JP2006215395A - Near-infrared absorption filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared absorbing dye having an absorption maximum at about 800-980 nm, excellent in heat resistance, wet heat resistance, etc., and having high solubility in a solvent, and a near-infrared absorption filter using the dye. <P>SOLUTION: The near-infrared absorption filter contains a compound represented by formula (1) wherein R<SP>1</SP>and R<SP>2</SP>each independently denote a monovalent organic group; X<SP>1</SP>and X<SP>2</SP>each independently denote -X(-R)<SB>(n-1)</SB>(where X denotes O, N, S or Si; R denotes a monovalent organic group, a plurality of symbols R may be the same or different; and n denotes the valence of X); R<SP>1</SP>and X<SP>1</SP>, and R<SP>2</SP>and X<SP>2</SP>may independently form a ring through a linking group; and M<SP>1</SP>denotes a metal atom. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a near-infrared absorption filter, and more particularly to a near-infrared absorption filter that has a high transmittance in the visible light region and effectively blocks near-infrared rays.

In general, plastic near-infrared absorption filters made of a resin containing a near-infrared absorbing dye are well known, and can be used for sunglasses, welding glasses, buildings, automobiles, trains, airplane windows, or information reading. For example, an optical reading device.
Recently, a plasma display panel (hereinafter referred to as “PDP”), which has been attracting attention as a large and thin wall-mounted TV, generates near infrared rays, such as a video deck using a cordless phone or a near infrared remote control. There is a demand for a filter containing an infrared-absorbing dye that absorbs near-infrared rays of 800 nm to 1100 nm as a filter for PDP because it acts on equipment and causes malfunction.

As a near-infrared absorbing dye used for such a near-infrared absorbing filter, a dithiol metal complex compound having an absorption maximum in the vicinity of 800 to 980 nm is known (Patent Document 1, Patent Document 2).
JP 2002-132176 A JP-A 64-69686

However, when the present inventors manufactured a near-infrared absorbing filter using the near-infrared absorbing dye described in Patent Document 1, since the solubility in a solvent is low, the dye concentration of the coating liquid containing the near-infrared absorbing dye is There was a problem that it could not be raised. Moreover, the near-infrared absorbing dye described in Patent Document 2 has a problem of poor heat resistance and moist heat resistance.
Therefore, in the present invention, a near-infrared absorbing dye having an absorption maximum in the vicinity of the target 800-980 nm, excellent in heat resistance, moist heat resistance, and the like, and having high solubility in a solvent, and near infrared using the same It is an object of the present invention to provide an absorption filter, particularly a near infrared absorption filter for electronic displays.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have introduced a substituent having a hetero atom at a specific site in a dithiolate metal complex, thereby having an absorption maximum in the vicinity of 800-980 nm. The present inventors have found that a near-infrared absorbing dye having high solubility in a solvent, excellent heat resistance and heat-and-moisture resistance, and suppressing side absorption in the visible region can be obtained, and the present invention has been completed. That is, the gist of the present invention is the following general formula (1).

(In the formula, R ¹ and R ² each independently represent a monovalent organic group. X ¹ and X ² each independently represent —X (—R) _(n−1) (X represents an oxygen atom ₎ , A nitrogen atom, a sulfur atom, a silicon atom or a halogen atom, R represents a hydrogen atom or a monovalent organic group, a plurality of R may be the same or different, and n represents the valence of X.) R ¹ and X ¹ and R ² and X ¹ may each independently form a ring via a linking group, and M ¹ represents a metal atom. It exists in the near-infrared absorption filter containing the compound represented by these.

  According to the present invention, there is provided a near-infrared absorbing filter in which a near-infrared absorbing dye has high solubility, is excellent in light resistance, heat resistance, and the like, and suppresses side absorption in the visible region.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited to these unless it exceeds the gist.
1. Compound Represented by General Formula (1) In the general formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited as long as the atom bonded to the dithiol ring is not a heteroatom and does not adversely affect the stability of the metal complex. Examples thereof include a hydrogen group, an aryl group which may have a substituent, and a heterocyclic group which may have a substituent.

  Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, 2-methylpropyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, neopentyl group, 2- Linear, branched or cyclic alkyl groups such as ethylbutyl, isopropyl, 2-butyl, cyclohexyl, 3-pentyl, tert-butyl and 1,1-dimethylpropyl; 2-propenyl Alkenyl groups such as 2-butenyl group, 3-butenyl group and 2,4-pentadienyl group; and alkynyl groups such as ethynyl group. Of these, a branched primary, secondary or tertiary alkyl group having 10 or less carbon atoms is preferred.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a fluorenyl group, a phenanthrenyl group, an azulenyl group, and a metallocene ring group. Among these, a monocyclic or condensed bicyclic aryl group having 12 or less carbon atoms is preferable.
Examples of the heterocyclic group include thienyl group, furyl group, pyrrolyl group, pyridyl group, imidazolyl group, pyrazolyl group, indoleyl group, quinoxalinyl group, acridinyl group, thiazolyl group, pyrazinyl group and the like. Of these, a monocyclic or bicyclic 5-membered heterocyclic group having 12 or less carbon atoms is preferable.

The substituent for the aliphatic hydrocarbon group, aryl group and heterocyclic group of R ¹ and R ² is not particularly limited as long as it does not adversely affect the stability of the metal complex. Hydroxyl group, nitro group, cyano group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group, Acyl group, aminoacyl group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, heteroaryl Sulfonyl group, imide group and And a group selected from the group consisting of a tolyl group and the like. Specific examples of these substituents include alkyl groups having about 1 to 6 carbon atoms such as a methyl group and an ethyl group; alkenyl groups having about 1 to 6 carbon atoms such as an ethynyl group and a propylenyl group; An alkynyl group of about 6; an aryl group of about 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a heteroaryl group of about 3 to 20 carbon atoms such as a thienyl group, a furyl group and a pyridyl group; an ethoxy group and a propoxy group An alkoxy group having about 1 to 6 carbon atoms; an aryloxy group having about 6 to 20 carbon atoms such as a phenoxy group and a naphthoxy group; a heteroaryloxy having about 3 to 20 carbon atoms such as a pyridyloxy group and a thienyloxy group Group: an alkylthio group having about 1 to 6 carbon atoms such as methylthio group and ethylthio group; 6 carbon atoms such as phenylthio group and naphthylthio group An arylthio group having about 20; a heteroarylthio group having about 3 to 20 carbon atoms such as a pyridylthio group and a thienylthio group; a substituent having about 1 to 20 carbon atoms such as a dimethylamino group and a diphenylamino group; A good amino group; an acyl group having about 2 to 20 carbon atoms such as an acetyl group and a pivaloyl group; an acylamino group having about 2 to 20 carbon atoms such as an acetylamino group and a propionylamino group; and a carbon number such as a 3-methylureido group A ureido group having about 2 to 20; a sulfonamide group having about 1 to 20 carbon atoms such as methanesulfonamide group and benzenesulfonamide group; a carbamoyl group having about 1 to 20 carbon atoms such as dimethylcarbamoyl group and ethylcarbamoyl group; A sulfamoyl group having about 1 to 20 carbon atoms such as a sulfamoyl group; dimethylsulfa A sulfamoylamino group having about 1 to 20 carbon atoms such as an ylamino group; an alkoxycarbonyl group having about 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; 7 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group An aryloxycarbonyl group having about 20 carbon atoms; a heteroaryloxycarbonyl group having about 6-20 carbon atoms such as a pyridyloxycarbonyl group; a methanesulfonyl group, an ethanesulfonyl group, a fluoromethanesulfonyl group having about 1-6 carbon atoms An alkylsulfonyl group; an arylsulfonyl group having about 6 to 20 carbon atoms such as a benzenesulfonyl group and a monofluorobenzenesulfonyl group; a heteroaryloxysulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; and a carbon number of 4 such as phthalimide ~ 2 An imide group of about 0; or a silyl group that is trisubstituted with a substituent selected from the group consisting of an alkyl group and an aryl group.

Among the above R ¹ and R ² , preferred are an alkyl group which may have a substituent which does not contain a heterocycle, a monocyclic aryl group or a monocyclic heteroaryl group, and particularly preferably a branched chain Or a monocyclic aryl group.
X ¹ and X ² are each independently -X (-R) _(n-1) (X represents an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom. R represents a hydrogen atom or a single atom. A plurality of Rs may be the same or different, and n represents a valence of X.)

X is preferably a sulfur atom or a silicon atom, and more preferably a sulfur atom.
The monovalent organic group for R includes an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. It is.
Examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group are the same as those described for R ¹ and R ² .

The substituent of the aliphatic hydrocarbon group, aryl group and heterocyclic group is not particularly limited as long as it does not adversely affect the stability of the metal complex, but the same as those described for R ¹ and R ² Things can be raised.
When X ¹ and X ² are nitrogen atoms, oxygen atoms or sulfur atoms which may have a substituent, X ¹ and R ¹ and X ² and R ² are combined with each other as —CH ₂ —. _{CH 2 -, - CH 2 -CH} 2 -CH 2 -, CH 2 -CH 2 -CH2-CH 2 -, - CH (Ph) -CH 2 -, - CH (Me) -
An optionally substituted alkylene group such as CH ₂ —; —CH═CH—, —C (Me) ═CH
—, —CH═CH—CH ₂ —CH ₂ —CH═CH— and the like, an optionally substituted alkenylene group; —CH ₂ —S—CH ₂ —, —CH ₂ —O—CH ₂ —, —CH _{2 -C (= O) -CH 2} -, - CH 2 -CH 2 -S-CH 2 -CH 2 -, - contain a linking group such as _{- CH 2 -CH 2 -O-CH} 2 -CH 2 An alkylene group or the like may be formed. Specific examples of the basic skeleton include the following. (Wherein R represents an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent or a sulfonyl group which may have a substituent, and preferred examples are , R ¹ and R ² are the same as described above.)

(Wherein R represents an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent or a sulfonyl group which may have a substituent, and preferred examples are , R ¹ and R ² are the same as described above.)
Among the substituents represented by -X (-R) _(n-1) , when R is an aromatic hydrocarbon group and X is sulfur, heat resistance, moist heat resistance and light resistance, particularly heat resistance and It is preferable because the heat and humidity resistance is good.

Moreover, in the compound represented by the general formula (1), R ¹ and R ² , X ¹ and X ² may be the same or different, but are preferably the same.
M ¹ is not particularly limited as long as it is a metal atom that can take a tetracoordinated form.
i, Pd, or Pt group 10 metal atom; Co; Fe; Cu; Ag; or Zn, and more preferably a group 10 metal atom, and particularly preferably Ni or Pd.

  Preferable specific examples of the compound used in the near infrared absorption filter of the present invention include, for example, those exemplified below. However, it is not limited to the following compounds.

The compound represented by the above general formula (1) used in the near-infrared absorption filter of the present invention as described above is preferably a compound having a ligand moiety molecular weight of preferably 1000 or less, more preferably 600 or less.
Further, the molar extinction coefficient of the compound represented by the general formula (1) is usually 5000 or more, preferably 8000 or more.

In addition, the solubility of the compound represented by the above general formula (1) at 25 ° C. in an aromatic hydrocarbon solvent such as toluene, an ether solvent such as tetrahydrofuran and dimethoxyethane, and a solvent selected from a ketone solvent such as methyl ethyl ketone Is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and further preferably 0.2% by weight or more.
Moreover, it is 20 weight% or less normally, Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less, More preferably, it is 3 weight% or less, Most preferably, it is 2 weight% or less. In particular, the solubility in toluene at 25 ° C. is usually 0.8% by weight or more, preferably 0.9% by weight or more, more preferably 1.0% by weight or more.
The solubility at 25 ° C. in methyl ethyl ketone is usually 0.15% by weight or more, preferably 0.2% by weight or more, more preferably 0.3% by weight or more, and particularly preferably 0.4% by weight or more. it can.
And when it is contained in a filter as a near-infrared absorption pigment | dye as it explains in full detail at the term of a near-infrared absorption filter, it has favorable heat resistance and a heat-and-moisture resistant body.
Such a compound represented by the general formula (1) can be obtained by a known method described in, for example, Mol. Cryst. Liq. Crst. (Lett), 56, 249 (1980) [1,3]- After obtaining a dithiol-2-one derivative, the target precursor is obtained by reacting with a low nucleophilic base; for example, lithium hexamethyldisilazide or lithium diisopropylamide, and then reacting with various electrophiles. . This is described, for example, in J. Org. Mat. Chem. , 1861 (1994) and the like, and metallization is carried out to obtain the target metal complex. Moreover, the absorption maximum wavelength is 800-980 nm, and it can be used conveniently as a near-infrared absorbing dye.

Specific examples of producing the compound of the present invention include, for example, [1,3] -dithiol-2-one derivatives and 1.5 to 2 equivalents of compounds represented by the following formulas (a) to (d) RS-SRR ... Formula (a)
R'N-NR'R Formula (b)
RO-OR ... Formula (c)
RR′R ″ SiCl Formula (d)
(In the formulas (a) to (d), RR ′ and R ″ are each independently an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, and a substituent. A heterocyclic group which may have a group is shown.Preferable specific examples are the same as those of R1 and R2 above.)
Alternatively, an anhydrous THF solution mixed with halogen molecules is cooled to -78 ° C.
Here, the amount of anhydrous THF solution as a solvent is preferably about 1 to 10 ml with respect to 1 mmol of the [1,3] -dithiol-2-one derivative.

In this reaction solution, 1.05 to 1.2 times equivalent of 1M lithium hexamethyldisilazide hexane solution or 2M lithium diisopropylamide heptane / THF with respect to [1,3] -dithiol-2-one derivative. The solution is added dropwise in about 5 to 10 minutes.
The mixed solution is gradually warmed to 0 ° C. over 2 hours, poured into ice-saturated aqueous ammonium chloride solution, and ester solvent such as ethyl acetate (or halogen solvent such as chloroform or ether such as diethyl ether). The solvent is removed under reduced pressure to obtain the target intermediate.

Usually, since this reaction does not produce a by-product, the subsequent nickel metallization can be carried out as it is, but it may be purified by silica gel column chromatography if necessary.
2. Near-infrared absorbing compounds represented by general formulas (2) to (11) The near-infrared absorbing filter of the present invention further includes a compound selected from the group consisting of compounds represented by the following general formulas (2) to (11) By containing at least one or more, it is possible to absorb a wide range of near-infrared regions in the range of 750 to 1050 nm.

In the general formula (2), A and A ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl that may have a substituent. Indicates a group. Here, R ⁵ and R ⁶ may be linked directly or via a linking group. M ²
May be the same as those described for M ¹ .

  The skeleton constituting the aryl group and heteroaryl group of A and A ′ is preferably a 6-membered monocyclic ring or a condensed ring thereof. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, An aryl group such as a pyrenyl group or a fluorenyl group; or a heteroaryl group such as a thienyl group, a furyl group, a pyridyl group, an imidazolyl group, a pyrazinyl group, or a pyrazolyl group. Among these, an aryl group is preferable, and an aryl group such as a benzene ring or a naphthalene ring is more preferable.

Examples of the substituent of the aryl group and heteroaryl group of A and A ′ include the same substituents as those described above as the substituents of R ^{1 to} R ^2. , A nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, and a substituent Examples thereof include an alkoxy group which may be substituted, an aryloxy group which may have a substituent, and an amino group which may have a substituent. More specifically, halogen atoms such as chlorine atom, bromine atom and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group A halogen atom such as a cyclohexyl group, a benzyl group, a phenethyl group or a trifluoromethyl group or an aryl group which may be substituted; an alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Groups: heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group Alkoxy group; aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, di Eniruamino group include an alkyl group and an amino group which may be substituted with a substituent selected from the group consisting of aryl groups such as methylphenylamino group.

Further, two adjacent substituents on A and A ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as-may be formed.
Examples of the alkyl group of R ⁵ and R ⁶ include methyl group, ethyl group, n-propyl group, n-butyl group, 2-methylpropyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, and neopentyl group. , A linear, branched or cyclic alkyl group such as 2-ethylbutyl group, isopropyl group, 2-butyl group, cyclohexyl group, 3-pentyl group, 1,1-dimethylpropyl group. Among these, a primary or secondary alkyl group having 10 or less carbon atoms is preferable, and a primary alkyl group having 10 or less carbon atoms is particularly preferable.
Examples of the substituent for the alkyl group of R ⁵ and R ⁶ include the same substituents as those described above as the substituents for R ^{1 to} R ² , and particularly preferably an unsubstituted or halogen atom (particularly Preferably a fluorine atom), a cyano group, an alkoxy group and an aryl group.
The aryl group and heteroaryl group of R ⁵ and R ⁶ include phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group or fluorenyl group, thienyl group, furyl group, pyridyl group, imidazolyl group, pyrazinyl group or pyrazolyl group. 5-membered or 6-membered monocyclic ring or a condensed ring thereof. Of these, an aryl group which may have a substituent is preferable, and a phenyl group which may have a substituent is more preferable.

Furthermore, among the phenyl groups which may have a substituent, particularly preferably, the carbon atom adjacent to the carbon atom bonded to the nitrogen atom to which R ⁵ and R ⁶ are bonded is the substituent R ⁴³ and R ^This is the case with ⁴⁴ . R ⁴³ and R ⁴⁴ represent a monovalent substituent. R ⁴³ and R ⁴⁴ are not particularly limited as long as they are groups that do not adversely affect the stability of the dye. More preferably, they may have an alkyl group that may have a substituent or a substituent. Alkoxy group, aryl group which may have a substituent, aryloxy group which may have a substituent, heterocyclic group which may have a substituent, heterocyclic oxy group which may have a substituent A group having a high steric hindrance such as a substituent selected from the group consisting of an optionally substituted alkylthio group, an optionally substituted arylthio group and an optionally substituted heterocyclic thio group, Alternatively, an electron-withdrawing group having a Hammett substituent constant sm of 0.00 <sm <0.90 can be given.
Examples of the electron-withdrawing group include J.I. Med. Chem. 16, 1207 (1973) and J.A. Med. Chem. , 20, 304 (1977), more specifically, halogen atoms, cyano groups, nitro groups, haloalkyl groups, haloalkoxy groups, haloaryloxy groups, acyl groups, Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a haloalkylsulfonyl group, a haloarylsulfonyl group, and the like.

In the case where R ⁵ and R ⁶ are aromatic rings, the substituents on the aromatic ring are formed by combining two adjacent substituents, such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —. An alkylene group having about 2 to 5 carbon atoms, an alkylenedioxy group having about 1 to 4 carbon atoms such as —OCH ₂ O— or —O (CH ₂ ) ₂ O— may be formed.
X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. R ^{'
, R '', R ''} ', R'''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl group, the substituent of the alkyl group and aryl group Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ⁴ . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.
Preferably, those not forming a salt are better than those forming a salt.

  Preferable specific examples of the dye represented by the general formula (2) include compounds represented by the following structural formula.

In the general formula (3), B and B ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl which may have a substituent. Indicates a group. Here, R ⁷ and R ⁸ may be connected to each other directly or via a linking group. M ³
Can use the same metals as described for M ¹ .

  The skeleton constituting the aryl group and heteroaryl group of B and B ′ is preferably a 6-membered monocyclic ring or a condensed ring thereof. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, An aryl group such as a pyrenyl group or a fluorenyl group; or a heteroaryl group such as a thienyl group, a furyl group, a pyridyl group, an imidazolyl group, a pyrazinyl group, or a pyrazolyl group. Among these, an aryl group is preferable, and an aryl group such as a benzene ring or a naphthalene ring is more preferable.

Examples of the substituent for the aryl group and heteroaryl group for B and B ′ include the same substituents as those described above as the substituents for R ^{1 to} R ^2. , A nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, and a substituent. Examples thereof include an alkoxy group which may be substituted, an aryloxy group which may have a substituent, and an amino group which may have a substituent. More specifically, halogen atoms such as chlorine atom, bromine atom and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group A halogen atom such as a cyclohexyl group, a benzyl group, a phenethyl group or a trifluoromethyl group or an aryl group which may be substituted; an alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Groups: heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group Alkoxy group; aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, di Eniruamino group include an alkyl group and an amino group which may be substituted with a substituent selected from the group consisting of aryl groups such as methylphenylamino group.

Also, two adjacent substituents on B and B ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as-may be formed.
Examples of the alkyl group, aryl group or heteroaryl group for R ⁷ and R ⁸ include the same groups as those described above for the alkyl group, aryl group or heteroaryl group for R ⁵ and R ⁶ . Examples of the substituent of the alkyl group, aryl group or heteroaryl group of R ⁷ and R ⁸ include the same substituents as those described above as the substituents of R ^{1 to} R ² . A halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group and an aryloxy group;
R ⁷ and R ⁸ may be linked to each other directly or via a linking group, but the case as shown in the figure below is particularly preferred.

Specific preferred examples of R ^{45 to} R ⁵⁴ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom and bromine atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, propyl group, i-propyl group, Halogen atom or aryl group such as i-butyl group, t-butyl group, n-butyl group, n-pentyl group, trichloromethyl group, trifluoromethyl group, benzyl group, phenethyl group, etc. An alkyl group having 1 to 10 carbon atoms; a phenyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a t-butoxy group and an n-butoxy group; a phenoxy group and a methylphenoxy group And an aryloxy group having 6 to 10 carbon atoms which may be substituted with an alkyl group. Two adjacent substituents of R ^{33 to} R ⁴¹ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O - or -O (CH _{2) 2} O- carbon atoms such as 1 to 4
A certain degree of alkylenedioxy group or the like may be formed.

Among these, preferably, an electron-withdrawing group such as a halogen atom, a nitro group, a cyano group, a haloalkyl group, a haloalkoxy group, a haloaryloxy group, or a hydrogen atom is used. Among R ^{45 to} R ⁵⁴ , at least One is not a hydrogen atom. Furthermore, it is preferable that at least one of R ^{45 to} R ⁵⁴ is a fluorine atom, a chlorine atom or a cyano group, and the rest are hydrogen atoms.

X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. R ^{'
, R '', R ''} ', R'''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl group, the substituent of the alkyl group and aryl group Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ² . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.
Preferably, those not forming a salt are better than those forming a salt.

  The thing represented by the following structural formula is mentioned as a preferable specific example of the pigment | dye represented by the said General formula (3).

In the general formula (4), C and C ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
R ³ , R ⁴ , R ⁹ and R ¹⁰ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. The heteroaryl group which may be present is shown. Here, R ³ and R ⁴ , and R ⁹ and R ¹⁰ may be connected to each other directly or via a linking group. M ⁴ can be the same metal as described for M ¹ .

The skeleton constituting the aryl group and heteroaryl group of C and C ′ is a 6-membered monocyclic ring or a condensed ring thereof. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group Or an aryl group such as a fluorenyl group; or a heteroaryl group such as a thienyl group, a furyl group, a pyridyl group, an imidazolyl group, a pyrazinyl group, or a pyrazolyl group. Among these, an aryl group is preferable, and an aryl group such as a benzene ring or a naphthalene ring is more preferable.
Examples of the substituent of the aryl group and heteroaryl group of C and C ′ include the same substituents as those described above as the substituents of R ^{1 to} R ^2. , A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, and a substituent. Examples thereof include an alkoxy group, an aryloxy group which may have a substituent, and an amino group which may have a substituent. More specifically, halogen atoms such as chlorine atom, bromine atom and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group A halogen atom such as a cyclohexyl group, a benzyl group, a phenethyl group or a trifluoromethyl group or an aryl group which may be substituted; an alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Groups: heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group Alkoxy group; aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, di Eniruamino group include an alkyl group and an amino group which may be substituted with a substituent selected from the group consisting of aryl groups such as methylphenylamino group.

Further, two adjacent substituents on C and C ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as-may be formed.
Examples of the alkyl group, aryl group or heteroaryl group of R ³ , R ⁴ , R ⁹ and R ¹⁰ are the same as those described above for the alkyl group, aryl group or heteroaryl group of R ^{1 to} R ^2. Can be given. Examples of the substituent of the alkyl group, aryl group or heteroaryl group of R ³ , R ⁴ , R ⁹ and R ¹⁰ include the same substituents as those described above as the substituents of R ^{1 to} R ^2. Are particularly preferably a halogen atom, an alkyl group, a nitro group, an alkoxy group, an aryl group and an aryloxy group.

Further, formula (4) may form a salt form, and X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ² . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

Preferably, those not forming a salt are better than those forming a salt.
Preferred examples of the dye represented by the general formula (4) include those represented by the following structural formula.

In the general formula (5), D and D ′ each independently represent an aryl group which may have a substituent.
M ⁵ can be the same metal as described for M ¹ .
The skeleton constituting the aryl group of D and D ′ is preferably a 6-membered monocycle or a condensed ring thereof, and specifically includes a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. It is done. More preferred is an aryl group such as a benzene ring or a naphthalene ring.

Examples of the substituent of the aryl group of D and D ′ include the same substituents as those described above as the substituents of R ^{1 to} R ^2. Among them, a halogen atom, a hydroxyl group, a nitro group, A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkoxy which may have a substituent Group, an aryloxy group which may have a substituent, or an amino group which may have a substituent. More specifically, halogen atoms such as chlorine atom, bromine atom and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group A halogen atom such as a cyclohexyl group, a benzyl group, a phenethyl group or a trifluoromethyl group or an aryl group which may be substituted; an alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Groups: heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group Alkoxy group; aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, di Eniruamino group include an alkyl group and an amino group which may be substituted with a substituent selected from the group consisting of aryl groups such as methylphenylamino group.
Further, two adjacent substituents on D and D ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O—
An alkylenedioxy group having about 1 to 4 carbon atoms such as may be formed.

Formula (5) may form a salt form, and X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ² . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

In general formula (5), those forming a salt and those not forming a salt are preferred.
Preferred examples of the dye represented by the general formula (5) include those represented by the following structural formula.

In the general formula (6), R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a cyano group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an optionally substituted carbon. A hydrogen group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, preferably an optionally substituted aryl group or an optionally substituted aliphatic hydrocarbon group; is there. M ⁶ may be the same metal as described in M ¹ above.

Examples of the substituent for the aliphatic hydrocarbon group, aryl group and heterocyclic group include the same groups as those described above for R ^{1 to} R ² .
In addition, the substituents of the aryl group and heteroaryl group of R ^{11 to} R ¹⁴ are combined to form an alkylene having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —. group, -OCH ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as — or —O (CH ₂ ) ₂ O— may be formed.

Formula (6) may form a salt form, and X represents a Group 15 atom, and particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ² . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.
In general formula (6), those forming a salt and those not forming a salt are preferred.

  Preferable specific examples of the dye represented by the general formula (6) include compounds represented by the following structural formula.

In the general formula (7), E and E ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
M ⁷ can be the same metal as described for M ¹ .
The skeleton constituting the aryl group and heteroaryl group of E and E ′ is preferably a 6-membered monocyclic ring or a condensed ring thereof. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, An aryl group such as a pyrenyl group or a fluorenyl group; or a heteroaryl group such as a thienyl group, a furyl group, a pyridyl group, an imidazolyl group, a pyrazinyl group, or a pyrazolyl group. Among these, an aryl group is preferable, and an aryl group such as a benzene ring or a naphthalene ring is more preferable.

Examples of the substituent of the aryl group and heteroaryl group of E and E ′ include the same substituents as those described above as the substituents of R ^{1 to} R ^2. Nitro group, cyano group, optionally substituted alkyl group, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted. Examples thereof include an alkoxy group, an aryloxy group which may have a substituent, and an amino group which may have a substituent. More specifically, halogen atoms such as chlorine atom, bromine atom and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group A halogen atom such as a cyclohexyl group, a benzyl group, a phenethyl group or a trifluoromethyl group or an aryl group which may be substituted; an alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Groups: heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group Alkoxy group; aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, di Eniruamino group include an alkyl group and an amino group which may be substituted with a substituent selected from the group consisting of aryl groups such as methylphenylamino group.

Further, two adjacent substituents on E and E ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as-may be formed.
Formula (7) may form a salt form, and X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ² . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

In the general formula (7), those forming a salt are more preferable than those not forming a salt.
Preferred examples of the dye represented by the general formula (7) include those represented by the following structural formula.

In the general formula (8), F and F ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
M ⁸ may be the same as described for M ¹ .
The skeleton constituting the aryl group and heteroaryl group of F and F ′ is preferably a 6-membered monocyclic ring or a condensed ring thereof. Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, An aryl group such as a pyrenyl group or a fluorenyl group; or a heteroaryl group such as a thienyl group, a furyl group, a pyridyl group, an imidazolyl group, a pyrazinyl group, or a pyrazolyl group. Among these, an aryl group is preferable, and an aryl group such as a benzene ring or a naphthalene ring is more preferable.
Examples of the substituent of the aryl group and heteroaryl group of F and F ′ include the same substituents as those described above as the substituents of R ^{1 to} R ² . Halogen atom, hydroxyl group, nitro group, cyano group, optionally substituted alkyl group, optionally substituted aryl group, optionally substituted heteroaryl group, substituted Examples thereof include an optionally substituted alkoxy group, an optionally substituted aryloxy group, and an optionally substituted amino group. More specifically, halogen atoms such as chlorine atom, bromine atom and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group A halogen atom such as a cyclohexyl group, a benzyl group, a phenethyl group or a trifluoromethyl group or an aryl group which may be substituted; an alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Groups: heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group Alkoxy group; aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, di Eniruamino group include an alkyl group and an amino group which may be substituted with a substituent selected from the group consisting of aryl groups such as methylphenylamino group.

Further, two adjacent substituents on F and F ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as-may be formed.
Formula (8) may form a salt form, and X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ² . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

  In the general formula (8), those not forming a salt are more preferable than those forming a salt.

In the general formula (9), R ¹⁵ ~R ³⁰ represents an optional substituent is not particularly limited as long as they do not impair the basic performance of the compounds of the present invention, for example, as a substituent of R ¹⁵ to R ³⁰ The same groups as those mentioned can be mentioned.
M ⁹ in the general formula (9) is not particularly limited as long as it is an element capable of forming a complex with the phthalocyanine skeleton, and preferably includes a copper atom, a vanadium oxy group, or a tin chloride group.

  Among the compounds represented by the above general formula (9), preferred specific examples include JP-A-10-78509, JP-A-11-116826, JP-A-11-65463, and JP-A 2000-26748. Those described in the publication can be mentioned, and among them, fluorine-containing phthalocyanine compounds as described below are preferable.

In the general formula (10), R ³¹ and R ³² , and R ³³ and R ³⁴ each independently represent an optionally substituted aliphatic hydrocarbon group or an optionally substituted aryl group. . M ¹⁰ may be the same metal as described for M ¹ . Examples of the aliphatic hydrocarbon group and aryl group for R ^{31 to} R ³⁴ are the same as those described for R ^{1 to} R ² , and more specifically, a methyl group, an ethyl group, n- Propyl group, n-butyl group, 2-methylpropyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, neopentyl group, 2-ethylbutyl group, isopropyl group, 2-butyl group, cyclohexyl group, 3-pentyl Group, tert-butyl group, 1,1-dimethylpropyl group and the like linear, branched or cyclic alkyl group; 2-propenyl group, 2-butenyl group, 3-butenyl group, 2,4-pentadienyl group An alkynyl group such as an ethynyl group. Of these, a primary or secondary alkyl group having 10 or less carbon atoms is preferred. Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the substituent for the aliphatic hydrocarbon group and aryl group of R ^{31 to} R ³⁴ are the same as those described for R ^{1 to} R ² .
Further, R ³¹ and R ³² , and R ³³ and R ³⁴ are combined to form —CH ₂ —CH ₂ —, —CH _{2.
-CH 2 -CH 2 -, - CH} 2 -CF 2 -CH 2 -, - CH 2 -CH 2 -CH2-CH 2 -, - CH (Ph) -CH 2 -, - CH (Me) -CH 2 An optionally substituted alkylene group such as —CH—CH—, —C (Me) ═CH—, —CH═CH—CH ₂ —CH ₂ —CH═CH— and the like may be substituted; Alkenylene group; —CH ₂ —S—CH ₂ —, —CH ₂ —O—CH ₂ —, —CH ₂ —C (═O) —CH ₂ —, —CH ₂ —CH ₂ —S—CH ₂ —CH ₂ -, - CH ₂ -
An alkylene group containing a linking group such as CH ₂ —O—CH ₂ —CH ₂ — may be formed.

R ³¹ and R ³² , R ³³ and R ³⁴ are preferably unsubstituted alkyl groups or optionally substituted alkyl groups, particularly preferably unsubstituted alkyl groups, halogen atoms (particularly preferably A fluorine atom), a cyano group, an alkyl group and an aryl group which may have a substituent selected from the group consisting of an aryl group.
Formula (10) may form a salt form, and X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those exemplified as the substituents for R ^{1 to} R ² . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

  In the general formula (10), those not forming a salt are more preferable than those forming a salt. Preferable specific examples of the dye represented by the general formula (10) include those represented by the following.

In the general formula (11), R ^{35 to} R ⁴² are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Here, in R ^{35 to} R ^42, two adjacent substituents may be bonded to each other through a linking group. Specific examples of the substituent for R ^{35 to} R ⁴² are the same as those described in the description of R ¹ and R ^{2 in} the general formula (1).

R ^{35 to} R ⁴² are an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; ₂ O— or —O (CH ₂ ) ₂ O—
An alkylenedioxy group having about 1 to 4 carbon atoms such as may be formed.
X represents an anion, specifically, fluorine anion, chlorine anion, bromine anion, iodine anion, perchlorate anion, hexafluoroantimonate ion, nitrate anion, hexafluorophosphate anion, tetrafluoroborate anion. The monovalent anion represented is shown.

  Among the compounds represented by the general formula (11), preferred specific examples include JP-A-10-18092, JP-A-11-170700, JP-A2000-80071, and JP-A-2000-81511. And those described in Japanese Patent Application Laid-Open No. 2001-174626, among others, such as “Kayasorb IRG022” and “kayasarb IRG023” manufactured by Nippon Kayaku Co., Ltd., and Nippon Carlit Dyes such as those commercially available as “CIR1080”, “CIR1081”, “CIR1083” and “CIR1085” are preferred.

Here, the compounds represented by the general formulas (2) to (8) and (10) are those having a molecular weight of the ligand moiety of usually 800 or less, preferably 500 or less.
The molar extinction coefficient of the compounds represented by the general formulas (2) to (8) and (10) is usually 5000 or more, preferably 8000 or more.
The phthalocyanine compound described in the general formula (9) has a molecular weight of 900 to 3000, preferably 1000 to 2500.

Further, the molar extinction coefficient of the compound represented by the general formula (9) is usually 5000 or more, preferably 8000 or more.
The diimmonium compound described in the general formula (11) has a molecular weight of 600 to 3000, preferably 900 to 2100.
The molar extinction coefficient of the compound represented by the general formula (11) is usually 70000 or more, preferably 90000 or more.

In addition, the solubility of the compounds represented by the general formulas (2) to (11) in a solvent selected from aromatic hydrocarbon solvents such as toluene, ether solvents such as tetrahydrofuran and dimethoxyethane, and ketone solvents such as methyl ethyl ketone Is usually 0.1% or more, preferably 0.5% or more.
The above compound (2) is, for example, Russ. J. Gen. Chem., 66, 1842 (19
96), and the above compound (3) can be synthesized, for example, by the method described in JP-A No. 2001-89492. Am. Chem. Soc. 88, p. 5201 (1966). Compound (5) can be synthesized, for example, according to J. Am. Am. Chem. Soc. , 88 卷, 43 and 4870 (1966). Compound (6) can be synthesized, for example, according to J. Am. Am. Chem. Soc. , 87 卷, page 1483 (1965), and the compound (7) and the compound (8) can be synthesized, for example, by the method described in JP-A-2000-26748, For example, the compound (10) can be synthesized by the method described in The Porphyrin Handbook (2003). Mater. Chem. , P. 1861 (1994), and compound (11) can be synthesized, for example, by the method described in JP-A-61-246391.

3. Near-infrared absorption filter The near-infrared absorption filter of the present application has a maximum absorption in the vicinity of 800 to 980 nm by using the compound represented by the general formula (1). By using in combination with the compound represented, a near-infrared absorption filter covering a wavelength range of 750 to 1050 nm can be efficiently obtained. In addition, in the plasma display panel, near-infrared emission near 820 nm, 880 nm, and 980 nm is particularly strong. Therefore, it is preferable that the light transmittance of this portion is 15% or less.

Further, since the visible light transmittance is particularly 45% or more at an average transmittance of 400 to 450 nm, and the transmittance at 550 to 600 nm is 60% or more, preferably 70% or more, When used, the color reproducibility (brightness) of the scenery and the brightness of the display screen can be ensured.
The near-infrared absorption filter of the present invention is excellent in heat resistance and moist heat resistance, and after 500 hours heat resistance test in a constant temperature bath at 80 ° C. and 500 hours heat resistance in a constant temperature bath at 60 ° C. and 90% humidity. No new peak appears in the visible light region after the test.

Preferably, the filter of the present application has a dye residual ratio of 60% or more, more preferably 70% or more, more preferably 80% or more, particularly preferably 85% or more, and most preferably 90% or more in the above heat resistance test and moist heat resistance test. It will be. Here, the dye residual ratio is determined from the degree of decrease in the absorption intensity before and after the test of the maximum absorption wavelength (λmax) of the target dye in the region of 750 to 1050 nm.
Furthermore, the near-infrared absorption filter of the present invention has an excellent dye residual rate after a 280-hour light resistance test using a xenon lamp with a UV-resistant filter manufactured by Fuji Film Co., Ltd. The residual ratio is usually 70% or more, more preferably 80% or more, and still more preferably 90% or more.

(Filter manufacturing method)
Examples of the method for producing the infrared absorbing filter of the present invention include a method of coating a transparent substrate with a coating liquid containing a near infrared absorbing dye, a method of melting and kneading a near infrared absorbing dye with a binder resin, and forming a film. In order to reduce the load on the near-infrared absorbing dye, the method of coating the coating liquid is preferred.

Below, the method of apply | coating the coating liquid containing a near-infrared absorption pigment | dye to a transparent substrate and manufacturing an infrared rays absorption filter is demonstrated in detail.
(substrate)
The transparent substrate constituting the infrared absorption filter of the present invention is not particularly limited as long as it is a substrate that is substantially transparent and does not significantly absorb and scatter. Specific examples include glass, polyolefin resin, amorphous polyolefin resin, polyester resin, polycarbonate resin, poly (meth) acrylate resin, polystyrene, polyvinyl chloride, polyvinyl acetate, poly Examples include arylate resin and polyethersulfone resin. Among these, amorphous polyolefin resin, polyester resin, polycarbonate resin, poly (meth) acrylate resin, polyarylate resin, and polyethersulfone resin are particularly preferable.

These resins should contain known additives such as phenolic and phosphorus antioxidants, halogen and phosphoric acid flame retardants, heat aging inhibitors, ultraviolet absorbers, lubricants and antistatic agents. Can do.
The transparent substrate is obtained by molding these resins into a film using a molding method such as injection molding, T-die molding, calender molding, compression molding, or a method of dissolving and casting in an organic solvent. Used. The resin formed into a film may be stretched or unstretched. Moreover, the film which consists of a different material may be laminated | stacked.

The thickness of the transparent substrate is usually selected from the range of 10 μm to 5 mm depending on the purpose.
Further, the transparent substrate may be subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, or coating with an anchor coating agent or a primer. Good.
(Near-infrared absorbing dye layer)
The coating liquid containing a near infrared absorbing dye can be prepared by dissolving or dispersing the near infrared absorbing dye together with a binder resin in a solvent. Moreover, when making it disperse | distribute, a near-infrared absorption pigment | dye can also be prepared by making a particle size into 0.1-3 micrometers normally using a dispersing agent as needed, and making it disperse | distribute to a solvent with a binder.

  At this time, the concentration of the total solid content such as the near-infrared absorbing dye, the dispersant, and the binder resin dissolved or dispersed in the solvent is usually 5 to 50% by weight. Moreover, the density | concentration of the metal complex with respect to the total solid is 0.1 to 50 weight% normally as a near red absorption pigment | dye total, Preferably it is 0.2 to 30 weight%. Moreover, when using together the compound represented by General formula (2)-(11) other than the compound represented by General formula (1), you may coexist in the same layer, or it laminates | stacks as another layer The ratio of the total amount of the compounds represented by the general formulas (2) to (11) to the compound represented by the general formula (1) is 1: 0.1 to 1:10, preferably 1: 0.2-1: 5.

The concentration of the near-infrared absorber with respect to the binder resin naturally depends on the film thickness of the near-infrared absorption filter. It becomes lower than the concentration.
Examples of the dispersant include polyvinyl butyral resin, phenoxy resin, rosin-modified phenol resin, petroleum resin, cured rosin, rosin ester, maleated rosin, and polyurethane resin. The amount of its use is 0-100 weight% normally with respect to a metal complex compound, Preferably it is 0-70 weight%.

Examples of the binder include polymethyl methacrylate resin, polyethyl acrylate resin, polycarbonate resin, ethylene-vinyl alcohol copolymer resin, and polyester resin. The amount of the metal complex compound used is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on the binder.
As the solvent, halogenated aliphatic hydrocarbons such as 1,2,3-trichloropropane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, 1,2-dichloroethane, methanol, ethanol, propanol, butanol , Alcohols such as pentanol, hexanol, cyclohexanol, octanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, methyl propionate, methyl enanthate, methyl linoleate, methyl stearate, cyclohexane , Aliphatic hydrocarbons such as hexane, octane, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, nitrobenzene, squalane, dimethyl sulfoxide, sulfora Sulfoxides such as N, N-dimethylformamide, amides such as N, N, N ′, N′-tetramethylurea, tetrahydrofuran (hereinafter referred to as “THF”), dioxane, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol Ethers such as dimethyl ether and tetraethylene glycol dimethyl ether, or a mixture thereof can be used.

  Moreover, you may add near-infrared absorbers other than the above to the coating liquid containing a near-infrared absorption pigment | dye as needed. Other near-infrared absorbers include organic substances such as nitroso compounds and their metal complexes, cyanine compounds, squarylium compounds, thiol nickel complex compounds, phthalocyanine compounds, naphthalocyanine compounds, triallylmethane compounds, and immonium compounds. Compound, diimmonium compound, naphthoquinone compound, anthraquinone compound, amino compound, aminium salt compound, inorganic carbon black, indium tin oxide, antimony tin oxide, periodic table 4A, 5A or 6A group Examples thereof include metal oxides, carbides, borides, and the like.

Coating on a transparent substrate with a coating solution containing a metal complex is a known dipping method, flow coating method, spray method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, etc. It is performed by the coating method.
The layer containing the metal complex is applied so that the film thickness after drying is usually 0.1 to 30 μm, preferably 0.5 to 10 μm.

(UV cut layer)
The infrared absorption filter of the present invention can significantly improve the light resistance of the infrared absorption filter due to the synergistic effect with the metal complex by further providing an ultraviolet cut layer. The ultraviolet cut layer is capable of efficiently cutting ultraviolet rays having a wavelength of 400 nm or less, and preferably absorbs 70% or more of light having a wavelength of 350 nm. The type of the ultraviolet cut layer is not particularly limited, but a resin film (ultraviolet cut film) containing an ultraviolet absorber is preferable.

  As an ultraviolet absorber used for the ultraviolet cut layer, any organic or inorganic compound can be used without particular limitation as long as it has a maximum absorption between 300 to 400 nm and can efficiently cut light in the region. be able to. For example, the organic UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylic acid ester UV absorbers, triazine UV absorbers, paraaminobenzoic acid UV absorbers, and cinnamic acid UV absorbers. Acrylate ultraviolet absorbers, hindered amine ultraviolet absorbers and the like, and inorganic ultraviolet grade agents include titanium oxide ultraviolet absorbers, zinc oxide ultraviolet absorbers, and particulate iron oxide ultraviolet absorbers. In the case of inorganic ultraviolet absorbers, organic ultraviolet absorbers are preferred because they exist in the form of fine particles in the ultraviolet cut layer and may impair the efficiency of the infrared absorption filter.

  Examples of such ultraviolet absorbers include Tinuvin P, Tinuvin P, Tinuvin 120, 213, 234, 320, 326, 327, 328, 329, 384, 400, 571, Sumitomo Chemical Co., Ltd. , 300, 577, Kyodo Pharmaceutical Co., Ltd. Biosorb 582, 550, 591, Johoku Chemical Co., Ltd. JF-86, 79, 78, 80, Asahi Denka Co., Ltd. Adekastab LA-32, LA-36, LA- 34, Cipro Chemical Co., Ltd. Seasolv 100, 101, 101S, 102, 103, 501, 201, 202, 612NH, Otsuka Chemical Co., Ltd. RUVA93, 30M, 30S, BASF Corporation Ubinar 3039, etc. .

These ultraviolet absorbers may be used alone or in combination. In addition, fluorescent whitening agents such as Ubitex OB and OB-P manufactured by Ciba Geigy Co., Ltd. that absorb ultraviolet rays and convert the wavelength into the visible region can also be used.
The UV cut film may be a commercially available UV cut filter, such as SC-38, SC-39, SC-42 from Fuji Film Co., Ltd., acrylene from Mitsubishi Rayon Co., Ltd. or the like. . The UV cut filter, SC-39, and acrylene are both UV cut films that absorb 99% or more of the wavelength of 350 nm.

  Thus, the near-infrared absorption filter of the present invention provided with the ultraviolet ray absorption tank has a dye residual ratio of 80% or more, preferably 85% or more, particularly preferably 90 after the light resistance test by irradiating the Xe lamp for 200 hours. %, And no new absorption peak appears in the visible light region. Here, the dye residual ratio is determined from the degree of decrease in absorption intensity before and after the test in the 800 to 1100 nm region.

The near-infrared absorption filter may be used alone or as a laminate laminated with transparent glass or other transparent resin plate.
In addition to the display panel filter of the present invention, the near-infrared absorption filter obtained by the present invention can be used in a wide range of applications such as a heat ray blocking film, sunglasses, protective glasses, and a remote control receiver.

4). Filter for electronic display Further, the infrared absorption filter of the present invention includes an electromagnetic wave cut layer, an antireflection layer for preventing reflection of external light such as a fluorescent lamp on the surface, and an antiglare layer (non-glare layer) as necessary. Further, a color tone correction layer is provided, and it can be used as a filter for an electronic display, more preferably a plasma display panel.

The filter for electronic display of the present invention is not particularly limited except that the near-infrared absorption filter described above is used, and the configuration and manufacturing method used can be arbitrarily selected. The case where it is used as a filter for a display panel will be described as a representative example.
(Electromagnetic wave cut layer)
As the electromagnetic wave cut layer used in the filter for the plasma display panel of the present invention, vapor deposition of metal oxide or the like, sputtering method and the like can be used. Usually, indium tin oxide (ITO) is common, but light of 1000 nm or more can also be cut by alternately laminating a derivative layer and a metal layer on a substrate by sputtering or the like. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy, and usually three, five, and seven layers from the dielectric layer. Laminate about 11 layers. As the substrate, the infrared absorption filter of the present invention may be used as it is, or after deposition or sputtering on a resin film or glass to provide an electromagnetic wave cut layer, it may be bonded to the infrared absorption filter of the present invention. good.

(Antireflection layer)
The antireflection layer used in the plasma display panel filter of the present invention includes a metal oxide, fluoride, silicide, boride, carbide, nitride in order to suppress reflection on the surface and improve the transmittance of the filter. In addition, a method of laminating inorganic substances such as sulfides in a single layer or multiple layers by vacuum deposition, sputtering, ion plating, ion beam assist, etc., single layers of resins having different refractive indexes such as acrylic resins and fluororesins Alternatively, there is a method of laminating in multiple layers. Moreover, the film which gave the antireflection process can also be affixed on this filter.

(Color tone correction layer)
The color tone correction layer used in the plasma display panel filter of the present invention is not particularly limited as long as it can cut neon orange light in the wavelength range of 590 to 600 nm emitted from the plasma display, and is well-known squarylium compound, tetraazaporphyrin type Compounds such as compounds, cyanine compounds, methine compounds, pyromethene compounds, and dipyrromethene compounds are included. In addition, other dyes may be added so that the color of the display at the time of extinction becomes neutral gray.

(Non-glare layer)
In addition to the above layers, a glare prevention layer (non-glare layer) may be provided. In order to scatter the transmitted light, the non-glare layer may be formed by coating fine powders such as silica, melamine, and acrylic and coating the surface in order to scatter transmitted light. The ink can be cured by thermal curing or photocuring. Further, a non-glare-treated film can be stuck on the filter. Further, if necessary, a hard coat layer can be provided.

Embodiments of the present invention will be described below by way of examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
Example 1 (Production of Exemplified Compound 1)

4-phenyl- [1,3] dithiol-2-one 3 g (15.5 mmol) and diphenyl disulfide 5.06 g (23.2 mmol) were dissolved in anhydrous THF (30 mL) and cooled to -78 ° C. To this reaction solution was added LiN (TMS) ₂ hexane solution (1M, 17.2 mL) over 5 min.
The reaction solution was warmed to 0 ° C. over 2 hours and poured into an ice-saturated aqueous ammonium chloride solution. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The obtained crude product was purified by column chromatography (developing solvent; 3% ethyl acetate / hexane) to quantitatively obtain 4-phenyl-5-phenylthio- [1,3] dithiol-2-one.
EI MS; 302

To a solution of 2.4 g (13.2 mmol) of 4-phenyl-5-phenylthio- [1,3] dithiol-2-one in 25 mL of THF was added a 1M sodium methoxide-methanol solution (17 mL), and the mixture was stirred at 25 ° C. for 30 minutes. Stir for minutes. To this reaction solution, 0.5 equivalent of nickel chloride hexahydrate dissolved in 3 mL of methanol was added, and the mixture was further stirred at 25 ° C. for 30 minutes. This mixed solution was poured into a mixed solvent of 60 mL of toluene and 8.5 mL of acetic acid, and stirred for 8 hours while bubbling air. After concentrating the solvent, the resulting crude product was washed with methanol and filtered. The precipitate was washed again with ethyl acetate and filtered to obtain Exemplified Compound 1 in 1.78 g (74% yield) (λmax (in THF) 911 nm).
EI MS: 606
Example 2 (Production of Exemplified Compound 2)

The same method as in Example 1 except that 4- (2,5-dimethylphenyl)-[1,3] dithiol-2-one was used instead of 4-phenyl- [1,3] dithiol-2-one Gave 4- (2,5-dimethylphenyl) -5-phenylthio- [1,3] dithiol-2-one in 89% yield.
EI MS: 330

Others using 4- (2,5-dimethylphenyl) -5-phenylthio- [1,3] dithiol-2-one instead of 4-phenyl-5-phenylthio- [1,3] dithiol-2-one Produced Example Compound 2 in 69% yield by the same method as in Example 1 (λmax (in THF) 898 nm).
EI MS: 662
Example 3 (Production of Exemplified Compound 3)

4-Phenyl-5-n-butylthio- [1,3] dithiol-2-one was obtained in 69% yield by the same method as in Example 1 except that dibutyl disulfide was used instead of diphenyl disulfide.
EI MS: 282

Example 1 except that 4-phenyl-5-n-butylthio- [1,3] dithiol-2-one was used instead of 4-phenyl-5-phenylthio- [1,3] dithiol-2-one By a similar method, Exemplified Compound 3 was obtained in a yield of 61% (λmax (in THF) 952 nm).
EI MS: 656
Example 4 (Production of Exemplified Compound 4)

According to the same method as in Example 1, except that 4-methyl-5-phenylthio- [1,3] dithiol-2-one was used instead of 4-phenyl- [1,3] dithiol-2-one, 4 -Methyl-5-phenylthio- [1,3] dithiol-2-one was obtained in 96% yield.
EI MS: 240

The same as Example 1 except that 4-methyl-5-phenylthio- [1,3] dithiol-2-one was used instead of 4-phenyl-5-phenylthio- [1,3] dithiol-2-one. By the method, Exemplified Compound 4 was obtained in a yield of 72% (λmax (in THF) 852 nm).
EI MS: 482
Example 5 (Production of Exemplified Compound 5)

According to the same method as in Example 1, except that 4-t-butyl-5-phenylthio- [1,3] dithiol-2-one was used instead of 4-phenyl- [1,3] dithiol-2-one. 4-t-butyl-5-phenylthio- [1,3] dithiol-2-one was obtained in 86% yield.
EI MS: 282

Example 1 except that 4-t-butyl-5-phenylthio- [1,3] dithiol-2-one was used instead of 4-phenyl-5-phenylthio- [1,3] dithiol-2-one By the same method, Exemplified Compound 5 was obtained in a yield of 72% (λmax (in THF) 848 nm).
EI MS: 566
Example 6 (Production of Exemplified Compound 6)

4-t-butyl- [1,3] dithiol-2-one was used instead of 4-phenyl- [1,3] dithiol-2-one, and di (4-t-butyl-2-one was used instead of diphenyl disulfide. 4-t-butyl-5- (4-t-butyl-2-methylphenyl) thio- [1,3] dithiol-2-one was prepared in the same manner as in Example 1 except that methylphenyl) disulfide was used. Was obtained in 83% yield.
EI MS: 352

4-t-butyl-5- (4-t-butyl-2-methylphenyl) thio- [1,3] dithiol in place of 4-phenyl-5-phenylthio- [1,3] dithiol-2-one
Except that 2-one was used, Exemplified Compound 6 was obtained in a 77% yield by the same method as in Example 1 (λmax (in THF) 876 nm).
EI MS: 706
Example 7 (Production of Exemplified Compound 24)

3.2 g (16.5 mmol) of 4-phenyl- [1,3] dithiol-2-one and 3.3 mL (24.8 mmol) of trimethylsilyl chloride were dissolved in anhydrous THF (20 mL), and -78
Cooled to ° C. To this reaction solution was added LiN (TMS) 2 hexane solution (1M, 17.2 mL) over 5 minutes. The reaction solution was heated to 0 ° C. over 2 hours and poured into an ice-saturated aqueous ammonium chloride solution. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The resulting crude product was purified by column chromatography (developing solvent; 5% ethyl acetate / hexane) to give 4-phenyl-5-trimethylsilyl- [1,3] dithiol-2-one in 95% yield. It was.
EI MS; 266

To a solution of 2.1 g (7.89 mmol) of 4-phenyl-5-trimethylsilyl- [1,3] dithiol-2-one in 25 mL of THF was added 1M sodium methoxide-methanol solution (17 mL), and the mixture was stirred at 25 ° C. for 30 minutes. Stir for minutes. To this reaction solution, 0.5 equivalent of nickel chloride hexahydrate dissolved in 3 mL of methanol was added, and the mixture was further stirred at 25 ° C. for 30 minutes. This mixed solution was poured into a mixed solvent of 60 mL of toluene and 8.5 mL of acetic acid, and stirred for 8 hours while bubbling air. After concentrating the solvent, the resulting crude product was washed with methanol and filtered. The precipitate was dissolved in chloroform, and the organic layer was washed with saturated brine and then concentrated. The obtained solid was again washed with methanol and filtered to obtain Exemplary Compound 24 in 1.71 g (81% yield). (Λmax (in THF) 818 nm).
EI MS: 534
Example 8 (Solubility of Compounds of the Invention)
The solubility of Exemplified Compound 5 produced in Example 5 in toluene and methyl ethyl ketone was measured. The solubility was measured at 25 ° C. The results are shown in Table 1.

Comparative Example 1 (Solubility of Known Dithiol Metal Complex)
The solubility of a known dithiol metal complex represented by the following formula (A) used in Example 1 of JP-A-2002-132176 in toluene and methyl ethyl ketone was measured. The results are shown in Table 1.

Comparative Example 2 (Solubility of Known Dithiol Metal Complex)
The solubility of a known dithiol metal complex represented by the following formula (B) used in Example 2 of JP-A-64-669686 in toluene and methyl ethyl ketone was measured. The results are shown in Table 1.

From the above results, it can be seen that when a near-infrared absorbing filter is produced using the compound of the present invention as a near-infrared absorbing dye, the solubility is high. Therefore, according to the present invention, it can be seen that a large amount of pigment can be contained in a small amount of resin, and as a result, the near-infrared absorption filter can be thinned.
Example 9 (Near-infrared absorption filter containing Exemplified Compound 1)
Illustrative compound 1 (34.3 mg) was added to 0.80 g of toluene, and 3.2 g of a MEK / toluene (= 1/1) solution of acrylic resin (Optreso OZ1100) (resin concentration 25 wt%) was added to these. After adding, dissolving by applying ultrasonic waves, and filtering, this coating solution is applied to a polyethylene terephthalate film with a bar coater (No. 18; manufactured by Eto Kikai Co., Ltd.) and dried to obtain near infrared rays. An absorption filter was obtained.

Λmax of this filter was 911 nm.
Furthermore, in order to evaluate heat resistance and moist heat resistance, the test was conducted for 500 hours in a constant temperature bath at 80 ° C. and a constant temperature layer at 60 ° C. and 90% humidity (measurement of absorption strength before and after the test at 911 nm). ), The residual ratio of the dye (strength after the test ÷ strength before the test × 100) was 95.1% and 99.3%, respectively, indicating good heat resistance and moist heat resistance, and the color change of the filter was There wasn't.

Example 10 (Near-infrared absorption filter containing Exemplified Compound 2)
A near-infrared absorption filter was obtained in the same manner as in Example 9 except that Illustrative Compound 2 was used.
Λmax of this filter was 897 nm.
When heat resistance and heat-and-moisture resistance tests (measurement of absorption intensity before and after the test at 897 nm) were performed in the same manner as in Example 9, the residual dye ratios were 95.5% and 99.7%, respectively, and good heat resistance And resistance to wet heat, and there was no color change of the filter.

Example 11 (Near-infrared absorption filter containing Exemplified Compound 3)
A near-infrared absorption filter was obtained in the same manner as in Example 9 except that the exemplified compound 3 was used.

This filter had a λmax of 946 nm.
When heat resistance and heat-and-moisture resistance tests (measurement of absorption strength before and after the test at 946 nm) were performed in the same manner as in Example 9, the residual dye ratios were 94.5% and 100.0%, respectively, and good heat resistance And resistance to wet heat, and there was no color change of the filter.

Example 12 (Near-infrared absorption filter containing Exemplified Compound 4)
A near-infrared absorption filter was obtained in the same manner as in Example 9 except that the exemplified compound 4 (34.3 mg) was used.
This filter had a λmax of 855 nm.
When heat resistance and heat-and-moisture resistance tests (measurement of absorption intensity before and after the test at 855 nm) were performed in the same manner as in Example 9, the residual dye ratios were 90.7% and 93.1%, respectively, and good heat resistance And resistance to wet heat, and there was no color change of the filter.

Example 13 (Near-infrared absorption filter containing Exemplified Compound 5)
A near-infrared absorption filter was obtained in the same manner as in Example 9 except that Example Compound 5 (34.3 mg) was used.

This filter had a λmax of 844 nm.
When heat resistance and moist heat resistance tests (measurement of absorption intensity before and after the test at 844 nm) were conducted in the same manner as in Example 9, the residual dye ratios were 96.2% and 100%, respectively, and good heat resistance and It showed resistance to moist heat, and there was no color change of the filter.

Example 14 (Near-infrared absorption filter containing Exemplified Compound 6)
A near-infrared absorbing filter was obtained in the same manner as in Example 9 except that the exemplified compound 6 (34.3 mg) was used.
Λmax of this filter was 875 nm.
When heat resistance and moist heat resistance tests (measurement of absorption intensity before and after the test at 875 nm) were carried out in the same manner as in Example 9, the residual dye ratios were 94.8% and 99.7%, respectively, and good heat resistance And resistance to wet heat, and there was no color change of the filter.

Example 15 (Near-infrared absorption filter containing Exemplified Compound 24)
A near-infrared absorption filter was obtained in the same manner as in Example 9 except that Exemplified Compound 24 (34.3 mg) (34.3 mg) was used.

Λmax of this filter was 822 nm.
When heat resistance and moist heat resistance tests (measurement of absorption intensity before and after the test at 822 nm) were performed in the same manner as in Example 9, the residual dye ratios were 94.1% and 97.7%, respectively, and good heat resistance And resistance to wet heat, and there was no color change of the filter.

Comparative Example 3 (Near-infrared absorption filter containing a compound of formula (A))
A near-infrared absorption filter was obtained in the same manner as in Example 9 except that the compound represented by the formula (A) used in Comparative Example 1 (34.3 mg) was used.
This filter had a λmax of 856 nm.
When heat resistance and heat-and-moisture resistance tests (measurement of absorption strength before and after the test at 856 nm) were performed in the same manner as in Example 9, the dye residual ratios were 96.5% and 98.7%, respectively.

Comparative Example 4 (Near-infrared absorption filter containing a compound of formula (B))
A near-infrared absorption filter was obtained in the same manner as in Example 9 except that the compound represented by the formula (B) used in Comparative Example 2 (34.3 mg) was used.
Λmax of this filter was 1007 nm.
When heat resistance and heat-and-moisture resistance tests (measurement of absorption intensity before and after the test at 1007 nm) were carried out in the same manner as in Example 9, the dye residual ratios were 85.3% and 88.9%, respectively.

  The results of the heat resistance and moist heat resistance tests of the near infrared absorption filter are summarized in Table 2 below.

From the above results, it is clear that the near-infrared absorption filter using the compound of the present invention as a near-infrared absorbing dye is excellent in heat resistance and moist heat resistance with respect to the compound of formula (B).
Example 16 (Near-infrared absorption filter containing Compound represented by Exemplary Compound 4 and General Formula (6))
Compound (99.0 mg) represented by the following formula represented by Exemplary Compound 4 (68.2 mg) and General Formula (6)

Add to 3.0 g of tetrahydrofuran, add 8.0 g of tetrahydrofuran solution (resin concentration 30% by weight) of acrylic resin (Optreso OZ1100), dissolve with ultrasonic waves, filter, and apply this coating. The liquid was applied to a polyethylene terephthalate film with a bar coater (No. 18; manufactured by Eto Kikai Co., Ltd.) and dried to obtain a near infrared absorption filter.

This filter had an average transmittance of 800 to 1100 nm of 13.4%, and effectively shielded the region of 800 to 1100 nm as a near infrared absorption filter for PDP. (Figure 1)
Furthermore, in order to evaluate the heat resistance and the heat and humidity resistance, a heat resistance and a heat and humidity resistance test were conducted for 500 hours in a constant temperature bath at 80 ° C. and a constant temperature layer at 60 ° C. and a humidity of 90%. The region of 1100 nm was effectively shielded, and there was no color change of the filter. (Fig. 2, Fig. 3)
A UV cut filter (SC-42) manufactured by Fuji Photo Film Co., Ltd. was attached to this filter, and irradiated for 280 hours with a xenon long life fade meter (FAL-25AX-HCB-EC) (product of Suga Test Instruments Co., Ltd.). When measured after the test, the region of 800 to 1100 nm was effectively shielded, and there was no filter color change. (Fig. 4)

It is a transmission spectrum of the near-infrared absorption filter of Example 16. It is a transmission spectrum after the heat resistance test of the near-infrared absorption filter of Example 16. It is the transmission spectrum after the heat-and-moisture resistance test of the near-infrared absorption filter of Example 16. It is the transmission spectrum after the light resistance test of the near-infrared absorption filter of Example 16.

Claims (6)

The following general formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group. X ¹ and X ² each independently represent —X (—R) _(n−1) (X Represents an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom, R represents a hydrogen atom or a monovalent organic group, a plurality of Rs may be the same or different, and n represents the valence of X. R ¹ and X ¹ and R ² and X ¹ may each independently form a ring via a linking group, and M ¹ represents a metal atom. A near-infrared absorption filter comprising a compound represented by: The following general formula (2),

(In the formula, A and A ′ each independently represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ⁵ and R ⁶ each represents Independently, an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom .) Here, R ⁵ and R ⁶ may be connected to each other directly or via a linking group. Alternatively, XRR′R ″ R ′ ″ R ″ ″ may be coordinated with formula (2) to take a salt form.
Here, X represents Group 15, and R ′, R ″, R ′ ″, R ″ ″ represents an aliphatic hydrocarbon group which may have a substituent, or a substituent. The aryl group which may have is shown. M ² represents a metal atom. ), A compound represented by the following general formula (3)

(In the formula, B and B ′ each independently represent an aliphatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, and R ⁷ and R ^8. Each independently represents an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or hydrogen. Here, R ⁷ and R ⁸ may be bonded to each other directly or via a linking group. Alternatively, XRR′R ″ R ′ ″ R ″ ″ may coordinate to formula (3) to take a salt form.
Here, X represents Group 15, and R ′, R ″, R ′ ″, R ″ ″ represents an aliphatic hydrocarbon group which may have a substituent, or a substituent. The aryl group which may have is shown. M ³ represents a metal atom. ), The following general formula (4)

(In the formula, C and C ′ each independently represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ³ and R ⁴ and R ^9. And R ¹⁰ are each independently an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, Alternatively, it represents a hydrogen atom.) Here, R ³ and R ^4, and R ⁹ and R ¹⁰ may be connected to each other directly or via a linking group. Alternatively, XRR′R ″ R ′ ″ R ″ ″ may coordinate to formula (4) to take a salt form. Here, X represents Group 15, and R ′, R ″, R ′ ″, R ″ ″ are aliphatic hydrocarbon groups which may have a substituent, or substituents An aryl group which may have M ⁴ represents a metal atom. ), A compound represented by the following general formula (5)

(In the formula, D and D ′ each independently represents an aryl group which may have a substituent.) Or, XRR′R ″ R ′ ″ R ′ ″ in the formula (5) 'May coordinate and take a salt form. Here, X represents Group 15, and R ′, R ″, R ′ ″, R ″ ″ represents an aliphatic hydrocarbon group which may have a substituent, or a substituent. The aryl group which may have is shown. M ⁵ represents a metal atom. ), A compound represented by the following general formula (6)

Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a cyano group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a substituted group. A good aliphatic hydrocarbon group, an optionally substituted aryl group or an optionally substituted heterocyclic group, wherein R ^{11 to} R ¹⁴ are adjacent two substituents via a linking group; Alternatively, XRR′R ″ R ′ ″ R ″ ″ may be coordinated to formula (6) to form a salt form, where X represents Group 15 and R ', R ″, R ′ ″, R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent. ⁶ represents a metal atom) and the following general formula (7)

(In the formula, E and E ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.) Or in formula (7) XRR′R ″ R ′ ″ R ″ ″ may be coordinated to take a salt form. Here, X represents Group 15, and R ′, R ″, R ′ ″, R ″ ″ represents an aliphatic hydrocarbon group which may have a substituent, or a substituent. The aryl group which may have is shown. M ⁷ represents a metal atom. ), A compound represented by the following general formula (8)

(In the formula, F and F ′ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent.) Or in formula (8) XRR′R ″ R ′ ″ R ″ ″ may be coordinated to take a salt form. Here, X represents Group 15, and R ′, R ″, R ′ ″, R ″ ″ represents an aliphatic hydrocarbon group which may have a substituent, or a substituent. The aryl group which may have is shown. M ⁸ represents a metal atom. ), A compound represented by the following general formula (9)

(Wherein R ^{15 to} R ³⁰ each independently represents an arbitrary substituent, and two adjacent substituents may form a ring via a linking group. M ⁹ is a hydrogen atom or a metal An atom (wherein the metal atom may be a metal oxide, a metal halide or a metal carbonyl compound, or may form a salt with an acid). Compound, the following general formula (10)

(Wherein R ^{31 to} R ³⁴ each independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group or an optionally substituted heterocyclic group, R ^{31 to} R ³⁴ may be combined to form a ring through a linking group, if necessary, M ¹⁰ represents a metal atom, or XRR′R ′ in formula (10) 'R''' R '''' may be coordinated to take a salt form, where X represents Group 15, and R ', R'',R''', R '''' are , An aliphatic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent. M ⁶ represents a metal atom), and Formula (11)

(In the formula, R ^{35 to} R ⁴² each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Here, R ^{35 to} R ⁴² may be those in which two adjacent substituents may be connected via a linking group, and Y ⁻ represents an anion. The near-infrared absorption filter according to claim 1, further comprising at least one of selected compounds.   The near-infrared absorption filter according to claim 1, further comprising an ultraviolet cut layer.   The filter for electronic displays using the near-infrared absorption filter of any one of Claims 1-3. The following general formula (1)

(In the formula, R ¹ and R ² each independently represent a monovalent organic group. X ¹ and X ² each independently represent —X (—R) _(n−1) (X represents an oxygen atom ₎ , A nitrogen atom, a sulfur atom, a silicon atom or a halogen atom, R represents a hydrogen atom or a monovalent organic group, a plurality of R may be the same or different, and n represents the valence of X.) R ¹ and X ¹ and R ² and X ¹ may each independently form a ring via a linking group, and M ¹ represents a metal atom. A compound represented by   A near-infrared absorbing dye comprising the compound according to claim 5.

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