JP2002022935A - Optical filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical filter which prevents the malfunction of a remote control due to IR rays. SOLUTION: In the optical filter having a filter layer containing a dye and polymer binder, the dye is a cyanine dye having the absorption maximum within the range of 750 to 1100 nm and a metal complex is added to the filter layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an optical filter having a transparent support and a filter layer. In particular,
The present invention is to prevent malfunction and improve color reproduction on the surface of an image display device such as a plasma display panel (PDP), a liquid crystal display (LCD), an electroluminescence display (ELD), a fluorescent display tube, and a field emission display. The present invention relates to an optical filter attached to the optical filter.

[0002]

2. Description of the Related Art Plasma display panels (PDs)
P), liquid crystal display (LCD), electroluminescence display (ELD), cathode ray tube display (CR)
T), an image display device such as a fluorescent display tube or a field emission display displays a color image by a combination of light of three primary colors of red, blue and green in principle. However, it is very difficult (practically impossible) to make light for display ideal three primary colors. For example, in a plasma display panel (PDP), it is known that light emitted from three primary color phosphors contains extra light (wavelength is in a range of 500 to 620 nm). Therefore, it has been proposed to perform color correction using a filter that absorbs light of a specific wavelength in order to correct the color balance of display colors. Japanese Patent Application Laid-Open No. 58-153 discloses color correction using a filter.
Nos. 904 and 61-188501, JP-A-3-231
No. 988, No. 5-205564, No. 9-145918
Nos. 9-306366 and 10-26704. Further, a problem has been reported that a remote control device (remote control) malfunctions due to infrared rays (mainly 750 nm to 1100 nm) generated from the display. In order to solve this problem, an infrared absorption filter is used. The dye used for the infrared absorption filter is described in US Pat. No. 5,941,520.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an optical filter having an excellent color balance, which selectively cuts off infrared light and light having a wavelength which lowers color purity and does not cause malfunction. An object is to provide an image display device using the same.

[0004]

The object of the present invention has been attained by the following optical filters, plasma display panels and plasma display devices (1) to (6). (1) An optical filter in which a transparent support and a filter layer are laminated, wherein the filter layer has a polymer binder and a cyanine represented by the following general formula (1) having an absorption maximum in a wavelength region of 750 nm to 1100 nm. An optical filter comprising a dye and a metal complex represented by the general formula (2a).

[0005]

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In the formula, Z ¹ and Z ² are a group of non-metallic atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and R ¹ and R ² are each an aliphatic group L ¹ is a methine chain composed of an odd number of methines, a, b and c are each 0 or 1, and x is an anion.

[0007]

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In the formula, L represents a ligand, M represents a metal atom, n1 represents an integer of 1 to 10, and m1 represents 1 or 2. (2) The optical filter according to (1), wherein the cyanine dye and the metal complex form a salt represented by the following formula (3).

[0009]

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In the formula, Z ³ and Z ⁴ are a group of non-metallic atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and R ³ and R ⁴ are each an aliphatic group L ² is a methine chain consisting of an odd number of methines, d and e are each 0 or 1, R ⁵ ,
R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom, an alkyl group,
Aryl group, cyano group or R ⁵ and R ⁶ or R ⁷ and R
⁸ represents a nonmetallic atom necessary to form an aromatic ring linked to each other, Y ¹ and Y ² each represent O, and S, or NH, M represents a metal atom. (3) The optical filter according to (1), wherein a light transmittance at an absorption maximum in a range of 750 to 1100 nm is in a range of 0.01 to 30%. (4) The optical filter according to (1), comprising an association of a cyanine dye represented by the following general formula (4) having an absorption maximum in a range of 560 nm to 620 nm.

[0011]

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In the formula, Z ⁵ and Z ⁶ are a group of nonmetal atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be independently condensed, and R ⁹ and R ¹⁰ are each Is independently an aliphatic group or an aromatic group, L ³ is a methine chain composed of an odd number of methines, f, g, and h are each independently 0 or 1, and x ² is an anion. (5) A plasma display panel having a display surface covered with the optical filter according to (1). (6) The plasma display panel according to (5), wherein the plasma display has no front plate, and the optical filter is directly attached to the display surface.

[0013]

DETAILED DESCRIPTION OF THE INVENTION [Plasma Display Panel]
In the present invention, a plasma display panel (PDP)
Is composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. There are two glass substrates, a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled, and gas is sealed between them. The front plate is a substrate located in front of the plasma display panel. The front plate preferably has sufficient strength to protect the plasma display panel. The front panel can be used with a gap from the plasma display panel, or can be used directly attached to the plasma display body. The plasma display device according to the present invention is an entire display device including at least a plasma display panel main body and a housing. If it has a front panel, this is also included in the plasma display device. Plasma display panel (P
DP) is already commercially available. Regarding the plasma display panel, JP-A-5-205643, 9-
There is a description in each publication of 306366.

[Filter Layer] The optical filter of the present invention has a thickness of 750 to 1100 nm, more preferably 790 to 1050 nm, and most preferably 80 to 1100 nm.
It has a light absorption maximum between 0 and 1030 nm, and its transmittance at the wavelength of maximum is between 0.01% and 30%, preferably between 0.05% and 20%, most preferably Is between 0.1 and 10%. In the present invention, a filter is formed using a dye (dye or pigment) in order to impart the above-mentioned absorption spectrum. Also,
One or more dyes may be used because the wavelength region is wide.

The filter layer has a thickness of 400 nm to 700 n.
It is preferable that the absorption of m in the visible region is small. In the filter layer, the filter dye represented by the following (1) and the following (2)
It is used in combination with the metal complex represented by a).

[0016]

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In the formula (1), Z ¹ and Z ² are each independently a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring. Another heterocyclic ring, aromatic ring or aliphatic ring may be condensed to the nitrogen-containing heterocyclic ring. Examples of the nitrogen-containing heterocyclic ring and a fused ring thereof include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring,
Oxazolocarbazole ring, oxazolo benzofuran ring, thiazole ring, benzothiazole ring, naphthothiazole ring, indolenine ring, benzoindolenine ring, imidazole ring, benzimidazole ring, naphthymidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring , A flop pyrrole ring, an indolizine ring, an imidazoquinoxaline ring, and a quinoxaline ring. The nitrogen-containing heterocycle is preferably a 5-membered ring rather than a 6-membered ring. More preferably, a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring. A benzothiazole ring, naphthothiazole ring, indolenine ring or benzoindolenine ring is preferred.

Nitrogen-containing heterocycles and rings condensed therewith
May have a substituent. Examples of substituents include halo
Gen atom, cyano, nitro, aliphatic group, aromatic group, complex
Ring group, -OR¹¹, -COR¹², -COOR¹³, -OCOR¹⁴, -NR^FifteenR¹⁶, -NHCOR
¹⁷, -CONR¹⁸R¹⁹, NHCONR²⁰R^{twenty one}, NHCOOR^{twenty two}, -SR^{twenty three}, -SO_TwoR^{twenty four},
−SO_TwoOR^{twenty five}, −NHSO_TwoR²⁶Or -SO_TwoNR²⁷R²⁸It is. R¹¹~
R ²⁸Is independently a hydrogen atom, an aliphatic group, an aromatic
Group or heterocyclic group. Ona-COOR¹³R¹³Is hydrogen
Case (ie, carboxyl) and -SO_TwoOR^{twenty five}R
^{twenty five}Is a hydrogen atom (that is, sulfo)
May be dissociated or in a salt state.

In the present invention, the aliphatic group is an alkyl group,
Represents an alkenyl group, an alkynyl group or an aralkyl group. These groups may have a substituent. The alkyl group may be cyclic or chain. The chain alkyl group may have a branch. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, and most preferably 1 to 8.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, cyclopropyl, cyclohexyl and 2-ethylhexyl. The alkyl part of the substituted alkyl group is the same as the above-mentioned alkyl group. The substituent of the substituted alkyl group is the same as the substituent of the nitrogen-containing heterocyclic ring of Z ¹ and Z ² (excluding the cyano group and the nitro group). Examples of the substituted alkyl group include 2-
Includes hydroxyethyl, 2-carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, 3-sulfopropyl and 4-sulfobutyl.

The alkenyl group may be cyclic or chain. The chain alkenyl group may have a branch. The number of carbon atoms of the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and most preferably 2 to 8. Examples of alkenyl groups include vinyl, allyl, 1
-Propenyl, 2-butenyl, 2-pentenyl and 2-
Hexenyl is included. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The substituent of the substituted alkenyl group is the same as the substituent of the alkyl group. The alkynyl group may be cyclic or chain. The chain alkynyl group may have a branch. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 22 to 12 carbon atoms, and most preferably 2 to 8 carbon atoms. Examples of the alkynyl group include ethynyl and 2-propynyl. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The substituent of the substituted alkynyl group is the same as the substituent of the alkyl group. The alkyl part of the aralkyl group is the same as the above-mentioned alkyl group. The aryl part of the aralkyl group is the same as the aryl group described later. Examples of the aralkyl group include benzyl and phenethyl. The aralkyl part of the substituted aralkyl group is
The same as the above aralkyl group. The aryl part of the substituted aralkyl group is the same as the aryl group described later.

In the present invention, the aromatic group means an aryl group or a substituted aryl group. The aryl group preferably has 6 to 25 carbon atoms, and has 6 to 15 carbon atoms.
Is more preferable, and most preferably 6 to 10. Examples of the aryl group include phenyl and naphthyl. Examples of the substituent of the substituted aryl group include Z ¹
And is the same as the nitrogen-containing heterocyclic ring substituents Z ^2. Examples of the substituted aryl group include 4-carboxyphenyl, 4-acetamidophenyl, 3-methanesulfonamidophenyl, 4-methoxyphenyl, 3-carboxyphenyl,
Includes 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl and 4-butanesulfonamidophenyl.

In the present invention, the heterocyclic group may have a substituent. The heterocyclic ring of the heterocyclic group is preferably a 5- or 6-membered ring. An aliphatic ring, an aromatic ring, or another hetero ring may be condensed with the hetero ring. Examples of heterocycles (including fused rings) include pyridine, piperidine, furan, furfuran, thiophene, pyrrole, quinoline, morpholine, indole, imidazole, pyrazole, carbazole and phenothiazine Ring, phenoxazine ring, indoline ring, thiazole ring,
Includes pyrazine, thiadiazine, benzoquinoline and thiadiazole rings. The substituent of the heterocyclic ring is the same as the substituent of the nitrogen-containing heterocyclic ring of Z ¹ and Z ² .

The aliphatic group and the aromatic group represented by R ¹ and R ² in the formula (1) are the same as described above. L ¹ is a methine chain composed of an odd number of methines, and preferably 5, 7 or 9 methines. The methine group may have a substituent. The substituted methine group is preferably a central (meso-position) methine group. Examples of the substituent are the same as the substituents of the nitrogen-containing heterocyclic ring of Z ¹ and Z ² . Further, two substituents of the methine chain may be combined to form a 5- or 6-membered ring.

X ¹ is an anion. Examples of the anion include a halide ion (Cl chromatography, Br chromatography, I over), p-toluenesulfonate ion, ethyl sulfate ion, PF ₆ chromatography,
BF ₄ -or ClO ₄ -is included. a, b and c are each independently 0 or 1. a and b are preferably 0. c is a case where the cyanine dye has an anionic substituent such as sulfo or carboxyl to form an inner salt, and when the metal complex represented by the formula (2a) functions as a counter anion corresponding to X, 0.

[0025]

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L represents a ligand. Examples of ligands include:
"Organic metal compound synthesis method and usage method", supervised by Akio Yamada, Tokyo Chemistry Dojin page 25. M is a metal atom. Examples of the metal atom include metals belonging to groups II to IV of the periodic table. Preferably, the transition metal is Cr, M
n, Fe, Co, Ni, Cu, Zn, Pd, Mo or Cd. More preferably, F
e, Co, Cu or Zn. n1 is 1 to 10
And m1 is 1 or 2. When a metal complex is used as a counter anion of cyanine, the following formula (2)
It is preferable to use the metal complex represented by b).

[0027]

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In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom, an alkyl group, an aryl group, a cyano group or
⁵ and R ⁶ and / or R ⁷ and R ⁸ are linked to each other to form an aromatic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring, and may be substituted with the substituents described for Z ¹ and Z ² in the formula (1). The alkyl group and the aryl group are the same as described above. Y ¹ and Y ² each represent O, S or NH, with S being preferred. M is a metal atom. The definition of the metal atom is the same as that of M in the formula (2a). When the metal complex is added separately from the cyanine dye, the following formula (2)
It is preferable to use the metal complex represented by c).

[0029]

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In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom, an alkyl group, an aryl group, a cyano group or
⁵ and R ⁶ and / or R ⁷ and R ⁸ are linked to each other to form an aromatic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring, and may be substituted with the substituents described for Z ¹ and Z ² in the formula (1). The alkyl group and the aryl group are the same as described above. Y ¹ and Y ² each represent O, S or NH, with S being preferred. M is a metal atom. The definition of the metal atom is the same as that of M in the formula (2a). A is 4
Represents a quaternary ammonium salt or a quaternary phosphonium salt. Four
Examples of the quaternary ammonium salt include tetramethylammonium, tetraethylammonium, tetrabutylammonium, octyltriethylammonium, phenyltrimethylammonium, triphenylbutylammonium, triphenylbenzylammonium, and tetraphenylammonium. Examples of the quaternary phosphonium salt include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, octyltriethylphosphonium, phenyltrimethylphosphonium, triphenylbutylphosphonium, triphenylbenzylphosphonium, and tetraphenylphosphonium. n4 is 0, 1 or 2.
Further, as a preferable cyanine dye, as represented by the following formula (3), the cyanine dye and the metal complex form a salt.

[0031]

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Where Z^ThreeAnd Z^FourA nitrogen-containing heterocycle represented by
Is the Z of equation (1)¹And Z^TwoAnd a nitrogen-containing heterocyclic ring represented by R^ThreeAnd R^Four
An aliphatic group or an aromatic group represented by the formula (1)¹You
And R ^TwoAn aliphatic group and an aromatic group represented by^TwoIn table
The methine chain is represented by L of the formula (1) ¹With a methine chain represented by
And d and e are each 0 or 1
You. R^Five, R⁶, R⁷And R⁸An alkyl group represented by
And the aryl group are the same as described above. Y¹And Y^TwoAre each
Represents O, S or NH, with S being preferred. M is a metal atom
It is. The definition of the metal atom is the same as that of M in the formula (2a).
You. Specific examples of the cyanine dye and the metal complex are shown below.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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In the filter layer, in addition to the IR dye, it is preferable to use a dye having a maximum absorption in the wavelength range of 560 nm to 620 nm as a color correction dye. Wavelength is 560n
The absorption spectrum of a dye having an absorption maximum in the range of m to 620 nm is preferably sharpened in order to selectively cut off the light so as not to affect the necessary emission region of the green phosphor as much as possible. Specifically, the half width is preferably 5 to 100 nm, and 10 to 70 nm.
More preferably, it is most preferably 10 to 50 nm. In order to obtain the preferred absorption waveform as described above, the dye used is preferably a dye represented by the following general formula.

[0044]

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In the formula, P and Q each represent a group selected from an acidic nucleus, a basic nucleus, and an aromatic ring, and L represents a methine chain in which 1 to 5 methines or azamethines are conjugated. The bond represented by a solid line and a broken line indicates that P and L, and Q and L are connected by a single bond or a double bond, respectively, and the color of the dye molecule composed of P, L, and Q The bond order is chosen such that the groups (chromophores) are connected by conjugated chains. P, Q and L may each have a substituent, and those substituents may be bonded to each other to form a 4- to 7-membered ring. The ring formed is, for example, a ring formed on a methine chain, such as cyclobutenone such as a squarylium dye, and a ring formed by combining the substituents of P and Q includes xanthene and thioxanthene. Can be.

The acidic nucleus may be a cyclic ketomethylene compound or an open-chain compound having a methylene group sandwiched between electron-withdrawing groups. Rings, aromatic rings, or aliphatic rings may be fused. As the cyclic acidic nucleus, there are an aliphatic ring and a hetero ring, but a hetero ring is preferable.
Acidic nuclei include keto- and enol-type tautomers (including imino and amino, thioketo and thiol tautomers in which an oxygen atom is changed to a nitrogen atom or a sulfur atom) as in the case of oxonol dyes. Can also be taken. Also,
It may be used as a dissociator. Examples of the acidic nucleus and its fused ring include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxo, and dioxo. Pyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,
5-dihydrofuran-2-one, pyrrolin-2-one,
Examples include pyrazolotriazole and pyrrolotriazole. These may have a substituent.

The basic nucleus may be open-chain or cyclic, but is more preferably cyclic. Further, another heterocyclic, aromatic or aliphatic ring may be condensed. As the cyclic basic nucleus, a nitrogen-containing heterocyclic ring is preferable. The basic nucleus can also take onium form as in the case of cyanine dyes. Examples of the nitrogen-containing heterocycle and its fused ring include oxazole, isoxazole, benzoxazole, naphthoxazole, oxazolocarbazole, oxazolobenzobenzofuran, thiazole, benzothiazole, naphthothiazole, indolenine, benzoindolenine, imidazole, Includes benzimidazole, naphthoimidazole, quinoline, pyridine, oxazoline, pyrrolopyridine, pyrrole, flopyrrole, indolizine, imidazoquinoxaline and quinoxaline. Each of these may have a substituent.

The aromatic ring may be a carbocyclic or heterocyclic ring. And what has a substituent chosen from an amino group, a hydroxyl group, and an alkoxy group in the position which can be couple | bonded with the methine chain represented by L is preferable. Examples of the carbocycle include benzene, naphthalene and the like. Examples of heterocycles include pyrrole, indole, indolenine, benzoindolenine, carbazole, flopyrrole, thiophene, benzothiophene, furan, benzofuran, dibenzofuran, oxazole, benzoxazole, naphthoxazole, isoxazole, thiazole, benzothiazole, naphtho. Thiazole, isothiazole,
Pyrazole, imidazole, indazole, naphthimidazole, benzimidazole, indolizine, quinoline, phenothiazine, phenoxazine, indoline, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, pyrrolo Examples thereof include pyridine, imidazoquinoline, imidazoquinoxaline, tetrazole, coumarin, and coumarone, each of which may have a substituent.

As the dye represented by the general formula, methine dyes (for example, cyanine, merocyanine, oxonol,
Pyrromethene, styryl, arylidene), diphenylmethane dye, triphenylmethane dye, xanthene dye,
Squarylium dye, croconium dye, azine dye,
Acridine dyes, thiazine dyes, and oxazine dyes can be mentioned.

These dyes can be used after forming a complex with a metal. By forming a complex, the robustness can be increased. The dye used as the metal complex is
Pyrromethene dyes are preferred. Specific examples of these dyes are
Japanese Patent Application Nos. 10-316875, 11-276525, 11-36046, 11-25
2731, 11-121699, 11-124273, Japanese Patent Application 2000-40694
No., JP-A-11-92682, JP-A-11-255774, JP-A-11-256057, JP-A-11
-227332. These dyes are preferably used in association. The dye in the associated state forms a so-called J band and shows a sharp absorption spectrum peak. Various references (eg, Photographic Science and eng
ineering Vol. 18, No. 323-335 (1974)).
The absorption maximum of the dye in the J-association state moves to a longer wavelength side than the absorption maximum of the dye in the solution state. Therefore, whether the dye contained in the filter layer is in an associated state or a non-associated state can be easily determined by measuring the absorption maximum. In the dye in the associated state, the movement of the absorption maximum is preferably 30 nm or more, more preferably 40 nm or more, and most preferably 45 nm or more. The dye used in the associated state is preferably a methine dye, most preferably a cyanine dye or an oxonol dye. Particularly, a cyanine dye represented by the following general formula (4) is preferable.

[0051]

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The nitrogen-containing heterocyclic rings represented by Z ³ and Z ⁴ are the same as Z ¹ and Z ^{2 in} the general formula (1). The aliphatic group or the aromatic group of R ³ and R ⁴ is the same as R ¹ and R ^{2 in} the general formula (1). , A and, L ³ is 5 be methine chain consisting of an odd number of methine preferred. f, g and h are each independently 0 or 1, and the anion of x ² is X ^{1 in the} general formula (1).
Is the same as Representative examples of the dye represented by formula (4) are shown below.

[0053]

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[0054]

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The cyanine dyes of the present invention are described in FM Harmer, "Heterocyclic Compounds Cyanine Dyes and Relative Compounds".
ated Compounds), John Wiley & Sons-New York, London,
Published in 1964, and DMS
rmer), Heterocyclic Compounds-Special topics in heterocyclic compounds.
terocyclic chmistry) ", Chapter 18, Section 14, 482
515 pages, John Willy and Sons (John
Wiley & Sons)-New York, London, 1977
Annual, Rodds Chemistry of Carbon Compounds, 2n
d.Ed.vol.IV, partB, 1977, Chapter 15, 369-42
Page 2, Elsevier Science Publishing Company In
c.) The compound can be easily synthesized with reference to a company, New York, JP-A-6-313939 and JP-A-5-88293.

Further, the optical filter has a wavelength of 500 nm.
It is preferable to have an absorption maximum at 550 nm. 50
The transmittance in the range of 0 nm to 550 nm is preferably in the range of 20% to 85%. Wavelength of 500 nm to 550
The maximum of light absorption in the range of nm is set to adjust the emission intensity of the green phosphor having high visibility. It is preferable that the emission region of the green phosphor be cut smoothly. The half-width at the absorption maximum in the wavelength range of 500 nm to 550 nm (the width of the wavelength region showing half the absorbance at the absorption maximum) is preferably 30 nm to 300 nm,
It is more preferably 40 nm to 300 nm,
nm to 150 nm, more preferably 60 nm
Most preferably, it is m to 150 nm. Wavelength is 50
As the dye having an absorption maximum in the range of 0 nm to 550 nm, squarylium-based, azomethine-based, cyanine-based, oxonol-based, anthraquinone-based, azo-, or benzylidene-based compounds and metal chelate compounds thereof are preferably used.

Further, a wavelength of 350 to
It is preferable to use a dye having an absorption maximum in the range of 450 nm and 470 to 530 nm. The dyes include squarylium, azomethine, cyanine,
Merocyanine, oxonol, anthraquinone,
Azo- or benzylidene-based compounds and their metal chelate compounds are preferably used.

An anti-fading agent, an antioxidant and an ultraviolet inhibitor may be added to the filter layer. Examples of discoloration inhibitors include hydroquinone derivatives described in US Pat. Nos. 3,935,016 and 982944, US Pat.
Hydroquinone diethers described in JP-A-5-210004, phenol derivatives described in JP-A-54-145530, G
Spiroindane, methylenedioxybenzene, and US34323 described in B2077475 and B2062888.
00, 3573050, 3574627, 3
765337, JP-A-52-152225, JP-A-53-225
No. 20327, No. 53-17729, No. 61-901
No. 56, chromane, spirochroman, coumaran derivative, GB134756, JP2066695, JP-B-54-12337, hydroquinone monoether described in JP-A-55-6321, p-aminophenol derivative, US Pat. No. 3,700,455, JP-B-48 -31625
And the bisphenol derivatives described in the item (1). Also US
Metal complexes and singlet oxygen quenchers described in Japanese Patent No. 4245018 and JP-A-60-97353 may be used. A singlet oxygen quencher is disclosed in JP-A-2-3002.
No. 88, a diimmonium compound described in US Pat. No. 4,656,612, a nickel complex described in JP-A-4-146189, and an antioxidant described in EP820057A1.

In the optical filter of the present invention, two or more kinds of dyes as described above can be used in combination. The thickness of the optical filter that can be used in the present invention is preferably 0.1 μm to 1 cm,
More preferably, it is 0.5 μm to 100 μm.

The optical filter preferably further contains a polymer binder. Natural polymers (eg, gelatin, cellulose derivatives, alginic acid) or synthetic polymers (eg, polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol,
Polyvinyl chloride, styrene-butadiene copolymer, polystyrene, polycarbonate, water-soluble polyamide) can be used as the polymer binder. Hydrophilic polymer (the above natural polymer, polyvinyl butyral,
Polyvinyl pyrrolidone, polyvinyl alcohol, water-soluble polyamide) are particularly preferred.

[Transparent support] Examples of the transparent support include cellulose esters (eg, diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose,
Nitrocellulose), polyamide, polycarbonate,
Polyester (eg, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate,
Poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,
4'-dicarboxylate, polybutylene terephthalate), polyarylate (eg, condensate of bisphenol A and phthalic acid), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), acrylic (Polymethylmethacrylate), polysulfone, polyethersulfone, polyetherketone, polyetherimide and polyoxyethylene. Preferred are triacetyl cellulose, polycarbonate, polymethyl methacrylate, polyethylene terephthalate and polyethylene naphthalate. The thickness of the transparent support is preferably 5 μm or more and 5 cm or less, and 25 μm or more and 1 cm or less.
And more preferably 80 μm or more and 1.2 μm or less.
Most preferably, it is not more than mm. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably at most 2%, more preferably at most 1%.
The refractive index is preferably from 1.45 to 1.70.

An ultraviolet absorber may be added to the transparent support. The amount of the ultraviolet absorber added is 0.01% of the transparent support.
Preferably, it is 20 to 20% by weight, more preferably 0.05 to 10% by weight. Further, as a slipping agent, particles of an inert inorganic compound may be added to the transparent support. Examples of inorganic compounds include SiO ₂ , TiO ₂ , BaS
O _4, CaCO _3, talc and kaolin. It is preferable to apply a surface treatment to the transparent support. Examples of surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment,
Examples include an active plasma treatment, a laser treatment, a mixed acid treatment, and an ozone oxidation treatment. A glow discharge treatment, an ultraviolet irradiation treatment, a corona discharge treatment, and a flame treatment are preferable, and the corona discharge treatment is more preferable.

[Undercoat layer] An undercoat layer can be provided between the transparent support and the filter layer. The undercoat layer has a modulus of elasticity at room temperature of 1,000 to 1 MPa, preferably 800
Preferred is a soft polymer of from 5 to 5 MPa, more preferably from 500 to 10 MPa. The thickness is preferably 2
nm to 20 μm, more preferably 5 nm to 5 μm
m, most preferably 50 nm to 1 μm. The polymer used in the undercoat layer preferably has a glass transition temperature of 60C or lower and -60C or higher. Glass transition temperature is 60
Examples of a polymer having a temperature of -60 ° C or lower include vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, neoprene (registered trademark), styrene, chloroprene, acrylate, methacrylate, acrylonitrile or methyl vinyl ether. Polymerized ones can be mentioned. The undercoating can be provided in a plurality of layers, and is preferably provided in two layers.

[Anti-reflection layer] The regular reflectance is preferably 3.0% or less, more preferably 1.8%.
It is as follows. Usually, a low refractive index layer is provided as an antireflection layer. The refractive index of the low refractive index layer is lower than the refractive index of the lower layer. The refractive index of the low refractive index layer is preferably from 1.2 to 1.55, and more preferably from 1.20 to 1.50. The thickness of the low refractive index layer is 50 nm to 400 nm.
And more preferably 50 nm to 200 nm. Examples of the low refractive index layer include a layer made of a fluoropolymer having a low refractive index (JP-A-57-34).
No. 526, JP-A-3-130103 and 6-1150
Nos. 23, 8-313702, and 7-168004), and layers obtained by a sol-gel method (JP-A-5-208811, JP-A-6-299091, and JP-A-7-19081).
68003) or a layer containing fine particles (JP-B-60-59250, JP-A-5-13021).
Nos. 6-56478, 7-92306, 9-
288201). In the layer containing fine particles, voids can be formed in the low refractive index layer as microvoids between the fine particles or in the fine particles. The layer containing the fine particles preferably has a porosity of 3% to 50% by volume, and more preferably 5% to 35% by volume.

In order to prevent reflection in a wide wavelength range,
It is preferable that a layer having a high refractive index (medium / high refractive index layer) is laminated on the low refractive index layer. The refractive index of the high refractive index layer is 1.6
Preferably, it is 5 to 2.40, and 1.70 to 2.2.
More preferably, it is 0. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is
It is preferably 1.50 to 1.90. The thickness of the middle / high refractive index layer is preferably from 5 nm to 100 μm, more preferably from 10 nm to 10 μm,
Most preferably, it is 30 nm to 1 μm. The haze of the middle / high refractive index layer is preferably 5% or less,
%, More preferably 1% or less. The middle / high refractive index layer can be formed using a polymer having a relatively high refractive index. Examples of high refractive index polymers include polystyrene, styrene copolymers, polycarbonates, melamine resins, phenolic resins, epoxy resins, and polyurethanes obtained by reacting cyclic (alicyclic or aromatic) isocyanates with polyols. . Other polymers having a cyclic (aromatic, heterocyclic, alicyclic) group and polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. A polymer may be formed by a polymerization reaction of a monomer capable of radical curing by introducing a double bond.

In order to obtain a higher refractive index, inorganic fine particles may be dispersed in a polymer binder. The refractive index of the inorganic fine particles is preferably from 1.80 to 2.80. The inorganic fine particles are preferably formed from a metal oxide or sulfide. Examples of metal oxides or sulfides include titanium dioxide (eg, rutile, rutile / anatase mixed crystals, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Titanium oxide, tin oxide and indium oxide are particularly preferred. The inorganic fine particles contain oxides or sulfides of these metals as main components and may further contain other elements. The main component means a component having the largest content (% by weight) of the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn,
Pb, Cd, As, Cr, Hg, Zn, Al, Mg, S
i, P and S are included. Inorganic materials that are film-forming and can be dispersed in solvents or are themselves liquid, such as alkoxides of various elements, salts of organic acids, coordination compounds (eg, chelate compounds) combined with coordination compounds, activity The middle / high refractive index layer can be formed using an inorganic polymer.

[Electromagnetic Wave Shielding Layer] The layer having an electromagnetic wave shielding effect has a surface resistance of 0.01 to 500 Ω / □, more preferably 0.01 to 10 Ω / □. In order to impart an electromagnetic wave shielding effect, it is preferable to use a transparent conductive layer so as not to lower the transmittance of the front plate. Examples of the transparent conductive layer include a metal layer, a metal oxide layer, and a conductive polymer layer. As the metal forming the transparent conductive layer, for example, silver,
Palladium, gold, platinum, rhodium, aluminum, iron,
Cobalt, nickel, copper, zinc, ruthenium, tin, tungsten, iridium, lead alone or an alloy of two or more of these can be mentioned, preferably silver, palladium, gold, platinum, rhodium alone or an alloy thereof. is there. Among them, an alloy of silver and palladium is preferable. At this time, the silver content is preferably 60% by weight to 99% by weight, more preferably 80% by weight to 98% by weight. The thickness of the metal layer is preferably 1 to 100 nm, more preferably 5 to 40 nm, and most preferably 10 to 30 nm. The film thickness is 1
If it is less than nm, the electromagnetic wave shielding effect is poor, and if it exceeds 100 nm, the transmittance of visible light decreases. Examples of the metal oxide forming the transparent conductive layer include tin oxide, indium oxide, antimony oxide, zinc oxide, ITO, and ATO. This film thickness is preferably from 20 to 1000 nm. More preferably, it is 40 to 100 nm.
It is also preferable to use the metal transparent conductive layer and the oxide transparent conductive layer together. It is also preferable that a metal and a conductive metal oxide coexist in the same layer. A transparent oxide layer can be laminated to protect the metal layer, prevent oxidative deterioration, and increase visible light transmittance. This transparent oxide layer may or may not be conductive. Examples of the transparent oxide layer include thin films of oxides of divalent to tetravalent metals, zirconium oxide, titanium oxide, magnesium oxide, silicon oxide, aluminum oxide, and metal alkoxide compounds. The method for forming the transparent conductive layer and the transparent oxide layer is not particularly limited, and any processing method can be selected. For example, any known technique such as sputtering, vacuum deposition, ion plating, plasma CVD or PVD, application of ultrafine particles of a corresponding metal or metal oxide, and adhesion of a metal sheet can be used.

[Other Layers] A layer having an infrared shielding effect may be provided separately. The dye of the present invention may be contained in this layer. Infrared light from 750 nm to 1100 nm is the most problematic, and preferably has a shielding effect in this region. In order to impart an infrared shielding effect, a method of mixing a near infrared absorbing compound with a transparent plastic support can also be used. For example, a resin composition containing a copper atom (JP-A-6-118228), a resin composition containing a copper compound and a phosphorus compound (JP-A-62-5190),
It can be easily produced by forming a resin composition containing a copper compound and a thiourea derivative (JP-A-6-73197) and a resin composition containing a tungsten-based compound (US Pat. No. 3,647,729). The method of forming silver on a transparent film can have an infrared shielding effect in addition to the electromagnetic shielding.

In the present invention, it is also preferable to provide the surface with an anti-glare function (a function of scattering incident light on the surface to prevent a scene around the film from shifting to the film surface).
For example, by forming fine irregularities on the surface of a transparent film, and forming an antireflection layer on the surface, or after forming the antireflection layer, by forming irregularities on the surface with an embossing roll, an anti-glare function is obtained. be able to. An anti-reflection layer having an anti-glare function is generally 3
Has a haze of ３０30%.

In the present invention, it is also preferable to provide a hard coat layer, a lubricating layer, an antifouling layer, an antistatic layer or an intermediate layer. The hard coat layer preferably contains a cross-linked polymer. The hard coat layer can be formed using an acrylic, urethane, epoxy, or siloxane-based polymer, oligomer, or monomer (eg, an ultraviolet curable resin). A silica-based filler can be added to the hard coat layer. A lubrication layer may be formed on the outermost surface of the antireflection film. The lubricating layer has a function of imparting lubricity to the surface of the antireflection film and improving scratch resistance. The lubricating layer can be formed using polyorganosiloxane (eg, silicone oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or a derivative thereof. The thickness of the lubricating layer is preferably from 2 to 20 nm. Alternatively, an antifouling layer can be provided on the outermost surface of the antireflection film. The antifouling layer lowers the surface energy of the antireflection layer and makes it difficult to adhere to hydrophilic and lipophilic stains. In addition, the antifouling layer can be formed using a fluorine-containing polymer. The thickness of the antifouling layer is 2 nm to 100 n
m, preferably 5 nm to 30 nm.

Various layers in the present invention, that is, an antireflection layer (low-refractive index layer), a filter layer, an infrared or electromagnetic wave shielding layer, an undercoat layer, a hard coat layer, a lubricating layer, an antifouling layer,
Other layers can be formed by a general coating method. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and an extrusion coating method using a hopper (described in US Pat. No. 2,681,294). Is included. Two or more layers may be formed by simultaneous coating. The simultaneous coating method is described in U.S. Pat.
Nos. 3,508,947 and 3,526,528, and Yuji Harazaki, "Coating Engineering", page 253 (1
973 Asakura Shoten). In addition, as a method for forming a layer in the present invention, a sputtering method, a vacuum evaporation method, an ion plating method, a plasma CVD method, or a PVD method can be appropriately selected.

[Application of Optical Filter] The present invention relates to a liquid crystal display (LCD), a plasma display panel (PD).
P), electroluminescent display (EL)
D) or an image display device such as a cathode ray tube display device (CRT). The front plate of the present invention is particularly applicable to a plasma display panel (PDP) and a cathode ray tube display (CR)
When used as the front plate of T), a remarkable effect can be obtained.

[0073]

EXAMPLES Example 1 After a corona treatment was applied to both sides of a transparent biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, both sides had a refractive index of 1.55 and a glass transition temperature of 3
A latex made of a styrene-butadiene copolymer (LX407C5, manufactured by Zeon Corporation) at 7 ° C. was applied to form an undercoat layer. The film was dried so as to have a thickness of 300 nm on one side and a thickness of 150 nm on the other side.

On the side of the subbing layer having a thickness of 150 nm, an aqueous gelatin solution containing acetic acid and glutaraldehyde was applied with a thickness of 40 nm.
nm, and coated with polyvinyl butyral (PV
B: 3.0 g of PVB-3000K (manufactured by Denka Co., Ltd.) was dissolved in 80 g of chloroform, and dye 3-1 was 100 mg / m2.
² and dye 3-7, 110 mg / m ² were added, and the mixture was stirred for 30 minutes, filtered through a polypropylene filter having a pore size of 1 μm, applied so as to have a dry film thickness of 0.4 μm, and heated at 120 ° C. for 3 minutes After drying, an optical filter was prepared. (Measurement of Absorbance) When the spectral transmittance of the prepared optical filter was examined, it was found that the optical filter had absorption maximums at 830 nm and 920 nm. The transmittance at the absorption maximum at 830 nm was 5%, and the transmittance at the absorption maximum at 920 nm was 4%. Example 2 180 g of a 10% by weight aqueous solution of gelatin was p
1N sodium hydroxide solution was added so that H was 7, 20 mg / m ² of Dye 4-7 was added, and the mixture was stirred at 30 ° C. for 24 hours. The obtained coating solution for filter layer was applied to the undercoat layer side of the transparent support of Example 1 having a thickness of 300 nm.
An optical filter was prepared in the same manner as in Example 1 except that the coating was performed so that the dry film thickness became 3.5 μm, and the coating was dried at 120 ° C. for 10 minutes. (Measurement of Absorbance) The spectral transmittance of the prepared optical filter was examined. As a result, the optical filter had absorption maximums at 595 nm, 830 nm and 920 nm. The transmittance at the absorption maximum at 595 nm was 30%, the transmittance at the absorption maximum at 830 nm was 5%, and the transmittance at the absorption maximum at 920 nm was 4%.

Comparative Example An optical filter was prepared in the same manner as in Example 1 without using a dye. (Evaluation of optical filter) The outermost surface film of the front plate of a commercially available plasma display panel (PDS4202J-H, manufactured by Fujitsu Ltd.) was peeled off, and the optical filter thus prepared was attached with an adhesive. An evaluation was made as to whether there was a malfunction of the remote control of the television set facing the plasma display panel. In the comparative example, a malfunction often occurred, but the use of the filter of the present invention eliminated the malfunction. Further, the filter of the present invention was excellent in contrast and improved in white light and red light.

[0076]

The optical filter of the present invention can selectively cut off infrared light and light having a wavelength that reduces color purity. By using this optical filter for a plasma display panel, it is possible to prevent malfunction of the remote controller and correct the color balance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/41 C08K 5/41 5/42 5/42 5/45 5/45 C08L 101/00 C08L 101 / 00 C09B 23/00 C09B 23/00 LF term (reference) 2H048 CA04 CA12 CA14 CA19 CA27 4H056 CA01 CC02 CC08 CE03 DD03 FA01 FA05 4J002 BC031 BC051 BD041 BE021 BE061 BG061 BJ001 CG001 CL001 EU026 EU056 EV118 EV0306 EV256 EV258

Claims (6)

[Claims] 1. An optical filter comprising a transparent support and a filter layer laminated thereon, wherein the filter layer is represented by the following general formula (1) having a polymer binder and an absorption maximum in a wavelength region of 750 nm to 1100 nm. An optical filter comprising a cyanine dye and a metal complex represented by the general formula (2a). Embedded image In the formula, Z ¹ and Z ² each may be a 5-membered or 6-membered ring
R ¹ and R ² are each an aliphatic group or an aromatic group, and L ¹
Is a methine chain consisting of an odd number of methines, a, b and c are each 0 or 1, and x is an anion. Embedded image In the formula, L represents a ligand, M represents a metal atom, n1 represents an integer of 1 to 10, and m1 represents 1 or 2. 2. The optical filter according to claim 1, wherein the cyanine dye and the metal complex form a salt represented by the following formula (3). Embedded image In the formula, Z ³ and Z ⁴ each may be a 5-membered or 6-membered ring
R ³ and R ⁴ are each an aliphatic group or an aromatic group, and L ²
Is a methine chain consisting of an odd number of methines, d and e
Is 0 or 1, respectively, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom, an alkyl group, an aryl group, a cyano group or R ⁵ and R ⁶ or R ⁷ and R ⁸ are linked to each other and represents a non-metallic atoms necessary to form an aromatic ring, Y ¹
And Y ² represent O, S or NH, respectively, and M represents a metal atom. 3. The optical filter according to claim 1, wherein a light transmittance at an absorption maximum in a range of 750 to 1100 nm is in a range of 0.01 to 30%. 4. The optical filter according to claim 1, comprising an association of a cyanine dye represented by the following general formula (4) having an absorption maximum in a range of 560 nm to 620 nm. Embedded image In the formula, Z ⁵ and Z ⁶ are a group of non-metal atoms forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be independently condensed, and R ⁹ and R ¹⁰ are each independently an aliphatic group L ³ is a methine chain consisting of an odd number of methines, f, g and h are each independently 0 or 1, and x ² is an anion. 5. A plasma display panel having a display surface covered with the optical filter according to claim 1. 6. The plasma display panel according to claim 5, wherein no front plate is provided on the plasma display, and the optical filter is directly attached to the display surface.