JP2000321419A - Optical filter and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical filter with a suitable color correcting function by utilizing dye which is an associated body composed of an anionic dye and a multivalent cation. SOLUTION: An optical filter provided with an antireflection layer has a construction of which filter layer 2 is provided on the side of a transparent supporting body 1 opposite to the reflection preventing layer. The filter layer 2 contains dye and a polymer binder and an associated body composed of an anionic dye and a multivalent cation is used as the dye. The anionic dye is the dye having at least an anionic group in its molecule and still more, the dye optionally has a cationic group. The associated body of the anionic dye and the multivalent cation is added to a coating liquid of the filter layer 2, provided it is preferable to add a salt of the anionic dye with a monovalent cation and a salt of the multivalent cation with an anion to the coating liquid of the filter layer 2 so as to form the associated body of the anionic dye and the multivalent cation in the coating liquid. A multivalent metal ion or a multivalent organic cation is used as the multivalent cation.

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. Also,
The present invention relates to a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, and a surface of an image display device such as a field emission display. The present invention also relates to an antireflection film attached for antireflection or improving color reproducibility.

[0002]

2. Description of the Related Art A liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT),
2. Description of the Related Art 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 extra light (wavelength in the range of 560 to 620 nm) is included in light emission from the three primary color phosphors. Therefore, it has been proposed to perform color correction using an optical filter that absorbs light of a specific wavelength in order to correct the color balance of display colors. Japanese Patent Laid-Open No. 58-153 discloses color correction using an optical filter.
No. 904, No. 60-118748, No. 60-1874
No. 9, No. 61-188501, JP-A-3-23198
No. 8, No. 5-203804, No. 5-205564,
No. 7-307133, No. 9-145918, No. 9-
These are described in JP-A Nos. 306366 and 10-26704.

[0003] In addition to the color correction, the image display device also needs to prevent reflection. That is, the image display device has a problem that the contrast is reduced due to the background being reflected on the display. As a solution to this problem,
Various antireflection films have been proposed. The antireflection functional layers of the antireflection films proposed so far can be classified into vapor deposition layers and coating layers. Although the vapor deposition layer is superior from the viewpoint of optical functions, the coating layer has an advantage that it is easy to manufacture.
The vapor deposition layer has been used for a long time as an antireflection film for lenses such as glasses and cameras. The deposition layer is a vacuum deposition method,
It is formed by a sputtering method, an ion plating method, a CVD method or a PVD method. The coating layer is generally
It is formed by applying fine particles and a binder. Coating layers are described in JP-A-59-49501 and JP-A-59-50.
No. 401, 60-59250, JP-A-7-4852
No. 7 describes each.

It is also conceivable to incorporate an antireflection function into the optical filter. The above-mentioned JP-A-61-188.
No. 501, JP-A-5-205643 and 9-1459
No. 18, No. 9-306366, and No. 10-26704 disclose optical filters having an antireflection function incorporated therein. JP-A-61-188501, JP-A-5-205643, JP-A-9-145918 and JP-A-9-145918
In the optical filter described in each publication of 306366,
A dye or a pigment is added to the transparent support so that the support functions as a filter. JP-A-10-26704
In the optical filter described in the publication, a hard coat layer (surface hardened layer) provided between the transparent support and the antireflection layer
And the hard coat layer functions as a filter.

[0005]

If the transparent support or the hard coat layer is colored, the transparent support or the hard coat layer functions as a filter. However, the types of dyes that can be added to the transparent support and the hard coat layer are very limited. The transparent support is made from plastic or glass (usually plastic). The dye to be added to the transparent support is required to have a very high heat resistance enough to withstand the temperature during the production of the support. The hard coat layer is generally a layer containing a crosslinked polymer. The crosslinking reaction of the polymer is carried out after the application of the layer. Under the reaction conditions for crosslinking, there are many dyes that fade. The dye which can be added to the transparent support or the hard coat layer has a broad peak at the absorption maximum (broad half width), and it is difficult to perform appropriate color correction corresponding to the image display device. Methine dyes developed in the field of silver halide photography are compounds having various absorption spectral properties. It is known that the use of a methine dye in an associated state reduces the half width. However, methine dyes have been developed on the premise that they are added to a layer of a silver halide photographic material, and when a methine dye is added to a transparent support or a hard coat layer, a problem of fading occurs.

The inventor of the present invention added a methine dye aggregate to a polymer layer which can be formed under mild conditions, instead of a transparent support or a hard coat layer which has many restrictions on the types of dyes that can be used, and formed a polymer layer on a filter layer. We considered making it function. However, the polymer layer has a weaker dye protection function than the transparent support or the hard coat layer. In order to add a dye to the polymer layer, it is necessary to improve the stability and durability (particularly, light fastness) of the aggregate of the methine dye.
An object of the present invention is to provide an optical filter having an appropriate color correction function. Another object of the present invention is to provide an antireflection film having an appropriate color correction function in addition to the antireflection function.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide the following optical filters (1) to (4) and the following (5) to (5).
This was achieved by the antireflection film of (12). (1) An optical filter having a filter layer containing a dye and a polymer binder on a transparent support, wherein the dye is an aggregate comprising an anionic dye and a polyvalent cation. (2) The optical filter according to (1), wherein the anionic dye is a cyanine dye having two or more anionic groups. (3) The optical filter according to (1), which is for a plasma display panel. (4) The optical filter according to (1), wherein the aggregate comprising the anionic dye and the polyvalent cation has an absorption maximum in a wavelength range of 560 to 620 nm.

(5) A filter layer containing a dye and a polymer binder, a transparent support, and a low refractive index layer having a refractive index lower than that of the transparent support are the antireflection films laminated in this order. Wherein the dye is an aggregate comprising an anionic dye and a polyvalent cation. (6) The antireflection film according to (5), wherein the anionic dye is a cyanine dye having two or more anionic groups. (7) The antireflection film according to (5), which is for a plasma display panel. (8) The antireflection film according to (5), wherein the aggregate comprising the anionic dye and the polyvalent cation has an absorption maximum in a wavelength region of 560 to 620 nm.

(9) An anti-reflection film in which a transparent support, a filter layer containing a dye and a polymer binder, and a low refractive index layer having a refractive index lower than that of the transparent support are laminated in this order. Wherein the dye is an aggregate comprising an anionic dye and a polyvalent cation. (10) The antireflection film according to (9), wherein the anionic dye is a cyanine dye having two or more anionic groups. (11) The antireflection film according to (9), which is for a plasma display panel. (12) The antireflection film according to (9), wherein the aggregate comprising the anionic dye and the polyvalent cation has an absorption maximum in a wavelength range of 560 to 620 nm.

[0010]

As described above, it is considered that a plurality of dye molecules are one-dimensionally associated with each other, and are two-dimensionally and three-dimensionally associated with each other. Salts composed of anionic dyes and polyvalent cations promote the association of the dye molecule in one dimension, thereby strengthening the association structure in two and three dimensions. Therefore, a salt in which a plurality of anionic dye molecules are ion-bonded with a polyvalent cation can easily form an aggregate. Further, since the ionic bond is partially involved in the formation of the aggregate, the stability of the aggregate is excellent. Thereby, it became possible to add the aggregate of the dye to the polymer layer in a stable state. That is, by using a salt in which the molecules of a dye developed in the technical field of silver halide photography are ion-bonded, an aggregate of the dye suitable for use in an optical filter or an antireflection film can be obtained. As a result, the optical filter and the antireflection film of the invention have an appropriate color correction function according to the type of the image display device.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical layer structure of an antireflection film (optical filter provided with an antireflection layer) will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a layer configuration of an antireflection film in which a filter layer is provided on the side opposite to the transparent support from the antireflection layer. The embodiment shown in FIG. 1A includes a filter layer (2), a transparent support (1), and a low refractive index layer (3).
In the following order. The transparent support (1) and the low refractive index layer (3) have a refractive index satisfying the following relationship. Refractive index of low refractive index layer <refractive index of transparent support

The embodiment shown in FIG. 1B has a layer structure in the order of a filter layer (2), a transparent support (1), a hard coat layer (4), and a low refractive index layer (3). The mode shown in FIG. 1 (c) is a filter layer (2), a transparent support (1), a hard coat layer (4), a high refractive index layer (5), and a low refractive index layer (3). Having a configuration. The transparent support (1), the low refractive index layer (3) and the high refractive index layer (5)
It has a refractive index satisfying the following relationship. The refractive index of the low refractive index layer <the refractive index of the transparent support <the refractive index of the high refractive index layer In the embodiment shown in FIG. 1D, the filter layer (2), the transparent support (1), and the hard coat layer ( 4), a middle refractive index layer (6), a high refractive index layer (5), and a low refractive index layer (3). The transparent support (1), the low refractive index layer (3), the high refractive index layer (5) and the medium refractive index layer (6)
It has a refractive index satisfying the following relationship. Refractive index of low refractive index layer <refractive index of transparent support <refractive index of medium refractive index layer <refractive index of high refractive index layer

FIG. 2 is a schematic sectional view showing a layer structure of an antireflection film in which a filter layer and an antireflection layer are provided on the same side of a transparent support. The embodiment shown in FIG. 2A has a layer structure in the order of the transparent support (1), the filter layer (2), and the low refractive index layer (3). The relationship between the refractive index of the transparent support (1) and the refractive index of the low refractive index layer (3) is the same as that of FIG.
The embodiment shown in FIG. 2B has a layer structure in the order of the transparent support (1), the filter layer (2), the hard coat layer (4), and the low refractive index layer (3). The mode shown in FIG. 2C is a transparent support (1), a filter layer (2), a hard coat layer (4), a high refractive index layer (5), and a low refractive index layer (3).
In the following order. The relationship between the refractive indices of the transparent support (1), the low refractive index layer (3) and the high refractive index layer (5) is the same as that in FIG. The mode shown in FIG.
The transparent support (1), the filter layer (2), the hard coat layer (4), the medium refractive index layer (6), the high refractive index layer (5), and the low refractive index layer (3) have a layer structure in this order. . The relationship among the refractive indices of the transparent support (1), the low refractive index layer (3), the high refractive index layer (5) and the middle refractive index layer (6) is the same as that in FIG.

(Transparent Support) Examples of materials for forming 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, poly Butylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethylmethacrylate , Syndiotactic polystyrene, polysulfone, polyethersulfone, polyetherketone, polyetherimide and polyoxyethylene. Triacetyl cellulose, polycarbonate and polyethylene terephthalate are preferred. The transmittance of the transparent support is preferably 80% or more,
More preferably, it is 86% or more. Haze is 2
%, More preferably 1% or less. The refractive index is preferably from 1.45 to 1.70.

An infrared absorber or an ultraviolet absorber may be added to the transparent support. The amount of infrared absorber added
The content is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight of the transparent support. Further, as a slipping agent, particles of an inert inorganic compound may be added to the transparent support. Examples of inorganic compounds include S
_{iO 2, TiO 2, BaSO 4} , CaCO 3, talc and kaolin. The transparent support may be subjected to a surface treatment. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred. Further, an undercoat layer for strengthening the adhesion with the upper layer may be provided.

(Filter Layer) The thickness of the filter layer is preferably 0.1 μm to 5 cm. The filter layer preferably has an absorption maximum in a wavelength range of 560 to 620 nm (between green and red). 560 to 6
The transmittance of the filter layer at the absorption maximum in the wavelength region of 20 nm is preferably in the range of 0.01 to 80%, more preferably in the range of 0.1 to 60%. The absorption maximum in the wavelength range of 560 to 620 nm has a function of selectively cutting the sub-band that reduces the color purity of the red phosphor. In a plasma display panel, 595 n emitted by excitation of neon gas
Unnecessary light emission near m can also be cut. By separating the absorption maximum as described above, light can be selectively cut without adversely affecting the color tone of the green phosphor. 560 to 6 to further reduce the effect of the green phosphor on the color tone
The absorption maximum in the wavelength region of 20 nm is preferably sharp. Specifically, at the absorption maximum in the wavelength region of 560 to 620 nm, the half width value (width of the wavelength region showing half the absorbance of the absorbance of the absorption maximum) is preferably 10 to 120 nm, and more preferably 15 to 100 nm. More preferably, it is more preferably from 20 to 70 nm, and most preferably from 30 to 50 nm.

The filter layer contains a dye and a polymer binder. In the present invention, an aggregate composed of an anionic dye and a polyvalent cation is used as the dye. An anionic dye is a dye having at least one anionic group in a molecule. The dye may further have a cationic group. However, the number of anionic groups in the molecule is preferably larger than the number of cationic groups. Preferably, the anionic dye is a methine dye. Methine dyes can be classified into cyanine dyes, merocyanine dyes, arylidene dyes, styryl dyes and oxonol dyes. Each methine dye is defined by the following formula.

Cyanine dye: Bs = Lo-Bo Merocyanine dye: Bs = Le = Ak arylidene dye: Ak = Lo-Ar styryl dye: Bo-Le-Ar oxonol dye: Ak = Lo-Ae In the formula, Bs is a base. Bo is the onium form of the basic nucleus; Ak is the keto-type acidic nucleus; Ae
Is an enol-type acidic nucleus; Ar is an aromatic nucleus; Lo is a methine chain consisting of an odd number of methines;
Le is a methine chain composed of an even number of methines. The onium compound (Bo) of the basic nucleus is cationic, and the enol type acidic nucleus (Ae) is anionic. Oxonol dyes contain an enol-type acidic nucleus (Ae) and thus function as an anionic dye without an anionic group. Other methine dyes having an anionic group as a substituent can be used as an anionic dye. However, cyanine dye or styryl dye,
Since it contains an onium compound (Bo) of a basic nucleus, it preferably has at least two anionic groups in the molecule.

As the methine dye, a cyanine dye or an oxonol dye having two or more anionic groups is preferably used. The cyanine dye having two or more anionic groups is preferably a compound represented by the following formula (I).

[0020]

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In the formula (I), 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 its condensed ring include an oxazole ring, an oxazoline ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, a thiazole ring, a thiazoline ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, and a selenazoline ring. , Benzoselenazole ring, indolenine ring, benzoindolenine ring, imidazole ring, imidazoline ring, benzimidazole ring,
It includes a naphthoimidazole ring, a quinoline ring, a pyridine ring, a pyrrolopyridine ring, a fluorpyrrole ring, an indolizine ring, an imidazoquinoxaline ring, a quinoxaline ring, an oxadiazole ring, a thiadiazole ring, a tetrazole ring and a pyrimidine ring. The nitrogen-containing heterocyclic ring is more preferably a 5-membered ring than a 6-membered ring. It is more preferable that a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring. Most preferred are benzimidazole, benzoxazole and benzothiazole rings. The nitrogen-containing heterocycle and the ring condensed therewith may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group,
Aralkyl group, alkoxy group, aryl group, aryloxy group, halogen atom (Cl, Br, F), alkoxycarbonyl group, alkylthio group, arylthio group, acyl group, acyloxy group, amino, substituted amino group, amide group, sulfonamide Groups, ureido, substituted ureido, carbamoyl, substituted carbamoyl, sulfamoyl, substituted sulfamoyl, alkylsulfonyl, arylsulfonyl, hydroxyl, cyano, nitro, sulfo, carboxyl and heterocyclic groups.

The alkyl group may have a branch.
The alkyl group preferably has 1 to 20 carbon atoms. The alkyl group may have a substituent. Examples of the substituent include a halogen atom (Cl, Br, F), an alkoxy group (eg, methoxy, ethoxy), hydroxyl and cyano. Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, propyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl and trifluoromethyl. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl. The aralkyl group preferably has 7 to 20 carbon atoms. Examples of the aralkyl group include benzyl and 2-phenethyl. The alkoxy group may have a branch. The number of carbon atoms in the alkoxy group is 1
It is preferably from 12 to 12. The alkoxy group may have a substituent. Examples of the substituent of the alkoxy group include an alkoxy group and hydroxyl. Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, methoxyethoxy and hydroxyethoxy.

The aryl group is preferably phenyl. The aryl group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom and nitro. Examples of substituted aryl groups include p
-Tolyl, p-methoxyphenyl, o-chlorophenyl and m-nitrophenyl. The aryloxy group is preferably phenoxy. The aryloxy group may have a substituent. Examples of substituents include
Includes alkyl groups, alkoxy groups and halogen atoms. Examples of the substituted aryloxy group include p-chlorophenoxy, p-methylphenoxy and o-methoxyphenyl. The alkoxycarbonyl group preferably has 2 to 20 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The number of carbon atoms of the alkylthio group is 1 to 1
It is preferably 2. Examples of the alkylthio group include methylthio, ethylthio and butylthio. The arylthio group is preferably phenylthio.
The arylthio group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and a carboxyl. Examples of substituted arylthio groups include p-methylphenylthio, p-methoxyphenylthio and o-
Carboxyphenylthio is included. The acyl group preferably has 2 to 20 carbon atoms. Examples of the acyl group include acetyl and butyroyl. The acyloxy group preferably has 2 to 20 carbon atoms. Examples of the acyloxy group include acetoxy and butyryloxy. The number of carbon atoms of the substituted amino group is
It is preferably from 1 to 20. Examples of the substituted amino group include methylamino, anilino and triazinylamino. The amide group preferably has 2 to 20 carbon atoms. Examples of amide groups include acetamido,
Includes propionamide and isobutanamide.
The sulfonamide group preferably has 1 to 20 carbon atoms. Examples of the sulfonamide group include methanesulfonamide and benzenesulfonamide.

The substituted ureido group has 2 to 2 carbon atoms.
It is preferably 0. Examples of substituted ureido groups include 3
-Methylureide and 3,3-dimethylureide. The substituted carbamoyl group has 2 to 2 carbon atoms.
It is preferably 0. Examples of the substituted carbamoyl group include methylcarbamoyl and dimethylcarbamoyl. The substituted sulfamoyl group preferably has 1 to 20 carbon atoms. Examples of the substituted sulfamoyl group include dimethylsulfamoyl and diethylsulfamoyl. The alkylsulfonyl group preferably has 1 to 20 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl. The arylsulfonyl group is preferably benzenesulfonyl. Examples of the heterocyclic group include pyridyl and thienyl.

In the formula (I), R ¹ and R ² are each independently an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Alkyl groups are preferred. The alkyl group may have a branch. The alkyl group preferably has 1 to 20 carbon atoms. The alkyl group may have a substituent. Examples of the substituent include a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl),
Includes hydroxyl, sulfo and carboxyl.
Sulfo and carboxyl may be in the form of a salt. The alkenyl group may have a branch. The alkenyl group preferably has 2 to 10 carbon atoms. Examples of alkenyl groups include 2-pentenyl, vinyl, allyl,
Includes 2-butenyl and 1-propenyl. The alkenyl group may have a substituent. Examples of the substituent of the alkenyl group are the same as the examples of the substituent of the alkyl group.

The aralkyl group has 7 to 12 carbon atoms.
It is preferred that Examples of the aralkyl group include benzyl and phenethyl. The aralkyl group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, propyl), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg,
Phenoxy, p-chlorophenoxy), halogen atoms (Cl, Br, F), alkoxycarbonyl groups (eg, ethoxycarbonyl), halogenated carbon groups (eg, trifluoromethyl), alkylthio groups (eg, methylthio, ethylthio, butylthio) ), An arylthio group (phenylthio, o-carboxylphenylthio), a cyano, nitro, amino, alkylamino group (eg, methylamino, ethylamino), an amide group (eg, acetamido, propionamido), an acyloxy group (eg, acetoxy) , Butyryloxy), hydroxyl, sulfo and carboxyl. Examples of the aryl group include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent of the aryl group are the same as the examples of the substituent of the aralkyl group.

In the formula (I), L ¹ is a methine chain composed of an odd number of methines. The number of methine is preferably 1, 3 or 5, and particularly preferably 3. The methine chain may have a substituent. The methine having a substituent is preferably methine at the center (meso position) of the methine chain. Examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom,
Includes alkoxycarbonyl, halogenated carbon, alkylthio, arylthio, cyano, nitro, amino, alkylamino, amide, acyloxy, hydroxyl, sulfo and carboxyl. Two substituents may combine to form a 5- or 6-membered ring. The cyanine dye represented by the formula (I) has two or more anionic groups as substituents. As the anionic group, sulfo or carboxyl is preferable. The anionic group is preferably contained in a substituent of a 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ¹ or Z ² or a condensed ring thereof.

The oxonol dye is preferably a compound represented by the following formula (II).

[0030]

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In the formula (II), Y ¹ and Y ² are each independently a group of nonmetallic atoms forming an aliphatic ring or a heterocyclic ring. Heterocycles are preferred over aliphatic rings.
Examples of the aliphatic ring include an indandione ring. Examples of the heterocyclic ring include a 5-pyrazolone ring, an oxazolone ring, a barbituric acid ring, a pyridone ring, a rhodanine ring, a pyrazolidinedione ring, and a pyrazolopyridone ring. The aliphatic ring and the heterocyclic ring may have a substituent. Examples of the substituent are the same as the examples of the substituent of the nitrogen-containing heterocyclic ring formed by Z ¹ and Z ² in the formula (I). In the formula (II),
L ³ is a methine chain consisting of an odd number of methine. The number of methines is preferably 3, 5 or 7, preferably 3
It is particularly preferred that the number is one. The methine chain may have a substituent. The methine having a substituent is preferably methine at the center (meso position) of the methine chain. Examples of the substituent are the same as the substituent of L ^{1 in} the formula (I). Two substituents may combine to form a 5- or 6-membered ring. However, the methine chain is preferably unsubstituted.

The following are specific examples of the anionic dye.

[0033]

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(A1) Ra: —CH ₃ , Rb: —Cl, Rc: —Cl (A2) Ra: —CH ₃ , Rb: —Cl, Rc: —CF
_{3 (A3) Ra: -CH 3} , Rb: -H, Rc: -Cl (A4) Ra: -CH 3, Rb: -H, Rc: -CON
_{H 2 (A5) Ra: -C} 2 H 5, Rb: -Cl, Rc: -C
l (A6) Ra: -n- C 3 H 7, Rb: -Cl, Rc:
_{-Cl (A7) Ra: -C 2} H 4 OC 2 H 5, Rb: -Cl,
Rc: -Cl (A8) Ra: -C 2 H 4 OH, Rb: -Cl, Rc:
_{-Cl (A9) Ra: -CH 2} -Ph, Rb: -Cl, Rc:
-Cl (A10) Ra: -Ph, Rb: -Cl, Rc: -Cl Note: Ph is phenyl

[0035]

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(A11) Ra: —C ₂ H ₄ SO ₃ ⁻ , R
b: -Cl, Rc: -Cl ( A12) Ra: -C 3 H 6 SO 3 -, Rb: -Cl, R
_{c: -CF 3 (A13) Ra} : -CH 2 CH 2 CH (CH 3) S
O ₃ ⁻ , Rb: —H, Rc: —CN (A14) Ra: —C ₂ H ₄ SO ₃ ⁻ , Rb: —H, R
c: -CN (A15) Ra: -C 4 H 8 SO 3 -, Rb: -H, R
c: -CN

[0037]

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[0038]

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(A19) Ra: —CH ₃ , Rb: —Ph, Z: —S— (A20) Ra: —C ₂ H ₅ , Rb: —Ph, Z: —S
_{- (A21) Ra: -C 2} H 4 OCH 3, Rb: -Ph,
Z: -S- (A22) Ra: -Ph, Rb: -Ph, Z: -S- (A23) Ra: -CH 2 Ph, Rb: -Ph, Z: -
_{S- (A24) Ra: -CH 3} , Rb: -Cl, Z: -S- (A25) Ra: -CH 3, Rb: -Cl, Z: -O- (A26) Ra: -C 2 H 5 , Rb: -Ph, Z: -O
_{- (A27) Ra: -C 2} H 5, Rb: -Cl, Z: -S
_{e- (A28) Ra: -C 2} H 5, Rb: -Cl, Z: -C
_{(CH 3) 2 - (A29} ) Ra: -CH 3, Rb: -Ph, Z: -Se
-Note: Ph is phenyl

[0040]

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[0041] (A30) Ra: -H, Rb : -C 3 H 6 SO 3 - (A31) Ra: -SO 3 -, Rb: -C 3 H 6 SO 3 - (A32) Ra: -SO 3 - _{, Rb: -C 3 H 6 SO} 3 - (A33) Ra: -SO 3 -, Rb: -CH 2 CH 2 CH
(CH ₃₎ SO ₃ ^-

[0042]

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(A34) Ra: —C ₃ H ₆ SO ₃ ⁻ , R
_{b: -C 3 H 6 SO 3} -, Rc: -H, Rd: -Cl, R
_{e: -C 2 H 5 (A35} ) Ra: -C 4 H 8 SO 3 -, Rb: -C 4 H 8
SO ₃ ⁻ , Rc: —H, Rd: —Cl, Re: —C ₂ H ₅ (A36) Ra: —C ₂ H ₄ SO ₃ ⁻ , Rb: —C ₄ H _{8
^{SO 3 -, Rc: -Cl,}} Rd: -Cl, Re: -C 2 H
_{5 (A37) Ra: -C 2} H 4 SO 3 -, Rb: -C 2 H 4
SO ₃ ⁻ , Rc: —CH ₃ , Rd: —CH ₃ , Re: —C
_{2 H 5 (A38) Ra:} -C 4 H 8 SO 3 -, Rb: -C 4 H 8
SO ₃ ⁻ , Rc: —CH ₃ , Rd: —CH ₃ , Re: —C
_{2 H 5 (A39) Ra:} -C 4 H 8 SO 3 -, Rb: -C 3 H 6
SO ₃ ⁻ , Rc: —H, Rd: —Ph, Re: —C ₂ H ₅ (A40) Ra: —C ₄ H ₈ SO ₃ ⁻ , Rb: —C ₄ H ₈
SO ₃ ⁻ , Rc: —H, Rd: —OCH ₃ , Re: —CH
_{3 (A41) Ra: -C 4} H 8 SO 3 -, Rb: -C 4 H 8
SO ₃ ⁻ , Rc: —H, Rd: —OCH ₃ , Re: —CH
₃ Note: Ph is phenyl

[0044]

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(A42) Ra: -C_ThreeH₆SO_Three ^-, R
b: -C_ThreeH₆SO_Three ^-, Rc: -C_TwoH _Five (A43) Ra: -C_ThreeH₆SO_Three ^-, Rb: -C_ThreeH₆
SO_Three ^-, Rc: -CH_Three (A44) Ra: -C_FourH₈SO_Three ^-, Rb: -C_FourH₈
SO_Three ^-, Rc: -C_TwoH _Five

[0046]

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(A45) R: —C ₄ H ₈ SO ₃ ⁻ , Rb: —H (A46) R: —C ₄ H ₈ SO ₃ ⁻ , Rb: —CH ₃ (A47) R: —C ₃ H ₆ SO ₃ ^-, Rb: -H

[0048]

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(A48) n: 1 (A49) n: 2 (A50) n: 3

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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(A60) Ra: -H, Rb: -H (A61) Ra: -OH, Rb: -H (A62) Ra: -H, Rb: -OH

[0056]

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[0057]

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(A65) Ra: —C ₄ H ₈ SO ₃ ⁻ , R
_{b: -C 4 H 8 SO 3} -, Rc: -H, Rd: -OCH 3 (A66) Ra: -C 4 H 8 SO 3 -, Rb: -C 4 H 8
SO ₃ ⁻ , Rc: —H, Rd: —Cl (A67) Ra: —C ₄ H ₈ SO ₃ ⁻ , Rb: —C ₄ H ₈
SO ₃ ⁻ , Rc: —H, Rd: —Ph (A68) Ra: —C ₄ H ₈ SO ₃ ⁻ , Rb: —C ₄ H ₈
SO ₃ ⁻ , Rc: —CH ₃ , Rd: —CH ₃ (A69) Ra: —C ₄ H ₈ SO ₃ ⁻ , Rb: —C ₄ H ₈
SO ₃ ⁻ , Rc: —Cl, Rd: —Cl (A70) Ra: —C ₃ H ₆ SO ₃ ⁻ , Rb: —C ₄ H ₈
SO ₃ ⁻ , Rc: —H, Rd: —Cl (A71) Ra: —C ₃ H ₆ SO ₃ ⁻ , Rb: —C ₃ H ₆
SO ₃ ⁻ , Rc: —H, Rd: —Cl (A72) Ra: —C ₄ H ₈ SO ₃ ⁻ , Rb: —C ₃ H _{6
^{SO 3 -, Rc: -H,}} Rd: -Ph Note: Ph is phenyl

Anionic dyes are described in FM Harmer, Heterocyclic Compounds Cyanine Dyes and Rela.
ted Compounds) ", John Wiley and Sons, New York, London, 1964, and JP-A-6-313939.

The above anionic dye forms an aggregate with the polyvalent cation. An aggregate of an anionic dye and a polyvalent cation can be added to the coating solution for the filter layer. However, a salt of an anionic dye and a monovalent cation and a salt of a polyvalent cation and an anion are added to the coating solution of the filter layer to form an aggregate of the anionic dye and the polyvalent cation in the coating solution. Is preferred. Examples of monovalent cations include alkali metal (eg, Na, K), ammonium, triethylammonium, tributylammonium, pyridinium and tetrabutylammonium ions.

As the polyvalent cation, a polyvalent metal ion or a polyvalent organic cation can be used. Examples of polyvalent metal ions include alkaline earth metal ions (eg, M
g ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ ) and transition metal ions (eg, Zn ²⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ³⁺ , Ni
²⁺ , Cu ²⁺ ). Other polyvalent metal ions (eg, Al ³⁺ , Si ⁴⁺ , Sn ⁴⁺ ) may be used.

The organic cation contained in the polyvalent organic cation is preferably an ammonium ion, a pyridinium ion or an imidazolium ion. Below, the example of a polyvalent organic cation is shown.

[0063]

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(C1) n: 620 to 1200 (C2) n: 1300 to 2200 (C3) n: 2500 to 3100

[0065]

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[0066]

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[0067]

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[0068]

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[0069] _{(C15) L :-( CH 2)} 2 - (C16) L :-( CH 2) 3 - (C17) L: -C 2 H 4 -N + H 2 -C 2 H 4 - (C18 _{) L: -C 2 H 4 -N} + H 2 -C 2 H 4 -N +
H ₂ -C ₂ H ₄ -

[0070]

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The polyvalent cation is preferably a polyvalent metal ion, more preferably an alkaline earth metal ion.
Ca ²⁺ and Ba ²⁺ are most preferred. As previously mentioned,
A salt of an anionic dye and a monovalent cation and a salt of a polyvalent cation and an anion are added to the coating solution of the filter layer to form an aggregate of the anionic dye and the polyvalent cation in the coating solution. preferable. Examples of anions that form salts with polyvalent cations include halide ions (Cl ⁻ , Br
^-, I -), p-toluenesulfonate ion, ethyl sulfate ion, PF ₆ ^-, BF ₄ ^- and ClO ₄ ^- are included.

The ratio of the amounts of the anionic dye and the polyvalent cation used is determined according to the number of anionic groups of the anionic dye and the number of cationic groups of the polyvalent cation. Generally, the amount of the polyvalent cation used is 1 to 1000% by weight (preferably 2 to 500% by weight, more preferably 50 to 200% by weight) of the amount of the anionic dye used.

The combination of the anionic dye and the polyvalent cation is not particularly limited. However, it is preferable to use one kind of anionic dye and one kind of polyvalent cation in combination.

Hereinafter, examples of the combination of an anionic dye and a polyvalent cation will be described. As for the anionic dye (A) and the polyvalent organic cation (C), reference is made to the numbers of the above specific examples.

(1) (A1) ₂ .Ca ²⁺ (2) (A1) ₂ .Ba ²⁺ (3) (A1) ₂ .Mg ²⁺ (4) (A1) ₂ .Sr ²⁺ (5) (A1) ₂ .Zn ²⁺ (6) (A5) ₂ .Ca ²⁺ (7) (A6) ₂ .Ca ²⁺ (8) (A9) ₂ .Ca ²⁺ (9) (A10) ₂ .Ca ²⁺ (10) (A1) ₂ · C11 (11) (A1) ₂ · C19 (12) (A1) ₂ · C20 (13) (A1) ₂ · C21 (14) (A1) ₂ · C23 (15) (A1) ₂ · C22 (16) (A11) ₃ · Al ³⁺ (17) (A12) ₃ · Al ³⁺ (18) (A1) ₃ · Al ³⁺ (19) (A34) ₂ · Ca ²⁺ (20) (A42) ₂ .Ca ²⁺ (21) (A53) ₂ .Ca ²⁺ (22) (A66) ₂ .Ca ²⁺ (23) (A67) ₂ .Ca ²⁺

In the present invention, a salt of an anionic dye and a polyvalent cation is used in an associated state. The dye in an associated state forms a so-called J band, and thus shows a sharp absorption spectrum peak. For dye association and J band,
Literature (eg, Photographic Science and Engineering
Vol. 18, No. 323-335 (1974)). The absorption maximum of the dye in the associated 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 this specification, a state in which the absorption maximum moves to a longer wavelength side by 40 nm or more than the absorption maximum of the dye in a solution state is referred to as an association state. In the dye in an associated state, the movement of the absorption maximum is preferably 45 nm or more, more preferably 50 nm or more, and most preferably 60 nm or more.

The salt of an anionic dye and a polyvalent cation is
Easily forms an association state. The meeting state is also stable. Two or more types of aggregates may be used in combination. In addition to the association of the anionic dye and the polyvalent cation, another dye may be used in combination. The filter layer is formed of 560 to 62 described above.
In addition to the absorption maximum in the 0 nm wavelength region (between green and red),
It is preferable to have an absorption maximum also in a wavelength region of 500 to 550 nm (green). When an aggregate of an anionic dye and a polyvalent cation is used in combination with another dye, the association of the anionic dye and the polyvalent cation is 560 to 620 nm.
Has an absorption maximum in the wavelength region of
It preferably has an absorption maximum in a wavelength region of 50 nm. The transmittance at the absorption maximum of 500 to 550 nm is preferably 30 to 85%. Oxonol dyes, azo dyes, azomethine dyes, anthraquinone dyes, cyanine dyes, merocyanine dyes, as dyes having an absorption maximum in the wavelength region of 500 to 550 nm,
A benzylidene dye or a xanthene dye is preferably used.

The wavelength range described above (500 to 550 nm)
And 560 to 620 nm). As such a dye, a near infrared absorbing dye can be used. As a near-infrared absorbing dye, a cyanine dye (JP-A-9-9689)
No. 1), metal chelate dyes, aminium dyes,
A diimonium dye, a quinone dye, a squarylium dye (described in JP-A-9-90547 and JP-A-10-204310) and various methine dyes can be used.
As for the near infrared absorbing dye, a coloring material, 61 [4] 215-
226 (1988) and Chemical Industries 43-53 (198).
May, 2006).

As the polymer binder for the filter layer, natural polymers (eg, gelatin, cellulose derivatives,
Alginic acid) or a synthetic polymer (eg, polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, polycarbonate, water-soluble polyamide) can be used. Hydrophilic polymers (the above-mentioned natural polymers, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, and water-soluble polyamide) are preferred, and gelatin is particularly preferred.

An anti-fading agent may be added to the filter layer. Examples of anti-fading agents that function as dye stabilizers include hydroquinone derivatives (US Pat. No. 3,935,016).
Nos. 3,982,944), hydroquinone diether derivatives (described in U.S. Pat. No. 4,254,216 and JP-A-55-21004), phenol derivatives (described in JP-A-54-145530),
Derivatives of spiroindane or methylenedioxybenzene (UK Patent Publications Nos. 2077455 and 2062888)
And the derivatives of chroman, spirochroman or coumaran (U.S. Pat. Nos. 3,432,300 and 3,573,050).
Nos. 3574627 and 3764337 and JP-A Nos. 52-152225 and 53-20327.
Nos. 53-17729 and 61-90156), hydroquinone monoether or paraaminophenol derivatives (UK Patent 1347556,
Nos. 2066975 and JP-B-54-12
337, JP-A-55-6321) and bisphenol derivatives (described in US Pat. No. 3,700,455 and JP-B-48-31625).

In order to improve the stability of the dye to light or heat, a metal complex (described in US Pat. No. 4,245,018 and JP-A-60-97353) may be used as an anti-fading agent. In order to further improve the light fastness of the dye, a singlet oxygen quencher may be used as an anti-fading agent. Examples of the singlet oxygen quencher include a nitroso compound (described in JP-A-2-300288), a diimmonium compound (described in US Pat. No. 4,656,612), a nickel complex (described in JP-A-4-146189), and antioxidant. Agent (European Patent Publication 820057A1)
Description).

(Undercoat layer) It is preferable to provide an undercoat layer between the transparent support and the filter layer. The undercoat layer is formed as a layer containing a polymer having a glass transition temperature of −60 ° C. to 60 ° C., a layer having a rough surface on the filter layer side, or a layer containing a polymer having an affinity for the polymer of the filter layer. An undercoat layer is provided on the surface of the transparent support on which the filter layer is not provided to improve the adhesion between the transparent support and a layer provided thereon (for example, an antireflection layer or a hard coat layer). Is also good. The undercoat layer may be provided to improve the affinity between the adhesive for bonding the antireflection film and the image forming apparatus and the antireflection film. The thickness of the undercoat layer is preferably 2 nm to 20 μm, more preferably 5 nm to 5 μm, and most preferably 50 nm to 5 μm.

The undercoat layer containing a polymer having a glass transition temperature of -60 to 60 ° C. adheres the transparent support and the filter layer due to the tackiness of the polymer. Glass transition temperature 2
Polymers at 5 ° C or lower include vinyl chloride, vinylidene chloride,
It can be obtained by polymerization or copolymerization of vinyl acetate, butadiene, neoprene, styrene, chloroprene, acrylate, methacrylate, acrylonitrile or methyl vinyl ether. The glass transition temperature is preferably 20 ° C. or lower, more preferably 15 ° C. or lower, further preferably 10 ° C. or lower, still more preferably 5 ° C. or lower, and further preferably 0 ° C. or lower. Is most preferred. The undercoat layer having a rough surface adheres the transparent support and the filter layer by forming a filter layer on the rough surface. The undercoat layer having a rough surface can be easily formed by applying a polymer latex. The average particle size of the latex is preferably 0.02 to 3 μm,
More preferably, it is 5 to 1 μm. Examples of polymers having an affinity for the binder polymer of the filter layer include acrylic resins, cellulose derivatives, gelatin, casein, starch, polyvinyl alcohol, soluble nylon, and polymer latex. Two or more undercoat layers may be provided. The undercoat layer may contain a solvent for swelling the transparent support, a matting agent, a surfactant, an antistatic agent, a coating aid and a hardener.

(Anti-reflection layer) As an anti-reflection function of the anti-reflection layer, the regular reflectance is preferably 3% or less.
More preferably, it is 1.8% or less. When providing an antireflection layer, a low refractive index layer is essential. The refractive index of the low refractive index layer is lower than the refractive index of the transparent support. The low refractive index layer preferably has a refractive index of 1.20 to 1.55, more preferably 1.30 to 1.55. The thickness of the low refractive index layer is preferably from 50 to 400 nm, more preferably from 50 to 200 nm. The low refractive index layer is a layer made of a fluorine-containing polymer having a low refractive index (Japanese Patent Application Laid-Open No. 57-34526,
No. 130103, No. 6-115023, No. 8-313
702, 7-168004), and a layer obtained by a sol-gel method (JP-A-5-208811,
JP-A-6-299091 and JP-A-7-168003) or a layer containing fine particles (JP-B-60-5925).
No. 0, JP-A-5-13021, JP-A-6-56478,
7-92306 and 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, more preferably 5 to 35% by volume.

In order to prevent reflection in a wide wavelength range,
It is preferable to laminate a layer having a high refractive index (middle / high refractive index layer) in addition to the low refractive index layer. The high refractive index layer preferably has a refractive index of 1.65 to 2.40.
More preferably, it is 70 to 2.20. 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 preferably from 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, and most preferably from 30 nm to 1 μm. The haze of the middle / high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The middle / high refractive index layer can be formed using a polymer binder 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 crystal, 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) among 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.

The anti-reflection layer can provide a 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 antireflection layer having an antiglare function generally has a haze of 3 to 30%.

(Other Layers) The optical filter may be provided with 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 is made of acrylic, urethane, or epoxy polymer,
It can be formed using an oligomer or a monomer (eg, an ultraviolet curable resin). The hard coat layer can also be formed from a silica-based material. A lubricating layer may be formed on the outermost surface of the optical filter. 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 2 to 20 nm. The antifouling layer can be formed using a fluorine-containing polymer. The thickness of the antifouling layer is 2 to 10
The thickness is preferably 0 nm, more preferably 5 to 30 nm.

The anti-reflection layer (medium-refractive-index layer, high-refractive-index layer, low-refractive-index layer), filter layer, undercoat layer, hard coat layer, lubricating layer and other layers are formed by a general coating method. Can be. 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.
No. 41898, No. 3508947, No. 3526528
Issue specifications and Yuji Harazaki, "Coating Engineering" 2
It is described on page 53 (published by Asakura Shoten in 1973).

(Application of Optical Filter) The optical filter is applied to an image display device such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT). . When the antireflection layer is provided, the antireflection layer is arranged such that the surface on which the low refractive index layer is not provided faces the image display surface of the image display device. When the optical filter of the present invention is used as an antireflection filter of a plasma display panel (PDP), a particularly remarkable effect is obtained. A plasma display panel (PDP) includes 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. Plasma display panels (PDPs) are already commercially available. Regarding the plasma display panel, Japanese Patent Laid-Open No.
No. 43 and No. 9-306366.

[0091]

[Example 1] (Formation of undercoat layer) After corona treatment was applied to both sides of a transparent polyethylene terephthalate film having a thickness of 100 µm,
One side was coated with a latex made of a styrene-butadiene copolymer to a thickness of 130 nm to form an undercoat layer.

(Formation of Second Undercoat Layer) On the undercoat layer,
A gelatin aqueous solution containing acetic acid and glutaraldehyde was applied to a thickness of 50 nm to form a second undercoat layer.

(Formation of Low Refractive Index Layer) Reactive Fluoropolymer (JN-7219, manufactured by Nippon Synthetic Rubber Co., Ltd.) 2.50
1.3 g of t-butanol was added to the resulting mixture, and the mixture was stirred at room temperature for 10 minutes and filtered with a polypropylene filter having a pore size of 1 μm. The obtained coating solution for a low refractive index layer is applied to the surface opposite to the undercoat surface of the transparent support using a bar coater so that the dry film thickness becomes 110 nm, and dried at 120 ° C. for 30 minutes. And cured to form a low refractive index layer.

(Formation of Filter Layer) In 180 g of a 10% by weight aqueous solution of gelatin, 0.1 g of sodium salt of anionic dye (A1) and 0.1 g of calcium chloride were dissolved, and stirred at 40 ° C. for 30 minutes. Was filtered with a polypropylene filter. The obtained coating liquid for a filter layer was coated on the second undercoat layer with a dry film thickness of 3.5 μm.
And dried at 120 ° C. for 10 minutes to form a filter layer, thereby producing an optical filter.

Example 2 An optical filter was produced in the same manner as in Example 1, except that the sodium salt of the anionic dye (34) was used in the same amount instead of the sodium salt of the anionic dye (A1). .

[Example 3] Instead of calcium chloride,
Salt of a multivalent organic cation (C19) (counter ion: Cl ^-)
An optical filter was manufactured in the same manner as in Example 1 except that the same amount was used.
Was prepared.

Comparative Example 1 An optical filter was manufactured in the same manner as in Example 1 except that calcium chloride was not added.

Comparative Example 2 An optical filter was manufactured in the same manner as in Example 2 except that calcium chloride was not added.

(Measurement of Absorbance) The transmission spectrum of the prepared optical filter was measured using a spectrophotometer (U-3210, manufactured by Hitachi, Ltd.). Reference was made with air. From the spectrum, the absorption maximum (λmax) and the half width were determined. The results are shown in Table 1.
In addition, the transmittance | permeability in the absorption maximum of all the optical filters was in the range of 10-20%.

(Light fastness test) The prepared optical filter was irradiated with light from the side opposite to the filter layer by a xenon lamp so that the illuminance was 150,000 lux.
The residual amount of the dye after irradiation for 0 hours was measured. The residual amount was calculated according to the following equation. Residual amount = 100 × (100−transmittance after irradiation) / (10
0—Transmittance Before Irradiation) The transmittance is a value measured at the absorption maximum wavelength of the dye. The results are shown in Table 1.

[0101]

[Table 1] Table 1 フ ィ ル タ ー Optical Filter Dye λmax Half-width Lightfastness Properties ──────────────────────────────────── Example 1 (1) (A1) ₂ · Ca ^{2 +} 594 nm 35 nm 90% Example 2 (19) (A34) ₂ · Ca ²⁺ 597 nm 37 nm 93% Example 3 (11) (A1) ₂ · C19 595 nm 36 nm 90% Comparative example 1 (x) A1 · Na ⁺ 593 nm 32 nm 80% Comparative Example 2 (y) A34.Na ⁺ 600 nm 38 nm 85% ───────────────────────────────── ───

When the optical filters of Examples 1 to 3 were attached to the surface of the plasma display panel, an image with good contrast was obtained, and improvement in white light and red light was recognized.

Example 4 (Formation of Undercoat Layer) On one surface of a transparent triacetyl cellulose film having a thickness of 80 μm, gelatin dispersed in methanol and acetone was applied so as to have a thickness of 200 nm, and dried. Was formed.

(Formation of Hard Coat Layer) 25 parts by weight of dipentaerythritol hexaacrylate (DPHA,
Nippon Kayaku Co., Ltd.), 25 parts by weight of a urethane acrylate oligomer (UV-6300B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 2 parts by weight of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 0 5 parts by weight of a sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
It was dissolved in 0 parts by weight of methyl ethyl ketone. The obtained coating solution was applied to the surface opposite to the undercoat layer of the transparent support using a bar coater, dried, and then irradiated with ultraviolet rays to form a hard coat layer (layer thickness: 6 μm).

(Formation of Low Refractive Index Layer) A low refractive index layer was formed on the hard coat layer in the same manner as in Example 1 using a coating liquid for a low refractive index layer.

(Formation of Filter Layer) In 180 g of a 10% by weight aqueous solution of gelatin, 0.1 g of sodium salt of anionic dye (A1) and 0.1 g of calcium chloride were dissolved. After the solution was stirred at 40 ° C. for 30 minutes, the solution was filtered with a 2 μm polypropylene filter to prepare a filter layer coating solution. A filter layer coating solution was applied on the undercoat layer so that the dry film thickness was 3.5 μm.
After drying for 0 minutes, a filter layer was formed to produce an optical filter. For the manufactured optical filter, the absorption maximum, the transmittance at the absorption maximum, and the half width were measured, and the same result as that of the optical filter manufactured in Example 1 was obtained.

[Example 5] (Formation of undercoat layer) In the same manner as in Example 1, an undercoat layer (a) and a second undercoat layer (a) were formed on one surface of the transparent support. A latex comprising vinylidene chloride-acrylic acid-methyl acrylate copolymer was applied to a thickness of 120 nm on the side of the transparent support on which the undercoat layer was not provided, to form an undercoat layer (b).

(Formation of Second Undercoat Layer) On the undercoat layer (b), an acrylic latex (HA16, manufactured by Nippon Acrylic Co., Ltd.) was applied to a thickness of 50 nm to form a second undercoat layer (b). Was formed.

(Formation of Filter Layer) In 180 g of a 10% by weight aqueous solution of gelatin, 0.1 g of the sodium salt of the anionic dye (A1) and 0.1 g of calcium chloride were dissolved. After the solution was stirred at 40 ° C. for 30 minutes, the solution was filtered with a 2 μm polypropylene filter to prepare a filter layer coating solution. The filter layer coating solution is applied to the second undercoat layer (b).
Is applied so that the dry film thickness becomes 3.5 μm.
After drying at 20 ° C. for 10 minutes, a filter layer was formed.

(Formation of Hard Coat Layer) A hard coat layer was formed on the filter layer in the same manner as in Example 2.

(Formation of Low Refractive Index Layer) A low refractive index layer was formed on the hard coat layer using the coating liquid for a low refractive index layer in the same manner as in Example 1 to produce an optical filter. For the manufactured optical filter, the absorption maximum, the transmittance at the absorption maximum, and the half width were measured, and the same result as that of the optical filter manufactured in Example 1 was obtained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of an antireflection film in which a filter layer is provided on a side opposite to a transparent support from an antireflection layer.

FIG. 2 is a schematic cross-sectional view showing a layer configuration of an antireflection film in which a filter layer and an antireflection layer are provided on the same side of a transparent support. DESCRIPTION OF SYMBOLS 1 Transparent support 2 Filter layer 3 Low refractive index layer 4 Hard coat layer 5 High refractive index layer 6 Medium refractive index layer

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kaji Yabuki 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2H048 CA04 CA09 CA14 CA19 CA24 2K009 AA02 AA15 BB24 CC24 CC26 DD02 DD17 5C040 GH01 GH10 KA14 KB02 KB13 KB14 MA05 MA08 MA10

Claims (12)

[Claims] 1. An optical filter having a filter layer containing a dye and a polymer binder on a transparent support, wherein the dye is an aggregate comprising an anionic dye and a polyvalent cation. . 2. The optical filter according to claim 1, wherein the anionic dye is a cyanine dye having two or more anionic groups. 3. The optical filter according to claim 1, which is used for a plasma display panel. 4. The optical filter according to claim 1, wherein the aggregate comprising the anionic dye and the polyvalent cation has an absorption maximum in a wavelength region of 560 to 620 nm. 5. An antireflection film comprising: a filter layer containing a dye and a polymer binder; a transparent support; and a low refractive index layer having a refractive index lower than that of the transparent support. An anti-reflection film, wherein the dye is an aggregate comprising an anionic dye and a polyvalent cation. 6. The antireflection film according to claim 5, wherein the anionic dye is a cyanine dye having two or more anionic groups. 7. The antireflection film according to claim 5, which is used for a plasma display panel. 8. The anti-reflection coating according to claim 5, wherein the aggregate comprising the anionic dye and the polyvalent cation has an absorption maximum in a wavelength region of 560 to 620 nm. 9. An antireflection film comprising a transparent support, a filter layer containing a dye and a polymer binder, and a low refractive index layer having a refractive index lower than that of the transparent support, which are laminated in this order. An anti-reflection film, wherein the dye is an aggregate comprising an anionic dye and a polyvalent cation. 10. The antireflection film according to claim 9, wherein the anionic dye is a cyanine dye having two or more anionic groups. 11. The antireflection film according to claim 9, which is used for a plasma display panel. 12. The anti-reflection coating according to claim 9, wherein the aggregate comprising the anionic dye and the polyvalent cation has an absorption maximum in a wavelength region of 560 to 620 nm.