JPWO2015083605A1 - NOVEL COMPOUND AND COMPOSITION CONTAINING THE COMPOUND - Google Patents

Abstract

The present invention provides a novel compound suitable as a dye for a colored photosensitive composition excellent in heat resistance (colored alkali-developable photosensitive composition) and a colored photosensitive composition using the novel compound, Specifically, it is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region and having 1 to 10 substituents represented by the following general formula (1) in the molecule, preferably cyano The present invention provides a colored photosensitive composition in which a styrene compound, a triarylmethane compound or a cyanine compound, and a polymerizable compound having an ethylenically unsaturated bond having an acid value and a radical photopolymerization initiator are used in combination. The specific contents of the general formula (1) are as described in this specification.

Description

  The present invention relates to an organic dye compound having a phenolic antioxidant structure and a composition containing the compound. Furthermore, the present invention relates to a colored photosensitive composition that can be polymerized by energy rays using the composition, and a color filter that uses the colored photosensitive composition.

  Compounds having high intensity absorption for specific light include recording layers of optical recording media such as CD-R, DVD-R, DVD + R, BD-R, liquid crystal display devices (LCD), plasma display panels (PDP). ), An electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, and an optical display element such as a field emission display.

In an optical filter for an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, a field emission display, etc., 300 Various compounds that absorb light having a wavelength of ˜1100 nm are used as light absorbers.
These light absorbers are required to have particularly steep light absorption, that is, having a small half-value width of λmax and not to lose its function due to light, heat, or the like.

An optical filter mainly used for a liquid crystal display (LCD) includes a color filter. In general, three primary colors of RGB have been used for a color filter, but it is difficult to have a pure RGB hue with a single color material, and a pure RGB hue using a plurality of color materials. Efforts have been made to get closer to. Therefore, color materials such as yellow, orange and purple are required instead of RGB.
Organic and / or inorganic pigments have been used as light absorbers for color filters due to their high heat resistance. However, since they are pigments, there is a problem in that the luminance of a display device is lowered. This problem has been solved by increasing the brightness of the. However, with the trend toward lower power consumption, development of color filters using dyes has become active.

In recent years, in color filters used in solid-state imaging devices, it is required to reduce the color pattern from the viewpoint of improving the image quality, and in order to reduce the thickness, it is necessary to increase the dye concentration in terms of color density. . In addition, a large amount of dye must be added even when the molar absorption coefficient of the dye is low.
However, when the dye concentration is increased, when heat treatment (post-bake) is performed after film formation, color mixing is likely to occur between adjacent pixels or between upper and lower layers in a laminated structure, and thus heat resistance is required.

Patent Documents 1 to 3 disclose a colored resin composition for a color filter containing an organic dye having a specific structure.
Patent Documents 4 and 5 disclose a coloring composition for a color filter containing a pigment and an antioxidant.
However, the compounds used in the coloring compositions for color filters described in these documents are not satisfactory in terms of heat resistance.

WO2012 / 039286 WO2012 / 101946 WO2012 / 111400 JP 2010-008650 A JP 2011-141356 A

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

  As a result of extensive studies, the present inventor has 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. However, it has been found that it is suitable for a color filter for an image display device such as a liquid crystal display panel without reducing the luminance of an optical filter (particularly a color filter), and has reached the present invention.

  The present invention has been made on the basis of the above knowledge, and is an organic dye having an absorption maximum in the wavelength region from ultraviolet to near infrared, wherein the substituent represented by the following general formula (1) is 1 to A compound having 10 is provided.

（式中、Ｒ⁰¹、Ｒ⁰²、Ｒ⁰³、Ｒ⁰⁴及びＲ⁰⁵は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又は−Ｏ−Ｒ¹を表し、
Ｒ⁰¹、Ｒ⁰²、Ｒ⁰³、Ｒ⁰⁴及びＲ⁰⁵のうち少なくとも１つは−Ｏ−Ｒ¹で表され、
Ｒ¹は、水素原子、炭素原子数１〜４０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又はトリアルキルシリル基を表し、
Ｒ⁰¹、Ｒ⁰²、Ｒ⁰³、Ｒ⁰⁴及びＲ⁰⁵並びにＲ¹で表されるアルキル基、アリール基、アリールアルキル基又は複素環含有基は、置換基を有しているか又は無置換であり、
Ｒ⁰¹、Ｒ⁰²、Ｒ⁰³、Ｒ⁰⁴及びＲ⁰⁵並びにＲ¹で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素−炭素二重結合、−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−、−ＮＲ²−、＞Ｐ＝Ｏ、−Ｓ−Ｓ−又は−ＳＯ₂−で置き換わっていてもよく、
Ｒ²は、水素原子又は炭素原子数１〜８のアルキル基を表す。）

(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, or 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 heterocyclic ring-containing group having 2 to 20 carbon atoms, or —O—R ¹ ;
At least one of R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ is represented by —O—R 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 Represents a trialkylsilyl group,
The alkyl group, aryl group, arylalkyl group or heterocyclic ring-containing group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ has a substituent or is unsubstituted,
The methylene group in the alkyl group or arylalkyl group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and 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, -S-S- or -SO ₂ - may be replaced by,
R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

  Further, the present invention is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region, and having 1 to 10 substituents represented by the following general formula (1) in the molecule The composition containing this is provided.

  The present invention also provides a colored photosensitive composition containing a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator in addition to the above composition.

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

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

  First, a compound having at least one structure represented by the general formula (1) in the molecule, which is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region 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. 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, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, carbonium compound, rhodamine compound, perylene compound, polyenenaphtholactam compound, coumarin compound, squaryli Compounds, croconium compounds, spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pyrylium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, naphthalimide compounds, cinnoline compounds, naphthoquinone compounds, anthraquinone compounds, azaanthraquinone compounds , Porphyrin compounds, azaporphyrin compounds, pyromethene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, azomethine compounds, aniline compounds, quinophthalone compounds, quinoneimine compounds, oligophenylene compounds, iridium complex compounds, europium Examples include dyes such as complex compounds. Good.

  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 examples thereof include a method using a known reaction. However, for example, a method utilizing a reaction such as esterification or amidation can be 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 or different. The number of substituents is preferably 2 to 6 from the viewpoint of ease of synthesis.

Examples of the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ in the general formula (1) include fluorine, chlorine, bromine and iodine.
R ^01, R ^02, the alkyl group of R ^03, R ⁰⁴ and R ⁰⁵ and having 1 to 40 carbon atoms represented by R ^1, 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-norbornyl methyl and the like,
Examples of 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 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-cyclohexyl Phenyl, 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-butylphenol 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, etc.
Examples of 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 include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl group, 2- Phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like,
Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl and pyrrolyl. Quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinone-1- Yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl and the like,
Examples of the trialkylsilyl group represented by R ¹ include trimethylsilane, triethylsilane, and ethyldimethylsilane.

^{Examples of} the substituent for substituting the alkyl group, aryl group, arylalkyl group and heterocyclic-containing group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ include vinyl, allyl, acryl, methacryl Ethylenically unsaturated groups such as fluorine, chlorine, bromine, iodine and the like; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, Acyl groups such as pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acyloxy groups such as acetyloxy and benzoyloxy; amino, ethylamino, dimethyl Amino, 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-butoxy Carbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxy Substituted amino groups such as nonoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo Groups, hydroxyl groups, nitro groups, mercapto groups, imide groups, carbamoyl groups, sulfonamido groups, phosphonic acid groups, phosphoric acid groups or carboxyl groups, sulfo groups, phosphonic acid groups, and phosphoric acid group salts.
The methylene group in the alkyl group or arylalkyl group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and 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, -S-S- or -SO ₂ - may be replaced by, replacing The position and number are arbitrary.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the alkyl group having 1 to 40 carbon atoms represented by R ^1. Among these, groups satisfying a predetermined number of carbon atoms are exemplified.

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, or 7 to 20 carbon atoms. An arylalkyl group or a group containing 2 to 20 carbon atoms in a heterocyclic ring, one in which R ⁰³ is —O—R ¹ , particularly R ¹ is a hydrogen atom or an alkoxycarbonyl group having 2 to 9 carbon atoms. In particular, 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 40 carbon atoms, having 6 to 20 carbon atoms. An aryl group, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic-containing group having 2 to 20 carbon atoms, in particular, R ¹ is a hydrogen atom or an alkoxycarbonyl group having 2 to 9 carbon atoms; and R ⁰² or R ⁰⁴ At least one of those is an alkyl group having 1 to 10 carbon atoms are preferred from the viewpoint of heat resistance.
Examples of the alkoxycarbonyl group having 2 to 9 carbon atoms include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, s-butyloxycarbonyl, t-butyloxycarbonyl, isobutyloxycarbonyl Pentyloxycarbonyl, isoamyloxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, cyclohexylmethyloxycarbonyl, tetrahydrofuranyloxycarbonyl, tetrahydropyranyloxycarbonyl and the like.

  Among those exemplified as the organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region, a cyanostyrene compound, a triarylmethane compound, and a cyanine compound are preferable from the viewpoint of ease of synthesis and molecular design.

  Among the above cyanostyrene compounds, those represented by the following general formula (2) are preferable from the viewpoint of ease of synthesis and molecular design.

（式中、Ａは、ベンゼン環、ナフタレン環又はアントラセン環を表し、これらの環は、上記一般式（１）で表される置換基、ハロゲン原子、シアノ基、水酸基、ニトロ基、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数１〜８のハロゲン化アルキル基若しくは炭素原子数１〜８のハロゲン化アルコキシ基で置換されているか又は無置換であり、
Ｒ⁵は、水素原子、フェニル基、シアノ基、ニトロ基、ハロゲン原子、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数１〜８のハロゲン化アルキル基又は炭素原子数１〜８のハロゲン化アルコキシ基を表し、
Ｙは、シアノ基又は−ＣＯＯＲ⁸を表し、
Ｒ⁸は、水素原子、炭素原子数１〜８のアルキル基又は上記一般式（１）で表される置換基を表し、
Ｒ⁸で表されるアルキル基中のメチレン基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で置き換わっていてもよく、
Ｘは、単結合、窒素原子、−ＮＲ⁹−、酸素原子、硫黄原子、リン原子、−ＰＲ¹⁰−又は下記＜１＞〜＜５＞の何れかの条件を満たす有機基であり、且つ、Ｙが−ＣＯＯＲ⁸で表されるときのＲ⁸、Ａ、Ｒ⁶又はＲ⁷の何れか１つ以上と結合しており、
Ｒ⁶、Ｒ⁷、Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は上記一般式（１）で表される置換基を表し、
Ｒ⁶、Ｒ⁷、Ｒ⁹及びＲ¹⁰で表されるアルキル基、アリール基及びアリールアルキル基は、上記一般式（１）で表される置換基、ハロゲン原子、水酸基又はニトロ基で置換されていてもよく、
Ｒ⁶、Ｒ⁷、Ｒ⁹及びＲ¹⁰で表されるアルキル基及びアリールアルキル基中のメチレン基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で置き換わっていてもよく、
ｍは、１〜６の整数であり、
分子内に上記一般式（１）で表される置換基を少なくとも一つ有する。）

(In the formula, A represents a benzene ring, a naphthalene ring or an anthracene ring, and these rings represent the substituent represented by the general formula (1), a halogen atom, a cyano group, a hydroxyl group, a nitro group, and the number of carbon atoms. Substituted or unsubstituted by 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 ,
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, or 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 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),
The methylene group in the alkyl group represented by R ⁸ may be replaced by —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 that satisfies any of the following <1> to <5>, and Bonded to any one or more of R ⁸ , A, R ⁶ or R ⁷ when Y is 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, or an arylalkyl group having 7 to 20 carbon atoms. Or the substituent represented by the said General formula (1) is represented,
The alkyl group, aryl group and arylalkyl group represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are substituted with a substituent represented by the above general formula (1), a halogen atom, a hydroxyl group or a nitro group. You can,
The methylene group in the alkyl group and arylalkyl group represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ is —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—. May be replaced with
m is an integer of 1 to 6,
It has at least one substituent represented by the general formula (1) in the molecule. )

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

（式中、Ｘ¹は、−ＮＲ¹³−、二価の炭素原子数１〜３５の脂肪族炭化水素基、二価の炭素原子数３〜３５の脂環式炭化水素基、二価の炭素原子数６〜３５の芳香環含有炭化水素基若しくは二価の炭素原子数２〜３５の複素環基又は下記（３−１）〜（３−３）の何れかで表される置換基を表し、
Ｘ¹で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹及びＺ²は、それぞれ独立に、直接結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＯ−、−ＮＲ¹³−、−ＰＲ¹⁴−を表し、
Ｒ¹³及びＲ¹⁴は、それぞれ独立に、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、
Ｒ¹³及びＲ¹⁴で表されるアルキル基、アリール基及びアリールアルキル基は、ハロゲン原子、水酸基又はニトロ基で置換されていてもよく、
Ｒ¹³及びＲ¹⁴で表されるアルキル基及びアリールアルキル基中のメチレン基は、−ＣＯＯ−、−Ｏ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−又は−ＣＯＮＨ−で置き換わっていてもよい。
但し、上記一般式（３）で表される基は炭素原子数１〜３５の範囲内である。）

(In the formula, 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 carbon. The aromatic ring-containing hydrocarbon group having 6 to 35 atoms, a divalent heterocyclic group having 2 to 35 carbon atoms, or a substituent represented by any of the following (3-1) to (3-3) ,
The methylene group in the aliphatic hydrocarbon group represented by X ¹ is replaced with —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof. Well,
Z ¹ and Z ² each independently represent 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,
The methylene group in the alkyl group and arylalkyl group represented by R ¹³ and R ¹⁴ may be replaced by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—. .
However, the group represented by the general formula (3) is in the range of 1 to 35 carbon atoms. )

（式中、Ｒ²¹は水素原子、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基により置換されてもよいフェニル基又は炭素原子数３〜１０のシクロアルキル基を表し、
Ｒ²²は炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、
Ｒ²¹及びＲ²²で表されるアルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されているか又は無置換であり、
ｄは０〜５の整数である。）

(In the formula, R ²¹ represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. ,
R ²² represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group 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 substituted with a halogen atom or unsubstituted,
d is an integer of 0-5. )

（式中、Ｒ²³及びＲ²⁴は、それぞれ独立に、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数６〜２０のアリールオキシ基、炭素原子数６〜２０のアリールチオ基、炭素原子数８〜２０のアリールアルケニル基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基又はハロゲン原子を表し、
Ｒ²³及びＲ²⁴で表されるアルキル基、アリール基、アリールオキシ基、アリールチオ基、アリールアルケニル基、アリールアルキル基及び複素環含有基は、ハロゲン原子で置換されているか又は無置換であり、
Ｒ²³及びＲ²⁴で表されるアルキル基及びアリールアルキル基中のメチレン基は、不飽和結合、−Ｏ−又は−Ｓ−で置き換わっていてもよく、
Ｒ²³は、隣接するＲ²³同士で環を形成していてもよく、
ｅは０〜４の数を表し、ｆは０〜８の数を表し、ｇは０〜４の数を表し、ｈは０〜４の数を表し、ｇとｈの数の合計は２〜４である。）

(In the formula, 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, or 6 carbon atoms. Represents an arylthio group of -20, an arylalkenyl group of 8-20 carbon atoms, an arylalkyl group of 7-20 carbon atoms, a heterocyclic-containing group of 2-20 carbon atoms, or a halogen atom,
The alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocyclic group-containing group represented by R ²³ and R ²⁴ are substituted with a halogen atom or unsubstituted,
The methylene group in the alkyl group and arylalkyl group represented by R ²³ and R ²⁴ may be replaced with an unsaturated bond, —O— or —S—,
R ²³ may form a ring with adjacent R ²³ ,
e represents a number from 0 to 4, f represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, and the total number of g and h is 2 to 2. 4. )

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

（式中、Ｘ²は、Ｒ²⁵で置換された炭素原子、三価の炭素原子数１〜３５の脂肪族炭化水素基、三価の炭素原子数３〜３５の脂環式炭化水素基、三価の炭素原子数６〜３５の芳香環含有炭化水素基又は三価の炭素原子数２〜３５の複素環含有基を表し、
Ｒ²⁵は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、
Ｘ²で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ³は、それぞれ独立に、上記一般式（３）におけるＺ¹及びＺ²で表される基と同じである。
但し、上記一般式（４）で表わされる基は炭素原子数１〜３５の範囲内である。）

(In the formula, X ² is a carbon atom substituted with R ²⁵ , a trivalent C1-C35 aliphatic hydrocarbon group, a trivalent C3-C35 alicyclic hydrocarbon group, Represents a trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a trivalent heterocyclic 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,
The methylene group in the aliphatic hydrocarbon group represented by X ² is replaced with —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof. Well,
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 general formula (4) is in the range of 1 to 35 carbon atoms. )

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

（式中、Ｘ³は、炭素原子、四価の炭素原子数１〜３５の脂肪族炭化水素基、四価の炭素原子数３〜３５の脂環式炭化水素基、四価の炭素原子数６〜３５の芳香環含有炭化水素基又は四価の炭素原子数２〜３５の複素環含有基を表し、
Ｘ³で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ⁴は、それぞれ独立に、上記一般式（３）におけるＺ¹及びＺ²で表される基と同じである。
但し、上記一般式（５）で表される基は炭素原子数１〜３５の範囲内である。）

(In the formula, X ³ represents a carbon atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms having a tetravalent carbon number, an alicyclic hydrocarbon group having 3 to 35 carbon atoms having a tetravalent carbon atom, and the number of tetravalent carbon atoms. Represents a 6-35 aromatic ring-containing hydrocarbon group or a tetravalent C2-C35 heterocycle-containing group,
The methylene group in the aliphatic hydrocarbon group represented by X ³ is replaced with —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof. Well,
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 general formula (5) is in the range of 1 to 35 carbon atoms. )

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

（式中、Ｘ⁴は、五価の炭素原子数２〜３５の脂肪族炭化水素基、五価の炭素原子数３〜３５の脂環式炭化水素基、五価の炭素原子数６〜３５の芳香環含有炭化水素基又は五価の炭素原子数２〜３５の複素環含有基を表し、
Ｘ⁴で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ⁵は、それぞれ独立に、上記一般式（３）におけるＺ¹及びＺ²で表される基と同じである。
但し上記一般式（６）で表される基は炭素原子数２〜３５の範囲内である。）

(In the formula, X ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an alicyclic hydrocarbon group having 5 to 35 carbon atoms, and a pentavalent carbon atom having 6 to 35 carbon atoms. An aromatic ring-containing hydrocarbon group or a pentavalent C2-C35 heterocycle-containing group,
The methylene group in the aliphatic hydrocarbon group represented by X ⁴ is replaced with —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof. Well,
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 general formula (6) is in the range of 2 to 35 carbon atoms. )

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

（式中、Ｘ⁵は、六価の炭素原子数２〜３５の脂肪族炭化水素基、六価の炭素原子数３〜３５の脂環式炭化水素基、六価の炭素原子数６〜３５の芳香環含有炭化水素基又は六価の炭素原子数２〜３５の複素環含有基を表し、
Ｘ⁵で表される脂肪族炭化水素基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−又はこれらを組み合わせた基で置き換わっていてもよく、
Ｚ¹〜Ｚ⁶は、それぞれ独立に、上記一般式（３）におけるＺ¹及びＺ²で表される基と同じである。
但し上記一般式（７）で表される基は炭素原子数２〜３５の範囲内である。）

(In the formula, 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, or a 6 to 35 carbon atom number. An aromatic ring-containing hydrocarbon group or a hexavalent heterocyclic group having 2 to 35 carbon atoms,
The methylene group in the aliphatic hydrocarbon group represented by X ⁵ is replaced with —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof. Well,
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 general formula (7) is in the range of 2 to 35 carbon atoms. )

In the above general formula (2), the benzene ring represented by A, the naphthalene ring and the halogen atom which may be substituted for the anthracene, the halogen atom represented by R ⁵ , and R ⁶ , R ⁷ , R ⁹ and R ¹⁰ As the halogen atom that may be substituted for the alkyl group, aryl group, and arylalkyl group represented by the above, the groups exemplified as the halogen atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ Named,
Examples of the alkyl group having 1 to 8 carbon atoms that 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 R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ , and groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ include groups satisfying a predetermined carbon number, and the like.
Examples of the alkoxy group having 1 to 8 carbon atoms and the alkoxy group having 1 to 8 carbon atoms represented by R ⁵ which may substitute the benzene ring, naphthalene ring and anthracene represented by A include methoxy, ethoxy, Propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, etc. And
As the halogenated alkyl group having 1 to 8 carbon atoms and the halogenated alkyl group having 1 to 8 carbon atoms represented by R ^5, which may be substituted for the benzene ring, naphthalene ring and anthracene represented by A, , Wherein at least one hydrogen atom of the alkyl group having 1 to 8 carbon atoms is substituted by the halogen atom described above, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, fluoromethyl, trifluoromethyl, Nonafluorobutyl and the like,
As the halogenated alkoxy group having 1 to 8 carbon atoms and the halogenated alkoxy group having 1 to 8 carbon atoms represented by R ^5, which may be substituted for the benzene ring, naphthalene ring and anthracene represented by A, , Wherein at least one hydrogen atom of the alkoxy group having 1 to 8 carbon atoms is substituted by the halogen atom described above, for example, chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, fluoromethyloxy , Trifluoromethyloxy, 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 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^1. The group illustrated as an aryl group of several 6-20 is mentioned,
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ include carbons represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^1. The group illustrated as an arylalkyl group of 7-20 atoms 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, and tert-butane. , Iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane, tert-octane, A divalent group in which a group such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like is substituted with Z ¹ and Z ² , and aliphatic hydrocarbon The methylene group in the group is -O-, -S-, -CO-, -COO-, -OCO-, -NH- or These groups may be replaced by a combination of these. Examples of the combination of these include -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, and -CO-NH. -, -NH-CO-, etc., among which -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O- are replaced. Is preferred,
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, noradamantyl, 2- Methyl adamantyl, 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. .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, cedrol, cyclododecanyl, etc., divalent groups 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 a group such as phenyl, naphthyl, and biphenyl is substituted with Z ¹ and Z ^2. Named,
The divalent heterocyclic ring-containing group having a carbon number of 2 to 35 represented by X ^1, pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chroman, xanthene, thiophene And divalent groups in which a group such as thiolane is substituted with Z ¹ and Z ² .
These groups may be further substituted with a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹³ and R ^14, alkyl of ^{R 01, R 02, R 03} , R 04 and R ⁰⁵ and having 1 to 40 carbon atoms represented by R ¹ Among the groups exemplified as the group, groups satisfying a predetermined carbon number can be mentioned,
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include aryl having 6 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^1. Examples include groups exemplified as the group,
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include those having 7 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ . Groups exemplified as arylalkyl groups,
Examples of the halogen atom which may be substituted for the alkyl group, aryl group and arylalkyl group represented by R ¹³ and R ¹⁴ include halogen atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ And the groups exemplified as above.

In the substituent represented by (3-1) above, the phenyl group represented by R ²¹ and the alkyl group having 1 to 10 carbon atoms which may be substituted with the cycloalkyl group having 3 to 10 carbon atoms and R Examples of the alkyl group having 1 to 10 carbon atoms represented by ^22, exemplified as the alkyl group of ^{R 01, R 02, R 03} , R 04 and R ⁰⁵ and having 1 to 40 carbon atoms represented by R ¹ Among the groups, groups satisfying a predetermined carbon number, etc. are mentioned,
A phenyl group represented by R ²¹ and an alkoxy group having 1 to 10 carbon atoms which may be substituted with a cycloalkyl group having 3 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms represented by R ²² As the groups exemplified as the benzene ring, naphthalene ring represented by A and the alkoxy group having 1 to 8 carbon atoms which may be substituted for anthracene and the alkoxy group having 1 to 8 carbon atoms represented by R ⁵ Etc.
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ²¹ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohebutyl, cyclooctyl and the like, and these groups are the above alkyl groups having 1 to 10 carbon atoms or carbon Groups substituted with an alkoxy group having 1 to 10 atoms, and the like.
Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ²² include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like. ,
Examples of the halogen atom represented by R ²² and the halogen atom that may substitute the alkyl group, alkoxy group and alkenyl group represented by R ²¹ and R ²² include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and group exemplified as the halogen atom represented by R ⁰⁵ can be mentioned.
The substitution position of the halogen atom that may substitute the alkyl group, alkoxy group and alkenyl group represented by R ²² is not 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 Among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ , a group satisfying a predetermined carbon number, and the like can be mentioned.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ include aryl having 6 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^1. Examples include groups exemplified as the group,
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-vinylphenyl. 2-oxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyl Oxy, 4- (2-ethylhexyl) phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethylphenyloxy, 3.4-dimethylphenyl Oxy, 3.5-dimethylphenyloxy, 2 4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2.4-di-tert-pentylphenyloxy, 2,5-tert-amylphenyl Groups such as oxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy, etc., and groups in which these groups are substituted with halogen atoms, etc.
As the arylthio group having 6 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 halogen atom is substituted with a sulfur atom. The foundations are dedicated,
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 halogen atom is vinyl, allyl, Groups substituted with alkenyl groups such as 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, and the like,
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ²³ and R ²⁴ include those having 7 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ . The group etc. which were illustrated as an arylalkyl group are mentioned.
Examples of the heterocyclic 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, chroman, xanthene, thiophene. And groups such as thiofuran and groups in which these groups are substituted with a halogen atom.
Examples of the halogen atom that may be substituted for the alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group, and heterocyclic group represented by R ¹³ and R ¹⁴ include R ⁰¹ , R ^The groups exemplified as the halogen atoms represented by ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ can be mentioned.

Examples of the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ² in the general formula (4) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). Are trivalent groups substituted with Z ¹ , Z ² and Z ³ , and the methylene group in the aliphatic hydrocarbon group is —O—, —S—, —CO—, —CO—O. —, —O—CO—, —SO ₂ —, —NH—, or a combination thereof may be replaced by, for example, —COO—O—, —COO—S—, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among others, -COO-, -O-, -OCO-, -NHCO-, -NH-,- CONH -, - O-CONH- or preferably one is replaced with -NHCO-O-, trivalent represented by X ² The alicyclic hydrocarbon group having a carbon number of 3 to 35, an alicyclic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3) is substituted with Z ^1, Z ² and Z ³ Trivalent groups, etc.
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 Z ¹ , And trivalent groups substituted with Z ² and Z ³ , etc.
The trivalent heterocyclic containing group having a carbon number of 2 to 35 represented by X ^2, the heterocyclic ring-containing groups exemplified in the description of X ¹ in the general formula ^{(3), Z 1, Z} 2 and Z ^And trivalent groups substituted with ³ .
The alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms, or the arylalkyl group having 7 to 20 carbon atoms represented by R ²⁵ is represented by R ¹³ and R ^14. Examples thereof include a group similar to 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 tetravalent C1-C35 aliphatic hydrocarbon group represented by X ³ in the general formula (5) is an aliphatic hydrocarbon group exemplified in the description of X ¹ in the general formula (3). Are tetravalent groups substituted with Z ¹ , Z ² , Z ³ and Z ⁴ , and the methylene group in the aliphatic hydrocarbon group is —O—, —S—, —CO—, — COO—, —OCO—, —NH—, or a combination thereof may be replaced with, for example, —COO—O—, —COO—S—, —O—OCO—. , -S-OCO-, -CO-NH-, -NH-CO-, etc., among them -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O Those substituted with —CONH— or —NHCO—O— are preferred,
The tetravalent alicyclic hydrocarbon group having a carbon number of 3 to 35 represented by X ^3, alicyclic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3), Z ^1, And trivalent groups substituted with Z ² , Z ³ and Z ⁴ , etc.
As the tetravalent C6-C35 aromatic ring-containing hydrocarbon group 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 , And tetravalent groups substituted with Z ² , Z ³ and Z ⁴ , etc.
The tetravalent heterocyclic containing group having a carbon number of 2 to 35 represented by X ^3, heterocyclic ring-containing groups exemplified in the description of X ¹ in the general formula ^{(3), Z 1, Z} 2, Z ^And tetravalent groups substituted with ³ and Z ⁴ .

Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁴ in the general formula (6) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). Are pentavalent groups substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ , and the methylene group in the aliphatic hydrocarbon group is —O—, —S—, —CO -, - CO-O -, - O-CO -, - SO 2 -, - NH
-Or a combination thereof may be replaced by a combination of these, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO -NH-, -NH-CO-, etc., among them -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O- Is preferably replaced with
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 , And pentavalent groups substituted with Z ² , Z ³ , Z ⁴ and Z ⁵ , etc.
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 , And pentavalent groups substituted with Z ² , Z ³ , Z ⁴ and Z ⁵ , etc.
As the pentavalent C2-C35 heterocycle-containing group represented by X ⁴ , the heterocycle-containing groups exemplified in the description of X ¹ in the general formula (12) are Z ¹ , Z ² , Z ^3, Z ⁴ and Z ⁵ pentavalent group substituted with the like.

Examples of the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁵ in the general formula (7) include the aliphatic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3). Are hexavalent groups substituted with Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ , and the methylene group in the aliphatic hydrocarbon group is —O—, —S—. , —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, or a combination thereof may be substituted with, for example, —COO—O—, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among others, -COO-, -O-, -OCO-, -NHCO- , -NH-, -CONH-, -O-CONH- or -NHCO-O- are preferred,
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 , And pentavalent groups substituted with Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ , etc.
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 , And hexavalent groups substituted with Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ , etc.
As the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by X ⁵ , the heterocyclic group exemplified in the description of X ¹ in the general formula (3) is Z ¹ , Z ² , Z ³ , a hexavalent group substituted with Z ⁴ , Z ⁵ and Z ⁶ , and the like.

Among the compounds represented by the above general formula (2), those in which A is a benzene ring; those in which R ⁵ is a hydrogen atom; R ⁶ , R ⁷ or R ⁸ is represented by the above general formula (1) One having a substituent; when m is 2, X is represented by the 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 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} 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: , Raw material acquisition and production It is preferable because it is easy to manufacture and has high heat resistance.

（式中、Ｒ⁵は、上記一般式（１）におけるＲ⁵と同じ基であり、基中に二つ以上ある場合、同じであっても異なっていてもよく、ｐは１〜３の整数を表し、ｑは０〜３の整数を表し、ｒは０〜１９の整数を表す。）

(In the formula, R ⁵ is the same group as R ⁵ in the general formula (1), and when there are two or more in the group, they may be the same or different, and p is an integer of 1 to 3) Q represents an integer of 0 to 3, and r represents an integer of 0 to 19.)

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

  Among the triarylmethane compounds, those represented by the following general formula (8) are preferable from the viewpoint of ease of synthesis and molecular design.

（式中、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ³⁵、Ｒ³⁶、Ｒ³⁷、Ｒ³⁸、Ｒ³⁹、Ｒ⁴⁰、Ｒ⁴¹及びＲ⁴²は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、水酸基、炭素原子数１〜８のアルキル基、炭素原子数６〜１２のアリール基、炭素原子数７〜２０のアリールアルキル基又は−Ｘ¹¹−Ｙ¹¹を表し、
Ｘ¹¹は酸素原子又は硫黄原子を表し、
Ｙ¹¹は、炭素原子数１〜８のアルキル基、炭素原子数６〜１２のアリール基、炭素原子数７〜２０のアリールアルキル基を表し、
Ｒ³¹〜Ｒ⁴²及びＹ¹¹で表されるアルキル基、アリール基又はアリールアルキル基は、ハロゲン原子で置換されているか又は無置換であり、
Ｒ³²とＲ⁴³、Ｒ³³とＲ⁴⁴、Ｒ³⁶とＲ⁴⁵、Ｒ³⁷とＲ⁴⁶、Ｒ⁴⁰とＲ⁴⁷、Ｒ⁴¹とＲ⁴⁸、Ｒ³¹とＲ³²、Ｒ³³とＲ³⁴、Ｒ³⁵とＲ³⁶、Ｒ³⁷とＲ³⁸、Ｒ³⁹とＲ⁴⁰及びＲ⁴¹とＲ⁴²は、連結して６員環を形成していてもよく、
Ｒ³¹とＲ⁴²、Ｒ³⁴とＲ³⁵及びＲ³⁸とＲ³⁹は、単結合、酸素原子、硫黄原子、セレン原子、ＣＲ⁴⁹Ｒ⁵⁰、ＣＯ、ＮＲ⁵¹、ＰＲ⁵²又はＳＯ₂を介して連結して環を形成していてもよく、
Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁷及びＲ⁴⁸は、それぞれ独立に、炭素原子数１〜８のアルキル基、フェニル基又はベンジル基を表し、
Ｒ⁴³〜Ｒ⁴⁸で表されるアルキル基は、水酸基、ハロゲン原子、シアノ基又はニトロ基で置換されているか又は無置換であり、
Ｒ⁴³〜Ｒ⁴⁸で表されるフェニル基及びベンジル基は、炭素原子数１〜４のアルキル基、ハロゲン原子、シアノ基又はビニル基で置換されているか又は無置換であり、
Ｒ⁴³とＲ⁴⁴、Ｒ⁴⁵とＲ⁴⁶、及びＲ⁴⁷とＲ⁴⁸は、連結して３〜６員環を形成していてもよく、
Ａｎ^q-はｑ価のアニオンを表し、ｑは１又は２を表し、ｐは電荷を中性に保つ係数を表し、
分子内に上記一般式（１）で表される置換基を少なくとも一つ有する。）

(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 or a halogen atom. , 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 aryl group, or -X ¹¹ -Y ¹¹ having 7 to 20 carbon atoms,
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, 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 substituted with a halogen atom or unsubstituted,
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 via a single bond, oxygen atom, sulfur atom, selenium atom, CR ⁴⁹ R ⁵⁰ , CO, NR ⁵¹ , PR ⁵² or SO _2. To form a ring,
R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represents 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 substituted or unsubstituted with a hydroxyl group, a halogen atom, a cyano group or a nitro group,
The phenyl group and benzyl group represented by R ^{43 to} R ⁴⁸ are substituted or unsubstituted 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 linked to form a 3- to 6-membered ring,
An ^q− represents a q-valent anion, q represents 1 or 2, p represents a coefficient for maintaining a neutral charge,
It has at least one substituent represented by the general formula (1) in the molecule. )

In the general 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 , an aryl group or a halogen atom that may be substituted with an arylalkyl group, Examples of the halogen atom that may be substituted for the alkyl group, phenyl group and benzyl group represented by R ^{43 to} R ⁴⁸ are the halogen atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^05. Group.
Alkyl group having 1 to 8 carbon atoms represented by R ^{31 to} R ⁴⁸ and Y ¹¹ , and alkyl having 1 to 4 carbon atoms which may be substituted with phenyl group and benzyl group represented by R ^{43 to} R ⁴⁸ Examples of groups include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and groups satisfying a predetermined carbon number among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ^1. Named,
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 6 to 6 carbon atoms represented by R ¹ . Among the groups exemplified as the 20 aryl group, a group satisfying a predetermined number of carbons and the like can be mentioned.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ^{31 to} R ⁴² and Y ¹¹ include 7 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^1. Groups exemplified as ˜20 arylalkyl groups, and the like,
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 such as a piperidine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, or a julolidine ring. Ring, etc.
R ³¹ and R ⁴² , R ³⁴ and R ³⁵ and R ³⁸ and R ³⁹ are linked via a single bond, oxygen atom, sulfur atom, selenium atom, CR ⁴⁹ R ⁵⁰ , CO, NR ⁵¹ , PR ⁵² or SO _2. Examples of the ring that can be formed include a dihydroanthracene ring, an acridine ring, a xanthene ring, and a thioxanthene ring.
Examples of the 3- to 6-membered heterocyclic ring that can be formed by linking R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , and R ⁴⁷ and R ⁴⁸ include a piperidine ring, piperazine ring, pyrrolidine ring, morpholine ring, thiol Morpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, isoxazolidine ring, isothiazolidine ring, and the like. It may be condensed with a ring or may be substituted.

In the above general formula (8), examples of the anion represented by An ^q- include monovalent ions such as chloride ions, bromide ions, iodide ions, fluoride ions, and the like; perchlorine Inorganic anions such as acid ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion; methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate 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, Phthalocyanine sulfonic acid Sulfonate ions having a polymerizable substituent, JP-A-10-235999, JP-A-10-337959, JP-A-11-102808, JP-A-2000-108510, JP-A-2000-168223, JP-A-2001-209969, JP 2001-322354, JP-A-2006-248180, JP-A-2006-297907, JP-A-8-253705, JP-T-2004-503379, JP-A-2005-336150, International Publication 2006/28006, etc. Organic sulfonate anions such as sulfonate ions; octyl phosphate ions, dodecyl phosphate ions, octadecyl phosphate ions, phenyl phosphate ions, nonylphenyl phosphate ions, 2,2′-methylenebis (4,6- Di-t-butylphenyl) phosphonic acid Organic phosphate anions such as ON, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis (pentafluorophenyl) borate ion, tris (fluoroalkyl) Sulfonyl) carbanion and the like, and examples of the divalent include benzene disulfonate ion, naphthalenedisulfonate ion and the like. In addition, quencher anions that have the function of deexciting (quenching) active molecules in the excited state, and ferrocenes having an anionic group such as a carboxyl group, phosphonic acid group, or sulfonic acid group on the cyclopentadienyl ring. Metallocene compound anions such as luteocene can also be used as necessary. Also, p is selected so 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 include anions represented by the following [Chemical 19A], but the present invention is not limited to these anions.

  Examples of the quencher anion include, for example, JP-A-60-234892, JP-A-5-43814, JP-A-5-305770, JP-A-6-239028, JP-A-9-309886. JP-A-9-323478, JP-A-10-45767, JP-A-11-208118, JP-A-2000-168237, JP-A-2002-201373, JP-A-2002-206061, Examples include anions as described in JP-A-2005-297407, JP-B-7-96334, WO98 / 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- Ethylcyclohexanesulfonate ion, benzenedisulfonate ion, and naphthalenedisulfonate ion are preferable from the viewpoint 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 [Chemical 20A] and [Chemical 20B], but the present invention is not limited to these compounds.

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

（式中、Ｄは下記の群Ｉの（ａ）〜（ｍ）から選ばれる基を表し、Ｄ’は下記の群IIの（ａ’）〜（ｍ’）から選ばれる基を表し、
Ｑは炭素原子数１〜９のメチン鎖を構成し、鎖中に環構造を含んでもよい連結基を表し、該メチン鎖中の水素原子は水酸基、ハロゲン原子、シアノ基、−ＮＲ⁵¹Ｒ⁵²、炭素原子数６〜１２のアリール基、炭素原子数７〜１２のアリールアルキル基又は炭素原子数１〜８のアルキル基で置換されていてもよく、該−ＮＲ⁵¹Ｒ⁵²、アリール基、アリールアルキル基及びアルキル基は、更に水酸基、ハロゲン原子、シアノ基又は−ＮＲ⁵¹Ｒ⁵²で置換されていてもよく、−ＮＲ⁵¹Ｒ⁵²、アリール基、アリールアルキル基及びアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で置き換わっていてもよく、
Ｒ⁵¹及びＲ⁵²は、炭素原子数６〜１２のアリール基、炭素原子数７〜１２のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、
Ａｎ^q-はｑ価のアニオンを表し、ｑは１又は２を表し、ｐは電荷を中性に保つ係数を表し、
分子内に上記一般式（１）で表される置換基を少なくとも一つ有する。）

(In the formula, D represents a group selected from (a) to (m) of the following group I, D ′ represents a group selected from (a ′) to (m ′) of the following group II,
Q represents a methine chain having 1 to 9 carbon atoms, and represents a linking group that may include a ring structure in the chain. The hydrogen atom in the methine chain is a hydroxyl group, a halogen atom, a cyano group, —NR ⁵¹ R ^52. , 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, the —NR ⁵¹ R ⁵² , aryl group, aryl The alkyl group and the alkyl group may be further 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 in the alkyl group are -O -, - S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - substituted N = CH- or -CH = CH- You may,
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 a q-valent anion, q represents 1 or 2, p represents a coefficient for maintaining a neutral charge,
It has at least one substituent represented by the general formula (1) in the molecule. )

（式中、Ｄは、下記の群Ｉの（ａ）〜（ｍ）から選ばれる基を表し、Ｄ’は、下記の群IIの（ａ’）〜（ｍ’）から選ばれる基を表す。）

(In the formula, D represents a group selected from groups (a) to (m) of the following group I, and D ′ represents a group selected from groups (a ′) to (m ′) of the following group II: .)

（式中、環Ｇ及び環Ｇ’は、ベンゼン環、ナフタレン環、フェナントレン環又はピリジン環を表し、
Ｒ⁵³及びＲ⁵³’は、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基、フェロセニル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数１〜８のアルキル基を表し、
Ｒ⁵³及びＲ⁵³’で表されるアリール基、アリールアルキル基及びアルキル基は、水酸基、ハロゲン原子、ニトロ基、シアノ基、−ＳＯ₃Ｈ、カルボキシル基、アミノ基、アミド基又はフェロセニル基で置換されていてもよく、
Ｒ⁵³及びＲ⁵³’で表されるアリール基、アリールアルキル基及びアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で置き換わっていてもよく、 Ｒ⁵⁴〜Ｒ⁶¹及びＲ⁵⁴’〜Ｒ⁶¹’は、Ｒ⁵³及びＲ⁵³’と同様の基又は水素原子を表し、
Ｘ¹²、Ｘ¹²’、Ｘ¹³及びＸ¹³’は、酸素原子、硫黄原子、セレン原子、−ＣＲ⁶²Ｒ⁶³−、炭素原子数３〜６のシクロアルカン−１，１−ジイル基、−ＮＨ−又は−ＮＹ¹³−を表し、
Ｒ⁶²及びＲ⁶³は、Ｒ⁵³及びＲ⁵³’と同様の基又は水素原子を表し、
Ｙ¹²、Ｙ¹²’及びＹ¹³は、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、
Ｙ¹²、Ｙ¹²’及びＹ¹³で表されるアルキル基、アリール基及びアリールアルキル基は、水酸基、ハロゲン原子、シアノ基、カルボキシル基、アミノ基、アミド基、フェロセニル基、−ＳＯ₃Ｈ若しくはニトロ基で置換されているか又は無置換であり、
Ｙ¹²、Ｙ¹²’及びＹ¹³で表されるアルキル基、アリール基及びアリールアルキル基中のメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で置き換わっていてもよく、
ｒ及びｒ’は、０又は（ａ）〜（ｅ）、（ｇ）〜（ｊ）、（ｌ）、（ｍ）、（ａ’）〜（ｅ’）、（ｇ’）〜（ｊ’）、（ｌ’）及び（ｍ’）において置換可能な数を表す。）

(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, or a carbon atom number of 7 Represents an arylalkyl group of ˜30 or an alkyl group of 1 to 8 carbon atoms,
The aryl group, arylalkyl group and alkyl group represented by R ⁵³ and R ⁵³ ′ are 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. May have been
The aryl group represented by R ⁵³ and R ⁵³ ′, the arylalkyl group and the methylene group in the alkyl group are —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, -NH -, - CONH -, - NHCO -, - N = CH- or may be replaced by -CH = CH-, R ⁵⁴ ~R ⁶¹ and R ⁵⁴ '~R ^61' is, R ⁵³ and R ⁵³ Represents the same group or hydrogen atom as
X ¹² , X ¹² ′, X ¹³ and X ¹³ ′ are an oxygen atom, a sulfur atom, a selenium atom, —CR ⁶² R ⁶³ —, a C 3-6 cycloalkane-1,1-diyl group, —NH - or -NY ¹³ - represents,
R ⁶² and R ⁶³ represent the same group or hydrogen atom as R ⁵³ and R ⁵³ ′,
Y ¹² , Y ¹² ′ and Y ^{13 each} represents 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,
The alkyl group, aryl group and arylalkyl group represented by Y ¹² , Y ¹² ′ and Y ¹³ are 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 nitro. Substituted or unsubstituted with a group,
The alkyl group represented by Y ¹² , Y ¹² ′ and Y ¹³ , the aryl group and the methylene group in the arylalkyl group are —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) to (e), (g) to (j), (l), (m), (a ′) to (e ′), (g ′) to (j ′) ), (L ′) and (m ′) represent the number that can be substituted. )

In the above general formula (9), Q constitutes a methine chain having 1 to 9 carbon atoms, and the linking group that may contain a ring structure in the chain includes the following (Q-1) to (Q-11): A group represented by any one is preferable because it is easy to produce. 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 that further substitutes the linking group (for example, R ^{62 to} R ⁶⁷ below, Z ′) carbon atoms (for example, carbon atoms at both ends in the linking group (Q-1)) are not included.

（式中、Ｒ⁶²、Ｒ⁶³、Ｒ⁶⁴、Ｒ⁶⁵、Ｒ⁶⁶、Ｒ⁶⁷及びＺ’は、各々独立に、水素原子、水酸基、ハロゲン原子、シアノ基、−ＮＲＲ’、炭素原子数６〜１２のアリール基、炭素原子数７〜１２のアリールアルキル基又は炭素原子数１〜８のアルキルを表し、
Ｒ⁶²〜Ｒ⁶⁷及びＺ’で表される−ＮＲＲ’、アリール基、アリールアルキル基及びアルキル基は、水酸基、ハロゲン原子、シアノ基又は−ＮＲＲ’で置換されていてもよく、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で中断されていてもよく、
Ｒ及びＲ’は、炭素原子数６〜１２のアリール基、炭素原子数７〜１２のアリールアルキル基又は炭素原子数１〜８のアルキルを表す。）

(In the formula, 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 ′, a carbon atom number of 6 to 12 represents an aryl group, an arylalkyl group having 7 to 12 carbon atoms, or an alkyl having 1 to 8 carbon atoms,
—NRR ′, aryl group, arylalkyl group and 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 ′, and —O—, Even if interrupted by —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, —CONH—, —NHCO—, —N═CH— or —CH═CH—. Often,
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 atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ .
The aryl group having 6 to 12 carbon atoms represented by R ^{62 to} R ⁶⁷ , Z ′, R and R ′ is represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ . Among the groups exemplified as the aryl group having 6 to 20 carbon atoms, a group satisfying a predetermined carbon number, and the like can be mentioned.
Examples of the arylalkyl group having 7 to 12 carbon atoms represented by R ^{62 to} R ⁶⁷ , Z ′, R, and R ′ include R ⁰¹ , R ⁰² , R ⁰³ , R ^04, R ⁰⁵ , and R ¹ . Of the groups exemplified as the aryl group having 6 to 20 carbon atoms, groups that satisfy a predetermined number of carbons can be given.
In the general formula (9), An as the anion represented by ^q-, etc. exemplified groups as an anion represented by An ^q- in the general formula (8) below.

Two Ds in the general formula (10) and D and D ′ in the general formulas (11) and (12) are one nonionic group and one cationic group so that the charge becomes neutral as a compound. Select one.
R ^{53 to} R ⁶³ and R ⁵³ ′ to R ⁶³ ′ in the above general formulas (10) to (12), a halogen atom represented by R ⁵³ and R ⁵³ ′, an aryl group, an arylalkyl group and an alkyl group As the halogen atom that may be substituted, and the halogen atom that may be substituted for the alkyl group, aryl group, and arylalkyl group represented by Y ¹² , Y ¹² ′, and Y ¹³ , R ⁰¹ , R ⁰² , R ^The group illustrated as a halogen atom represented by ⁰³ , ^R04, and ^R05 is mentioned.
Examples of the aryl group having 6 to 30 carbon atoms represented by R ^{53 to} R ⁶³ and R ⁵³ ′ to R ⁶³ ′ and Y ¹² , Y ¹² ′ and Y ¹³ include 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, etc.
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-phenylpropane-2 -Yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, ferrocenylmethyl, ferrocenylpropyl and the like,
An alkyl group having 1 to 8 carbon atoms represented by R ^{53 to} R ⁶³ and R ⁵³ ′ to R ⁶³ ′, and an alkyl group having 1 to 20 carbon atoms represented by Y ¹² , Y ¹² ′ and Y ¹³ As R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and groups exemplified as alkyl groups having 1 to 40 carbon atoms represented by R ¹ , groups satisfying a predetermined carbon number, etc. It is done.

In the general formulas (10) to (12), the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X ¹² , X ¹² ′, X ¹³ and X ¹³ ′ 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, And cyclohexane-1,1-diyl.

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

  There is no particular limitation on the method for producing the compound of the present invention, which is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region and having at least one structure represented by the general formula (1) in the molecule. For example, a cyanostyrene compound, a triarylmethane compound, and a cyanine compound are produced by a known method as an organic dye having an absorption maximum in a wavelength region from ultraviolet to near infrared, and then, an acid chloride and a Boc reagent are added thereto. , Alkyl halide compounds, silyl chloride compounds, allyl ether compounds, and the like, and a method obtained by introducing the structure represented by the general formula (1).

The 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 the molecule will be described below as a dye. In addition to colored photosensitive compositions, optical filters used in displays and optical lenses, silver halide photographic photosensitive materials, dyed articles, paints, inks, electrophotographic photoreceptors, toners, thermal recording paper, transfer ribbons, optical recording dyes , Solar cells, organic semiconductors, clinical laboratory reagents, laser therapeutic dyes, dyeing, etc.
In addition to being used as a photocurable composition, a thermosetting composition or a polymerizable composition as an antioxidant, it is also used as a color developer in a heat-sensitive material.

The 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 following general formula (1) in the molecule is the above 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 a pre-baking step at room temperature or 150 ° C., and the protective group is formed by heating at 100 to 250 ° C. or heating at 80 to 200 ° C. in the presence of an acid / base catalyst. Detachable and active, specifically, latent resin additives such as latent antioxidants and latent UV absorbers; latent developer for thermal paper; latent storage stability for thermal paper Agents; latent curing agents and the like.

Subsequently, the organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region of the present invention, comprising a compound having at least one structure represented by the general formula (1) in the molecule Will be described.
The composition containing 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 the molecule is colored. In addition to being used as a photosensitive composition, it is also used as a polymerizable composition.
When used as the colored photosensitive composition, it is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region of the present invention, and has at least one structure represented by the general formula (1) in the molecule 0.01-50 mass% is preferable and, as for content of the compound which has, 0.1-30 mass% is more preferable.

The colored photosensitive composition is cured by light irradiation, and may be any of photocation curable, photoanion curable, or photo radical curable, but is preferably a photo radical curable.
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 according to the present invention, In addition to the compound having at least one structure represented by the formula (1), a polymerizable compound having an ethylenically unsaturated bond having an acid value and a radical photopolymerization initiator are essential components. Hereinafter, this colored photosensitive composition is also referred to as a colored photosensitive composition of the present invention.

  Examples of the polymerizable compound having an ethylenically unsaturated bond having an acid value include (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, and isocrotonic acid. , Vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypoly Mono (meth) acrylate, hydroxyethyl (meth) acrylate / malate, hydroxypropyl (meth) acrylate / malate, dicyclopentadiene / malate, which has a carboxy group and a hydroxyl group at both ends, such as caprolactone mono (meth) acrylate 1 carboxyl group and 2 or more (meth) acrylo Unsaturated polybasic acid such as polyfunctional (meth) acrylate having an yl group; phenol and / or cresol novolac epoxy resin, biphenyl skeleton, novolak epoxy resin having naphthalene skeleton, bisphenol A novolac type epoxy compound, dicyclopentadiene novolak An unsaturated monobasic acid acts on an epoxy group of an epoxy resin such as a novolak type epoxy compound such as an epoxy compound, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy compound represented by the following general formula (13) Resin obtained by further reacting with polybasic acid anhydride, polyfunctional acrylate containing hydroxyl group such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. Polymers such as polyfunctional acrylate having an acid value which is a reaction product of a dibasic acid anhydride.

（式中、Ｘ⁴¹は直接結合、メチレン基、炭素原子数１〜４のアルキリデン基、炭素原子数３〜２０の脂環式炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−、−ＯＣＯ−又は上記（３−１）〜（３−３）で表される置換基を表し、該アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ⁶⁸、Ｒ⁶⁹、Ｒ⁷⁰及びＲ⁷¹は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｓは０〜１０の整数である。）

(In the formula, 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 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. Alternatively, it represents a halogen atom, and the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and s is an integer of 0 to 10.)

  These polymerizable compounds can be used alone or in admixture of two or more, and can be used in combination with a polymerizable compound having an ethylenically unsaturated bond having no acid value. When two or more kinds are mixed and used, they may be copolymerized in advance and used 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 compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Enoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, 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, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinyl benzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; indene Indene such as 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as til (meth) acrylate and polysiloxane; (meth) acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate and other vinyls (Meth) acrylic acid, a compound, a macromonomer such as a polymethyl methacrylate macromonomer and a polystyrene macromonomer, monomethacrylate having a tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, and the like. Polymers and copolymers of (meth) acrylic acid in which an isocyanate compound having an unsaturated bond such as Karenz MOI and AOI manufactured by Showa Denko Co., Ltd. is reacted, vinyl chloride, vinylidene chloride, divinyl succin Naruto, Allyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and polyisocyanate vinyl urethane compounds, hydroxyl group-containing vinyl monomers And a reaction product of a polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate with a hydroxyl group-containing polyfunctional acrylate such as a vinyl epoxy compound of a polyepoxy compound, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

  In order to improve the developability of the colored photosensitive composition of the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound may be used together with the polymerizable compound having an ethylenically unsaturated bond having the acid value. it can. The polymerizable compound having an ethylenically unsaturated bond having the above acid value preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the amount of the monofunctional or polyfunctional epoxy compound used is the above acid. It is preferable to select so as to satisfy the value.

  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, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl 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 monooxide, 1,2-epoxy-4-vinyl Examples include cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, and propylene oxide.

As the polyfunctional epoxy compound, it is preferable to use one or more selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a colored photosensitive composition with better characteristics can be obtained. As the bisphenol type epoxy compound, an epoxy compound represented by the general formula (13) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, 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 cyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like can also be used.

In the colored photosensitive composition of the present invention, the content of the polymerizable compound having an ethylenically unsaturated bond having an acid value is 1 to 95% by mass, particularly 10 to 80%, in the colored photosensitive composition of the present invention. Mass% is preferred.
Moreover, when using the polymeric compound which has the ethylenically unsaturated bond which does not have the said acid value, the content is with respect to 100 mass parts of polymeric compounds which have the ethylenically unsaturated bond which has the said acid value, It is preferable to set it as 10-1000 mass parts.

  The photo radical polymerization initiator may be any compound that can initiate radical polymerization upon receiving light irradiation, such as acetophenone compounds, benzyl compounds, benzophenone compounds, oxime compounds, thioxanthone compounds, for example. Examples of preferable compounds include ketone compounds such as compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl- 2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidoben Salacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1, benzo In, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one etc. are mentioned.

  Examples of the benzyl compound include benzyl and anisyl.

    Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. It is done.

  Examples of the oxime compounds include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl). ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), methanone, (2-methylphenyl) [6-nitro-9- [3- (trimethylsilyl) propyl] -9H-carbazole-3 -Yl]-, 1-O-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetyloxime, methanone, (9-ethyl) -6-nitro-9H-carbazol-3-yl) [2-methyl-4- (4-morpholinyl) phenyl), O-acetyloxime, methanone, (3,5-dinitroph Nyl) (9-ethyl-6-nitro-9H-carbazol-3-yl) (2-methylphenyl), O-acetyloxime, methanone, (9-ethyl-6-nitro-9H-carbazol-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-butanedione, 1- [4- (phenylthio) Phenyl]-, 2- (O-acetyloxime), 1,2-butanedione, 1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl]-, 2- (O-acetyloxime) 1,2-butanedio 1,1 ′-(thiodi-4,1-phenylene) bis-, 2,2-bis (O-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2, -[O- (4-methylbenzoyl) oxime] and the like.

  Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

  Other radical photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl)] titanium. Etc.

  These radical photopolymerization initiators can be used alone or in combination according to the desired performance.

  The radical photopolymerization initiator as described above is a radical polymerizable organic substance (polymerizable compound having an ethylenically unsaturated bond having an acid value, polymerizable compound having an ethylenically unsaturated bond having no acid value, a single compound, The stoichiometrically required amount may be used for the functional or polyfunctional epoxy compound), preferably 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight with respect to the radical polymerizable organic substance. It is better to mix part. If this range is exceeded, a cured product having sufficient strength may not be obtained, and if it is less than this range, the resin may not be sufficiently cured.

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

  The colored photosensitive composition of the present invention is dissolved or dispersed in an organic solvent as necessary, and the obtained coating liquid is spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, etc. It can be applied on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. by a known means and cured by light irradiation.

  The organic solvent is usually a solvent that can dissolve or disperse each of the above components as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone. Ketones such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc .; methyl acetate, ethyl acetate, acetic acid-n-propyl, acetic acid Ester solvents such as isopropyl, 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 ethanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate ( PGMEA), ether ester solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; aliphatics such as hexane, heptane, octane and cyclohexane Hydrocarbon solvents: terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene, etc .; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (E Parachemical solvents such as Son Chemical Co., Ltd .; Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic ring-containing hydrocarbon systems such as chlorobenzene Solvent; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because the compatibility of the resist and the photopolymerization initiator is good in the colored photosensitive composition.

A colorant can be further added to the colored photosensitive composition of the present invention, and examples of the colorant include dyes and pigments.
The dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm. For example, azo compounds, anthraquinone compounds, indigoid compounds, triarylmethane compounds, xanthene compounds, alizarin compounds, acridine compounds, stilbene compounds, thiazoles. Compound, naphthol compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound, perylene compound, polyenenaphtholactam compound, coumarin compound, squarylium compound, Croconium compounds, spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, stiri Compound, pyrylium compound, rhodanine compound, oxazolone compound, phthalimide compound, cinnoline compound, naphthoquinone compound, azaanthraquinone compound, porphyrin compound, azaporphyrin compound, pyromethene compound, quinacridone compound, diketopyrrolopyrrole compound, indigo compound, acridine compound, azine Examples thereof include dyes such as compounds, azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinoneimine compounds, iridium complex compounds, and europium complex compounds, and these may be used in combination.

As the pigment, inorganic pigments or organic pigments can be used, for example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, Isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acids; azo dyes, metal complex compounds of cyanine dyes Lake pigments; carbon black obtained by furnace method, channel method, thermal method, acetylene black, ketjen black or lamp black, etc. Carbon black: prepared by coating and coating the above carbon black with an epoxy resin, carbon black previously dispersed with a resin in a solvent and adsorbing 20 to 200 mg / g of resin, and the above carbon black being acidic or alkaline Surface treatment, average particle diameter of 8 nm or more, DBP oil absorption of 90 ml / 100 g or less, total oxygen amount calculated from CO and CO ₂ in volatile matter at 950 ° C. is 9 mg or more per 100 m 2 of carbon black surface area Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue , Koval Green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), An inorganic content or organic pigment such as cadmium red, synthetic iron black, or amber can be used. These pigments can be used alone or in combination.

  As the inorganic pigment or organic pigment, commercially available pigments can also be used. 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, 3, 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, and the like.

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

  The colored photosensitive composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Etc.

  In the colored photosensitive composition, when a pigment and / or an inorganic compound is used, a dispersant can be added. As the dispersant, any pigment or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie, Inc. can be used. Polymer dispersant made of ether, polyurethane, having a nitrogen atom as a basic functional group, the 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 Are preferably used.

  In the colored photosensitive composition of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine, etc .; plasticizer; adhesion promoter; filler; Agents; leveling agents; surface conditioning agents; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; UV absorbers; dispersion aids; aggregation inhibitors; catalysts; Conventional additives such as cross-linking agents; thickeners can be added.

  Moreover, the characteristic of the hardened | cured material of the colored photosensitive composition of this invention can also be improved by using another organic polymer with the polymeric compound which has the 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. 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, polyacrylamide, saturated Polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc. are mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin are used. Masui.

  The colored photosensitive composition of the present invention may further contain a thermal radical polymerization initiator, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like.

  Examples of the thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, Azo initiators such as 1′-azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, di (4-t-butylcyclohexyl) ) Peroxide initiators such as peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. These can be used alone or in combination of two or more.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound 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-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Showen Denko Karenz MT BD1, PE1, NR1, and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and 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. A ring agent is preferably used.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

  Moreover, as a light source of the active light used when hardening the colored photosensitive composition of this invention, what emits light with a wavelength of 300-450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, Carbon arc, xenon arc, etc. can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The colored photosensitive composition of the present invention (or a cured product thereof) is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, a color television, a PC monitor, a personal digital assistant, a digital camera, or the like. Color filters for liquid crystal display panels, color filters for CCD image sensors, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, dental compositions, resin for stereolithography, gel coats, electronics Structures for manufacturing photoresists, electroplating resists, etching resists, both liquid and dry films, solder resists, color filters for various display applications or in the manufacturing process of plasma display panels, electroluminescent display devices, and LCDs Composition for encapsulating resist, electrical and electronic components for forming For manufacturing 3D objects by solder resist, magnetic recording materials, micro mechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing stencils, stereolithography Materials, holographic recording materials, image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and It can be used for various applications such as photoresist material for visible laser direct image system, photoresist material used for dielectric layer formation in sequential lamination of printed circuit boards or protective film, and there are no particular restrictions on its use .

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

  The color filter for a display device includes (1) a step of forming a coating film of the colored photosensitive composition on a substrate, and (2) irradiating the coating film with active light through a mask having a predetermined pattern shape. It is preferably formed by a step, (3) a step of developing the film after exposure with a developer, and (4) a step of heating the film after development. In addition, the colored photosensitive composition of the present invention is also useful as an inkjet-type colored photosensitive composition without a development step.

  Hereinafter, although an example etc. are given and the present invention is explained still in detail, the present invention is not limited to these examples.

[Example 1-1] Compound No. 1 Synthesis of 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, and the mixture was added in an ice bath for 30. The mixture was stirred for 4 minutes, 4.5 equivalents of EDC hydrochloride was added, and the mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere. After oil-water separation with ethyl acetate / water, washing with water and drying were performed, and the solvent was distilled off to obtain Compound 4.

<Step 2> Compound No. Synthesis of 1 1 equivalent of Compound 4 obtained in Step 1 and 2.05 g of pyridine were mixed, 0.1 equivalent of 4-dimethylaminopyridine was added and stirred, and then 10 ° C. or less of t-butyl dicarbonate was added. 12 equivalents were added dropwise and stirred at room temperature for 20 hours. After oil-water separation with ethyl acetate / water, the mixture was washed with water and dried, and the solvent was distilled off. Purification by column chromatography (ethyl acetate: hexane = 1: 1), crystallization from methanol, compound no. 1 was obtained in a yield of 24%. It was confirmed by ¹ H-NMR and IR that the obtained compound was the target product. Moreover, the absorption wavelength characteristic was measured. The results are shown in [Table 1] and [Table 2].

[Example 1-2] Compound No. 1 Synthesis of 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 -t- 3 equivalents of butyl were added dropwise and stirred at room temperature for 3 hours. After oil-water separation with ethyl acetate / water, washing with water and drying were performed, and the solvent was distilled off to obtain Compound 6.

<Step 2> Compound No. Synthesis of 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 then the ethyl acetate layer was separated and dried to obtain a theoretical yield of 5 Concentrated to double. The concentrated ethyl acetate solution was dispersed in hexane and crystallized. 2 was obtained with a yield of 70%. It was confirmed by ¹ H-NMR and IR that the obtained compound was the target product. Moreover, the absorption wavelength characteristic was measured. The results are shown in [Table 1] and [Table 2].

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

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

<Step 2> Compound No. 3 In a toluene solution containing 1 equivalent of the compound 9 obtained in Step 1, 4 g of chloroform and 1 eq. Was added, and the mixture was stirred and separated into oil and water. 3 was obtained in 80% yield. It was confirmed by ¹ H-NMR and IR that the obtained compound was the target product. Moreover, the absorption wavelength characteristic was measured. The results are shown in [Table 1] and [Table 2].

[Examples 2-2 to 2-3] Colored photosensitive composition No. 1-No. Preparation of Step 3 <Step 1> Photosensitive Composition No. Preparation of 1 30.3 g of ACA Z250 (manufactured by Daicel Cytec Co., Ltd.) as a polymerizable compound component having an ethylenically unsaturated bond having an acid value, and Aronix as a polymerizable compound component having an ethylenically unsaturated bond having no acid value 11.04 g of M-450 (manufactured by Toa Gosei Co., Ltd.), 1.93 g of Irgacure 907 (manufactured by BASF) as a photo radical polymerization initiator component, 36.60 g of PGMEA as a solvent, 20.08 g of cyclohexanone, and others As a component, 0.01 g of FZ2122 (manufactured by Toray Dow Corning Co., Ltd.) was mixed and stirred until insoluble matter disappeared. 1 was obtained.

<Step 2> Dye solution No. 1-No. Preparation of Compound No. 3 obtained above 1-No. 3. To 1.10 g of No. 3 was added 1.90 g of dimethylacetamide and dissolved by stirring. 1-No. 3 were prepared respectively.

<Step 3> Colored photosensitive composition No. 1-No. Preparation of photosensitive composition No. 3 obtained in step 1 1 of 5.0 g and the dye solution No. obtained in Step 2. 1-No. 3 and 1.0 g of each were mixed and stirred until uniform, and the colored photosensitive composition No. 1 of the present invention was stirred. 1-No. 3 were obtained respectively.

[Comparative Examples 1-1 to 1-3] Comparative coloring photosensitive composition No. 1-No. Preparation of Compound No. 3 in Step 2 of Example 2 1 was compared with the following comparative compound No. 1. 1-No. Except for the change to any of No. 3, the comparative colored photosensitive composition No. 1 was prepared in the same manner as in Example 2-1. 1-No. 3 was obtained.

[Comparative Examples 2-1 to 2-3] Comparative coloring photosensitive composition No. 1A-No. Preparation of 3A Comparative coloring photosensitive composition No. 1-No. 3 was added in the same manner as in Example 2-1, except that the following compound α was added as an antioxidant. 1A-No. 3A was obtained.

[Evaluation Examples 1-1 to 1-3 and Comparative Evaluation Examples 1-1 to 1-3] Evaluation of Heat Resistance by Firing The colored photosensitive composition No. obtained above. 1-No. 3 and comparative colored photosensitive composition no. 1-No. 3 was coated on a glass substrate under the condition 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 ultrahigh pressure mercury lamp. The coated film after exposure was baked under conditions of 230 ° C. × 30 min. When 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 are measured, and the absorbance of the coating film before firing (after exposure) is 100 Was evaluated as relative strength. In addition, it shows that heat resistance is so high that the light absorbency of the coating film after baking is close to 100. Further, the color difference (ΔE _{ab *} ) before and after firing was examined. The results are shown in [Table 3].

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

[Evaluation Examples 2-1 to 2-3 and Comparative Evaluation Examples 2-1 to 2-3] Evaluation of Antioxidation Function First, the colored photosensitive composition Nos. 1-No. 3 shows comparative compound no. 1 was added in the same manner as in Example 2-1, except that the colored photosensitive composition No. 1 was added. 1A-No. 3A was obtained respectively.
The colored photosensitive composition No. obtained above. 1A-No. 3A and comparative colored photosensitive composition Nos. Obtained in Comparative Examples 2-1 to 2-3. 1A-No. 3A was coated on a glass substrate under the condition 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 ultrahigh pressure mercury lamp.
The coated film after exposure was baked under conditions of 230 ° C. × 30 min. When 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 are measured, and the absorbance of the coating film before firing (after exposure) is 100 Was evaluated as relative strength. Further, the color difference (ΔE _{ab *} ) before and after firing was examined. The results are shown in [Table 4].

  From the above results, it is clear that the colored photosensitive composition obtained by adding the compound of the present invention to the conventional dye has higher heat resistance than the comparative colored photosensitive composition obtained by adding the antioxidant to the conventional dye. . Therefore, this shows that the compound of the present invention has a high antioxidant function.

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

Claims (10)

An organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region, and having 1 to 10 substituents represented by the following general formula (1) in the molecule.

(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, or 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 heterocyclic ring-containing group having 2 to 20 carbon atoms, or —O—R ¹ ;
At least one of R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ is represented by —O—R 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 Represents a trialkylsilyl group,
The alkyl group, aryl group, arylalkyl group or heterocyclic ring-containing group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ has a substituent or is unsubstituted,
The methylene group in the alkyl group or arylalkyl group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and 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, -S-S- or -SO ₂ - may be replaced by,
R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) The compound according to claim 1, wherein R ¹ in the general formula (1) is a hydrogen atom. In the general formula (1), at least one of R ⁰² or R ⁰⁴ is an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a carbon atom. The compound according to claim 2, which is a heterocyclic ring-containing group of formula 2 to 20, wherein R ⁰³ is represented by —O—R ¹ . The compound according to claim 1, wherein R ¹ in the general formula (1) is an alkoxycarbonyl group having 2 to 9 carbon atoms. In the general formula (1), at least one of R ⁰² or R ⁰⁴ is an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a carbon atom. The compound according to claim 4, wherein the compound is a heterocyclic ring-containing group having a number of 2 to 20, and R ⁰³ is represented by —O—R ¹ .   The compound according to any one of claims 1 to 5, wherein the organic dye having an absorption maximum in a wavelength region from ultraviolet to near infrared is a cyanostyrene compound.     The compound according to any one of claims 1 to 5, wherein the organic dye having an absorption maximum in a wavelength region from ultraviolet to near infrared is a triarylmethane compound.   The compound according to any one of claims 1 to 5, wherein the organic dye having an absorption maximum in a wavelength region from ultraviolet to near infrared is a cyanine compound.   The composition containing the compound of any one of Claims 1-8.   A colored photosensitive composition comprising a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator in the composition according to claim 9.