JP4632930B2 - Near infrared absorption filter - Google Patents

Description

  The present invention relates to a near-infrared absorbing filter, and more particularly to a near-infrared absorbing filter that blocks a wide range of near-infrared rays.

In general, plastic near-infrared absorption filters made of a resin containing a near-infrared absorption pigment are well known, and their uses include 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 the near-infrared absorption filter as described above, those containing metal ions such as copper and iron, nitroso compounds and metal complex salts thereof, cyanine compounds, squarylium compounds, dithiol metal complexes, aminothiophenol metals Included near-infrared absorbing dyes such as complex compounds, phthalocyanine compounds, naphthalocyanine compounds, triarylmethane compounds, immonium compounds, diimonium compounds, naphthoquinone compounds, anthraquinone compounds, amino compounds, aminium salt compounds Various studies have been made (see, for example, Patent Document 1 and Patent Document 2), but in practice, only a part of limited dithiol-based metal complex compounds, phthalocyanine compounds, and diimmonium compounds are used.

Such a near-infrared absorbing dye cannot cover the above-mentioned range of 800 to 1100 nm with only one kind of dye, and usually a plurality of dyes are used in combination. At this time, in view of labor and cost during production, a filter in which a plurality of types of pigments are mixed and contained in the same resin layer is preferable.
JP 2003-262719 A JP-A 64-69686

  In order to obtain a filter that absorbs a wide range of near-infrared rays by mixing pigments that absorb different wavelengths, the present inventors have described two types of near-infrared-absorbing pigments in the same resin layer, specifically described in Patent Document 1. The dithiol metal complex compound and the dithiol metal complex compound substituted with an alkylthio group described in Patent Document 2 were mixed and measured for near infrared absorption characteristics. As a result, the near infrared absorption region changed, It became clear that the intended absorption could not be obtained.

  Therefore, to provide a near-infrared absorbing dye that has excellent light resistance and heat resistance, and whose absorption wavelength does not change even when mixed with other dyes, and a near-infrared absorbing filter containing the same, particularly a near-infrared absorbing filter for electronic displays. Let it be an issue.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a dithiolate metal complex having a specific asymmetric structure represented by the general formula (1), thereby completing the present invention. I let you.
That is, the gist of the present invention is the following general formula (1).

[Wherein R ¹ is a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a silyl group which may have a substituent, a hydrogen atom, a cyano group. Or a halogen atom is shown. R ² has a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a hydrocarbon thio group which may have a substituent, and a substituent. Or a good silyl group, hydrogen atom, cyano group or halogen atom. Y ¹ and Y ² each independently represent a hydrocarbon group which may have a substituent. Here, R ¹ and R ² and Y ¹ and Y ² may form a ring via a linking group. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated to formula (1) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ¹ represents a metal atom. ]
A near-infrared absorbing dye comprising a compound represented by formula (1), a near-infrared absorbing filter having a layer containing the compound, and a filter for electronic display using the near-infrared absorbing filter.

  According to the present invention, near-infrared absorbing dyes that have excellent light resistance and heat resistance and do not change the absorption wavelength even when mixed with other dyes, particularly near infrared rays that do not change the absorption wavelength even when mixed with dithiolate dyes. An absorption dye and a near-infrared absorption filter that absorbs a wide range of near-infrared rays with little alteration are provided.

Hereinafter, the present invention will be described in detail.
(Compound represented by the general formula (1))
In the general formula (1), R ¹ represents a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a silyl group which may have a substituent, hydrogen. An atom, a cyano group or a halogen atom.

  Examples of the hydrocarbon group include 1) an aliphatic hydrocarbon group; a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a 2-methylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, and a cyclohexylmethyl group. Linear, branched or cyclic alkyl such as neopentyl, 2-ethylbutyl, isopropyl, 2-butyl, cyclohexyl, 3-pentyl, tert-butyl, 1,1-dimethylpropyl Groups; alkenyl groups such as 2-propenyl group, 2-butenyl group, 3-butenyl group and 2,4-pentadienyl group; and alkynyl groups such as ethynyl group. Among these, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, and a branched chain aliphatic hydrocarbon group having 1 to 10 carbon atoms is particularly preferable. 2) Aryl group; phenyl group, naphthyl group, anthranyl group, fluorenyl group, phenanthrenyl group, azulenyl group, metallocene ring group and the like can be mentioned. Among these, a monocyclic or condensed bicyclic aryl group having 6 to 12 carbon atoms is preferable. 3) Heterocyclic group: thienyl group, furyl group, pyrrolyl group, pyridyl group, imidazolyl group, pyrazolyl group, indolyl group, quinoxalinyl group, acridinyl group, thiazolyl group, pyrazinyl group and the like. Of these, a monocyclic or bicyclic 5-membered heterocyclic group having 3 to 12 carbon atoms is preferable.

  Examples of the carbonyl group include an acyl group (—COR), a carbamoyl group (—CONRR ′), an alkoxycarbonyl group (—C (O) OR), an aryloxycarbonyl group (—C (O) OR), and a heterocyclic oxycarbonyl group. (—C (O) OR), and more specifically, R of the acyl group (—COR) and R and R ′ of the carbamoyl group (—CONRR ′) are the aliphatic groups listed above. Examples of the hydrocarbon group, aryl group and heterocyclic group are the same as those described above, and R of the alkoxycarbonyl group (—C (O) OR) is the same as the specific examples of the aliphatic hydrocarbon group described above. R of the aryloxycarbonyl group (—C (O) OR) is the same as the specific examples of the aryl group described above, and the heterocyclic oxycarbonyl group (—C (O)) OR) R first Was like are exemplified as the specific examples of the heterocyclic group, a substituted group is an aldehyde group is hydrogen.

Examples of the silyl group include silyl groups such as a trimethylsilyl group, a t-butyldiphenylsilyl group, an n-butyldimethylsilyl group, a dimethylethylsilyl group, a dimethylphenylsilyl group, a dimethylisopropylsilyl group, and a triisopropylsilyl group. An alkylsilyl group having 1 to 18 carbon atoms is preferred.
Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Particularly preferred are a fluorine atom and a chlorine atom.
R ² has a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a hydrocarbon thio group which may have a substituent, and a substituent. Also good silyl group, hydrogen atom, cyano group or halogen atom.

Examples of the hydrocarbon group include the same hydrocarbon groups as those exemplified for R ¹ .
Examples of the hydrocarbon thio group include: 1) alkylthio group; n-propylthio group, n-butylthio group, 2-methylpropylthio group, 2-methylbutylthio group, 3-methylbutylthio group, cyclohexylmethylthio group, neopenty Linear, branched or cyclic alkyl groups such as ruthio group, 2-ethylbutylthio group, isopropylthio group, 2-butylthio group, cyclohexylthio group, 3-pentylthio group, 1,1-dimethylpropylthio group Among them, preferred is an alkylthio group having 10 or less carbon atoms, and particularly preferred is a branched alkylthio group having 10 or less carbon atoms. 2) Alkenylthio group; propenylthio group, vinylthio group, isopropenylthio group, styrylthio group and the like can be mentioned. Among them, alkenylthio group having 12 or less carbon atoms is preferable. Examples of the alkynylthio group include an ethynylthio group, a 1-pentenylthio group, a phenethynylthio group, and a t-butylethynyl group, and among them, an alkynylthio group having 12 or less carbon atoms is preferable. 3) Arylthio group: phenylthio group, p-tert-butylphenylthio group, o-tolylthio group, mesitylthio group, xylylthio group, cumenylthio group, naphthylthio group, etc., preferably monocyclic or two-membered having 12 or less carbon atoms An arylthio group consisting of a ring. 4) Heterocyclic thio group; a thienylthio group, a furylthio group, a pyrazolylthio group, a pyrrolylylthio group, an isoxazolylthio group, a pyridylthio group, an indoleylthio group, and the like. It is a ring thio group. Examples of the carbonyl group include those similar to the specific examples of the carbonyl group exemplified for R ¹ . Examples of the silyl group include those similar to the specific examples of the silyl group exemplified for R ¹ . Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Particularly preferred are a fluorine atom and a chlorine atom.

Y ¹ and Y ² are each independently a hydrocarbon group which may have a substituent, specifically, 1) an aliphatic hydrocarbon group; an aliphatic hydrocarbon group exemplified as R ¹ 2) aryl group; the same as the specific examples of the aryl group represented by R ¹ , and 3) the heterocyclic group; the specific examples of the heterocyclic group represented by R ¹ Some examples are the same.
The hydrocarbon group and carbonyl group and silyl group substituent of R ^1, the hydrocarbon group and hydrocarbon thio group and the carbonyl group and silyl group substituent of R ² , and the Y ¹ and Y ² substituents The substituent of the hydrocarbon group is not particularly limited as long as it does not adversely affect the stability of the metal complex. For example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an 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, sulfonamide group, carbamoyl group, Sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryl Le oxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, heteroarylsulfonyl group, an imide group and a group selected from the group consisting of silyl groups.

  Specifically, an alkyl group having about 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having about 1 to 6 carbon atoms such as an ethynyl group or a propylenyl group; an alkynyl group having about 1 to 6 carbon atoms such as an acetylenyl group An aryl group having about 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a heteroaryl group having about 3 to 20 carbon atoms such as a thienyl group, a furyl group or a pyridyl group; 1 to 1 carbon atoms such as an ethoxy group or a propoxy group; An alkoxy group of about 6; an aryloxy group of about 6 to 20 carbon atoms such as a phenoxy group and a naphthoxy group; a heteroaryloxy group of about 3 to 20 carbon atoms such as a pyridyloxy group and a thienyloxy group; a methylthio group; Alkylthio group having about 1 to 6 carbon atoms such as ethylthio group; aryl having about 6 to 20 carbon atoms such as phenylthio group and naphthylthio group O group; heteroarylthio group having about 3 to 20 carbon atoms such as pyridylthio group and thienylthio group; amino optionally having a substituent having about 1 to 20 carbon atoms such as dimethylamino group and diphenylamino 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 2 to 20 carbon atoms such as a 3-methylureido group About 1 to 20 carbon atoms such as methanesulfonamide group and benzenesulfonamide group; about 1 to 20 carbon atoms such as dimethylcarbamoyl group and ethylcarbamoyl group; ethylsulfamoyl group A sulfamoyl group having about 1 to 20 carbon atoms, such as a group; A sulfamoylamino group having about 1 to 20 prime atoms; an alkoxycarbonyl group having about 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; an aryl having about 7 to 20 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group Oxycarbonyl group; heteroaryloxycarbonyl group having about 6 to 20 carbon atoms such as pyridyloxycarbonyl group; alkylsulfonyl group having about 1 to 6 carbon atoms such as methanesulfonyl group, ethanesulfonyl group and trifluoromethanesulfonyl group; benzenesulfonyl Group, arylsulfonyl group having about 6 to 20 carbon atoms such as monofluorobenzenesulfonyl group; heteroaryloxysulfonyl group having about 3 to 20 carbon atoms such as thienylsulfonyl group; imide group having about 4 to 20 carbon atoms such as phthalimide ;or Includes a silyl group that is trisubstituted with a substituent selected from the group consisting of an alkyl group and an aryl group.

Particularly preferably, R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a substituent, a monocyclic aryl group having 6 to 12 carbon atoms which may have a substituent, A 5-membered ring heterocyclic group having 3 to 10 carbon atoms, which may have a substituent, a cyano group, a fluorine atom, a chlorine atom, or a hydrogen atom, most preferably 1 or more carbon atoms An alkyl group having a halogen atom as a substituent of 10 or less, a monocyclic aryl group having a total carbon number of 6 to 12 and optionally having a substituent, a substituent having a total carbon number of 3 to 10 And a 5-membered ring heterocyclic group, a cyano group, a fluorine atom, a chlorine atom, or a hydrogen atom.

R ² is particularly preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a monocyclic aryl group having 6 to 12 carbon atoms which may have a substituent. An alkylthio group having 3 to 10 carbon atoms, which may have a substituent, an aryl group having 6 to 15 carbon atoms, which may have a substituent, or a group having 3 to 18 carbon atoms in total , A silyl group which may have a substituent, a cyano group, a fluorine atom, a chlorine atom or a hydrogen atom, most preferably as a substituent having a total carbon number of 1 to 10 An alkyl group having a halogen atom, a monocyclic aryl group having 6 to 12 carbon atoms in total, which may have a substituent, an alkylthio group having 3 to 10 carbon atoms in total which may have a substituent, a total Ali which may have a substituent having 6 to 15 carbon atoms Group or a total carbon number of 3 to 18 substituents silyl group which may have a or a cyano group, or a fluorine atom, or a chlorine atom, or a hydrogen atom.

In order to increase the stability of the compound of general formula (1) itself, R ¹ and / or R ² is selected from the carbon atom, oxygen atom, sulfur atom, nitrogen atom, and silicon atom at the ortho position of the aryl group. An aryl group having at least 4 substituents in which the total of at least one atom is preferred. Specific examples of the substituent include a branched alkyl group which may further have a substituent, and a branched alkoxy group which may further have a substituent.

Y ¹ and Y ² are each independently and particularly preferably an alkyl group which may have a substituent having a total carbon number of 10 or less, or a substituent having a total carbon number of 12 or less. It is a monocyclic aryl group or a 5-membered heterocyclic group which may have a substituent having a total carbon number of 10 or less. Particularly preferred is a branched alkyl group having a total carbon number of 10 or less.
Further, the R ¹ and R ^2, and Y ¹ and Y ² are, -CH ₂ -CH ₂ connected to each other _{-, - CH 2 -CH 2 -CH} 2 -, CH 2 -CH 2 -CH 2 -CH 2 -, - CH (Ph) -CH 2 -, - CH (Me) -CH 2 - alkylene group which may have a substituent such as; -CH = CH -, - C (Me) = CH-, _{-CH = CH-CH 2 -CH 2} -CH = CH- may alkenylene group which may have a substituent such _{as; -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 -CH 2 -O-CH 2 -CH 2 - groups such as to form It may be a ring structure.

Moreover, in the compound represented by the general formula (1), Y ¹ and Y ² may be the same or different, but are preferably the same. R ¹ and R ² may be the same or different from each other, but are preferably different.
The compound represented by the general formula (1) may take a salt form by coordination of XRR ′ R ″ R ′ ″ R ″ ″. X represents a Group 15 atom, and particularly preferably a nitrogen atom or a phosphorus atom. R ′, R ″, R ′ ″ and R ″ ″ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. is there. Examples of the aliphatic hydrocarbon group and aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group and aryl group for R ¹ . In addition, examples of the substituent for the aliphatic hydrocarbon group and aryl group include the same substituents as those exemplified as the substituent for R ¹ . R ′, R ″, R ′ ″, R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group, n-hexyl. Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as benzyl group and phenethyl group.

As the compound of the general formula (1) according to the present invention, a compound that does not form a salt is preferable to a compound that forms a salt.
M ¹ is not particularly limited as long as it is a metal atom that can take a tetracoordinate form, but preferably includes a group 10 metal atom of Ni, Pd, or Pt; Co; Fe; Cu; Ag; Au or Zn, More preferred is a group 10 metal atom, and particularly preferred is 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.

  Such a compound represented by the general formula (1) is, for example, Mol. Cryst. Liq. Crst. (Lett), 56, 249 (1980), a 1,3-dithiol-2-one derivative is obtained by a known method, and then metallized to obtain a symmetric metal complex. On the other hand, for example, J.A. Mat. Chem. 1, 2, 443 (1992), etc., to obtain a 1,3-dithiol-2-one-4,5-dithiolate derivative and then metallize to obtain a symmetric metal complex. From the obtained two types of symmetrical metal complexes, stirring in an organic solvent (specifically, toluene, xylene, dioxane, dichloroethane, THF, dimethoxyethane, etc.) at room temperature to reflux for about 30 minutes to 24 hours, It converts into the compound represented by General formula (1). Refluxing is preferably performed in THF because the ligand exchange reaction is promoted. Further, the absorption maximum wavelength is about 800 nm to about 980 nm.

(Compounds represented by general formulas (2) to (9))
The near-infrared absorption filter of the present invention further contains at least one compound selected from the group consisting of compounds represented by the following general formulas (2) to (9), thereby allowing the near-infrared filter in the range of 750 to 1050 nm. Since it can absorb a wide infrared region, it is particularly preferred when used for a filter for an electronic display.

In the general formula (2), A and A ′ each independently represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
R ⁵ and R ⁶ are each independently an aliphatic hydrocarbon group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic ring that may have a substituent. A group or a hydrogen atom is shown. Here, R ⁵ and R ⁶ may be linked directly or via a linking group. M ² can be the same metal as described for M ¹ .

  The skeleton constituting the aryl group and heterocyclic 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 a monocyclic or 2-membered cyclic aryl group such as a benzene ring and a naphthalene ring is more preferable.

Examples of the substituent of the aryl group and heterocyclic group of A and A ′ include the same substituents as those described above as the substituent of R ^1. Among them, preferred are a halogen atom, a hydroxyl group, and 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, 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 and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group, cyclohexyl group An alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom such as benzyl group, phenethyl group or trifluoromethyl group or an aryl group; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group An aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, diphenyl Mino 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 An alkylenedioxy group having about 1 to 4 carbon atoms such as ₂ O— or —O (CH ₂ ) ₂ O— may be formed.
Examples of the aliphatic hydrocarbon group for R ⁵ and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a 2-methylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, and a cyclohexylmethyl group. Linear, branched or cyclic alkyl groups such as neopentyl group, 2-ethylbutyl group, isopropyl group, 2-butyl group, cyclohexyl group, 3-pentyl group, 1,1-dimethylpropyl group; 2-propenyl Groups, alkenyl groups such as 2-butenyl group, 3-butenyl group and 2,4-pentadienyl group; alkynyl groups such as ethynyl 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 aliphatic hydrocarbon group of R ⁵ and R ⁶ include the same substituents as those described above as the substituent for R ¹ , and particularly preferably an unsubstituted, halogen atom (especially Preferably a fluorine atom), a cyano group, an alkoxy group and an aryl group.
The aryl group and heterocyclic 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 in which Hammett's substituent constant σm is 0.00 <σm <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.

The compound represented by the general formula (2) may be in a salt form by coordination of XR ′ R ″ R ′ ″ R ″ ″. Here, X represents a Group 15 atom, and particularly preferably a nitrogen atom or a phosphorus atom. R ′, R ″, R ′ ″ and R ″ ″ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. is there. Examples of the aliphatic hydrocarbon group and aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group and aryl group for R ¹ . In addition, examples of the substituent for the aliphatic hydrocarbon group and aryl group include the same substituents as those exemplified as the substituent for R ¹ . R ′, R ″, R ′ ″, R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group, n-hexyl. Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as benzyl group and phenethyl 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 heterocyclic group which may have a substituent.
R ⁷ and R ⁸ are each independently an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic ring which may have a substituent. A group or a hydrogen atom is shown. Here, R ⁷ and R ⁸ may be connected to each other directly or via a linking group. M ³ can be the same metal as described for M ¹ .

  The skeleton constituting the aryl group and heterocyclic 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 of the aryl group and heterocyclic group of B and B ′ include the same substituents as those described above as the substituent of R ^1. Among them, preferred are a halogen atom, a hydroxyl group, and 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, 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 and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group, cyclohexyl group An alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom such as benzyl group, phenethyl group or trifluoromethyl group or an aryl group; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group An aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, diphenyl Amino group, 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 An alkylenedioxy group having about 1 to 4 carbon atoms such as ₂ O— or —O (CH ₂ ) ₂ O— may be formed.
Examples of the aliphatic hydrocarbon group, aryl group or heterocyclic group for R ⁷ and R ⁸ are the same as those described above for the aliphatic hydrocarbon group, aryl group or heterocyclic group for R ⁵ and R ^6. Is given. Examples of the substituent for the aliphatic hydrocarbon group, aryl group or heterocyclic group for R ⁷ and R ⁸ include the same substituents as those described above as the substituent for R ¹ . 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 bonded to each other directly or via a linking group, but particularly preferred is a case having the following structure.

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, Carbon number which may be substituted with halogen atoms or aryl groups such as i-butyl group, t-butyl group, n-butyl group, n-pentyl group, trichloromethyl group, trifluoromethyl group, benzyl group, phenethyl group 1-10 alkyl groups; phenyl groups; methoxy groups, ethoxy groups, propoxy groups, i-propoxy groups, t-butoxy groups, n-butoxy groups and other alkoxy groups having 1 to 6 carbon atoms; phenoxy groups, methylphenoxy groups And an aryloxy group having 6 to 10 carbon atoms which may be substituted with an alkyl group such as Two adjacent substituents of R ^{45 to} R ⁵⁴ 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 An alkylenedioxy group having about 1 to 4 carbon atoms such as — or —O (CH ₂ ) ₂ O— 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.

The compound represented by the general formula (3) may have a salt form in which XR ′ R ″ R ′ ″ R ″ ″ coordinates. Here, X represents a Group 15 atom, and particularly preferably a nitrogen atom or a phosphorus atom. R ′, R ″, R ′ ″ and R ″ ″ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. is there. Examples of the aliphatic hydrocarbon group and aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group and aryl group for R ¹ . In addition, examples of the substituent for the aliphatic hydrocarbon group and aryl group include the same substituents as those exemplified as the substituent for R ¹ . R ′, R ″, R ′ ″, R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group, n-hexyl. Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as benzyl group and phenethyl 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 (3) include compounds represented by the following structural formula.

In the general formula (4), C and C ′ each independently represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
R ³ , R ⁴ , R ⁹ and R ¹⁰ each independently have an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a substituent. An optionally substituted heterocyclic group or hydrogen atom 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 heterocyclic 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 for the aryl group and heterocyclic group of C and C ′ include the same substituents as those described above as the substituent for R ^1. Among them, preferred are a halogen atom, a hydroxyl group, and 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 group which may have a substituent, Examples thereof include 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 and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group, cyclohexyl group An alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom such as benzyl group, phenethyl group or trifluoromethyl group or an aryl group; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group An aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, diphenyl Mino 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 An alkylenedioxy group having about 1 to 4 carbon atoms such as ₂ O— or —O (CH ₂ ) ₂ O— may be formed.
Examples of the aliphatic hydrocarbon group, aryl group or heterocyclic group represented by R ³ , R ⁴ , R ⁹ and R ¹⁰ include the above aliphatic hydrocarbon group, aryl group or heterocyclic group represented by R ⁵ and R ^6. The same thing is given. Examples of the substituent for the aliphatic hydrocarbon group, aryl group or heterocyclic group for R ³ , R ⁴ , R ⁹ and R ¹⁰ include the same substituents as those described above as the substituent for R ^1. Are particularly preferably a halogen atom, an alkyl group, a nitro group, an alkoxy group, an aryl group and an aryloxy group.

In the formula (4), XR ′ R ″ R ′ ″ R ″ ″ may be coordinated to form a salt form, where X represents a Group 15 atom, particularly preferably Is a nitrogen atom or a phosphorus atom. R ′, R ″, R ′ ″ and R ″ ″ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. is there. Examples of the aliphatic hydrocarbon group and aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group and aryl group for R ¹ . In addition, examples of the substituent for the aliphatic hydrocarbon group and aryl group include the same substituents as those exemplified as the substituent for R ¹ . R ′, R ″, R ′ ″ and R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group and n-hexyl. Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as benzyl group and phenethyl 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 (4) include compounds 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 mentioned as the substituent of R ¹ above. 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 group which may have a substituent, a substituent Examples thereof include an aryloxy group which may have a group 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 An alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom such as a cyclohexyl group, benzyl group, phenethyl group or trifluoromethyl group or an aryl group; 6 to 10 carbon atoms such as a phenyl group or a tolyl group Aryl group; heteroaryl group having 4 to 8 carbon atoms such as pyridyl group and thienyl group; 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group An alkoxy group of 6 to 10 carbon atoms such as a phenoxy group and a methylphenoxy group; or an amino group, a dimethylamino group, a diethylamino group, Phenylamino 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 An alkylenedioxy group having about 1 to 4 carbon atoms such as ₂ O— or —O (CH ₂ ) ₂ O— may be formed.
Further, in the formula (5), XR ′ R ″ R ′ ″ R ″ ″ may be coordinated to form a salt form, where X represents a Group 15 atom, particularly preferably Is a nitrogen atom or a phosphorus atom. R ′, R ″, R ′ ″ and R ″ ″ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. is there. Examples of the aliphatic hydrocarbon group and aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group and aryl group for R ¹ . In addition, examples of the substituent for the aliphatic hydrocarbon group and aryl group include the same substituents as those exemplified as the substituent for R ¹ . R ′, R ″, R ′ ″, R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group, n-hexyl. Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as benzyl group and phenethyl group.
In general formula (5), those forming a salt and those not forming a salt are preferred.
Preferable specific examples of the dye represented by the general formula (5) include compounds 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 carbonyl group which may have a substituent, a carboxyl group which may have a substituent, 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. Particularly preferred are a hydrogen atom and an aryl group which may have a substituent. M ⁶ may be the same metal as described in M ¹ above.

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

In the formula (6), XR′R ″ R ′ ″ R ″ ″ may be coordinated to form a salt form, where X represents a Group 15 atom, particularly preferably Is a nitrogen atom or a phosphorus atom. R ′, R ′ ′, R ′ ″ and R ″ ″ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. is there. Examples of the aliphatic hydrocarbon group and aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group and aryl group for R ¹ . Moreover, as a substituent of this aliphatic hydrocarbon group and an aryl group, the same substituent as what was mention | raise | lifted as a substituent of R < ¹ > -R < ² > is mentioned. R ′, R ″, R ′ ″, R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group, n-hexyl. Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as benzyl group and phenethyl 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), R ^{15 to} R ³⁰ represent an arbitrary substituent, and are not particularly limited as long as the basic performance of the compound of the present invention is not impaired. For example, as a substituent for R ^{1 to} R ² The same groups as those mentioned can be mentioned.
M ⁷ in the general formula (7) 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. The compound represented by the general formula (7) may form a salt with an acid.

  Of the compounds represented by the general formula (7), 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 (8), R ³¹ and R ³² , and R ³³ and R ³⁴ each independently have an aliphatic hydrocarbon group which may have a substituent or a substituent. Or an aryl group or a heterocyclic group which may have a substituent. M ⁸ can be the same metal as described for M ¹ . Examples of the aliphatic hydrocarbon group, aryl group, and heterocyclic group represented by R ^{31 to} R ³⁴ are the same as those described for R ^{1 to} R ² , and more specifically, methyl group, ethyl group, and the like. 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 A linear, branched or cyclic alkyl group such as 3-pentyl group, tert-butyl group, 1,1-dimethylpropyl group; 2-propenyl group, 2-butenyl group, 3-butenyl group, 2, Examples thereof include alkenyl groups such as 4-pentadienyl group; alkynyl groups such as 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 or a naphthyl group. Examples of the heterocyclic group include a thienyl group, a furyl group, a pyridyl group, an imidazolyl group, a pyrazinyl group, or a pyrazolyl group.
Examples of the substituent for the aliphatic hydrocarbon group, aryl group and heterocyclic group of R ^{31 to} R ³⁴ are the same as those described for R ¹ .

Moreover, the R ³¹ and R ^32, and, R ³³ and R ³⁴ together form _{-CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 2 -, - CH 2 -CF 2 -CH 2 - , —CH ₂ —CH ₂ —CH ₂ —CH ₂ —, —CH (Ph) —CH ₂ —, —CH (Me) —CH ₂ — and the like, an optionally substituted alkylene group; —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 —, —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ An alkylene group containing a linking group such as-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.
In the formula (8), XR ′ R ″ R ′ ″ R ″ ″ may be coordinated to form a salt form, where X represents a Group 15 atom, particularly preferably Is a nitrogen atom or a phosphorus atom. R ′, R ″, R ′ ″ and R ″ ″ each independently represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. is there. Examples of the aliphatic hydrocarbon group and aryl group include the same groups as those exemplified as the aliphatic hydrocarbon group and aryl group for R ¹ . Moreover, as a substituent of this aliphatic hydrocarbon group and an aryl group, the same substituent as what was mention | raise | lifted as a substituent of R < ¹ > -R < ² > is mentioned. R ′, R ″, R ′ ″, R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group, n-hexyl. Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as benzyl group and phenethyl group.
In the general formula (8), those not forming a salt are more preferable than those forming a salt. Preferable specific examples of the dye represented by the general formula (8) include compounds represented by the following.

In the general formula (9), 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 which may have a substituent. Indicates a group. Examples of the alkyl group, aryl group and heteroaryl group include the same groups as those described above for the alkyl group, aryl group and heteroaryl group of R ¹ . In R ^{35 to} R ^42, two adjacent substituents may be bonded together through a linking group. Specific examples of the substituent for R ^{35 to} R ⁴² include the same substituents as those described in the description of R ^{1 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 —; An alkylenedioxy group having about 1 to 4 carbon atoms such as ₂ O— or —O (CH ₂ ) ₂ O— 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.

  Of the compounds represented by the general formula (9), preferred specific examples include JP-A Nos. 10-18092, 11-170700, 2000-80071, and 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, in the compounds represented by the general formulas (2) to (6) and (8), the molecular weight of the ligand moiety is usually 800 or less, preferably 500 or less.
The molar extinction coefficient of the compounds represented by the general formulas (2) to (6) and (8) is usually 5000 or more, preferably 8000 or more.
The phthalocyanine compound described in the general formula (7) 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 (7) is usually 5000 or more, preferably 8000 or more.
The diimmonium compound described in the general formula (9) has a molecular weight of 600 to 3000, preferably 900 to 2100.
Further, the molar extinction coefficient of the compound represented by the general formula (9) is usually 70000 or more, preferably 90000 or more.

In addition, the solubility of the compounds represented by the above general formulas (2) to (9) in a solvent selected from an aromatic hydrocarbon solvent such as toluene, an ether solvent such as tetrahydrofuran and dimethoxyethane, and a ketone solvent such as methyl ethyl ketone. Is usually 0.1% or more, preferably 0.5% or more.
In addition, the said compound (2) is Russ. J. et al. Gen. Chem. 66, p. 1842 (1996). The above compound (3) can be synthesized, for example, by the method described in JP-A-2001-89492, and the compound (4) can be synthesized by, for example, J . Am. Chem. Soc. , 88, p. 5201 (1966). Compound (5) can be synthesized, for example, according to J. Am. Am. Chem. Soc. , 88 卷, p. 43 and p. 4870 (1966). Compound (6) can be synthesized, for example, according to J. Am. Am. Chem. Soc. 87, 1483 (1965). Compound (7) can be synthesized, for example, by the method described in The Porphyrin Handbook (2003), and compound (8) can be synthesized by, for example, J. Chem. Mater. Chem. , Page 1861 (1994), and compound (9) can be synthesized, for example, by the method described in JP-A No. 61-246391.

(Near infrared absorption filter)
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 dye residual ratio is 70% or more, more preferably 80% or more, and still more preferably 90% or more.

(Filter manufacturing method)
As a manufacturing method of the near-infrared absorbing filter of the present invention, a method of coating a transparent substrate with a coating liquid containing a near-infrared absorbing dye, a method of forming a film by melting and kneading a near-infrared absorbing dye with a binder resin, etc. However, 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 near-infrared absorption filter of the present invention is not particularly limited as long as it is substantially transparent and does not have large absorption and scattering. 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 phosphorous antioxidants, halogen and phosphoric acid flame retardants, heat aging inhibitors, ultraviolet absorbers, lubricants, antistatic agents and the like. 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 near-infrared absorbing dye, dispersant, and binder resin dissolved or dispersed in the solvent is usually 5 to 50% by weight. Moreover, the density | concentration of the near-infrared absorptive pigment | dye with respect to a total solid is 0.1-50 weight% normally as a near-infrared absorptive pigment total, Preferably it is 0.2-30 weight%. Moreover, when using together the compound represented by General formula (2)-(9) other than the compound represented by General formula (1), you may coexist in the same layer, and it laminates | stacks as another layer The ratio of the total amount of the compounds represented by the general formulas (2) to (9) to the compound represented by the general formula (1) may be 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 used is usually 0 to 100% by weight, preferably 0 to 70% by weight, based on the near-infrared absorbing dye.

Examples of the binder include polymethyl methacrylate resin, polyethyl acrylate resin, polycarbonate resin, ethylene-vinyl alcohol copolymer resin, and polyester resin. The amount used thereof is 0.01 to 20% by weight, preferably 0.1 to 10% by weight of the near-infrared absorbing dye 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 and octanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters cyclohexane such as ethyl acetate, methyl propionate, methyl enanthate, methyl linoleate and methyl stearate , 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 transparent substrates with coating solutions containing near-infrared absorbing dyes includes dipping, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, air knife coating, etc. It is performed by a known coating method.
The layer containing the near-infrared absorbing dye 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 near-infrared absorption filter of the present invention can significantly improve the light resistance of the near-infrared absorption filter due to a synergistic effect with the near-infrared absorption dye 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 near infrared absorption filter.

  Examples of such an ultraviolet absorber 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, Sipro 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 absorption layer 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.

(Electronic display filter)
Furthermore, the near-infrared absorption filter of the present invention includes an electromagnetic wave cut layer, an antireflection layer for preventing external light from being reflected on the surface, a glare prevention layer (non-glare layer), a color tone correction, if necessary. A layer can be provided and used as a filter for electronic displays, more preferably for plasma display panels.

The filter for electronic display of the present invention is not particularly limited except that the near-infrared absorption filter is used, and the configuration and manufacturing method used can be arbitrarily selected. A case where the filter is used as a display panel filter will be described as a representative example.
(Electromagnetic wave cut layer)
As an electromagnetic wave cut layer used in the filter for a plasma display panel of the present invention, vapor deposition of metal oxide or the like, a 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. Usually, the dielectric layer has three, five, and seven layers. Laminate about 11 layers. As the substrate, to may be directly utilizing the near infrared absorption filter of the present invention, after providing the electromagnetic wave-cutting layer by vapor deposition or sputtering on a resin film or a glass, bonding the near infrared absorption filter of the present invention May be.

(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. 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.
(Production Example 1)

Compound 1 (3.0 g, 7.67 mmol) and compound 2 (4.1 g, 7.67 mmol) were added to toluene (100 mL) and refluxed for 20 hours. After removing toluene, the mixture was extracted with chloroform, and the organic layer was washed with saturated brine. The organic layer was dried over sodium sulfate and then concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography, and further washed with methanol to obtain Exemplified Compound 1 (5.76 g) in 81% yield.
EI MS: 462
λmax: 890 nm (in THF)
1H NMR (CDCl3) 1.60-1.63 (d, 12H) 4.19-4.30 (m, 2H) 7.38-7.49 (m, 3H) 7.87-7.94 (m , 2H) 8.83 (s, 1H)
(Production Example 2)

Exemplified Compound 2 was obtained in 86% yield according to Production Example 1 except that Compound 3 was used instead of Compound 1.
EI MS: 538
λmax: 908 nm (in THF)
(Production Example 3)

Exemplified Compound 3 was obtained in 83% yield according to Production Example 1 except that Compound 4 was used instead of Compound 1.
EI MS: 498
λmax: 882 nm (in THF)
(Production Example 4)

Exemplified Compound 7 was obtained in 54% yield according to Production Example 1 except that Compound 5 was used instead of Compound 1.
EI MS: 442
λmax: 866 nm (in THF)
(Production Example 5)

Exemplified Compound 8 was obtained in 51% yield according to Production Example 1 except that Compound 6 was used instead of Compound 1.
EI MS: 440
λmax: 894 nm (in THF)
(Production Example 6)

Exemplified Compound 10 was obtained in 76% yield according to Production Example 1, except that Compound 7 was used instead of Compound 1.
EI MS: 492
λmax: 910 nm (in THF)
(Production Example 7)

Exemplified Compound 71 was obtained in 64% yield according to Preparation Example 1 except that Compound 3 was used instead of Compound 1 and Compound 8 was used instead of Compound 2.
EI MS: 608
λmax: 913 nm (in THF)
Example 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.

This filter had a λmax of 904 nm.
Furthermore, in order to evaluate heat resistance and heat-and-moisture resistance, it was placed in a thermostatic chamber at 80 ° C. and a constant-temperature and humidity chamber at 60 ° C. and a humidity of 90% for 500 hours to test the heat resistance and moist heat resistance (absorption intensity before and after irradiation at 904 nm). Measurement), the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was 95.5% and 99.9%, respectively, indicating good heat resistance and moist heat resistance, and the color of the filter There was no change.

  A UV cut filter (SC-39) 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 the absorption intensity before and after irradiation at 904 nm was measured, the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was very good at 92.1%, and there was no change in filter color.

Example 2
Illustrative compound 2 (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 thereto. 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.

This filter had a λmax of 912 nm.
Furthermore, in order to evaluate the heat resistance and the heat and humidity resistance, it was placed in a thermostatic chamber at 80 ° C. and a constant temperature and humidity chamber at 60 ° C. and a humidity of 90% for 500 hours to test the heat resistance and heat and humidity resistance (absorption intensity before and after irradiation at 912 nm). Measurement), the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was 97.3% and 99.2%, respectively, indicating good heat resistance and moist heat resistance, and the color of the filter There was no change.

  A UV cut filter (SC-39) 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 the absorption intensity before and after irradiation at 912 nm was measured, the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was very good at 93.7%, and there was no filter color change.

From Example 1 and Example 2, it is clear that the near-infrared absorbing dye of the present invention is excellent in durability.
Example 3
Illustrative compound 71 (34.3 mg) was added to 0.80 g of toluene, and 3.2 g of a MEK / toluene (= 1/1) solution (resin concentration: 25% by weight) of an acrylic resin (Optreso OZ1100) was added thereto. 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.

The filter had a λmax of 916 nm.
Furthermore, in order to evaluate heat resistance and heat-and-moisture resistance, it was placed in a constant-temperature bath at 80 ° C. and a constant-temperature and humidity bath at 60 ° C. and a humidity of 90% for 500 hours to test heat resistance and heat and humidity resistance (absorption intensity before and after irradiation at 916 nm). Measurement), the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was 88.5% and 94.1%, respectively, indicating good heat resistance and moist heat resistance, and the color of the filter There was no change.

  A UV cut filter (SC-39) 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 the absorption intensity before and after irradiation at 916 nm was measured, the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was very good at 91.4%, and there was no filter color change.

By comparison with Example 2 and Example 3, Y ¹ and Y ² in the general formula (1) of the present invention are higher in heat resistance and moist heat resistance in the alkyl group than in the aryl group, and have a dye residual ratio. It turns out that it is favorable.
Example 4
138.0 mg of Exemplified Compound 1 (λmax: 904 nm) and 63.0 mg of Compound 2 (λmax: 1005 nm) are added to 2.5 g of toluene, and MEK / toluene (= 1/1 /) of an acrylic resin (Optreso OZ1100) is added to these. 1) 10.0 g of a solution (resin concentration: 25% by weight) was added, dissolved by applying ultrasonic waves, and filtered to obtain a coating solution. The maximum absorption of Exemplified Compound 1 and Compound 2 showed the same maximum absorption as before mixing them. This coating solution 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 800-1000 nm of 5.9%, and effectively shielded the 800-1000 nm region used as a near infrared absorption filter for PDP. (Figure 1)
Furthermore, in order to evaluate heat resistance and moist heat resistance, a heat resistance and moist heat resistance test was conducted for 500 hours in a constant temperature and humidity chamber at 80 ° C. and a constant temperature and humidity chamber at 60 ° C. and 90% humidity. The region of 800-1000 nm was effectively shielded, and there was no color change of the filter. (Fig. 2, Fig. 3)
A UV cut filter (SC-39) 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 800-1000 nm was effectively shielded, and there was no filter color change. (Fig. 4)
Comparative Example 1
A coating solution was produced in the same manner as in Example 3 except that the following dithiol metal complex (Compound 9) (λmax: 922 nm) was used instead of the exemplified compound 1, and the coating solution absorbed at 946 nm at the maximum. Had a wavelength.

FIG. 5 shows the absorbance of the coating solution (Comparative Example 1), Compound 2 and Compound 9. From FIG. 5, it is clear that when compound 2 and compound 9 are mixed, the maximum absorption wavelength of the original compound is not maintained and the absorption wavelength changes.
Comparative Example 2
A coating solution was produced in the same manner as in Example 3 except that the following dithiol metal complex (Compound 10) (λmax: 878 nm) was used instead of the exemplified compound 1. The coating solution had an absorption wavelength at 922 nm.

  In FIG. 6, the light absorbency of this coating liquid (comparative example 2), the compound 2, and the compound 10 is shown. From FIG. 6, it is clear that when compound 2 and compound 10 are mixed, the maximum absorption wavelength of the original compound is not maintained and the absorption wavelength changes.

Light transmittance of the near-infrared absorbing filter of Example 3 Light transmittance after heat resistance test of near-infrared absorbing filter of Example 3 Light transmittance after wet heat resistance test of near-infrared absorbing filter of Example 3 Light transmittance after light resistance test of near-infrared absorbing filter of Example 3 Near-infrared absorption characteristics of coating liquid, compound 2 and compound 9 obtained in Comparative Example 1 Near-infrared absorption characteristics of coating liquid, compound 2 and compound 10 obtained in Comparative Example 2

Claims (7)

The following general formula (1)

[Wherein R ¹ is a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a silyl group which may have a substituent, a hydrogen atom, a cyano group. Or a halogen atom is shown. R ² has a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a hydrocarbon thio group which may have a substituent, and a substituent. Or a good silyl group, hydrogen atom, cyano group or halogen atom. Y ¹ and Y ² each independently represent a hydrocarbon group which may have a substituent. Here, R ¹ and R ² and Y ¹ and Y ² may form a ring via a linking group. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated to formula (1) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ¹ represents a metal atom. ]
The near-infrared absorption filter characterized by having a layer containing the compound represented by these. The compound represented by the general formula (1) and 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 linked directly or via a linking group. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated with formula (2) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ² represents a metal atom. ]
A compound represented by the following general formula (3)

[Wherein, B and B ′ each independently represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ⁷ and R ⁸ each represent 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 ⁷ and R ⁸ may be connected to each other directly or via a linking group. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated with the formula (3) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ³ represents a metal atom. ]
A compound represented by the following general formula (4)

[Wherein, 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 , R ⁴ , 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, Or a hydrogen atom is shown. Here, R ³ and R ⁴ and R ⁹ and R ¹⁰ may be linked to each other directly or via a linking group. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated to formula (4) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ⁴ represents a metal atom. ]
A compound represented by the following general formula (5)

[Wherein, D and D ′ each independently represents an aryl group which may have a substituent. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated to formula (5) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. 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, an optionally substituted carbonyl group, or an optionally substituted carboxyl. A group, 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; Here, in R ^{11 to} R ^14, two adjacent substituents may be connected via a linking group. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated to formula (6) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ⁶ represents a metal atom. ]
A compound represented by the following general formula (7)

[Wherein, R ^{15 to} R ³⁰ each independently represent an arbitrary substituent, and two adjacent substituents may form a ring via a linking group. M ⁷ is a hydrogen atom or a metal 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). Show. ]
A compound represented by the following general formula (8)

[Wherein R ^{31 to} R ³⁴ each independently has an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a substituent. In which R ^{31 to} R ³⁴ may form a ring integrally with a linking group as necessary. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated to formula (8) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ⁸ represents a metal atom. ]
And a compound represented by the following general formula (9)

[Wherein, 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. Show. Here, in R ^{35 to} R ⁴² , two adjacent substituents may be connected via a linking group. X ⁻ represents an anion. ]
The near-infrared absorption filter of Claim 1 which has a layer containing 1 or more types among the compounds chosen from the group which consists of a compound represented by these.   Furthermore, the near-infrared absorption filter of Claim 1 or 2 which has a ultraviolet-ray cut layer.   The near-infrared absorption filter in any one of Claims 1-3 was used, The filter for electronic displays characterized by the above-mentioned. The following general formula (1 ')

[Wherein R ¹ is a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a silyl group which may have a substituent, a hydrogen atom, a cyano group. Or a halogen atom is shown. R ² has a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a hydrocarbon thio group which may have a substituent, and a substituent. Or a good silyl group, hydrogen atom, cyano group or halogen atom. Y ¹ and Y ² each independently represent a hydrocarbon group which may have a substituent. Here, R ¹ and R ² and Y ¹ and Y ² may form a ring via a linking group. Alternatively, XRR ′ R ″ R ′ ″ R ″ ″ may be coordinated to formula (1) to form a salt form (where X represents a Group 15 atom, R ′ , R ″, R ′ ″ and R ″ ″ each represents an aliphatic hydrocarbon group which may have a substituent or an aryl group which may have a substituent. M ¹ represents a metal atom. ]
A compound represented by the formula: The compound according to claim 5, wherein M ¹ is a Group 10 atom or a Group 11 atom.   A near-infrared absorbing dye comprising the compound according to claim 5 or 6.

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