JP2003139946A - Near ir ray absorbing filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near IR ray absorbing filter having high absorbance for near IR rays and showing little color change into yellow with time. SOLUTION: The near IR ray absorbing filter has a resin layer containing a dithiol metal complex-based near IR ray absorbing dye and no diimonium- based near IR ray absorbing dye. The filter shows the absorption maximum at 900 to 1000 nm, <=20% transmittance in the wavelength region from 800 to 1050 nm, and >=60% transmittance in the region from 550 to 600 nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared absorption filter, and more particularly to a near-infrared absorption filter which has a high transmittance in the visible light region and effectively blocks near-infrared rays. More specifically, it does not use a diimmonium compound. In particular, the present invention relates to a near infrared ray absorbing filter having an excellent near infrared ray absorbing effect.

The near-infrared absorption filter of the present invention can be used as a part of a display filter, particularly a plasma display panel filter, by combining it with a layer having another function.

[0003]

2. Description of the Related Art Generally, a plastic near-infrared absorption filter made of a resin containing a near-infrared absorption dye is
It is well known and its uses include sunglasses, welding glasses, windows of buildings, automobiles, trains, airplanes, and filters for compensating the sensitivity of semiconductor light receiving elements.

In addition, recently, a display such as a plasma display panel (hereinafter referred to as "PDP"), which has been attracting attention as a large and thin wall-mounted television, generates near-infrared rays to generate a cordless phone and a near-infrared remote controller. 800 nm to 10 nm because it may cause malfunctions by affecting electronic devices in the vicinity such as VCRs that use
There is a demand for a filter containing an infrared absorbing dye that absorbs near infrared rays of 00 nm.

As the above-mentioned near-infrared absorption filter, one containing a metal ion such as copper or iron, a nitroso compound and its metal complex salt, a cyanine compound, a squarylium compound, a dithiol metal complex compound, aminothiophenol. Metal complex compounds, phthalocyanine compounds, naphthalocyanine compounds, triallylmethane compounds, immonium compounds, diimmonium compounds,
Various studies have been made such as those containing near-infrared absorbing dyes such as naphthoquinone-based compounds, anthraquinone-based compounds, amino compounds, and aminium salt-based compounds. Among the above-mentioned near-infrared absorbing dyes, maximum absorption at 900-1000 nm is exhibited. There are few that have the property that they have and have little absorption in the visible region, and even if these optical properties are good, there is a problem that the light resistance is low and the dye deteriorates and becomes colored. There are also many.

At present, the most commonly used dyes for optical filters include nickel dithiol complex compounds and fluorinated phthalocyanine compounds, but conventionally known nickel dithiol complex compounds and fluorinated phthalocyanine compounds. The compound has an absorption maximum of 700 to 900 nm, and in practice, in practice, usually, it is used in combination with an aminium-based compound having an absorption maximum in a longer wavelength region than the above-mentioned compound, particularly by using a diimmonium-based compound. It is almost always said that an effective near infrared absorption effect is obtained.

However, the above-mentioned diimmonium compound also has a problem that the pigment becomes yellowish even if it is deteriorated by a small amount. In addition, the display filter is color-corrected to neutral gray or neutral blue whose transmission color is suitable as a display filter, and reduces unnecessary light emission from the display.
It is important to improve the color purity and contrast of the emission color. For this reason, it is important to perform color correction by using a dye that absorbs in the visible region for a display filter, and particularly in the region of 550 nm to 600 nm, a toning dye for cutting unnecessary neon light emitted by a plasma display. In this region, it is required that the near infrared absorbing dye itself has a high transmittance.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is a near-infrared absorption filter containing a dithiol metal complex-based near-infrared absorption dye and not containing a diimmonium-based compound, which has a near-infrared light of 900 to 1000 nm. Has a large absorption in the region, the light transmittance in the wavelength region of 800 nm to 1050 nm is 20% or less, is chemically stable, and has excellent near-infrared absorption performance, heat ray absorption performance, visible light transmission performance and light resistance, It is an object of the present invention to provide a near-infrared absorption filter which has a good film forming property, does not yellow due to photodegradation, and has a high transmittance in the visible region of 550 nm to 600 nm.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned problems, and as a result, among dithiol nickel complexes, those containing thiophenes have large absorption at 900 nm or more, and The inventors found that the transmittance was high at 550 nm to 600 nm, and completed the present invention.

That is, the gist of the present invention is a near-infrared absorption filter having a resin layer containing a 1, dithiol metal complex-based near-infrared absorption dye and containing no diimmonium-based near-infrared absorption dye, which is 900-
Maximum absorption at 1000 nm, 800-1050 nm
Near-infrared absorption filter having a light transmittance of 20% or less in the wavelength range of 60% or more and a transmittance of 60% or more at 550 nm to 600 nm. 2, the following general formula (1) in the resin

[0011]

[Chemical 5] (In the formula, A _{1 to} A ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent which may have a substituent. A good alkoxy group, an aryloxy group which may have a substituent,
It represents an amino group, a nitro group, a halogen atom or a cyano group which may have a substituent, and two adjacent substituents may be linked via a linking group, and M ¹ is
Indicates nickel, palladium, platinum, cobalt or copper. ) The near-infrared absorption filter described in 1 above, which contains at least one dithiol metal complex represented by the formula (1). 3, and further the following general formula (2)

[0012]

[Chemical 6] (In the formula, M ² represents a metal atom. R _{1 to} R ₈ are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group which may have a substituent, a nitro group, a halogen atom or a cyano group, and X _{1 to} X ₁₀ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, a substituent A compound represented by an aryloxy group which may have a group, a nitro group, a halogen atom, a hydroxy group or a cyano group), the following general formula (3)

[0013]

[Chemical 7] (In the formula, B¹~ B⁸Are each independently a hydrogen atom or
Optionally substituted alkyl group, optionally substituted
Aryl group, alkoxy optionally having substituent (s)
Group, aryloxy group which may have a substituent, nit
Group, halogen atom, hydroxy group or cyano group
And here, B¹~ B⁸Is a link between two adjacent substituents
It may be connected through a group, Y¹And Y²Is it
Each independently represents a sulfur atom or an oxygen atom, and X is nitrogen.
An atom or a phosphorus atom, R⁹~ R^{1 2}Are each German
Optionally an optionally substituted alkyl group or a substituted
Represents an optionally substituted aryl group, M³Indicates a metal atom
A compound represented by the following general formula (4)

[0014]

[Chemical 8] (In the formula, C ^{1 to} C ⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or a cyano group, wherein C ¹ to C ⁴ C ⁴
Two adjacent substituents may be linked via a linking group, and M ⁴ represents a metal atom) and contains at least one compound selected from the group consisting of compounds represented by 3. The near-infrared absorption filter described in 2 above. 4. The near-infrared absorption filter according to any one of 1 to 3 above, which further comprises an ultraviolet cut layer. Another aspect of the present invention is the near-infrared absorption filter according to 1 to 4 above. Contained as a part of the layer, and if necessary, an electromagnetic wave cut layer, an antireflection layer and / or
Alternatively, it exists in a display filter provided with a color correction layer, particularly in a plasma display filter.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present specification, Me is a methyl group, Et is an ethyl group, Bu is a butyl group, Pr is a propyl group, Hex is a hexyl group, Ph is a phenyl group, i- is iso and n- is Linear, t- is tertiary, c- is cyclo (cyclic).

The near infrared absorbing filter of the present invention has a resin layer containing a near infrared absorbing dye of dithiol metal complex type,
A near-infrared absorption filter which does not contain a diimmonium-based near-infrared absorption dye, and is 900 to 1000
has a maximum absorption in nm, a light transmittance of 20% or less in a wavelength range of 800 to 1050 nm, and 550 n
It has a transmittance of 60% or more at m to 600 nm.

By cutting the light rays in the wavelength range of 800 to 1050 nm at a constant value of 20% or less, preferably 15% or less, the near-infrared absorption effect is stable and high. Since the transmittance at 550 to 600 nm is 60% or more, preferably 70% or more, more preferably 75% or more, the color reproducibility (brightness) of scenery and the brightness of the screen of the display when used for car window glass Etc. can be secured. In particular, when used as a filter for a plasma display, in addition to a near-infrared absorption filter, an electromagnetic wave shielding material is laminated to form a multilayer body, so that the transmittance of the filter as a whole is lowered and a dye is used for color correction. Since it is added, it is necessary that the transmittance is particularly high at 550 to 600 nm.

Further, since it does not contain a diimmonium-based near-infrared absorbing dye, the change in color tone over time is smaller than that of a conventional near-infrared absorbing filter, and it is particularly preferable for use as a display filter. The dithiol metal complex-based near-infrared absorbing dye used in the near-infrared absorbing filter of the present invention preferably includes the compound represented by the general formula (1).

In the general formula (1), A ^{1 to} A ^1
12 independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. It is an optionally substituted aryloxy group, an optionally substituted amino group, a nitro group, a halogen atom or a cyano group, preferably a hydrogen atom, an alkyl group, an aryl group or a halogen atom.

The substituent of the above alkyl group, aryl group, alkoxy group or aryloxy group is not particularly limited as long as it does not affect the stability of the dye. Among them, a halogen atom, a cyano group and an alkyl group are preferable. Group, an aryl group, an alkoxy group or an aryl group, and preferably a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or a phenoxy group.

The substituent of the amino group may be an alkyl group or a phenyl group, preferably an alkyl group having 1 to 4 carbon atoms. Preferred specific examples of A ^{1 to} A ¹² are hydrogen atom; methyl group, ethyl group, i
-Butyl group, t-butyl group, n-butyl group, n-hexyl group, c-hexyl group, benzyl group, phenethyl group, trifluoromethyl group and like alkyl groups having 1 to 10 carbon atoms; phenyl group, tolyl group An aryl group having 6 to 10 carbon atoms such as methoxy group, ethoxy group, t-butoxy group, n-
C1-C6 alkoxy group such as butoxy group; C6-C10 aryloxy group such as phenoxy group, methylphenoxy group; halogen atom such as chlorine atom, bromine atom, fluorine atom; amino group, dimethylamino group And unsubstituted or substituted amino groups having 1 to 15 carbon atoms such as diethylamino group and diphenylamino group.

A above¹~ A¹²Of the particularly preferred substituents
As a combination of, when all are hydrogen atoms,
Means that the substituents on the same thiophene ring are
When combined with an alkyl group or an aryl group
It In addition, the above A¹~ A¹²Is when two adjacent substituents
-(CH₂)₃-Or- (CH₂)_Four-Carbon number of 1 to 4
Degree alkylene group, -OCH₂O-, -O (CH₂) ₂O
-, Etc., such as an alkylenedioxy group having about 1 to 4 carbon atoms, etc.
It may be connected via a linking group.

In the general formula (2), R _{1 to} R ₈ and X _{1 to} X ₁₀ may be the same groups as described above for A ^{1 to} A ¹² . Specific examples of preferred R _{1 to} R ₈ include the same groups as those described above in A ^{1 to} A ¹² , and also when two adjacent substituents are connected via a linking group. Good.

Preferred specific examples of X _{1 to} X ₁₀ are hydrogen atom; methyl group, ethyl group, i-butyl group, t
-Alkyl group having 1 to 10 carbon atoms such as butyl group, n-butyl group, n-pentyl group, trichloromethyl group, trifluoromethyl group, benzyl group and phenethyl group; phenyl group; methoxy group, ethoxy group, t- C1-C6 alkoxy groups such as butoxy group and n-butoxy group; C6-C10 aryloxy groups such as phenoxy group and methylphenoxy group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; hydroxy Group; a nitro group or a cyano group can be mentioned.

Of the above, preferably, a haloalkyl group,
An electron-withdrawing group such as an alkoxy group, an aryloxy group, a nitro group, a halogen atom, a hydroxy group or a cyano group,
Alternatively, a hydrogen atom may be mentioned, and at least one of X _{1 to} X ₁₀ is not a hydrogen atom. Further, it is preferable that at least one of X _{1 to} X ₁₀ is a fluorine atom, a chlorine atom or a cyano group, and the rest are hydrogen atoms.

In the general formula (3), B ^{1 to} B ⁸ are
The same groups as those described above for A ^{1 to} A ¹² can be used, and of these, an alkyl group which may be substituted or a halogen atom is preferable. Also, the above B ^{1 to} B
⁸ is an adjacent 2 in the same manner as described in A ^{1 to} A ¹² above.
The individual substituents may be connected via a linking group such as an alkylene group having about 1 to 4 carbon atoms or an alkylenedioxy group having about 1 to 4 carbon atoms.

Y ¹ and Y ² each independently represent a sulfur atom or an oxygen atom, preferably a sulfur atom. Further, it is preferable that Y ¹ and Y ² are the same atom. R ⁹ ~
R ^12's each independently represent an optionally substituted alkyl group or an optionally substituted aryl group, and examples of the substituents on the alkyl group and the aryl group include a halogen atom, an alkyl group and an aryl group. To be

Preferred examples of R ^{9 to} R ¹² are methyl group, ethyl group, i-butyl group, t-butyl group, n-butyl group, n-hexyl group, c-hexyl group,
An alkyl group having 1 to 10 carbon atoms such as a trichloromethyl group, a trifluoromethyl group, a benzyl group and a phenethyl group;
A phenyl group is mentioned. X is a nitrogen atom or a phosphorus atom.

In the general formula (4), C ^{1 to} C ⁴ are
It is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or a cyano group, and preferably an optionally substituted aryl group. As the substituent of the alkyl group or the aryl group, the above A ¹ to
The same groups as those described for A ¹² can be mentioned.

Specific preferred examples of C ^{1 to} C ⁴ are:
Methyl group, ethyl group, i-butyl group, t-butyl group, n
-Butyl group, n-hexyl group, c-hexyl group, benzyl group, phenethyl group, trifluoromethyl group and other alkyl groups having 1 to 10 carbon atoms; phenyl group, tolyl group, chlorophenyl group, cyanophenyl group, methoxyphenyl Group, and an aryl group having 6 to 15 carbon atoms such as a phenoxyphenyl group.

Further, in the above C ^{1 to} C ⁴ , two adjacent substituents are connected via a linking group such as an alkylene group or an alkylenedioxy group in the same manner as described in the above A ^{1 to} A ^12. Good. Further, M ^{1 to} M ⁴ represent a metal element, preferably Ni, Pd, Pt, Co, Fe, Ti, Sn or C.
u is used, and more preferably Ni, Pd, Pt, or Co is used. Ni is most preferable because it is excellent in performance and economically advantageous.

If the molecular weight of the compounds of the above-mentioned general formulas (1) to (4) is too large, the g extinction coefficient becomes low and the amount of dye used becomes large, which is not preferable.
It is usually 2000 or less, preferably 1500 or less. Compound (1) and compound (4) were prepared according to J. Am. Chem. Soc., 87.
No. 1483 (1965), the compound (2) can be synthesized by the method described in JP-A-2001-89492.
(3) is J. Am. Chem. Soc., 88, 43 and 4870 (1966).
Year).

The method for producing the infrared absorbing filter of the present invention includes a method of coating a transparent substrate with a coating solution containing a near infrared absorbing dye, a method of melting and kneading a metal complex with a binder resin, and forming into a film. However, in order to reduce the load on the near-infrared absorbing dye, the method of coating the coating liquid is preferable. less than,
A method for producing an infrared absorption filter by applying a coating liquid containing a metal complex on a transparent substrate will be described in detail.

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 or scatter. Specific examples thereof include glass, polyolefin resin,
Examples thereof include amorphous polyolefin-based resins, polyester-based resins, polycarbonate-based resins, poly (meth) acrylic acid ester-based resins, polystyrene, polyvinyl chloride, polyvinyl acetate, polyarylate resins, and polyether sulfone resins. Of these, amorphous polyolefin-based resins, polyester-based resins, polycarbonate-based resins, poly (meth) acrylic acid ester-based resins, polyarylate resins, and polyether sulfone resins are particularly preferable. These resins are usually used for preparing resin plates such as phenol-based and phosphorus-based antioxidants, halogen-based and phosphoric acid-based flame retardants, heat-resistant anti-aging agents, ultraviolet absorbers, lubricants and antistatic agents. Such known additives can be blended.

The transparent substrate is formed by injection molding these resins.
A film-shaped material is used by using a molding method such as T-die molding, calender molding, compression molding, or a method of dissolving in an organic solvent and casting. The resin molded into a film may be stretched or unstretched. Further, the thickness of the transparent substrate on which films made of different materials may be laminated is usually selected from the range of 10 μm to 5 mm depending on the purpose.

Further, the transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, surface roughening treatment and chemical treatment, and coating with anchor coating agent or primer. May be given. The coating liquid containing the metal complex can be prepared by dissolving or dispersing the metal complex in a solvent together with the binder resin. When dispersed, the particle size of the metal complex is usually 0.1 to 3 by using a dispersant if necessary.
It is also possible to make fine particles of μm and disperse it in a solvent together with the binder for adjustment.

At this time, the concentration of the total solid content of the metal complex, the dispersant, the binder resin and the like dissolved or dispersed in the solvent is usually 5 to 50% by weight. The concentration of the metal complex relative to the total solid content is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight, as the total amount of the near red absorbing dye.
Is. The ratio of the total amount of the compounds represented by the formulas (2) to (4) to the compound represented by the formula (1) is 1: 0.1 to 1:10, preferably 1: 0. .2 to 1: 5
Is.

The concentration of the near-infrared absorbing agent with respect to the binder resin naturally depends on the film thickness of the near-infrared absorbing filter. Therefore, when melt kneading to form a film, It is lower than the above-mentioned dye concentration. As the dispersant, polyvinyl butyral resin,
Phenoxy resin, rosin-modified phenol resin, petroleum resin, cured rosin, rosin ester, maleated rosin,
Examples include polyurethane resins. The amount used is usually 0 to 100% by weight, preferably 0 to 70% by weight, based on the metal complex compound.

As the binder, polymethylmethacrylate resin, polyethylacrylate resin, polycarbonate resin, ethylene-vinyl alcohol copolymer resin,
Examples include polyester resins. The amount of the metal complex compound used relative to the binder is 0.01 to 20% by weight, preferably 0.1 to 10% by weight. As the solvent, 1,2,3-trichloropropane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, 1,2
-Halogenated aliphatic hydrocarbons such as dichloroethane, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, octanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propion Esters such as methyl acidate, methyl enanthate, methyl linoleate, methyl stearate, etc. Aliphatic hydrocarbons such as cyclohexane, hexane, octane, benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, nitrobenzene, squalane, etc. Aromatic hydrocarbons, sulfoxides such as dimethyl sulfoxide and sulfolane, amides such as N, N-dimethylformamide, N, N, N ′, N′-tetramethylurea, and tetrahydo Rofuran (hereinafter referred to as "THF"), diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether or may be a mixture thereof.

Further, other near infrared absorbing agent may be added to the coating liquid containing the metal complex. Other near-infrared absorbers include organic substances such as nitroso compounds and metal complexes thereof, cyanine compounds, squarylium compounds, thiol nickel complex compounds, phthalocyanine compounds, naphthalocyanine compounds, triallylmethane compounds, immonium compounds. Compounds, diimmonium compounds, naphthoquinone compounds, anthraquinone compounds, amino compounds, aminium salt compounds, or inorganic carbon black, indium tin oxide, antimony tin oxide, belonging to Group 4A, 5A or 6A of the periodic table Examples thereof include metal oxides, carbides, and borides.

The coating of the coating liquid containing the metal complex on the transparent substrate is performed by a dipping method, a flow coating method, a spraying method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, an air knife coating method or the like. The known coating method is used. The layer containing the metal complex has a thickness after drying of usually 0.1 to 30 μm, preferably 0.3 to 2
The thickness is 0 μm, more preferably 0.5 to 10 μm. The near infrared absorption filter of the present invention has one
The dye residual rate after 100-hour heat resistance test in a constant temperature bath at 00 ° C is 75% or more, preferably 80% or more, particularly preferably 85% or more, and a new absorption peak may appear in the visible light region. Absent. Here, the dye residual rate is 800 to 1
It is determined from the degree of decrease in absorption intensity before and after the test in the 050 nm region.

The near-infrared absorption filter of the present invention can further improve the light resistance of the infrared-absorption filter due to a synergistic effect with the metal complex by further providing an ultraviolet-cutting layer. As a UV blocking layer,
It is possible to efficiently block ultraviolet rays having a wavelength of 400 nm or less and preferably absorb 70% or more of light having a wavelength of 350 nm. The type of the UV cut layer is not particularly limited, but a resin film containing a UV absorber (UV cut film) is preferable. Further, it is preferable that the ultraviolet ray blocking layer is provided on the side (outside side) opposite to the display adhesive surface of the infrared absorbing filter.

The UV absorber used in the UV cut layer has a maximum absorption in the range of 300 to 400 nm,
Any organic or inorganic compound can be used without particular limitation, as long as it is a compound that efficiently cuts light in that region. For example, as the organic UV absorber, a benzotriazole UV absorber, a benzophenone UV absorber, a salicylate UV absorber, a triazine UV absorber, a paraaminobenzoic UV absorber, a cinnamic UV absorber. , Acrylate UV absorber,
Hindered amine-based UV absorbers and the like, and inorganic UV graders include titanium oxide-based UV absorbers, zinc oxide-based UV absorbers, particulate iron oxide-based UV absorbers, etc. In this case, the organic ultraviolet absorber is preferable because it may be present in a fine particle state in the ultraviolet cut layer, which may impair the efficiency of the infrared absorption filter.

Examples of such an ultraviolet absorber include, for example, Tinuvin P and Tinuvin 12 from Ciba-Geigy Co., Ltd.
0, 213, 234, 320, 326, 327, 32
8, 329, 384, 400, 571, Sumitomo Chemical Co., Ltd.
Sumisorb 250, 300, 577, Kyodo Pharmaceutical Co., Ltd.
Biosorb 582, 550, 591, Johoku Chemical Co., Ltd.
No. JF-86, 79, 78, 80, Asahi Denka Co., Ltd. ADEKA STAB LA-32, LA-36, LA-34, Cypro Kasei Co., Ltd. Ceesolve 100, 101, 101S, 1.
02, 103, 501, 201, 202, 612NH,
RUVA93, 30M, 30S, BASF of Otsuka Chemical Co., Ltd.
Ubinar 3039 manufactured by Co., Ltd. and the like can be mentioned.

These ultraviolet absorbers may be used alone or in combination of several kinds. In addition, Ciba Geigy Co., Ltd., which absorbs ultraviolet rays and converts the wavelength to the visible range
Optical brighteners such as Ubitex OB and OB-P can also be used. A commercially available UV cut filter may be used for the UV cut layer. For example, SC-38 and SC-39 of Fuji Film Co., Ltd., Mitsubishi Rayon Co., Ltd.
And the like. The above UV cut filter, SC-39 and acryprene are both 350n
It is an ultraviolet cut film that absorbs 99% or more of the wavelength of m. The near-infrared absorption filter of the present invention thus provided with the ultraviolet absorption layer has a dye residual rate of 80% or more, preferably 85% or more, particularly preferably 90% after the light resistance test by irradiating the Xe lamp for 200 hours. % Or more, and no new absorption peak appears in the visible light region. Here, the dye residual rate is obtained from the degree of decrease in absorption intensity before and after the test in the region of 800 to 1050 nm.

The near-infrared absorption filter may be used alone or as a laminated body which is laminated with transparent glass or another transparent resin plate. Further, 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, in addition to the display filter application of the present invention.

Further, the near-infrared absorption filter of the present invention comprises, if necessary, an electromagnetic wave cut layer, an antireflection layer for preventing external light such as a fluorescent lamp from being reflected on the surface, a glare prevention (non-glare) layer, By providing a color tone correction layer, it can be used as a filter for a display, more preferably a plasma display panel. The display filter of the present invention, other than using the near-infrared absorption filter, can have any configuration and manufacturing method that are usually used, and is not particularly limited, but A case where the filter is used as a plasma display filter will be described as a typical example.

As the electromagnetic wave cut layer used in the plasma display panel filter of the present invention, a vapor deposition or sputtering method of metal oxide or the like can be used. Indium tin oxide (ITO) is generally used, but light of 1000 nm or more can be cut by alternately laminating a derivative layer and a metal layer on a substrate by sputtering or the like. Indium oxide as the dielectric layer,
It is a transparent metal oxide such as zinc oxide, etc., and silver or silver-palladium alloy is generally used as the metal layer. Usually, about 3, 5, 7 or 11 layers are laminated from the dielectric layer. As the substrate, the infrared absorption filter of the present invention may be used as it is, or may be laminated with the infrared absorption filter of the present invention after providing an electromagnetic wave cut layer by vapor deposition or sputtering on a resin film or glass. good.

The antireflection layer used in the filter for plasma display panel of the present invention is a metal oxide, a fluoride, a silicide, a boride, or a carbide in order to suppress the reflection on the surface and improve the transmittance of the filter. , Nitrides, sulfides, and other inorganic substances such as vacuum deposition, sputtering, ion plating, and ion beam assisted methods to form a single layer or multiple layers, acrylic resins, fluororesins, and other resins with different refractive indices There is a method of laminating a single layer or multiple layers. Further, a film that has been subjected to antireflection treatment can be attached on the filter.

The color tone correcting layer used in the plasma display panel filter of the present invention is specifically 590 to 60 emitted from the plasma display.
The dye is not particularly limited as long as it can cut neon orange light in the wavelength range of 0 nm, and a known dye such as a squarylium compound or a tetraazaporphyrin compound is contained. Other dyes may be added so that the color of the display during extinction becomes neutral gray.

A glare prevention layer (non-glare layer) may be provided in addition to the above layers. For the non-glare layer, for the purpose of widening the viewing angle of the filter, in order to scatter transmitted light, a method in which fine powder of silica, melamine, acrylic or the like is made into an ink and coated on the surface can be used. For curing the ink, heat curing or light curing can be used. Also, a non-glare-treated film can be attached on the filter. Further, if necessary, a hard coat layer can be provided.

[0052]

EXAMPLES The embodiments of the present invention will be described below with reference to examples, but the scope of the present invention is not limited thereto. Example The following formula (5)

[0053]

[Chemical 9] Of the dithiol complex-based near-infrared absorbing dye represented by
To 0.6 g of a weight% THF (tetrahydrofuran) solution,
1. A THF / toluene (= 1/1) solution (resin concentration 20% by weight) of a polymethylmethacrylate resin (trade name; Dianal BR-80: product of Mitsubishi Rayon Co., Ltd.) was added to 1.
After adding 5 g and applying ultrasonic waves to dissolve it, this coating solution was applied to a polyethylene terephthalate film with a bar coater (NO.24; manufactured by Eto Kikai Co., Ltd.) PET film "T 100E" manufactured by Mitsubishi Kagaku Polyester Film Co., Ltd. ], Thickness 10
0 μm) coated on one side and dried, then the other side of the formula (6)

[0054]

[Chemical 10] 0.6 g of a 3.0 wt% THF (tetrahydrofuran) solution of the near-infrared absorbing dye shown in Fig. 2 and a THF / toluene (= 1/1) polymethylmethacrylate resin (trade name; Dianal BR-80: product of Mitsubishi Rayon Co., Ltd.) ) 1.5 g of a solution (resin concentration: 20% by weight) was added, ultrasonic waves were applied, and the dissolved coating liquid was applied and dried to obtain a near infrared absorption filter. The coating film thickness was about 6 μm.

The transmittance of this filter was measured with a Hitachi spectrophotometer (U-3500). The results are shown in Fig. 1. 80
The transmittance at 0 to 1050 nm is 20% or less,
The transmittance at 550 to 600 nm was 80% or more, which had a sufficient near infrared absorptivity and had a good visible light transmittance. Furthermore, in order to evaluate the heat resistance, 100
A heat resistance test was carried out by placing it in a thermostat at 100 ° C. for 100 hours, and the absorption intensities before and after irradiation at 840 nm and 975 nm were measured to be 85.9% and 96.2, respectively.
%, Indicating good heat resistance. In addition, the color of the filter did not change.

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) was attached.
-HCB-EC) (product of Suga Test Instruments Co., Ltd.), 200
When the absorption intensity before and after irradiation at 840 nm and 975 nm was measured, the dye residual ratio (intensity before irradiation / intensity after irradiation × 100) was 98.5%, respectively.
80.1% was good and there was no filter color change.

Comparative Example Near-infrared absorbing dye (Kayasorb IRG-02 manufactured by Nippon Kayaku Co., Ltd.
2) 0.6 g of 3.0 wt% THF (tetrahydrofuran) solution, polymethylmethacrylate resin (trade name;
Diinal BR-80: Mitsubishi Rayon Co., Ltd. product)
1.5 g of a THF / toluene (= 1/1) solution (resin concentration: 20% by weight) was dissolved in an ultrasonic cleaner, and the coating solution was made of polyethylene terephthalate with a bar coater # 24. A near-infrared absorption filter was obtained by coating on a film and drying. Coating thickness is about 6
was μm.

In order to evaluate the heat resistance, a heat resistance test was carried out by putting it in a constant temperature bath at 100 ° C. for 100 hours. 977 nm
The absorption intensity before and after irradiation was measured at 94.
It was 0%, which was good, but the filter after the test was
It was a little yellow. For the light resistance test, 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 Instruments Co., Ltd.) was used. Product), the absorption intensity before and after irradiation at 977 nm was measured for 200 hours, and the dye residual ratio (intensity before irradiation / intensity after irradiation × 100) was 81.8.
%, Which was good, but the filter after the test was slightly yellowed.

[0059]

The near-infrared absorption filter of the present invention is 9
It has a large absorption in the near-infrared light region of 00 nm or more, is chemically stable, has excellent near-infrared absorption performance, heat-ray absorption performance, visible-light transmission performance and light resistance, and has good film-forming properties. It is possible to provide an infrared absorbing dye material which does not yellow and has a high transmittance in the visible region of 550 nm to 600 nm. Also, by combining this with other near infrared absorbing dyes, 800
It is possible to provide a near-infrared absorption filter and a near-infrared absorption layer suitable for a PDP having a transmittance of 10% or less in the wavelength region of nm to 1000 nm.

[Brief description of drawings]

FIG. 1 is a diagram showing a transmission spectrum of a filter of the present invention obtained in an example.

Claims (9)

[Claims] 1. A near-infrared absorption filter having a dithiol metal complex-based near-infrared absorption dye-containing resin layer and containing no diimmonium-based near-infrared absorption dye, having a maximum absorption at 900 to 1000 nm. 800 ~
A near infrared absorption filter having a light transmittance of 20% or less in a wavelength range of 1050 nm and a transmittance of 60% or more in a wavelength of 550 nm to 600 nm. 2. A resin represented by the following general formula (1): (In the formula, A _{1 to} A ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent which may have a substituent. A good alkoxy group, an aryloxy group which may have a substituent,
It represents an amino group, a nitro group, a halogen atom or a cyano group which may have a substituent, and two adjacent substituents may be linked via a linking group, and M ¹ is
Indicates nickel, palladium, platinum, cobalt or copper. The near-infrared absorption filter according to claim 1, containing at least one kind of a dithiol metal complex represented by the formula (1). 3. The following general formula (2): [Chemical 2] (In the formula, M²Indicates a metal atom. R₁~ R₈Is it
Independently of each other, a hydrogen atom or an alkyl which may have a substituent.
Kill group, optionally substituted aryl group, substituent
Optionally having an alkoxy group, having a substituent
Aryloxy group, which may have a substituent
Indicates a mino group, nitro group, halogen atom or cyano group.
Then X₁ ~ X_TenAre each independently a hydrogen atom or a substituent
May have an alkyl group, or may have a substituent
Good aryl group, optionally substituted alkoxy
Group, aryloxy group which may have a substituent, nit
Group, halogen atom, hydroxy group or cyano group
You ) A compound represented by the following general formula (3) [Chemical 3] (In the formula, B¹~ B⁸Are each independently a hydrogen atom or
Optionally substituted alkyl group, optionally substituted
Aryl group, alkoxy optionally having substituent (s)
Group, aryloxy group which may have a substituent, nit
Group, halogen atom, hydroxy group or cyano group
And here, B¹~ B⁸Is a link between two adjacent substituents
It may be connected through a group, Y¹And Y²Is it
Each independently represents a sulfur atom or an oxygen atom, and X is nitrogen.
An atom or a phosphorus atom, R⁹~ R^{1 2}Are each German
Optionally an optionally substituted alkyl group or a substituted
Represents an optionally substituted aryl group, M³Indicates a metal atom
A compound represented by the following general formula (4) [Chemical 4] (In the formula, C¹~ C^FourAre each independently a hydrogen atom or
Optionally substituted alkyl group, optionally substituted
Represents an aryl group or a cyano group, wherein C ¹~ C^Four
Is two adjacent substituents connected via a linking group.
May be M^FourIs a compound represented by
Contain one or more compounds selected from the group consisting of
The near-infrared absorbing film according to claim 2, wherein
Filter. 4. The near-infrared absorption filter according to claim 1, further comprising an ultraviolet cut layer. 5. A display filter containing the near-infrared absorption filter according to claim 1 as a layer as a part of the filter. 6. The display filter according to claim 5, further comprising an electromagnetic wave cut layer. 7. The display filter according to claim 5, further comprising an antireflection layer. 8. The display filter according to claim 5, further comprising a color tone correction layer. 9. The display filter according to claim 5, wherein the display is a plasma display.