxy)-3-[3-[(1E)-1-[(acetyloxy)iminoethyl]-6-nitro-9H-carbazol-9-yl]propyl]-, 1,2-butane Dione,1-[4-(phenylthio)phenyl]-,2-(O-acetyloxime), 1,2-butanedione,1-[4-[[4-(2-hydroxyethoxy)phenyl] Thio]phenyl]-,2-(O-acetyloxime), 1,2-butanedione,1,1'-(thiodi-4,1-phenylene)bis-,2,2-bis(O-acetyl oxime), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-[O-(4-methylbenzoyl)oxime], etc. are mentioned.

As the thioxanthone-based compound, thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc. can be heard

Other radical photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyru-1-yl)] Titanium etc. are mentioned.

These radical photopolymerization initiators may be used alone or in combination of two or more according to desired performance.

The radical photopolymerization initiator as described above is a radically polymerizable organic material (a polymerizable compound having an ethylenically unsaturated bond having the above acid value, a polymerizable compound having an ethylenically unsaturated bond having no acid value, a monofunctional or polyfunctional epoxy compound) It is good to use a stoichiometric amount with respect to, Preferably it is 0.05-10 mass parts with respect to a radically polymerizable organic substance, Furthermore, it is good to mix|blend preferably 0.1-10 mass parts. When it exceeds this range, the hardened|cured material which has sufficient intensity|strength may not be obtained, and when it falls below this range, resin may not fully harden|cure.

The coloring photosensitive composition of this invention WHEREIN: As for content of the said radical photopolymerization initiator, in the coloring photosensitive composition of this invention, 0.1-30 mass %, 0.5-10 mass % especially is preferable. When content of the said photoinitiator is less than 0.1 mass %, hardening by exposure may become inadequate, and when larger than 30 mass %, an initiator may precipitate in the coloring photosensitive composition.

The coloring photosensitive composition of the present invention can be obtained by dissolving or dispersing a coating solution obtained by dissolving or dispersing in an organic solvent as needed with a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, immersion, etc. It can be applied on a supporting substrate such as glass, quartz glass, semiconductor substrate, metal, paper plastic, or the like, and cured by irradiation with light.

The organic solvent is usually a solvent capable of dissolving or dispersing each of the above components as needed, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone. , ketones such as cyclohexanone and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. of an ether ester solvent; BTX solvents, such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Terpene hydrocarbon oils, such as turpentine oil, D-limonene, and pinene; Paraffinic solvents, such as mineral spirit, Swasol #310 (Cosmo Matsuyama Sekiyu Co., Ltd.), and Solvesso #100 (Ekuson Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic ring-containing hydrocarbon solvents such as chlorobenzene; Carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water etc. are mentioned, These solvent can be used as 1 type or 2 or more types of mixed solvent. Among these, ketones, ether ester solvents, and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because of good compatibility between the resist and the photopolymerization initiator in the colored photosensitive composition.

A colorant may also be added to the colored photosensitive composition of the present invention, and the colorant may include a dye or a pigment.

The dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm. For example, an azo compound, an anthraquinone compound, an indigoid compound, a triarylmethane compound, a xanthene compound, an alizarin compound, an acridine compound , stilbene compound, thiazole compound, naphthol compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, dimonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound , perylene compound, polyennaphtholactam compound, coumarin compound, squarylium compound, croconium compound, spiropyran compound, spirooxazine compound, merocyanine compound, oxonol compound, styryl compound, pyrylium compound, rhoda Nin compound, oxazolone compound, phthalimide compound, cinnoline compound, naphthoquinone compound, azaanthraquinone compound, porphyrin compound, azaporphyrin compound, pyromethene compound, quinacridone compound, diketopyrrolopyrrole compound, indigo compound and dyes such as acridine compound, azine compound, azomethine compound, aniline compound, quinacridone compound, quinophthalone compound, quinoneimine compound, iridium complex compound, europium complex compound, etc. you can use it.

An inorganic pigment or an organic pigment may be used as the pigment, for example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, iso Indolinone compound, isoindoline compound, quinacridone compound, ananthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound , naphthalenetetracarboxylic acid; metal complex compounds of azo dyes and cyanine dyes; lake pigments; carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black; The carbon black is adjusted and coated with an epoxy resin, the carbon black is previously dispersed with a resin in a solvent to adsorb 20 to 200 mg/g of the resin, the carbon black is surface-treated with an acidic or alkaline surface; an average particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less, _{a total oxygen amount calculated from CO and CO 2} in volatile matter at 950° C. of 9 mg or more per 100 m 2 of surface area of carbon black; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; aniline black, pigment black 7, titanium black; Hydrophobic resin, chromium oxide green, milory blue, cobalt green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine blue, blue blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc sulfur , iron (鐵丹) (red iron (III) oxide), cadmium red, synthetic iron black, amber, etc. inorganic content or organic pigments can be used. These pigments can be used individually or in mixture of plurality.

Commercially available pigments may be used as the inorganic or organic pigments. For example, 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. are mentioned.

The coloring photosensitive composition of this invention WHEREIN: As for content of the said coloring agent, 0-99 mass % in the coloring photosensitive composition of this invention, 0-80 mass % is especially preferable.

The coloring photosensitive composition of this invention can also be made to 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, silica, and alumina; Layered clay mineral, Milori blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfide, selenide, aluminum silicate, calcium silicate, aluminum hydroxide , platinum, gold, silver, copper, and the like.

In the above colored photosensitive composition, when a pigment and/or an inorganic compound is used, a dispersing agent may be added. As the dispersant, any dispersant capable of dispersing and stabilizing pigments and inorganic compounds may be used, and a commercially available dispersing agent, for example, a product made by Bikchemi, BYK series, etc. may be used, and polyester, polyether, poly having a basic functional group may be used. A polymer dispersing agent made of urethane, having a nitrogen atom as a basic functional group, a functional group having a nitrogen atom is an amine and/or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH/g is preferably used.

In the colored photosensitive composition of the present invention, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizer; adhesion promoter; filler; antifoam; leveling agent; surface conditioning agents; antioxidants such as phenol antioxidants, phosphite antioxidants, and thioether antioxidants; UV absorbers; dispersing aids; anti-agglomerate; catalyst; effect accelerator; crosslinking agent; Conventional additives, such as a thickener, can be added.

Moreover, the cured|cured material characteristic of the colored photosensitive composition of this invention can also be improved by using another organic polymer with the polymeric compound which has an ethylenically unsaturated bond which has the said acid value. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene-(meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Crylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylic Amide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc. are mentioned, Among these, polystyrene, (meth)acrylic acid-methylmethacrylate copolymer, and an epoxy resin are preferable. do.

A thermal radical polymerization initiator, a chain transfer agent, a sensitizer, surfactant, a silane coupling agent, a melamine compound, etc. can be used together with the coloring photosensitive composition of this invention further.

As the thermal radical polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutylate), 2,2'-azobis-2,4-dimethylvaleronitrile, azo initiators such as 1,1'-azobis(1-acetoxy-1-phenylethane); Peroxide-based initiators such as benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, and di(4-t-butylcyclohexyl)peroxydicarbonate, ammonium persulfate, sodium persulfate, potassium persulfate Persulfates, such as these, etc. are mentioned. These can be used 1 type or in mixture of 2 or more types.

As the chain transfer agent and sensitizer, a compound containing a sulfur atom is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercapto Ethanesulfonic 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-mercaptobenzoimidazole, 2-mercapto-3-pyridinol Mercapto compounds, such as 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and the mercapto compound A disulfide compound obtained by oxidizing an iodide compound, an alkyl iodide compound such as iodine acetic acid, iodinepropionic acid, 2-iodethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid, trimethylolpropanetris(3-mercaptoisobutylate); Butanediolbis (3-mercaptoisobutylate), hexanedithiol, decanedithiol, 1,4-dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, Trimethylolpropane tristhioglycolate, butanediolbisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakistioglycol, trishyde Aliphatic polyfunctional thiol compounds such as oxyethyl trithiopropionate, compound No. C1 below, and tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, Karenz MT BD1, PE1 manufactured by Showa Denko Corporation , NR1, and the like.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, higher amine halides, and quaternary surfactants. Cationic surfactants such as quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and nonionic surfactants such as fatty acid monoglycerides, surfactants such as amphoteric surfactants and silicone surfactants can be used, These may 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, and among them, KBE-9007, KBM-502, KBE-403, etc., a silane coupling agent having an isocyanate group, a methacryloyl group, and an epoxy group I am used appropriately.

_{As the melamine compound, an active methylol group (CH 2} OH group) in a nitrogen compound such as (poly) methylolmelamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea) compounds in which all or part (at least two) have been alkyletherified. Here, a methyl group, an ethyl group, or a butyl group is mentioned as an alkyl group which comprises an alkyl ether, and it may mutually be same or different. Moreover, the methylol group which is not alkyl-etherified may self-condensate within 1 molecule, and may condense between 2 molecules, and as a result, the oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, or the like can be used. Among these, alkyl-etherified melamines, such as hexamethoxymethylmelamine and hexabutoxymethylmelamine, are preferable.

In addition, as a light source of the actinic light used when curing the colored photosensitive composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be used

In addition, the laser direct drawing method in which an image is formed directly from digital information such as a computer without using a mask by using laser light as the exposure light source is useful because it can improve not only productivity but also resolution and positional accuracy. , As the laser beam, light having a wavelength of 340 to 430 nm is suitably used, but argon ion lasers, helium neon lasers, YAG lasers, and semiconductor lasers that emit light in the visible to infrared range are also used. When these lasers are used, a sensitizing dye that absorbs the above-mentioned region from visible to infrared is added.

The colored photosensitive composition (or its cured product) of the present invention is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color display liquid crystal display panel for a color TV, PC monitor, portable information terminal, digital camera, etc. Color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, stereolithography resins, gel coats, photoresists for electronic engineering, electroplating resists , etching resists, both liquid and dry films, solder resists, resists for manufacturing color filters for various display applications, or for forming structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs, electrical and Compositions for encapsulating electronic components, solder resists, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils , a material for manufacturing a three-dimensional object by stereolithography, a material for holographic recording, an image recording material, a microelectronic circuit, a decolorizing material, a decolorizing material for an image recording material, a decolorizing material for an image recording material using microcapsules , photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, and photoresist materials or protective films used to form dielectric layers in sequential lamination of printed circuit boards. There is no particular limitation.

The coloring photosensitive composition of this invention is used for the purpose of forming the pixel of a color filter, and is useful especially as a photosensitive composition for forming the color filter for display devices for image display apparatuses, such as a liquid crystal display panel.

The color filter for a display device includes (1) a step of forming a coating film of the colored photosensitive composition on a substrate, (2) a step of irradiating the coating film with actinic light through a mask having a predetermined pattern shape, (3) exposure It is preferably formed by the step of developing the subsequent coating film with a developer, and (4) heating the developed coating film. Moreover, the coloring photosensitive composition of this invention is useful also as a coloring photosensitive composition of the inkjet system without a developing process.

Example

Hereinafter, the present invention will be described in more detail with reference to 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 equivalents of Compound 2 and 2.42 g of 4-dimethylaminopyridine were added, stirred for 30 minutes under an ice bath, and 4.5 equivalents of EDC hydrochloride (等量) ) was added, and the mixture was stirred for 5 hours at room temperature under a nitrogen atmosphere. After oil-water separation with ethyl acetate/water, it was washed with water and dried, and the solvent was distilled off to obtain compound 4.

<Step 2> Synthesis of compound No. 1

1 equivalent of compound 4 obtained in step 1 and 2.05 g of pyridine are mixed, 0.1 equivalent of 4-dimethylaminopyridine is added and stirred, and then 12 equivalents of -t-butyl dicarbonate are added dropwise at 10° C. or lower, followed by 20 at room temperature. time was stirred. After oil-water separation with ethyl acetate/water, it washed with water and dried, and the solvent was distilled off. It purified by column chromatography (ethyl acetate:hexane = 1:1) and crystallized from methanol to obtain compound No. 1 in a yield of 24%. ^{It was confirmed by 1} H-NMR and IR that the obtained compound was the target product. In addition, absorption wavelength characteristics were measured. A result is shown in [Table 1] and [Table 2].

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

<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 then 3 equivalents of -t-butyl dioxide was added dropwise at 10° C. or less and stirred at room temperature for 3 hours. did. After oil-water separation with ethyl acetate/water, it 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, 10 g of ethyl acetate, and 10 g of water were mixed, 1 equivalent of compound 6 obtained in step 1 was added and stirred, and the ethyl acetate layers were separated, dried, and concentrated to 5 times the theoretical amount. The concentrated ethyl acetate solution was dispersed in hexane and crystallized to obtain compound No. 2 in a yield of 70%. ^{It was confirmed by 1} H-NMR and IR that the obtained compound was the target product. In addition, absorption wavelength characteristics were measured. A result is shown in [Table 1] and [Table 2].

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

<Step 1> Synthesis of compound 9

1 equivalent of compound 8 in the above scheme, sodium hydroxide 2eq. 2 g of water and 2 g of toluene were mixed and stirred at room temperature. Then, under ice-cooling, 2 ml of 1N hydrochloric acid aqueous solution was added, it was made into an acidic solution, oil-water separation was performed, and the toluene solution containing the compound 9 was obtained.

<Step 2> Synthesis of compound No.3

4 g of chloroform and 1 eq. of compound 6 were added to a toluene solution containing 1 equivalent of compound 9 obtained in step 1, stirred and oil-water separation was performed, dispersed in hexane and crystallized to obtain compound No. 3 in a yield of 80% . ^{It was confirmed by 1} H-NMR and IR that the obtained compound was the target product. In addition, absorption wavelength characteristics were measured. A result is shown in [Table 1] and [Table 2].

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

<Step 1> Preparation of photosensitive composition No. 1

30.3 g of ACA Z250 (manufactured by Daicel Cytech) as a polymerizable compound component having an ethylenically unsaturated bond having an acid value, Aronix M-450 (Toa) as a polymerizable compound component having an ethylenically unsaturated bond having no acid value 11.04 g (manufactured by Kosei Corporation), 1.93 g of Irgacure 907 (manufactured by BASF) as a component of a radical photopolymerization initiator, 36.60 g of PGMEA and 20.08 g of cyclohexanone as a solvent, and FZ2122 (Toray) as other components ㆍDow Corning Co.) was mixed with 0.01 g and stirred until insoluble matter disappeared to obtain photosensitive composition No. 1.

<Step 2> Preparation of dye solutions 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, stirred and dissolved to prepare dye solutions No. 1 to No. 3, respectively.

<Step 3> Preparation of coloring photosensitive composition No.1-No.3

5.0 g of photosensitive composition No. 1 obtained in step 1 and 1.0 g of dye liquid No. 1 - No. 3 obtained in step 2 are respectively mixed and stirred until uniform, and coloring photosensitive composition No. 1 - of this invention No. 3 was obtained, respectively.

[Comparative Examples 1-1 to 1-3] Preparation of Comparative Colorable Photosensitive Compositions No. 1 to No. 3

Comparative coloring photosensitive composition No.1-No in the same method as Example 2-1 except having changed compound No.1 in step 2 of Example 2 into any one of following comparative compound No.1-No.3 .3 was obtained.

[Comparative Examples 2-1 to 2-3] Preparation of Comparative Colorable Photosensitive Compositions No. 1A to No. 3A

Comparative coloring photosensitive composition No.1A-No.3A was obtained by the method similar to Example 2-1 except having added the following compound (alpha) as antioxidant to comparative coloring photosensitive composition No.1 - No.3.

[Evaluation Examples 1-1 to 1-3 and Comparative Evaluation Examples 1-1 to 1-3] Heat resistance evaluation by firing

The colored photosensitive compositions No. 1 to No. 3 and comparative colored photosensitive compositions No. 1 to No. 3 obtained above were respectively coated on a glass substrate under conditions of 410 rpm×7 sec, and dried on a hot plate (90° C., 90 sec). The obtained coating film was exposed (150 mJ/cm<2>) with an ultra-high pressure mercury lamp. The coating film after exposure was baked on the conditions of 230 degreeC x 30 min. The absorbance of the coating film before firing (after exposure) and the absorbance of the coating film after firing at the maximum absorption wavelength (λmax) of the compound used were measured, and the absorbance of the coating film before firing (after exposure) was evaluated as the relative intensity when 100. . On the other hand, the closer the absorbance of the coating film after firing to 100, the higher the heat resistance. In addition, the color difference (ΔE _ab* ) before and after firing was investigated. A result is shown in [Table 3].

It is clear from the said result that the coloring photosensitive composition of this invention has high heat resistance.

[Example of evaluation 2-1~2-3 and Comparative Evaluation Example 2-1~2-3] Antioxidant function evaluation

First, coloring photosensitive composition No.1A - No.3A was obtained by the method similar to Example 2-1 except having added comparative compound No.1 to coloring photosensitive composition No.1-No.3, respectively.

Colored photosensitive compositions No.1A to No.3A obtained above and Comparative Colored photosensitive compositions No.1A to No.3A obtained in Comparative Examples 2-1 to 2-3 were respectively coated on a glass substrate under conditions of 410 rpm x 7 sec. The plate was dried (90° C., 90 sec). The obtained coating film was exposed (150 mJ/cm<2>) with an ultra-high pressure mercury lamp.

The coating film after exposure was baked on the conditions of 230 degreeC x 30 min. The absorbance of the coating film before firing (after exposure) and the absorbance of the coating film after firing at the maximum absorption wavelength (λmax) of the compound used were measured, and the absorbance of the coating film before firing (after exposure) was evaluated as the relative intensity when 100. . In addition, the color difference (ΔE _ab* ) before and after firing was investigated. A result is shown in [Table 4].

It is clear from the said result that the color photosensitive composition which added the compound of this invention to the conventional dye has high heat resistance compared with the comparative coloring photosensitive composition which added the antioxidant to the conventional dye. Accordingly, this indicates that the compound of the present invention has a high antioxidant function.

From the above result, it is clear that the heat resistance in the coloring photosensitive composition using the novel compound of this invention, and its hardened|cured material is high. Therefore, the dye and coloring photosensitive composition of this invention are useful for the color filter for display devices, and the liquid crystal display panel which uses the same.

Claims (4)

A cyanostyrene compound represented by the following general formula (2), which is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region, and has 1 to 10 substituents represented by the following general formula (1) in a molecule; A triarylmethane compound represented by the following general formula (8) or a cyanine compound represented by the following general formula (9).

( ^{Wherein, R 01} , R ⁰² , R ⁰⁴ and R ⁰⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 40 carbon atoms, or -OR ¹ ,
At least one of R ⁰² or R ⁰⁴ is an alkyl group having 1 to 40 carbon atoms,
R ⁰³ is represented by -OR ¹ ,
R ¹ is an alkoxycarbonyl group having 2 to 9 carbon atoms,
The ^{alkyl group represented by R 01} , R ⁰² , R ⁰⁴ and R ⁰⁵ has a substituent or is unsubstituted,
Among the alkyl groups represented by R ⁰¹ , R ⁰² , R ⁰⁴ and R ⁰⁵ , a methylene group is 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 - may be substituted,
R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

(Wherein, A represents a benzene ring, a naphthalene ring or an anthracene ring, and these rings are a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or substituted or unsubstituted with a halogenated alkoxy group having 1 to 8 carbon atoms;
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or a halogenated alkoxy group having 1 to 8 carbon atoms,
Y represents a cyano group,
X is an organic group that satisfies the conditions of <1>, and is bonded to ^{R 6 ,}
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 8 carbon atoms,
The ^{alkyl group represented by R 7} may be substituted with a substituent represented by the general formula (1),
Among the alkyl groups represented by R ⁷ , the methylene group may be substituted with -OCO-,
m is 2.)
<1> X is represented by the following general formula (3).

(Wherein, X ¹ represents a divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms,
Z ¹ and Z ² represent a direct bond.)

(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 are each independently a hydrogen atom, a halogen atom or a carbon atom represents an alkyl group of numbers 1 to 8,
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,
An ^q- represents an organic sulfonic acid anion having at least one substituent represented by the general formula (1), q represents 1 or 2, and p represents a coefficient for maintaining a neutral charge.)

(Wherein, D represents a group represented by (a) of the following group I, and D' represents a group represented by (a') of the following group II,
Q represents a linking group constituting a methine chain having 1 to 9 carbon atoms, and a hydrogen atom in the methine chain is a hydroxyl group, a halogen atom, a cyano group, -NR ⁵¹ R ⁵² , and 6 to 12 carbon atoms may be substituted with an aryl group, an arylalkyl group having 7 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, the -NR ⁵¹ R ⁵² , the aryl group, the arylalkyl group and the alkyl group may be further substituted with a halogen atom, -NR ⁵¹ R ⁵² , an aryl group, a methylene group among the arylalkyl group and the alkyl group is -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, - NHCO-, -N=CH- or -CH=CH- may be substituted,
R ⁵¹ and R ⁵² represent an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms,
An ^q- represents an organic sulfonic acid anion having at least one substituent represented by the general formula (1), q represents 1 or 2, and p represents a coefficient for maintaining a neutral charge.)

(In the formula, ring G and ring G' represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,
R ⁵³ and R ^53' represent a halogen atom, a nitro group or an alkyl group having 1 to 8 carbon atoms,
The ^{alkyl group represented by R 53} and R ^{53' may} be substituted with a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amide group or a ferrocenyl group,
Among the alkyl groups represented by R ⁵³ and R ^53' , a methylene group is -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, - may be substituted with N=CH- or -CH=CH-,
X ¹² and X ^12' 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 group as R 53} and R ^53' or a hydrogen atom,
Y ¹² , Y ^{12 '} and Y ¹³ represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms,
Y ¹² , Y ^12' and Y ^{13 The} alkyl group, aryl group and arylalkyl group are substituted with or unsubstituted with a halogen atom,
Among the alkyl, aryl and arylalkyl groups represented by Y ¹² , Y ^{12 '} and Y ¹³ , the methylene group is -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NH-, -CONH-, -NHCO-, -N=CH- or -CH=CH- may be substituted,
r and r' represent an integer of 0 to 2.) According to claim 1,
In the general formula (1), R ⁰¹ , R ⁰² , R ⁰⁴ and R ⁰⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 40 carbon atoms,
In the general formula (2), R ⁵ represents a hydrogen atom,
In Formula (8), 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 are each independently a hydrogen atom or carbon represents an alkyl group having 1 to 8 atoms,
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,
In the above general formulas (a) and (a')
R ⁵³ and R ^53' represent a nitro group,
X ¹² and X ^12' represents -CR ⁶² R ⁶³ -,
R ⁶² and R ⁶³ represent an alkyl group having 1 to 8 carbon atoms or a hydrogen atom,
Y ¹² and Y ^12' represent an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms,
A compound in which the methylene group in the alkyl group and the arylalkyl group represented by Y ¹² and Y ^{12' may be substituted with -O-.} A composition containing the compound according to claim 1 or 2 . A colored photosensitive composition comprising a polymerizable compound having an ethylenically unsaturated bond having an acid value and a radical photopolymerization initiator in the composition according to claim 3 further.