JP4793977B2 - Near infrared absorption filter - Google Patents

Description

The present invention relates to a near-infrared absorption filter, and more particularly to a near-infrared absorption filter that has a high visible light region transmittance and effectively blocks near-infrared rays. Is.
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 absorbing 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 reader.
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 to 1050 nm as a PDP filter because it acts on the device and causes a 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 dyes such as aminium salt compounds, etc. Various studies have been made. For example, it is described in Patent Document 1 that a dithiolate compound having an alkylthio group or an arylthio group is used as an optical filter (see Patent Document 1).
JP-A 64-69686

The near-infrared absorbing dye cannot cover the range of 800 to 1050 nm as described above with only one kind of dye, and usually has a relatively short wavelength among a plurality of kinds of dyes, specifically, near-infrared rays. Are used in combination with a dye that absorbs near infrared rays and a dye that absorbs relatively long-wavelength near infrared rays.
At this time, considering the labor and cost at the time of manufacture, it is preferable to mix a plurality of types of dyes and include them in the same resin layer, but the mixed dyes interact with each other and used alone. Compared with performance degradation. Therefore, the actual product often has each dye-containing layer laminated.

As dyes that absorb near infrared rays having a relatively long wavelength, immonium, phthalocyanine, and naphthalocyanine are generally used.
However, when immonium is contained in the same resin layer as the complex compound dye or the non-metal-containing compound dye, immonium deteriorates, and there is a problem that absorption occurs near 400 to 450 nm and yellowing occurs. Further, although phthalocyanine and naphthalocyanine are highly durable and are difficult to cause yellowing due to deterioration, there is a problem that the degree of freedom in use as an optical filter is reduced because of low visible light transmittance.

In other words, conventional near-infrared absorption filters using these dyes change the yellow color due to long-term use or visible light when trying to mix multiple kinds of dyes in consideration of the labor and cost at the time of manufacture. There was a problem of low transmittance.
Accordingly, an object of the present invention is to provide a near-infrared absorption filter that efficiently absorbs near-infrared rays, has high visible light transmittance, and has a small yellow change even after long-term use.

In view of the above problems, the present inventors have intensively studied combinations of pigments to be mixed. As a result, the present invention efficiently absorbs a wide range of near infrared rays such as 800 to 1050 nm, has little yellow change even after long-term use, and is 400 to 400- A near-infrared absorption filter having a high light transmittance in the visible light region of 700 nm was found and the present invention was completed.
That is, the gist of the present invention is that a near-infrared absorption filter comprising a near-infrared absorbing dye and satisfying the following conditions (a) to (c): (a) transmittance at wavelengths of 825 nm, 880 nm, and 980 nm 10% or less (b) The transmittance at wavelengths of 450 nm, 525 nm, and 625 nm is 40% or more. (C) The change rate (%) of absorbance at 430 nm before and after the heat resistance test held at a temperature of 80 ° C. for 500 hours is −20% to 20 %
Exist.
Furthermore, the following general formula (1)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent an optionally substituted aliphatic hydrocarbon group or an optionally substituted aryl group. R ¹ and R ² , R ³ and R ⁴ may be combined to form a ring, or a compound represented by XR ′ R ″ R ′ ″ R ″ ″ is coordinated to formula (1). Or X may represent a group 15 atom, and R ′, R ″,
R ′ ″ and R ″ ″ each represents an alkyl group which may have a substituent or an aryl group which may have a substituent. M ¹ represents a metal atom. ) And a compound represented by
The following general formula (2)

(In the formula, A and A ′ each independently represent an aryl group which may have a substituent or a 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 ″ in formula (2).
The compound represented by 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 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 ″ in formula (3).
The compound represented by 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 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, XRR ′ in formula (4)
The compound represented by 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 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, XRR in formula (5) The compound represented by '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. Compounds,
The following general formula (6)

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

(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, XRR in formula (7) The compound represented by '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. Compounds,
The following general formula (8)

(In the formula, F and F ′ each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Alternatively, XRR in formula (8) The compound represented by '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. Compounds,
And the following general formula (9)

(Wherein R ^{15 to} R ³⁰ each independently represents an arbitrary substituent, and two adjacent substituents may form a ring via a linking group. M ⁹ is a hydrogen atom or a metal An atom (wherein the metal atom may be a metal oxide, a metal halide or a metal carbonyl compound, or may form a salt with an acid). It exists in the near-infrared absorption filter characterized by having a layer containing 1 or more types of compounds chosen from the group which consists of a compound.

  According to the present invention, there is provided a near-infrared absorption filter that efficiently absorbs a wide range of near-infrared rays of 800 to 1050 nm, has high visible light transmittance, and has little yellowing change even after long-term use.

Hereinafter, the present invention will be described in detail.
1, near-infrared absorption filter The near-infrared absorption filter of this invention is a near-infrared absorption filter which contains a near-infrared absorption pigment | dye and covers the wavelength range of 800-1050 nm, Comprising: The condition (c) is satisfied.
(A) The transmittance at wavelengths of 825 nm, 880 nm, and 980 nm is 10% or less

  In a plasma display panel, near-infrared emission around 825 nm, 880 nm, and 980 nm is particularly strong, and a filter that absorbs these wavelengths is useful. The near-infrared absorption filter of the present invention has a light transmittance of 10% or less at these wavelengths. Moreover, it is preferable that the average light transmittance in a wavelength range of 800-1050 nm is 20% or less, and it is more preferable that it is 15% or less.

(B) The transmittance at wavelengths of 450 nm, 525 nm, and 625 nm is 40% or more. The visible light emission of a normal plasma display has a blue light emission at 400 to 500 nm with a peak at 450 nm, and 500 to 550 nm with a peak at 525 nm. In addition, green light emission exists, and red light emission exists as sharp light emission at 595 nm, 610 nm, and 625 nm. However, among the red light emission, 595 nm light emission is usually caused by causing the front filter to contain a dye having absorption in this region as light emission causing the red color of the plasma display to appear red. (See JP 2000-258624 A).
For these reasons, in plasma display applications, the transmittance of 450 nm, 525 nm, and 625 nm is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more, from the viewpoint of securing the brightness of the display screen.
Further, the visible light transmittance, particularly the average transmittance at 400 to 450 nm is preferably 35% or more, more preferably 40% or more. In addition, when the average transmittance at 550 to 600 nm is preferably 60% or more, more preferably 70% or more, the color reproducibility (brightness) of scenery and the brightness of the display screen when used for car window glass. It is also possible to ensure the thickness.

(C) The change rate (%) of absorbance at 430 nm before and after the heat resistance test held at a temperature of 80 ° C. for 500 hours is −20% to 20%
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 even after a 500-hour heat test in a thermostat at 80 ° C. Absorbance at 430 nm Change (%) (change in absorbance = (absorbance after test−absorbance before test) / absorbance before test) is −20% or more, preferably −15% or more, more preferably −10% or more, and 20% Below, it is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less. Here, 430 nm is a wavelength related to yellow, and a small change in absorbance at 430 nm means that there is little yellow change.
ΔE * ab in the L * a * b * color system before and after the test is usually −5.0 or more, preferably −3.0 or more, more preferably −2.0 or more, and further preferably −1.0 or more. In general, it is 10.0 or less, preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less. In particular, Δb * is −3.0 or more, preferably −2.0 or more, more preferably −1.5 or more, and 3.0 or less, preferably 2.0 or less, more preferably 1.0 or less. It is.
Further, as defined in (a) above, the near infrared absorption filter of the present invention has a light transmittance of 10% or less at 820 nm, 880 nm, and 980 nm. After that, 15% or less can be maintained.

In addition to the conditions (a) to (c), the following condition (d) is preferably satisfied. (D) The rate of change (%) in absorbance at 430 nm before and after the wet heat resistance test held at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours is −40% to 40%
The near-infrared absorption filter of the present invention is also excellent in moisture and heat resistance, and a new peak may appear in the visible light region even after a 500 hour moisture and heat resistance test in a thermostat at 60 ° C. and a humidity of 90%. Absorbance change (%) at 430 nm (absorbance change = (absorbance after test−absorbance before test) / absorbance before test) is usually −40% or more, preferably −20% or more, more preferably −15%. More preferably, it is -10% or more, usually 40% or less, preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, and particularly preferably 5% or less.

  ΔE * ab in the L * a * b * color system before and after the test is usually −5.0 or more, preferably −3.0 or more, more preferably −2.0 or more, and further preferably −1.0 or more. In general, it is 10.0 or less, preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less. In particular, Δb * is −3.0 or more, preferably −2.0 or more, more preferably −1.5 or more, and 3.0 or less, preferably 2.0 or less, more preferably 1.0 or less. It is.

Further, as defined in (a) above, the near infrared absorption filter of the present invention has a light transmittance of 10% or less at 820 nm, 880 nm, and 980 nm, but 500 hours in a constant temperature bath at 60 ° C. and 90% humidity. Even after the moisture and heat resistance test is performed, 15% or less can be maintained.
In addition to the conditions (a) to (c), the following condition (e) is preferably satisfied. (E) Absorbance change rate (%) at 430 nm is -20% to 20% before and after the light resistance test in which light having a radiation intensity of 320 w / m ² is irradiated for 280 hours with a xenon lamp.
The near-infrared absorption filter of the present invention has excellent light resistance, and a new peak is observed in the visible light region even after a light resistance test in which light having a radiation intensity of 320 w / m ² is irradiated for 280 hours with a xenon lamp. Absorbance change at 430 nm (%) without change (absorbance change = (absorbance after test−absorbance before test) / absorbance before test) is usually −20% or more, preferably −15% or more, more preferably − It is 10% or more, usually 20% or less, preferably 15% or less, more preferably 10% or less, and further preferably 5% or less.
The method of the light resistance test is not particularly limited as long as it can irradiate light having the above-mentioned radiation intensity. For example, with the UV cut filter (SC-39) manufactured by Fuji Film Co., Ltd. attached, 320 w with a xenon lamp. The light resistance test is conducted for 280 hours with light of / m ² . The light irradiated by the xenon lamp usually includes light of 300 to 700 nm and does not substantially include light of 300 nm or less.

  In addition, ΔE * ab in the L * a * b * color system before and after the test is usually −5.0 or more, preferably −3.0 or more, more preferably −2.0 or more, and further preferably −1. 0 or more and usually 10.0 or less, preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less. In particular, Δb * is −3.0 or more, preferably −2.0 or more, more preferably −1.5 or more, and 3.0 or less, preferably 2.0 or less, more preferably 1.0 or less. It is.

Further, as defined in (a) above, the near infrared absorption filter of the present invention has a light transmittance of 10% or less at 820 nm, 880 nm, and 980 nm, but the xenon lamp emits light having a radiation intensity of 320 w / m ² to 280. Even after performing a light resistance test with time irradiation, the light transmittance at 820 nm, 880 nm, and 980 nm can be maintained at 15% or less.
Among these, those satisfying all the conditions (a) to (e) are preferable.
2, Near-infrared absorbing dye used in the present application filter The near-infrared absorbing filter of the present invention usually contains two or more kinds of near-infrared absorbing dyes and has a layer containing two or more kinds of near-infrared absorbing dyes. Those are preferred.
The two or more types of near infrared absorbing dyes preferably include at least the following two types of near infrared absorbing dyes (i) and (ii).
Among them, the compound represented by the following general formula (1) as the near infrared absorbing dye of (i) is selected from the group consisting of the following general formulas (2) to (9) as the near infrared absorbing dye of (ii). Those containing at least one of the compounds are more preferred. Since the compound represented by the general formula (1) and the compounds represented by the general formulas (2) to (9) have extremely small interaction, they can be contained in the same resin layer.
(I) As a pigment | dye which has the near-infrared absorption pigment | dye maximum absorption wavelength which has a maximum absorption wavelength in 900 nm-1200 nm in 900 nm-1200 nm, the compound represented by following General formula (1) is preferable.

In the general formula (1), R ¹ and R ² , R ³ and R ⁴ each independently represent an optionally substituted aliphatic hydrocarbon group or an optionally substituted aryl group.
Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, 2-methylpropyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, neopentyl group, 2- Linear, branched or cyclic alkyl groups such as ethylbutyl, isopropyl, 2-butyl, cyclohexyl, 3-pentyl, tert-butyl and 1,1-dimethylpropyl; 2-propenyl Alkenyl groups such as 2-butenyl group, 3-butenyl group and 2,4-pentadienyl group; and alkynyl groups such as ethynyl group.

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

R ¹ and R ² , R ³ and R ⁴ may be integrated to form a ring. _{Specifically, -CH 2 -CH 2 -, -} CH 2 -CH 2 -CH 2 -, - CH 2 -CF 2 -CH 2 -, - CH 2
-CH ₂ -CH ₂ -CH ₂ -, and _{-CH (Ph) -CH 2 -,} - CH (Me) -CH 2 -
An optionally substituted alkylene group such as —CH═CH—, —C (Me) ═CH—, and —CH═CH—CH ₂ —CH ₂ —CH═CH—. Alkenylene group; —CH ₂ —S—CH ₂ —, —CH ₂ —O—CH ₂ —, —CH ₂ —C (═O) —CH ₂ —, —CH ₂ —CH ₂ —S—CH ₂ —CH ₂ -, and _{-CH 2 -CH 2 -O-CH 2} -CH 2 - may form an alkylene group containing a linking group, and the like.

R ¹ and R ² , R ³ and R ⁴ are preferably an unsubstituted alkyl group or a good alkyl group having a substituent, particularly preferably an unsubstituted alkyl group, a halogen atom (particularly preferably a fluorine atom), An alkyl group having a substituent selected from the group consisting of a cyano group, an alkyl group and an aryl group.
R ¹ and R ² , R ³ and R ⁴ may be the same or different, but the same is preferable.

M ¹ represents a metal element, preferably a Group 10 element such as Ni, Pd, or Pt; Au, Co, Fe, Ti, Sn, or Cu, more preferably a Group 10 element, and particularly Ni. preferable.
In addition, the compound represented by the general formula (1) may take a salt form by coordination with a compound represented by XR ′ R ″ R ′ ″ R ″ ″. In the case of forming a salt, the salt is usually represented by the following formula (X1) in which X is a cation or the following formula (X2) in which XR ′ R ″ R ′ ″ R ″ ″ is a cation as a whole. And a salt represented by the formula (X2) is preferable.

Here, 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 R ^{1 to} R ⁴ . R ′, R ″, R ′ ″, R ″ ″ are preferably methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, n-butyl group, n-hexyl. And alkyl groups such as cyclohexyl group; haloalkyl groups such as trichloromethyl group and trifluoromethyl group; phenyl groups; aryl groups such as benzyl group; and aralkyl groups such as phenethyl group.

Among those exemplified above, those not forming a salt are more preferable than those forming a salt.
Among those not forming a salt, R ¹ and R ² , R ³ and R ⁴ are preferably primary or secondary alkyl groups having 10 or less carbon atoms, and secondary alkyl groups having 10 or less carbon atoms are preferred. Some are more preferred.

The molar extinction coefficient is usually 5000 or more, preferably 8000 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.

  Preferred examples of the near-infrared absorbing compound used in the filter of the present application include a combination of compounds that are preferred in the description of each substituent. Specific examples that are preferred as the compound represented by the general formula (1) Examples of such a compound include those represented by the following structural formula. However, it is not limited to the following compounds.

(Ii) As a near-infrared absorbing dye having a maximum absorption wavelength of 750 nm to 900 nm having a maximum absorption wavelength of 750 nm to 900 nm, dyes represented by the following general formulas (2) to (9) are preferable.
The compounds represented by the following general formulas (2) to (9) are represented by XR ′ R ″ R ′ ″ R ″ ″ as in the case of the compound represented by the general formula (1). The compound may be coordinated to take a salt form. The salt in the case of forming a salt is usually a salt in which X is a cation or a salt in which XR ′ R ″ R ′ ″ R ″ ″ is a cation as a whole, and XR ′ R ″ R ′ ″ R Salts in which '''' is entirely a cation are preferred.

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.
R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl that may have a substituent. Indicates a group. Here, R ⁵ and R ⁶ may be linked directly or via a linking group. M ² may be the same as 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 for the aryl group and heteroaryl group of A and A ′ include the same substituents as those described above as the substituents for R1 to R4. Among them, a halogen atom, a hydroxyl group, a nitro group are preferable. Group, cyano group, alkyl group which may be substituted, aryl group which may have substituent, heteroaryl group which may have substituent, alkoxy group which may have substituent And 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 A and A ′ are combined to form — (CH ₂ ) ₃ — or — (
An alkylene group having about 2 to 5 carbon atoms such as 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, 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. In particular, the case as shown below is 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 ^This is the case with ³² . 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, Alternatively, an electron-withdrawing group in which Hammett's substituent constant σm is 0.00 <σm <0.90 can be given. 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.

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

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.
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 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.

Further, two adjacent substituents on B and B ′ are combined to form — (CH ₂ ) ₃ — or — (
An alkylene group having about 2 to 5 carbon atoms such as 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, an aryl group or a heteroaryl group of the R7 and R8, but the same substituents as those raised by a substituent of the previous R ¹ to R ⁴ can be mentioned, particularly preferably a halogen atom , A cyano group, a nitro group, an alkoxy group and an aryl group.
R ⁷ and R ⁸ may be bonded to each other directly or via a linking group, but a case of the following general formula (3 ′) is particularly preferable.

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.

  Preferred examples of the dye represented by the general formula (3) include those represented by the following structural formula.

The following general formula (4)

In C, C and C ′ each independently represents 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 which may have a substituent. Indicates a group. 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 for the aryl group and heteroaryl group for C and C ′ include the same substituents as those described above as the substituents for R1 to R4. Among them, a halogen atom, a hydroxyl group, a nitro group are preferable. Group, cyano group, alkyl group which may be substituted, aryl group which may have substituent, heteroaryl group which may have substituent, alkoxy group which may have substituent And 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 C and C ′ are combined to form — (CH ₂ ) ₃ — or — (
An alkylene group having about 2 to 5 carbon atoms such as 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;
Preferred examples of the dye represented by the general formula (4) include those represented by the following structural formula.

The following general formula (5)

In the above, D and D ′ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
M ⁵ 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.

Further, as described for the substituents of D and D ′ above, two adjacent substituents are 2 to 5
It may be connected via a linking group such as an alkylene group of about 1 to 5 carbon atoms and an alkylenedioxy group of about 1 to 5 carbon atoms.
Preferred examples of the dye represented by the general formula (5) include those represented by the following structural formula.

The following general formula (6)

R ^{11 to} R ¹⁴ are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or a cyano group, preferably a substituted group. An aryl group which may be substituted or an alkyl group 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.

In addition, the substituents of the aryl group and heteroaryl group of R ^{11 to} R ¹⁴ are the above-described D and D ′.
Two adjacent substituents may be connected via a linking group such as an alkylene group or an alkylenedioxy group in the same manner as described above.
Preferable specific examples of the dye represented by the general formula (6) include compounds represented by the following structural formula.

The following general formula (7)

In the formula, E and E ′ each independently represents 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.

Further, as described for the substituents of D and D ′ above, two adjacent substituents are 2 to 5
It may be connected via a linking group such as an alkylene group of about 1 to 5 carbon atoms and an alkylenedioxy group of about 1 to 5 carbon atoms.
Preferred specific examples of the dye represented by the general formula (7) include those represented by the following structural formula.

The following general formula (8)

In the formula, F and F ′ each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
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 ′, two adjacent substituents are 2 to 5
It may be connected via a linking group such as an alkylene group of about 1 to 5 carbon atoms and an alkylenedioxy group of about 1 to 5 carbon atoms.

The following general formula (9)

In the formula, R ^{15 to} R ³⁰ represent an arbitrary substituent and are not particularly limited as long as the basic performance of the compound of the present invention is not impaired. For example, the same as those mentioned as the substituents for R ^{15 to} R ³⁰ The group of.
M ⁹ in the general formula (9) is a hydrogen atom or a metal atom. The metal atom is not particularly limited as long as it can form a complex with the phthalocyanine skeleton, and may be a metal oxide, a metal halide, or a metal carbonyl compound, or may form a salt with an acid. . A copper atom, a vanadium oxy group, or a tin chloride group is preferable.

  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 addition, the solubility of the compounds represented by the above general formulas (2) to (9) in a solvent selected from an aromatic hydrocarbon solvent such as toluene, an ether solvent such as tetrahydrofuran and dimethoxyethane, and a ketone solvent such as methyl ethyl ketone. Is usually 0.1% or more, preferably 0.5% or more.
In addition, the said compound (1) is J.I. Mater. Chem. , P. 1861 (1994), and the compound (2) is Russ. J. Gen. Chem., 66, 1842 (19
96), and the above compound (3) can be synthesized by the method described in JP-A-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.

3. Manufacturing method of near-infrared absorbing filter The manufacturing method of the infrared absorbing filter of the present invention includes a method of coating a transparent substrate with a coating liquid containing a near-infrared absorbing dye, a film obtained by melting and kneading a near-infrared absorbing dye with a binder resin. 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%. 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 1:10 or more, preferably 1: 5 or more, : 0.1 or less, preferably 1: 0.2 or less.

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 usually include polymethyl methacrylate resin, polyethyl acrylate resin, polycarbonate resin, ethylene-vinyl alcohol copolymer resin, polyester resin, and the like. The amount of the metal complex compound used is 0.01% by weight or more, preferably 0.1% by weight or more and 20% by weight or less, preferably 10% by weight or less, based on the binder.
Moreover, as a binder used for the near-infrared absorption filter in the case of containing a compound selected from the group consisting of the compound represented by (1) and a salt type compound thereof, the moisture absorption rate at a temperature of 60 ° C. and a humidity of 90% is 2%. The following binders are preferred.

  Such a polymer binder is not particularly limited as long as it has a moisture absorption rate of 2% or less at a temperature of 60 ° C. and a humidity of 90%, and can be appropriately selected from ordinary polymer binders. Methyl methacrylate, polycarbonate, polystyrene, polyarylate, polyethylene terephthalate, polyester and the like have high solubility in organic solvents and are effectively used. These polymer binders may be used alone or in combination of two or more.

  The molecular weight of these polymer binders is usually 1000 or more, preferably 5000 or more, more preferably 10,000 or more, and usually 1 million or less, preferably 500,000 or less, more preferably 300,000 or less. When the molecular weight is small, the polymer binder having a hydrophilic substituent at the end tends to increase the hygroscopicity. When the molecular weight is large, the solubility in an organic solvent tends to be low and handling tends to be complicated. .

  The acid value of the polymer binder is usually 0 mg-KOH / g or more, usually 10 mg-KOH / g or less, preferably 5 mg-KOH / g or less, more preferably 2 mg-KOH / g or less. If the acid value of the polymer binder is large, the moisture absorption rate tends to be high, and if the acid value is small, the moisture absorption rate tends to be low. Therefore, it is preferable that the acid value is as small as possible.

  In order to measure the acid value of the polymer binder, the polymer binder is dissolved in a solvent such as ether or ethanol, then neutralized with a KOH solution, and KOH (potassium hydroxide) consumption per 1 g of the polymer binder ( mg). The solvent used here is not particularly limited as long as it does not affect the titration and sufficiently dissolves the polymer binder. For example, ether solvents, alcohol solvents and the like are common and can be appropriately selected and used for the polymer binder.

  In the present invention, the polymer binder having a low moisture absorption rate is preferably one having a small amount of hydrophilic substituents such as a hydroxyl group, a carboxyl group and a sulfonyl group. Since the acid value correlates with the amount of these hydrophilic substituents, if the acid value of the polymer binder is small, the hydrophilicity of the polymer binder is lowered, and as a result, the moisture absorption rate tends to be lowered.

In the present invention, the moisture absorption rate of the polymer binder at a temperature of 60 ° C. and a humidity of 90% (hereinafter sometimes referred to as “60 ° C., 90% moisture absorption rate”) is as follows. The polymer binder was allowed to stand in a constant temperature and high humidity bath at 90 ° C. and a humidity of 90% for a predetermined time, and the weight was measured to determine the change in weight increase. The change in weight was substantially eliminated (for example, 0.05% / day). From the weight W ₁ when the weight is heaviest and the initial weight (dry weight) W ₀ , it can be calculated by the following formula. Usually, it is left to stand in the constant temperature and high humidity tank for one week, and W ₁ is measured.
60 ° C., 90% moisture absorption = (W ₁ −W ₀ ) ÷ W ₀ × 100

In the present invention, when the polymer binder used has a 60 ° C., 90% moisture absorption rate exceeding 2%, sufficient heat resistance, moisture resistance, and light resistance cannot be obtained. The 60 ° C., 90% moisture absorption is preferably as low as possible, particularly 1.5% or less, particularly 1% or less.
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 μm or more, preferably 0.5 μm or more, usually 30 μm or less, preferably 10 μm or less.

(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, Seasolv 100, 101, 101S, 102, 103, 501, 201, 202, 612NH of Sipro Kasei Co., Ltd., RUVA93, 30M, 30S of Otsuka Chemical Co., Ltd. .

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

  Thus, the near-infrared absorption filter of the present invention provided with the ultraviolet absorption layer has a dye residual ratio of 80% or more, preferably 85% or more, particularly preferably 90 after the light resistance test by irradiating the Xe lamp for 200 hours. %, And no new absorption peak appears in the visible light region. Here, the dye residual ratio is determined from the degree of decrease in absorption intensity before and after the test in the 800 to 1050 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, 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.

In general, the near-infrared absorption filter including the near-infrared absorption filter of the present invention is slightly greenish. When used for display applications such as a plasma display, it is preferable that the color is an achromatic color. Therefore, a color material having an absorption at 500 to 600 nm so as to be a complementary color of green is used so that the luminance of the display is not greatly impaired. It is preferably contained and achromatic.
In addition, light bulbs, halogen bulbs, etc. have many red components in their emission spectra. Under a lighting such as a fluorescent lamp, it looks achromatic, but under these illuminations it often becomes reddish. In such a case, it is preferable to add a coloring material having absorption in the vicinity of 600 to 700 nm to such an extent that the luminance of the display is not significantly impaired, so that the color becomes achromatic even under illumination by a light bulb or a halogen bulb lamp. .
Furthermore, when used as a filter for a plasma display, it is preferable to perform color correction by containing a colorant capable of absorbing 590 to 600 nm neon orange light emitted from the plasma display.
The layer containing these dyes may be prepared as a layer separate from the near-infrared absorbing layer and used as a laminate laminated with the near-infrared absorbing layer, or mixed with a near-infrared absorbing agent. If there are no problems in various properties such as color developability and durability, the same layer as the near infrared absorber may be used. However, the latter is preferable from the viewpoint of process simplification and cost reduction.
Examples of the coloring material used here include general pigments such as inorganic pigments, organic pigments, organic dyes, and pigments. Examples of inorganic pigments include cobalt compounds, iron compounds, and chromium compounds, and examples of organic pigments include azo, indolinone, quinacridone, vat, phthalocyanine, and naphthalocyanine. Organic dyes and pigments include azine, azo, nickel azo complex, azomethine, anthraquinone, indigoid, indoaniline, oxazine, oxonol, xanthene, quinophthalone, cyanine, squarylium, Examples include stilbene, tetraazaporphyrin, triphenylmethane, naphthoquinone, pyrarozone, pyromethene, dipyrromethene, benzylidene, polymethine, methine, and chromium complex salts.
Specific examples of coloring materials having an absorption wavelength of 500 to 600 nm that are complementary colors of green include Hoizeya Chemical Co., Ltd. Aizen SOT Violet-1, Aizen SOT Blue-3, Aizen SOT Pink-1, Aizen SOT Red-1, Aizen SOT Red-2, Aizen SOT Red-3, Aizen Spilon Red BEH Special, Aizen Spilon Red GEH Special, Kayaset Blu made by Nippon Kayaku Co., Ltd.
e AS, Kayaset Red 130, Kayaset Red AG, Kayaset Red 2G, Kayaset Red BR, Kayaset
Red SF-4G, Kayaset Red SF-B, Kayaset Violet AR, Diamond Resin Blue-J, Diamond Resin Blue-G, Diamond Resin Violet-D, Diamond Resin Red H5B, Diamond Resin Red S, Diamond manufactured by Mitsubishi Chemical Corporation Resin Red A, Diamond Resin Red K, Diamond Resin Red Z, PTR63
And Violet-RB, Red-G, Pink-5BGL, Red-BL, Red-2B, Red-3GL, Red-GR, and Red-GA manufactured by Ciba Specialty Chemicals. Among them, when the same layer as the near infrared absorber is used, a chromium complex salt system is preferable from the viewpoint of the stability of the near red absorber.
In addition, specific examples of color materials having absorption in the vicinity of 600 to 700 nm include Aizen SOT Blue-1, Aizen SOT Blue-2, Aizen SOT Blue-3, Aizen SOT Blue- manufactured by Hodogaya Chemical Co., Ltd. 4, Aizen Spilon Blue 2BNH, Aizen Spilon Blue GNH, Kayaset Blue N, Kayaset Blue FR, KAYASORB IR-750 made by Nippon Kayaku Co., Ltd., Diamond Resin Blue-H3G, Diamond Resin Blue- 4G, Diamond Resin Blue-LR, PTB31, PBN, PGC
KBN, KBFR, Blue-GN, Blue-GL, Blue-BL, Blue-R and CISolvent Blu3 63 manufactured by Ciba Specialty Chemicals.
Specific examples of the coloring material having absorption at 560 to 600 nm include organic dyes described in JP-A No. 2000-258624, JP-A No. 2002-040233, JP-A No. 2002-363434 and JP-A No. 2004-505157. And organic pigments such as quinacridone described in JP-A No. 2004-233979.

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

Embodiments of the present invention will be described below by way of examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
Example 1
0.055 g of the compound represented by the following formula (1-11), 0.028 g of the compound represented by the following formula (2-51) and 0.033 g of the compound represented by the following formula (3-33) .25 g, 1.50 g of toluene and 2.5 g of an acrylic resin (Optretz OZ1100) MEK solution (resin concentration 35 wt%) were mixed and dissolved by applying ultrasonic waves to prepare a coating solution.
Here, 1.0616 g of acrylic resin (Optretz OZ1100 manufactured by Hitachi Chemical Co., Ltd.) was put in a petri dish, and left in a constant temperature and high humidity tank at a temperature of 60 ° C. and a humidity of 90%, and the weight was measured after one week. It was 1.0656 g (weight increase rate 0.37%). Accordingly, it was confirmed that the moisture absorption rate was 2% or less (60 ° C., 90%).

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.
This near-infrared absorption filter had a transmittance at 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance at 450 nm, 525 nm, and 625 nm was 40% or more. That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
This filter was placed in a constant temperature bath at 80 ° C. and a constant temperature layer at 60 ° C. and a humidity of 90% for 500 hours to conduct heat resistance and heat and humidity resistance tests, respectively. Furthermore, in order to check the light resistance, a UV cut filter (SC-39) manufactured by Fuji Photo Film Co., Ltd. was attached to this filter, and a xenon long life fade meter (FAL-25AX-HCB-EC) (Suga Test Machine) The product was subjected to a light resistance test by irradiation with light having a radiation intensity of 320 w / m ² for 280 hours.

Tables 1 to 3 show the transmittance at 825 nm, 880 nm, and 980 nm before and after these tests, and ΔE * ab and Δb * in the L * a * b * color system.
The transmittance at 825 nm, 880 nm, and 980 nm after the test was 15% or less in all cases, the deterioration of the dye was small, and the color change in the visible region was small. In addition, the yellow color change of the filter by heat resistance, heat resistance and light resistance test was evaluated by the change rate of absorbance at 430 nm (absorbance after test−absorbance before test / absorbance before test). And -7, -3, and -1 in the order of the light resistance test.

Example 2
A near-infrared absorption filter was obtained in the same manner as in Example 1 except that the compound represented by the following formula (1-12) was used instead of the compound of the formula (1-11).

This near-infrared absorption filter had a transmittance at 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance at 450 nm, 525 nm, and 625 nm was 40% or more. That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
Tables 1 to 3 show the results of performing heat resistance, moist heat resistance and light resistance tests of this filter in the same manner as in Example 1.
The transmittance at 825 nm, 880 nm, and 980 nm after the test was 15% or less in all cases, the deterioration of the dye was small, and the color change in the visible region was small. The yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated for absorbance at 430 nm in the same manner as in Example 1. The change rates were −7, −2 and −1.

Comparative Example 7
The compound represented by the following formula (1-2) is used in place of the compound of the formula (1-11), and the compound represented by the following formula (6-1) is used in place of the compound of the following formula (3-33). A near-infrared absorption filter was obtained in the same manner as in Example 1.

This near-infrared absorption filter had a transmittance at 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance at 450 nm, 525 nm, and 625 nm was 40% or more. That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
Tables 1 to 3 show the results of performing heat resistance, moist heat resistance and light resistance tests of this filter in the same manner as in Example 1.
The transmittance at 825 nm, 880 nm, and 980 nm after the test was 15% or less in all cases, the deterioration of the dye was small, and the color change in the visible region was small. When the yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated by the absorbance at 430 nm, the rate of change was -7, -3 and 4, which were small.

Example 4
The same as Example 1 except that the compound represented by the following formula (1-3) was used instead of the compound of the formula (1-11) and (2-52) was used instead of the compound of the formula (2-51). Thus, a near infrared absorption filter was obtained.

This near-infrared absorption filter had a transmittance at 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance at 450 nm, 525 nm, and 625 nm was 40% or more. That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
Tables 1 to 3 show the results of performing heat resistance, moist heat resistance and light resistance tests of this filter in the same manner as in Example 1.
The transmittance at 825 nm, 880 nm, and 980 nm after the test was 15% or less in all cases, the deterioration of the dye was small, and the color change in the visible region was small. When the yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated by the absorbance at 430 nm, the rate of change was −6, −3 and −0 and was small.

この近赤外線吸収フィルターは表４、表５、表６に示す通り、８２５ｎｍ、８８０ｎｍ、９８０ｎｍでの透過率が１０％以下であり、４５０ｎｍ、５２５ｎｍ、６２５ｎｍでの透過率が４０％以上であった。すなわち、ＰＤＰ本体からの近赤外線発光を有効に遮断し、なおかつＰＤＰ本体から発せられる青色・緑色・赤色発光を十分に透過するものである。
このフィルターの耐熱性、耐湿熱性及び耐光性試験を実施例１と同様に行った結果を表１〜３に示す。
試験後の８２５ｎｍ、８８０ｎｍおよび９８０ｎｍにおける透過率は、いずれの場合も１５％以下であったが、可視領域における色変化があった。耐熱性、耐湿熱性及び耐光性試験によるフィルターの黄色変化を、４３０ｎｍにおける吸光度で評価したところ、その変化率は、２３、４９および２６であり大きかった。
比較例２
式（１−１１）の化合物０．０５５ｇの代わりに、下記式（Ｆ）で表されるインモニウム化合物（日本カーリット（株）製 ＣＩＲ−１０８５）０．０５５ｇを用いた以外は
実施例１と同様に近赤外線吸収フィルターを得た。

この近赤外線吸収フィルターは表４、表５、表６に示す通り、８２５ｎｍ、８８０ｎｍ、９８０ｎｍでの透過率が１０％以下であり、４５０ｎｍ、５２５ｎｍ、６２５ｎｍでの透過率が４０％以上であった。すなわち、ＰＤＰ本体からの近赤外線発光を有効に遮断し、なおかつＰＤＰ本体から発せられる青色・緑色・赤色発光を十分に透過するものである。
試験後の８２５ｎｍ、８８０ｎｍおよび９８０ｎｍにおける透過率は、いずれの場合も１５％以下であったが、可視領域における色変化があった。耐熱性、耐湿熱性及び耐光性試験によるフィルターの黄色変化を、４３０ｎｍにおける吸光度で評価したところ、その変化率は、３３、４８および２８であり大きかった。
比較例３
実施例１に対して、式（１−１１）で表される化合物および式（２−５１）で表される化合物の代わりに下式（Ｅ）で表されるインモニウム化合物を用いた。
下式（３−３３）０．０８７５ｇ、下式（Ｅ）で表されるインモニウム化合物０．１６５ｇを、ＭＥＫ２．８５ｇ、トルエン２．１６ｇ及びアクリル系樹脂（オプトレッツＯＺ１１００）のＭＥＫ／トルエン（＝１／１）溶液（樹脂濃度３５重量％）５．０ｇと混合し、超音波をかけて（３−３３）及び（Ｅ）を溶解させ塗工液を調製した以外は実施例１と同様に近赤外線吸収フィルターを得た。 Comparative Example 1
Example 1 except that 0.057 g of an immonium compound (CIR-1081 manufactured by Nippon Carlit Co., Ltd.) represented by the following formula (E) was used instead of 0.055 g of the compound of formula (1-11). Similarly, a near infrared absorption filter was obtained.

As shown in Table 4, Table 5, and Table 6, the near-infrared absorption filter had a transmittance of 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance of 450 nm, 525 nm, and 625 nm was 40% or more. . That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
Tables 1 to 3 show the results of performing heat resistance, moist heat resistance and light resistance tests of this filter in the same manner as in Example 1.
The transmittance at 825 nm, 880 nm and 980 nm after the test was 15% or less in all cases, but there was a color change in the visible region. When the yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated by the absorbance at 430 nm, the rate of change was large as 23, 49 and 26.
Comparative Example 2
Example 1 except that 0.055 g of an immonium compound (CIR-1085 manufactured by Nippon Carlit Co., Ltd.) represented by the following formula (F) was used instead of 0.055 g of the compound of formula (1-11). Similarly, a near infrared absorption filter was obtained.

As shown in Table 4, Table 5, and Table 6, the near-infrared absorption filter had a transmittance of 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance of 450 nm, 525 nm, and 625 nm was 40% or more. . That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
The transmittance at 825 nm, 880 nm and 980 nm after the test was 15% or less in all cases, but there was a color change in the visible region. When the yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated by the absorbance at 430 nm, the rate of change was 33, 48 and 28 and was large.
Comparative Example 3
For Example 1, an immonium compound represented by the following formula (E) was used in place of the compound represented by the formula (1-11) and the compound represented by the formula (2-51).
0.0875 g of the following formula (3-33), 0.165 g of the immonium compound represented by the following formula (E), 2.85 g of MEK, 2.16 g of toluene, and MEK / toluene of an acrylic resin (Optretz OZ1100) ( = 1/1) Same as Example 1 except that 5.0 g of solution (resin concentration 35% by weight) was mixed and ultrasonic waves were applied to dissolve (3-33) and (E) to prepare a coating solution. A near infrared absorption filter was obtained.

As shown in Table 4, Table 5, and Table 6, the near-infrared absorption filter had a transmittance of 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance of 450 nm, 525 nm, and 625 nm was 40% or more. . That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
Tables 1 to 3 show the results of performing heat resistance, moist heat resistance and light resistance tests of this filter in the same manner as in Example 1. The transmittance at 825 nm, 880 nm and 980 nm after the test was 15% or less in all cases, but there was a color change in the visible region. When the yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated by the absorbance at 430 nm, the change rate was 46, 102 and 62 and was large.

Comparative Example 4
A near-infrared absorption filter was obtained in the same manner as in Comparative Example 3 except that the compound represented by the following formula (3-17) was used instead of the compound represented by the formula (3-33).

この塗工液を、バーコーター（No.７５；江藤器械（株）製）でポリエチレンテレ
フタレート製フィルムに塗工し乾燥した後、さらにバーコーター（No.１２；江藤器械（
株）製）で塗工膜上に塗工し、乾燥することにより近赤外線吸収フィルターを得
た。
この近赤外線吸収フィルターは表４、表５、表６に示す通り、８２５ｎｍ、８８０ｎｍ、９８０ｎｍでの透過率が１０％以下であったが、４５０ｎｍ、５２５ｎｍ、６２５ｎｍでの透過率が４０％以下であった。すなわち、ＰＤＰ本体からの近赤外線発光を有効に遮
断するものの、ＰＤＰ本体から発せられる青色・緑色・赤色発光を十分に透過するものではない。
試験後の８２５ｎｍ、８８０ｎｍおよび９８０ｎｍにおける透過率は、いずれの場合も１５％以下であり、可視領域における色変化があった。耐熱性、耐湿熱性及び耐光性試験によるフィルターの黄色変化を、４３０ｎｍにおける吸光度で評価したところ、その変化率は、−１、７および−２であり、小さかった。 As shown in Table 4, Table 5, and Table 6, the near-infrared absorption filter had a transmittance of 825 nm, 880 nm, and 980 nm of 10% or less, and a transmittance of 450 nm, 525 nm, and 625 nm was 40% or more. . That is, it effectively blocks near-infrared light emission from the PDP main body and sufficiently transmits blue, green, and red light emitted from the PDP main body.
Tables 1 to 3 show the results of performing heat resistance, moist heat resistance and light resistance tests of this filter in the same manner as in Example 1.
The transmittance at 825 nm, 880 nm and 980 nm after the test was 15% or less in all cases, but there was a color change in the visible region. When the yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated by the absorbance at 430 nm, the rate of change was 29, 65 and 30, which were large.
Comparative Example 5
For Example 1, instead of the compound represented by the formula (1-11) and the compound represented by the formula (2-51), a phthalocyanine compound (e-color EX- manufactured by Nippon Shokubai Co., Ltd.)
901B) was used.
Using 0.061 g of the phthalocyanine compound and 0.023 g of the compound represented by the formula (3-33), 2.22 g of toluene and a mixed solution of acrylic resin (Optretz OZ1100) in toluene / MEK (resin concentration: 25 wt. Part, toluene / MEK weight ratio = 1/1) 7.0 g was mixed, stirred at room temperature for 1 hour, and the above compound was dissolved to prepare a coating solution.
This coating solution was applied to a polyethylene terephthalate film with a bar coater (No. 36; manufactured by Eto Kikai Co., Ltd.) and dried to obtain a near infrared absorption filter.
As shown in Table 4, Table 5, and Table 6, this near-infrared absorption filter had a transmittance of 10% or less at 825 nm, 880 nm, and 980 nm, but had a transmittance of 40% or less at 450 nm, 525 nm, and 625 nm. there were. That is, although the near-infrared light emission from the PDP body is effectively blocked, the blue, green, and red light emitted from the PDP body is not sufficiently transmitted.
The transmittance at 825 nm, 880 nm, and 980 nm after the test was 15% or less in all cases, and there was a color change in the visible region. When the yellow change of the filter by heat resistance, moist heat resistance and light resistance test was evaluated by the absorbance at 430 nm, the rate of change was 3, 1 and 1, and was small.
Comparative Example 6
For Example 1, a nickel dithiolate compound represented by the following formula (G) (NKX114 manufactured by Hayashibara Biochemical Laboratories Co., Ltd.) was used instead of the compound represented by the formula (1-11).
0.046 g of the nickel dithiolate compound of the following formula (G), 0.009 g of the compound represented by the formula (2-51), and 0.011 g of the compound represented by the formula (3-33) .42 g and 14.0 g of a chloroform solution (resin concentration: 25 parts by weight) of an acrylic resin (Optretz OZ1100) are mixed and stirred in a water bath at 40 ° C. for 2 hours to dissolve the above compound, thereby providing a coating solution. Adjusted.

This coating solution was applied to a polyethylene terephthalate film with a bar coater (No. 75; manufactured by Eto Instruments Co., Ltd.) and dried, and then further coated with a bar coater (No. 12; Eto Instrument (
The near-infrared absorption filter was obtained by coating on the coating film and drying it.
As shown in Table 4, Table 5, and Table 6, this near-infrared absorption filter had a transmittance of 10% or less at 825 nm, 880 nm, and 980 nm, but had a transmittance of 40% or less at 450 nm, 525 nm, and 625 nm. there were. That is, although the near-infrared light emission from the PDP body is effectively blocked, the blue, green, and red light emitted from the PDP body is not sufficiently transmitted.
The transmittance at 825 nm, 880 nm, and 980 nm after the test was 15% or less in all cases, and there was a color change in the visible region. When the yellow change of the filter by heat resistance, heat-and-moisture resistance, and a light resistance test was evaluated by the light absorbency in 430 nm, the change rate was -1, 7 and -2, and was small.

表１〜３に示された結果から明らかな通り、実施例１〜４の近赤外線吸収フィルターは、（ａ）８２５ｎｍ、８８０ｎｍおよび９８０ｎｍの透過率が１０％以下であって、（ｂ）４５０ｎｍ、５２５ｎｍおよび６２５ｎｍの透過率が４０％以上であり、（ｃ）温度８０℃に５００時間保持する耐熱性試験後の４３０ｎｍにおける吸光度の変化率が−２０％〜２０％である。
更には、（ｄ）温度６０℃で相対湿度９０％に５００時間保持する耐湿熱性試験前後の４３０ｎｍにおける吸光度の変化率（％）が−４０％〜４０％であり、（ｅ）キセノンランプにより放射強度３２０ｗ／ｍ²の光を２８０時間照射する耐光性試験前後の、４３０ｎｍにおける吸光度の変化率（％）が−２０％〜２０％である。
これに対して比較例の近赤外線吸収フィルターは、長期間の使用により黄色変化するか、または可視領域である４５０ｎｍ、５２５ｎｍおよび６２５ｎｍの透過率が低いため、光学フィルターとしての性能が劣る。
すなわち、最大吸収波長を９００ｎｍ〜１２００ｎｍに有する近赤外線吸収色素として、ジインモニウムを用いた比較例１〜４の近赤外線吸収フィルターは、（ｃ）、（ｄ）および（ｅ）の要件を満たすことはできない。すなわち、長期間の使用により黄色変化する。また、最大吸収波長を９００ｎｍ〜１２００ｎｍに有する近赤外線吸収色素として、フタロシアニン化合物を用いた比較例５、およびニッケルジチオレート化合物を用いた比較例６は、（ａ）と（ｂ）の要件を同時に満たすことができない。すなわち、近赤外線を充分に吸収しようとすると可視光の透過率が低くなり、一方、可視光を充分透過させようとすると近赤外線も透過してしまう。

As is apparent from the results shown in Tables 1 to 3, the near-infrared absorption filters of Examples 1 to 4 have (a) transmittances of 825 nm, 880 nm, and 980 nm of 10% or less, and (b) 450 nm, The transmittance at 525 nm and 625 nm is 40% or more, and (c) the rate of change in absorbance at 430 nm after a heat resistance test held at a temperature of 80 ° C. for 500 hours is −20% to 20%.
Furthermore, (d) the change rate (%) of absorbance at 430 nm before and after the heat and humidity resistance test held at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours is −40% to 40%, and (e) emitted by a xenon lamp. The change rate (%) of absorbance at 430 nm before and after the light resistance test in which light having an intensity of 320 w / m ² is irradiated for 280 hours is −20% to 20%.
On the other hand, the near-infrared absorption filter of the comparative example changes yellow when used for a long period of time or has a low transmittance at 450 nm, 525 nm, and 625 nm, which are visible regions, and therefore has poor performance as an optical filter.
That is, the near-infrared absorbing filter of Comparative Examples 1 to 4 using diimmonium as a near-infrared absorbing dye having a maximum absorption wavelength of 900 nm to 1200 nm satisfies the requirements of (c), (d) and (e). Can not. That is, the color changes yellow after long-term use. Comparative Example 5 using a phthalocyanine compound and Comparative Example 6 using a nickel dithiolate compound as near-infrared absorbing dyes having a maximum absorption wavelength of 900 nm to 1200 nm simultaneously satisfy the requirements of (a) and (b). I can't meet. That is, if the near infrared ray is sufficiently absorbed, the visible light transmittance is lowered. On the other hand, if the visible light is sufficiently transmitted, the near infrared ray is also transmitted.

It is the transmittance | permeability of the near-infrared absorption filter of Example 1. FIG.

Claims (3)

As a near-infrared absorbing dye, at least (i) a compound represented by the following general formula (1) having a maximum absorption wavelength at 900 nm to 1200 nm, and (ii) a following general formula (2) having a maximum absorption wavelength at 750 nm to 900 nm. and a layer containing one or more compounds selected from the group consisting of compounds represented by (3), near infrared absorbing filter, characterized in satisfying the following (a) ~ (c) .
(A) Transmittance at wavelengths of 825 nm, 880 nm, and 980 nm is 10% or less (b) Transmittance at wavelengths of 450 nm, 525 nm, and 625 nm is 40% or more (c) At 430 nm before and after a heat resistance test held at a temperature of 80 ° C. for 500 hours Absorbance change rate (%) is -20% to 20%

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represents a branched alkyl group having 10 or less carbon atoms. Alternatively, in formula (1), XR ′ R ″ R ′ A compound represented by “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 ¹ represents a metal atom.)

(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 ″ in formula (2).
The compound represented by 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 ² represents a metal atom. )

(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 ″ in formula (3).
The compound represented by 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 ³ represents a metal atom. ) Furthermore, the near-infrared absorption filter of Claim 1 which satisfy | fills the conditions of (d) and / or (e).
(D) The rate of change (%) in absorbance at 430 nm before and after the wet heat resistance test held at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours is −40% to 40%
(E) Absorbance change rate (%) at 430 nm is -20% to 20% before and after the light resistance test in which light having a radiation intensity of 320 w / m ² is irradiated for 280 hours with a xenon lamp.   The filter for electronic displays using the near-infrared absorption filter of Claim 1 or 2.

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