JP2000258605A - Optical filter and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure appropriate color correction function as well as antireflection function by forming a filter layer containing a dye and a polymer binder on a transparent substrate and using a mixture of a cyanine dye in an associated state and an azo or azomethine dye in a non-associated state as the dye. SOLUTION: The filter layer 2 contains a mixture of a cyanine dye in an associated state and an azo or azomethine dye in a non-associated state. The thickness of the filter layer 2 is preferably 1-15 μm. The filter layer 2 has an absorption maximum in the wavelength range of 560-610 nm (between green and red) due to the cyanine dye and another absorption maximum in the wavelength range of 500-550 nm (green) due to the azo or azomethine dye. The transmittance of the filter layer 2 at the absorption maximum in the wavelength range of 560-610 nm is preferably 5-50%.

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 to be attached for improving antireflection and 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.

[0004] Evaporated layers have long been used as antireflection films for lenses such as glasses and cameras. The deposited layer is
It is formed by a vacuum evaporation method, a sputtering method, an ion plating method, a CVD method or a PVD method. The coating layer is generally formed by applying fine particles and a binder. For the coating layer, JP-A-59-49501,
Nos. 59-50401, 60-59250 and JP-A-7-48527. It is conceivable to incorporate an anti-reflection function into the optical filter. JP-A-61-188501 and JP-A-5-25-2.
No. 05643, No. 9-145918, No. 9-3063
Nos. 66 and 10-26704 each disclose an optical filter having an antireflection function incorporated therein. JP-A-61-188501, JP-A-5-205643,
In the optical filters described in JP-A Nos. 9-145918 and 9-306366, a dye or a pigment is added to a transparent support, and the support functions as a filter. In the optical filter described in JP-A-10-26704, a hard coat layer (surface hardened layer) provided between a transparent support and an antireflection layer is colored, 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 and pigments 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). Dyes and pigments to be added to the transparent support are required to have extremely 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 and pigments that fade. Dyes and pigments that can be added to the transparent support or the hard coat layer have a broad peak at the absorption maximum (wide half width), making it difficult to perform appropriate color correction corresponding to the image display device. 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.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide the following optical filters (1) and (2) and the following optical filters (3) and (3).
This was achieved by the antireflection film of (6). (1) An optical filter having a filter layer containing a dye and a polymer binder on a transparent support, wherein the dye is a mixture of an associated cyanine dye and a non-associated azo dye or azomethine dye. Characteristic optical filter. (2) The cyanine dye in an associated state is 560 to 620 nm
The optical filter according to (1), wherein the azo dye or azomethine dye in a non-associated state has an absorption maximum in a wavelength region of 500 to 550 nm.

(3) 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 an antireflection film laminated in this order. Wherein the dye is a mixture of an associative cyanine dye and a non-associative azo dye or azomethine dye. (4) 560 to 620 nm of cyanine dye in an associated state
The antireflection film according to (3), wherein the azo dye or azomethine dye in a non-associated state has an absorption maximum in a wavelength region of 500 to 550 nm.

(5) 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 a mixture of an associative cyanine dye and a non-associative azo dye or azomethine dye. (6) The cyanine dye in an associated state is 560 to 620 nm
The antireflection film according to (5), wherein the azo dye or azomethine dye in a non-associated state has an absorption maximum in a wavelength region of 500 to 550 nm.

[0009]

According to the present invention, the dye is added 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 the polymer layer functions as a filter layer. I thought about making it. If a filter layer is provided, various kinds of dyes can be used for the optical filter and the antireflection film. For example,
In the field of silver halide photography, various photographic dyes have been developed. The absorption spectral properties of photographic dyes have also been studied in detail. However, even when a photographic dye is used, the peak at the absorption maximum is broad (the half width is wide), and it is difficult to perform appropriate color correction corresponding to the image display device. Also, from the viewpoint of the difference in use, it is desirable for the purpose of color correction that the absorption maximum of the dye be on the longer wavelength side than in the case of a photograph.

The present inventors have found that the use of a mixture of an associative cyanine dye and a non-associative azo or azomethine dye makes it possible to easily adjust the maximum absorption of the dye. Also, surprisingly, the use of a dye mixture in an associated state and a non-associated state improves the light fastness of the dye (less likely to cause light fading) than using one dye alone. found. 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 In the embodiment shown in FIG. 1B, the filter layer (2), the transparent support (1),
It has a layer structure in the order of the hard coat layer (4) and the low refractive index layer (3). The embodiment shown in FIG. 1C includes a filter layer (2), a transparent support (1), a hard coat layer (4),
It has a layer structure in the order of the high refractive index layer (5) and the low refractive index layer (3). The transparent support (1), the low refractive index layer (3) and the high refractive index layer (5) have 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 FIG. 1 (d) shows an embodiment in which the filter layer (2), the transparent support (1), the hard support It has a layer structure of a coat layer (4), a medium refractive index layer (6), a high refractive index layer (5), and a low refractive index layer (3) in this order. The transparent support (1), the low-refractive-index layer (3), the high-refractive-index layer (5) and the medium-refractive-index layer (6) have 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.

In the embodiment shown in FIG. 2B, the transparent support (1), the filter layer (2), the hard coat layer (4),
It has a layer configuration in the order of the low refractive index layer (3). The embodiment shown in FIG. 2 (c) is a layer in the order of the transparent support (1), the filter layer (2), the hard coat layer (4), the high refractive index layer (5), and the low refractive index layer (3). Having a configuration. 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 embodiment shown in FIG. 2D includes a transparent support (1), a filter layer (2), a hard coat layer (4), a medium refractive index layer (6), a high refractive index layer (5), and a low refractive index. It has a layer configuration in the order of layer (3). 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 1
It is preferably from 15 to 15 μm. The filter layer is
It is preferable to have an absorption maximum in a wavelength region of 560 to 610 nm (between green and red), and further to have an absorption maximum in a wavelength region of 500 to 550 nm (green). The transmittance of the filter layer at the absorption maximum in the wavelength region of 560 to 610 nm is preferably in the range of 5 to 50%.
The absorption maximum in the wavelength range of 560 to 610 nm has a function of selectively cutting the sub-band that reduces the color purity of the red phosphor. In the plasma display panel, unnecessary light emission near 595 nm emitted by excitation of neon gas can 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 610 to further reduce the effect on the color tone of the green phosphor
The absorption maximum in the wavelength region of nm is preferably sharp. Specifically, at the absorption maximum in the wavelength region of 560 to 610 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 transmittance of the filter layer at the absorption maximum in the wavelength region of 500 to 550 nm is preferably in the range of 50 to 85%. The absorption maximum in the wavelength region of 500 to 550 nm has a function of adjusting the coloring intensity of the green phosphor having high visibility. It is preferable that the emission region of the green phosphor be cut smoothly. Specifically 500 to 5
At the absorption maximum in the wavelength region of 50 nm, the half-width value (the width of the wavelength region showing half the absorbance of the absorption maximum) is 30.
To 300 nm, preferably 40 to 200 nm.
nm, more preferably 50 to 150 nm, and most preferably 50 to 100 nm. In the present invention, since a mixture of two types of dyes is used, it is possible to easily cope with the above two types of absorption maximum. The absorption maximum in the wavelength range of 560 to 620 nm can be obtained by the cyanine dye in an associated state, and the absorption maximum in the wavelength range of 500 to 550 nm is:
It can be obtained by an azo dye or an azomethine dye in a non-associated state.

The cyanine dye is represented by the following formula. Where Bs is a basic nucleus; Bo is an onium of the basic nucleus; and Lo is a methine chain consisting of an odd number of methines. The cyanine dye 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 isoxazole ring, a benzoxazole ring, a naphthooxazole ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenine ring, a benzoindolenine ring, and an imidazole ring. , A 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 and a quinoxaline 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. The benzimidazole ring is most preferred. The nitrogen-containing heterocycle and the ring condensed therewith may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aralkyl group,
An alkoxy group, an aryl group, an aryloxy group, a halogen atom (Cl, Br, F), an alkoxycarbonyl group,
Alkylthio, arylthio, acyl, acyloxy, amino, substituted amino, amide, sulfonamide, ureido, substituted ureido, carbamoyl, substituted carbamoyl, sulfamoyl, substituted sulfamoyl, alkylsulfonyl, arylsulfonyl ,
Includes hydroxyl, cyano, nitro, sulfo, carboxyl and heterocyclic groups. Sulfo and carboxyl may be in the form of a salt.

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. Preferably, the aryl group is 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 the substituted aryl group 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 the substituent include an alkyl group, an alkoxy group and a halogen atom. 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 preferably has 2 to 20 carbon atoms. Examples of substituted ureido groups include 3-methylureido and 3,3-dimethylureido. The substituted carbamoyl group preferably has 2 to 20 carbon atoms. 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 has 1 to 2 carbon atoms.
It is preferably 0. 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 preferably has 7 to 12 carbon atoms. 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), a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, ethoxycarbonyl), a halogenated carbon group (eg, trifluoromethyl), an alkylthio group (eg, methylthio, ethylthio, butylthio), an arylthio group (phenylthio, o-carboxylphenylthio), cyano , Nitro, amino, alkylamino group (eg, methylamino, ethylamino), amide group (eg,
Acetamide, propionamide), acyloxy group (eg, acetoxy, butyryloxy), hydroxyl,
Includes sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt. 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. Preferably, the number of methines is 3, 5 or 7. 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, an alkoxycarbonyl group, a halogenated carbon group, an alkylthio group, an arylthio group, a cyano,
Includes nitro, amino, alkylamino, amide, acyloxy, hydroxyl, sulfo and carboxyl. Two substituents may combine to form a 5- or 6-membered ring. In the formula (I), a, b and c are each independently 0 or 1. a and b are preferably 0. c is 0 when the cyanine dye has an anionic substituent such as sulfo or carboxyl to form an inner salt. In the formula (I), X is an anion. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonic acid ion, ethyl sulfate ion, PF ₆ ⁻ , BF ₄ ⁻ and ClO ₄ ⁻ .

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

[0027]

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In the formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl, alkenyl, aralkyl or aryl group. The definition and examples of each group are the same as those of R ¹ and R ^{2 in} the formula (I).
In the formula (II), R ⁷ and R ⁸ each independently represent an alkyl group (eg, methyl, ethyl, propyl), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg, phenoxy, p-chloro) Phenoxy), a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, ethoxycarbonyl), a halogenated carbon group (eg,
Trifluoromethyl), an alkylthio group (eg, methylthio, ethylthio, butylthio), an arylthio group (phenylthio, o-carboxylphenylthio), cyano,
Nitro, amino, alkylamino groups (eg, methylamino, ethylamino), amide groups (eg, acetamido, propionamido), acyloxy groups (eg, acetoxy,
Butyryloxy), hydroxyl, sulfo or carboxyl. Sulfo and carboxyl may be in the form of a salt. In the formula (II), L ² is a methine chain composed of an odd number of methines. The number of methines is preferably 3, 5 or 7, 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 L ^{1 of the} formula (I)
And the same as the above. Two substituents may combine to form a 5- or 6-membered ring. In the formula (II),
m2 and n2 are each independently 0, 1, 2, 3, or 4. In the formula (II), X is an anion. The definition and examples of the anion are the same as those of X in the formula (I). In the formula (II), c is 0 or 1.

The cyanine dye preferably has at least one water-soluble group (a strong hydrophilic group that renders the compound water-soluble). Examples of the water-soluble group include sulfo, carboxyl, phosphono, and salts thereof. Examples of the counter ion for forming a salt include an alkali metal ion (eg, Na, K), an ammonium ion, a triethylammonium ion, a tributylammonium ion, a pyridinium ion, a tetrabutylammonium ion and an onium ion.

The following are specific examples of the cyanine dye.

[0031]

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(1) R: Cl, R ': Cl, (2) R:
Cl, R ′: CF ₃ , (3) R: H, R ′: Cl,
(4) R: H, R ': CF 3, (5) R: H, R': C
OOH, (6) R: H, R ': CONH ₂

[0033]

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(7) R: C ₂ H ₅ , (8) R: nC _{3
H 7, (9) R:} i-C 3 H 7, (10) R: C 2 H 4
OCH ₃ , (11) R: C ₂ H ₄ OH

[0035]

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(12) R: C ₂ H ₄ SO ₃ ⁻ , R ′: C
₂ H ₄ SO ₃ K, (13) R: C ₃ H ₆ SO ₃ ⁻ ,
R ′: C ₃ H ₆ SO ₃ Na, (14) R: CH ₂ CH ₂
CH (CH ₃ ) SO ₃ ⁻ , R ′: CH ₂ CH ₂ CH (C
^{_{H 3) SO 3 - · (}} C 2 H 5) 3 N + H, (15) R:
R: C ₂ H ₄ COO ⁻ , R ′: C ₂ H ₄ COOK, (1
6) R: C ₄ H ₈ SO ₃ ⁻ , R ′: C ₄ H ₈ SO ₃ Na

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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The synthesis of cyanine dyes is described in
Reference can be made to the descriptions in the specifications of JP-A-230671, EP 0778493 and US Pat. No. 5,459,265.

The azo dye has an azo structure (-N = N) in the molecule.
-). The azo dye has the following formula (III)
Alternatively, the compound represented by (IV) is preferable.

[0048]

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[0049]

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In the formulas (III) and (IV), R ⁹ , R
¹⁰ and R ¹¹ are each independently an alkyl group (eg, methyl, ethyl, propyl), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg, phenoxy,
p-chlorophenoxy), a halogen atom (Cl, Br,
F), an alkoxycarbonyl group (eg, ethoxycarbonyl), a halogenated carbon group (eg, trifluoromethyl),
Alkylthio group (eg, methylthio, ethylthio, butylthio), arylthio group (phenylthio, o-carboxylphenylthio), cyano, nitro, amino, alkylamino group (eg, methylamino, ethylamino), arylamino group (eg, anilino ), Amide group (eg, acetamide, propionamide), sulfonamide group (eg,
Methanesulfonamide, benzenesulfonamide), acyloxy group (eg, acetoxy, butyryloxy), sulfamoyl, carbamoyl, alkylsulfonyl group,
An arylsulfonyl group, hydroxyl, sulfo or carboxyl. Sulfo and carboxyl may be in the form of a salt. In the formula (III), M is a metal atom. Transition metal atoms are preferred, Fe, Co, Ni, C
u, Zn and Cd are more preferred, and Cu is most preferred. In the formulas (III) and (IV), m3 and m5
Is each independently 0, 1, 2, 3 or 4.
m4 is 0, 1 or 2.

The following are specific examples of the azo dye.

[0052]

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[0053]

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(32) Ra: SO ₃ Na, Rb: H, R
c: SO ₃ Na, Rd: NHCOCH ₃ , Re: H,
(33) Ra: SO ₃ Na, Rb: H, Rc: SO ₃ N
a, Rd: SO ₃ Na, Re: H, (34) Ra: C
1, Rb: SO ₃ Na, Rc: SO ₃ Na, Rd: SO
_{3 Na, Re: H, (} 35) Ra: NO 2, Rb: NO
₂ , Rc: SO ₃ Na, Rd: SO ₃ Na, Re: NH
COCH ₃

[0055]

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(36) Ra: SO ₃ Na, Rb: H,
M: Cu, (37) Ra: Cl, Rb: SO ₃ Na,
M: Cu, (38) Ra: NO ₂ , Rb: NO ₂ , M:
Cu, (39) Ra: SO ₃ Na, Rb: SO ₃ Na,
M: Co, (40) Ra: SO ₃ Na, Rb: SO ₃ N
a, M: Ni, (41) Ra: SO ₃ Na, Rb: SO
₃ Na, M: Zn

[0057]

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(51) Ra: COCH ₃ , Rb: OH,
Rc: H, (52) Ra: H, Rb: H, Rc: H,
(53) Ra: COCH ₃ , Rb: H, Rc: CH ₃

[0059]

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[0060]

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[0061]

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(56) Ra: SO ₃ Na, Rb: H,
(57) Ra: H, Rb: SO ₃ Na

[0063]

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(58) L: SO ₂ , (59) L: CO

For the synthesis of azo dyes, see GB 53
Nos. 9703 and 575691, U.S. Pat.
No. 9 and the description of Hiroshi Horiguchi, Review, Synthetic Dyes (Sankyo Shuppan, published in 1968).

Azomethine dyes can be classified into the following basic and acidic karyotypes. Basic nucleated azomethine dyes are preferred. Basic karyotype: Bs = N-Ar Acid karyotype: Ak = N-Ar where Bs is a basic nucleus; Ak is a keto-type acidic nucleus; and Ar is an aromatic nucleus. is there. The azomethine dye is preferably a compound represented by the following formula (V).

[0067]

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In the formula (V), Za, Zb and Zc
They are each independently, -C (R ¹⁶⁾ = or -N =. Za and Zc are preferably -N =. Zb
Is, -C is preferably (R ¹⁶⁾ = a. In the formula (V), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent an alkyl group (eg, methyl, ethyl, propyl, t-butyl) or an alkoxy group (eg, methoxy, ethoxy) ), An aryloxy group (eg, phenoxy, p-chlorophenoxy), a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, ethoxycarbonyl), a halogenated carbon group (eg, trifluoromethyl), an alkylthio group (Eg, methylthio, ethylthio, butylthio),
Arylthio group (phenylthio, o-carboxylphenylthio), cyano, nitro, amino, alkylamino group (eg, methylamino, ethylamino), amide group (eg, acetamido, propionamido), acyloxy group (eg, acetoxy, butyryloxy) ), Hydroxyl, sulfo or carboxyl. Sulfo and carboxyl may be in the form of a salt. R ¹³ and R ¹⁴ are
It may combine with each other to form a heterocyclic ring. Examples of the heterocycle include a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring. R ¹³ or R ¹⁴ may combine with R ¹⁵ to form a heterocyclic ring. Examples of the heterocycle include a julolidine ring, a pyrrolidine ring and a piperidine ring.

Hereinafter, specific examples of the azomethine dye will be described.

[0070]

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(61) Ra: C ₂ H ₅ , Rb: C
_{2 H 5, (62) Ra} : C 2 H 4 CN, Rb: C 2 H 4
CN, (63) Ra: C ₂ H ₅ , Rb: C ₄ H ₈ SO ₃
K

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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The synthesis of azomethine dyes is described in JP-A-62-3250, JP-A-4-178646, and 5-
Reference can be made to the description of each publication of JP-A-323501. The above dyes and other dyes may be used in combination. As other dyes,
Near infrared absorbing dyes can be used. Examples of near infrared absorbing dyes include cyanine dyes (described in JP-A-9-96891), metal chelate dyes, aminium dyes, diimonium dyes, quinone dyes, and squarylium dyes (described in JP-A-9-96891).
-90547 and 10-204310) and various methine dyes can be used. For the near-infrared absorbing dye, a coloring material, 61 [4] 215-226
(1988) and Chemical Industry 43-53 (May 1986).
Month)).

In the present invention, a cyanine dye is added in an associated state,
Other dyes are used in a non-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, see literature (eg, Photographic Science and Eng).
ineering Vol. 18, No. 323-335 (1974)). Furthermore, 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 50 nm or more than the absorption maximum of the dye in a solution state is referred to as an association state. And the movement of the absorption maximum is 50n
A state of less than m is referred to as a non-associated state. In the dye in an associated state, the shift of the absorption maximum is preferably 60 nm or more, more preferably 70 nm or more, and 8 nm or more.
Most preferably, it is 0 nm or more. For a dye in a non-associated state, the shift of the absorption maximum is preferably less than 40 nm, more preferably less than 30 nm, and more preferably less than 30 nm.
Most preferably, it is less than 0 nm.

Some dyes form an aggregate only by dissolving in water. However, generally, gelatin or a salt (eg, barium chloride, ammonium chloride, sodium chloride) is added to an aqueous solution of the dye to form an aggregate.
A method of adding gelatin to an aqueous solution of a dye is particularly preferred. Dye aggregates can also be formed as solid particulate dispersions of the dye. In order to obtain solid fine particles, a known disperser can be used. Examples of the disperser include a ball mill, a vibration mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill and a roller mill. Vertical or horizontal media disperser (Japanese Patent Laid-Open No. 52-9 / 1982)
No. 2716 and International Patent Publication No. 88/074794) are preferred. Dispersion is accomplished by using a suitable medium (eg, water,
(Alcohol). It is preferable to use a surfactant for dispersion. Anionic surfactants (JP-A-52-92716 and International Patent No.
0774794) are preferably used. If necessary, an anionic polymer, a nonionic surfactant or a cationic surfactant may be used. After dissolving the dye in an appropriate solvent, the poor solvent may be added to obtain a fine powder. Also in this case, the above-mentioned surfactant can be used. Further, fine crystals of the dye may be precipitated by adjusting the pH of the solution. These microcrystals are also aggregates of the dye.

The dye in a non-associated state can be obtained by adding the solution to the coating solution for the filter layer. The mixture preferably contains 1 to 99% by weight, more preferably 2 to 98% by weight, and most preferably 5 to 95% by weight of the cyanine dye in an associated state. preferable. Many cyanine dyes are more likely to form an association state than other dyes. Therefore, even if a cyanine dye and another dye are added to the same solvent or aqueous gelatin solution, the cyanine dye alone can be in an associated state and the other dye can be in a non-associated state. The filter layer is
Further, a polymer binder is included. Natural polymers (eg,
Gelatin, cellulose derivatives, alginic acid) or synthetic polymers (eg, polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, polycarbonate, water-soluble polyamide) can be used as the polymer binder. it can.
Hydrophilic polymer (the above natural polymer, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol,
Water-soluble polyamides) are 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 a layer containing a polymer having a glass transition temperature of 25 ° C. or lower,
The filter layer is formed as a layer having a rough surface 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, and the transparent support and the layers provided thereon (for example, an antireflection layer and a hard coat layer)
May be improved. 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 from 20 nm to 1000 nm,
80 nm to 300 nm is more preferable. An undercoat layer containing a polymer having a glass transition temperature of 25 ° C. or lower adheres the transparent support and the filter layer due to the tackiness of the polymer.
Polymers having a glass transition temperature of 25 ° C. or lower include vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, neoprene, styrene, chloroprene, acrylate,
It can be obtained by polymerization or copolymerization of methacrylic acid ester, 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 from 0.02 to 3 μm, more preferably from 0.05 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. In the undercoat layer,
Solvent, matting agent, surfactant, which swells the transparent support,
Antistatic agents, coating aids and hardeners may be added.

(Anti-reflection layer) When an anti-reflection layer is provided, a low refractive index layer is essential. The refractive index of the low refractive index layer is
It is lower than the refractive index of the transparent support. The refractive index of the low refractive index layer is preferably 1.20 to 1.55,
More preferably, it is 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 (JP-A-57-34526, JP-A-3-13026).
No. 103, No. 6-115023, No. 8-313702
And the layers obtained by the sol-gel method (JP-A-5-208811, JP-A-6-208004).
No. 299091, 7-168003) or a layer containing fine particles (Japanese Patent Publication No. 60-59250).
And JP-A-5-13021, JP-A-6-56478, JP-A-7-92306, and JP-A-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.

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 1.55 to 1.70. 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 the surface with an anti-glare function (a function of scattering incident light on the surface to prevent a scene around the film from shifting to the film surface). For example, by forming fine irregularities on the surface of a transparent film, and forming an antireflection layer on the surface, or after forming the antireflection layer, by forming irregularities on the surface with an embossing roll, an anti-glare function is obtained. be able to.
An 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 antistatic layer or an intermediate layer. The hard coat layer preferably contains a cross-linked polymer. The hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or 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 is made of polyorganosiloxane (eg, silicone oil),
It can be formed using 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 antireflection 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.

[0093]

[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,
A latex made of a styrene-butadiene copolymer was applied on one side 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 1 μm polypropylene filter.
The obtained coating liquid for a low refractive index layer was coated on a surface opposite to the undercoat surface of the transparent support with a dry film thickness of 1 using a bar coater.
It was applied to a thickness of 10 nm, dried at 120 ° C. for 30 minutes and cured to form a low refractive index layer.

(Formation of Filter Layer) 0.05 g of cyanine dye (1) and 0.15 g of azo dye (36) were dissolved in 180 g of a 10% by weight aqueous solution of gelatin. Solution 40
After stirring at 30 ° C. for 30 minutes, the mixture was filtered through a 2 μm polypropylene filter to prepare a filter layer coating solution. The coating liquid for a filter layer was applied on the second undercoat layer so that the dry film thickness became 3.5 μm, and dried at 120 ° C. for 10 minutes to form a filter layer, thereby producing an optical filter.

Example 2 Instead of the azo dye (36),
An optical filter was produced in the same manner as in Example 1, except that the same amount of the azo dye (32) was used.

Example 3 Instead of the azo dye (36),
An optical filter was produced in the same manner as in Example 1, except that the same amount of the azo dye (58) was used.

Example 4 Instead of the azo dye (36),
Example 1 except that the same amount of the azomethine dye (62) was used
An optical filter was produced in the same manner as described above.

(Measurement of Absorption Maximum) For the optical filters produced in Examples 1 to 4, the absorption maximum, the transmittance at the absorption maximum and the half width were measured. The results are shown in Table 1.

[0101]

[Table 1] Table 1 ──────────────────────────────────── optical Fi cyanine dye other dye Luther Absorption maximum (difference) Transmittance FWHM Absorption maximum (difference) Transmittance FWHM ─────────────────────────────── ───── Example 1 594 (+84) 30% 35 534 (+11) 68% 110 Example 2 594 (+84) 29% 35 532 (+5) 70% 113 Example 3 594 (+84) 28% 35 536 (+25) 69% 103 Example 4 594 (+84) 30% 35 534 (+0) 71% 93 ───────── (Note) Unit of absorption maximum and half width: nm Difference: absorption maximum of dye in solution (cyanine dye is Nord, the difference between the other dyes measuring water as Solvent) (unit: nm)

Example 5 (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 to 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) 0.05 g of cyanine dye (1) and 0.15 g of azo dye (36) were dissolved in 180 g of a 10% by weight aqueous solution of gelatin. Solution 40
After stirring at 30 ° C. for 30 minutes, the mixture was filtered through a 2 μm polypropylene filter to prepare a filter layer coating solution. The coating liquid for a filter layer was coated on the undercoat layer to a dry film thickness of 3.
It was applied to a thickness of 5 μm and dried at 120 ° C. for 10 minutes to form a filter layer, thereby producing 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 6] (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) 0.05 g of cyanine dye (1) and 0.15 g of azo dye (36) were dissolved in 180 g of a 10% by weight aqueous solution of gelatin. Solution 40
After stirring at 30 ° C. for 30 minutes, the mixture was filtered through a 2 μm polypropylene filter to prepare a filter layer coating solution. The filter layer coating solution is applied on the second undercoat layer (b) so that the dry film thickness becomes 3.5 μm,
After drying for a minute, 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 a 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.

Comparative Example 1 (Formation of Undercoat Layer to Low Refractive Index Layer) As in Example 1, an undercoat layer, a second undercoat layer and a low refractive index layer were formed on a transparent polyethylene terephthalate film having a thickness of 100 μm. Formed.

(Formation of Filter Layer) 0.05 g of cyanine dye (1) was dissolved in 180 g of a 10% by weight aqueous solution of gelatin. The solution was stirred at 40 ° C. for 30 minutes and then 2 μm
And the mixture was filtered through a polypropylene filter to prepare a filter layer coating solution. A filter layer coating solution is applied on the second undercoat layer so that the dry film thickness becomes 3.5 μm,
After drying at 120 ° C. for 10 minutes to form a filter layer, an optical filter was produced.

(Measurement of absorption maximum) When the optical filter was measured for the absorption maximum and the transmittance and the half width at the absorption maximum, the absorption maximum was 594 nm (the difference from the absorption maximum of the dye in the solution state was +84 nm). The ratio was 30% and the half width was 35 nm.

Comparative Example 2 (Formation of Undercoat Layer to Low Refractive Index Layer) As in Example 1, an undercoat layer, a second undercoat layer and a low refractive index layer were formed on a transparent polyethylene terephthalate film having a thickness of 100 μm. Formed.

(Formation of Filter Layer) 0.15 g of the azo dye (36) was dissolved in 180 g of a 10% by weight aqueous solution of gelatin. 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 is applied on the second undercoat layer so that the dry film thickness becomes 3.5 μm.
After drying at 20 ° C. for 10 minutes to form a filter layer, an optical filter was produced.

(Measurement of absorption maximum) When the optical filter was measured for the absorption maximum and the transmittance and the half width at the absorption maximum, the absorption maximum was 534 nm (the difference from the absorption maximum of the dye in the solution state was +11 nm). The ratio was 69%, and the half width was 110 nm.

Comparative Example 3 (Formation of Undercoat Layer to Low Refractive Index Layer) As in Example 1, an undercoat layer, a second undercoat layer and a low refractive index layer were formed on a transparent polyethylene terephthalate film having a thickness of 100 μm. A sample for comparison was prepared (without providing a filter layer).

(Evaluation of Optical Filter) Frazma Display Panel (PDS4202J-H, Fujitsu Limited)
The optical filters produced in Examples and Comparative Examples were adhered to the sum of the back plates of the front plates of Examples and Comparative Examples with an adhesive so that the low-refractive-index layer was on the display side. For each sample, the display contrast, white light and red light were evaluated. Further, the optical filter is irradiated with light from the side opposite to the filter layer so that the illuminance becomes 100,000 lux with a xenon lamp, and the residual amount of the dye after irradiation for 100 hours is 530 n.
m and a wavelength of 594 nm. The residual amount of the dye is defined by the following formula. Dye residual amount = 100 × (100−transmittance of absorption maximum after irradiation) / (100−transmittance of absorption maximum before irradiation) Table 2 shows the results.

[0119]

[Table 2] Table 2 光学 Optical control other control white Red light-resistant ruthen dye Dye Last light Light 594 nm 530 nm ──────────────────────────────────── Example 1 (1) (36) 15: 1 good good 92% 97% Example 2 (1) (32) 15: 1 good good 92% 97% Example 3 (1) (58) 15: 1 good good 92% 95% Example 4 (1) (62) 15: 1 Good Good 92% 90% Example 5 (1) (36) 15: 1 Good Good 93% 97% Example 6 (1) (36) 15: 1 Good Good 93% 97% Comparative Example 1 (1) None 14: 1 Poor * Good 85%-Comparative Example 2 None (36) 13: 1 Good Poor **-97% Comparative Example 3 None None 0: 1 Bad * Bad **--──────────────────────────────────── (Note) Good : Improvement of white light or red light is observed. Defective *: Greenish white Defective **: Orangeish red

[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 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd.F-term (reference) DD02 EE01 FF02

Claims (6)

[Claims] 1. An optical filter having a filter layer containing a dye and a polymer binder on a transparent support, wherein the dye is a mixture of a cyanine dye in an associated state and an azo dye or an azomethine dye in an unassociated state. An optical filter, characterized in that: 2. The method according to claim 1, wherein the cyanine dye in an associated state is 560 to 6
An azo dye or an azomethine dye which has an absorption maximum in a wavelength region of 20 nm and is in a non-associated state is 500 to 550 n
The optical filter according to claim 1, having an absorption maximum in a wavelength region of m. 3. An anti-reflection 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 antireflection film, wherein the dye is a mixture of an associative cyanine dye and a non-associative azo dye or azomethine dye. 4. The method according to claim 1, wherein the cyanine dye in an associated state is 560 to 6
An azo dye or an azomethine dye which has an absorption maximum in a wavelength region of 20 nm and is in a non-associated state is 500 to 550 n
The antireflection film according to claim 3, which has an absorption maximum in a wavelength region of m. 5. 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 antireflection film, wherein the dye is a mixture of an associative cyanine dye and a non-associative azo dye or azomethine dye. 6. An associative cyanine dye comprising 560 to 6
An azo dye or an azomethine dye which has an absorption maximum in a wavelength region of 20 nm and is in a non-associated state is 500 to 550 n
The antireflection film according to claim 5, which has an absorption maximum in a wavelength region of m.