JP6518195B2 - Novel compound and composition containing the compound - Google Patents

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 using 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 (LCD), plasma display panel (PDP) ), Electroluminescent displays (ELDs), cathode ray tube displays (CRTs), fluorescent display tubes, field emission displays, etc.

Optical filters for image display devices such as liquid crystal display devices (LCDs), plasma display panels (PDPs), electroluminescent displays (ELDs), cathode ray tube displays (CRTs), fluorescent display tubes, field emission displays, etc. Various compounds that absorb light of a wavelength of ̃1100 nm are used as light absorbers.
For these light absorbing agents, it is required that the light absorption be particularly sharp, that is, the half width of λmax be small, and that the function be not lost by light, heat or the like.

An optical filter mainly used for a liquid crystal display (LCD) is a color filter. Although three primary colors of RGB have generally been used for color filters, it is difficult to provide pure RGB hues with a single colorant, and pure RGB hues using a plurality of colorants Efforts have been made to bring them closer to Therefore, color materials such as yellow, orange, and purple are also required instead of RGB.
Organic and / or inorganic pigments have been used as light absorbers for color filters due to their high heat resistance, but since they are pigments, they have the problem of lowering the brightness as a display device. 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.

Furthermore, in recent years, in color filters used in solid-state imaging devices, thinning of a colored pattern is required from the viewpoint of improving image quality, and to thin the film, it is necessary to increase dye concentration in terms of color density. . Further, even when the molar absorption light coefficient of the dye is low, it is necessary to add a large amount of the dye.
However, when the dye concentration is increased, heat resistance is required because color mixing tends to occur between adjacent pixels or between upper and lower layers in a laminated structure when heat treatment (post baking) is performed after film formation.

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

WO 2012/039286 WO 2012/101946 WO 2012/111400 JP, 2010-008650, A JP, 2011-141356, A

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

  As a result of intensive studies, the present inventor has found that a compound having a specific structure is excellent in heat resistance, and a colored photosensitive composition using this compound (colored alkaline developable photosensitive composition) However, it has been found that the present invention 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).

  The present invention has been made based on the above findings, and is an organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region, and a substituent represented by the following general formula (1) in a molecule is It is a thing which provides the compound which has ten pieces.

（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, an alkyl group having 1 to 40 carbon atoms And 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 -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 represents 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 heterocyclic group having 2 to 20 carbon atoms or Represents a trialkylsilyl group,
The alkyl group, aryl group, arylalkyl group or heterocycle-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- ,
R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

  The present invention is the above-mentioned organic dye having an absorption maximum in the ultraviolet to near infrared wavelength region, and a compound having 1 to 10 substituents represented by the following general formula (1) in the molecule Providing a composition containing

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

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

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

  First, 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 a molecule will be described.

  The organic dye having an absorption maximum in the ultraviolet to near-infrared wavelength region is not particularly limited as long as it is a compound having an absorption maximum in the ultraviolet to near-infrared wavelength region, that is, 380 to 1200 nm. Compound, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazolyl compound, naphthol compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, Compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, carbonium compound, rhodamine compound, perylene compound, polyene naphtholactam compound, coumarin compound, squaryli Compounds, croconium compounds, spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pyrilium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, naphthalimide compounds, cinnoline compounds, naphthoquinone compounds, anthraanthraquinone 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 compounds Dyes, such as complex compounds, etc. are mentioned, and these are used in mixture of multiple Good.

  It does not specifically limit as a method to introduce | transduce the structure represented by the said General formula (1) into the organic dye which has an absorption maximum in the said ultraviolet to near-infrared wavelength range, The method to which well-known reaction is applied is mentioned However, for example, methods utilizing reactions such as esterification, amidification and the like 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 in terms of easiness of synthesis.

Examples of the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ in the above general formula (1) include fluorine, chlorine, bromine and iodine.
The alkyl group having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ is 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-butyl fe , 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5- Di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like;
As a C7-C20 arylalkyl group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ , benzyl, fluorenyl, indenyl, 9-fluorenylmethyl group, 2- And phenylpropane-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like.
As a C2-C20 heterocyclic-containing group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ , pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl , Quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinone-1- And 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl and the like.
Examples of trialkylsilyl groups represented by R ¹ include trimethylsilane, triethylsilane, ethyldimethylsilane and the like.

As a substituent for substituting the alkyl group, aryl group, arylalkyl group and heterocycle-containing group represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ , vinyl, allyl, acrylic, methacrylic Ethylenic unsaturated groups such as, halogen atoms such as fluorine, chlorine, bromine and iodine; 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, fe Substituted amino groups such as noxoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and the like; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo Groups, hydroxyl groups, nitro groups, mercapto groups, imide groups, carbamoyl groups, sulfonamide groups, phosphonic acid groups, phosphoric acid groups or carboxyl groups, sulfo groups, phosphonic acid groups, salts of phosphoric acid groups, and the like.
Moreover, 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 The position and the number are arbitrary.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^2, exemplified as the alkyl group of ^{R 01, R 02, R 03} , R 04 and R ⁰⁵ as well as 1 to 40 carbon atoms represented by R ¹ Among these, a group satisfying a predetermined number of carbon atoms, and the like can be mentioned.

Among the structures represented by the above general formula (1), at least one of R ^{02 and} 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 And arylalkyl groups or heterocyclic groups containing 2 to 20 carbon atoms, those 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 Among them, 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, or 6 to 20 carbon atoms. An aryl group, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms, particularly, 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.
As the alkoxycarbonyl group having 2 to 9 carbon atoms, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, s-butyloxycarbonyl, t-butyloxycarbonyl, isobutyloxycarbonyl And pentyloxycarbonyl, isoamyloxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, cyclohexylmethyloxycarbonyl, tetrahydrofuranyloxycarbonyl, tetrahydropyranyloxycarbonyl and the like.

  Among the organic dyes having an absorption maximum in the ultraviolet to near infrared wavelength range, cyanostyrene compounds, triarylmethane compounds and cyanine compounds are preferable from the viewpoint of easiness of synthesis and molecular design.

  Among the cyanostyrene compounds, those represented by the following general formula (2) are preferable from the viewpoint of easiness 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。）

(Wherein, A represents a benzene ring, a naphthalene ring or an anthracene ring, and these rings have a substituent represented by the above general formula (1), a halogen atom, a cyano group, a hydroxyl group, a nitro group, the number of carbon atoms Or substituted with an alkyl group of 1 to 8, an alkoxy group of 1 to 8 carbon atoms, a halogenated alkyl group of 1 to 8 carbon atoms, or a halogenated alkoxy group of 1 to 8 carbon atoms ,
R ⁵ represents a hydrogen atom, a phenyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms Or 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 above 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 represents a single bond, a nitrogen atom, -NR ⁹ -, oxygen atom, sulfur atom, phosphorus atom, -PR ¹⁰ - a or below <1> to either satisfy organic group <5>, and, And when any one or more of R ⁸ , A, R ^{6 and} R ⁷ when Y is represented by —COOR ⁸ ,
R ⁶ , R ⁷ , R ⁹ and R ¹⁰ 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 Or a substituent represented by the above general formula (1),
The alkyl group, aryl group and arylalkyl group represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are substituted with the substituent represented by the above general formula (1), a halogen atom, a hydroxyl group or a nitro group May be
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 by,
m is an integer of 1 to 6,
The molecule has at least one substituent represented by the above 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。）

(Wherein, X ¹ represents —NR ¹³ —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, divalent carbon Represents an 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 by -O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination thereof. Well,
Z ¹ and Z ² are independently a direct bond, -O -, - S -, - SO 2 -, - SO -, - NR 13 -, - PR 14 - represents,
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 said General formula (3) exists in the range of C1-C35. )

（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。）

(Wherein, R ²¹ represents a phenyl group which may be substituted by a hydrogen atom, an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, or a cycloalkyl group of 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 or unsubstituted with a halogen atom,
d is an integer of 0 to 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。）

(Wherein, R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 6 carbon atoms To 20 arylthio group, an arylalkenyl group having 8 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom,
The alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocycle-containing group represented by R ²³ and R ²⁴ are substituted or unsubstituted with a halogen atom,
The methylene group in the alkyl group and arylalkyl group represented by R ²³ and R ²⁴ may be replaced by an unsaturated bond, -O- or -S-,
R ^{23 s} may form a ring with adjacent R ^{23 s} ,
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 sum of g and h is 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。）

(Wherein, X ² represents a carbon atom substituted with R ²⁵ , a trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, A trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a trivalent heterocyclic ring containing group having 2 to 35 carbon atoms,
R ²⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
The methylene group in the aliphatic hydrocarbon group represented by X ² is replaced with a group of -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 above 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。）

(Wherein, X ³ represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and a tetravalent carbon atom number 6 to 35 aromatic ring-containing hydrocarbon group or a tetravalent heterocyclic group having 2 to 35 carbon atoms,
The methylene group in the aliphatic hydrocarbon group represented by X ³ is replaced with a group of -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 above 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。）

(Wherein, X ⁴ represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and pentavalent carbon atoms having 6 to 35 carbon atoms) An aromatic ring-containing hydrocarbon group or a pentavalent heterocyclic ring-containing group having 2 to 35 carbon atoms,
The methylene group in the aliphatic hydrocarbon group represented by X ⁴ is replaced with a group of -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 above 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。）

(Wherein, X ⁵ represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, and 6 to 35 hexavalent carbon atoms Or 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 a group of -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 above general formula (7) is in the range of 2 to 35 carbon atoms. )

The benzene ring, the naphthalene ring and the halogen atom which may be substituted for the anthracene represented by A in the general formula (2), the halogen atom represented by R ⁵ and R ⁶ , R ⁷ , R ⁹ and R ¹⁰ As the halogen atom which may substitute the alkyl group, the aryl group and the arylalkyl group represented by these, the group exemplified as the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ is Listed
As the alkyl group having 1 to 8 carbon atoms which may be substituted for the benzene ring, naphthalene ring and anthracene represented by A, and the alkyl group having 1 to 8 carbon atoms represented by R ^{5 to} R ¹⁰ Among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ , a group satisfying a predetermined carbon number can be mentioned,
Examples of the alkoxy group having 1 to 8 carbon atoms which may substitute a benzene ring, a naphthalene ring and anthracene represented by A and an alkoxy group having 1 to 8 carbon atoms represented by R ⁵ include methoxy, ethoxy, Propyloxy, isopropyloxy, butyloxy, s-butyloxy, t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranylyloxy, tetrahydropyranyloxy and the like And
As the halogenated alkyl group having 1 to 8 carbon atoms which may be substituted with a benzene ring, a naphthalene ring and anthracene represented by A and the halogenated alkyl group having 1 to 8 carbon atoms represented by R ⁵ Or at least one hydrogen atom of the alkyl group having 1 to 8 carbon atoms is substituted by the above-mentioned halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, fluoromethyl, trifluoromethyl, Nonafluorobutyl etc. are mentioned,
As the halogenated alkoxy group having 1 to 8 carbon atoms which may be substituted with a benzene ring, a naphthalene ring and anthracene represented by A and the halogenated alkoxy group having 1 to 8 carbon atoms represented by R ⁵ Or at least one hydrogen atom of the above-mentioned alkoxy group having 1 to 8 carbon atoms is substituted by the above-mentioned halogen atom, for example, chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, fluoromethyloxy , Trifluoromethyloxy, nonafluorobutyloxy and the like;
R ^6, the R ^7, R ⁹ and aryl group having 6 to 20 carbon atoms represented by R ^10, carbon atoms represented by ^{R 01, R 02, R 03} , R 04 and R ⁰⁵ and R ¹ Groups exemplified as the aryl group of the formulas 6 to 20 can be mentioned,
As a C7-C20 arylalkyl group represented by R ⁶ , R ⁷ , R ⁹ and R ¹⁰ , a carbon represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ Groups exemplified as the arylalkyl group having 7 to 20 atoms can be mentioned.

Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ¹ in the above 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, Aliphatic hydrocarbons, including divalent groups in which groups such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like are substituted with Z ¹ and Z ² The methylene group in the group is -O-, -S-, -CO-, -COO-, -OCO-, -NH- or These groups may be replaced by a combined group, and the combined group is, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH. -, -NH-CO-, etc., among which -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O- Is preferred,
Examples of the divalent C3-C35 alicyclic hydrocarbon group represented by X ¹ include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2-adamantyl, noradamantyl, 2-adamantyl Methyladamantyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthracenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [3. .1.0] hexyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2.0] heptyl, bicyclo [3. .1.1] Heptyl, bicyclo [2.2.1] heptyl, bicyclo [5.1.0] octyl, bicyclo [4. .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] And Z ¹ and Z ² substituted groups such as nonanyl, spiro [4,5] decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, cedrol, cyclododecanyl and the like; ,
Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X ¹ include divalent groups in which a group such as phenyl, naphthyl and biphenyl is substituted by Z ¹ and Z ² , etc. Listed
Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by X ¹ include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene, thiophene And divalent groups in which a group such as thiolane is substituted by Z ¹ and Z ² .
These groups may be further substituted by 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,
The aryl group having 6 to 20 carbon atoms represented by R ¹³ and R ¹⁴ includes aryl having 6 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ Groups exemplified as the group,
As a C7-C20 arylalkyl group represented by R ¹³ and R ¹⁴ , R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and C 1-7 carbon atom represented by R ^{1 can} be mentioned. Groups exemplified as the arylalkyl group,
As a halogen atom which may substitute the alkyl group, aryl group, and arylalkyl group represented by R ¹³ and R ¹⁴ , halogen atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ And the groups exemplified as

In the substituents represented by (3-1) above, an alkyl group having 1 to 10 carbon atoms which may substitute the phenyl group represented by R ²¹ and the cycloalkyl group having 3 to 10 carbon atoms, and R The alkyl group having 1 to 10 carbon atoms represented by ²² is exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ Among the groups, groups having a predetermined number of carbon atoms are mentioned,
An alkoxy group having 1 to 10 carbon atoms which may substitute a phenyl group represented by R ²¹ and a cycloalkyl group having 3 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms represented by R ²² Are, for example, the alkoxy group having 1 to 8 carbon atoms which may be substituted with a benzene ring represented by A, a naphthalene ring and anthracene, and the groups exemplified as an 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, cyclobutyl, cyclooctyl and the like, and those groups each having the above-mentioned alkyl group 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. ,
The halogen atom represented by R ²² and the halogen atom which 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 The group illustrated as a halogen atom represented by R ⁰⁵ is mentioned.
Incidentally, the substitution position of alkyl group, halogen atom be substituted alkoxy group and alkenyl group represented by R ²² is not limited.

In the substituent represented by the above (3-3), examples of the alkyl group having 1 to 10 carbon atoms represented by R ²³ and R ²⁴ include R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and Among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ , groups having a predetermined carbon number, etc. may be mentioned.
The aryl group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ is an aryl having 6 to 20 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^1. Groups exemplified as the group, and the like;
The aryloxy group having 6 to 20 carbon atoms represented by R ²³ and R ²⁴ is phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyl Dioxy, 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 And groups such as oxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy and the like, and groups in which these groups are substituted with halogen atoms, etc.
The arylthio group having 6 to 20 carbon atoms denoted by R ²³ and R ^24, and the oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted with the halogen atom is replaced by sulfur atom The foundations are dedicated,
As an arylalkenyl group having 8 to 20 carbon atoms represented by R ²³ and R ²⁴ , an oxygen atom of an aryloxy group having 6 to 20 carbon atoms which may be substituted by the above-mentioned halogen atom can be vinyl, allyl, Groups substituted with an alkenyl group 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 R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and 7 to 20 carbon atoms represented by R ¹ The group etc. which were illustrated as an arylalkyl group are mentioned.
The heterocyclic group containing 2 to 20 carbon atoms represented by R ²³ and R ²⁴ includes pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene, thiophene And groups such as thiofuran and groups in which these groups are substituted with halogen atoms.
Examples of the halogen atom which may substitute the alkyl group, aryl group, aryloxy group, arylthio group, arylalkenyl group, arylalkyl group and heterocycle-containing group represented by R ¹³ and R ¹⁴ include R ⁰¹ and R ^The groups exemplified as the halogen atom represented by ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ can be mentioned.

The aliphatic hydrocarbon group exemplified in the description of X ¹ in the above general formula (3) as the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ² in the above general formula (4) And a trivalent group substituted by Z ¹ , Z ² and Z ³ and the like, and a methylene group in the aliphatic hydrocarbon group is represented by -O-, -S-, -CO-, -CO-O. -, -O-CO-, -SO _2- , -NH- or a combination thereof may be replaced, and the group combining these is, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO-NH-, -NH-CO-, etc., among which -COO-, -O-, -OCO-, -NHCO-, -NH-,- CONH -, - O-CONH- or 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 and the like.
Examples of the trivalent group having 2 to 35 carbon atoms represented by X ² include the heterocycle-containing groups exemplified in the description of X ¹ in the general formula (3), Z ¹ , Z ² and Z ^And trivalent groups substituted by ³ and the like.
Also, as 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, they are represented by R ¹³ and R ¹⁴ Examples thereof include alkyl groups having 1 to 8 carbon atoms, aryl groups having 6 to 20 carbon atoms, and arylalkyl groups having 7 to 20 carbon atoms.

The aliphatic hydrocarbon group exemplified in the description of X ¹ in the above general formula (3) as the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by X ³ in the above general formula (5) And a tetravalent group substituted by Z ¹ , Z ² , Z ³ and Z ⁴ and the like, and the methylene group in the aliphatic hydrocarbon group is —O—, —S—, —CO—, — COO-, -OCO-, -NH- or a combination thereof may be replaced, and the group combining these is, for example, -COO-O-, -COO-S-, -O-OCO- , -S-OCO-, -CO-NH-, -NH-CO-, etc., among them -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O. Preferred are those substituted with -CONH- or -NHCO-O-,
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 and the like.
As the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by X ³ , the aromatic ring-containing hydrocarbon group exemplified in the description of X ¹ in the general formula (3) is Z ¹ , And tetravalent groups substituted by Z ² , Z ³ and Z ⁴ and the like.
As the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by X ³ , the heterocyclic group exemplified in the description of X ¹ in the general formula (3) may be Z ¹ , Z ² or Z ^And tetravalent groups substituted with ³ and Z ⁴ and the like.

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). And a pentavalent group substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ and the like, and a methylene group in the aliphatic hydrocarbon group is —O—, —S—, —CO -, -CO-O-, -O-CO-, -SO _2- , -NH
-Or a combination of these may be replaced, and the combination of these is, for example, -COO-O-, -COO-S-, -O-OCO-, -S-OCO-, -CO. -NH-, -NH-CO-, etc., and among them, -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH- or -NHCO-O- Is preferably replaced by
The pentavalent alicyclic hydrocarbon group having a carbon number of 3 to 35 represented by X ^4, alicyclic hydrocarbon groups exemplified in the description of X ¹ in the general formula (3), Z ^1, And pentavalent groups substituted with Z ² , Z ³ , Z ⁴ and Z ⁵ and the like.
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 and the like.
As the pentavalent heterocyclic group having 2 to 35 carbon atoms represented by X ⁴ , the heterocyclic 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 substituted pentavalent groups and the like.

The aliphatic hydrocarbon group exemplified in the description of X ¹ in the above general formula (3) as the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by X ⁵ in the above general formula (7) And a hexavalent group substituted by Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ and the like, and the methylene group in the aliphatic hydrocarbon group is —O—, —S— And -CO-, -COO-, -OCO-, -SO _2- , -NH- or a combination of these may be substituted, and a group combining these is, 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-, which is preferably substituted,
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 by Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ and the like.
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 , A hexavalent group substituted by Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ and the like;
As the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by X ⁵ , the heterocyclic groups exemplified in the description of X ¹ in the above general formula (3) are Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ substituted hexavalent groups 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 are represented by the above general formula (1) Those having a substituent; when m is 2, X is represented by the above general formula (3), and X ¹ in the formula (3) is a group selected from the following group 1; when m is 3 , X is represented by the above 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 a group represented by the above 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; a group in which X is represented by the above general formula (7) when m is 6 and X ⁵ in the formula (7) is a group selected from the following group 5 is , Obtaining raw materials and making 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。）

(Wherein, R ⁵ is the same group as R ⁵ in the general formula (1), and when there are two or more in the group, it 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 above general formula (1) include compounds represented by the following [Formula 16] to [Formula 18], but the present invention is not limited to these compounds.

  Among the above triarylmethane compounds, those represented by the following general formula (8) are preferable in terms of easiness 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 each independently represent 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 arylalkyl group having 7 to 20 carbon atoms or -X ¹¹ -Y ¹¹ ,
X ¹¹ represents an oxygen atom or a sulfur atom,
Y ¹¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
The alkyl group, aryl group or arylalkyl group represented by R ^{31 to} R ⁴² and Y ¹¹ is substituted or unsubstituted with a halogen atom,
R ³² and R ⁴³ , R ³³ and R ⁴⁴ , R ³⁶ and R ⁴⁵ , R ³⁷ and R ⁴⁶ , R ⁴⁰ and R ⁴⁷ , R ⁴¹ and R ⁴⁸ , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁵ And R ³⁶ , R ³⁷ and R ³⁸ , R ³⁹ and R ^40, and R ⁴¹ and R ⁴² may combine 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, an oxygen atom, a sulfur atom, a selenium atom, CR ⁴⁹ R ⁵⁰ , CO, NR ⁵¹ , PR ⁵² or SO ₂ May form a ring,
R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group,
The alkyl group represented by R ^{43 to} R ⁴⁸ is 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 keeping the charge neutral,
The molecule has at least one substituent represented by the above general formula (1) in the molecule. )

In the above general formula (8), a halogen atom represented by R ^{31 to} R ⁴² , a halogen atom which may substitute the alkyl group represented by R ^{31 to} R ⁴² and Y ¹¹ , an aryl group or an arylalkyl group, The halogen atom which may substitute the alkyl group, phenyl group and benzyl group represented by R ^{43 to} R ⁴⁸ is exemplified as the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ Groups are mentioned.
The alkyl group having 1 to 8 carbon atoms represented by R ^{31 to} R ⁴⁸ and Y ¹¹ and the alkyl having 1 to 4 carbon atoms which may substitute the phenyl group and the benzyl group represented by R ^{43 to} R ⁴⁸ As the group, among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ¹ , a group satisfying a predetermined carbon number, etc. Listed
The aryl group having 6 to 12 carbon atoms represented by R ³¹ to R ⁴² and ^{Y 11, R 01, R 02} , R 03, R 04 and R ⁰⁵ as well as the number of carbon atoms from 6 represented by R ¹ Among the groups exemplified as the aryl group of 20, a group satisfying a predetermined carbon number and the like can be mentioned,
The arylalkyl group having 7 to 20 carbon atoms represented by R ^{31 to} R ⁴² and Y ^{11 includes} 7 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and R ^1. Groups exemplified as the arylalkyl group of
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 As a 6-membered ring which can be formed by linking R ³⁶ , R ³⁷ and R ³⁸ , R ³⁹ and R ^40, and R ⁴¹ and R ⁴² , a piperidine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a quinoline ring, an isoquinoline ring, julolidine Ring etc.,
R ³¹ and R ⁴² , R ³⁴ and R ³⁵ and R ³⁸ and R ³⁹ are linked via a single bond, an oxygen atom, a sulfur atom, a selenium atom, CR ⁴⁹ R ⁵⁰ , CO, NR ⁵¹ , PR ⁵² or SO ₂ Examples of the ring which can be formed include dihydroanthracene ring, acridine ring, xanthene ring, thioxanthene ring and the like.
As a 3- to 6-membered heterocyclic ring which can be formed by linking R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , and R ⁴⁷ and R ⁴⁸ , a piperidine ring, a piperazine ring, a pyrrolidine ring, a morpholine ring, thio And 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, and these rings It may be fused to a ring or may be substituted.

In the above general formula (8), examples of the anion represented by An ^q- include, as monovalent ions, halide ions such as chloride ion, bromide ion, iodide ion and fluoride ion; Inorganic anions such as acid ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion and tetrafluoroborate ion; methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, Toluene sulfonate ion, trifluoromethane sulfonate ion, naphthalene sulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzene sulfonate ion, 2-amino-5-nitrobenzene sulfonate ion, Phthalocyanine sulfonic acid B And sulfonic acid ions having a polymerizable substituent, as described in JP-A-10-235999, JP-A-10-337959, JP-A-11-102088, JP-A-2000-108510, JP-A-2000-168223, JP-A-2001-290969, and JP-A-2001-209969. 2001-322354, JP-A-2006-248180, JP-A-2006-297907, JP-A-8-253705, JP-A-2004-503379, JP-A-2005-336150, WO 2006/28006, etc. Organic sulfonic acid type anions such as sulfonate ion; octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2'-methylene bis (4,6- Di-t-butylphenyl) phosphonic acid Organic phosphoric acid anions such as one, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonic acid ion, tetrakis (pentafluorophenyl) borate ion, tris (fluoroalkyl) A sulfonyl) carbanion etc. are mentioned and a benzenedisulfonic acid ion, a naphthalene disulfonic acid ion etc. are mentioned as a bivalent thing, for example. In addition, a quencher anion having a function of de-exciting (quenching) an active molecule in an excited state, and ferrocene having an anionic group such as a carboxyl group, a phosphonic acid group or a sulfonic acid group in a cyclopentadienyl ring A metallocene compound anion such as luteothene can also be used if necessary. Also, p is chosen such that the charge is neutral throughout the molecule.

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

  Examples of the quencher anions described above include, for example, JP-A-60-234892, JP-A-5-43814, JP-A-5-305770, JP-A-6-239028 and 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, The anion as described in Unexamined-Japanese-Patent No. 2005-297407, Japanese Patent Publication No.7-96334, international publication 98/29257 etc. is mentioned.

As the anion represented by An ^q- in the above general formula (I), a monovalent organic sulfonic acid type anion, bis trifluoromethyl sulfonyl imide ion, bis perfluoro butane sulfonyl imide ion, perfluoro -4- From the viewpoint of heat resistance, ethylcyclohexanesulfonic acid ion, benzenedisulfonic acid ion and naphthalenedisulfonic acid ion are preferable, and bistrifluoromethylsulfonylimide ion is more preferable.

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

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

（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。）

(Wherein, D represents a group selected from (a) to (m) of group I described below, and D ′ represents a group selected from (a ′) to (m ′) of group II described below,
Q represents a linking group which constitutes a methine chain having 1 to 9 carbon atoms and may contain a ring structure in the chain, and a hydrogen atom in the methine chain is a hydroxyl group, a halogen atom, a cyano group, -NR ⁵¹ R ⁵² And the aryl group may be substituted with an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, the -NR ⁵¹ R ⁵² , an aryl group or an aryl group The alkyl group and the alkyl group may be further substituted by a hydroxyl group, a halogen atom, a cyano group or -NR ⁵¹ R ⁵² , and -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-, -N = CH- or -CH = CH- May be
R ⁵¹ and R ^{52 each} 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 keeping the charge neutral,
The molecule has at least one substituent represented by the above 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。）

(Wherein, D represents a group selected from (a) to (m) in group I below, and D ′ represents a group selected from (a ′) to (m ′) in group II below .)

（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。）

(Wherein, ring G and ring G ′ each represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,
R ⁵³ and R ⁵³ ′ each represents a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amido group, a ferrocenyl group, an aryl group having 6 to 30 carbon atoms, and 7 carbon atoms 30 to 30 arylalkyl group or an alkyl group having 1 to 8 carbon atoms,
The aryl group, arylalkyl group and alkyl group represented by R ⁵³ and R ⁵³ ′ 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 amido group or a ferrocenyl group May be
The methylene group in the aryl group, arylalkyl group and alkyl group represented by R ⁵³ and R ⁵³ ′ is —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, R ^{54 to} R ⁶¹ and R ⁵⁴ ′ to R ⁶¹ ′ may be R ⁵³ and R ⁵³ , each of which may be replaced by —NH—, —CONH—, —NHCO—, —N = CH— or —CH = CH— Represents a group similar to 'or a hydrogen atom,
^{X 12, X 12 ', X} 13 and X ^13' represents an oxygen atom, a sulfur atom, a selenium atom, -CR ⁶² R ⁶³ -, cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, -NH - or -NY ¹³ - represents,
R ⁶² and R ⁶³ each represent the same group as R ⁵³ and R ⁵³ ′ or a hydrogen atom,
Y ¹² , Y ¹² ′ and Y ^{13 each} represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms,
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 amido group, a ferrocenyl group, —SO ₃ H or a nitro Substituted or unsubstituted with a group,
Y ^12, Y ¹² 'and the alkyl group represented by Y ^13, a methylene group of the aryl group and in the arylalkyl group, -O -, - S -, - CO -, - COO -, - OCO -, - SO _It may be replaced by _2- , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-,
r and r 'are 0 or (a) to (e), (g) to (j), (l), (m), (a') to (e '), (g') to (j ') And (l ') and (m') represent substitutable numbers. )

In the above general formula (9), Q constitutes a methine chain having 1 to 9 carbon atoms, and as a linking group which may contain a ring structure in the chain, those of the following (Q-1) to (Q-11) The group represented by either is preferable because of easy production. The number of carbon atoms in the methine chain having 1 to 9 carbon atoms represents a methine chain and a linking group which may contain a ring structure in the chain, and a group further substituting the linking group (for example, R ^{62 to} R ⁶⁷ below It does not include carbon atoms of Z ′) (for example, carbon atoms at both ends of the linking group (Q-1)).

（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。）

(Wherein, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and Z ′ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, —NRR ′, 6 to 6 carbon atoms 12 aryl groups, arylalkyl groups having 7 to 12 carbon atoms, or alkyls 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 ', -O-, -S -, - CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - N = CH- or -CH = CH- be interrupted by Often,
R and R ′ each represent an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkyl having 1 to 8 carbon atoms. )

The halogen atom represented by the above R ⁶² to R ⁶⁷ and ^{Z ', R 01, R 02} , R 03, the groups exemplified as the halogen atom represented by R ⁰⁴ and R ⁰⁵ can be mentioned.
As the aryl group having 6 to 12 carbon atoms represented by R ^{62 to} R ⁶⁷ , Z ′, R and R ′ above, R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ , and R ¹ The group etc. which satisfy | fill a predetermined carbon number among the groups illustrated as a C6-C20 aryl group which is
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 and R ⁰⁵ and R ¹ The group etc. which satisfy | fill a predetermined carbon number among the groups illustrated as a C6-C20 aryl group represented are mentioned.
Examples of the anion represented by An ^q- in the general formula (9) include groups exemplified as the anion represented by An ^q- in the general formula (8).

As the two D in the general formula (10) and the D and D 'in the general formulas (11) and (12), one nonionic group and one cationic group are used so that the charge becomes neutral as a compound. Select one.
A halogen atom represented by R ^{53 to} R ⁶³ and R ⁵³ ′ to R ⁶³ ′ in the above general formulas (10) to (12), an aryl group represented by R ⁵³ and R ⁵³ ′, an arylalkyl group and an alkyl group As a halogen atom which may substitute, and a halogen atom which may substitute an alkyl group, an aryl group, and an arylalkyl group represented by Y ¹² , Y ¹² ′ and Y ¹³ , R ⁰¹ , R ⁰² , R ^The groups exemplified as the halogen atom represented by ⁰³ , R ⁰⁴ and R ⁰⁵ can be mentioned.
As an 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 , phenyl, naphthyl, 2-methylphenyl, 3- Methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl , 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6- Dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2,5-di- tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl and the like;
The arylalkyl group R ⁵³ to R ⁶³ and R ⁵³ '~R ^63' and Y ^12, Y ¹² 'and having 7 to 30 carbon atoms represented by Y ^13, 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 And R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ and the group exemplified as the alkyl group having 1 to 40 carbon atoms represented by R ¹ include groups having a predetermined carbon number and the like. Be

As the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms represented by X ¹² , X ¹² ′, X ¹³ and X ¹³ ′ in the general formulas (10) to (12), cyclopropane is a cyclopropane -1,1-diyl, cyclobutane-1,1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, Examples include cyclohexane-1,1-diyl and the like.

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

  The organic dye having an absorption maximum in the ultraviolet to near infrared wavelength region of the present invention and the method for producing a compound having at least one structure represented by the above general formula (1) in the molecule is not particularly limited. For example, as an 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 produced by a known method, and then an acid chloride, a Boc-forming reagent And alkyl halide compounds, silyl chloride compounds, allyl ether compounds and the like to react to introduce a structure represented by the above 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 above general formula (1) in the molecule is described below as a dye. Besides being used for colored photosensitive compositions, optical filters for use in displays and optical lenses, photosensitive materials for silver salt photography, dyes, paints, inks, electrophotographic photoreceptors, toners, thermosensitive recording papers, transfer ribbons, optical recording dyes , Solar cells, organic semiconductors, clinical examination reagents, dyes for laser treatment, dyes, etc.
In addition to being used in photocurable compositions, thermosetting compositions or polymerizable compositions as antioxidants, it is also used in heat-sensitive materials as color developers.

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 a compound represented by 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 inert in the prebaking step at room temperature or 150 ° C. or lower, and the protective group is heated by heating at 100 to 250 ° C. or by heating at 80 to 200 ° C. in the presence of an acid / base catalyst Specifically, latent resin additives such as latent antioxidants and latent UV absorbers; latent developers for thermal paper; latent storage stability for thermal paper Agents; latent curing agents and the like.

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

The above-mentioned colored photosensitive composition is cured by irradiation with light, and may be any of cationic light curing, anionic curing or radical curing, but is preferably radical curing.
When the above-mentioned colored photosensitive composition is a photo curable radical, the colored photosensitive composition is the organic dye having an absorption maximum in the ultraviolet to near infrared wavelength region of the present invention, and the above-mentioned general in the molecule 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 photoradical polymerization initiator are essential components. Hereinafter, this colored photosensitive composition is also referred to as the colored photosensitive composition of the present invention.

  As a polymerizable compound having an ethylenically unsaturated bond having the above acid value, (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, 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 of a polymer having a carboxy group and a hydroxyl group at both ends such as caprolactone mono (meth) acrylate, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or 1 carboxyl group and 2 or more (meth) acrylo Unsaturated polybasic acids such as polyfunctional (meth) acrylates having an alkyl group; phenol and / or cresol novolac epoxy resin, biphenyl skeleton, novolac epoxy resin having naphthalene skeleton, bisphenol A novolac epoxy compound, dicyclopentadiene novolac Action of unsaturated monobasic acid on epoxy group of epoxy resin such as novolak type epoxy compound such as epoxy type epoxy compound, polyphenylmethane type epoxy resin having polyfunctional epoxy group, epoxy compound represented by the following general formula (13) Resins obtained by reacting with polybasic acid anhydride, hydroxylated polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and 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。）

(Wherein, X ⁴¹ represents 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), and the alkylidene group may be substituted by a halogen atom R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an alkenyl group of 2 to 5 carbon atoms Or the above-mentioned alkyl group, alkoxy group and alkenyl group may be substituted by a halogen atom, and s is an integer of 0 to 10.)

  These polymerizable compounds can be used alone or in combination of two or more, and can be used in combination with a polymerizable compound having an ethylenically unsaturated bond having no acid value. When 2 or more types are mixed and used, they may be copolymerized beforehand and you may use as a copolymer.

  Examples of the polymerizable compound having an ethylenically unsaturated bond not having an acid value include (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, glycidyl (meth) acrylic acid, The following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (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, (meth ) Ethyl hexyl acrylate, (meth) acrylic acid Phenoxyethyl, 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, trimethylolethane tri ( Meta) 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) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid 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, trialkyltetrahydrofuran Phthalic anhydride-anhydrous Acid anhydride of unsaturated polybasic acid such as leic acid adduct, dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylene Unsaturated aromatic compounds such as 2-phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, 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-phenyl maleimide, N-cyclohexyl maleimide; And indenes such as 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- Macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chain such as chill (meth) acrylate and polysiloxane; (meth) acrylonitrile, other vinyl such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate Compounds, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyl oxetane, etc., and (meth) acrylic acid Polymers and copolymers of (meth) acrylic acid obtained by reacting an isocyanate compound having an unsaturated bond such as Karenz MOI manufactured by Showa Denko KK and AOI with these, vinyl chloride, vinylidene chloride, divinyl succ Nath, Allyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group-containing vinyl monomer And vinyl epoxy compounds of polyepoxy compounds, and reaction products of hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.

  In order to adjust the acid value to improve the developability of the colored photosensitive composition of the present invention, a monofunctional or polyfunctional epoxy compound may be used together with the polymerizable compound having an ethylenic unsaturated bond having the above acid value. it can. It is preferable that the acid value of solid content is the range of 5-120 mgKOH / g, and, as for the polymeric compound which has an ethylenically unsaturated bond which has the said acid value, the usage-amount of a monofunctional or polyfunctional epoxy compound is the said acid It is preferable to select to satisfy the price.

  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 glycidyl ether , 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 monoxide, 1,2-epoxy-4-vinyl Examples include cyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide and the like.

It is preferable to use one or more selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers as the above-mentioned polyfunctional epoxy compound, because a colored photosensitive composition having better characteristics can be obtained. As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the above general formula (13), 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, , 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.
In addition, 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, etc .; 3,4-epoxy-6-methyl; Alicyclic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane and the like Compounds; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diamino acid Glycidyl amines such as phenylmethane, triglycidyl-p-aminophenol, N, N-diglycidyl aniline, etc .; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin, 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 ethylenic unsaturated bond having the above acid value is 1 to 95% by mass, particularly 10 to 80% by mass in the colored photosensitive composition of the present invention. % By weight is preferred.
Moreover, when using the polymeric compound which has an ethylenically unsaturated bond which does not have the said acid value, the content is 100 mass parts of polymeric compounds which have an ethylenically unsaturated bond which has the said acid value, It is preferable to set it as 10-1000 mass parts.

  The above photo radical polymerization initiator may be any compound as long as it can start radical polymerization by receiving light irradiation, for example, acetophenone compound, benzyl compound, benzophenone compound, oxime compound, thioxanthone compound A ketone compound such as a compound can be exemplified as a preferable one.

  Examples of the above acetophenone compounds 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-tertiary butyl dichloroacetophenone, p-tertiary butyl trichloroacetophenone, 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- on and the like.

  Examples of the above-mentioned benzyl compounds 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. Be

  As the above oxime compounds, 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-dinitrophenyl (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-methyl benzoyl) oxime] etc. are mentioned.

  Thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4- diethyl thioxanthone etc. are mentioned as said thioxanthone type-compound.

  Other photoradical polymerization initiators include 2,4,6-trimethyl benzoyl diphenyl phosphene oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl)] titanium Etc.

  These photo radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.

  The photo radical polymerization initiator as described above is a radically polymerizable organic substance (a polymerizable compound having an acid value and having an ethylenically unsaturated bond, a polymerizable compound having an acid value and having an ethylenically unsaturated bond, a single compound The stoichiometrically required amount may be used with respect to the functional or polyfunctional epoxy compound), but preferably 0.05 to 10 parts by mass, more preferably 0.1 to 10 parts by mass with respect to the radically polymerizable organic substance. It is good to mix in parts. If this range is exceeded, a cured product having sufficient strength may not be obtained, and if it is below this range, the resin may not be cured sufficiently.

  In the colored photosensitive composition of the present invention, the content of the radical photopolymerization initiator is preferably 0.1 to 30% by mass, and more 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, and when it 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 solution is subjected to spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion, etc. It can be coated on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic and the like by a known means, and can be cured by light irradiation.

  As the organic solvent, a solvent which can dissolve or disperse each of the above components as needed, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone Ketones, etc .; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Ester solvents such as isopropyl, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; meta Alcohol solvents such as alcohol, 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 ether solvents such as dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc .; BTX solvents such as benzene, toluene, xylene etc .; aliphatics such as hexane, heptane, octane, cyclohexane etc. Hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene, etc .; mineral spirit, swazor # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (E. Paraffin 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 hydrocarbons such as chlorobenzene Solvents: carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. The solvent of can be used as one or more mixed solvents. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are preferable because they have good compatibility between the resist and the photopolymerization initiator in the colored photosensitive composition.

A coloring agent can be further added to the colored photosensitive composition of the present invention, and the coloring agent includes a dye or a pigment.
The dye is not particularly limited as long as it is a compound having an absorption at 380 to 1200 nm, but, for example, 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, rhodamine compound, perylene compound, polyene naphtholactam compound, coumarin compound, squalilium compound, Croconium compounds, spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styrol Compound, pyrilium compound, rhodanine compound, oxazolone compound, phthalimide compound, cinnoline compound, naphthoquinone compound, azaanthraquinone compound, porphyrin compound, azaporphyrin compound, pyrromethene compound, quinacridone compound, diketopyrrolopyrrole compound, indigo compound, aziridine compound Dyes, such as a compound, an azomethine compound, an aniline compound, a quinacridone compound, a quinophthalone compound, a quinone imine compound, an iridium complex compound, a europium complex compound, etc. are mentioned, You may mix and use these plurality.

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, anthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes, cyanine dyes Lake pigment; carbon black obtained by furnace method, channel method, thermal method, acetylene black, ketjen black or lamp black etc. Carbon black: one prepared by coating the above carbon black with an epoxy resin and coated, one obtained by dispersing the above carbon black in a solvent beforehand with a resin and adsorbing a resin of 20 to 200 mg / g, the above carbon black is acidic or alkaline Surface-treated, with an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in volatiles at 950 ° C., total oxygen amount calculated from CO ₂ 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 micro coil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue , Koval Red green, cobalt blue, manganese, ferrocyanide, phosphate blue, bitumen, ultramarine, cerulian blue, pyridinium, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), Inorganic contents such as cadmium red, synthetic iron black, amber and organic pigments can be used. These pigments may be used alone or in combination of two or more.

  Commercially available pigments can also be used as the above-mentioned inorganic pigment or organic pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 22, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment oranges 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, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 154, 154, 154, 154, 154, 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, and more preferably 0 to 80% by mass, in the colored photosensitive composition of the present invention.

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

  In the case of using a pigment and / or an inorganic compound in the above-mentioned colored photosensitive composition, a dispersant can be added. Any dispersant may be used as the dispersant, as long as it can disperse and stabilize pigments and inorganic compounds, and commercially available dispersants such as BYK series manufactured by Bick Chemie Co., Ltd. can be used, and polyesters and polys having a basic functional group Polymer dispersant containing ether, polyurethane, functional group having nitrogen atom as basic functional group and functional group having nitrogen atom is amine and / or its quaternary salt, and having an amine value of 1 to 100 mg KOH / g Is 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; Leveling agents; Surface conditioners; Antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants, etc .; UV absorbers; dispersion aids; aggregation inhibitors; catalysts; Cross-linking agents; conventional additives such as thickeners can be added.

  Moreover, the characteristic of the hardened | cured material of the coloring photosensitive composition of this invention can also be improved by using another organic polymer with the polymeric compound which has an ethylenically unsaturated bond which has the said acid value. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene-(meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate 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, polyamide imide resin, polyamic acid resin, epoxy resin, etc. may be mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin Masui.

  In the colored photosensitive composition of the present invention, a thermal radical polymerization initiator, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, etc. can be used in combination.

  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-butyl benzoyl peroxide, t-butyl peroxypivalate, di (4-t-butylcyclohexyl) 2. Peroxide initiators such as peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate. These may be used alone or in combination of two or more.

  A sulfur atom-containing compound is generally used as the chain transfer agent and the sensitizer. 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- 3- Mercapto compounds such as mercapto propionates, Disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acids, iodoacetic acids, iodopropionic acids, 2-iodoethanol, 2-iodoethanesulfonic acid, iodos such as 3-iodopropanesulfonic acid Alkylated compounds, 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, tris hydroxyethyl tris thiopropionate, compound No. 1 below. C1, Aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate; Kalens MT BD1, PE1, NR1 manufactured by Showa Denko K. K.

  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 halides and quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, nonionic surfactants such as fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  As the above-mentioned silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc., silane cup having isocyanate group, methacryloyl group, epoxy group Ring agents are preferably used.

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

  Moreover, as a light source of the actinic light used when hardening the coloring photosensitive composition of this invention, what light-emits the light of wavelength 300-450 nm can be used, for example, super-high pressure mercury, mercury vapor arc, A carbon arc, a xenon arc or the like can be used.

  Furthermore, by using a laser beam as an exposure light source, a laser direct writing method of directly forming an image from digital information of a computer or the like without using a mask improves not only productivity but also resolution and positional accuracy. It is useful because it can also be used, and light with a wavelength of 340 to 430 nm is suitably used as the laser light, but the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser Are also used. When using these lasers, sensitizing dyes that absorb the relevant region of visible to infrared are added.

  The colored photosensitive composition (or the cured product thereof) of the present invention is a photocurable coating or varnish, a photocurable adhesive, a printed circuit board, or a color display of color television, PC monitor, portable information terminal, digital camera, etc. Color filter for liquid crystal display panel, color filter for CCD image sensor, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, resin for stereolithography, gel coat, for electronics Photoresists, electroplating resists, etching resists, both liquid and dry films, solder resists, structures for manufacturing color filters for various display applications, plasma display panels, electroluminescent displays, and structures in manufacturing processes of LCDs , Compositions for encapsulating electrical and electronic components, and Solder resists, magnetic recording materials, micro mechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, for producing three-dimensional objects by stereolithography Materials, holographic recording materials, image recording materials, microelectronics, bleaching materials, bleaching materials for image recording materials, bleaching 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 materials for visible laser direct imaging systems, photoresist materials used to form dielectric layers in successive lamination of printed circuit boards, and protective films, and the applications are not particularly limited. .

  The colored photosensitive composition of the present invention is used to form 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 comprises the steps of (1) 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 the steps of: (3) developing the film after exposure with a developer; and (4) heating the film after development. In addition, the colored photosensitive composition of the present invention is also useful as a colored photosensitive composition of the ink jet system without a developing step.

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

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 are mixed, 2.5 equivalents of Compound 2 and 2.42 g of 4-dimethylaminopyridine are added, and the mixture is stirred in an ice bath 30 Stir for one minute, add 4.5 equivalents of EDC hydrochloride, and stir at room temperature for 5 hours under nitrogen atmosphere. After oil-water separation with ethyl acetate / water, it was washed with water and dried, and the solvent was distilled off to obtain Compound 4.

<Step 2> Compound No. Synthesis of 1 1 equivalent of the compound 4 obtained in Step 1 and 2.05 g of pyridine are mixed, 0.1 equivalent of 4-dimethylaminopyridine is added and stirred, and then t-butyl dicarbonate is obtained at 10 ° C. or less 12 equivalents were added dropwise and stirred at room temperature for 20 hours. After oil-water separation with ethyl acetate / water, it was washed with water, dried and the solvent was distilled off. Purification by column chromatography (ethyl acetate: hexane = 1: 1), crystallization from methanol was carried out, and compound no. 1 was obtained in a yield of 24%. It was confirmed by ¹ H-NMR and IR that the obtained compound is the desired product. In addition, absorption wavelength characteristics were 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 are mixed, 0.1 equivalent of 4-dimethylaminopyridine is added and the mixture is stirred, and after stirring at 10 ° C. Three equivalents of butyl were added dropwise and stirred at room temperature for 3 hours. After oil-water separation with ethyl acetate / water, it was washed with water and dried, and the solvent was distilled off to obtain Compound 6.

<Step 2> Compound No. Synthesis of 2 1 equivalent of compound 7 and 10 g of ethyl acetate and 10 g of water are mixed, 1 equivalent of compound 6 obtained in step 1 is added and stirred, then the ethyl acetate layer is separated and dried, and the theoretical yield of 5 Concentrated to double. The concentrated ethyl acetate solution was dispersed in hexane and crystallized. 2 were obtained in 70% yield. It was confirmed by ¹ H-NMR and IR that the obtained compound is the desired product. In addition, absorption wavelength characteristics were 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, under ice-cooling, 2 mL of 1 N hydrochloric acid aqueous solution was added to make an acidic solution, oil-water separation was performed, and a toluene solution containing compound 9 was obtained.

<Step 2> Compound No. Synthesis of M.3 4 g of chloroform, 1 eq. The mixture was stirred for oil-water separation, dispersed in hexane and crystallized. 3 was obtained in a yield of 80%. It was confirmed by ¹ H-NMR and IR that the obtained compound is the desired product. In addition, absorption wavelength characteristics were measured. The results are shown in [Table 1] and [Table 2].

[Examples 2-2 to 2-3] Colored photosensitive composition No. 1 1 to No. Preparation of <Step 1> Photosensitive Composition No. 3 Preparation of 1 30.3 g of ACA Z 250 (made by Daicel-Cytec) as a polymerizable compound component having an ethylenic unsaturated bond having an acid value, Alonicus as a polymerizable compound component having an ethylenic unsaturated bond having no acid value 11.04 g of M-450 (manufactured by Toagosei Co., Ltd.), 1.93 g of Irgacure 907 (manufactured by BASF Corp.) as a photo radical polymerization initiator component, 36.60 g of PGMEA as a solvent and 20.08 g of cyclohexanone, and others As components, 0.01 g of FZ2122 (manufactured by Toray Dow Corning Co., Ltd.) is mixed, and the mixture is stirred until insolubles are eliminated. I got one.

<Step 2> Dye solution No. 1 to No. Preparation of Compound No. 3 obtained above 1 to No. To 0.10 g of No. 3, 1.90 g of dimethylacetamide was added, and dissolved by stirring. 1 to No. Each 3 was prepared.

<Step 3> Colored photosensitive composition No. 1 1 to No. Preparation of Photosensitive Composition No. 3 obtained in Step 1 No. 1 of 5.0 g and dye solution No. 1 obtained in step 2 1 to No. The mixture was mixed with 1.0 g of each of the mixture No. 3 and stirred until it became uniform. 1 to No. I got 3 each.

Comparative Examples 1-1 to 1-3 Comparative Colored Photosensitive Composition No. 1 1 to No. Preparation of Compound No. 3 in Step 2 of Example 2 Comparative compound No. 1 below. 1 to No. Comparative colored photosensitive composition No. 1 was prepared in the same manner as in Example 2-1 except that the color composition was changed to any one of No. 3. 1 to No. I got three.

Comparative Examples 2-1 to 2-3 Comparative Colored Photosensitive Composition No. 1 1A-No. Preparation of 3A Comparative colored photosensitive composition No. 3 1 to No. Comparative coloring photosensitive composition No. 3 in the same manner as in Example 2-1 except that the following compound α was added to No. 3 as an antioxidant. 1A-No. I got 3A.

[Evaluation Examples 1-1 to 1-3 and Comparative Evaluation Examples 1-1 to 1-3] Heat Resistance Evaluation by Firing The above-obtained colored photosensitive composition No. 1 was obtained. 1 to No. 3 and Comparative Colored Photosensitive Composition No. 1 to No. Each 3 was applied to 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 to light (150 mJ / cm ² ) using an extra-high pressure mercury lamp. The coated film after exposure was fired at 230 ° C. for 30 minutes. Absorbance of the coating before baking (after exposure) at the maximum absorption wavelength (λ max) of the compound used and absorbance of the coating after baking are measured, and the absorbance of the coating before baking (after exposure) is 100 It was evaluated as relative strength of The heat resistance is higher as the absorbance of the coating film after firing is closer to 100. In addition, 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 Example 2-1 to 2-3 and Comparative Evaluation Example 2-1 to 2-3 First, evaluation of colored photosensitive composition No. 1 was carried out. 1 to No. Comparative compound no. Colored photosensitive composition No. 1 was added in the same manner as in Example 2-1 except that 1 was added. 1A-No. 3A was obtained respectively.
The colored photosensitive composition No. 1 obtained above was obtained. 1A-No. Comparative colored photosensitive composition Nos. 3A and 3A and Comparative Examples 2-1 to 2-3. 1A-No. Each 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 to light (150 mJ / cm ² ) using an extra-high pressure mercury lamp.
The coated film after exposure was fired at 230 ° C. for 30 minutes. Absorbance of the coating before baking (after exposure) at the maximum absorption wavelength (λ max) of the compound used and absorbance of the coating after baking are measured, and the absorbance of the coating before baking (after exposure) is 100 It was evaluated as relative strength of In addition, 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 . Thus, this indicates that the compound of the present invention has a high antioxidant function.

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

Claims (4)

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, which is represented by the following general formula (2) A cyanostyrene compound, a triarylmethane compound represented by the following general formula (8), or a cyanine compound represented by the following general formula (9) .

(Wherein, R ⁰¹ , R ⁰² , R ⁰⁴ and R ⁰⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, a carbon atom And 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 -O-R ¹
At least one of R ^{02 and} 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 heterocyclic ring having 2 to 20 carbon atoms Containing group,
R ⁰³ is represented by —O—R ¹
R ¹ is an alkoxycarbonyl group having 2 to 9 carbon atoms,
R ^01, R ^{0 2,} alkyl groups represented by R ⁰⁴ and R ^05, aryl group, arylalkyl group or heterocyclic ring-containing group is or unsubstituted have a substituent,
The methylene group in the alkyl group or arylalkyl group represented by R ⁰¹ , R ⁰² , R ⁰⁴ and R ⁰⁵ 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 substituted,
R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )

(Wherein, A represents a benzene ring, a naphthalene ring or an anthracene ring, and these rings are a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, and 1 to 8 carbon atoms Or substituted with an alkoxy group of 1 to 8 carbon atoms, a halogenated alkyl group of 1 to 8 carbon atoms, or a halogenated alkoxy group of 1 to 8 carbon atoms, or
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or a halogenated alkoxy group having 1 to 8 carbon atoms Represents
Y represents a cyano group,
X is an organic group satisfying the following condition <1> and is bonded to R ⁶ ,
R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 8 carbon atoms,
The alkyl group represented by R ⁷ is substituted by the substituent represented by the above general formula (1),
The methylene group in the alkyl group represented by R ⁷ may be replaced by -OCO-,
m is 2. )
<1> X is represented by the following general formula (3).

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

(Wherein, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a halogen atom Or an alkyl group having 1 to 8 carbon atoms,
R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group,
An ^q- represents an organic sulfonic acid type anion having at least one substituent represented by the general formula (1), q represents 1 or 2, and p represents a coefficient for keeping the charge neutral. . )

(Wherein, D represents a group represented by (a) in group I below, D ′ represents a group represented by (a ′) in group II below,
Q represents a linking group constituting a methine chain having 1 to 9 carbon atoms, and a hydrogen atom in the methine chain is a hydroxyl group, a halogen atom, a cyano group, -NR ⁵¹ R ⁵² , an aryl group having 6 to 12 carbon atoms And the arylalkyl group having 7 to 12 carbon atoms or the alkyl group having 1 to 8 carbon atoms may be substituted, and the -NR ⁵¹ R ⁵² , the aryl group, the arylalkyl group and the alkyl group further have a hydroxyl group, The methylene group in the aryl group which may be substituted with a halogen atom, a cyano group or -NR ⁵¹ R ⁵² , -NR ⁵¹ R ⁵² , an aryl group, an arylalkyl group and an alkyl group is -O-, -S-, -CO -, -COO-, -OCO-, -SO _2- , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-,
R ⁵¹ and R ^{52 each} represent an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms,
An ^q- represents an organic sulfonic acid type anion having at least one substituent represented by the general formula (1), q represents 1 or 2, and p represents a coefficient for keeping the charge neutral. . )

(Wherein, ring G and ring G ′ each represent a benzene ring, a naphthalene ring, a phenanthrene ring or a pyridine ring,
R ⁵³ and R ⁵³ ′ each represents a hydroxyl group, a halogen atom, a nitro group, a cyano group, -SO ₃ H, a carboxyl group, an amino group, an amido group, a ferrocenyl group, an aryl group having 6 to 30 carbon atoms, and 7 carbon atoms 30 to 30 arylalkyl group or an alkyl group having 1 to 8 carbon atoms,
The aryl group, arylalkyl group and alkyl group represented by R ⁵³ and R ⁵³ ′ 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 amido group or a ferrocenyl group May be
The methylene group in the aryl group, arylalkyl group and alkyl group represented by R ⁵³ and R ⁵³ ′ is —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH- may be substituted,
X ¹² and X ¹² 'represents an oxygen atom, a sulfur atom, a selenium atom, -CR ⁶² R ⁶³ -, cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, -NH- or -NY ¹³ - the Represent
R ⁶² and R ⁶³ each represent the same group as R ⁵³ and R ⁵³ ′ or a hydrogen atom,
Y ¹² , Y ¹² ′ and Y ^{13 each} represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms,
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 amido group, a ferrocenyl group, —SO ₃ H or a nitro Substituted or unsubstituted with a group,
Y ^12, Y ¹² 'and the alkyl group represented by Y ^13, a methylene group of the aryl group and in the arylalkyl group, -O -, - S -, - CO -, - COO -, - OCO -, - SO _It may be replaced by _2- , -NH-, -CONH-, -NHCO-, -N = CH- or -CH = CH-,
r and r ′ each represent 0 or a substitutable number in (a) or (a ′). ) In the general formula (1), R ⁰¹ , R ⁰² , R ⁰⁴ and R ⁰⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 40 carbon atoms ,
At least one of R ^{02 and} R ⁰⁴ is an alkyl group having 1 to 40 carbon atoms,
In the above general formula (2), R ⁵ represents a hydrogen atom,
In the above general formula (8), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are each independently hydrogen Represents an atom or an alkyl group having 1 to 8 carbon atoms,
R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent an alkyl group having 1 to 8 carbon atoms,
In the general formulas (a) and (a '),
R ⁵³ and R ⁵³ ′ represent a nitro group,
X ¹² and X ¹² ′ each represent —CR ⁶² R ⁶³ —
R ⁶² and R ⁶³ each represent an alkyl group having 1 to 8 carbon atoms or a hydrogen atom,
Y ¹² and Y ¹² ′ each represent an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms,
The compound according to claim 1, wherein the methylene group in the alkyl group and the arylalkyl group represented by Y ¹² and Y ¹² 'may be replaced by -O-. A composition containing the compound according to claim 1 or 2 . A colored photosensitive composition comprising, in the composition according to claim 3 , a polymerizable compound having an ethylenically unsaturated bond having an acid value and a photoradical polymerization initiator.