JP2008134282A - Visible light absorbing display front filter and filter for plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a visible light absorbing display front filter containing a dye of a specific structure having maximum absorption in the visible light region, and suitable for use in a color image display device such as a plasma display, and a filter for a plasma display panel using the same, and to provide a visible light absorbing display front filter excellent in weather resistance, having sufficiently stable durability irrespectively of a temperature change and a humidity change in the use environment, and capable of achieving good color reproducibility irrespectively of the use environment of a color image display device itself, in particular, an emission wavelength change of a luminescent device due to a temperature change of the use environment, and a filter for a plasma display panel using the same. <P>SOLUTION: The visible light absorbing display front filter contains the dye having maximum absorption in the visible light region and represented by general formula (A-1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a visible light absorption display front filter containing a specific dye having a maximum absorption in the visible light region, and a filter for a plasma display panel using the same. More specifically, the present invention relates to a front filter for a visible light absorption display characterized by containing a dye having a specific structure having a maximum absorption in a specific visible light region, and a filter for a plasma display panel using the same. The present invention relates to a filter for a plasma display panel that can effectively shield emitted neon light.

  Conventionally, as a color image display device, there are various image display devices that display characters and images by emitting or reflecting light by electricity by cathode tubes, fluorescent display tubes, field emission, plasma panels, liquid crystals, electroluminescence, and the like. Has been developed. In particular, in recent years, plasma display panels have been used as display panels for various electronic devices such as large-sized wall-mounted televisions, and the demand thereof has increased, and the number is expected to increase in the future.

  These color image display devices basically take the form of displaying an image using a combination of red, green, and blue light emission of the three primary colors. In particular, in plasma displays, a mixed gas of xenon and neon is excited by discharge to emit vacuum ultraviolet light, and light emission of three primary colors is obtained by using light emission of red, blue, and green phosphors by the vacuum ultraviolet light excitation. . In that case, the plasma display emits so-called neon orange light centered around 600 nm when neon atoms return to the ground state after being excited (see Non-Patent Document 1). For this reason, the plasma display has a drawback that a bright red color cannot be obtained because the orange color is mixed with the red color.

  In general, a color image display device absorbs light emission other than the above three primary colors using a so-called bandpass filter to obtain a clear color image and correct the color balance of the image.

  Various studies have been made on the use of a dye as the bandpass filter. In this case, there is no absorption other than the intended absorption, weather resistance such as heat resistance and light resistance of the dye, and further use. An important factor is that changes in various environmental factors such as temperature changes and humidity changes in the environment do not cause a decrease in color reproducibility due to changes in transmittance or discoloration due to devitrification of filters using pigments, etc. In addition, there is a problem that the color reproducibility of the color image changes due to a change in the light emission wavelength of the light emitting device due to a change in the temperature of the use environment, in particular, the color image display device itself.

  On the other hand, as an absorption filter for a visible light region, application of an imidazole squarylium dye and a dye having an analog structure thereof to a liquid crystal color filter is disclosed (see Patent Document 1). However, this Patent Document 1 is mainly intended to develop a dye for use as an image forming material, and does not actually disclose an example in which the imidazole squarylium dye itself is used as a so-called bandpass filter. Moreover, the composition containing an imidazole squarylium pigment | dye is disclosed (refer patent document 2). However, Patent Document 2 is also intended to be used for image forming material as a main application, and an example used as a so-called band-pass filter is not disclosed.

  Moreover, a filter for a plasma display panel using a dipyrrole squarylium dye is disclosed (see Patent Document 3). In Patent Document 3, it is sufficient to absorb unnecessary light emission, but there is no description about weather resistance such as heat resistance and light resistance of the dye. Further, a plasma display panel filter is disclosed in which light resistance is improved by using an additive such as an antioxidant and an ultraviolet absorber in combination with a filter for a plasma display panel containing a squarylium dye (see Patent Document 4). ). However, Patent Document 4 does not disclose an imidazole squarylium dye, and there is no description suggesting a metal complex compound as an additive, and there is no description about the stability of the filter with respect to temperature change. Although a filter for a plasma display panel using a dipyrazole squarylium dye is disclosed (see Patent Document 5), it is sufficient to absorb unnecessary light emission, but there is no description about the stability of the filter against temperature changes.

As can be seen in Patent Documents 3, 4, and 5 described above, various filters that are sufficient for cutting neon orange light or other unnecessary visible light have been disclosed. Further improvement is desired for having high light resistance even under high temperature and high humidity environmental conditions. Further, the filter has sufficient stability and durability regardless of temperature change and humidity change in the use environment. In addition, there has been a demand for further improvements in the deterioration of color reproducibility of color images caused by the change in the emission wavelength of the light emitting device due to the change in the use environment temperature. In view of the above current situation, along with further improving the weather resistance of the compound, it has sufficient stability and durability regardless of temperature changes and humidity changes in the usage environment, and the emission wavelength of the light emitting device changes due to changes in the usage environment temperature. However, a visible light absorption display front filter capable of obtaining a clear color image and a plasma display panel filter using the same are strongly desired.
JP 2000-345059 A (claims, examples) JP 2003-192978 A (Claims, Examples) JP 2001-183522 A (claims, examples) JP-A-2001-350013 (Claims, Compound Examples, Examples) JP 2002-97383 A (claims, examples) The Journal of the Institute of Image Information Media, Vol. 51, no. 4, P.I. 459-463 (1997)

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a visible light containing a dye having a specific structure having a maximum absorption in the visible light region that can be suitably used for a color image display device such as a plasma display. It is an object to provide a light absorption display front filter and a plasma display panel filter using the same. In addition, it has excellent weather resistance, has sufficient stability and durability regardless of temperature changes and humidity changes in the usage environment, and the emission wavelength of the light emitting device due to the use environment of the color image display device itself, especially the change in the usage environment temperature It is an object of the present invention to provide a visible light absorbing display front filter that enables good color reproducibility regardless of changes, and a filter for a plasma display panel using the same. In particular, it can effectively cut neon light emission, has excellent weather resistance, has sufficient stability and durability regardless of temperature changes and humidity changes in the environment of use, especially in the use environment of the color image display device itself, especially An object of the present invention is to provide a filter for a plasma display panel that enables good color reproducibility regardless of a change in emission wavelength of a light emitting device due to a change in use environment temperature.

  The present invention has been studied in various ways, and the above object can be achieved by a visible light absorbing display front filter containing a specific imidazole squarylium dye and a plasma display panel filter using the visible light absorbing display front filter. I found.

  That is, the gist of the present invention is a visible light absorption display front filter containing a dye having a maximum absorption in the visible light region represented by the general formula (A-1), and a plasma display comprising the same It is related with the filter for panels.

  The above object of the present invention can be achieved by the following constitution.

  1. A visible light absorbing display front filter comprising a dye having a maximum absorption in a visible light region and represented by the following general formula (A-1).

(In the formula, B represents a heterocyclic group, an aromatic hydrocarbon ring group, or a group represented by the following general formula (AX), and R ₁ , R _a1 and R _a2 each represents a hydrogen atom or a substituent. ).
General formula (AX)
-C (R ₂₎ = D
(In the formula, D represents a 5-membered or 6-membered ring group, and R ₂ represents a hydrogen atom or a substituent.)
2. 2. The visible light absorbing display front filter according to 1, wherein the dye represented by the general formula (A-1) is represented by the following general formula (AX-1).

(Wherein R ₁ , R _a1 , R _a2 , R ₃ , R _b1 and R _b2 each independently represents a hydrogen atom or a substituent)
3. 3. The dye represented by the general formula (A-1) or the dye represented by the general formula (AX-1) is represented by the following general formula (AX-2): Visible light absorption display front filter.

(Wherein R ₁ , R _a1 , R _a2 , R ₃ , R _b1 and R _b2 each independently represents a hydrogen atom or a substituent)
4). The visible light absorbing display front filter according to any one of 1 to 3, further comprising a metal-containing compound.

  5. 5. The visible light absorbing display front filter according to 4, wherein the metal-containing compound contains at least one selected from divalent ions of Ni, Co, Zn, and Cu.

6). 6. The visible light absorbing display front filter according to 4 or 5, wherein the metal-containing compound is represented by the following general formula (X-1).
Formula (X-1)
M (X ₁ ) _m (X ₂ ) _l · (W ₁ ) _s
(In the formula, M represents a divalent ion of Ni, Co, Zn or Cu, and X ₁ and X ₂ each independently represent a monodentate or bidentate ligand, which may be the same or different. , X ₁ and X ₂ may be linked, m, l and s represent an integer of 0 to 2 and m + 1> 1 (W ₁ ) _s is a pair necessary for neutralizing charges Represents an ion.)
7). Furthermore, resin is contained, The visible light absorption display front filter of any one of 1-6 characterized by the above-mentioned.

  8. The visible light absorption display front filter according to any one of 1 to 7, which has maximum absorption in a visible light region of 8.570 nm to 630 nm.

  A filter for a plasma display panel, wherein the visible light absorbing display front filter according to any one of 9.1 to 8 is used.

  ADVANTAGE OF THE INVENTION According to this invention, the visible light absorption display front filter containing the pigment | dye of the specific structure which has maximum absorption in the visible light area | region which can be used conveniently for color image display apparatuses, such as a plasma display, and a plasma display panel using the same A filter can be provided. In addition, it has excellent weather resistance, has sufficient stability and durability regardless of temperature changes and humidity changes in the usage environment, and the emission wavelength of the light emitting device due to the use environment of the color image display device itself, especially the change in the usage environment temperature It is possible to provide a visible light absorption display front filter that enables good color reproducibility regardless of changes, and a filter for a plasma display panel using the same. In particular, it can effectively cut neon light emission, has excellent weather resistance, has sufficient stability and durability regardless of temperature changes and humidity changes in the environment of use, especially in the use environment of the color image display device itself, especially It is possible to provide a plasma display panel filter that enables good color reproducibility regardless of a change in emission wavelength of the light emitting device due to a change in use environment temperature.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

  Hereinafter, the present invention will be described in detail.

  The visible light absorption display front filter of the present invention (hereinafter also referred to as the filter of the present invention) will be described. The visible light absorption display front filter of the present invention is characterized by containing a dye having a specific structure having a maximum absorption in the visible light region represented by the general formula (A-1).

  The filter of the present invention is a dye represented by the general formula (A-1) according to the present invention, that is, a dye having a specific structure having a maximum absorption in the visible light region represented by the general formula (A-1). It can be used in the form of being mixed and absorbing visible light. The filter of the present invention is preferably used for the purpose of improving color reproducibility such as color tone correction, and particularly preferably used for the purpose of improving color reproducibility by absorbing transmitted light.

  The filter of the present invention is a color image display device, and various images that display characters and images by emitting or reflecting light by electricity such as cathode tubes, fluorescent display tubes, field emission, plasma panels, liquid crystals, electroluminescence, etc. The display device can be used for the purpose of selectively absorbing unnecessary light emission, particularly so-called neon orange light centering around 600 nm when the neon atom in the plasma display is excited and returns to the ground state. In addition, various types of external light such as fluorescent lamps and sunlight pass through the front filter of the electronic display, and the external light component reflected by the surface of the electronic display passes through the front filter again to the human eye. However, the external light passes through the filter on the front of the electronic display twice, and when passing through the filter, a predetermined light component is absorbed, so the balance of the spectrum of the external light is lost, The filter itself may appear colored in an unnatural color such as, for example, bluish purple or red purple. The filter of the present invention can also be used for applications that reduce unnatural coloring of the filter itself due to external light.

  The dye represented by the general formula (A-1) according to the present invention contained in the visible light absorption display front filter of the present invention, that is, the maximum in the visible light region represented by the general formula (A-1) of the present invention. The dye having a specific structure having absorption (hereinafter also referred to as the dye of the present invention) will be described.

  If the dye of the present invention has absorption in the visible light region in a solution state and does not substantially absorb in the near infrared region, the dye of the present invention can be suitably used for the visible light absorption display front filter of the present invention. . The dye of the present invention preferably has an absorption maximum in the visible light region in a solution state, and the dye of the present invention preferably has an absorption maximum at 450 nm to 650 nm in the solution state. Most preferably, it has an absorption maximum at 570 nm to 610 nm.

  The dye represented by formula (A-1) according to the present invention will be described in detail.

In the general formula (A-1), B represents a heterocyclic group, an aromatic hydrocarbon ring group, or a group represented by the following general formula (AX), and R ₁ , R _a1 and R _a2 are each independently Represents a hydrogen atom or a substituent.
General formula (AX)
-C (R ₂₎ = D
In general formula (AX), D represents a 5-membered or 6-membered ring group, and R ₂ represents a hydrogen atom or a substituent.

  In the general formula (A-1), examples of the heterocyclic group or the aromatic hydrocarbon ring group represented by B include a benzene ring, a naphthalene ring, a pyran ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. , Triazine ring, purine ring, quinoline ring, isoquinoline ring, coumarin ring, chromone ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, thiadiazole ring, oxazole ring, thiazole ring, benzothiazole ring, Benzoxazole ring, benzoselenazole ring, benzotelrazole ring, benzimidazole ring, thiazoline ring, indolenine ring, oxadiazole ring, pyrazolone ring, isoxazolone ring, pyrrolidone ring, thioxathiazolone ring, pyrrolopyrrole ring, Pyrroloimidazole ring, pyrrolotriazol Derived from a ring, pyrazolopyrrole ring, pyrazoloimidazole ring, pyrazolotriazole ring, pyrazolopyrimidine ring, imidazolopyrazole ring, isoxazolidine ring, thioximidazolidine ring, imidazolidine ring, imidazolidinethione ring, thiazolidinone ring, etc. Each ring group can be raised, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, isoquinoline ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring , Thiadiazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, indolenine ring, oxadiazole ring, pyrazolone ring, pyrrolidone ring, pyrrolopyrrole ring, pyrroloimidazole , A pyrrolotriazole ring, a pyrazolopyrrole ring, a pyrazoloimidazole ring, a pyrazolotriazole ring, a pyrazolopyrimidine ring, and an imidazolopyrazole ring, preferably a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, Pyrazine ring, quinoline ring, isoquinoline ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, indolenine ring, pyrazolotriazole ring More preferred are a pyrazolopyrimidine ring and an imidazolopyrazole ring, a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, a quinoline ring, a pyrazole ring, an imidazole ring, a benzimidazole ring, an indolenine ring, and a pyrazolotriazol. Ring, imidazolopyrazole ring, more preferably benzene ring, naphthalene ring, pyridine ring, quinoline ring, pyrazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyrazolotriazole ring, imidazolopyrazole ring A cyclic group is more preferable, and a cyclic group derived from an imidazole ring is most preferable. These may have a substituent at an arbitrary position, and may further form a condensed ring with another aromatic hydrocarbon ring or heterocyclic ring.

  The substituent that can be substituted for B is not particularly limited. For example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group) , Trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aromatic hydrocarbon group (eg, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group) Etc.), alkylthio groups (eg methylthio group, ethylthio group etc.), arylthio groups (eg phenylthio group, naphthylthio group etc.), alkenyl groups (eg vinyl group, 2-propenyl group, 3-butenyl group, 1-methyl group) -3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexyl group Senyl group, cyclohexenyl group etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethyl) Sulfonyl group etc.), arylsulfonyl group (eg phenylsulfonyl group, naphthylsulfonyl group etc.), alkylsulfinyl group (eg methylsulfinyl group etc.), arylsulfinyl group (eg phenylsulfinyl group etc.), phosphono group, acyl group (For example, acetyl group, pivaloyl group, benzoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenyl group) Aminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group) , Dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.), alkoxy group (for example, methoxy group, Ethoxy group, propoxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg acetyloxy group) Benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group) , Dodecylamino group, etc.), anilino group (eg, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc.), imide group, ureido group (eg, methylureido group, ethyl) Ureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, phenol) Sicarbonylamino group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), heterocyclic thio group, thioureido group, carboxyl group, Examples include carboxylic acid salts, hydroxyl groups, mercapto groups, nitro groups, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), cyano groups, etc., preferably alkyl groups, aromatic Group hydrocarbon group, acylamino group, alkylthio group, arylthio group, alkenyl group, heterocyclic group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, acyl group, carbamoyl group, sulfamoyl group, sulfonamide group, Arco Si group, aryloxy group, heterocyclic oxy group, acyloxy group, aminocarbonyloxy group, amino group, anilino group, ureido group, alkoxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic thio group, thioureido group , A carboxyl group, a salt of a carboxylic acid, a hydroxyl group, a mercapto group, a cyano group, and a halogen atom, and these B-substitutable substituents may be further substituted with the same substituents. When there are a plurality of substituents that can be substituted for B, the respective substituents may be the same or different, and the substituents may be arbitrarily bonded to form a ring. In addition, a condensed ring in which substituents are arbitrarily bonded to each other can be introduced to adjust the color tone of the general formula (A-1) to a desired color tone. In this case, examples of the condensed ring include the above-described aromatic hydrocarbon group and heterocyclic group, and the condensed ring is further substituted with a substituent having the same meaning as the substituent capable of substituting B. May be.

  When B in the general formula (A-1) is a group represented by the general formula (AX), D in the general formula (AX) represents a 5-membered or 6-membered ring group. Examples of the group include pyrazolidinedione ring, isoxazolone ring, pyrazolone ring, pyrrolidone ring (for example, 1H-pyrrol-2 (5H) -one ring), thioxathiazolidinone ring (for example, rhodanine ring, 4-thioxa ring) Imidazolidin-2-one ring, 5-thioimidazolidin-2-one ring), pyrrolotriazole ring (for example, 7,7a-dihydro-1H-pyrrolo [1,2-b] [1,2,4] Triazole ring, 7,7a-dihydro-1H-pyrrolo [2,1-c] [1,2,4] triazole ring), pyrazolotriazole ring (eg, 7,7a-dihydro-1H-pyrazolo [5,1 -C] [1,2,4] triazo Ring, 7,7a-dihydro-1H-pyrazolo [1,5-b] [1,2,4] triazole ring), pyrazolopyrimidine ring, imidazole ring (for example, 4H-imidazole ring), imidazolopyrazole ring, Pyrrole ring, isoxazolidinedione ring, thiooxaimidazolidinone ring (for example, 4-thioximidazolidin-2-one ring), imidazolidinedione ring (for example, hydantoin ring), imidazolidinedithione ring (for example, imidazolidine-2) , 4-dithione ring), thiazolidinedione ring, pyrazoledione ring, indole ring, and the like, and these have a group having the same meaning as the substituent that can be substituted for B described above at an arbitrary position. May be.

  Examples of the 6-membered ring group represented by D in the general formula (AX) include a cyclohexadiene ring (1,3-cyclohexadiene ring, 1,4-cyclohexadiene ring), a dihydropyridine ring (1,4- Dihydropyridine ring, 3,4-dihydropyrazine ring), 4H-pyran ring, 4H-thiopyran ring, pyridone ring (for example, pyridine-2 (3H) -one ring), pyridinethione ring (for example, pyridine-2 (3H ) -Thione ring), pyridinedione ring (eg pyridine-2,4 (3H, 5H) -dione ring), barbituric acid ring, thiobarbituric acid ring, oxazine ring, thiazine ring, dihydropyrimidinedione ring (eg Dihydropyrimidine-4,6 (1H, 5H) -dione ring), dihydropyrimidinedithion ring (eg, dihydropyrimidine-4,6 (1H, 5 ) -Dithione ring), oxazinedione ring (for example, 4H-1,3-oxazine-4,6 (5H) -dione ring), oxadiazine ring (for example, 4H-1,2,3-oxadiazine ring), etc. Examples thereof include a cyclic group, and these may have a group having the same meaning as the above-described substituent capable of substituting for B at any position.

In the general formula (A-1), R ₁ represents a hydrogen atom or a substituent. Examples of the substituent include the same substituents as the substituents that can be substituted for B described above. Or an alkyl group is preferable.

In general formula (A-1), R _a1 and R _a2 each independently represent a hydrogen atom or a substituent. Examples of the substituent include the same substituents as those described above for B. Preferably, alkyl group, aromatic hydrocarbon group, acylamino group, alkylthio group, arylthio group, alkenyl group, heterocyclic group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, acyl group Carbamoyl group, sulfamoyl group, sulfonamide group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, aminocarbonyloxy group, amino group, anilino group, ureido group, alkoxycarbonylamino group, alkoxycarbonyl group, aryl Oxycarbonyl group, heterocyclic thio group, thioureido group Carboxyl group, salts of carboxylic acids, hydroxyl group, mercapto group, cyano group, a halogen atom, these substituents may be further substituted by similar substituents.

In the general formula (AX), R ₂ represents a hydrogen atom or a substituent, and examples of the substituent include the same substituents as the substituent that can be substituted for B described above. Groups are preferred.

  The dye represented by the general formula (A-1) is preferably represented by the general formula (AX-1).

In the general formula (AX-1), R ₁ , R _a1 , R _a2 , R ₃ , R _b1 and R _b2 each independently represent a hydrogen atom or a substituent.

In General Formula (AX-1), R ₁ and R ₃ each independently represent a hydrogen atom or a substituent, and examples of the substituent include the same substituents as those described above for B. A hydrogen atom or an alkyl group is preferred.

In the general formula (AX-1), R _a1 , R _a2 , R _b1 and R _b2 each independently represent a hydrogen atom or a substituent, and examples of the substituent include a substituent which can be substituted with B described above. And preferably have an alkyl group, aromatic hydrocarbon group, acylamino group, alkylthio group, arylthio group, alkenyl group, heterocyclic group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group. , Arylsulfinyl group, acyl group, carbamoyl group, sulfamoyl group, sulfonamido group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, aminocarbonyloxy group, amino group, anilino group, ureido group, alkoxycarbonylamino Group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic ring O group, thioureido group, a carboxyl group, salts of carboxylic acids, hydroxyl group, mercapto group, cyano group, a halogen atom, these substituents may be further substituted by similar substituents.

  The dye represented by the general formula (AX-1) is preferably represented by the general formula (AX-2).

In the general formula (AX-2), R ₁ , R _a1 , R _a2 , R ₃ , R _b1 and R _b2 each independently represent a hydrogen atom or a substituent, and each of the above-described general formula (AX-1) Are the same as R ₁ , R _a1 , R _a2 , R ₃ , R _b1 and R _b2 .

  Specific examples of the dyes represented by the general formulas (A-1), (AX-1), and (AX-2) are shown below, but the present invention is not limited to the following specific examples.

  Hereinafter, the general manufacturing method of the pigment | dye represented by general formula (A-1) is demonstrated.

  The dye represented by formula (A-1) can be synthesized with reference to a conventionally known method. For example, JP-A-6-250357, JP-A-7-175187, JP-A-3-82255, JP-A-3-261539, JP-A-4-13834, JP-A-63-1210167, JP-A-10 -36695, JP-A-2000-251958, 2000-285978, 2000-345059, 2002-97383, 2003-192978, WO2001 / 044,233, WO2002 / Reference can be made to 050, 190, WO 2004/007, 447 and the like. Specific examples of the synthesis method of the dye represented by the general formula (A-1) are shown below, but other compounds can be synthesized in the same manner, and the synthesis method is not limited thereto. .

[Synthesis Example 1]
<< Synthesis of Exemplified Compound A1 >>
Reaction scheme

According to the above reaction scheme, 110 g of n-butanol, 110 ml of xylene and 2.3 g of compound (b) were added to 3.0 g of compound (a), and the mixture was heated for 1 hour using a microwave synthesizer, and then the solvent was distilled under reduced pressure. Left. 20 ml of methanol was added to the residue, and the precipitate was collected by filtration to obtain 0.5 g of Compound A1. It was confirmed by MASS, ¹ H-NMR, ¹³ C-NMR, and IR spectrum.

  It was a red-purple to blue-purple solution in chloroform, acetone, methanol, THF, and N-methylpyrrolidone. In these solvents, it was confirmed that there was an absorption maximum in the range of 545 to 560 nm.

[Synthesis Example 2]
<< Synthesis of Exemplified Compound A9 >>
Reaction scheme

  According to the above reaction scheme, the same procedure as in Synthesis Example 1 except that Compound (a) described in Synthesis Example 1 was changed to 3.0 g of Compound (c) and Compound (b) was changed to 3.2 g of Compound (d). As a result, 0.3 g of Exemplified Compound A9 was obtained.

  It was a reddish purple to bluish purple solution in chloroform, acetone, methanol, THF, and N-methylpyrrolidone. In these solvents, it was confirmed that there was an absorption maximum in the range of 580 to 605 nm.

[Synthesis Example 3]
<< Synthesis of Exemplified Compound A14 >>
Reaction scheme

  According to the above reaction scheme, the same operation as in Synthesis Example 1 except that Compound (a) described in Synthesis Example 1 was changed to 3.0 g of Compound (e) and Compound (b) was changed to 4.1 g of Compound (f). As a result, 0.7 g of Exemplified Compound A14 was obtained.

  It was a purple-blue-purple solution in chloroform, acetone, methanol, THF, and N-methylpyrrolidone, and in these solvents, it was confirmed that there was an absorption maximum in the range of 590 to 615 nm.

[Synthesis Example 4]
<< Synthesis of Exemplified Compound A23 >>
Reaction scheme

  According to the above reaction scheme, the same procedure as in Synthetic Example 1 except that Compound (a) described in Synthesis Example 1 was changed to 3.0 g of Compound (g) and Compound (b) was changed to 1.1 g of Compound (h). As a result, 0.5 g of Exemplified Compound A23 was obtained.

  It was a purple-blue-purple solution in chloroform, acetone, methanol, THF, and N-methylpyrrolidone, and in these solvents, it was confirmed that there was an absorption maximum in the range of 590 to 615 nm.

[Synthesis Example 5]
Synthesis of exemplary compound A34 Reaction scheme

  According to the above reaction scheme, the same procedure as in Synthesis Example 1 except that Compound (a) described in Synthesis Example 1 was changed to 3.0 g of Compound (i) and Compound (b) was changed to 3.6 g of Compound (j). As a result, 0.6 g of Exemplified Compound A34 was obtained.

  It was a purple-blue-purple solution in chloroform, acetone, methanol, THF, and N-methylpyrrolidone. In these solvents, it was confirmed that there was an absorption maximum in the range of 595-625 nm.

  Next, the metal-containing compound according to the present invention will be described.

Examples of the metal-containing compound according to the present invention include inorganic or organic salts and metal complexes of metal ions, and among them, salts and complexes of organic acids are preferable. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the periodic table, among which Al, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn is preferred, Ni, Co, Zn and Cu are particularly preferred, Co, Zn and Cu are more preferred, and Zn and Cu are most preferred. Specific examples of the metal-containing compound include Ni ²⁺ , Co ²⁺ , Zn ²⁺ , and Cu ²⁺ and aliphatic salts such as acetic acid and stearic acid, or aromatic carboxylic acids such as benzoic acid and salicylic acid. Examples include salts.

Moreover, the metal containing compound represented by the following general formula (X-1) can be used particularly preferably.
Formula (X-1)
M (X ₁ ) _m (X ₂ ) _l · (W ₁ ) _s
In general formula (X-1), M represents a divalent ion of Ni, Co, Zn, or Cu, and X ₁ and X ₂ each independently represent a monodentate or bidentate ligand, They may be different and X ₁ and X ₂ may be linked. m, l, and s represent an integer of 0 to 2, and m + l> 1. (W ₁ ) _s represents a counter ion necessary for neutralizing the charge.

Examples of X ₁ and X ₂ include JP-A Nos. 2000-251957, 2000-31723, 2000-323191, 2001-6760, 2001-59062, and 2001-60467. As described in the above.

  Specifically, halogen ion, hydroxide ion, ammonia, pyridine, amine (such as methylamine, diethylamine, tributylamine, etc.), cyanide ion, cyanate ion, thiolate ion, thiocyanate ion, and bipyridines, aminopolycarboxylic acid Various chelate ligands such as acids, 8-hydroxyquinoline and the like can be mentioned, and the chelate ligands are exemplified in “Chelical Chemistry” by Keihei Ueno.

  As a monodentate ligand, a ligand coordinated by an acyl group, carbonyl group, thiocyanate group, isocyanate group, cyanate group, isocyanate group, halogen atom, cyano group, alkylthio group, arylthio group, alkoxy group or aryloxy group Or a ligand composed of dialkyl ketone or carbonamide is preferred.

  As bidentate ligands, acyloxy group, oxalylene group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate A ligand coordinated by a group, an alkylthio group or an arylthio group, or a ligand comprising a dialkyl ketone or a carbonamide is preferred.

  Specific examples are shown below, but the present invention is not limited thereto. It should be noted that the structural formula shown here is only one of the limit structures among the possible resonance structures, and the distinction between a covalent bond (indicated by-) and a coordination bond (indicated by ...) is also formal. It does not represent an absolute distinction.

  Moreover, the compound represented by the following general formula (8) is more preferable as a ligand.

In General Formula (8), E ₁ represents a substituent, E ₂ represents an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 to 0.9, and R ₈₁ represents an alkyl group or an aryl group. Represents a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group, and may have a substituent.

A substituent having a σp value represented by E ₁ and E ₂ of 0.1 or more and 0.9 or less will be described. As the value of Hammett's substituent constant σp here, Hansch, C .; It is preferable to use the values described in the report of Leo et al. (For example, J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)).

  For example, a substituent or atom having a value of σp of 0.10 or more includes a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, a cyano group, a nitro group, a halogen-substituted alkyl group (for example, trichloromethyl, trifluoromethyl, chloro Methyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), aliphatic / aromatic or heterocyclic acyl groups (eg formyl, acetyl, benzoyl), aliphatic / aromatic or heterocyclic sulfonyl groups (eg trifluoromethane) Sulfonyl, methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro-phenylcarbamoyl), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl) Bonyl, diphenylmethylcarbonyl), substituted aromatic groups (eg pentachlorophenyl, pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (eg 2-benzoxazolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo group (eg phenylazo), ditrifluoromethylamino group, trifluoromethoxy group, alkylsulfonyloxy group (eg methanesulfonyloxy), acyloxy group ( For example, acetyloxy, benzoyloxy), arylsulfonyloxy group (for example, benzenesulfonyloxy), phosphoryl group (for example, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (for example, N-ethylsulfuryl) Amoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl) and the like.

  In addition, as a substituent having a value of σp of 0.35 or more, a cyano group, a nitro group, a carboxyl group, a fluorine-substituted alkyl group (for example, trifluoromethyl, perfluorobutyl), an aliphatic / aromatic or heterocyclic acyl group (Eg, acetyl, benzoyl, formyl), aliphatic / aromatic or heterocyclic sulfonyl groups (eg, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro) -Phenylcarbamoyl), alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), fluorine or sulfonyl group substituted aromatic group (eg pentafluorophenyl, 2,4-dimethanesulfonylphenol) ), Heterocyclic residues (eg, 1-tetrazolyl), azo groups (eg, phenylazo), alkylsulfonyloxy groups (eg, methanesulfonyloxy), phosphoryl groups (eg, dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl groups, etc. Is mentioned.

  Examples of the substituent having a value of σp of 0.60 or more include a cyano group, a nitro group, an aliphatic / aromatic or heterocyclic sulfonyl group (for example, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like. It is done.

The substituent represented by E ₁ has the same meaning as R ₁₁ in the general formula (1), but preferably an alkyl group, an aryl group, a heterocyclic group, a carbonyl group, a cyano group, an alkoxycarbonyl group, or an alkylsulfonyl group. And an alkylsulfonyloxy group are preferable, and an electron-withdrawing group is preferable.

E ₁ and E ₂ are preferably a halogenated alkyl group (particularly a fluorine-substituted alkyl group), a carbonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfonyloxy group, and the like.

Preferred substituents for R ₈₁ include an alkyl group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, an aryloxy group, and an amino group, and more preferably an alkyl group having 4 to 18 carbon atoms or a carbon number. 4 to 18 alkoxy groups and aryloxy groups. Most preferably, it is a C6-C16 alkoxy group.

  Specific examples of the ligand represented by the general formula (8) are shown below, but the present invention is not limited thereto.

(W ₁ ) _s represents a counter ion necessary to neutralize the electric charge. For example, whether a certain dye is a cation, an anion, or a net ionic charge depends on its metal, coordination Depends on the child and substituent. When the substituent has a dissociable group, it may be dissociated to have a negative charge, and in this case as well, the charge of the entire molecule is neutralized by (W ₁ ) _s . Typical cations are inorganic or organic ammonium ions (eg tetraalkylammonium ions, pyridinium ions), alkali metal ions and protons, whereas anions are specifically either inorganic or organic anions. For example, halogen anion (for example, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion) ), Aryl disulfonate ions (for example, 1,3-benzenedisulfonate ions, 1,5-naphthalenedisulfonate ions, 2,6-naphthalenedisulfonate ions), alkyl sulfate ions (for example, methyl sulfate ions), sulfate ions , Thiocyanate ion , Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion, and the like.

  Specific examples of the metal compound represented by the general formula (X-1) are shown in Tables 1 and 2, but the present invention is not limited thereto.

  The ligand of the metal-containing compound represented by the general formula (X-1) can be synthesized with reference to JP-A Nos. 2002-332259 and 2003-237246. Specific examples of the method for synthesizing the compound represented by the general formula (X-1) are shown below, but other compounds can be synthesized in the same manner, and the synthesis method is not limited thereto.

(Synthesis example)
<< Synthesis of MS-41 >>
Reaction scheme

<Synthesis of Intermediate 11 (X-116)>
Intermediate 9: Stirring to 35.0 g, acetonitrile: 200 ml, calcium chloride: 26.3 g, and triethylamine: 36.3 g are added successively and cooled to 15 ° C. Next, while maintaining the internal temperature at 20 ° C. or less, 32.0 g of Intermediate 10 is added dropwise and reacted at room temperature for 2 hours. Extract by adding 200 ml of ethyl acetate and 100 ml of water, neutralize, wash with water and concentrate. The concentrate was purified by column chromatography to obtain Intermediate 11: 45.2 g. It was identified by MASS, H-NMR, and IR spectrum, and confirmed to be the target product.

<Synthesis of MS-41>
Water: 50 ml was added and dissolved in 2.73 g of copper chloride dihydrate: a solution of methanol: 5 ml added to 10.11 g of intermediate 11 was added dropwise with stirring, and the precipitated crystals were filtered. Recrystallization from acetonitrile gave MS-41: 9.20 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

  The visible light absorbing display front filter of the present invention preferably further contains a resin serving as a binder together with the dye of the present invention and the metal-containing compound of the present invention. Resins used as binders include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl resins. Examples thereof include alcohol resins, polyvinyl modified resins (PVB, EVA, etc.), and copolymer resins thereof.

  When the resin is used in the present invention, the concentration of the dye varies depending on the Gram extinction coefficient, the coating thickness, the target absorption strength, the target visible light transmittance, etc., but is usually 0.1 ppm with respect to the mass of the binder resin. -30 mass%. The density | concentration of the metal containing compound of this invention is 5 mass%-1000 mass% normally with respect to the mass of a pigment | dye.

  In preparing the visible light absorbing display front filter of the present invention, a solvent may be used for mixing the binder and the dye of the present invention. Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof. The concentration of the composition varies depending on the gram extinction coefficient, the thickness of the coating, the target absorption intensity, the target visible light transmittance, and the like. Therefore, an optimal concentration may be set according to the intended use. The solution or dispersion of the dye of the present invention and the binder resin includes, if necessary, polyvinyl butyral resin, polyurethane resin, phenol resin, phenoxy resin, petroleum resin, rosin resin, etc. A dispersant may be used.

  The visible light absorption display front filter of the present invention has generally known additives such as phenol-based and phosphorus-based antioxidants, halogen-based and phosphoric acid-based flame retardants, heat-resistant anti-aging agents, and ultraviolet absorption. An agent, a lubricant, an antistatic agent and the like can be blended.

  In the case of containing a plurality of the dyes of the present invention, each of them is separately mixed in a binder resin, and by laminating each binder resin containing the dye of the present invention, the form of a laminate in which individual compounds exist in separate layers You may take. In this case, the number of lamination operations increases, which is not preferable from the viewpoint of manufacturing, but it is possible to select a more preferable binder resin according to the compound, which is useful when fine color adjustment is necessary. .

  As a method for producing the above laminate, for example, 1) The dye of the present invention and a binder resin are used as a solution or dispersion of an appropriate solvent, and applied on a sheet-like or film-like transparent substrate by a known application method. 2) According to a conventional molding method for thermoplastic resins, the dye of the present invention and a binder resin are melt-kneaded and molded into a film or sheet by extrusion molding, injection molding, compression molding, etc. 3. Method of adhering the film or sheet on a transparent substrate with an adhesive or the like 3) Melting and kneading the dye of the present invention and a binder resin, extruding into a film or sheet, and extrusion laminating on the transparent substrate 4) Various methods such as a method of melt-kneading the dye of the present invention and a binder resin and co-extrusion molding with a transparent resin base material can be adopted. The Chi especially, the method of the above 1) is preferred.

  As the method for producing the latter single layer sheet or film, for example, 1) The dye of the present invention and a binder resin are cast on a carrier as a solution or dispersion of an appropriate solvent and dried. Method 2) According to a conventional molding method for thermoplastic resins, a method of melt-kneading the dye of the present invention and a binder resin and molding the film or sheet by extrusion molding, injection molding, compression molding, or the like is adopted. be able to.

  The visible light absorbing display front filter of the present invention may use a dispersant together with the dye of the present invention. Examples of the dispersant used as necessary include polyvinyl butyral resin, phenoxy resin, rosin-modified phenol resin, petroleum resin, cured rosin, rosin ester, maleated rosin, and polyurethane resin. The usage-amount is 0.5 to 150 mass times with respect to the gross mass of the pigment | dye of this invention, Preferably it is 10 to 100 mass times.

  The visible light absorption filter in the present invention contains the dye of the present invention alone or in combination. As its inclusion form, typically, a laminate in which the dye-containing resin layer of the present invention is formed with a binder resin containing the dye of the present invention on a sheet-like or film-like transparent substrate, or Examples thereof include a single-layer sheet or film of the dye-containing resin of the present invention, which comprises the binder resin itself containing the dye of the present invention.

  The display panel filter according to the present invention is disposed in front of a self-luminous display device such as a plasma display or an organic EL display, and is used to correct color tone or block light emission in an unnecessary wavelength region.

  Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass, and there is no particular limitation as long as the light transmittance at a wavelength of 400 to 700 nm is 40% or more. For example, polyimide, polysulfone (PSF), polyethersulfone (PES), polyethylene terephthalate (PET), polymethylene methacrylate (PMMA), polycarbonate (PC), polyetheretherketone (PEEK), polypropylene (PP), triacetyl A cellulose (TAC) etc. are mentioned. In particular, acrylic resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polymethyl methacrylate (PMMA), polycarbonate resins, and the like are preferably used.

  Although there will be no restriction | limiting in particular if the thickness of a base material has a certain amount of mechanical strength, Usually, they are 20 micrometers-10 mm, 20 micrometers-1 mm are preferable, and 20 micrometers-200 micrometers are especially preferable.

The method for producing the display panel filter of the present invention using the dye of the present invention is not particularly limited,
(1) Method of containing in transparent adhesive (2) Method of containing in polymer molded body (3) Method of coating on polymer molded body or glass surface, etc.

  Specific examples of the transparent adhesive listed in (1) include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), and ethylene-vinyl acetate adhesives (EVA). Etc., sheet-like or liquid pressure-sensitive adhesives such as polyvinyl ether, saturated amorphous polyester, melamine resin, etc., among which acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and polyvinyl butyral pressure-sensitive adhesives are preferable. The addition amount is usually 10 ppm to 30% by mass, preferably 10 ppm to 20% by mass, and particularly preferably 10 ppm to 10% by mass.

  (2) The polymer resin molded body listed in (2) includes (A) a method of kneading a dye mixture into a resin and heat molding, and (B) an organic solvent containing a resin or resin monomer and a dye mixture. Examples thereof include a method in which a polymer molded body is prepared by dispersing and dissolving and casting.

  The resin used in (A) is preferably as transparent as possible when a plate or film is produced. Specifically, polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate, poly Polyamides such as arylate, polyetherketone, polycarbonate, polyethylene, polypropylene and nylon 6, cellulose resins such as polyimide and triacetyl cellulose, fluorine resins such as polyurethane and polytetrafluoroethylene, vinyl compounds such as polyvinyl chloride, polyacrylic Acid, polyacrylic acid ester, polyacrylonitrile, addition polymer of vinyl compound, polymethacrylic acid, polymethacrylic acid ester, vinylidene chloride such as polyvinylidene chloride, vinylidene fluoride / trifluoroe Ren copolymers, copolymers of ethylene / vinyl compound-vinyl acetate copolymer, or a fluorine-based compound, polyether such as polyethylene oxide, epoxy resins, polyvinyl alcohol, and polyvinyl butyral.

  As processing conditions, the dye of the present invention is added to and mixed with the base polymer powder or pellet, heated and dissolved at 150 to 350 ° C., and then molded to form a plate, or formed into a film with an extruder. Examples thereof include a method, a method of producing a raw material with an extruder, and stretching the film in a uniaxial or biaxial manner 2 to 5 times at 30 to 120 ° C. to form a film having a thickness of 10 to 200 μm. In addition, when kneading, an additive used for ordinary resin molding such as plasticity may be added.

  In the casting method (B), a mixture containing the dye of the present invention is added to and dissolved in an organic solvent solution or organic solvent of resin or resin monomer, and if necessary, a plasticizer, a polymerization initiator, and an antioxidant are added. A plate or a film can be produced by pouring onto a mold or drum having a required surface state, followed by solvent volatilization / drying or polymerization / solvent volatilization / drying.

  Examples of resins used include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, Examples thereof include polyvinyl modified resins (PVA, EVA, etc.) or resin monomers of those copolymer resins. Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof.

  As a method of coating the polymer molded body or glass surface mentioned in (3), a method of forming a composition after dissolving the dye of the present invention in a binder resin and an organic solvent, and an uncolored acrylic emulsion Examples thereof include a method of dispersing a finely pulverized (50 to 500 nm) pigment of the present invention into a paint to obtain an acrylic emulsion-based aqueous paint. In the coating material, additives such as antioxidants used in ordinary coating materials may be added.

  Examples of binders include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, and polyvinyl resins. Examples thereof include modified resins (PVB, EVA, etc.) or copolymer resins thereof.

  Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof. Moreover, resin concentration is 1-50 mass% normally with respect to the whole coating material.

  The coating material produced by the above method is applied by forming a thin film on a substrate by a known method such as a bar coder, blade coater, spin coater, reverse coater, die coater, or spray coating method. be able to.

  The display panel filter of the present invention preferably has an electromagnetic wave shielding function or a near infrared ray blocking function. As the electromagnetic wave shield, a laminate using a silver thin film or a metal mesh mainly using copper can be used. As a laminate using a silver thin film, a laminate in which a dielectric such as indium oxide, zinc oxide, titanium oxide and silver are alternately laminated is preferable. As the metal mesh, a fiber mesh obtained by depositing metal on a fiber, an etching mesh that forms a pattern using a photolithography technique and obtains a mesh by etching, and the like can be used. In addition, a method of patterning with a metal-containing ink, a method of applying silver halide, developing and fixing, and the like are also preferably used.

  As for the near infrared ray blocking function, when an electromagnetic wave shield using a silver thin film is used, the near infrared ray can be simultaneously blocked due to scattering of silver by free electrons. In addition, when a mesh, ink patterning, or development method is used, a film that absorbs or reflects near infrared rays is used separately. Moreover, you may add a well-known various infrared absorber to a suitable layer.

  Furthermore, a functional transparent layer such as a known antireflection layer, antiglare layer, hard coat layer, antistatic layer, or antifouling layer can be added to the display panel filter of the present invention.

  In order to obtain an electronic display or a plasma display panel display device using the display panel filter of the present invention, any known display device or commercially available display device can be used without particular limitation.

  A plasma display panel display device is a device that displays a color image according to the following principle. A cell corresponding to each pixel (R (red), G (green), B (blue)) provided between two glass plates is provided between the front glass plate and the rear glass plate, and the cell Xenon gas or neon gas is sealed in the inside, and a phosphor corresponding to each pixel is applied to the back glass plate side in the cell. Due to the discharge between the display electrodes, the xenon gas and neon gas in the cell are excited to emit light, and ultraviolet rays are generated. By irradiating the phosphor with this ultraviolet ray, visible light corresponding to each pixel is generated. Then, an address electrode is provided on the rear glass plate, and by applying a signal to the address electrode, which discharge cell is displayed is controlled, and a color image is displayed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “part” or “%” in the examples represents “part by mass” or “mass%” unless otherwise specified.

Example 1
<< Production of Visible Light Absorption Optical Filter Sample 1-1 (Filters A and B) >>
(Preparation of visible light absorbing optical filter sample 1-1 (filter A))
A 0.5% by mass dimethoxyethane solution (that is, a dye solution) of Exemplified Dye A1 of the present invention is prepared, and coated on a glass substrate with a bar coater (Exemplary Dye A1: 0.3 g / m ² ). And dried to produce a visible light absorbing optical filter sample 1-1 (filter A).

(Preparation of visible light absorbing optical filter sample 1-1 (filter B))
As a dye, a 1.0% by mass tetrahydrofuran solution (that is, a dye solution) of the exemplified dye A1 of the present invention and a 20% by mass dimethoxyethane solution of a polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.) in a ratio of 2: 8. (Mass ratio), coated on a glass substrate with a bar coater (Exemplary dye A1: 0.2 g / m ² ), dried and visible light absorbing optical filter sample 1-1 (filter B) Was made.

<< Production of Visible Light Absorption Optical Filter Samples 1-2 (Filters A, B) to 1-6 (Filters A, B) >>
Samples 1-2 (filters A and B) to 1-6 (filters A and B) were prepared in the same manner except that the pigments of sample 1-1 (filters A and B) were changed as shown in Table 3. did. All samples absorbed visible light effectively. In addition, the weather resistance of each sample was also evaluated.

"Evaluation methods"
Evaluation of weather resistance of samples (Light resistance test I)
The visible light absorbing optical filter sample immediately after production is irradiated with visible light, and the transmittance (%) at each wavelength of 415 nm, 535 nm, 560 nm, 585 nm, and 595 nm (T ₀ : for example, the transmittance at 415 nm is T ₀ ( 415)) was measured. Subsequently, the visible light absorbing optical filter sample was irradiated with a xenon lamp at 70,000 lux for 40 hours, and then irradiated with visible light in the same manner, and the transmittance (%) at each wavelength of 415 nm, 535 nm, 560 nm, 585 nm, and 595 nm. (T ₁ : For example, the transmittance at 415 nm after the above xenon lamp irradiation test is expressed as T ₁ (415)). Integrating (Σ | ΔT | = | T ₀ (415) −T ₁ (415) | integrating the change in transmittance (%) at each wavelength before and after the xenon lamp irradiation (| ΔT | = | T ₀ −T ₁ |) + | T ₀ (535) −T ₁ (535) | + | T ₀ (560) −T ₁ (560) | + | T ₀ (585) −T ₁ (585) | + | T ₀ (595) − T ₁ (595) |) and evaluated according to the following evaluation criteria.

  The smaller the sum, the more stable it is with respect to the xenon lamp irradiation and the better the light resistance. “a” and “b” are at a level where there is no practical problem.

Evaluation criteria a: When Σ | ΔT | is less than 3% b: When Σ | ΔT | is 3% or more and less than 6% c: When Σ | ΔT | is 6% or more and less than 15% d: Σ | ΔT When | is 15% or more and less than 20% e: When Σ | ΔT | is 20% or more (Light Resistance Test II (Light Resistance Test after Storage at High Temperature and High Humidity))
The visible light absorbing optical filter sample immediately after production is irradiated with visible light, and the transmittance (%) at each wavelength of 415 nm, 535 nm, 560 nm, 585 nm, and 595 nm (T ₀ : for example, the transmittance at 415 nm is T ₀ ( 415)) was measured. Subsequently, after the visible light absorbing optical filter sample was stored for 5 days under the conditions of 60 ° C. and 85% RH, the xenon lamp was further irradiated with 70,000 lux for 40 hours, and then the visible light was irradiated in the same manner to 415 nm, Transmittance (%) at each wavelength of 535 nm, 560 nm, 585 nm, and 595 nm (T ₁ : For example, the transmittance at 415 nm after the above-mentioned “treatment of irradiation with xenon lamp after storage at high temperature and high humidity” is T ₁ (415 ))). Integrating (Σ | ΔT | = | transmittance change (%) (| ΔT | = | T ₀ −T ₁ |) at each wavelength before and after performing “processing to irradiate a xenon lamp after storage at high temperature and high humidity” T ₀ (415) -T ₁ (415) | + | T ₀ (535) -T ₁ (535) | + | T ₀ (560) -T ₁ (560) | + | T ₀ (585) -T ₁ (585) | + | T ₀ (595) −T ₁ (595) |) and evaluated according to the following evaluation criteria.

The smaller the sum, the more stable it is against xenon lamp irradiation and the better the light resistance after storage under high temperature and high humidity conditions. “a” and “b” are at a level where there is no practical problem.
a: When Σ | ΔT | is less than 3% b: When Σ | ΔT | is 3% or more and less than 6% c: When Σ | ΔT | is 6% or more and less than 15% d: Σ | ΔT | When 15% to less than 20% e: When Σ | ΔT | is 20% or more (Preservation test III (high temperature condition-low temperature condition repeated storage test))
When the visible light absorption optical filter sample immediately after preparation was put in a sealed container and stored in a thermostatic bath at 60 ° C. for 1 day, and then stored in a freezer at −20 ° C. for 1 day, one cycle thermo test was performed.

  After the cycle thermotest was performed 6 times, the sealed container was returned to room temperature at room temperature for 1 day, and then the filter was taken out and the state was visually observed and evaluated according to the following evaluation criteria.

“a” and “b” are levels that have no problem in practical use, and show that they are excellent for repeated storage under high temperature conditions and low temperature conditions.
a: Devitrification, cracks, cracks, etc. are not observed before and after storage b: Slight devitrification is observed after storage, but there are no practical problems c: Clearly, devitrification, cracks, cracks, etc. are observed Table 3 shows.

  (* 1): a dye represented by formula (A-1) of the present invention, and the like.

Dyes used as comparative examples:
Dye A: Compound No. described in JP-A-2001-183522, Table 1. 1A

  Dye B: Compound (VI) -1 described in JP-A-2001-350013, Table 6

  Dye C: Compound Nos. Described in JP-A-2002-97383, Table 1 3

  As is apparent from Table 3, the visible light absorbing optical filter of the present invention has good light resistance after storage under high temperature and high humidity conditions. It turns out that it is excellent also in high temperature condition-low temperature condition repeated storage by using binder resin.

Example 2
<< Production of Visible Light Absorption Optical Filter Samples 2-1 (Filters A, B) to 2-15 (Filters A, B) >>
In the visible light absorbing optical filter sample 1-1 (filter A) and the visible light absorbing optical filter sample 1-1 (filter B) of Example 1, the metals contained in Table 4 having the same mass as the dye together with the dye when preparing the dye solution. The visible light absorbing optical filter sample 2-1 (filter A) and the visible light absorbing optical filter sample 2-1 (filter B), ie, except that the compound was further added to prepare a dye solution (ie, A visible light absorbing optical filter sample 2-1 (filters A and B)) was prepared.

(Production of visible light absorbing optical filter sample 2-2 (filter A, B) to 2-15 (filter A, B))
In addition, in the visible light absorbing optical filter sample 2-1 (filter A) and the visible light absorbing optical filter sample 2-1 (filter B), the same applies except that the dyes and metal-containing compounds used were changed as shown in Table 4. The visible light absorbing optical filter samples 2-2 (filter A) to 2-15 (filter A) and the visible light absorbing optical filter samples 2-2 (filter B) to 2-15 (filter B) are produced. did.

<Evaluation of weather resistance of sample>
Evaluation was performed in the same manner as described in Example 1.

  The results are shown in Table 4 together with the evaluation results.

Used metal-containing compounds:
ML-1: Manganese (III) acetylacetonate (manufactured by Kanto Chemical Co., Inc., reagent)
ML-2: 2-ethylhexanoic acid copper (II) (manufactured by Kanto Chemical Co., Inc., reagent)
ML-3: zinc di-n-butyldithiocarbamate (manufactured by Kanto Chemical Co., Inc., reagent)
From Table 4, it can be seen that by using the metal-containing compound, the light resistance is further improved, and the light resistance after high temperature and high humidity condition storage and excellent high temperature condition-low temperature condition repeated storage are excellent. Furthermore, it turns out that the further improvement of weather resistance is seen by the metal seed | species and ligand to contain.

Example 3
<< Production of Visible Light Absorption Optical Filter Sample 3-1 (Filters A to F) >>
(Preparation of visible light absorbing optical filter sample 3-1 (filter A))
2% of a 20% dimethoxyethane solution of a tetrahydrofuran solution and a polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.) in which the exemplified compound A1 of the present invention and the metal-containing compound MS-41 of the present invention are each dissolved by 1.0% by mass : 8 mixed, coated on a glass substrate with a bar coater (Exemplified dye A1: 0.2 g / m ² ), dried and visible light absorbing optical filter sample 3-1 (filter A) Was made. This filter was reddish purple, and it was found that even a composition containing a binder effectively absorbs visible light.

(Preparation of visible light absorbing optical filter sample 3-1 (filter B))
A visible light absorbing optical filter sample 3-1 (filter B) was produced in the same manner except that the polyester resin of the visible light absorbing optical filter sample 3-1 (filter A) was changed to a polyvinyl chloride resin. This filter was reddish purple, and it was found that even a composition with a changed binder effectively absorbs visible light.

(Preparation of visible light absorbing optical filter sample 3-1 (filter C))
The polyester resin of the visible light absorbing optical filter sample 3-1 (filter A) is made of polystyrene resin (St / HEMA / SMA = 30/40/30 copolymer, St: styrene, HEMA: 2-hydroxyethyl methacrylate, SMA: stearyl. A visible light absorbing optical filter sample 3-1 (filter C) was produced in the same manner except that it was changed to (methacrylate). This filter was reddish purple, and it was found that even a composition with a changed binder effectively absorbs visible light.

(Preparation of visible light absorbing optical filter sample 3-1 (filter D))
Visible light absorbing optical filter sample 3-1 (filter), except that the polyester resin of visible light absorbing optical filter sample 3-1 (filter A) was changed to acrylic resin (Dianar BR-80; manufactured by Mitsubishi Rayon Co., Ltd.) D) was prepared. This filter was reddish purple, and it was found that even a composition with a changed binder effectively absorbs visible light.

(Preparation of visible light absorbing optical filter sample 3-1 (filter E))
20% dimethoxyethane of tetrahydrofuran solution in which exemplary compound A1 of the present invention and metal-containing compound MS-41 of the present invention are each dissolved in an amount of 1.0% by mass and a hot-melt polyester resin (trade name: SP3300X1 manufactured by Diabond Kogyo Co., Ltd.) The solution was mixed at a ratio of 2: 8, and applied to a polyester film for peeling (manufactured by Toyobo Co., Ltd., trade name: MRF75, thickness 75 μm) with a bar coater (Exemplary dye A1: 0.2 g / m ^2). ) After drying, a polyester film (manufactured by Toyobo Co., Ltd., trade name: A4300, thickness 100 μm) is applied to the coated surface using a hot roll laminator, the peeling polyester film is peeled off, and the SP3300X1 coated surface is made the glass side. Heat the surface with an iron with a temperature of about 100 ° C. for 1 minute, and bond it to a glass substrate. It was produced Luther (sample E). This filter was reddish purple, and it was found that even a composition with a changed binder effectively absorbs visible light.

(Preparation of visible light absorbing optical filter sample 3-1 (filter F))
Visible light absorption optical filter sample 3-1 (filter E) is visible in the same manner except that the hot-melt polyester resin is changed to a hot-melt ethylene-vinyl acetate copolymer resin (trade name: Mersen G, manufactured by Tosoh Corporation). A light absorption optical filter sample 3-1 (filter F) was produced. This filter was reddish purple, and it was found that even a composition with a changed binder effectively absorbs visible light.

<< Production of Visible Light Absorption Optical Filter Sample 3-2 (Filters A to F) to 3-41 (Filters A to F) >>
Visible light absorbing optical filter sample 3-2 (filters A to F) in the same manner except that the pigment and metal-containing compound of sample 3-1 (filters A to F) were changed as shown in Tables 5 and 6 ˜3-41 (filters A to F) were prepared. All samples absorbed visible light effectively.

<Evaluation of weather resistance of sample>
(Light resistance)
The visible light absorbing optical filter sample immediately after production is irradiated with visible light, and the transmittance (%) at each wavelength of 410 nm, 530 nm, 550 nm, 580 nm, and 590 nm (T ₀ : For example, the transmittance at 410 nm is T ₀ ( 410)). Subsequently, the visible light absorbing optical filter sample was irradiated with a xenon lamp at 70,000 lux for 5 days, and then irradiated with visible light in the same manner, and the transmittance (%) at each wavelength of 410 nm, 530 nm, 550 nm, 580 nm, and 590 nm. (T ₁ : For example, the transmittance at 410 nm after the test is expressed as T ₁ (410)). Integration (Σ | ΔT | = | T ₀ (410) −T ₁ (410) of transmittance change (%) at each wavelength before and after irradiation with a xenon lamp (| ΔT | = | T ₀ −T ₁ | etc.) | + | T ₀ (530) −T ₁ (530) | + | T ₀ (550) −T ₁ (550) | + | T ₀ (580) −T ₁ (580) | + | T ₀ (590) -T ₁ (590) |) and evaluated according to the following criteria.
a: When Σ | ΔT | is less than 2.5% b: When Σ | ΔT | is 2.5% or more and less than 5% c: When Σ | ΔT | is 5% or more and less than 8% d: Σ When | ΔT | is 8% or more and less than 15% e: When Σ | ΔT | is 15% or more The smaller the sum, the more stable it is against xenon lamp irradiation and the better the light resistance. “a”, “b”, and “c” are levels that are not problematic in practice.

(Heat-resistant)
The visible light absorbing optical filter sample immediately after production is irradiated with visible light, and the transmittance (%) at each wavelength of 410 nm, 530 nm, 550 nm, 580 nm, and 590 nm (T ₀ : For example, the transmittance at 410 nm is T ₀ ( 410)). Subsequently, the visible light absorbing optical filter sample was stored at 70 ° C. for 8 days, and then irradiated with visible light in the same manner, and the transmittance (%) at each wavelength of 410 nm, 530 nm, 550 nm, 580 nm, and 590 nm ( T ₁ : For example, the transmittance at 410 nm after the test is expressed as T ₁ (410)). Integration (Σ | ΔT | = | T) of transmittance change (%) (| ΔT | = | T ₀ −T ₁ | etc.) at each wavelength before and after the above “storage at 70 ° C. for 8 days” ₀ (410) −T ₁ (410) | + | T ₀ (530) −T ₁ (530) | + | T ₀ (550) −T ₁ (550) | + | T ₀ (580) −T ₁ ( 580) | + | T ₀ (590) −T ₁ (590) |) and evaluated according to the following criteria.
a: When Σ | ΔT | is less than 2.5% b: When Σ | ΔT | is 2.5% or more and less than 5% c: When Σ | ΔT | is 5% or more and less than 8% d: Σ When | ΔT | is 8% or more to less than 15% e: When Σ | ΔT | is 15% or more, the smaller the sum, the more stable it is to heat and the better the heat resistance. “a”, “b”, and “c” are levels that are not problematic in practice.

(Moisture resistance)
The visible light absorbing optical filter sample immediately after production is irradiated with visible light, and the transmittance (%) at each wavelength of 410 nm, 530 nm, 550 nm, 580 nm, and 590 nm (T ₀ : For example, the transmittance at 410 nm is T ₀ ( 410)). Subsequently, the visible light absorbing optical filter sample was stored for 8 days under conditions of 55 ° C. and 80% RH, and then irradiated with visible light in the same manner, and the transmittance at each wavelength of 410 nm, 530 nm, 550 nm, 580 nm, and 590 nm. (%) (T ₁ : For example, the transmittance at 410 nm after the test is expressed as T ₁ (410)). Integration of transmittance change (%) (| ΔT | = | T ₀ −T ₁ |, etc.) at each wavelength before and after the above “storage at 55 ° C. and 80% RH for 8 days” (Σ | ΔT | = | T ₀ (410) −T ₁ (410) | + | T ₀ (530) −T ₁ (530) | + | T ₀ (550) −T ₁ (550) | + | T ₀ (580) −T ₁ (580) | + | T ₀ (590) −T ₁ (590) |) and evaluated according to the following criteria.
a: When Σ | ΔT | is less than 2.5% b: When Σ | ΔT | is 2.5% or more and less than 5% c: When Σ | ΔT | is 5% or more and less than 8% d: Σ When | ΔT | is 8% or more and less than 15% e: When Σ | ΔT | is 15% or more, the smaller the sum, the more stable the humidity and the better the moisture resistance. “a”, “b”, and “c” are levels that have no practical problem.

  The results are also shown in Tables 5 and 6.

  (* 1): Sample numbers 3-1 (A to F) to 3-41 (A to F) mean sample numbers 3-1 (filters A to F) to 3-41 (filters A to F). .

  As is apparent from the table, the sample of the present invention has good weather resistance, whereas the comparative sample is inferior in weather resistance.

Example 4
《Preparation of filter for display panel》
(I) (Production example of neon emission absorption filter)
(Preparation of Sample 4-1)
In a polyethylene terephthalate film (thickness: 100 μm), 0.3% by mass of Exemplified Compound A23 of the present invention and 0.3% by mass of Exemplified Compound MS-41 (methyl ethyl ketone / toluene = 1: 1) 0 After mixing 0.5 g and 6.5 g of a 20% methyl ethyl ketone / toluene mixed solution of polyester resin, the mixture was applied with a bar coater and dried to obtain a neon light-emitting absorption layer coating film having a thickness of 5 μm. The transmittance curve of this coating film has a minimum value in the range of 590 to 595 nm, there is no clear minimum value other than this, and the wavelength of the minimum value of the visible light transmittance is 580 to 580 which is the wavelength region of neon emission. Since it is 600 nm, it was possible to provide a display panel filter having high transmittance and suitable for cutting neon light emission.

(II) (Further example of ultraviolet absorbing layer formation)
(Preparation of Sample 4-2)
Ultraviolet absorption containing an isocyanate resin as a binder and zinc oxide as an ultraviolet absorber on the surface of the polyethylene terephthalate opposite to the surface of the neon emission absorption layer of the neon emission absorption filter (display panel filter) of Sample 4-1 A coating solution (manufactured by Sumitomo Osaka Cement Co., Ltd.) was coated with a bar coater and dried to form an ultraviolet absorbing layer having a thickness of 3 μm. In each filter, the minimum wavelength of visible light transmittance did not change.

(III) (Further example of forming near-infrared absorbing layer)
A near-infrared absorbing dye (N, N, N) on the polyethylene terephthalate surface opposite to the neon light-emitting absorption layer surface of the filter for display panel of Sample 4-1 or 4-2 or on the ultraviolet absorption layer. A bar coater was prepared by mixing 0.3 g of a 0.5% cyclohexanone solution of ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium hexafluoroantimonate) and 3 g of a polyester resin 20% cyclohexanone solution. And dried to form 6 μm thick coating films. This filter was measured with a Hitachi spectrophotometer (U-3500). In each filter, the minimum wavelength of visible light transmittance did not change, and the wavelength at the minimum value of infrared transmittance was 1100 nm.

(IV) (Example of formation of a composition mixed film containing a near-infrared absorber and the compound of the present invention)
(Preparation of Sample 4-3)
0.5 g cyclohexanone solution of the above near infrared absorbing dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium hexafluoride antimonate) and the present invention A 0.5% cyclohexanone solution in which 0.4% of Exemplified Compound A23 and 0.3% of Exemplified Compound MS-41 were dissolved was mixed with 6.5 g of a 20% cyclohexane solution of a polyester resin, and a polyethylene terephthalate film (thickness 100 μm) was mixed. ) Was coated with a bar coater and dried to form a 6 μm-thick coating film (near infrared absorption / neon emission absorption layer), and a display panel filter sample 4-3 was produced.

(V) (Further examples of forming an electromagnetic wave cut layer and a non-glare layer)
(Preparation of Sample 4-4)
Prepared in the production of Sample 4-3 on the polyethylene terephthalate surface of a polyethylene terephthalate film (thickness: 100 μm) in which an ITO thin film was produced using argon gas and oxygen gas using an indium tin monoxide complex. The near-infrared absorption / neon emission absorption layer was laminated to a thickness of 6 μm using a coating solution containing the prepared near-infrared absorber and the compound of the present invention. Further, a PMMA plate having a non-glare layer having a thickness of 3 mm and coated with an anti-reflection layer is bonded to the opposite surface (that is, the ITO surface of the filter) on the surface where the non-glare layer is not formed, and the plasma display panel filter And a good filter could be produced.

(VI) Comparative display panel filter manufacturing example (comparative example)
(Preparation of Sample 4-5)
A display panel filter having a near-infrared absorbing layer was obtained in the same manner as in the above (III) except that the comparative dye A was used instead of the exemplified compound A-23 of the present invention.

"Evaluation methods"
Make a front plate by separately bonding the filters made in (III), (IV), (V) and (VI) to glass, and then attach this front plate to the plasma display without the front plate. did. This plasma display was placed in an environmental room where the operating environment temperature was set to 45 ° C. and 80% RH, used continuously for 24 hours, and color reproducibility after 24 hours was visually confirmed. Any plasma display equipped with a front plate using the filter of the present invention (filters produced in (III), (IV), (V)) emits neon light even after 24 hours in an environment of 45 ° C. and 80% RH. The plasma display equipped with the front plate using the filter of the comparative example (filter made with (VI)), while not showing the effect of wavelength fluctuation, showed good color reproducibility. It was confirmed that the color reproducibility was clearly deteriorated due to the influence of the fluctuation of the neon emission wavelength in the RH environment.

  As mentioned above, in the case of this invention, the visible light absorption optical filter excellent in light resistance and heat-and-moisture resistance was able to be provided. In particular, it can be seen that the light resistance in a high temperature and high humidity environment can be improved. Further, by applying the visible light absorption optical filter of the present invention to a front filter for a display, particularly a neon emission absorption filter capable of effectively absorbing neon emission, a display panel filter having good color reproducibility can be provided. did it.

Claims (9)

A visible light absorbing display front filter comprising a dye having a maximum absorption in a visible light region and represented by the following general formula (A-1).

(In the formula, B represents a heterocyclic group, an aromatic hydrocarbon ring group, or a group represented by the following general formula (AX), and R ₁ , R _a1 and R _a2 each represents a hydrogen atom or a substituent. ).
General formula (AX)
-C (R ₂₎ = D
(In the formula, D represents a 5-membered or 6-membered ring group, and R ₂ represents a hydrogen atom or a substituent.) The visible light absorbing display front filter according to claim 1, wherein the dye represented by the general formula (A-1) is represented by the following general formula (AX-1).

(Wherein R ₁ , R _a1 , R _a2 , R ₃ , R _b1 and R _b2 each independently represents a hydrogen atom or a substituent) The dye represented by the general formula (A-1) or the dye represented by the general formula (AX-1) is represented by the following general formula (AX-2). Item 5. The visible light absorption display front filter according to Item 2.

(Wherein R ₁ , R _a1 , R _a2 , R ₃ , R _b1 and R _b2 each independently represents a hydrogen atom or a substituent) Furthermore, a metal containing compound is contained, The visible light absorption display front filter of any one of Claims 1-3 characterized by the above-mentioned. The visible light absorption display front filter according to claim 4, wherein the metal-containing compound contains at least one selected from divalent ions of Ni, Co, Zn, and Cu. The visible light absorption display front filter according to claim 4, wherein the metal-containing compound is represented by the following general formula (X-1).
Formula (X-1)
M (X ₁ ) _m (X ₂ ) _l · (W ₁ ) _s
(In the formula, M represents a divalent ion of Ni, Co, Zn or Cu, and X ₁ and X ₂ each independently represent a monodentate or bidentate ligand, which may be the same or different. , X ₁ and X ₂ may be linked, m, l and s represent an integer of 0 to 2 and m + 1> 1 (W ₁ ) _s is a pair necessary for neutralizing charges Represents an ion.) Furthermore, resin is contained, The visible light absorption display front filter of any one of Claims 1-6 characterized by the above-mentioned. The visible light absorption display front filter according to claim 1, which has a maximum absorption in a visible light region of 570 nm to 630 nm. The filter for plasma display panels using the front filter of visible light absorption displays of any one of Claims 1-8.