JP2011018048A - Near-infrared ray absorbing filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-IR absorption filter that does not exhibit shift in the absorption maximum, even if another near-IR absorption dye is mixed.SOLUTION: The near-IR absorption filter contains at least one compound or more expressed by general formula (1). In the general formula (1), Rand R, independently represents monovalent groups; Xand X, independently represent a monovalent group having, in total, three or more of at least one atom selected from among carbon atoms, oxygen atoms, nitrogen atoms and silicon atoms.

Description

  The present invention relates to a near-infrared absorption filter, and more particularly to a near-infrared absorption filter having a high visible light region transmittance and effectively blocking 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 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 A near-infrared absorbing dye such as a complex compound, a phthalocyanine compound, a naphthalocyanine compound, a triallylmethane compound, an imonium compound, a diimmonium compound, a naphthoquinone compound, an anthraquinone compound, an amino compound, or an aminium salt compound was contained. Various studies have been made, but what is actually used is only a part of the limited dithiol-based metal complex compounds, phthalocyanine compounds, and diimmonium compounds.

In particular, for use in electronic displays, it has excellent heat resistance and light resistance, has high solubility in solvents, has an absorption maximum in the vicinity of 800 to 1000 nm, and has no large absorption in the visible light region. Is essential. In Patent Document 1, a compound having the following structure is used in a PDP filter as a near infrared dye.
JP 2003-262719 A

  However, the dithiol metal complex described in Patent Document 1 is mixed with other nickel metal complex near-infrared dyes, and when attempting to cut the absorption at 800-1000 nm, ligand exchange occurs and another compound is generated. It was revealed that the absorption maximum shifted. That is, when designing a near-infrared absorbing filter, if two or more near-infrared absorbing dyes having predetermined absorption characteristics are mixed, the maximum absorption changes, and the intended near-infrared absorbing filter cannot be obtained. There's a problem.

  From the above, in the present invention, even if it has an absorption maximum near the target 800-1000 nm and is mixed with other near infrared absorbing dyes, particularly nickel metal complex near infrared dyes, A near-infrared absorption filter, in particular near-infrared light for electronic displays, designed and synthesized with a compound group that does not cause ligand exchange and does not shift the absorption maximum, has excellent light resistance, heat resistance, etc., and improved solubility in solvents. It is an object to provide an absorption filter.

As a result of intensive studies to solve the above problems, the present inventors introduced a sterically bulky functional group at the ortho position of the aryl group in the dithiolate metal complex represented by the general formula (1), and sulfur. The inventors have found a group of dithiolate metal complexes capable of suppressing ligand exchange by preventing intermolecular substitution reaction with atoms, and have completed the present invention.
That is, the gist of the present invention is the following general formula (1).

(In General Formula (1), R ¹ and R ² are each independently a monovalent group.
X ¹ and X ⁶ are monovalent groups having a total of 3 or more of at least one kind selected from a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom.
X ^{2 to} X ⁵ and X ^{7 to} X ¹⁰ are each independently a monovalent group, and adjacent groups may be bonded via a linking group. M ¹ represents a metal atom. And a layer containing at least one kind of the compound represented by 1).

  According to the present invention, by combining a dithiolate metal complex that does not cause ligand exchange even when mixed with other metal complexes and other near infrared absorbing dyes, it has excellent light resistance, heat resistance, and moist heat resistance, and A near-infrared absorption filter that cuts the near-infrared region near 750-1050 nm over a wide range is provided.

Hereinafter, the best mode for carrying out the present invention will be described, but the embodiment of the present invention is not limited to the following mode.
1. A compound represented by the general formula (1);
In the general formula (1), R ¹ and R ² are each independently a monovalent substituent.
Examples of the monovalent substituent include a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted carbonyl group, an optionally substituted hydrocarbon thio group, an optionally substituted silyl group, Examples thereof include an optionally substituted hydrocarbon amino group, an optionally substituted hydrocarbon oxy group, a cyano group, and 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. Of these, an alkyl group having 10 or less carbon atoms is preferred. 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 12 or less carbon atoms is preferable. More preferably, it is an aryl group having 12 or less carbon atoms and having no substituent at the ortho position of the aryl group.
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 12 or less 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, and a heterocyclic oxycarbonyl group. Specifically, R in the acyl group (—COR) and R and R ′ in the carbamoyl group (—CONRR ′) are the same as the specific examples of the aliphatic hydrocarbon group, aryl group, and heterocyclic group described above. R of the alkoxycarbonyl group (—C (O) OR) is the same as the specific examples of the aliphatic hydrocarbon group described above, and the aryloxycarbonyl group (—C (O) ) OR) R is the same as the specific examples of the aryl group described above, and R of the heterocyclic oxycarbonyl group (—C (O) OR) is a specific example of the heterocyclic group described above. Similar to example Agerare, or aldehyde group.

  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. 3) Alkynylthio group; an ethynylthio group, a 1-pentenylthio group, a phenethynylthio group, a t-butylethynyl group, and the like. Among these, an alkynylthio group having 12 or less carbon atoms is preferable. 4) 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. 5) 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 silyl group include trimethylsilyl group, t-butyldiphenylsilyl group, n-butyldimethylsilyl group, dimethylethylsilyl group, dimethylphenylsilyl group, dimethylisopropylsilyl group, and triisopropylsilyl group. Is a silyl group having 18 or less carbon atoms.
Examples of R of the hydrocarbon oxy group (—OR) include those similar to the specific examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group described above, or a hydroxyl group.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Particularly preferred are a fluorine atom and a chlorine atom.
Among these groups, examples of the substituent of the group which may have a substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a 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, heteroarylsulfonyl group, imide group, silyl group and the like.

  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 dimethylsulfamoylamino 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 An oxycarbonyl group; a heteroaryloxycarbonyl group having about 6 to 20 carbon atoms such as a pyridyloxycarbonyl group; an alkylsulfonyl group having about 1 to 6 carbon atoms such as a methanesulfonyl group, an ethanesulfonyl group, and a fluoromethanesulfonyl group; benzene An arylsulfonyl group having about 6 to 20 carbon atoms such as a sulfonyl group or a monofluorobenzenesulfonyl group; a heteroaryloxysulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide having about 4 to 20 carbon atoms such as phthalimide Group; also Includes a silyl group that is trisubstituted with a substituent selected from the group consisting of an alkyl group and an aryl group.

R ¹ and R ² are particularly preferably an alkyl group or haloalkyl group having a total number of carbon atoms of 10 or less, which may have a substituent, an alkylthio group having a total number of carbon atoms of 10 or less, which may have a substituent, A monocyclic aryl group having 12 or less carbon atoms, which may have a substituent, a monocyclic arylthio group which may have a substituent having 12 or less total carbon atoms, a substituent having a total carbon number of 10 or less And may be a 5-membered heterocyclic group, a cyano group, a fluorine atom, a chlorine atom, or a hydrogen atom.

X ¹ and X ⁶ are monovalent groups having a total of 3 or more of at least one kind selected from a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom.
X ¹ and X ⁶ are preferably groups in which at least one kind of carbon atom, oxygen atom, nitrogen atom and silicon atom is linked in a chain. Here, the group connected 3 or more in a chain form includes a chain group containing 3 or more atoms counted from atoms bonded to the benzene ring, or 4 or more atoms including atoms bonded to the benzene ring. Means a cyclic group.

Examples of such a group include an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an oxy group, an aryloxy group, a heterocyclic oxy group, a substituted amino group, and a substituted silyl group. It is done.
Examples of the aliphatic hydrocarbon group include n-propyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-butyl group, 3-pentyl group, neopentyl group, 2-methylbutyl group and 2-ethylbutyl. Linear, branched or cyclic aliphatic hydrocarbon groups such as a group, 3-methylbutyl group, cyclohexyl group, and cyclohexylmethyl group, more preferably a linear or branched chain fatty acid having about 3 to 10 carbon atoms Group hydrocarbon group.

Examples of the aryl group include phenyl group, p-tolyl group, benzyl group, phenylethyl group, 3,4-xylyl group, 2-ethylphenyl group, 3,4,5-trimethylphenyl group, 2,4,6- An aryl group such as a trimethylphenyl group, more preferably a monocyclic aryl group having about 6 to 12 carbon atoms.
Examples of the heterocyclic group include heterocyclic groups such as thienyl group, furyl group, pyrrolyl group, pyridyl group, imidazolyl group, pyrazolyl group, and indoleyl group, and more preferably a monocyclic heterocyclic ring having about 5 to 10 carbon atoms. Groups.

  Examples of the aliphatic hydrocarbon oxy group include ethoxy group, n-propoxy group, n-butoxy group, n-hexyloxy group, isopropoxy group, cyclohexyloxy group, 2-butoxy group, amyloxy group, and t-butoxy group. And a linear, branched or cyclic aliphatic hydrocarbon oxy group, more preferably a linear or branched aliphatic hydrocarbon oxy group having about 2 to 10 carbon atoms.

Examples of the aryloxy group include those similar to the specific examples of the aryl group described above for R of (—OR).
Examples of the heterocyclic oxy group include those similar to the specific examples of the heterocyclic group described above for R of (—OR).
Examples of the amino group having a substituent include the same as the specific examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group described above for R and R ′ of (—NRR ′).

Examples of the silyl group having a substituent include a triethylsilyl group, a t-butyldiphenylsilyl group, an n-butyldimethylsilyl group, a dimethylethylsilyl group, a dimethylphenylsilyl group, a dimethylisopropylsilyl group, and a triisopropylsilyl group. And a silyl group having about 2 to 18 carbon atoms is preferred.
Among these, particularly preferably, an alkyl group which may have a substituent having about 3 to 10 total carbon atoms, or a monocyclic aryl group which may have a substituent having about 6 to 12 total carbon atoms, Alternatively, it is an alkoxy group which may have a substituent having about 2 to 10 total carbon atoms, or an aryloxy group which may have a substituent having about 6 to 12 total carbon atoms.

X ^{2 to} X ⁵ and X ^{7 to} X ¹⁰ are each independently a monovalent group, and adjacent groups may be bonded via a linking group.
The monovalent group is not particularly limited as long as it does not adversely affect the stability of the metal complex. For example, a halogen atom, 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, sulfonamide group, carbamoyl group, sulfamoyl group , Sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, imide group, silyl group and the like.

  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 dimethylsulfamoylamino 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 An oxycarbonyl group; a heteroaryloxycarbonyl group having about 6 to 20 carbon atoms such as a pyridyloxycarbonyl group; an alkylsulfonyl group having about 1 to 6 carbon atoms such as a methanesulfonyl group, an ethanesulfonyl group, and a fluoromethanesulfonyl group; benzene An arylsulfonyl group having about 6 to 20 carbon atoms such as a sulfonyl group or a monofluorobenzenesulfonyl group; a heteroaryloxysulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide having about 4 to 20 carbon atoms such as phthalimide Group; also Includes a silyl group that is trisubstituted with a substituent selected from the group consisting of an alkyl group and an aryl group.

The group adjacent groups is formed result of coupling through a linking _{group, -CH 2 -CH 2 -, -} CH 2 -CH 2 -CH 2 -, CH 2 -CH 2 -CH2-CH 2 -, An alkylene group optionally substituted by —CH (Ph) —CH ₂ —, —CH (Me) —CH ₂ — and the like; —CH═CH—, —C (Me) ═CH—, —CH═CH— An optionally substituted alkenylene group such as CH ₂ —CH ₂ —CH═CH—; —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 - , and the like preferably.

Among these, X ² and / or X ⁴ , and X ⁷ and / or X ¹⁰ are groups having a total of two or more atoms of at least one of carbon atoms, oxygen atoms, nitrogen atoms, and silicon atoms. Is preferred.
These are groups that make it possible to improve the solubility in an organic solvent at the same time as making the ligand exchange reaction difficult by making the benzene ring bulky.

Among these, a group having 3 or more atoms in total is more preferable. Specific examples include the groups listed for X ¹ and X ⁶ .
Particularly preferred is an alkyl group which may have a substituent having a total carbon number of about 2 to 10, or an alkoxy group which may have a substituent having a total carbon number of 10 or less.
Particularly preferably as X ³ and X ⁸ , an alkyl group which may have a substituent having a total carbon number of 10 or less, or a haloalkyl group, an alkylthio group which may have a substituent having a total carbon number of 10 or less, Or a monocyclic aryl group which may have a substituent having a total carbon number of 12 or less, or a monocyclic arylthio group which may have a substituent having a total carbon number of 12 or less, or a substituent having a total carbon number of 10 or less It may be a 5-membered ring heterocyclic group, a cyano group, a fluorine atom, a chlorine atom, or a hydrogen atom.

Examples of the substituent of the group which may have a substituent among X ^{1 to} X ¹⁰ include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hetero group Aryl 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, sulfa Examples include moylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, imide group and silyl group.

  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 dimethylsulfamoylamino 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 An oxycarbonyl group; a heteroaryloxycarbonyl group having about 6 to 20 carbon atoms such as a pyridyloxycarbonyl group; an alkylsulfonyl group having about 1 to 6 carbon atoms such as a methanesulfonyl group, an ethanesulfonyl group, and a fluoromethanesulfonyl group; benzene An arylsulfonyl group having about 6 to 20 carbon atoms such as a sulfonyl group or a monofluorobenzenesulfonyl group; a heteroaryloxysulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide having about 4 to 20 carbon atoms such as phthalimide Group; also Includes a silyl group that is trisubstituted with a substituent selected from the group consisting of an alkyl group and an aryl group.

In the compound represented by the general formula (1), among R ¹ and R ² , X ^{2 to} X ⁵ and X ^{7 to} X ¹⁰ , in particular, they may be the same or different, but they are the same. Some are more preferred.
M ¹ is not particularly limited as long as it is a metal atom that can take a tetracoordinated form, and preferably includes a group 10 metal atom of Ni, Pd, or Pt; Co; Fe; Cu; Au; Cr or Mn; More preferred is a group 10 metal atom, and particularly preferred is Ni or Pd.

Here, the molecular weight of the ligand moiety in the general formula (1) is usually 1000 or less, preferably 600 or less. The molar extinction coefficient is usually 8000 or more, preferably 10,000 or more.
In addition, the solubility of the compound represented by the general formula (1) 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 It is 0.1% or more, preferably 0.5% or more.

  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 obtained by a known method described in, for example, Mol. Cryst. Liq. Crst. (Lett), 56, 249 (1980). After obtaining a 2-one derivative, it can be metallized to obtain a symmetric metal complex. The absorption maximum wavelength is about 750 nm to 980 nm.
2. Near-infrared absorbing 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), so that the near-infrared filter in the range of 750 to 1050 nm can be obtained. Since it can absorb a wide infrared region, it is particularly preferred when used for a filter for an electronic display.

  In particular, when mixed with the dyes of (5), (6) and (8), it is difficult to exchange ligands with respect to conventional dyes, which is preferable.

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 can be the same metal as 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 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 heteroaryl group of A and A ′ include the same substituents as those described above as the substituents of X ³ and X ^8. , 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 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 A halogen atom such as benzyl group, phenethyl group, 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 phenyl group or tolyl group; A heteroaryl group having 4 to 8 carbon atoms such as a group or a thienyl 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, or an n-butoxy group; Aryloxy groups having 6 to 10 carbon atoms, such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, diphenylamine 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.

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 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 of the alkyl group of R ⁵ and R ⁶ include the same substituents as those described above as the substituents of X ³ and X ⁸ , 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 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 ″ ″ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Examples of the substituent include the same substituents as those mentioned as the substituents for X ³ and X ⁸ . 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 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 be the same metal 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 of the aryl group and heteroaryl group of B and B ′ include the same substituents as those described above as the substituents of X ³ and X ^8. , 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 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 A halogen atom such as benzyl group, phenethyl group, 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 phenyl group or tolyl group; A heteroaryl group having 4 to 8 carbon atoms such as a group or a thienyl 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, or an n-butoxy group; Aryloxy groups having 6 to 10 carbon atoms, such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, diphenylamine 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 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 X ³ and X ⁸ . 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 ^{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.

X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. R ′, R ″, R ′ ″, R ″ ″ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Examples of the substituent include the same substituents as those mentioned as the substituents for X ³ and X ⁸ . 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 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 (3) include those 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 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 X ³ and X ^8. , 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 A halogen atom such as benzyl group, phenethyl group, 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 phenyl group or tolyl group; A heteroaryl group having 4 to 8 carbon atoms such as a group or a thienyl 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, or an n-butoxy group; Aryloxy groups having 6 to 10 carbon atoms, such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, diphenylamine 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.

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 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 X ³ and X ^8. 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 X ³ and X ^8. 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 ″ ″ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Examples of the substituent include the same substituents as those mentioned as the substituents for X ³ and X ⁸ . 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 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 mentioned as the substituents of X ³ and X ⁸ 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 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 An alkylenedioxy group having about 1 to 4 carbon atoms such as ₂ O— or —O (CH ₂ ) ₂ O— 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 ″ ″ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Examples of the substituent include the same substituents as those mentioned as the substituents for X ³ and X ⁸ . 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 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 each independently represent a hydrogen atom, a cyano group, an optionally substituted carbonyl group, an optionally substituted alkyl group, or an optionally substituted group. An aryl group or an optionally substituted heteroaryl group. Particularly preferred are a hydrogen atom and an optionally substituted aryl group. M ⁶ may be the same metal as described in M ¹ above.

Examples of the substituent for the alkyl group, aryl group, heteroaryl group and carbonyl group include the same groups as those described above for X ³ and X ⁸ .
In addition, the aliphatic hydrocarbon group of R ^{11 to} R ¹⁴ and the substituents of the aryl group and heteroaryl group are combined to form a carbon number 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.

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 ″ ″ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Examples of the substituent include the same substituents as those mentioned as the substituents for X ³ and X ⁸ . 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 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), 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 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.

  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 are each independently an optionally substituted aliphatic hydrocarbon group or an optionally substituted aryl group, The heteroaryl group which may be substituted is shown. M ⁸ can be the same metal as described for M ¹ . Examples of the aliphatic hydrocarbon group, aryl group, and heteroaryl group for R ^{31 to} R ³⁴ are the same as those described for X ³ and X ⁸ , 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 and a naphthyl group. Examples of the heteroaryl group include thienyl group, furyl group, imidazolyl group, pyrazolyl group and the like.
Examples of the substituent for the aliphatic hydrocarbon group, aryl group and heteroaryl group of R ^{31 to} R ³⁴ are the same as those described for X ³ and X ⁸ .

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 -CH2-CH} 2 -, - CH (Ph) -CH 2 -, - CH (Me) -CH 2 - optionally substituted alkylene group such as; -CH = CH-, An optionally substituted alkenylene group such as —C (Me) ═CH—, —CH═CH—CH ₂ —CH ₂ —CH═CH—, etc .; —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.
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 ″ ″ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Examples of the substituent include the same substituents as those mentioned as the substituents for X ³ and X ⁸ . 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 phenethyl group such as benzyl 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 those represented by the following.

In the general formula (9), R ^{35 to} R ⁴² are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that 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 X ³ and X ^{8 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, the compounds represented by the general formulas (2) to (6) and (8) 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 (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.
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.
The compound (2) can be synthesized, for example, by the method described in Russ. J. Gen. Chem., 66, 1842 (1996). The compound (4) can be synthesized by the method described in Japanese Patent No. 89492. 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. , P. 1861 (1994), and compound (9) can be synthesized, for example, by the method described in JP-A-61-246391.

(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), and further, the compounds represented by the above (2) to (11) By using in combination, a near-infrared absorption filter that covers a wavelength range of 750 to 1050 nm can be efficiently obtained.

In addition, in the plasma display panel, near infrared emission around 820 to 825 nm, 880 nm, and 980 nm is particularly strong, and thus the light transmittance of this portion is preferably 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 has excellent heat resistance, and a new peak does not appear in the visible light region after a 500-hour heat test in a thermostat at 80 ° C.
The filter of the present application preferably has a dye residual ratio in the heat resistance test of 60% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 85% or more. Here, the dye residual ratio is determined from the degree of decrease in absorption intensity before and after the test 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 dye residual ratio is 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 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 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 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 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 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 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.

3. 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 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, 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. 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
Compound (A) represented by the following formula (34.3 mg) was added to 0.80 g of toluene, and an MEK / toluene (= 1/1) solution of acrylic resin (Optreso OZ1100) (resin concentration: 25% by weight). ) Add 3.2 g, dissolve by applying ultrasonic waves, and after filtration, apply this coating solution to a polyethylene terephthalate film with a bar coater (No. 18; manufactured by Eto Kikai Co., Ltd.) and dry. As a result, a near-infrared absorption filter was obtained.

Λmax of this filter was 851 nm.
Furthermore, in order to evaluate heat resistance and moist heat resistance, put it in a constant temperature bath at 80 ° C. and a constant temperature layer at 60 ° C. and 90% humidity for 500 hours to test heat resistance and moist heat resistance (measurement of absorption strength before and after the test at 851 nm). ), The residual ratio of the dye (strength after the test ÷ strength before the test × 100) was 85.6% and 98.9%, respectively, indicating good heat resistance and moist heat resistance, and the color change of the filter was There wasn't.

  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 851 nm was measured, the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was very good at 96.6%, and there was no change in filter color.

Example 2
In Example 1, a near-infrared absorption filter was obtained in the same manner as in Example 1 except that the compound (B) represented by the following formula was used instead of the compound (A).

This filter had a λmax of 855 nm.
Furthermore, in order to evaluate the heat resistance and the heat and humidity 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 855 nm). ), The residual pigment ratio (strength after the test ÷ strength before the test × 100) was applied to this filter, and UV cut filters (SC-3, 97.4% and 100.100%) manufactured by Fuji Photo Film Co., Ltd., respectively. 0% good heat resistance and moist heat resistance, no color change of the filter 9) Wearing xenon long life fade meter (FAL-25AX-HCB-EC) (Suga Test Instruments Co., Ltd.) When the absorption intensity before and after irradiation at 855 nm was measured after irradiation for 280 hours, the residual ratio of the dye (intensity after irradiation ÷ intensity before irradiation × 100) was 95.1%, which was not In is good, there was no filter color change.

Example 3
Compound (C) (34.3 mg) shown below was added to 1.0 g of THF (tetrahydrofuran), and 3.0 g of an acrylic resin (Optreso OZ1100) in THF (resin concentration: 30% by weight) was added thereto. Then, it was dissolved by applying ultrasonic waves, and after filtration, 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 absorb near infrared rays. A filter was obtained.

This filter had a λmax of 856 nm.
Furthermore, in order to evaluate heat resistance and heat-and-moisture resistance, it is placed in a thermostatic bath at 80 ° C. and a constant-temperature layer at 60 ° C. and 90% humidity for 500 hours to conduct a heat and moisture heat resistance test (absorption strength before and after the durability test at 856 nm). Measurement), the residual ratio of dye (strength after test ÷ strength before test × 100) was 96.2% and 99.0%, respectively, indicating good heat resistance and moist heat resistance, and the color change of the filter There was no.

  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 856 nm was measured, the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was very good at 96.7%, and there was no filter color change.

  In the following examples and comparative examples, a near-infrared absorbing filter in which two kinds of near-infrared absorbing dyes are mixed is manufactured, but the transmittance of the near-infrared absorbing filter at 825 nm, 880 nm, and 980 nm is 20% or less. The amount of the near-infrared absorbing dye was adjusted so as to be manufactured.

Example 4
A compound (A) (0.099 g) represented by the following formula and a compound (0.0684 g) represented by the following formula (D) were added to 2.0 g of toluene, and an MEK / acrylic resin (Optreso OZ1100) MEK / Toluene (= 1/1) solution (resin concentration: 25% by weight) (8.0 g) was added, dissolved by applying ultrasonic waves, filtered, and the coating solution was added to bar coater (No. 18; Eto Kikai Co., Ltd.). The product was coated on a polyethylene terephthalate film and dried to obtain a near infrared absorption filter.

This near-infrared absorption filter had a transmittance of 20% or less at 825 nm, 880 nm, and 980 nm, and effectively shielded light emission from the PDP main body.
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 bath at 80 ° C. and a constant temperature layer at 60 ° C. and 90% humidity. Results), FIG. 2 (results of moist heat resistance) and good heat resistance and moist heat resistance, and there was no color change of the filter.

  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 the absorption intensity before and after irradiation was measured, it was good as shown in FIG. 3, and there was no change in filter color.

Example 5
A compound (B) represented by the following formula and a compound (0.0684 g) represented by the following formula (D) were prepared in the same manner as in Example 4 except that the compound (B) represented by the following formula was used instead of the compound (A). ) Containing a near infrared absorption filter.

This near-infrared absorption filter had a transmittance of 20% or less at 825 nm, 880 nm, and 980 nm, and effectively shielded light emission from the PDP main body.
Furthermore, in order to evaluate heat resistance and heat and humidity resistance, a heat resistance and heat and humidity resistance test was conducted for 500 hours in a constant temperature bath of 80 ° C. and a constant temperature layer of 60 ° C. and 90% humidity. Results), FIG. 5 (result of moist heat resistance) and good heat resistance and moist heat resistance, and there was no color change of the filter.

  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 the absorption intensity before and after irradiation was measured, it was good as shown in FIG. 6, and there was no change in filter color.

Example 6
A compound (C) (0.099 g) represented by the following formula and a compound (0.0684 g) represented by the following formula (D) were added to 3.0 g of THF, and an acrylic resin (Optreso OZ1100) THF (resin) was added thereto. 8.0 g (concentration 30% by weight) was added and dissolved by applying ultrasonic waves. After filtration, this coating solution was applied to a polyethylene terephthalate film with a bar coater (No. 18; manufactured by Eto Kikai Co., Ltd.). Then, a near-infrared absorption filter was obtained by drying.

This near-infrared absorption filter had a transmittance of 20% or less at 825 nm, 880 nm, and 980 nm, and effectively shielded light emission from the PDP main body.
Furthermore, in order to evaluate heat resistance and heat and humidity resistance, a test for heat resistance and moist heat resistance was carried out for 500 hours in a constant temperature bath of 80 ° C. and a constant temperature layer of 60 ° C. and 90% humidity. Results), FIG. 8 (wet heat and heat resistance results) and good heat resistance and moist heat resistance, showing no color change of the filter.

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 the absorption intensity before and after irradiation was measured, it was good as shown in FIG. 9, and there was no change in filter color.
Tables 1 to 3 below show changes in transmittance at 825 nm, 880 nm, and 980 nm before and after the tests of the near-infrared absorption filters of Examples 4 to 6, heat resistance, moist heat resistance, and light resistance (after the test before the test). 1-9 show the transmission spectra before and after the test.

  By Examples 1-6, it is clear that the near-infrared absorption filter of this invention is excellent in heat resistance, heat-and-moisture resistance, and light resistance.

Example 7
The ink liquid prepared in the same manner as in Example 4 was allowed to stand at room temperature for 7 days, and the transmission spectrum before and after the measurement was measured. As a result, there was no change in the spectrum shape. (Fig. 10)
Example 8
The ink liquid prepared by the same method as in Example 5 was allowed to stand at room temperature for 7 days, and the transmission spectrum before and after the measurement was measured. As a result, there was no change in the spectrum shape. (Fig. 11)
Example 9
The ink liquid prepared by the same method as in Example 6 was allowed to stand at room temperature for 7 days, and the transmission spectrum before and after the measurement was measured. As a result, there was no change in the spectrum shape. (Fig. 12)
Table 4 below shows changes in transmittance at 825 nm, 880 nm, and 980 nm before and after the ink solutions of Examples 7 to 9 were left at room temperature for 7 days (after being left unattended).

Comparative Example 1
A compound (E) (0.0686 g) represented by the following formula and a compound (0.0740 g) represented by the following formula (D) were added to 1.6 g of toluene, and MEK / acrylic resin (Optreso OZ1100) was added to these. Toluene (= 1/1) solution (resin concentration 25% by weight) 6.4 was added and dissolved by applying ultrasonic waves to prepare a coating solution.

When this coating solution was allowed to stand at room temperature for 7 days and the transmission spectrum before and after the observation was observed, there was a marked change in the spectrum shape, and this coating solution was unstable. (Fig. 13)
Comparative Example 2
A compound (F) (0.0686 g) represented by the following formula and a compound (0.0740 g) represented by the following formula (D) were added to 2.0 g of THF, and an acrylic resin (Optreso OZ1100) in THF solution ( 8.0 (resin concentration: 30% by weight) was added and dissolved by applying ultrasonic waves to prepare a coating solution, and the coating solution was filtered.

When this coating solution was allowed to stand at room temperature for 7 days and the transmission spectrum before and after the observation was observed, there was a marked change in the spectrum shape, and this coating solution was unstable. (Fig. 14)
By comparing Examples 7 to 9 with Comparative Examples 1 and 2, the near-infrared absorbing filter of the present invention was mixed with other near-infrared absorbing dyes over time compared with conventional dithiolate dyes. It is clear that this is a stable near-infrared absorption filter with a very small spectral change.

It is a figure which shows the heat resistance test result in Example 4. It is a figure which shows the wet heat resistance test result in Example 4. It is a figure which shows the light resistance test result in Example 4. It is a figure which shows the heat resistance test result in Example 5. It is a figure which shows the wet heat resistance test result in Example 5. It is a figure which shows the light resistance test result in Example 5. It is a figure which shows the heat resistance test result in Example 6. It is a figure which shows the wet heat resistance test result in Example 6. It is a figure which shows the light resistance test result in Example 6. It is a figure which shows the shape change of the transmission spectrum in Example 7. FIG. It is a figure which shows the shape change of the transmission spectrum in Example 8. FIG. It is a figure which shows the shape change of the transmission spectrum in Example 9. FIG. It is a figure which shows the shape change of the transmission spectrum in the comparative example 1. FIG. It is a figure which shows the shape change of the transmission spectrum in the comparative example 2.

Claims (5)

The following general formula (1)

(In General Formula (1), R ¹ and R ² are each independently a monovalent group.
X ¹ and X ⁶ are monovalent groups having a total of 3 or more of at least one kind selected from a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom.
X ^{2 to} X ⁵ and X ^{7 to} X ¹⁰ are each independently a monovalent group, and adjacent groups may be bonded via a linking group. M ¹ represents a metal atom. A near-infrared absorption filter having a layer containing at least one compound represented by 2. The near-infrared absorption filter according to claim 1, wherein X ¹ and X ⁶ are groups in which at least one kind of carbon atom, oxygen atom, nitrogen atom, and silicon atom is linked in a chain. X ² and / or X ⁴ , and X ⁷ and / or X ⁹ are groups having a total of two or more atoms selected from carbon atoms, oxygen atoms, nitrogen atoms and silicon atoms. The near-infrared absorption filter as described.   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 Claims 1-4.

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