JP2006126226A - Near-infrared ray absorbing filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared ray absorbing filter having excellent heat resistance, light resistance, and wetproof pyrogenicity and including a dithiol metal complex having little deterioration possessing a wide half value of a near-infrared ray absorbing spectrum and possessing high dissolubility to an organic solvent to facilitate high coating. <P>SOLUTION: The near-infrared ray absorbing filter includes a layer containing at least one or more compounds denoted by general formula (1). Therein, R<SP>1</SP>denotes a hydrogen atom, R<SP>3</SP>denotes a group selected from a hydrogen atom, a hydrocarbon group which may be substituted, a cyano group, an acyl group, an alkyl oxy-carbonyl group, an aryl oxy-carbonyl group, an alkyl amino carbonyl group, and an aryl amino carbonyl group, R<SP>2</SP>and R<SP>4</SP>are independently a group selected from a hydrocarbon which may be substituted, a cyano group, an acyl group, an alkyl oxy-carbonyl group, an aryl oxy-carbonyl group, an alkyl amino carbonyl group and an aryl amino carbonyl group. M denotes a metal atom. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a near-infrared absorption filter, particularly a near-infrared absorption filter that has high transmittance in the visible light region and effectively blocks near-infrared rays, and in particular, has an excellent near-infrared absorption effect including a specific dye. It relates to a near-infrared absorption filter.
The near-infrared absorption filter of the present invention can also be used as a part of an electronic display filter such as a plasma display panel filter by combining with a layer having another function.

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 780 nm to 1000 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 complexes thereof, cyanine compounds, squarylium compounds, dithiol metal complex compounds, aminothiophenol metal complex compounds , Phthalocyanine compounds, naphthalocyanine compounds, triallylmethane compounds, immonium compounds, diimmonium compounds, naphthoquinone compounds, anthraquinone compounds, amino compounds, compounds containing near-infrared absorbing compounds such as aminium salt compounds, etc. Various studies have been made, and among these, dithiol metal complex compounds are generally excellent in heat resistance, and their use has been proposed for displays (Patent Document 1).

However, the dithiol metal complex described above has a problem that when the near-infrared absorption filter has a narrow near-infrared absorption half width, a large amount of the dye is required or a plurality of dyes must be used. . In addition, the dithiol metal complex described above has low solubility in organic solvents, so when preparing a near-infrared absorbing filter, it must be dissolved in a special solvent such as chloroform when kneaded with a resin or coated. Therefore, handling is very limited, and it is difficult to produce a filter industrially.
JP-A-9-230134

  In the present invention, a dithiol metal complex having a wide half-value width of a near infrared absorption spectrum, high solubility in an organic solvent, easy coating, and excellent heat resistance, light resistance, and moist heat resistance, and having little deterioration. It is an object to provide a near-infrared absorption filter including the above.

As a result of intensive studies on the types of substituents of the dithiol metal complex, the present inventors have found that not all substituents are the same as the substituents, and having a hydrogen atom and other substituents results in a half-width of the spectrum. It has been found that the solubility in organic solvents increases. And the near-infrared absorption filter having a layer containing at least one kind of these compounds has little deterioration with respect to heat and light, and when combined with a specific dye, efficiently absorbs a wide range of near-infrared light of 780 nm to 1000 nm. The present inventors have found that a near-infrared absorption filter that can be provided can be provided, and have completed the present invention.

  That is, the gist of the present invention is the following general formula (1).

Wherein R ¹ is a hydrogen atom, R ³ is a hydrogen atom, an optionally substituted hydrocarbon group, a cyano group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and an arylamino A group selected from a carbonyl group, R ² and R ⁴ are each independently an optionally substituted hydrocarbon group, cyano group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, And a group selected from arylaminocarbonyl groups, wherein M represents a metal atom.) A near-infrared absorption filter having a layer containing at least one compound represented by:

  Further, the compound represented by the above 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 heteroaryl group which may have a substituent, and R ⁵ and R ⁶ each represents Independently, it represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a hydrogen atom. , R ⁵ and R ⁶ may be connected to each other directly or via a linking group, or XR′R ″ R ′ ″ R ″ ″ is coordinated to formula (2). Wherein X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ represent an alkyl 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)

(In the formula, B and B ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and R ⁷ and R ⁸ each represents Independently, it represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a hydrogen atom. , R ⁷ and R ⁸ may be connected to each other directly or via a linking group, or XR′R ″ R ′ ″ R ″ ″ is coordinated to formula (3). Wherein X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ represent an alkyl 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)

(In the formula, C and C ′ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and R ⁹ and R ¹⁰ each represents Independently,
An alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a hydrogen atom is shown. Where R ⁹ and R ¹⁰ are
They may be connected to each other directly or via a linking group. Alternatively, XR′R ″ R ′ ″ R ″ ″ may coordinate to formula (4) to take a salt form. Here, X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ have an alkyl group which may have a substituent or a substituent. An aryl group that may be present is shown. M ⁴ represents a metal atom. ), A compound represented by the following general formula (5)

(In the formula, D and D ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Alternatively, XR in formula (5) 'R''R''' R '''' may be coordinated to take a salt form, where X represents a group 15 atom, and R ', R'',R''', R ''''Represents an alkyl group which may have a substituent or an aryl group which may have a substituent. M ⁵ represents a metal atom.) Formula (6)

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Here, R ¹¹ and R ¹² R ¹³ and R ¹⁴ may be combined to form a ring, and R ^{11 to} R ¹⁴ may have two adjacent substituents connected to each other via a linking group. 6) XR'R''R '''R
'''' May be coordinated to take a salt form. Here, X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ have an alkyl group which may have a substituent or a substituent. An aryl group that may be present is shown. M ⁶ represents a metal atom) and the following general formula (7)

(In the formula, E and E ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Alternatively, XR in formula (7) 'R''R''' R '''' may be coordinated to take a salt form, where X represents a group 15 atom, and R ', R'',R''', R ''''Represents an alkyl group which may have a substituent, or an aryl group which may have a substituent. M ⁷ represents a metal atom.) Formula (8)

(In the formula, F and F ′ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Alternatively, XR in formula (8) 'R''R''' R '''' may be coordinated to take a salt form, where X represents a group 15 atom, and R ', R'',R''', R ''''Represents an alkyl group which may have a substituent, or an aryl group which may have a substituent. M ⁸ represents a metal atom.) Formula (9)

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

(In the formula, R ^{31 to} R ³⁸ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Here, in R ^{17 to} R ²⁴ , two adjacent substituents may be connected via a linking group, Y ⁻ represents an anion. It exists in the near-infrared absorption filter characterized by having a layer containing 1 or more types of selected compounds.

  Since the near-infrared absorption filter of the present invention contains a dithiol nickel complex compound having high solubility and a broad spectrum half-value width, it is possible to easily provide a filter with high near-infrared absorption ability. Moreover, it is excellent in durability and is also useful as a filter for a plasma display panel by combining with near-infrared absorbing dyes in other wavelength regions.

Hereinafter, the present invention will be described in detail.
1. Near-infrared absorption filter The near-infrared absorption filter of the present invention contains at least one compound represented by the above general formula (1).
Moreover, this-application filter uses by combining the said compound with at least 1 sort (s) chosen from the compound represented by the compound represented by the said General formula (1), and the said General formula (2)-(10), A near-infrared absorption filter that covers a wavelength range of 780 to 1000 nm, which is useful as a display filter that can be used in a plasma display panel, can be efficiently obtained.

That is, as a physical property of the filter of the present application, the light transmittance in a wavelength range of 780 to 1000 nm is preferably 20% or less. In addition, in the plasma display panel, near-infrared emission near 820 nm, 880 nm, and 980 nm is particularly strong. Therefore, it is preferable that the light transmittance of this portion is 15% or less.
Further, the visible light transmittance, particularly, the average transmittance at 400 to 450 nm is 35% or more, preferably 40% or more. In addition, the transmittance at 550 to 600 nm is 60% or more, preferably 70% or more. Therefore, it is possible to ensure the color reproducibility (brightness) of scenery and the brightness of the screen of the display when used for a car window glass.

The near-infrared absorption filter of the present invention is also excellent in heat resistance and moist heat resistance, and after 500 hours heat test in a constant temperature bath at 80 ° C. or 500 hours in a constant temperature bath at 60 ° C. and 90% humidity. No new peak appears in the visible light region after the wet heat resistance test.
The filter of the present application preferably has a dye residual ratio of 70% or more, more preferably 75% or more, still more preferably 80% or more, particularly preferably 85% or more, and most preferably 90% or more in the above heat resistance test and moisture heat resistance test. It will be. Here, the dye residual ratio is obtained from the degree of decrease in absorption intensity before and after the test in the region of 780 to 1000 nm. Furthermore, the near infrared absorption filter of the present invention is equipped with a UV cut filter manufactured by Fuji Film Co., Ltd. The dye remaining rate after a 280-hour light resistance test with a xenon lamp in the obtained state is also excellent, preferably the dye remaining rate is 70% or more, more preferably 75% or more, still more preferably 80% or more, particularly preferably Is 85% or more, most preferably 90% or more.

2. Near-infrared absorbing dye used for filter of this application The near-infrared absorbing filter of this invention is characterized by containing the compound represented by the said General formula (1) at least 1 sort (s), and covers 800-1000 nm. Therefore, at least one compound selected from the group consisting of general formulas (2) to (10) and at least one compound represented by the general formula (1) is further included. It is characterized by containing.

In the general formula (1), R ¹ is a hydrogen atom, R ³ is a hydrogen atom, an optionally substituted hydrocarbon group, cyano group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl And a group selected from an arylaminocarbonyl group, R ² and R ⁴ are each independently an optionally substituted hydrocarbon group, cyano group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, It is a group selected from an alkylaminocarbonyl group and an arylaminocarbonyl group.

  Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, 2-methylpropyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, neopentyl group, and 2-ethylbutyl group. Linear, branched or cyclic alkyl groups such as isopropyl group, 2-butyl group, cyclohexyl group, 3-pentyl group, tert-butyl group, 1,1-dimethylpropyl group; 2-propenyl group, 2 -Alkenyl groups such as butenyl group, 3-butenyl group and 2,4-pentadienyl group; alkynyl groups such as ethynyl group; and aryl groups such as phenyl group and naphthyl group. Among these, an alkyl group having 10 or less carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. As the alkyl group, a primary or secondary alkyl group is more preferable.

Examples of the acyl group include formyl group, acetyl group, and benzoyl group.
Examples of the alkyloxycarbonyl group and the alkylaminocarbonyl group include methyl, ethyl, n-propyl, n-butyl, 2-methylpropyl, 2-methylbutyl, 3-methylbutyl, cyclohexylmethyl, neopentyl, 2-ethylbutyl, isopropyl, Examples include linear, branched or cyclic alkyl such as 2-butyl, cyclohexyl, 3-pentyl, tert-butyl, 1,1-dimethylpropyl, and alkyl having 10 or less carbon atoms is preferable. Further, primary or secondary alkyl is preferable.

Examples of the aryloxycarbonyl group and arylaminocarbonyl group include aryl having 6 to 18 carbon atoms such as phenyl and naphthyl.
The substituents of these groups are not particularly limited as long as they do not adversely affect the stability of the dithiolate complex, and examples thereof include halogen atoms, hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkenyl groups, alkynyls. 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, etc. The 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 18 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 the above alkyl groups and aryl groups.

Further, -CH ₂ -CH ₂ and R ³ and R ⁴ together _{-, - CH 2 -CH 2 -CH} 2 -, - C
_{H 2 -CF 2 -CH 2 -,} - CH 2 -CH 2 -CH2-CH 2 -, - CH (Ph) -CH 2 -,
An optionally substituted alkylene group such as —CH (Me) —CH ₂ —; —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 -, - form an alkylene group containing a linking group such as _{- CH 2 -CH 2 -O-CH} 2 -CH 2 You may do it.

R ² and R ⁴ are preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and particularly preferably an aryl group which may have a substituent.
R ³ is preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and particularly preferably a hydrogen atom.
M is a metal atom, and normally, among the metal atoms of Groups 6 to 11 of the periodic table, those having a planar 4-coordinate structure are used. Of these, Group 10 metal atoms are preferred. Examples of preferred metal atoms include iron, cobalt, nickel, palladium, platinum, copper, chromium, manganese and gold, nickel, palladium and platinum are more preferred, and nickel is particularly preferred.

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.

  Specific examples of preferable compounds represented by the general formula (1) include those represented by the following structural formulas. However, it is not limited to the following compounds.

(Dye represented by the general formulas (2) to (10))
The near-infrared absorption filter of the present invention contains at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compounds represented by the general formulas (2) to (10). They can be used in combination.
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 connected to each other directly or via a linking group. M ² may be the same 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 an aryl group such as a benzene ring or a naphthalene ring is more preferable.

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

Further, two adjacent substituents on A and A ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as-may be formed.
Examples of the alkyl group of R ⁵ and R ⁶ include methyl group, ethyl group, n-propyl group, n-butyl group, 2-methylpropyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, and neopentyl group. , A linear, branched or cyclic alkyl group such as 2-ethylbutyl group, isopropyl group, 2-butyl group, cyclohexyl group, 3-pentyl group, 1,1-dimethylpropyl group. Among these, a primary or secondary alkyl group having 10 or less carbon atoms is preferable, and a primary alkyl group having 10 or less carbon atoms is particularly preferable.
Examples of the substituent for the alkyl group of R ⁵ and R ⁶ include the same substituents as those described above as the substituents for R ^{1 to} R ⁴ , and particularly preferably an unsubstituted, halogen atom cyano group. , An alkoxy group and an aryl group. As the halogen atom, a fluorine atom is particularly preferable.
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 ³¹ and R ^The case with ³² , as shown below, is preferred.

R ³¹ and R ³² represent a monovalent substituent. R ³¹ and R ³² 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 or a substituent that may have 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, Or, Hammett's substituent constant sm is 0.00.
An electron withdrawing group such that <sm <0.90 is given. When R ⁵ and R ⁶ are aromatic rings,
As for the substituents on the aromatic ring, two adjacent substituents 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
An alkylenedioxy group having about 1 to 4 carbon atoms, such as O-, may be formed.

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

Those not forming a salt are preferred to 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 group which may have a substituent is shown. Here, R ⁷ and R ⁸ may be connected to each other directly or via a linking group. M ³ may be the same as described for M ¹ .

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

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

Also, two adjacent substituents on B and B ′ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O— or —O (CH ₂ ) ₂ O
An alkylenedioxy group having about 1 to 4 carbon atoms such as-may be formed.
Examples of the alkyl group, aryl group or heteroaryl group for R ⁷ and R ⁸ include the same groups as those described above for the alkyl group, aryl group or heteroaryl group for R ⁵ and R ⁶ . Examples of the substituent of the alkyl group, aryl group or heteroaryl group of R ⁷ and R ⁸ include the same substituents as those described above as the substituents of R ^{1 to} R ⁴ . A halogen atom, a cyano group, a nitro group, an alkoxy group and an aryl 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 ^{33 to} R ⁴¹ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom and bromine atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, propyl group, i-propyl group, Halogen atom or aryl group such as i-butyl group, t-butyl group, n-butyl group, n-pentyl group, trichloromethyl group, trifluoromethyl group, benzyl group, phenethyl group, etc. An alkyl group having 1 to 10 carbon atoms; a phenyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a t-butoxy group and an n-butoxy group; a phenoxy group and a methylphenoxy group And an aryloxy group having 6 to 10 carbon atoms which may be substituted with an alkyl group. Two adjacent substituents of R ^{33 to} R ⁴¹ are combined to form an alkylene group having about 2 to 5 carbon atoms such as — (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —, —OCH ₂ O 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, and among R ^{33 to} R ⁴¹ , One is not a hydrogen atom. Furthermore, it is preferable that at least one of R ^{33 to} R ⁴¹ is a fluorine atom, a chlorine atom or a cyano group, and the remainder is a hydrogen atom.

In general formula (3) ^{is, XR 'R''R'} '' R '''' may form a coordination to salt form. X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those mentioned as the substituents for R ^{1 to} R ⁴ . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

What does not form salt is better than that which forms 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 ⁹ and R ¹⁰ 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 group which may have a substituent is shown. Here, R ⁹ and R ¹⁰ may be connected to each other directly or via a linking group.
M ⁴ may be the same as described for M ¹ .

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

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

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

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

Those not forming a salt are preferred to 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 or a heteroaryl group which may have a substituent.
M ⁴ may be the same as described for M ¹ .
The skeleton constituting the aryl group and heteroaryl group of D and D ′ 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 D and D ′ include the same substituents as those described above as the substituents of R ^{1 to} R ⁴ . Halogen atom, hydroxyl group, nitro group, cyano group, optionally substituted alkyl group, optionally substituted aryl group, optionally substituted heteroaryl group, substituted Examples thereof include an optionally substituted alkoxy group, an optionally substituted aryloxy group, and an optionally substituted amino group. More specifically, halogen atoms such as chlorine atom, bromine atom and fluorine atom; nitro group; cyano group; methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group A halogen atom such as a cyclohexyl group, a benzyl group, a phenethyl group or a trifluoromethyl group or an aryl group which may be substituted; an alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a tolyl group; Groups: heteroaryl groups having 4 to 8 carbon atoms such as pyridyl group and thienyl group; having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group, i-propoxy group, t-butoxy group and n-butoxy group Alkoxy group; aryloxy group having 6 to 10 carbon atoms such as phenoxy group and methylphenoxy group; or amino group, dimethylamino group, diethylamino group, di Eniruamino group include an alkyl group and an amino group which may be substituted with a substituent selected from the group consisting of aryl groups such as methylphenylamino group.

In addition, as described above for B ^{1 to} B ⁸ , as described for the substituents of D and D ′, two adjacent substituents are alkylene groups having about 2 to 5 or alkyl groups having about 1 to 5 carbon atoms. You may connect through connecting groups, such as a range oxy group.
Further, the formula (5) ^{is, XR 'R''R'} '' R '''' may form a coordination to salt form. X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those mentioned as the substituents for R ^{1 to} R ⁴ . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

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

In the general formula (6), R ^{11 to} R ¹⁴ are a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted heteroaryl group, or a cyano group, and preferably substituted. Or an aryl group which may be substituted or an alkyl which may be substituted. M ⁶ may be the same as described for M ¹ above.
Examples of the substituent for the alkyl group, aryl group, and heteroaryl group include the same groups as those described above for R ^{1 to} R ⁴ .

Preferred examples of R ^{11 to} R ¹⁴ include a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, a t-butyl group, an n-butyl group, an n-hexyl group, a cyclohexyl group, An alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom or an aryl group such as a benzyl group, a phenethyl group, a trichloromethyl group or a trifluoromethyl group; a phenyl group, a tolyl group, a chlorophenyl group, a cyanophenyl group, An aryl group having 6 to 15 carbon atoms which may be substituted with a substituent selected from the group consisting of a halogen atom such as a methoxyphenyl group and a phenoxyphenyl group, an alkyl group, an alkoxy group and an aryloxy group is more preferable. Is an aryl group.

Further, the substituents of the aryl group and heteroaryl group of R ^{11 to} R ¹⁴ are the same as those described for D and D ′ above, and the two adjacent substituents are linked to an alkylene group, an alkylenedioxy group or the like. It may be connected through a group.
Further, equation (6) ^{is, XR 'R''R'} '' R '''' may form a coordination to salt form. X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those mentioned as the substituents for R ^{1 to} R ⁴ . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

In general formula (6), those forming a salt and those not forming a salt are preferred.
Preferable specific examples of the dye represented by the general formula (6) include compounds represented by the following structural formula.

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

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

In addition, as described for the substituents D and D ′ above, the adjacent two substituents may be a linking group such as an alkylene group having about 2 to 5 or an alkylenedioxy group having about 1 to 5 carbon atoms. You may connect through.
Further, equation (7) ^{is, XR 'R''R'} '' R '''' may form a coordination to salt form. X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those mentioned as the substituents for R ^{1 to} R ⁴ . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.

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

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

In addition, as described for the substituents F and F ′ above, the adjacent two substituents may be a linking group such as an alkylene group having about 2 to 5 or an alkylenedioxy group having about 1 to 5 carbon atoms. You may connect through.
Further, equation ^{(8), XR 'R''R'} '' R '''' may form a coordination to salt form. X represents a group 15 atom, particularly preferably a nitrogen atom or a phosphorus atom. ^{R ', R'', R} ''', R '''' are each independently, optionally be alkyl or substituted optionally substituted is also aryl groups, the alkyl and aryl groups Examples of the substituent include the same substituents as those mentioned as the substituents for R ^{1 to} R ⁴ . R ^{', R'',}R'^'', R ^'as''', among them preferably a methyl group, an ethyl group, a propyl group, i- propyl, i- butyl, n- butyl, n- hexyl Group, alkyl group such as cyclohexyl group; haloalkyl group such as trichloromethyl group and trifluoromethyl group; phenyl group; aralkyl group such as phenethyl group such as benzyl group.
In the general formula (8), those not forming a salt are more preferable than those forming a salt.

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

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

In the general formula (10), R ^{31 to} R ³⁸ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Here, in R ^{31 to} R ^38, two adjacent substituents may be bonded to each other through a linking group. Specific examples of the substituent for R ^{31 to} R ³⁸ R ^{17 to} R ²⁴ include R ¹ and R in the general formula (1).
And the same groups as described in the description of R ⁴ are selected. R ^{31 to} R ³⁸ are the same as those described for R ^{1 to} R ⁴ above, in which two adjacent substituents are alkylene groups having about 2 to 5 or alkylene dioxy groups having about 1 to 5 carbon atoms. It may be connected via a linking group such as.

X represents an anion, specifically, fluorine anion, chlorine anion, bromine anion, iodine anion, perchlorate anion, hexafluoroantimonate ion, nitrate anion, hexafluorophosphate anion, tetrafluoroborate anion. The monovalent anion represented is shown.
Among the compounds represented by the general formula (7), 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 them, 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.

In addition, the solubility of the compounds represented by the general formulas (2) to (10) in a solvent selected from aromatic hydrocarbon solvents such as toluene, ether solvents such as tetrahydrofuran and dimethoxyethane, and ketone solvents such as methyl ethyl ketone Is usually 0.1% or more, preferably 0.5% or more.
In addition, the said compound (1) is J.I. Chem. Soc. Dalton Trans. 587 (1995), and the above compound (2) is Russ. J. Gen. Chem., 66, 1
842 (1996). The above compound (3) can be synthesized by the method described in JP-A No. 2001-89492. Am. Chem. Soc. 88, p. 5201 (1966). Am. Chem. Soc. , 88 卷, 43 and 4870 (1966). Am. Chem. Soc. 87, p. 1483 (1965), and compound (7), compound (8), and compound (9) can be synthesized by the method described in JP-A-2000-26748.

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

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

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

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

  At this time, the concentration of the total solid content such as the near-infrared absorbing dye, the dispersant, and the binder resin dissolved or dispersed in the solvent is usually 5 to 50% by weight. Moreover, the density | concentration of the metal complex with respect to the total solid is 0.1 to 50 weight% normally as a near red absorption pigment | dye total, Preferably it is 0.2 to 30 weight%. 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) is 1: 0.1 to 1:10, preferably 1: 0. .2 to 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%.
As the polymer binder, any polymer binder having solubility in a non-chloro solvent of 3% or more can be used. Specifically, methacrylate, polycarbonate, polystyrene, polyarylate, polyethylene terephthalate, and polyester are preferably used. . 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 polymer binder.

  Solvents include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, octanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, methyl propionate, methyl enanthate, linole Esters such as methyl acid and methyl stearate Aliphatic hydrocarbons such as cyclohexane, hexane and octane, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, nitrobenzene and squalane, dimethyl sulfoxide Sulfoxides such as sulfolane, amides such as N, N-dimethylformamide, N, N, N ′, N′-tetramethylurea, tetrahydrofuran (hereinafter referred to as “THF”) Dioxane, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether or may be a mixture thereof.

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

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

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

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

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

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

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

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

3. Filter for electronic display Furthermore, the infrared absorption filter of the present invention is provided with an anti-glare layer, a glare-preventing layer (non-glare layer), if necessary, an electromagnetic wave cut layer, an anti-reflection layer for preventing external light such as fluorescent light from being reflected on the surface. Layer) and a color tone correction layer are provided, and can be used as a filter for an electronic display, more preferably a plasma display panel.

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

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

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

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

Embodiments of the present invention will be described below by way of examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
Examples 1-7
About the compound described in following Table 1, the half value width was calculated | required using the spectrum measured in the tetrahydrofuran solution. The half-value width is a width of Abs. = 0.5 of the spectrum obtained by normalizing the absorbance (Abs.) At 1 to the maximum absorption wavelength (λmax) at 800 to 1000 nm. The measurement results are shown in Table 1.
Comparative Example 1
The full width at half maximum was determined in the same manner as in Example 1 using a spectrum obtained by measuring the compound of the following formula (11) used in Example 4 of JP-A-9-230134 in a tetrahydrofuran solution. The measurement results are shown in Table 1.

Comparative Example 2
The full width at half maximum was determined in the same manner as in Example 1 using a spectrum obtained by measuring a compound of the following formula (12) used in Example 1 of JP-A-9-230134 in a tetrahydrofuran solution. The measurement results are shown in Table 1.

As described above, the compound used in the near-infrared absorption filter of the present invention has a half-value width of about 140 nm to 200 nm, whereas the half-value widths of formulas (11) and (12), which are known near-infrared absorbing dyes, are They are 125 nm and 122 nm, respectively. That is, since the compound used for the near-infrared absorption filter of the present invention has a wide half-value width, it is clear that it is excellent as a dye used for the near-infrared absorption filter.
Example 8
(Exemplary Compound 1) 27.5 mg is mixed with 1.78 g of toluene, 2.5 g of a toluene / MEK (= 1/1) solution of acrylic resin (Optrez OZ1100) (resin concentration 35 wt%), and ultrasonic waves are mixed. And dissolved to prepare a coating solution.

This coating solution was applied to a polyethylene terephthalate film with a bar coater (No. 12; manufactured by Eto Kikai Co., Ltd.) and dried to obtain a near infrared absorption filter.
Λmax of this filter was 820 nm.
Furthermore, in order to evaluate heat resistance and heat-and-moisture resistance, heat resistance and heat-and-moisture resistance tests were conducted for 500 hours in a constant-temperature bath at 80 ° C. and a constant-temperature layer at 60 ° C. and 90% humidity, and absorption before and after irradiation at 820 nm. When the intensity was measured, the dye residual ratio (absorption intensity after irradiation ÷ absorption intensity before irradiation × 100) was 92.6% and 99.6%, 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. is attached to this filter, and light is 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 820 nm was measured, the dye residual ratio (intensity after irradiation ÷ intensity before irradiation × 100) was as good as 84.1%, and there was no filter color change.

Example 9
(Exemplary Compound 2) 34.3 mg is mixed with 2.0 g of THF (tetrahydrofuran) and 4.0 g of an acrylic resin (Optrez OZ1100) in THF (resin concentration: 30% by weight) and dissolved by applying ultrasonic waves. A working solution was prepared.

After filtering this coating liquid, it was coated on 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.
Λmax of this filter was 781 nm.
Furthermore, in order to evaluate heat resistance and heat-and-moisture resistance, a constant temperature bath of 80 ° C., 60 ° C., humidity 9
The sample was placed in a 0% constant temperature layer for 500 hours to conduct heat resistance and moist heat resistance tests, and the absorption intensity before and after irradiation at 781 nm was measured. The residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was 94.5% and 98.1% respectively showed good heat resistance and moist heat resistance, and there was no color change of the filter.

  A UV cut filter (SC-39) manufactured by Fuji Photo Film Co., Ltd. is attached to this filter, and light is 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 781 nm was measured, the residual ratio of the dye (intensity after irradiation ÷ intensity before irradiation × 100) was 91.0% and the filter color did not change.

Example 10
(Exemplary Compound 3) 34.3 mg is mixed with 2.0 g of THF (tetrahydrofuran) and 4.0 g of an acrylic resin (Optretz OZ1100) in THF (resin concentration: 30% by weight) and dissolved by applying ultrasonic waves. A working solution was prepared.

After filtering this coating liquid, it was coated on 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.
Λmax of this filter was 823 nm.
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, and absorption before and after irradiation at 823 nm. When the intensity was measured, the dye residual ratio (intensity after irradiation ÷ intensity before irradiation × 100) was 92.4% and 98.3%, 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. is attached to this filter, and light is 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 823 nm was measured, the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was as good as 82.0%, and there was no filter color change.

Example 11
(Exemplary Compound 5) 34.3 mg is mixed with 2.0 g of THF (tetrahydrofuran) and 4.0 g of an acrylic resin (Optretz OZ1100) in THF (resin concentration: 30% by weight) and dissolved by applying ultrasonic waves. A working solution was prepared.
After filtering this coating liquid, it was coated on 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.
Λmax of this filter was 841 nm.
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, and absorption before and after irradiation at 841 nm. When the intensity was measured, the dye residual ratio (intensity after irradiation ÷ intensity before irradiation × 100) was 97.1% and 99.9%, 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. is attached to this filter, and light is 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 841 nm was measured, the residual dye ratio (intensity after irradiation ÷ intensity before irradiation × 100) was 87.5%
The filter color was not changed.

  The results of Examples 8 to 11 are shown below.

From Table 2, the filter of the present invention has good heat resistance, moist heat resistance, and light resistance, and there is no color change of the filter after the test. It turns out that it is excellent as an infrared absorption filter.
Comparative Example 3
A filter was produced in the same manner as in Example 8, except that the compound of formula (11) was used instead of (Exemplary Compound 1). However, since the compound of formula (11) hardly dissolved in the toluene / MEK solution and remained undissolved when preparing the coating solution, the finally obtained filter had almost no absorption in the near infrared region.

Comparative Example 4
A filter was produced in the same manner as in Example 8, except that the compound of formula (12) was used instead of (Exemplary Compound 1). However, since the compound of the formula (12) was not completely dissolved in the toluene / MEK solution when the coating solution was prepared, the filter finally obtained had almost no absorption in the near infrared region.

  The solubility of Exemplified Compound 1 and the compound of the formula (12) having higher solubility than that of the formula (11) in toluene was measured at room temperature, and as shown in Table 2 below.

  From the above results, since the dithiol metal complex of the present invention has high solubility, it is clear that the near infrared absorption layer of the near infrared absorption filter can be formed by coating, and the near infrared absorption filter can be easily produced. .

Claims (10)

The following general formula (1)

Wherein R ¹ is a hydrogen atom, R ³ is a hydrogen atom, an optionally substituted hydrocarbon group, a cyano group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and an arylamino A group selected from a carbonyl group, R ² and R ⁴ are each independently an optionally substituted hydrocarbon group, cyano group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, And a group selected from an arylaminocarbonyl group, wherein M represents a metal atom.) A near-infrared absorption filter comprising a layer containing at least one compound represented by: The following general formula (1)

Wherein R ¹ is a hydrogen atom, R ³ is a hydrogen atom, an optionally substituted hydrocarbon group, a cyano group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and an arylamino A group selected from a carbonyl group, R ² and R ⁴ are each independently an optionally substituted hydrocarbon group, cyano group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, And a group selected from arylaminocarbonyl groups, M represents a metal atom), 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 heteroaryl group which may have a substituent, and R ⁵ and R ⁶ each represents Independently, it represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a hydrogen atom. , R ⁵ and R ⁶ may be connected to each other directly or via a linking group, or XR′R ″ R ′ ″ R ″ ″ is coordinated to formula (2). Wherein X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ represent an alkyl 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)

(In the formula, B and B ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and R ⁷ and R ⁸ each represents Independently, it represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a hydrogen atom. , R ⁷ and R ⁸ may be connected to each other directly or via a linking group, or XR′R ″ R ′ ″ R ″ ″ is coordinated to formula (3). Wherein X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ represent an alkyl 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)

(In the formula, C and C ′ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and R ⁹ and R ¹⁰ each represents Independently,
An alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a hydrogen atom is shown. Where R ⁹ and R ¹⁰ are
They may be connected to each other directly or via a linking group. Alternatively, XR′R ″ R ′ ″ R ″ ″ may coordinate to formula (4) to take a salt form. Here, X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ have an alkyl group which may have a substituent or a substituent. An aryl group that may be present is shown. M ⁴ represents a metal atom. ), A compound represented by the following general formula (5)

(In the formula, D and D ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Alternatively, XR in formula (5) 'R''R''' R '''' may be coordinated to take a salt form, where X represents a group 15 atom, and R ', R'',R''', R ''''Represents an alkyl group which may have a substituent or an aryl group which may have a substituent. M ⁵ represents a metal atom.) Formula (6)

(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents an optionally substituted alkyl group or an optionally substituted aryl group. Here, R ¹¹ and R ¹² R ¹³ and R ¹⁴ may be combined to form a ring, and R ^{11 to} R ¹⁴ may have two adjacent substituents connected to each other via a linking group. 6) XR'R''R '''R
'''' May be coordinated to take a salt form. Here, X represents a group 15 atom, and R ′, R ″, R ′ ″, R ″ ″ have an alkyl group which may have a substituent or a substituent. An aryl group that may be present is shown. M ⁶ represents a metal atom) and the following general formula (7)

(In the formula, E and E ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Alternatively, XR in formula (7) 'R''R''' R '''' may be coordinated to take a salt form, where X represents a group 15 atom, and R ', R'',R''', R ''''Represents an alkyl group which may have a substituent, or an aryl group which may have a substituent. M ⁷ represents a metal atom.) Formula (8)

(In the formula, F and F ′ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Alternatively, XR in formula (8) 'R''R''' R '''' may be coordinated to take a salt form, where X represents a group 15 atom, and R ', R'',R''', R ''''Represents an alkyl group which may have a substituent, or an aryl group which may have a substituent. M ⁸ represents a metal atom.) Formula (9)

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

(In the formula, R ^{31 to} R ³⁸ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Here, in R ^{17 to} R ²⁴ , two adjacent substituents may be connected via a linking group, Y ⁻ represents an anion. A near-infrared absorption filter having a layer containing one or more selected compounds. The near-infrared absorption filter according to claim 1, wherein R ³ is a hydrogen atom. The near-infrared absorption filter according to claim 1 or 2, wherein R ² and R ⁴ are each independently an optionally substituted alkyl group or an optionally substituted aryl group. The near-infrared absorbing filter according to claim 1, further comprising an ultraviolet cut layer. A display filter comprising the infrared absorption filter according to claim 1. The display filter according to claim 6, further comprising an electromagnetic wave shielding layer. The display filter according to claim 6 or 7, further comprising an antireflection layer. The display filter according to any one of claims 6 to 8, wherein a color tone correction layer is provided. A filter for a plasma display panel, comprising the display filter according to claim 6.