JP2000043175A - Reflection preventing film and plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To permit color adjustment of a display panel by laminating a layer containing a specified dye and a low refractive index layer in turn on a transparent support. SOLUTION: A layer containing visible light-absorbing dyes expressed by formula I, formula II, formula III, and formula IV and a layer whose refractive index is lower than that of a transparent support are laminated in turn on the support. In the formulas, Z1 and Z2 are nonmetallic atom groups (P) forming a nitrogen-containing heterocycle; R1 and R2 are alkyl (Q), alkenyl, or aralkyl; L1 and L2 are a methylene chain comprising an odd number of methylene; X1 is an anion; Ar1 and Ar2 are aryl and an aromatic heterocyclic group; Y1, Y2, and Y3 are P forming an aliphatic cycle or heterocycle; R4 and R5 are Q; R6 is hydrogen, Q, alkoxy, aryloxy, halogen, alkoxycarbonyl, cyano, nitro, amino, amide, acyloxy, sufo, or carboxyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film having a transparent support, a dye-containing layer and a low refractive index layer. Further, the present invention provides a plasma display panel,
The present invention also relates to an antireflection film for mounting as an antireflection filter on a display surface of a display device such as a CRT, a fluorescent display, a field emission display, and a liquid crystal display. Furthermore, the present invention relates to a plasma display panel provided with an antireflection filter on the display surface side.

[0002]

2. Description of the Related Art Plasma display panels, CRTs,
Display devices such as a fluorescent display tube, a field emission display, and a liquid crystal display have a problem that display contrast is reduced due to reflection of external light on the display surface. As a countermeasure, an antiglare film having fine irregularities or an antireflection layer having a multilayer structure in which a high refractive index material and a low refractive index material are combined is formed on the display surface. 2. Description of the Related Art In a display device using a phosphor such as a plasma display panel, a CRT, a fluorescent display tube, and a field emission display, the applied phosphor is irradiated with an electron beam or an ultraviolet ray to cause the phosphor to emit light and transmit through a phosphor screen or Display is performed by the reflected light. Phosphors are generally white and have high reflectivity, so that external light is often reflected on the phosphor screen. Therefore, the problem of lowering the display contrast due to reflection of external light,
This is particularly serious in a display device using a phosphor. It is technically difficult to prevent reflection on the phosphor screen by improving the phosphor. The above countermeasures using an antiglare film or a multilayered antireflection layer are often insufficient for a display device using a phosphor. In a display device using a phosphor, a neutral gray filter may be provided on the front surface of the display as another measure to absorb reflected light. The neutral gray filter is also called an ND filter, and its transmittance is generally 40 to 80%.

When color display is performed by a phosphor light emitting type display device, light emission of three primary color phosphors of red, blue and green is used. In a plasma display panel or a fluorescent display tube, the display screen tends to be greenish because the luminance of green, which has the highest visibility, is strong. In order to correct the color balance of the display color, a color adjustment filter for suppressing the luminance of green light emission is provided on the front of the display. As described above, in the display device, in order to improve display contrast and display quality, a color adjustment filter, a neutral gray filter, or a filter that has been subjected to anti-glare processing or anti-reflection processing is installed on the front of the display. (Usually pasted). When a plurality of filters are used, a color adjustment filter or a neutral gray filter is provided on the display surface side, and a filter subjected to an anti-glare treatment or an anti-reflection treatment is provided outside the filter. Such a filter is disclosed in
JP-A-188501 and JP-A-10-26704 disclose a transparent plastic filter having a layer structure in the order of a transparent support, a dye-containing layer, and an antireflection layer. The anti-reflection layer is formed by vacuum evaporation. JP 9
JP-A-306366 discloses an antireflection layer, a dye-containing layer,
A plasma display panel filter having an ultraviolet cut layer and an EMI layer is disclosed. The antireflection layer is formed by applying a fluororesin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antireflection film capable of adjusting the color of a display panel. Another object of the present invention is to provide a plasma display panel in which the color balance of display colors is corrected and reflection is prevented.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antireflection film of the following [1] to [8] and a following [9].
Achieved by the plasma display panel. [1] On one surface of a transparent support, a dye-containing layer and a low refractive index layer having a refractive index lower than that of the transparent support are provided as a coating layer in this order, and a dye is provided. The containing layer has the following formula (1), (2), (4), (5)
Or an antireflection film containing a visible light absorbing dye represented by (6).

[0006]

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[0007] In the formula, Z ¹ and Z ² are each independently a non-metallic atomic group forming a nitrogen-containing heterocyclic ring; R ¹
And R ² are each independently an alkyl, alkenyl or aralkyl group; L ¹ is a methine chain consisting of an odd number of methines; a, b and c are each independently 0 or 1 Yes; and X ¹ is an anion.

[0008]

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In the formula, Ar ¹ and Ar ² are each independently an aryl group, an aromatic heterocyclic group or a group represented by the formula (3).

[0010]

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Wherein Z ³ is a group of non-metallic atoms forming a nitrogen-containing heterocyclic ring; R ³ is an alkyl group, an alkenyl group or an aralkyl group; and d is 0 or 1
It is.

[0012]

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Wherein Y ¹ and Y ² are each independently a group of non-metallic atoms forming an aliphatic or heterocyclic ring; and L ² is a methine chain consisting of an odd number of methines.

[0014]

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Wherein Y ³ is a group of nonmetallic atoms forming an aliphatic ring or a heterocyclic ring; R ⁴ and R ⁵ are each independently an alkyl group; and R ⁶ is a hydrogen atom , An alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, a cyano, nitro, amino, amide group, acyloxy group, sulfo or carboxyl.

[0016]

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Wherein R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aralkyl group or an aryl group; R ⁹ is an alkyl group, an alkoxy group, a halogen atom, an amide group, an alkoxycarbonyl group , Cyano, sulfonamide, carbamoyl, sulfamoyl, ureido, alkoxycarbonylamino or hydroxyl; n is 1, 2, 3 or 4; R ⁷ and R ⁸ are It may form a heterocyclic ring bonded to adjacent R ^9; R ¹⁰ is
Hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, cyano, amide group, alkoxycarbonylamino group, sulfonamide group, ureido group, alkylthio group, arylthio group, alkoxy Carbonyl, carbamoyl, sulfamoyl, sulfonyl, acyl, amino, alkylamino or arylamino; Za, Zb and Zc each independently represent-
And C (R ¹¹ ) = or -N =; and R ¹¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino, an alkylamino group, an arylamino Or an alkoxycarbonyl group.

[2] On one surface of the transparent support, a dye-containing layer is provided as a coating layer, and on the other surface,
A low refractive index layer having a refractive index lower than the refractive index of the transparent support is provided as a coating layer, and the dye-containing layer is formed of the above formula (1), (2), (4), (5) or An antireflection film containing the visible light absorbing dye represented by (6). [3] The visible light-absorbing dye has a wavelength region of 470 to 510 nm, a wavelength region of 540 to 600 nm, or 64.
The antireflection film according to [1] or [2], which has a maximum absorption wavelength in a wavelength range of 0 to 730 nm. [4] The dye-containing layer further comprises the following formula (7):
(8) The antireflection film according to (1) or (2), comprising the infrared light absorbing dye represented by (10) or (11).

[0019]

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Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group; and X ² is an anion.

[0021]

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Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group; and X ² is an anion.

[0023]

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Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group; and X ³ is an anion.

[0025]

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Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group; and X ³ is an anion.

[0027]

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Wherein R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or an acyl group. One or two adjacent groups are joined to form a 5- or 6-membered ring; R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group,
An alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, a cyano, a nitro, an amino, an amide group, an acyloxy group, a sulfo or a carboxyl; l is an integer of 1 to 6; It is an integer of 3. [5] The antireflection according to [1], wherein a high refractive index layer having a refractive index higher than that of the transparent support is provided between the dye-containing layer and the low refractive index layer as a coating layer. Film. [6] The antireflection according to [2], wherein a high refractive index layer having a refractive index higher than that of the transparent support is provided between the transparent support and the low refractive index layer as a coating layer. Film.

[7] On one surface of the transparent support, a dye-containing layer and a low refractive index layer having a refractive index lower than that of the transparent support are provided as a coating layer in this order. And the dye-containing layer has a wavelength range of 470 to 510 nm, a wavelength range of 540 to 600 nm, or 640.
An antireflection film containing a visible light absorbing dye having a maximum absorption wavelength in a wavelength region of from 730 nm to 730 nm. [8] On one surface of the transparent support, a low refractive index layer having a refractive index lower than that of the transparent support is provided on the other surface as a dye-containing layer coating layer. An antireflection film provided as a coating layer, wherein the dye-containing layer contains a visible light absorbing dye having a maximum absorption wavelength in a wavelength range of 470 to 510 nm, a wavelength range of 540 to 600 nm or a wavelength range of 640 to 730 nm. [9] A plasma display panel provided on a display surface side using the anti-reflection film according to any one of [1] to [8] as an anti-reflection filter.

[0030]

DETAILED DESCRIPTION OF THE INVENTION The visible light absorbing dyes used in the present invention preferably have a maximum absorption wavelength in the wavelength region between the emission spectral peaks of the illuminant displays for which antireflection films are to be used. Emission spectral peaks vary with the type of illuminant display, but are generally the three primary colors blue, green and red. Specifically, 4
70 to 510 nm wavelength region (between blue and green), 540
-600 nm wavelength range (between green and red) or 640
To 730 nm wavelength range (visible light longer than red)
It is preferable to use a visible light absorbing dye having a maximum absorption wavelength. It is more preferable to use a visible light absorbing dye having a maximum absorption wavelength in a wavelength range of 480 to 510 nm, a wavelength range of 560 to 600 nm, or a wavelength range of 660 to 730 nm. The dye having the maximum absorption wavelength in the above-mentioned wavelength region may be one kind or a mixture of two or more kinds of dyes. The peak of the absorption spectrum of the dye is preferably sharp. Specifically, the half width value (the width of the wavelength region showing half the absorbance of the absorbance at the maximum absorption wavelength of the dye in the solution) is preferably 10 to 100 nm, more preferably 20 to 70 nm, Most preferably, it is 20 to 50 nm.

The visible light absorbing dyes preferably used in the present invention are represented by the following formulas (1), (2), (4), (5) and (6).

[0032]

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In the formula (1), Z ¹ and Z ² are each independently a group of non-metallic atoms forming a nitrogen-containing heterocyclic ring. The nitrogen-containing heterocycle is preferably a 5- or 6-membered ring. A 5-membered ring is more preferable than a 6-membered ring.
An aromatic ring, an aliphatic ring, or another hetero ring may be condensed to the nitrogen-containing hetero 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. , Benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, floppyrrole ring,
Includes indolizine, imidazoquinoxaline and quinoxaline rings. A ring in which a 5-membered nitrogen-containing heterocycle is fused with a benzene ring or a naphthalene ring is particularly preferred.
The nitrogen-containing heterocycle and the ring condensed therewith 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, B
r, F), alkoxycarbonyl groups (eg, ethoxycarbonyl), cyano, nitro, amino, amide groups (eg, acetamido, propionamido), acyloxy groups (eg, acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl are
It may be in a salt state.

In the formula (1), R ¹ and R ² are each independently an alkyl group, an alkenyl group or an aralkyl group. Alkyl groups are particularly preferred. The alkyl group preferably has 1 to 18 carbon atoms. The alkyl group may have a branch. Examples of the alkyl group include methyl, ethyl, propyl and butyl. The alkyl group may have a substituent. Examples of the substituent include a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), a hydroxyl, an acyloxy group (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy), sulfo And carboxyl.
Sulfo and carboxyl may be in the form of a salt. The alkenyl group preferably has 2 to 10 carbon atoms. The alkenyl group may have a branch. Examples of alkenyl groups include 2-pentenyl, vinyl,
Allyl, 2-butenyl and 1-propenyl are included. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), a hydroxyl, an acyloxy group (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) sulfo and Contains carboxyl.
Sulfo and carboxyl may be in the form of a salt. 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), alkoxycarbonyl groups (eg, ethoxycarbonyl), cyano, nitro, amino, amide groups (eg, acetamido, propionamide), acyloxy groups (eg, acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt.

In the formula (1), L ¹ is a methine chain composed of an odd number of methines. The number of methines is preferably one, three or five. The methine chain may have a substituent. The position where the substituent is bonded is preferably methine at the center of the methine chain (methine at the meso position). Examples of the substituent include an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy), an aryl group (phenyl, naphthyl), an aryloxy group (eg, phenoxy), a halogen atom (Cl, Br) ,
F), an alkoxycarbonyl group (eg, ethoxycarbonyl), cyano, an acylamide group (eg, acetamido),
Includes nitro, amino, alkylamino, arylamino, hydroxyl, mercapto, alkylthio and arylthio groups. Two substituents of the methine chain may combine to form a 5- or 6-membered ring.

In the formula (1), a, b and c are each independently 0 or 1. It is preferable that a and b have the same value. c is generally 1. However,
When an anionic substituent forms an inner salt with N ⁺ like carboxyl, c becomes 0.

In the formula (1), X ¹ is an anion. Examples of anions include halide ions (Cl ⁻ , Br)
^-, I -), p-toluenesulfonate ion, ethyl sulfate _{^{ion, PF 6 -, BF 4 -}} , ClO 4 -, AsF 6 -, Sb
F ₆ ^- and CF ₃ COO ^- are included.

[0038]

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In the formula (2), Ar ¹ and Ar
² is each independently an aryl group, an aromatic heterocyclic group or a group represented by the formula (3). Examples of the aryl group include phenyl and naphthyl. The aryl group may have a substituent. In the case of phenyl, the substituent is preferably bonded to the ortho or para position of the phenyl. 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), cyano, nitro, amino, alkylamino group, arylamino group, amide group (eg, acetamido, propionamido), acyloxy group (eg, acetoxy, butyryloxy), hydroxyl, Includes heterocyclic groups (eg, morpholino, pyrrolidino, piperidino, piperazino), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt. The aromatic heterocyclic group generally has an unsaturated heterocyclic ring. Examples of the unsaturated heterocyclic ring include a pyrrole ring, an indole ring, a thiophene ring, a thiazole ring and a selenazole ring. The aromatic heterocyclic 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), cyano, nitro, amino, alkylamino groups, arylamino groups, amide groups (eg, acetamide, propion) Amide), acyloxy groups (eg, acetoxy, butyryloxy), heterocyclic groups (eg, morpholino, pyrrolidino, piperidino, piperazino), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt.

[0040]

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In the formula (3), Z ³ is a group of non-metallic atoms forming a nitrogen-containing heterocyclic ring. The nitrogen-containing heterocycle is preferably a 5- or 6-membered ring. A 5-membered ring is more preferable than a 6-membered ring. An aromatic ring, an aliphatic ring, or another hetero ring may be condensed to the nitrogen-containing hetero 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.
A ring in which a 5-membered nitrogen-containing heterocycle is fused with a benzene ring or a naphthalene ring is particularly preferred. The nitrogen-containing heterocycle and the ring condensed therewith 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), alkoxycarbonyl groups (eg, ethoxycarbonyl), cyano, nitro, amino, amide groups (eg, acetamido, propionamide), acyloxy groups (eg, acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt.

In the formula (3), R ³ is an alkyl group,
It is an alkenyl group or an aralkyl group. Alkyl groups are particularly preferred. The alkyl group has 1 to 18 carbon atoms.
It is preferred that The alkyl group may have a branch. Examples of the alkyl group include methyl, ethyl, propyl and butyl. The alkyl group may have a substituent. Examples of the substituent include a halogen atom (C
l, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), hydroxyl,
Acyloxy groups (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) sulfo and carboxyl are included. Sulfo and carboxyl are
It may be in a salt state. The alkenyl group preferably has 2 to 10 carbon atoms. The alkenyl group may have a branch. Examples of alkenyl groups include 2-
Pentenyl, vinyl, allyl, 2-butenyl and 1
-Propenyl. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom (C
l, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), hydroxyl,
Acyloxy groups (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) sulfo and carboxyl are included. Sulfo and carboxyl are
It may be in a salt state. The carbon atom of the aralkyl group is
It is preferably 7 to 12. 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), alkoxycarbonyl groups (eg, ethoxycarbonyl), cyano, nitro, amino, amide groups (eg, acetamido, propionamide), acyloxy groups (eg, acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt. In the formula (3), d is 0 or 1.

[0043]

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In the formula (4), Y ¹ and Y ² are each independently a non-metallic atomic group 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 heterocycle include a 5-pyrazolone ring, an oxazolone ring, a barbituric acid ring, a pyridone ring, a rhodanine ring, a pyrazolidinion ring and a pyrazolopyridone ring. The aliphatic ring and the heterocyclic ring 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), alkoxycarbonyl groups (eg, ethoxycarbonyl), cyano, nitro, amino, amide groups (eg, acetamido, propionamide), acyloxy groups (eg, acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt.

In the formula (4), L ² is a methine chain composed of an odd number of methines. The methine chain may have a substituent. The position where the substituent is bonded is preferably methine at the center of the methine chain (methine at the meso position).
Examples of the substituent include an alkyl group (eg, methyl, ethyl),
Alkoxy groups (eg, methoxy, ethoxy), aryl groups (phenyl, naphthyl), aryloxy groups (eg, phenoxy), halogen atoms (Cl, Br, F), alkoxycarbonyl groups (eg, ethoxycarbonyl), cyano,
Includes acylamide groups (eg, acetamido), nitro, amino, alkylamino groups, arylamino groups, hydroxyl, mercapto, alkylthio and arylthio groups. Two substituents of the methine chain may combine to form a 5- or 6-membered ring.

[0046]

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In the formula (5), Y ³ is 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 heterocycle include a 5-pyrazolone ring, an oxazolone ring, a barbituric acid ring, a pyridone ring, a rhodanine ring, a pyrazolidinion ring and a pyrazolopyridone ring. Aliphatic rings and heterocyclic rings are
It 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 atom (Cl, Br, F), alkoxycarbonyl group (eg, ethoxycarbonyl), cyano, nitro, amino, amide group (eg, acetamido, propionamide), acyloxy group (eg, Acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt.

In the formula (5), R ⁴ and R ⁵ are each independently an alkyl group. The alkyl group preferably has 1 to 18 carbon atoms. The alkyl group may have a branch. Examples of the alkyl group include methyl, ethyl, propyl and butyl. The alkyl group may have a substituent. Examples of substituents include
Includes halogen atoms (Cl, Br, F), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl), hydroxyl, acyloxy groups (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt.

In the formula (5), R ⁶ represents a hydrogen atom, 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), cyano, nitro, amino, amide groups (eg, acetamido, propionamido), acyloxy groups (eg, acetoxy, butyryloxy), sulfo Or carboxyl. Sulfo and carboxyl may be in the form of a salt.

[0050]

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In the formula (6), R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. Alkyl groups are particularly preferred. The alkyl group preferably has 1 to 20 carbon atoms. The alkyl group may have a branch. Examples of the alkyl group include methyl, ethyl, propyl, and isopropyl. The alkyl group may have a substituent. Examples of the substituent include an alkoxy group (eg, methoxy, ethoxy), cyano, a halogen atom (Cl, Br, F),
Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), sulfonamide group (eg, methanesulfonamide), carbamoyl group (eg, N-methylcarbamoyl, N, N-dimethylcarbamoyl), amide group (eg, acetamide, propion Amide) and acyloxy groups (eg, acetyloxy). Examples of the substituted alkyl group include 2-methoxyethyl, 3-methoxypropyl, ethoxyethyl, 2-cyanoethyl, cyanomethyl, 2-chloroethyl, 3-bromopropyl, 2-methoxycarbonylethyl, 3-ethoxycarbonylpropyl, methanesulfone Amidoethyl, 2- (N-methylcarbamoyl) ethyl, 3- (N, N-dimethylcarbamoyl) propyl, 2-acetamidoethyl, 3-propionamidopropyl and 2-acetoxyethyl are included. The aralkyl group preferably has 7 to 20 carbon atoms. Examples of the aralkyl group include benzyl and phenethyl. The aryl group preferably has 6 to 14 carbon atoms. Examples of the aryl group include phenyl and 2-naphthyl. The aryl group may have a substituent. Examples of substituents include
Includes alkyl groups (eg, methyl), alkoxy groups (eg, methoxy), halogen atoms (Cl, Br, F), nitro and cyano. Examples of substituted aryl groups include p-tolyl, p-methoxyphenyl, 2,4-chlorophenyl, p-nitrophenyl, and 2,4-dicyanophenyl.

In the formula (6), R ⁷ and R ⁸ may combine with each other to form a heterocyclic ring. Examples of the heterocycle formed include a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring. In the formula (6), R
⁹ is an alkyl group, an alkoxy group, a halogen atom (C
l, Br, F), an amide group, an alkoxycarbonyl group,
A cyano, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group or hydroxyl. Amido, sulfonamido, ureido and alkoxycarbonylamino groups are preferred. R ⁹ is preferably bonded at the ortho position to the azo bond (= N-). The alkyl group preferably has 1 to 12 carbon atoms. The alkyl group may have a branch. Examples of alkyl groups include methyl,
Includes ethyl, propyl and butyl. The alkoxy group preferably has 1 to 12 carbon atoms.
Examples of the alkoxy group include methoxy, ethoxy, methoxyethoxy and isopropoxy. The amide group preferably has 1 to 12 carbon atoms. Examples of amide groups include formamide, acetamido, propionamido, cyanoacetamide, benzamide, p-methylbenzamide, pentafluorobenzamide, m-
Methoxybenzamide is included. The alkoxycarbonyl group preferably has 2 to 13 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl. The sulfonamide group preferably has 1 to 10 carbon atoms. Examples of the sulfonamide group include methanesulfonamide, ethanesulfonamide and N-methylmethanesulfonamide.

The carbamoyl group has 1 to 1 carbon atoms.
It is preferably 5. Examples of the carbamoyl group include methylcarbamoyl, dimethylcarbamoyl, butylcarbamoyl, isopropylcarbamoyl, t-butylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, methoxyethylcarbamoyl, chloroethylcarbamoyl, cyanoethylcarbamoyl, ethylcyanoethylcarbamoyl, benzylcarbamoyl,
Ethoxycarbonylmethylcarbamoyl, furfurylcarbamoyl, tetrahydrofurfurylcarbamoyl, phenoxymethylcarbamoyl, allylcarbamoyl, crotylcarbamoyl, prenylcarbamoyl, 2,3-
Dimethyl-2-butenylcarbamoyl, homoallylcarbamoyl, homocrotylcarbamoyl, homoprenylcarbamoyl, phenylcarbamoyl, p-tolylcarbamoyl, m-methoxyphenylcarbamoyl, 4,5
-Dichlorophenylcarbamoyl, p-cyanophenylcarbamoyl, p-acetamidocarbamoyl, p-methoxycarbonylphenylcarbamoyl, m-trifluoromethylphenylcarbamoyl, o-fluorophenylcarbamoyl, 1-naphthylcarbamoyl, 2-pyridylcarbamoyl, 3-pyridylcarbamoyl , 4-pyridylcarbamoyl, 2-thiazolylcarbamoyl, 2
-Benzthiazolylcarbamoyl, 2-benzimidazolylcarbamoyl and 2- (4-methyl) -1,3,
4-thiadiazolylcarbamoyl is included. The sulfamoyl group preferably has 0 to 12 carbon atoms. Examples of the sulfamoyl group include methylsulfamoyl and dimethylsulfamoyl. The number of carbon atoms of the ureido group is preferably 1 to 10. Examples of ureido groups include methylureide and dimethylureide. The alkoxycarbonylamino group preferably has 2 to 10 carbon atoms. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

In the formula (6), n is 1, 2, 3 or 4. In the formula (6), R ⁷ or R ⁸ may combine with an adjacent R ⁹ to form a heterocyclic ring. Examples of the heterocyclic ring formed include a julolidine ring, a pyrrolidine ring and a piperidine ring.

In the formula (6), R ¹⁰ is a hydrogen atom, a halogen atom (Cl, Br, F), an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, a cyano, an amide group. , An alkoxycarbonylamino group, a sulfonamide group, a ureido group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, an amino, an alkylamino group or an arylamino group. Aryl groups are particularly preferred. The alkyl group preferably has 1 to 12 carbon atoms. The alkyl group may have a branch. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl and t-butyl. The alkyl group may have a substituent. Examples of substituents include hydroxy, alkoxy groups (eg, methoxy), cyano, and halogen atoms (Cl, Br, F). Examples of the substituted alkyl group include hydroxyethyl, methoxyethyl, cyanoethyl and trifluoromethyl. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl. The alkoxy group preferably has 1 to 12 carbon atoms. Examples of alkoxy groups include methoxy,
Includes ethoxy, isopropoxy and methoxyethoxy. The alkoxy group may have a substituent.
Examples of the substituent include hydroxy. Examples of the substituted alkoxy group include hydroxyethoxy. Examples of the aryl group include phenyl. The aryl group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl), an alkoxy group (eg, methoxy), a halogen atom (Cl, Br, F) and nitro.
Examples of substituted aryl groups include p-tolyl, p-methoxyphenyl, o-chlorophenyl, m-nitrophenyl, p-tolylphenyl
-Chlorophenyl and o-methoxyphenyl.

Examples of the aryloxy group include phenoxy. The aryloxy group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl) and an alkoxy group (eg, methoxy). Examples of the substituted aryloxy group include p-methylphenyl, p-methoxyphenyl and o-methoxyphenyl.
Examples of the aralkyl group include benzyl and 2-phenethyl. Examples of amide groups include acetamido, propionamido and isobutanamide. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino and isopropoxycarbonylamino. Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide and trifluoromethanesulfonamide.
Examples of ureido groups include 3-methylureide, 3,3-dimethylureide, and 1,3-dimethylureide. Examples of the alkylthio group include methylthio and ethylthio. Examples of the arylthio group include phenylthio and p-tolylthio. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl. Examples of the carbamoyl group include methylcarbamoyl and dimethylcarbamoyl. Examples of the sulfamoyl groups include dimethylsulfamoyl and sometimes ethylsulfamoyl. Examples of the sulfonyl group include methanesulfonyl, butanesulfonyl and benzenesulfonyl. Examples of the acyl group include acetyl and butyroyl. Examples of the alkylamino group include methylamino and dimethylamino. Examples of the arylamino group include anilino.

In the formula (6), Za, Zb and Zc
They are each independently, -C (R ¹¹⁾ = or -N =. Za and Zc are -N =, and Zb is -C
It is particularly preferred that (R ¹¹ ) =. . R ¹¹ is
A hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino, an alkylamino group, an arylamino group or an alkoxycarbonyl group. The definition and examples of the alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group and alkoxycarbonyl group are the same as the definition and examples for R ^10. The azo dye represented by the formula (6) is characterized in that the absorption peak is sharp. Hereinafter, specific examples of the visible light absorbing dyes represented by Formulas (1), (2), (4), (5), and (6) will be shown.

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The visible light absorbing dyes are described in various documents (eg,
Liebigis Ann. Chem. 712,123
-137 (1968); Org. Chem. 199
2,57,3278-3286, EP 412379
A1, JP-A-63-145281, JP-A-1
Nos. -134447, 4-178646 and 5-14
No. 902) can be synthesized.

It is preferable to use an infrared light absorbing dye in addition to the visible light absorbing dye. The infrared light absorbing dye is 700
It preferably has a maximum absorption wavelength in a wavelength region of from 800 to 1200 nm, and more preferably has a maximum absorption wavelength in a wavelength region of from 800 to 1000 nm. Preferred infrared light absorbing dyes are represented by the following formulas (7) to (11).

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In the formula (7), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group. The alkyl group preferably has 1 to 18 carbon atoms. The alkyl group may have a branch. Examples of the alkyl group include methyl, ethyl, propyl and butyl. The alkyl group may have a substituent. Examples of the substituent include a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), a hydroxyl, an acyloxy group (eg,
Acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt. In the formula (7), X ² is an anion. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I
^-), p-toluenesulfonate ion, ethyl sulfate _{^{ion, PF 6 -, BF 4 -}} , ClO 4 -, AsF 6 -, SbF 6 - and CF ₃ COO ^- is included.

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In the formula (8), R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group. The definition and examples of the alkyl group are the same as those of the alkyl group of the formula (7). In the formula (8), X ² is an anion. Examples of the anion are the same as the anion of the formula (7).

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In the formula (9), R ¹⁶ , R ¹⁷ , R ¹⁸ , R
¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group. The definition and examples of the alkyl group are the same as those of the alkyl group of the formula (7). In the formula (9), X ³ is an anion. Examples of the anion are the same as the anion of the formula (7).

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In the formula (10), R ¹⁶ , R ¹⁷ , R ¹⁸ ,
R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group. The definition and examples of the alkyl group are the same as those of the alkyl group of the formula (7). In the formula (10), X ³ is an anion. Examples of the anion are the same as the anion of the formula (7).

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In the formula (11), R ²² , R ²³ , R ²⁴ ,
R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group. , An alkynyl group or an acyl group, or two adjacent groups are combined to form a 5- or 6-membered ring. The definition and examples of the alkyl group are the same as those of the alkyl group of the formula (7). Examples of the cycloalkyl group include cyclopentyl and cyclohexyl. The cycloalkyl group may have a substituent. Examples of substituents include
Includes halogen atoms (Cl, Br, F), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl), hydroxyl, acyloxy groups (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) 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 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), alkoxycarbonyl groups (eg, ethoxycarbonyl), cyano, nitro, amino, amide groups (eg, acetamido, propionamide), acyloxy groups (eg, acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt.

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), halogen atom (Cl, Br, F), alkoxycarbonyl group (eg, ethoxycarbonyl), cyano, nitro, amino, amide group (eg, acetamido, propionamide), acyloxy group (eg, Acetoxy, butyryloxy), sulfo and carboxyl. Sulfo and carboxyl may be in the form of a salt. The alkenyl group preferably has 2 to 10 carbon atoms. The alkenyl group may have a branch. Examples of alkenyl groups include
Includes 2-pentenyl, vinyl, allyl, 2-butenyl and 1-propenyl. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), a hydroxyl, an acyloxy group (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) sulfo and Contains carboxyl. Sulfo and carboxyl may be in the form of a salt.

The alkynyl group has 2 to 10 carbon atoms.
It is preferred that Examples of the alkynyl group include ethynyl and 2-propynyl. An alkynyl group is
It may have a substituent. Examples of the substituent include a halogen atom (Cl, Br, F), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), a hydroxyl, an acyloxy group (eg, acetoxy, butyryloxy, hexanoyloxy, benzoyloxy) sulfo and Contains carboxyl. Sulfo and carboxyl may be in the form of a salt. The acyl group preferably has 2 to 10 carbon atoms. Examples of the acyl group include acetyl, propionyl and benzoyl. ^{R 22, R 23, R 24} , R 25, R 26, R 27,
Among the R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² and R ³³ , the 5-membered ring or the 6-membered ring formed by bonding adjacent two is a saturated heterocyclic ring or a saturated aliphatic ring (cycloalkyl ring). ) Is preferable.

In the formula (11), R ³⁴ , R ³⁵ and R
³⁶ independently represent a hydrogen atom, 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), cyano, nitro, amino, amide group (eg, acetamide, propionamide), acyloxy group (eg, acetoxy, butyryloxy), sulfo or carboxyl. Sulfo and carboxyl may be in the form of a salt. In the formula (11), 1 is an integer of 1 to 6. In the formula (11), m is an integer of 1 to 3. Equations (7), (8), (9), (10)
Specific examples of the infrared light absorbing dye represented by (11) are shown below.

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The infrared light absorbing dyes are described in, for example,
It can be synthesized with reference to JP-A-13326.
The visible light absorbing dye and the infrared light absorbing dye are used in the form of a solution or a solid fine particle dispersion dissolved in a solvent. In order to prepare solid fine particles of a dye, a known disperser can be used. Examples of the disperser include a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill and a roller mill. The disperser is disclosed in Japanese Patent Application Laid-Open No. 52-92716 and International Patent No. 88.
/ 074794. Vertical or horizontal media dispersers are preferred. Dispersion can be performed in any suitable medium (eg,
(Water, alcohol). It is preferable to use a surfactant for dispersion. As the surfactant for dispersion, an anionic surfactant (JP-A-52-92716) is used.
And International Patent Publication No. 88/074794) are preferably used. If necessary, an anionic polymer, a nonionic surfactant or a cationic surfactant may be used. After dissolving the dye in a suitable solvent, a poor solvent for the dye may be added to the resulting solution to form fine particles (powder) of the dye. The above-mentioned surfactant for dispersion may be added to the solution. P of the solution of the dye
By adjusting H, the dye can be precipitated to form fine particles (microcrystals) of the dye. You may use together a dye and a fading inhibitor, an antioxidant, or an ultraviolet inhibitor.

(Layer Configuration of Antireflection Film) The basic configuration of the antireflection film will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing a main layer configuration of an antireflection film in which a dye-containing layer is provided between a transparent support and a low refractive index layer. The embodiment shown in FIG. 1A has a layer structure in the order of a transparent support (1), a dye-containing layer (2), and a low refractive index layer (5). The transparent support (1) and the low 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 In the embodiment shown in FIG. 1B, the transparent support (1), the dye-containing layer (2), the high refractive index layer (4), and the low refractive index It has a layer configuration in the order of the rate layer (5). The transparent support (1), the high refractive index layer (4) and the low 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 In the embodiment shown in FIG. 1 (c), the transparent support (1), the dye-containing layer (2), the medium refractive index It has a layer structure of a layer (3), a high refractive index layer (4), and a low refractive index layer (5) in this order. The transparent support (1), the medium refractive index layer (3), the high refractive index layer (4) and the low refractive index layer (5) 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 the main layer structure of an antireflection film in which a dye-containing layer is provided on the surface of a transparent support opposite to the low refractive index layer. The embodiment shown in FIG. 2D has a layer configuration in the order of the dye-containing layer (2), the transparent support (1), and the low refractive index layer (5). The transparent support (1) and the low 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. In the embodiment shown in FIG. 2E, the dye-containing layer (2), the transparent support (1), the high-refractive-index layer (4), and the low refractive index It has a layer configuration in the order of the rate layer (5). The transparent support (1), the high refractive index layer (4) and the low 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 In the embodiment shown in FIG. 2 (f), the dye-containing layer (2), the transparent support (1), the medium refractive index It has a layer structure of a layer (3), a high refractive index layer (4), and a low refractive index layer (5) in this order. The transparent support (1), the medium refractive index layer (3), the high refractive index layer (4) and the low refractive index layer (5) 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

(Transparent Support) As the transparent support, a glass plate or a plastic film is preferably used. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate) , Poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene) ,
Polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate and polyetherketone. Triacetyl cellulose, polycarbonate and polyethylene terephthalate are preferred. The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, more preferably 1.0% or less.
The refractive index of the transparent support is preferably from 1.4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The amount of the infrared absorber added is preferably 0.01 to 20% by weight of the transparent support, more preferably 0.05 to 10% by weight. As a slipping agent, particles of an inert inorganic compound may be added to the transparent support. Examples of inorganic compounds include SiO ₂ ,
TiO ₂ , BaSO ₄ , CaCO ₃ , talc and kaolin. The transparent support may be subjected to a surface treatment. Examples of 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 are included. 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, a layer for strengthening the adhesion with the upper layer may be provided.

(Dye-Containing Layer) The dye-containing layer is a layer containing the above-mentioned visible light absorbing dye (preferably, an infrared light absorbing dye). The dye-containing layer is formed on a transparent support by coating. The dye-containing layer preferably functions also as a hard coat layer (a layer that imparts scratch resistance to the transparent support). In this case, it is preferable that the dye-containing layer also has a function of enhancing the adhesion between the transparent support and the layer thereon.
The dye-containing layer preferably contains a polymer, and more preferably contains a cross-linked polymer. Examples of the polymer include various 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. The dye-containing layer containing a crosslinked polymer can be formed by applying a coating solution containing a dye, a polyfunctional monomer and a polymerization initiator on a transparent support and polymerizing the polyfunctional monomer. The polyfunctional monomer is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-cyclohexanol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyol and polyester polyol. . Trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyols are preferred. Two or more polyfunctional monomers may be used in combination.

It is preferable to use a photopolymerization initiator in the polymerization reaction of the polyfunctional monomer. Examples of photopolymerization initiators include
Includes acetophenones, benzophenones, α-amyloxime esters, tetramethylthiuram monosulfide and thioxanthones. A photosensitizer may be used in addition to the photopolymerization initiator. Examples of photosensitizers include n-
Butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone are included. The photopolymerization initiator is preferably used in an amount of 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the polyfunctional monomer. The photopolymerization reaction is preferably performed by ultraviolet irradiation after coating and drying of the dye-containing layer.
A filler may be added to the dye-containing layer to suppress curing shrinkage of the polyfunctional monomer. It is preferable to use inorganic fine particles or organic fine particles as the filler. The average particle diameter of the fine particles is preferably 0.01 to 2 μm,
More preferably, it is 0.02 to 0.5 μm.
The thickness of the dye-containing layer is preferably from 1 to 15 μm. An antifoaming agent, a thickening agent, a leveling agent, a flame retardant, an ultraviolet absorber, an antioxidant, a modifying resin, or an anti-fading agent may be further added to the dye-containing layer or its coating solution.

As the anti-fading agent, a dye stabilizer can be used. Examples of the dye stabilizer include hydroquinone derivatives (described in U.S. Pat. Nos. 3,935,016 and 3,982,944) and hydroquinone diether derivatives (U.S. Pat. No. 4,254,216 and JP-A-55-254).
21004), phenol derivatives (Japanese Unexamined Patent Publication No.
No. 4-145530), a derivative of spiroindane or methylenedioxybenzene (UK Patent Publication 20)
Nos. 77455 and 2062888 and JP-A-61-90155), chroman, spirochroman or coumaran derivatives (US Pat. No. 34323).
Nos. 00, 3573050, 3574627 and 3764337 and JP-A-52-152.
No. 225, No. 53-20327, No. 53-17729
And the derivatives of hydroquinone monoether or para-aminophenol (British Patent Nos. 1347556 and 2066975, Japanese Patent Publication No. 54-12337, and Japanese Patent Application Laid-open No. 55-337).
No. 6321) and bisphenol derivatives (US Pat. No. 3,700,455 and JP-B-48-3).
No. 1625). In order to improve the stability of the dye to light or heat, metal complexes (U.S. Pat. No. 4,245,018 and JP-A-60-97353)
May be used as an anti-fading agent. To improve the lightfastness 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) and a diimmonium compound (US Pat.
No. 12), nickel complex (JP-A-4-146)
189) and antioxidants (European Patent Publication 8
200057A1).

(High Refractive Index Layer and Medium Refractive Index Layer) As shown in FIG. 1B, a high refractive index layer may be provided between the dye-containing layer and the low refractive index layer. Further, as shown in FIG. 1C, a middle refractive index layer may be provided between the dye-containing layer and the high refractive index layer. Further, as shown in FIG. 2E, a high refractive index layer may be provided between the transparent support and the low refractive index layer. Furthermore, as shown in FIG.
A middle refractive index layer may be provided between the transparent support and the high refractive index layer. The refractive index of the high refractive index layer is preferably from 1.65 to 2.40, and more preferably from 1.70 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 transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is 1.55 to 1.
Preferably it is 70. The thickness of the high refractive index layer and the middle 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 high refractive index layer and the middle refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less.

The high refractive index layer and the medium refractive index layer preferably contain inorganic fine particles having a high refractive index. The inorganic fine particles
The refractive index 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:
Includes titanium dioxide (eg, rutile, mixed crystals of rutile / anatase, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Titanium oxide, tin oxide and indium oxide are particularly preferred. The inorganic fine particles contain oxides or sulfides of these metals as main components and may further contain other elements. The main component means a component having the largest content (% by weight) of the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, P
b, Cd, As, Cr, Hg, Zn, Al, Mg, S
i, P and S are included. The inorganic fine particles may be surface-treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for surface treatment include:
Includes alumina, silica, zirconium oxide and iron oxide. Alumina and silica are preferred. Examples of the organic compound used for the surface treatment include a polyol, an alkanolamine, stearic acid, a silane coupling agent, and a titanate coupling agent. Silane coupling agents are most preferred. Two or more types of surface treatments may be performed in combination. The processing may be performed by combining the above.

For the high refractive index layer and the middle refractive index layer, it is preferable to use a polymer having a relatively high refractive index as a binder. 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. . Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups, and polymers having a halogen atom other than fluorine as a substituent,
High refractive index. When inorganic fine particles having a high refractive index are added to the high refractive index layer and the medium refractive index layer, it is particularly preferable to use a crosslinked anionic polymer as a binder. The crosslinked anionic polymer has a structure in which the main chain of the polymer having an anionic group is crosslinked. The anionic group has a function of maintaining the dispersed state of the inorganic fine particles. The crosslinked structure has a function of imparting a film-forming ability to the polymer to strengthen the high refractive index layer and the medium refractive index layer. Examples of the main chain of the polymer are preferably polyolefin (saturated hydrocarbon) and polyether. If a polymer is formed by a polymerization reaction at the same time as or after the application of the layer, these monomers can be effectively functioned before the application of the layer. As the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. Photopolymerization reactions are preferred. When a polymer is formed by a photopolymerization reaction, a low-pressure mercury lamp, a high-pressure mercury lamp,
An ultra-high pressure mercury lamp, a chemical lamp or a metal halide lamp can be used. Most preferably, a high-pressure mercury lamp having good irradiation efficiency is used. The same binder is used for other layers. In addition to the components described above, the high refractive index layer, the medium refractive index layer, and their coating solutions may contain a polymerization inhibitor, a leveling agent, a thickener, a coloring inhibitor, an ultraviolet absorber, a silane coupling agent, and an antistatic agent. Or an adhesion-imparting agent may be added.

(Low Refractive Index Layer) The refractive index of the low refractive index layer is as follows.
1.20 to 1.55, preferably 1.30
It is more preferably from 1.55 to 1.55. The thickness of the low refractive index layer is preferably 50 to 400 nm,
More preferably, it is 50 to 200 nm. The low refractive index layer preferably has a porosity of 3 to 50% by volume, and more preferably 5 to 35% by volume. The voids in the low refractive index layer can be formed as microvoids between particles or within particles using fine particles. The average particle size of the fine particles is 0.5 to 200 mm
Is preferably 1 to 100 nm, more preferably 3 to 70 nm, and most preferably 5 to 40 nm. The particle size of the fine particles is preferably as uniform (monodispersed) as possible. As the fine particles, inorganic fine particles (for example,
Fine particles made of SiO ₂ or MgF ₂ ) or organic fine particles (for example, fluorine-containing polymer fine particles) are used.

Microvoids between particles can be formed by stacking at least two or more fine particles. Increasing the porosity lowers the refractive index of the low refractive index layer. When microparticles are formed by stacking fine particles,
By adjusting the particle size of the fine particles, the size of the microvoids between the particles can be easily adjusted to an appropriate value (without scattering light and causing no problem in the strength of the low refractive index layer). Further, by making the particle diameter of the fine particles uniform, an optically uniform low refractive index layer in which the size of the microvoids between particles is also uniform can be obtained. Thus, the low refractive index layer can be a microvoid-containing porous film microscopically, but can be an optically or macroscopically uniform film. The microvoids between particles are
It is preferable that the inside of the low refractive index layer is closed by the fine particles and the polymer. Preferably, the low refractive index layer comprises a polymer in an amount of 5 to 50% by weight. The polymer has a function of adhering the fine particles and maintaining the structure of the low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the void. The amount of the polymer is 10 to 30% by weight of the total amount of the low refractive index layer.
It is preferred that

In order to adhere the fine particles with a polymer, it is preferable to form the polymer shell around the fine particles as a core or to use a polymer as a binder between the fine particles. The polymer used as the shell or the binder is preferably a polymer having a saturated hydrocarbon or polyether as a main chain, and more preferably a polymer having a saturated hydrocarbon as a main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as a main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of the monomer having two or more ethylenically unsaturated groups include esters of a polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol Tetra (meta)
Acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (Meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester) , 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylic acid Amides include. The polymer having a polyether as a main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound.

Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by a reaction of a crosslinkable group.
Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. Vinyl sulfonic acid, acid anhydride, cyanoacrylate derivative, melamine,
Etherified methylols, esters and urethanes can also be used as monomers to introduce the crosslinked structure. A functional group that exhibits crosslinkability as a result of a decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above-mentioned compound, but may be one which shows reactivity as a result of decomposition of the above-mentioned functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the monomer, a photopolymerization initiator is more preferable than a thermal polymerization initiator. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides,
There are 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-
Hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone . Examples of benzoins include benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,
4-Dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone are included.
Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

The polymer used as the binder is preferably formed by adding a monomer to the coating solution for the low-refractive-index layer, and simultaneously or after the application of the low-refractive-index layer, by a polymerization reaction (and, if necessary, a crosslinking reaction). . A small amount of polymer (eg, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate,
Polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) may be added.

(Anti-reflection film) The anti-reflection film may be provided with layers other than those described above. For example, an undercoat layer, a hard coat layer, an adhesive layer, a shield layer, a slip layer, or an antistatic layer may be provided on the transparent support in addition to the dye-containing layer. The shield layer is provided to shield electromagnetic waves and infrared rays. The anti-reflection film may have an anti-glare function for scattering external light.
The anti-glare function is obtained by forming irregularities on the surface of the antireflection film. An overcoat layer may be provided on the low refractive index layer. The overcoat layer preferably contains a fluorine-containing compound. The haze of the antireflection film is preferably from 3 to 30%, more preferably from 5 to 20%, and most preferably from 7 to 20%. Anti-reflection film is used for liquid crystal display (LCD), plasma display panel (PD)
P), electroluminescent display (EL)
D) or an image display device such as a cathode ray tube display device (CRT). The transparent support side of the antireflection film is adhered to the image display surface of the image display device. When the antireflection film of the present invention is used as an antireflection filter of a plasma display panel (PDP), a particularly remarkable effect is obtained.

[0123]

EXAMPLES Example 1 (Preparation of Transparent Support) Both surfaces of a transparent polyethylene terephthalate film having a thickness of 90 μm were subjected to corona discharge treatment. A styrene-butadiene copolymer latex to which a hardening aid and a coating aid were added was applied on both sides of the film to provide a first undercoat layer having a thickness of 0.15 μm. First
Acrylic latex (HA16, manufactured by Nippon Acrylic Co., Ltd.) in which a hardening aid and a coating aid are added on the undercoat layer
Was applied to form a second undercoat layer having a thickness of about 0.1 μm.

(Formation of Dye-Containing Layer) 5% by weight of dipentaerythritol hexaacrylate and 0.5% by weight of a photopolymerization initiator (Irgacure 90) were added to methyl ethyl ketone.
7, Ciba-Geigy), 0.2% by weight of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 0.2% by weight of visible light absorbing dye (compound 4), 0.4% by weight Was dissolved in the visible light absorbing dye (Compound 5). The resulting solution was applied using a wire bar on the second undercoat layer on one side of the transparent support so that the dry film thickness was 8 μm.
After drying, the mixture was heated to 100 ° C. and irradiated with ultraviolet rays for 1 minute using a 12 / Wcm high-pressure mercury lamp to crosslink. Thereafter, the mixture was allowed to cool to room temperature to form a dye-containing layer. The absorption of the obtained film had peaks at 488 nm and 580 nm, the peak absorbances were 0.4 and 0.5, respectively, and the half widths were 35 nm and 30 nm, respectively.

(Preparation of Titanium Dioxide Dispersion) Titanium dioxide (primary particle weight average particle diameter: 50 nm, refractive index 2.7)
0) 30 parts by weight, 3 parts by weight of the following anionic monomer (1), 3 parts by weight of the following anionic monomer (2), and 64 parts by weight of methyl ethyl ketone were dispersed by a sand grinder to prepare a titanium dioxide dispersion. .

[0126]

Embedded image

[0127]

Embedded image

(Preparation of Coating Solution for High Refractive Index Layer) To 151 g of the above titanium dioxide dispersion, 30 g of dipentaerythritol hexaacrylate, 1.68 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), and a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.56 g,
483 g of methyl ethyl ketone and cyclohexanone 1
834 g was added, the mixture was stirred at room temperature for 30 minutes, and filtered through a 1 μm polypropylene filter to prepare a coating liquid for a high refractive index layer.

(Formation of High Refractive Index Layer) On the dye-containing layer,
Apply the coating solution for high refractive index layer with a bar coater,
After drying, the layer was cured by irradiating ultraviolet rays. Thus, a high refractive index layer having a thickness (dry film thickness) of 80 nm was formed.

(Preparation of Coating Solution for Low Refractive Index Layer) 26 g of dipentaerythritol hexaacrylate, 1.0 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) )
Was dissolved in 4296 g of isopropyl alcohol, and 478 g of a 30% by weight methanol dispersion of colloidal silica whose surface was treated with a silane coupling agent was added. The mixture was stirred at room temperature for 30 minutes, and then filtered through a 1 μm polypropylene filter. Thus, a coating solution for a low refractive index layer was prepared.

(Formation of Low Refractive Index Layer) A coating solution was applied on the high refractive index layer to a thickness of 95 nm using a wire bar.
After drying at 20 ° C., ultraviolet irradiation was performed to crosslink. Thereafter, the mixture was allowed to cool to room temperature to form a low refractive index layer. Thus, an antireflection film was prepared. The average reflectance of the obtained antireflection film was 0.4%. When the transparent support side of the antireflection film was adhered to the display surface of a plasma display (three primary color emission wavelengths: 450 nm, 530 nm, 610 nm), the display contrast was improved from 10: 1 to 14: 1.

Example 2 In Example 1, the dye-containing layer further contained 0.1% by weight of an infrared light absorbing dye (Compound Example 112) and 0.1% by weight of an infrared light absorbing dye (Compound Example). 1
An anti-reflection film was prepared in the same manner as in Example 2 except that 14) was added. The reflectance of this filter was 0.4%. When this antireflection film was mounted on a plasma display, the contrast of the display was 10: 1.
To 14: 1. In addition, when we tested the operability of the remote control by attaching it to the plasma display,
The filter of Example 1 had no malfunction which occurred 15 times out of 100 times, whereas the filter of Example 2 did not.

Example 3 An antireflection film was prepared in exactly the same manner as in Example 2 except that a glass plate was used instead of polyethylene terephthalate as the transparent support. The same results as in Example 2 were obtained. Obtained.

[Comparative Example 1] On the dye-containing layer prepared in Example 1, using a vacuum evaporation method, magnesium fluoride, silicon dioxide, titanium dioxide, and magnesium fluoride were formed in the order of an optical film thickness of λ / 4. The layers were stacked so as to satisfy the conditions. This film and the film of Example 1 were subjected to a tape peeling test by a cross-cut method.
While the peeling was zero during 0 times, the film of Comparative Example 1 showed peeling points on 3 out of 100 films.

Example 4 (Formation of Dye-Containing Layer) In 49.3 g of acetone, 0.23 g of a visible light absorbing dye (Compound 56), 30 g of dipentaerythritol hexaacrylate, a photopolymerization initiator (Irgacure 907, Ciba-Geigy) 1.50 g) and a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
0.50 g was added, the mixture was stirred at room temperature for 30 minutes, and filtered through a 1 μm polypropylene filter to prepare a coating solution for a dye-containing layer. The obtained solution was applied on the second undercoat layer of the transparent support prepared in Example 1 with a bar coater, dried at 120 ° C., and irradiated with ultraviolet rays to cure the layer. Thus, a dye-containing layer having a thickness (dry film thickness) of 7.0 μm was formed. The absorption of the obtained film is 5
It had a peak at 74 nm, the peak absorbance was 0.7, and the half width was 60 nm.

(Formation of High Refractive Index Layer) In a mixed solvent of 1921 g of methyl ethyl ketone and 1921 g of cyclohexanone, 134 g of the titanium dioxide dispersion prepared in Example 1 was added.
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH
A, 52 g of Nippon Kayaku Co., Ltd., 3.0 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.)
0 g was added, the mixture was stirred at room temperature for 30 minutes, and filtered with a 1 μm polypropylene filter to prepare a coating solution for a high refractive index layer. A coating solution for a high refractive index layer was applied on the dye-containing layer with a bar coater, dried at 120 ° C., and irradiated with ultraviolet rays to cure the layer. In this way, the thickness (dry film thickness)
Formed a high refractive index layer having a thickness of 80 nm.

(Preparation of coating solution for low refractive index layer) Reactive fluoropolymer (JN-7219, manufactured by Nippon Synthetic Rubber Co., Ltd.)
1.3 g of t-butanol was added to 2.50 g, and 1
After stirring for 0 minutes, the mixture was filtered through a 1 μm polypropylene filter to prepare a coating solution for a low refractive index layer.

(Formation of Low Refractive Index Layer) A coating solution was applied on the high refractive index layer using a bar coater so as to have a dry film thickness of 95 nm, and dried at 120 ° C. for 30 minutes to cure the layer. A low refractive index layer was formed. Thus, an antireflection film was prepared. The average reflectance of the obtained antireflection film was 0.4%. The contact angle of water on the surface of the anti-reflection film was 102 degrees, and even a fingerprint could be easily wiped off. On the transparent support side, a plasma display (three primary color emission wavelengths 450 nm, 530 nm, 610 n)
When attached to the display surface of m), the display contrast was improved from 10: 1 to 14: 1.

Example 5 (Preparation of Coating Solution for Medium Refractive Index Layer) To the titanium dioxide dispersion prepared in Example 1, dipentaerythritol hexaacrylate, a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), A photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) and methyl ethyl ketone were added.
The addition amount was adjusted such that the refractive index of the middle refractive index layer became 1.72.

(Formation of Medium Refractive Index Layer) On the dye-containing layer prepared in Example 1, a coating liquid for a medium refractive index layer was applied using a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, a middle refractive index layer having a thickness (dry film thickness) of 75 nm was formed.

(Preparation of Coating Solution for High Refractive Index Layer) Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) was added to the titanium dioxide dispersion prepared in Example 1.
), A photopolymerization initiator (Irgacure 907, Ciba-Geigy), a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) and methyl ethyl ketone. The addition amount was adjusted so that the refractive index of the high refractive index layer was 2.20.

(Formation of High Refractive Index Layer) A coating liquid for a high refractive index layer was applied on the medium refractive index layer with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, a high refractive index layer having a thickness (dry film thickness) of 80 nm was formed.

(Formation of Low Refractive Index Layer) As in Example 1,
A low refractive index layer having a thickness of 80 nm was provided on the high refractive index layer to prepare an antireflection film. The reflectance of the obtained antireflection film was 0.4%. When this antireflection film was mounted on a plasma display, the contrast of the display was improved from 10: 1 to 14: 1.

Example 6 An anti-reflection coating was prepared in the same manner as in Example 1 except that no infrared light absorbing dye and visible light absorbing dye were added to the dye-containing layer in the preparation of the anti-reflection film of Example 1. A membrane was made. The layer to which the infrared light absorbing dye and the visible light absorbing dye were not added functions as a hard coat layer. To methyl ethyl ketone, 5% by weight of polyvinyl butyral (Denka butyral 2000L, manufactured by Denki Kagaku Kogyo KK), 0.2% by weight of a visible light absorbing dye (compound 56) and 0.4% by weight of an infrared light absorbing dye ( Compound 114) was dissolved to prepare a dye-containing layer coating solution. A dye-containing layer coating solution is applied on the second undercoat layer on which the hard coat layer (the layer from which the dye has been removed from the dye-containing layer) is not provided so that the dry film thickness is 8 μm,
After drying at 120 ° C. for 5 minutes, a dye-containing (back) layer was formed. The absorption of the obtained film was 488 nm and 580 nm.
It had a peak at nm, the peak absorbance was 0.4 and 0.5, respectively, and the half width was 35 nm and 30 nm, respectively. When the dye-containing (back) layer side of the antireflection film was pasted on the plasma display, the display contrast was improved from 10: 1 to 14: 1.

[0145]

According to the present invention, it is possible to suppress deterioration of contrast in a self-luminous display panel. Further, an antireflection film having high strength can be manufactured at low cost.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a main layer configuration of an antireflection film in which a dye-containing layer is provided between a transparent support and a low refractive index layer.

FIG. 2 is a schematic cross-sectional view showing a main layer structure of an antireflection film in which a dye-containing layer is provided on a surface of a transparent support opposite to a low refractive index layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent support 2 Dye containing layer 3 Medium refractive index layer 4 High refractive index layer 5 Low refractive index layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01J 11/02 G02B 1/10 Z

Claims (9)

[Claims] 1. A coating layer comprising a dye-containing layer and a low-refractive-index layer having a refractive index lower than that of the transparent support on one surface of the transparent support in this order, The dye-containing layer has the following formulas (1), (2),
(4) An antireflection film containing a visible light absorbing dye represented by (5) or (6). Embedded image Wherein, Z ¹ and Z ² are each independently a non-metallic atomic group forming a nitrogen-containing heterocyclic ring; R ¹ and R ^2,
Each independently an alkyl, alkenyl or aralkyl group; L ¹ is a methine chain consisting of an odd number of methines; a, b and c are each independently 0 or 1; ¹ is an anion. Embedded image In the formula, Ar ¹ and Ar ² are each independently an aryl group, an aromatic heterocyclic group, or a group represented by the formula (3). Embedded image In the formula, Z ³ is a group of non-metallic atoms forming a nitrogen-containing heterocyclic ring; R ³ is an alkyl group, an alkenyl group or an aralkyl group; and d is 0 or 1. Embedded image Wherein Y ¹ and Y ² are each independently a group of non-metallic atoms forming an aliphatic ring or a heterocyclic ring;
² is a methine chain consisting of an odd number of methines. Embedded image Wherein Y ³ is a group of non-metallic atoms forming an aliphatic ring or a heterocyclic ring; R ⁴ and R ⁵ are each independently an alkyl group; and R ⁶ is a hydrogen atom, an alkyl group , An alkoxy group, an aryloxy group, a halogen atom,
It is an alkoxycarbonyl group, cyano, nitro, amino, amide group, acyloxy group, sulfo or carboxyl. Embedded image In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom,
An alkyl group, an aralkyl group or an aryl group;
⁹ is an alkyl group, an alkoxy group, a halogen atom, an amide group, an alkoxycarbonyl group, a cyano, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group or a hydroxyl; Or 4; R ⁷ and R
⁸ may combine with each other or with adjacent R ⁹ to form a heterocyclic ring; R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryl group Oxy, aralkyl, cyano, amide, alkoxycarbonylamino, sulfonamide, ureido, alkylthio, arylthio, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfonyl, acyl, amino, alkylamino Or an arylamino group; Za,
Zb and Zc each independently, -C (R ¹¹⁾ = or a -N =; and, R ¹¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group,
It is an alkoxy group, an aryloxy group, an amino, an alkylamino group, an arylamino group or an alkoxycarbonyl group. 2. A low refractive index having a lower refractive index than that of the transparent support, provided on one surface of the transparent support as a dye-containing layer coating layer, and provided on the other surface. An anti-reflection film comprising a visible light absorbing dye represented by the following formula (1), (2), (4), (5) or (6): . Embedded image Wherein, Z ¹ and Z ² are each independently a non-metallic atomic group forming a nitrogen-containing heterocyclic ring; R ¹ and R ^2,
Each independently an alkyl, alkenyl or aralkyl group; L ¹ is a methine chain consisting of an odd number of methines; a, b and c are each independently 0 or 1; ¹ is an anion. Embedded image In the formula, Ar ¹ and Ar ² are each independently an aryl group, an aromatic heterocyclic group, or a group represented by the formula (3). Embedded image In the formula, Z ³ is a group of non-metallic atoms forming a nitrogen-containing heterocyclic ring; R ³ is an alkyl group, an alkenyl group or an aralkyl group; and d is 0 or 1. Embedded image Wherein Y ¹ and Y ² are each independently a group of non-metallic atoms forming an aliphatic ring or a heterocyclic ring;
² is a methine chain consisting of an odd number of methines. Embedded image Wherein Y ³ is a group of non-metallic atoms forming an aliphatic ring or a heterocyclic ring; R ⁴ and R ⁵ are each independently an alkyl group; and R ⁶ is a hydrogen atom, an alkyl group , An alkoxy group, an aryloxy group, a halogen atom,
It is an alkoxycarbonyl group, cyano, nitro, amino, amide group, acyloxy group, sulfo or carboxyl. Embedded image In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom,
An alkyl group, an aralkyl group or an aryl group;
⁹ is an alkyl group, alkoxy group, halogen atom, amide group, alkoxycarbonyl group, cyano, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group or hydroxyl; n is 1, 2, 3 Or 4; R ⁷ and R
⁸ may combine with each other or with adjacent R ⁹ to form a heterocyclic ring; R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryl group Oxy group, aralkyl group, cyano, amide group, alkoxycarbonylamino group, sulfonamide group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino, alkylamino group Or an arylamino group; Za,
Zb and Zc each independently, -C (R ¹¹⁾ = or a -N =; and, R ¹¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group,
It is an alkoxy group, an aryloxy group, an amino, an alkylamino group, an arylamino group or an alkoxycarbonyl group. 3. The method according to claim 1, wherein the visible light absorbing dye is 470 to 51.
3. The antireflection film according to claim 1, having a maximum absorption wavelength in a wavelength region of 0 nm, a wavelength region of 540 to 600 nm, or a wavelength region of 640 to 730 nm. 4. The dye-containing layer according to claim 1, further comprising an infrared-absorbing dye represented by the following formula (7), (8), (9), (10) or (11). 3. The anti-reflection film according to 2. Embedded image Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group; and X ² is an anion. Embedded image Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group; and X ² is an anion. Embedded image Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group; and X ³ is an anion. Embedded image Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group; and X ³ is an anion. Embedded image Wherein R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R
²⁹ , R ³⁰ , R ³¹ , R ³² and R ³³ are each independently
A hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or an acyl group, or 5
R ³⁴ , R ³⁵ and R ³⁶ form a membered or 6-membered ring;
Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, a cyano, a nitro, an amino, an amide group, an acyloxy group, a sulfo or a carboxyl;
And m is an integer from 1 to 3. 5. The method according to claim 1, wherein the dye-containing layer and the low refractive index layer have
2. The antireflection film according to claim 1, wherein a high refractive index layer having a refractive index higher than that of the transparent support is provided as a coating layer. 6. Between the transparent support and the low refractive index layer,
3. The antireflection film according to claim 2, wherein a high refractive index layer having a refractive index higher than that of the transparent support is provided as a coating layer. 7. On one surface of the transparent support, a dye-containing layer and a low refractive index layer having a refractive index lower than that of the transparent support are provided as a coating layer in this order, An antireflection film in which the dye-containing layer contains a visible light absorbing dye having a maximum absorption wavelength in a wavelength region of 470 to 510 nm, a wavelength region of 540 to 600 nm, or a wavelength region of 640 to 730 nm. 8. A low refractive index, which is provided as a dye-containing layer coating layer on one surface of a transparent support and has a refractive index lower than that of the transparent support on the other surface. Layer is provided as a coating layer and the dye-containing layer
70 to 510 nm wavelength range, 540 to 600 nm
Or an antireflection film containing a visible light absorbing dye having a maximum absorption wavelength in the wavelength region of 640 to 730 nm. 9. A plasma display panel provided with the anti-reflection film according to claim 1 as an anti-reflection filter on a display surface side.