JP2000275432A - Display filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color purity and contrast of a luminescent color and to provide a display filter having good transmission characteristic, transmittance, reflectance of visible radiation without largely impairing luminance and visibility, by forming it from a transparent conductive layer with a specific surface resistance and a coloring material layer, and setting a minimum transmittance at a specific wavelength within a specific range of a maximum transmittance at a different specific wavelength. SOLUTION: This display filter comprises at least a transparent conductive layer 10 with 1-10 Ω/(square) surface resistance and a coloring material layer, and a minimum transmittance at 580-605 nm wavelength is 20-85% of a maximum transmittance at 615-640 nm wavelength. A PET film (thickness: 75 μm) is used as a transparent substrate 20, and a SnO2 thin film, a silver thin film, a silver-palladium alloy thin film are laminated on one of the main surfaces of the substrate to form the transparent conductive layer 10 to obtain a sputtered film. As a transparent support body 40 as the coloring material layer, adding an organic coloring material and an ultraviolet absorbent provides 3 mm thick polymethyl methacrylate plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a filter for a display, and more particularly, to a filter for a plasma display, while improving the color purity and contrast of the emission color of a color plasma display while improving the luminance and brightness.
It has excellent transmission characteristics that do not significantly impair visibility, transmittance, visible light reflectance, and furthermore, an electromagnetic wave shielding ability that shields electromagnetic waves generated from a plasma display, which is said to be harmful to health, and The present invention relates to a filter for a display having a near-infrared cutoff function of blocking near-infrared rays that may cause erroneous operation of peripheral electronic devices.

[0002]

2. Description of the Related Art Optoelectronics-related components and equipment have been remarkably advanced and spread as society has become highly information-oriented. Among them, displays have become extremely popular for televisions, personal computers, etc., and their thickness and size have been reduced. 2. Description of the Related Art In recent years, plasma displays have attracted attention for use in large-sized thin TVs and thin display devices, and have already begun to appear on the market. However, a plasma display generates a strong leakage electromagnetic field due to its structure and operating principle. In recent years, the effects of leaked electromagnetic fields on the human body and other devices have been reported. For example, the VCCI (Voluntary Control
l Council for Interference by data processing equi
pment electronic office machine).

[0003] In addition, the plasma display emits near-infrared light and acts on peripheral electronic devices such as a cordless phone to cause a malfunction. A wavelength that is particularly problematic is used in remote control and transmission optical communication.82
0 nm, 880 nm, and 980 nm. Therefore, it is necessary to cut light in the near-infrared wavelength range of 800 to 1000 nm to a level that does not cause any practical problem.

With respect to the near-infrared cut ability, it has been conventionally known to produce a near-infrared absorbing filter using a near-infrared absorbing dye. However, the near-infrared absorbing dye has a problem that deterioration due to environment such as humidity, heat, and light occurs, and changes in optical characteristics such as near-infrared cut ability and transmission color of a display filter occur with time. Furthermore, since a plasma display emits near-infrared light of a problematic intensity over a wide near-infrared wavelength region, it is necessary to use a near-infrared absorption filter having a large absorption rate in the near-infrared region over a wide wavelength region. However, in order to reduce the transmittance of near-infrared rays to a level that does not cause a problem,
The amount of the near-infrared dye to be contained in the display filter had to be increased, and the accompanying decrease in the visible light transmittance was also a problem. Since there is a decrease in transmittance due to the formation of a member for shielding electromagnetic waves or the like, the display filter has a lower transmittance.

[0005] In order to shield a leakage electromagnetic field (electromagnetic wave), it is necessary to cover the display surface with a conductive material having high conductivity. Generally grounded metal mesh or synthetic fiber or metal fiber mesh with metal coating, or
After the metal film is formed, for example, a conductive lattice pattern film that is etched into a lattice pattern is used.The conductive mesh or the conductive lattice pattern film may have a portion that does not transmit light emitted from the display or may have a moiré. Problems such as generation and high cost due to poor yield are problems. Therefore, a transparent conductive film typified by ITO (Indium Tin Oxide) is sometimes used for the electromagnetic wave shielding layer. As the transparent conductive film, a metal thin film such as gold, silver, copper, platinum, and palladium, an oxide semiconductor thin film such as indium oxide, stannic oxide, and zinc oxide, a metal thin film and a high-refractive-index transparent thin film are alternately laminated. There are multilayer thin films. Among them, a metal thin film can have conductivity, but cannot have a high visible light transmittance due to reflection and absorption of metal over a wide wavelength range. Further, the oxide semiconductor thin film is superior in transparency to the metal thin film, but inferior in conductivity, and has poor near-infrared reflectivity.

A color plasma display is a red (R) light-emitting phosphor such as (Y, Gd, Eu) BO ₃ which emits light by excitation with vacuum ultraviolet light generated by a DC or AC discharge of a rare gas;
n) Green (G) light emitting phosphor such as ₂ SiO ₄ , (Ba, Eu) MgAl ₁₀ O
₁₇ : Blue (B) light-emitting phosphor such as EU is formed in a display cell constituting a pixel. In addition to the color purity, the phosphor is selected based on the applicability to the discharge cell, short afterglow time, luminous efficiency, heat resistance, etc. Many require. In particular, the emission spectrum of the red light emitting phosphor has a wavelength of 580 nm to 700 nm.
It shows several emission peaks up to the extent, and the emission peak on the short wavelength side with relatively high intensity is yellow-orange emission, so that red emission has poor orange-color purity. There is. Xe and Ne for rare gases
In the case of using a mixed gas of the above, orange light emission due to light emission relaxation in the Ne excited state also deteriorates color purity. Further, blue light emission and green light emission are broad bands, and the peak wavelength and its broadness, that is, unnecessary light emission, are factors that lower the color purity.

[0007] The high color purity is determined by, for example, using RGB three colors as vertices in a coordinate system representing hue and saturation by chromaticity x on the horizontal axis and chromaticity y on the vertical axis determined by the International Commission on Illumination (CIE). It can be represented by the size of the color reproduction range indicated by the size of the triangle.
Due to the low color purity, the color reproduction range of plasma display emission is NTSC (National Television System Committ).
ee) It is usually narrower than the color range indicated by the chromaticity of the three colors RGB defined by the method.

Further, in addition to bleeding of light emission between display cells, emission of each color contains unnecessary light over a wide range, and the required light emission is inconspicuous. It is also a factor that lowers the contrast. Further, a plasma display generally has a lower contrast in a bright state in which external light due to indoor lighting or the like is present than in a dark state. This occurs because the phosphor or the like reflects external light and unnecessary light does not make the necessary light stand out. The contrast ratio of the plasma display panel is 100 to 200 in the hint, and the ambient illuminance is 100 lx.
The brightness is about 10 to 30 and the improvement is required. The low contrast also narrows the color reproduction range.

Attempts to improve the color purity of displays using dyes include, for example, JP-A-58-153904.
There are JP-A-60-22102 and JP-A-59-221943, and JP-A-58-153904 actually mentions application to a plasma display panel (plasma display panel). However, in these prior arts, there is no mention of a combination with a transparent conductive layer as an electromagnetic wave shield which is essential when used in a plasma display panel. Further, there is no specific reference to the dye used in the present invention. As can be seen from the spectra shown in the examples, the dye disclosed in JP-A-58-153904 has not only an unnecessary emission but also a suitable emission reduction amount, that is, an absorption amount that cannot be ignored. Therefore, when combined with a transparent conductive layer, the disclosed dyes are insufficient for improving both the color purity of emitted light and the emission luminance.

The plasma display filter is installed on the front of the display to block near infrared rays and electromagnetic waves emitted from the plasma display. In order to improve the contrast, there is a method of lowering the visible light transmittance to reduce the transmission of external light reflection or the like in the phosphor, but if the visible light transmittance is extremely low, the brightness and the sharpness of the image are reduced. Will do.

[0011]

SUMMARY OF THE INVENTION In view of the above-mentioned prior art, an object of the present invention is to provide a plasma display filter that significantly impairs luminance and visibility while improving the color purity and contrast of emission color of a color plasma display. It has excellent transmission characteristics, transmittance and visible light reflectance, and also has the ability to shield electromagnetic waves generated from the plasma display, which are said to be harmful to health, and erroneous operation of peripheral electronic devices It is an object of the present invention to provide a display filter having a near-infrared cut ability for blocking near-infrared rays.

[0012]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have developed a display filter capable of shielding extremely intense electromagnetic waves generated from a plasma display. In order to obtain a transparent conductive layer of 1 to 10 Ω / □, a wavelength of 5
The minimum transmittance at 80 to 605 nm is 615 to 6
The present inventors have found that a display filter having a maximum transmittance of 20 to 85% at a wavelength of 40 nm can improve the color purity and contrast of the emission color of a plasma display, and have reached the present invention. That is, the present invention (1) comprises at least a transparent conductive layer having a sheet resistance of 1 to 10 Ω / □ and a dye layer, and has a minimum transmittance at a wavelength of 580 to 605 nm of 10 to a maximum transmittance at a wavelength of 615 to 640 nm. (2) a maximum transmittance at a wavelength of 450 to 480 nm, a maximum transmittance at a wavelength of 510 to 535 nm, and a maximum transmittance at a wavelength of 615 to 640 nm are 45% to 85%, respectively. (3) The display filter according to (1), wherein the minimum transmittance at a wavelength of 540 to 580 nm is 510 to 550.
The display filter according to any one of (1) and (2), which has a maximum transmittance at 535 nm of 10 to 90%, and (4) a wavelength of 520 to 540 n.
m, the transmittance monotonously decreases as the wavelength becomes longer. (5) The filter for a display according to any one of (1) to (3), (5) a wavelength of 480 to 510n.
m, wherein the minimum transmittance at m is 50 to 90% of the maximum transmittance at a wavelength of 450 to 480 nm and / or the maximum transmittance at a wavelength of 510 to 535 nm. (6) The high refractive index transparent thin film layer (B) and the metal thin film layer (C), wherein the transparent conductive layer is formed on at least one main surface of the transparent substrate (A). (A) is a transparent conductive film which is repeatedly laminated 1 to 4 times in sequence with (B) / (C) as a repeating unit, and further laminated thereon at least the high refractive index transparent thin film layer (B). The display filter according to any one of (1) to (5), (7) the transparent support (D),
The display filter according to any one of (1) to (6), which is formed via an adhesive material (E), (8) antireflection properties, antiglare properties, and antireflection antiglare properties. A functional transparent layer (F) having at least one function selected from antistatic property, anti-Newton ring property, gas barrier property, hard coat property and antifouling property is formed directly or via an adhesive (E). (1) The display filter according to any one of (1) to (7), (9) a transparent substrate (A) in which the chromaticity correction layer contains a dye, and a transparent support containing a dye. (D), comprising at least one of a dye-containing adhesive (E) and a dye-containing functional transparent layer (F). Related to display filters That. (10) The display filter according to any one of claims 1 to 9, wherein the dye is one or more types of dyes, at least one of which is a tetraazaporphyrin compound. (1
1) The display filter according to (10), wherein the tetraazaporphyrin compound is a dye represented by the formula (1) [formula 2].

[0013]

Embedded image [In the formula (1), A ^{1 to} A ⁸ each independently represent a hydrogen atom,
Halogen atom, nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, 1-2 carbon atoms
An alkyl group, a halogenoalkyl group, an alkoxy group,
Alkoxyalkoxy group, aryloxy group, monoalkylamino group, dialkylamino group, aralkyl group, aryl group, heteroaryl group, alkylthio group, or
Represents an arylthio group, A ¹ and A ² , A ³ and A ⁴ , A
⁵ and A ⁶ , A ⁷ and A ⁸ may each independently form a ring other than an aromatic ring via a linking group, and M is two hydrogen atoms, a divalent metal atom, or a trivalent one. Represents a substituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom. ]

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The display filter of the present invention comprises at least a transparent conductive layer having a sheet resistance of 1 to 10 Ω / □ and a dye layer, and has a minimum transmittance at a wavelength of 580 to 605 nm and a maximum transmittance at a wavelength of 615 to 640 nm. The transmittance is 20 to 85%.

The transparent conductive layer in the present invention is composed of at least one transparent conductive film formed of a single layer or a multilayer thin film formed on the main surface of the transparent substrate (A). A transparent conductive layer is formed on the transparent substrate (A) to obtain a transparent conductive laminate. As the single-layer transparent conductive film, there are the above-mentioned conductive mesh and conductive lattice pattern film, metal thin film and oxide semiconductor thin film. Preferably, a multilayer thin film having a high conductivity for absorbing electromagnetic waves and a large number of reflection interfaces for reflecting electromagnetic waves, in which a metal thin film and a high-refractive-index transparent thin film are laminated, is preferable. A multilayer thin film consisting of a metal thin film and a high-refractive-index transparent thin film is laminated. Has favorable characteristics in all of conductivity, near-infrared cut ability, and visible light transmittance.

Examples of the transparent substrate (A) include molded articles of inorganic compounds such as glass and quartz and transparent molded articles of organic polymers. Polymer molded articles can be used more preferably because they are light and hard to break. The polymer molded article may be transparent in the visible wavelength region, and specific examples thereof include polyethylene terephthalate, polyether sulfone, polystyrene, polyethylene naphthalate, polyarylate, polyether ether ketone, polycarbonate,
Polyamides such as polyethylene, polypropylene, and nylon 6, polyimides, cellulose resins such as triacetyl cellulose, polyurethanes, fluorine resins such as polytetrafluoroethylene, vinyl compounds such as polyvinyl chloride, polyacrylic acid, polyacrylic acid esters, Polyacrylonitrile, addition polymer of vinyl compound, vinyl compound such as polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride, vinyl compound such as vinylidene fluoride / trifluoroethylene copolymer, ethylene / vinyl acetate copolymer, or fluorine Examples thereof include, but are not limited to, copolymers of system compounds, polyethers such as polyethylene oxide, epoxy resins, polyvinyl alcohol, and polyvinyl butyral. These transparent polymer molded products may be in the form of a plate (sheet) or film as long as the main surface is smooth. When a sheet-like polymer molded product is used as the substrate, the substrate has excellent dimensional stability and mechanical strength, and thus a transparent conductive laminate having excellent dimensional stability and mechanical strength is obtained. When it is required, it can be suitably used. In addition, since a transparent polymer film has flexibility and a transparent conductive film can be continuously formed by a roll-to-roll method, when this is used, it is efficient and long. This is because the transparent conductive laminate can be produced over a large area, and the film-like transparent conductive laminate can be attached to the display glass or the glass support of the display filter to prevent scattering when glass breaks. Can also be suitably used. In this case, the thickness of the film is usually 10 to 25.
One having a thickness of 0 μm is used. When the thickness of the film is 10 μm or less, the mechanical strength as a base material is insufficient, and the thickness is 250 μm.
Above is insufficient in flexibility, so that it is not suitable for winding and using a film with a roll.

These substrates are preliminarily subjected to an etching process such as a sputtering process, a corona process, a flame process, an ultraviolet ray irradiation, an electron beam irradiation or the like, or an undercoating process, and a transparent substrate of a transparent conductive film formed thereon. A treatment for improving the adhesion to A) may be performed. Transparent substrate (A)
An inorganic layer such as an arbitrary metal may be formed between the transparent conductive film and the transparent conductive film. Before forming the transparent conductive film, dust-proofing treatment such as solvent cleaning or ultrasonic cleaning may be performed as necessary. In order to improve the scratch resistance of the transparent conductive laminate, a hard coat layer may be formed between the transparent substrate (A) and the thin film layer, or on the other main surface where the transparent conductive film is not formed.

In VCCI, the radiated electric field intensity is less than 50 dBμV / m in Class 1 which indicates a regulation value for industrial use, and 40 dBμ in Class 2 which indicates a regulation value for home use.
V / m, but the radiated electric field intensity of the plasma display is in the range of 20 to 90 MHz, 40 dBμV / m for a diagonal of about 20 inches, and 50 d for a diagonal of about 40 inches.
Since it exceeds BμV / m, it cannot be used for home use as it is. The radiated electric field strength of the plasma display is higher as the size and brightness of the screen, that is, the larger the power consumption, the stronger the electromagnetic wave shielding material having a high shielding effect is required.

The present inventors have proposed that a transparent conductive layer serving as an electromagnetic wave shield must have a sheet resistance of 10 to 1 Ω in order to have an electromagnetic wave shield function required for a plasma display in addition to a high visible light transmittance and a low visible light reflectivity. / □ It is necessary to have low-resistance conductivity. In the present invention, the visible light transmittance and the visible light reflectance are JIS (R-3106) based on the wavelength dependence of the transmittance and the reflectance.
It is calculated according to:

Further, in order to cut off near-infrared rays of high intensity emitted from the plasma display to a level that does not cause a practical problem, a filter for display of 800 to 1000 nm is required.
It has been found that it is preferable to make the light transmittance in the near-infrared wavelength region of 20% or less. However, due to the demand for reducing the number of members and the limit of near-infrared absorption using a dye, the transparent conductive layer has a near-infrared cut property. It is desirable to have For the near-infrared cut, reflection by free electrons of a metal can be used. However, if the metal thin film layer is thickened, the visible light transmittance is reduced as described above, and if the metal thin film layer is thinned, the near-infrared reflection is weakened. Therefore, by stacking one or more layers of a laminated structure in which a metal thin film layer having a certain thickness is sandwiched between high refractive index transparent thin film layers,
The visible light transmittance can be increased and the overall thickness of the metal thin film layer can be increased, and the visible light transmittance and the visible light reflection can be controlled by controlling the number of layers and / or the thickness of each layer. Rate, near-infrared transmittance, transmitted color, and reflected color can be changed within a certain range. When the visible light reflectance is high, the reflection of a lighting fixture or the like on a screen becomes large, and visibility, contrast, and color purity decrease. A white, blue, or violet system in which the reflection color is not conspicuous is preferable. For this reason, it is preferable to use a multilayer lamination that is easily designed and controlled optically.

Hereinafter, unless otherwise specified, the multilayer thin film refers to a multi-layered transparent conductive film in which a metal thin film layer is sandwiched between high refractive index transparent thin film layers and at least one layer is stacked. That is, on one main surface of the transparent substrate (A), a high-refractive-index transparent thin film layer (B) and a metal thin film layer (C) are arranged in the order of (B) /
(C) is repeated one or more times as a repeating unit,
Furthermore, by laminating at least a high refractive index transparent thin film layer (B) thereon, a transparent conductive film having low resistance for electromagnetic wave shielding, near infrared cut ability, transparency, and visible light reflectance is formed. The obtained transparent conductive laminate is obtained. For a display filter for a plasma display, the number of repeated laminations is preferably 1 to 4 times. That is, (A) / (B) / (C) / (B) or (A) / (B) / (C) / (B) / (C) /
(B) or (A) / (B) / (C) / (B) /
(C) / (B) / (C) / (B) or (A) /
(B) / (C) / (B) / (C) / (B) / (C) /
(B) / (C) / (B). If the number of repeated laminations is 5 or more, the limitation of production equipment and the problem of productivity will increase,
In addition, the visible light transmittance decreases and the visible light reflectance increases. When only one or two transparent conductive laminates can be obtained due to limitations of production equipment, etc.
If it is necessary to block more intense electromagnetic waves or near-infrared rays, such as by laminating two or more transparent conductive laminates,
An optical filter having two or more transparent conductive films can also be provided. A transparent conductive film is formed on a transparent support (D) to be described later.
When two or more are formed, they may be bonded to both principal surfaces of the transparent support, or may be laminated to one principal surface. Also,
A transparent conductive film may be formed on both main surfaces of the transparent substrate (A). For electromagnetic wave shielding properties, it is important that even if two or more transparent conductive films are formed, electrical contact can be obtained from any of them. From the viewpoint of productivity, at most two transparent conductive films are preferable.

In the present invention, the transparent conductive layer is
It is composed of one or more transparent conductive films, and the sheet resistance of the transparent conductive layer composed of two or more transparent conductive films is a combined sheet resistance. As a material for the metal thin film (C), silver is preferable because of its excellent conductivity, infrared reflectivity, and visible light transmittance when laminated in multiple layers. However, silver lacks chemical and physical stability, and pollutants in the environment, water vapor,
An alloy containing one or more environmentally stable metals such as gold, platinum, palladium, copper, indium, tin, or the like, or an environmentally stable metal can be suitably used because it is deteriorated by heat, light, or the like. In particular, gold and palladium are preferable because of their excellent environmental resistance and optical properties. Here, the silver content of the alloy containing silver is not particularly limited, but it is preferable that the silver content is not largely different from the conductivity and optical characteristics of the silver thin film, and is 50% by weight.
It is at least about 100% by weight. However, the addition of other metals to silver impairs its excellent conductivity and optical properties. Therefore, when having a plurality of metal thin film layers,
If possible, it is desirable to use at least one layer without alloying silver, or to alloy only the first layer and / or the outermost thin metal layer viewed from the substrate. When the all-metal thin-film layer is made of silver, a transparent conductive layer having excellent conductivity and optical properties can be obtained, but the environmental resistance is not sufficient.

The thickness of the metal thin film layer is determined optically and experimentally from the viewpoint of conductivity and optical characteristics, and is not particularly limited as long as the transparent conductive layer has the required characteristics. Is preferably 4 nm or more because it is necessary to have a continuous state instead of an island-like structure. If the metal thin film layer is too thick, transparency becomes a problem. When there are a plurality of metal thin film layers, the layers are not necessarily all the same thickness, and may not be all silver or an alloy containing the same silver. For the formation of the metal thin film layer, any of conventionally known methods such as sputtering, ion plating, vacuum deposition, and plating can be employed.

The transparent thin film forming the high refractive index transparent thin film layer (B) is not particularly limited as long as it has transparency in the visible region and has an effect of preventing light reflection in the visible region of the metal thin film layer. However, a material having a high refractive index to visible light of 1.6 or more, preferably 1.8 or more, more preferably 2.0 or more is used. Specific materials for forming such a transparent thin film include indium, titanium, zirconium, bismuth,
Examples include oxides of tin, zinc, antimony, tantalum, cerium, neodymium, lanthanum, thorium, magnesium, gallium, and the like, a mixture of these oxides, and zinc sulfide. These oxides or sulfides may have a difference in stoichiometric composition with metal and oxygen or sulfur as long as the optical characteristics are not significantly changed. Above all, zinc oxide, titanium oxide, indium oxide or a mixture of indium oxide and tin oxide (ITO)
Can be suitably used because, in addition to transparency and refractive index, the film formation rate is high and the adhesion to the metal thin film layer is good. The thickness of the high refractive index transparent thin film layer is determined optically and experimentally from the optical properties of the transparent substrate, the thickness and optical properties of the metal thin film layer, and the refractive index of the transparent thin film layer, and is particularly limited. However, it is preferably 5 nm or more and 200 nm or less, more preferably 10 nm or more and 100 nm or less.
It is as follows. Also, a first layer of high refractive index transparent thin film...
The +1 layer (n ≧ 1) is not necessarily the same thickness and may not be the same transparent thin film material. For forming the high refractive index transparent thin film layer, any of conventionally known methods such as sputtering, ion plating, ion beam assist, vacuum deposition, and wet coating can be employed.

In order to improve the environmental resistance of the transparent conductive layer, an optional organic or inorganic protective layer may be provided on the surface of the transparent conductive film to such an extent that the conductivity and optical properties are not significantly impaired. In addition, to improve the environmental resistance of the metal thin film layer and the adhesion between the metal thin film layer and the high refractive index transparent thin film layer,
An arbitrary inorganic layer may be formed between the metal thin film layer and the high-refractive-index transparent thin film layer so as not to impair the conductivity and the optical characteristics. Specific materials include copper, nickel, chromium, gold,
Platinum, zinc, zirconium, titanium, tungsten, tin, palladium and the like, or alloys composed of two or more of these materials are mentioned. Its thickness is preferably about 0.2 nm to 2 nm.

In order to obtain a transparent conductive layer having desired optical properties,
Conductivity for electromagnetic wave shielding ability to be obtained, that is,
In consideration of the metal thin film material and thickness, optical design using the vector method using the optical constants (refractive index, extinction coefficient) of the transparent substrate (A) and the thin film material, the method using the admittance diagram, and the like are performed. , The number of layers, the film thickness, etc. are determined. At this time, when there is a layer formed on the transparent conductive film, it is good to consider an adjacent layer. This is because the transmission color (and the transmittance, the reflection color, and the reflectance) changes because the incident medium of light to the transparent conductive film is different from the incident medium having a refractive index of 1, such as air or vacuum. That is, when the adhesive (E) is formed on the transparent conductive layer, the design is performed in consideration of the optical constant of the adhesive (E). The optical constant can be measured by ellipsometry (ellipsometry) or Abbe refractometer. In addition, film formation can be performed by controlling the number of layers, film thickness, and the like while observing optical characteristics.

The atomic composition of the transparent conductive film formed by the above method can be determined by Auger electron spectroscopy (AES), inductively coupled plasma (ICP), Rutherford backscattering (RB).
S) and the like. The layer configuration and film thickness are
It can be measured by observation in the depth direction of Auger electron spectroscopy, cross-section observation using a transmission electron microscope, or the like. Further, the film thickness is controlled by clarifying the relationship between the film forming conditions and the film forming speed in advance, or by monitoring the film thickness during the film forming using a quartz oscillator or the like. Improving the color purity and contrast of the emission color of a color plasma display can be achieved by reducing unnecessary light emission and external light reflection that cause a reduction in color purity and contrast.

In particular, it is remarkable that red light emission is orangeish, and it has been found that the color purity of red light emission can be improved by reducing the light emission having a wavelength of 580 nm to 605 nm using a display filter. The reduction can be carried out by forming a dye layer containing a dye having an absorption wavelength in this wavelength region on a display filter. At this time, it is necessary that the display filter does not significantly impair the transmission of light having a wavelength of 615 nm to 640 nm where a red emission peak occurs. In general, a dye has a broad absorption range, and even if it has a desired absorption peak, it absorbs light having a suitable wavelength due to absorption at the bottom. Therefore, even if the dye has an absorption at the wavelength of the light to be absorbed, if the amount is large, the amount of the dye is reduced to a suitable level, and the luminance is significantly reduced.
The present inventors have proposed a display filter in which the minimum transmittance at a wavelength of 580 nm to 605 nm is 10 to 85%, preferably 20 to 70%, more preferably 20 to 45% of the maximum transmittance at a wavelength of 615 nm to 640 nm. However, it was found that the color purity of red light emission was improved and the light emission luminance was not significantly impaired. When light emission by Ne is present, the orange light emission can be reduced, so that the color purity of light emission from the RGB display cells is improved.

Further, in order not to significantly impair the light emission luminance when the display filter is mounted, it is necessary to use blue,
Wavelength 450n-48 where green and red emission peaks exist
It has been found that a maximum transmittance at 0 m, a maximum transmittance at a wavelength of 510 to 535 nm, and a maximum transmittance at a wavelength of 615 to 640 nm of 45% or more are suitable for a display filter. The maximum transmittance of the display filter in these wavelength ranges is 85% depending on the constituent members such as the dye layer and the transparent conductive laminate.
% Or less. Furthermore, similarly to the improvement of the color purity of red light emission, the improvement of the color purity of green light emission requires wavelengths of 510 to 535.
The wavelengths of 540 nm to 580 nm, which are yellow green to green yellow to yellow and adjacent to the long wavelength side of green of about nm, may be reduced to some extent. Display filter wavelengths 540-58
The minimum transmittance at 0 nm is 10 to 90% of the maximum transmittance at a wavelength of 510 to 535 nm, preferably 20 to 5%.
It has been found that 0% is preferable. As a result, it is possible to prevent green from taking on yellow and to improve the color purity. Also, if the transmission color of the display filter has a strong yellowish green to greenish color, the contrast of the display may decrease. This is because the light of 550 nm, which is yellowish green to green, has the highest visibility.

The multilayer thin film is generally inferior in transmission color tone when importance is placed on visible light transmittance and visible light reflectance. The higher the electromagnetic wave shielding ability, that is, the conductivity and the near-infrared cut ability, the greater the total thickness of the metal thin film needs to be. However, as the total thickness of the metal thin film increases, the color tone of the multilayer thin film tends to be green to yellow-green, which lowers the color purity and contrast of the display emission color. In order to improve the visibility of the display, in order to reduce the visible light reflectance of the display filter, a high-refractive-index transparent thin film layer is used to prevent the reflection of metal in the visible region around the wavelength of about 550 nm where the visibility is high. However, on the short wavelength and long wavelength sides of the visible region, the matching condition of antireflection is broken mainly due to the wavelength dispersion of the optical constant of the metal thin film, and the transmission spectrum peaks at green to yellow-green with high visibility. Therefore, the color tone of the multilayer thin film tends to be green to yellowish green. Therefore, also from this point, the wavelengths of 540 nm to 58
It is preferable to reduce 0 nm to some extent.

Further, similarly, in order to improve the color purity of blue light emission and the color purity of green light emission, unnecessary light emission at a wavelength of 480 nm to 510 nm between the respective preferable light emission wavelengths may be reduced. The minimum transmittance of the display filter in the wavelength range is 450 to 480 nm.
Maximum transmittance and / or wavelength 510 to 535 nm
50 to 90%, preferably 50 to 90% of the maximum transmittance in
It has been found that 75% is preferable. Thereby, it is possible to prevent blue from becoming green and / or green from being blue, and to improve the color purity. Improvement in color purity can improve contrast. In addition, absorption by a dye at a specific wavelength for reducing unnecessary light emission can reduce external light reflection on the phosphor by reducing incidence of external light on the phosphor. This can also improve color purity and contrast.

In some cases, it is preferable to have absorption outside the above absorption wavelength range. Since the red emission peak is strong, RG
If it is not significant on the B light emission balance, it may be reduced. In addition, the emission peak of the blue light-emitting phosphor may be present in the red region, and in this case, the blue display cell has a color close to purple by applying red to blue. Therefore, it may be preferable that the red region is reduced. If the green light emission is not significantly reduced, as described above, it is preferable that the display filter has absorption in the green wavelength region in order to eliminate the green color of the transmitted color of the display filter and improve the contrast. There are cases. As described above, the color purity can be improved, the reflection of external light can be reduced, and the contrast can be improved also by the absorption by the dye at a suitable wavelength of light emission.

The peak of the green emission of the plasma display may be slightly longer than the green required in the NTSC system, for example, on the yellow-green side. It has also been found that shaving the peak to have a peak on the short wavelength side is also effective for improving the color purity of green light emission. That is, in the wavelength range of 520 to 540 nm, the transmittance may monotonously decrease as the wavelength increases. To improve contrast and color purity, neutral
As with the density (ND) filter, there is a method of lowering the transmittance in the entire visible wavelength region. However, the display filter of the present invention reduces the brightness by lowering the transmittance in the entire visible wavelength region, that is, including the preferable emission wavelength. And the color purity and contrast are excellent in order to highlight suitable light emission. Also, the display filter may be required to have a transmission color of neutral gray or blue gray.
This is because the contrast is lowered due to the strong green transmission, the blue emission is weaker than the red and green emission colors, and white having a color temperature slightly higher than the standard white is preferred.

As the dye layer, (1) a plastic plate or a polymer film obtained by kneading at least one kind of organic dye having an absorption wavelength in the visible region with a transparent resin,
(2) A plastic plate or polymer film prepared by a casting method by dispersing and dissolving at least one or more organic dyes having an absorption wavelength in the visible region in a resin or a resin concentrate of a resin monomer / organic solvent, and (3) A) adding at least one or more organic dyes having an absorption wavelength in the visible region to a resin binder and an organic solvent to form a paint;
(4) a transparent adhesive containing at least one or more organic dyes having an absorption wavelength in the visible region, and (5) colored glass containing metal ions or colloids in glass. You can select one or more. In the present invention, the term “containing” means not only a state of being contained in a substrate or a layer such as a coating film or an adhesive, but also a state of being applied to the surface of the substrate or the layer.

The organic dye may be a general dye or pigment having a desired absorption wavelength in the visible region, and the type thereof is not particularly limited. For example, anthraquinone, phthalocyanine, methine, azomethine, oxazine And commercially available organic dyes such as azo, styryl, coumarin, porphyrin, dibenzofuranone, diketopyrrolopyrrole, rhodamine, xanthene, and pyrromethene. The type and concentration depend on the absorption wavelength and absorption coefficient of the organic dye, the color tone of the transparent conductive layer, and the transmission characteristics required for display filters.
It is determined by the transmittance and the type and thickness of the medium or coating film to be dispersed, and is not particularly limited. Since the temperature of the panel surface of the plasma display panel is high and the temperature of the display filter particularly increases when the temperature of the environment is high, it is preferable that the organic dye does not deteriorate significantly at 80 ° C. due to decomposition or the like. Some dyes have poor light fastness in addition to heat resistance. If the emission of the plasma display or the deterioration of external light due to ultraviolet light or visible light becomes a problem, it is possible to reduce the deterioration of the dye due to ultraviolet light by using a member containing an ultraviolet absorber or a part that does not transmit ultraviolet light. It is important to use a dye that does not significantly deteriorate due to light or visible light.
In addition to heat and light, the same applies to humidity and a combined environment of these. Deterioration changes the transmission characteristics of the display filter. Furthermore, solubility in an appropriate solvent is also important for dispersing in a medium or a coating film. Two or more organic dyes having different absorption wavelengths in the visible region may be contained in one medium or coating film.

It should be noted that the fact that the surface temperature of the plasma display panel actually changes from 70.degree. C. to 80.degree.
220303. The light generated from the plasma display panel is, for example, 300 cd / m ^2.
(Fujitsu Limited Imagesite
Catalog AD25-0061C Oct. 1997
M), when the solid angle is 2π and this is irradiated for 20,000 hours, 2π × 20,000 × 3000 = 38,000,000 (lx ·
Time), it is understood that light resistance of about tens of millions (lx · hour) is required for practical use.

The display filter of the present invention has excellent transmission characteristics and transmittance without significantly impairing the brightness and visibility of a color plasma display as a filter for a plasma display. Can be improved. The present inventors have found that when at least one of the one or more dyes contained in the dye layer is a tetraazaporphyrin compound, 580 nm to 605 are particularly desired to be reduced.
The main absorption wavelength is at or near the peak wavelength of unnecessary emission of nm, and the absorption wavelength width is relatively narrow, so that loss of luminance and visibility due to absorption of suitable emission is reduced. It was found that a filter for a display having excellent transmission characteristics, transmittance, color purity of emitted color, and ability to improve contrast was obtained.

The tetraazaporphyrin compound of the present invention can be represented by the formula (1). The formula (1) can be abbreviated as in the following structural formula (2) [formula 3].

[0039]

Embedded image

[0040] In the formula (2), ^{A m} and ^{A n} are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, having 1 to 20 carbon atoms alkyl group, halogenoalkyl group, alkoxy group, alkoxyalkoxy group, an aryloxy group, a monoalkylamino group, a dialkylamino group, an aralkyl group, an aryl group, a heteroaryl group, an alkylthio group, or arylthio group, a ^m And ^An may each independently form a ring other than an aromatic ring via a linking group, and M represents two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, and a tetravalent divalent metal atom. A substituted metal atom, or
Represents an oxymetal atom.

Specific examples of the tetraazaporphyrin compound represented by the formula (1) are described below. In the formula, specific examples of A ^{1 to} A ⁸ each independently represent a hydrogen atom: fluorine, chlorine,
Halogen atom of bromine or iodine: nitro group: cyano group: hydroxy group: amino group: carboxyl group: sulfonic acid group: methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl Group, sec-
Butyl group, t-butyl group, n-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group,
1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-
Methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2- Dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group,
1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, c
cycl-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2 -Ethylhexyl group, 2,5-
Dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl Group, 4-ethyloctyl group,
4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n -Tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2, 2,
5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo
1 carbon number such as -hexyl-2,2-dimethylpropyl group
Straight-chain, branched or cyclic alkyl having 20 to 20 carbon atoms: a halogenoalkyl group having 1 to 20 carbon atoms such as a chloromethyl group, a dichloromethyl group, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a nonafluorobutyl group. :
Methoxy, ethoxy, n-propoxy, iso-
Propoxy group, n-butoxy group, iso-butoxy group,
sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n
-Alkoxy groups having 1 to 20 carbon atoms such as -hexyloxy group and n-dodecyloxy group: methoxyethoxy group, ethoxyethoxy group, 3-methoxypropyloxy group, 3-
An alkoxyalkoxy group having 2 to 20 carbon atoms such as (iso-propyloxy) propyloxy group: a phenoxy group,
2-methylphenoxy group, 4-methylphenoxy group, 4
6 to 6 carbon atoms such as -t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group, etc.
20 aryloxy groups: methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n
A monoalkylamino group having 1 to 20 carbon atoms such as -hexylamino group: dimethylamino group, diethylamino group, di-
n-propylamino group, di-n-butylamino group, N-
2-2 carbon atoms such as methyl-N-cyclohexylamino group
0 dialkylamino group: benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, dichloromouth benzyl group, methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzyl Aralkyl groups having 7 to 20 carbon atoms such as a group, a naphthylmethyl group, a nitronaphthylmethyl group, a cyanonaphthylmethyl group, a hydroxynaphthylmethyl group, a methylnaphthylmethyl group, a trifluoromethylnaphthylmethyl group: a phenyl group, a nitrophenyl group, Cyanophenyl group, hydroxyphenyl group,
Methylphenyl group, dimethylphenyl group, trimethylphenyl group, dichlorophenyl group, methoxyphenyl group,
Ethoxyphenyl group, trifluoromethylphenyl group,
Aryl groups having 6 to 20 carbon atoms such as N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group: pyrrolyl group, thienyl group, Heteroaryl groups such as furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoyl group, benzoxazoyl group, benzothiazoyl group, benzimidazoyl group, benzofuranyl group, indoyl group: methylthio group, ethylthio group, n-propylthio Group, iso-propylthio group, n-butylthio group, is
o-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropyl C1-C20 alkylthio groups such as thio group and 1,1-dimethylpropylthio group: phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-
An arylthio group having 6 to 20 carbon atoms such as a t-butylphenylthio group can be exemplified.

[0042] A¹And A², A³And A⁴, A⁵And A⁶,or
Is A⁷And A⁸Forms a ring through a linking group
Is -CH₂CH₂CH₂CH₂-, -CH₂CH₂C
H (NO₂) CH₂-, -CH₂CH (CH₃) CH₂
CH₂-, -CH₂CH (Cl) CH₂CH₂-
I can do it. As an example of a divalent metal represented by M
Represents Cu, Zn, Fe, CO, Ni, Ru, Rh, P
d, Pt, Mn, Sn, Mg, Hg, Cd, Ba, T
i, Be, Ca, etc., and examples of monosubstituted trivalent metals
Al-F, Al-Cl, Al-Br, Al-
I, Ga-F, Ga-Cl, Ga-Br, Ga-I, I
n-F, In-I, In-Br, In-I, Tl-F,
Tl-Cl, Tl-Br, Tl-I, Al-C₆H₅,
Al-C₆H₄(CH₃), In-C₆H₅, In-C
₆H₄(CH₃), Mn (OH), Mn (OC₆H_Five),
Mn [OSi (CH₃)₃], Fe-Cl, Ru-Cl
Examples of disubstituted tetravalent metals include CrC
l₂, SiF₂, SiCl₂, SiBr₂, SiI₂,
SnF₂, SnCl₂, SnBr₂, ZrCl₂, Ge
F₂, GeCl₂, GeBr₂, GeI₂, TiF₂,
TiCl₂, TiBr₂, Si (OH)₂, Sn (O
H)₂, Ge (OH)₂, Zr (OH)₂, Mn (O
H)₂, TiA₂, CrA₂, SiA_Two, SnA_Two, Ge
A_Two[A represents an alkyl group, a phenyl group, a naphthyl group,
Represents a derivative of ], Si (OA ')_Two, Sn (O
A ')_Two, Ge (OA ')_Two, Ti (OA ')₂, Cr (O
A ')₂[Al is an alkyl group, phenyl group, naphthyl
Group, trialkylsilyl group, dialkylalkoxysilyl
And a derivative thereof. ], Si (SA ")₂,
Sn (SA ")₂, Ge (SA ")₂[A "is alkyl
Group, phenyl group, naphthyl group and derivatives thereof
You. And the like, and examples of oxymetals include VO,
MnO, TiO and the like can be mentioned. Preferably, Pd, C
u, Ru, Pt, Ni, CO, Rh, Zn, VO, Ti
O, Si (Y)₂, Ge (Y) ₂(Y is a halogen atom,
An alkoxy group, an aryloxy group, an acyloxy group,
Droxy, alkyl, aryl, alkylthio
Group, arylthio group, trialkylsilyloxy group,
Lialkyltinoxy group or trialkylgermanium
Represents an oxy group). More preferably, Cu,
VO, Ni, Pd, Pt, and CO.

The present inventors have further found that the azaporphyrin compound of the formula (1) can be, for example, a tetra-t-butyl-tetraazaporphyrin complex or a tetra-neo-pentyl-
When it is a tetraazaporphyrin complex, it is relatively easy to produce, has good solubility in a solvent, the complex is stable, has excellent absorption properties, and has a tertiary butyl group and a tetra-neo-pentyl group. As a result, the solubility of the complex in a solvent is increased due to the stericity of the complex,
It was found that a dye was easily contained, and an excellent display filter could be obtained.

When a multilayer thin film is used for the transparent conductive layer, it has a near-infrared cut ability in addition to an electromagnetic wave shielding ability. In the case where no dye is present, one or more kinds of near-infrared absorbing dyes may be used in combination with the dye in order to impart near-infrared cut ability to the display filter. The near-infrared absorbing dye compensates for the near-infrared cut ability of the transparent conductive layer, and if it absorbs the near-infrared of the intensity emitted by the plasma display to the extent that it becomes sufficiently practical,
It is not particularly limited, and the concentration is not limited. Examples of the near infrared absorbing dye include a phthalocyanine compound, an anthraquinone compound, a dithiol compound, and a diiminium compound. The near-infrared absorbing dye is used in a plasma display panel because the temperature of the panel surface is high and the temperature of the display filter is particularly high when the temperature of the environment is high.
It is preferable that the composition does not deteriorate significantly due to decomposition or the like at ℃.
Some dyes have poor light fastness in addition to heat resistance. If the emission of the plasma display or the deterioration of external light due to ultraviolet light or visible light becomes a problem, by using a member containing an ultraviolet absorber or a member that does not transmit ultraviolet light, the deterioration of the dye due to ultraviolet light can be reduced. It is important to use a dye that does not significantly deteriorate due to visible light. In addition to heat and light, the same applies to humidity and a combined environment of these. Deterioration changes the near-infrared cut ability and visible light transmission characteristics of the display filter. Furthermore, solubility in an appropriate solvent is also important for dispersing in a medium or a coating film.

The coloring matter referred to in the present invention means the above-mentioned organic coloring matter and a trace amount of a coloring matter for coloring colored glass.
The forms (1) to (5) of the dye layer include a dye-containing transparent substrate (A), a dye-containing transparent support (D) described later, and a dye-containing adhesive material (E) described later. ), And any one or more forms of a functional transparent layer (F) containing a dye described below can be used for the display filter of the present invention. Two or more dye layers may be provided.

The functional transparent layer (F) described below containing a dye
Is a film containing a dye and having each function, even if a film containing a dye and having each function is formed on the transparent molded product, the film having each function is formed on the transparent molded product containing the dye. May be formed. Examples of the transparent molded product containing a dye include a transparent plastic plate, a transparent polymer film, and glass.

First, in the method of (1) in which a dye is kneaded with a resin and heat-molded, the resin material is preferably as transparent as possible when formed into a plastic plate or a polymer film. Polyethylene terephthalate, polyether sulfone, polystyrene, polyethylene naphthalate, polyarylate, polyether ether ketone, polycarbonate, polyethylene, polypropylene, polyamide such as nylon 6, cellulose resin such as polyimide, triacetyl cellulose, polyurethane, polytetrafluorocarbon Fluorinated resins such as ethylene, vinyl compounds such as polyvinyl chloride, polyacrylic acid, polyacrylate, polyacrylonitrile, addition polymers of vinyl compounds, polymethacrylic acid,
Vinylidene compounds such as polymethacrylic acid esters and polyvinylidene chloride; vinylidene fluoride / trifluoroethylene copolymers; vinyl compounds such as ethylene / vinyl acetate copolymers; and copolymers of fluorine compounds; polyethers such as polyethylene oxide; Examples thereof include an epoxy resin, polyvinyl alcohol, and polyvinyl butyral, but are not limited to these resins.

The processing method and the film forming conditions are slightly different depending on the dye and base polymer to be used. Usually, (i) the dye is added to the base polymer powder or pellet, After heating and melting at a temperature of 0 ° C., a method of forming a plastic plate by molding, (ii) a method of forming a film with an extruder, (iii) preparing a raw material with an extruder, 2 to 5 at 30 to 120 ° C. And a method of stretching the film uniaxially or biaxially to form a film having a thickness of 10 to 200 μm. At the time of kneading, an additive such as a plasticizer used for ordinary resin molding may be added.
The amount of the dye to be added varies depending on the absorption coefficient of the dye, the thickness of the polymer molded article to be produced, the target absorption intensity, the target transmission characteristics / transmittance, and the like. ~ 20%.

In the casting method (2), a resin concentrate obtained by dissolving a resin or a resin monomer in an organic solvent is added to
Add and dissolve the dye, add a plasticizer, polymerization initiator, and antioxidant if necessary, pour into a mold or drum having the required surface condition, and evaporate and dry the solvent or evaporate and dry the solvent. By doing so, a plastic plate and a polymer film are obtained. Normally, aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, modified polyvinyl resins ( PVB, EVA, etc.) or a resin monomer of a copolymer resin thereof. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof is used. The concentration of the dye varies depending on the absorption coefficient of the dye, the thickness of the plate or film, the desired absorption intensity, the desired transmission characteristics and the desired transmittance, and is usually 1 ppm to 20% based on the weight of the resin monomer. The resin concentration is usually 1 to 90% with respect to the whole paint.

As the method (3) for coating and coating, a method of dissolving a dye in a binder resin and an organic solvent to form a coating, or a method of pulverizing a non-colored acrylic emulsion paint (50 to 500 nm). A method of dispersing things into an acrylic emulsion-based water-based paint,
Etc. In the former method, usually, an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, a polyvinyl resin, a polyvinyl alcohol resin, A modified polyvinyl resin (PVB, EVA, etc.) or a copolymer thereof is used as a binder resin. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof is used. The concentration of the dye varies depending on the absorption coefficient of the dye, the thickness of the coating, the desired absorption intensity, the desired visible light transmittance, and the like, but is usually 0.1 to 30% based on the weight of the binder resin. Also,
The binder resin concentration is usually 1 to
50%. Similarly, in the case of an acrylic emulsion-based water-based paint, it is obtained by dispersing a finely pulverized pigment (50 to 500 nm) in an uncolored acrylic emulsion paint. Additives such as antioxidants and the like used in ordinary paints may be added to the paint.

The paint prepared by the above method is prepared by coating a known coating such as a bar coater, blade coater, spin coater, reverse coater, die coater or spray on a transparent polymer film, transparent resin, transparent glass or the like. Thus, a substrate containing a dye is prepared. A protective layer may be provided to protect the coated surface, or other components of the display filter may be bonded to the coated surface to protect the coated surface.

Adhesives (4) containing a dye include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), ethylene-vinyl acetate adhesives (EVA) and other polyvinyl adhesives. 10 ppm to 30% pigment in sheet or liquid adhesive or adhesive such as ether, saturated amorphous polyester, melamine resin, etc.
It has been added. The pressure-sensitive adhesive (E) of the present invention is an adhesive or a pressure-sensitive adhesive or a pressure-sensitive adhesive. The pressure-sensitive adhesive containing the above-mentioned dye can be used for bonding each member constituting the display filter.

The colored glass (5) is a colored glass, and is a blue-blue-green-yellow-green colored glass containing transition metal ions such as cobalt, copper, and chromium, a red colored glass containing a colloid of gold and selenium, A brown colored glass containing a metal sulfide colloid may be used. The color tone and darkness vary depending on the type and content of the selected trace content, the glass composition, the melting temperature, and the melting atmosphere. These conditions are the color tone of the transparent conductive layer and the transmission characteristics and transmission required for the display filter. It is determined by the rate and is not particularly limited. In order to increase the light resistance of the dye-containing display filter, a transparent film (UV cut film) containing an ultraviolet absorber can be attached,
An ultraviolet absorber may be contained together with the dye. The type and concentration of the ultraviolet absorber are not particularly limited.

When a polymer film is used as the transparent substrate (A), the transparent conductive layer has a smooth plate-like transparent support on the main surface due to problems of strength, flatness at the time of bonding to a display, and an installation method. It is desirable to use it by bonding it to the body (D). When the bonding is performed between the main surface of the transparent support (D) and the main surface of the transparent laminate that is not the thin film forming surface via the transparent adhesive material (E), the electrodes can be easily formed, and the display body and Suitable for obtaining electrical contact. In the case of a display filter that does not require electromagnetic wave shielding capability, the bonding may be performed on either main surface of the transparent laminate. As the transparent support (D), a plastic plate that is transparent in the visible region is desirable because of its mechanical strength, lightness, and resistance to cracking, but a glass plate is also preferably used because of its low thermal deformation and low thermal stability. it can. Specific examples of the plastic plate include acrylic resin including polymethyl methacrylate (PMMA), polycarbonate resin, transparent ABS resin, and the like, but are not limited to these resins. In particular, PMMA can be suitably used because of its high transparency in a wide wavelength region and high mechanical strength. The thickness of the plastic plate is not particularly limited as long as it has sufficient mechanical strength and rigidity for maintaining flatness without sagging, and is not particularly limited, but is usually about 1 mm to 10 mm. When a glass plate is used as the transparent support (D), it is desirable to use a semi-tempered glass plate or a tempered glass plate that has been subjected to chemical strengthening or air-cooling to add mechanical strength. The transparent support (D) may contain a dye to form a dye layer.

For bonding (laminating) in the present invention, any transparent adhesive (E) can be used. Specifically, an acrylic adhesive, a silicone adhesive, a urethane adhesive, a polyvinyl butyral adhesive (PVB),
Examples thereof include an ethylene-vinyl acetate adhesive (EVA), polyvinyl ether, a saturated amorphous polyester, and a melamine resin. At this time, it is important that the adhesive used in the central portion, which is the light transmitting portion from the display, needs to be sufficiently transparent to visible light. The adhesive may be a sheet or a liquid as long as it has practical adhesive strength. As the pressure-sensitive adhesive, a sheet-shaped pressure-sensitive adhesive can be suitably used. After the sheet-like adhesive material is attached or the adhesive material is applied, the members are laminated by laminating the respective members. The liquid is an adhesive which is cured by being left at room temperature or heated after application and bonding. Examples of the coating method include a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, and the like. The thickness of the pressure-sensitive adhesive or the adhesive layer is not particularly limited, but is 0.5 μm to 50 μm, preferably 1 μm to 50 μm.
μm to 30 μm. It is preferable that the surface on which the adhesive material is formed and the surface on which the adhesive material is to be bonded are improved in wettability in advance by an easy-adhesion coating or an easy-adhesion treatment such as a corona discharge treatment. Furthermore, after bonding using an adhesive, air that has entered between the members at the time of bonding can be defoamed or dissolved in the adhesive, and then pressurized, if possible, to improve the adhesion between the members. It is important to perform curing under heating conditions. At this time, the pressurizing condition is
The heating conditions are about 20 atm or less, and the heating conditions are about room temperature or more and about 80 ° C. or less, depending on the heat resistance of each member. However, these are not particularly limited. The adhesive (E) contains a pigment,
It can be a dye layer. The display filter of the present invention has an anti-reflective property, an anti-glare property, an anti-reflective anti-glare property,
The functional transparent layer (F), which has at least one of an antistatic property, an anti-Newton ring property, a gas barrier property, a hard coat property, and an antifouling property and transmits visible light,
Need to be formed. One functional transparent layer (F)
It is preferable to have a plurality of functions, since the number of components or layers can be reduced to reduce the number of steps, cost, and interfacial reflection between members.

The display filter of the present invention may have a plurality of functional transparent layers (F). The functional transparent layer (F) in the present invention may have any of the functions described above, whether it is a functional film having at least one of the above functions, or a transparent substrate formed by coating or printing a functional film or by various conventionally known film forming methods. May be used. In the case of the functional film itself, it is formed by coating or printing on the main surface of the transparent conductive layer, the dye layer, or the transparent support (D) forming the functional transparent layer (F) or directly by various conventionally known film forming methods. In the case of a transparent substrate on which a functional film is formed, or a transparent substrate having various functions, a transparent conductive layer, a dye layer, or a transparent support is provided via an adhesive (E) or an adhesive (E) containing a dye. It may be attached to the main surface of (D). There is no particular limitation on the method of making these. The transparent substrate is a transparent plastic plate or a polymer film or a glass plate, the type and thickness of which are not particularly limited, and a pigment is contained in the transparent substrate to make the functional transparent layer a pigment layer. You can also. Even if the functional transparent layer (F) is a functional film itself, a dye layer can be formed by incorporating a dye into the film.

In order to obtain a display filter having an electromagnetic wave shielding function, it is necessary to electrically connect the conductive layer to the outside, so that the functional transparent layer (F) is formed on the conductive surface of the transparent conductive layer. In addition, the functional transparent layer (F) must not interfere with this electrical connection. For example, it is important that the functional transparent layer (F) is formed so as to leave the periphery of the conductive layer. Since the display screen becomes difficult to see due to the reflection of a lighting fixture or the like on the display, anti-reflection (A) for suppressing external light reflection on at least one surface, preferably both surfaces of the display filter.
It is necessary to form a functional transparent layer (F) having R: anti-reflection) properties, anti-glare (AG: anti-glare) properties, or anti-reflection anti-glare (ARAG) properties. When the visible light reflectance of the display filter is low, the incidence and reflection of external light on the phosphor of the plasma display are reduced, which leads to not only prevention of reflection but also improvement in contrast and color purity. Also, antireflection by AR or ARAG can improve the light transmittance of the display filter.

When the display filter is used with the main surface of the display filter and the display surface in close contact, the degree of adhesion between the display surface and the display filter varies depending on the portion, and Newton is caused by the gap generated thereby. A ring occurs. Therefore, it is necessary to form a functional transparent layer (F) having an anti-Newton ring (AN) property on the main surface of the display filter that is in close contact with the display surface.

Functional transparent layer (F) having antireflection properties
Determines the components of the antireflection film and the thickness of each component by the above-described optical design in consideration of the optical characteristics of the substrate on which the antireflection film is formed. Specifically, the refractive index in the visible region is 1.5 or less, preferably 1.4 or less,
A single layer of a thin film of a fluorine-based transparent polymer resin, magnesium fluoride, silicon-based resin, or silicon oxide, for example, having an optical thickness of 1/4 wavelength, metal oxides, fluorides, silicon oxides having different refractive indices , Boride, carbide, nitride,
A thin film of an inorganic compound such as a sulfide or an organic compound such as a silicon-based resin, an acrylic resin, or a fluorine-based resin may be formed by laminating two or more layers in the order of a high refractive index layer and a low refractive index layer when viewed from the base. Although a single layer is easy to manufacture, the antireflection property is inferior to that of a multilayer laminate. The four-layer structure has an antireflection function over a wide wavelength range, and there is little restriction on the optical design due to the optical characteristics of the base. Any of conventionally known methods such as sputtering, ion plating, vacuum deposition, and wet coating can be employed for forming these inorganic compound thin films. A conventionally known method such as wet coating can be used for forming the organic compound thin film.

The functional transparent layer (F) having an anti-Newton ring property and the functional transparent layer (F) having an antiglare property comprise:
It refers to a layer that is transparent to visible light and has a surface state of minute irregularities of about 0.1 μm to 10 μm only for different purposes. The anti-Newton ring property has antiglare properties. Specifically, in addition to thermosetting or photosetting resins such as acrylic resins, silicone resins, melamine resins, urethane resins, alkyd resins, and fluorine resins, silica, organic silicon compounds, melamine, acrylic, etc. The particles obtained by dispersing the inorganic compound or organic compound particles into an ink are coated on a substrate by a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method or the like, and cured. The average particle size of the particles is 1 to 40 μm
It is. Alternatively, a thermosetting or photocurable resin such as an acrylic resin, a silicon resin, a melamine resin, a urethane resin, an alkyd resin, or a fluororesin is applied to a substrate, and a mold having a desired haze or surface state is provided. , And the composition is pressed and cured to obtain an anti-Newton ring property or an antiglare property. Furthermore, anti-glare properties can also be obtained by treating the substrate with a chemical, such as etching a glass plate with hydrofluoric acid or the like. In this case, the antiglare haze can be adjusted by the processing time and the etching property of the chemical. In short, it is important to have appropriate irregularities, and it is not necessarily limited to the above method. The anti-glare or anti-Newton ring haze is 0.5% or more, 20% or less, preferably 1% or more,
10% or less. If the haze is too small, it is not enough,
If the haze is too large, the parallel light transmittance will be low, and the visibility of the display will be poor.

When the functional transparent layer (F) having antiglare properties is relatively far from the display surface, for example, when the display filter is installed separately from the display body without being in close contact with the display body, blur due to image diffusion is caused. May occur. Therefore, in the case of such an installation method, it is important to select a haze that maintains the anti-glare property and has no blurring of the image even at an appropriate distance from the display.

The functional transparent layer (F) having antireflection and antiglare properties can be obtained by forming the above-mentioned antireflection film on a film having antiglare properties or a substrate. At this time, when the film having antiglare properties is a film having a high refractive index, a relatively high antireflection property can be imparted even if the antireflection film is a single layer. The functional transparent layer (F) having antireflection and antiglare properties can also have antinewton ring properties.

In order to add abrasion resistance to the display filter, a hard coat property having transparency to the extent that the characteristics of the display filter including optical characteristics are not impaired, especially on the human surface or thin film of the filter. May be formed. Acrylic resin, silicon resin,
Examples thereof include thermosetting or photocurable resins such as melamine-based resins, urethane-based resins, alkyd-based resins, and fluorine-based resins, but the type and forming method are not particularly limited. The thickness of these films is about 1 to 100 μm. The hard coat film is used as a high refractive index layer or a low refractive index layer of the transparent functional layer (F) having antireflection properties, or an antireflection film is formed on the hard coat film to form a functional transparent layer (F). May have both antireflection properties and hard coat properties. Similarly, it may have both anti-glare properties and / or anti-Newton ring properties and hard coat properties. In this case, the hard coat film may have irregularities such as particles dispersed therein, and if an antireflection film is formed thereon, a functional transparent layer having both antireflection antiglare properties and hard coat properties (F) is obtained.

Further, the display filter includes:
Dust tends to adhere due to electrostatic charging, and may be discharged when a human body comes into contact with it, causing an electric shock. Therefore, antistatic treatment may be required. Therefore, a conductive layer may be provided as a functional transparent layer (F) having an antistatic function on the surface of the display filter in order to impart an antistatic function to the optical filter. The conductivity required in this case may be a sheet resistance of about 10 ¹¹ Ω / □ or less, but it should not impair the transparency and resolution of the display screen. I as the conductive layer
Known transparent conductive films such as TO and conductive films in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed are exemplified. In addition, the conductive film is included in the functional transparent layer (F) having at least one of the above-described antireflection properties, antiglare properties, antireflection antiglare properties, anti-Newton ring properties, and hard coat properties. It is preferable to have

When silver is used for the multilayer thin film, silver lacks chemical and physical stability, and is deteriorated by environmental contaminants, water vapor, etc., causing aggregation and whitening. It is important that the thin film forming surface of the body is covered with a functional transparent layer (F) having a gas barrier property so that the thin film is not exposed to pollutants and water vapor in the use environment.
The required gas barrier property is 10 g / m ²
day or less. Specific examples of the film having gas barrier properties include silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, and the like, or a mixture thereof, or a metal oxide thin film obtained by adding a trace amount of another element thereto. And, polyvinylidene chloride,
Examples of the resin include an acrylic resin, a silicon resin, a melamine resin, a urethane resin, and a fluorine resin, but are not particularly limited thereto. The thickness of these films is 10 to 200 nm for a metal oxide thin film and 1 for a resin.
１００100 μm, and may be a single layer or a multilayer, but this is not particularly limited. Examples of the polymer film having a low water vapor vapor permeability include polyethylene, polypropylene, nylon, polyvinylidene chloride, vinylidene chloride and vinyl chloride, a copolymer of vinylidene chloride and acrylonitrile, and a fluorine-based resin. Is not particularly limited as long as it is 10 g / m ² day or less. Even when the moisture permeability is relatively high, the moisture permeability decreases by increasing the thickness of the film or adding an appropriate additive. When the multilayer thin film has excellent environmental resistance, there is no need to provide a functional transparent layer (F) for protection on the multilayer thin film. In this case, it is preferable that the multilayer thin film has an antireflection property.

The functional transparent layer (F) adjacent to the thin film
However, the functional transparent layer (F) having at least one of the above-described antireflection properties, antiglare properties, antireflection antiglare properties, antistatic properties, anti-Newton ring properties, and hard coat properties
It is preferable to have a film having a gas barrier property in the structure of the above or to have the above gas barrier property in whole or in combination with an adhesive.

For example, the functional transparent layer (F) having an antireflection property, a hard coat property, an antistatic property, and a gas barrier property, which is a dye layer, may be a dye-containing polyethylene terephthalate film / hard coat film / ITO / silicon-containing film. Compound / ITO / silicon-containing compound, and the like. The functional transparent layer (F) having antireflection antiglare property, anti-Newton ring property, hard coat property, antistatic property and gas barrier property is a triacetyl cellulose film. / I
TO fine particle-dispersed hard coat film / silicon-containing compound compound. Further, the surface of the display filter may be provided with antifouling property so that fingerprints and the like can be prevented from being stained and can be easily removed when stains are attached.
For this purpose, a functional transparent layer (F) having at least antifouling property is formed on the outermost surface of the display filter. Those having antifouling properties have non-wetting properties with respect to water and / or fats and oils, and include, for example, fluorine compounds and silicon compounds. When combined with other functions such as antireflection properties and antistatic properties, those functions must not be obstructed. In this case, using a fluorine compound having a low refractive index as a constituent material of the antireflection film,
By coating one or several molecules of a fluorine-based organic molecule on the outermost surface, it is possible to impart antifouling properties while maintaining antireflection properties and antistatic properties. For example, as the functional transparent layer (F) having antifouling property, antireflection property, hard coat property, antistatic property and gas barrier property, hard coat film / IT
O / silicon-containing compound / ITO / silicon-containing compound / monomolecular coat film of fluorine organic molecules.

For a device requiring an electromagnetic wave shield, a metal layer is provided inside the case of the device, or a radio wave is blocked by using a conductive material for the case. When transparency is required as in a display, a window-like display filter having a transparent conductive layer is provided. Since the electromagnetic wave induces electric charge after being absorbed in the conductive layer, if the electric charge is not escaped by grounding, the electromagnetic wave shielding body again acts as an antenna to oscillate the electromagnetic wave and reduce the electromagnetic wave shielding ability. Therefore, it is necessary that the display filter provided with the electromagnetic wave shielding property and the conductive portion inside the case of the display body are in ohmic contact. Therefore, in the transparent conductive layer, a part of the transparent conductive film forming surface which is a current-carrying part is exposed, and the layers formed on the thin film forming surface including the above-described functional transparent layer (F) obtain electrical contact. It must be formed in a part other than the part.

To improve the electrical contact, an electrode is formed on the transparent conductive film. The electrode shape is not particularly limited. However, between the display filter and the device,
It is important that there are no gaps where electromagnetic waves leak.
Therefore, it is preferable to form electrodes continuously on the transparent conductive film and on the peripheral portion. That is, a flat electrode including a metal is formed in a frame shape except for a central portion that is a light transmitting portion from the display. The surface on which the electrodes are formed is determined by the ground position of the display set, and may be a person-side surface or a display-side surface when installed.

The material used for the electrode is a simple substance such as silver, gold, copper, platinum, nickel, aluminum, chromium, iron, zinc, carbon, etc., from the viewpoints of conductivity, contact resistance, and adhesion to the transparent conductive film. Alternatively, an alloy composed of two or more kinds, a synthetic resin and a mixture of these simple substances or alloys, or a paste composed of a borosilicate glass and a mixture of these simple substances or alloys can be used. For forming the electrode, a conventionally known method such as a printing method or a coating method can be employed for a paste or the like such as a plating method, a vacuum evaporation method, and a sputtering method. Also, a commercially available conductive tape can be suitably used. Although the thickness of the electrode is also not particularly limited, it may be several μm to several m.
m. Further, even without forming an electrode, the display filter of the present invention has excellent transmission characteristics and near-infrared cut properties, and thus can be suitably used as a luminescent color correction filter and a near-infrared cut filter. Therefore, in this case, the layers formed on the thin film forming surface including the above-mentioned functional transparent layer (F) may entirely cover the thin film forming surface. When mounted on a display, the display filter of the present invention may be subjected to arbitrary frame printing in order to prevent a mounting jig, an electrode portion, and the like from being seen by a viewer. The printing shape, printing surface, printing color, and printing method are not particularly specified. Further, processing such as hole processing and corner processing for mounting on a display may be performed.

The display filter of the present invention has excellent transmission characteristics, transmittance, and visible light reflectance, so that the brightness and visibility of the plasma display are not significantly impaired.
Its color purity and contrast can be improved. Furthermore, it has excellent electromagnetic wave shielding ability to cut off electromagnetic waves which are said to be harmful to health generated from the plasma display. Furthermore, in order to efficiently cut near-infrared rays near 800 to 1000 nm emitted from the plasma display, the peripheral electronic It is possible to prevent the wavelengths used by the remote controller of the device, the transmission system optical communication and the like from being adversely affected, and to prevent the malfunction thereof. Further, it has excellent weather resistance and environmental resistance, and also has anti-reflection properties and / or anti-glare properties, anti-Newton ring properties, scratch resistance, anti-fouling properties, anti-static properties and the like.

[0072]

Next, the present invention will be described in detail with reference to examples. The present invention is not limited by these. The thin film of the transparent conductive layer in the examples and comparative examples was formed on one main surface of the substrate by a magnetron DC sputtering method. The thickness of the thin film is a value obtained from film forming conditions, and is not an actually measured film thickness. The ITO thin film which is the high refractive index transparent thin film layer (B) has a target indium oxide / tin oxide sintered body (composition ratio In ₂ O ₃ : SnO ₂ =
90:10 wt%) using an argon / oxygen mixed gas (total pressure 266 mPa: oxygen partial pressure 5 mPa) as a sputtering gas. The SnO ₂ thin film which is the high refractive index transparent thin film layer (B) has a target made of a tin oxide sintered body, and a sputtered gas of an argon / oxygen mixed gas (total pressure 266 mPa: oxygen partial pressure 5).
mPa). The silver thin film as the metal thin film layer (C) was formed using silver as a target and argon gas (total pressure of 266 mPa) as a sputtering gas. The silver-palladium alloy thin film as the metal thin film layer (C) was formed by using a silver-palladium alloy (palladium 10 wt%) as a target and an argon gas (total pressure 266 mPa) as a sputtering gas. The silver-gold alloy thin film as the metal thin film layer (C) was formed by using a silver-gold alloy (gold 10 wt%) as a target and an argon gas (total pressure 266 mPa) as a sputtering gas.

The display filters of the examples and comparative examples were manufactured by combining the following members. still,
To determine the visible light reflectance (Rvis) of one side of the anti-reflection film surface, first cut out a small side of the object to be measured, roughen the surface on which the anti-reflection film is not formed with sandpaper, and then use a matte black spray. Then, the reflection on this surface was eliminated, and the total light reflectance in the visible region was measured by a spectrophotometer (U-3400, manufactured by Hitachi, Ltd.) using a reflection integrating sphere (light incidence angle 6 °). JISR310 from the calculated reflectance
Calculated according to 6. Further, evaluation of anti-Newton's ring property is performed by forming a functional transparent film having anti-Newton's ring property on a substrate having a size of 200 mm × 200 mm and a thickness of 2 mm, or a film-like substrate on which the functional transparent film is formed. 200mm x 200mm 2 with adhesive
It is laminated on a flat glass, with the surface on which the film is formed facing down, placed on a flat glass, and puts a weight of 500 g on the four corners of the filter for display.
A three-wavelength emission fluorescent lamp (Lupika 20W manufactured by Mitsubishi Electric Corporation) was irradiated from directly above, and the presence or absence of generation of Newton rings was observed from an angle of 10 to 80 ° with respect to the sample plane. Furthermore, the evaluation of the antifouling property is as follows.
After touching the surface with a finger and applying human fat, it was determined whether or not it could be wiped lightly with a cloth.

(Structure 1) A biaxially stretched polyethylene terephthalate (PET) film (hereinafter referred to as PET) (thickness: 75 μm) is used as a transparent substrate (A), and an ITO thin film and a silver thin film are laminated on one main surface thereof to form a transparent conductive layer. Was formed to obtain a sputtered film 1. Ethyl acetate / toluene (50: 50wt
%) An organic dye was dispersed and dissolved in a solvent to prepare a diluent of an acrylic pressure-sensitive adhesive. Acrylic adhesive / dilution solution containing pigment (80:20 wt%) was mixed, coated on a release film with a comma coater to a dry film thickness of 25 μm, dried, laminated with a release film on the adhesive surface, and released. An adhesive material (E) (adhesive material 1) as a dye layer sandwiched between mold films was obtained.

On one main surface of a triacetyl cellulose (hereinafter referred to as TAC) film (thickness: 80 μm), a photopolymerization initiator was added to a polyfunctional methacrylate resin, and ITO fine particles (average particle size: 10 nm) were further dispersed. The coating liquid is applied by a gravure coater, and a conductive hard coat film (thickness: 3 μm) is formed by ultraviolet curing, and a fluorine-containing organic compound solution is applied thereon by a microgravure coater, and dried at 90 ° C. Heat cured to form an antireflection film (thickness: 100 nm) with a refractive index of 1.4, hard coat property (pencil hardness: 2H according to JIS K5400), gas barrier property (1.8 g / m according to ASTM-E96). ² · da
y), antireflection property (Rvis on one side of the antireflection film side: 1.
0%), antistatic property (surface resistance: 7 × 10 ⁹ Ω /
□), an antireflection film 1 was obtained as a functional transparent layer (F) having antifouling properties. On the other main surface of the anti-reflection film 1, the adhesive / diluent is applied and dried without adding a dye similarly to the adhesive 1, to form an adhesive (E) (adhesive 2) having a thickness of 25 μm. Then, a release film was laminated. 3 mm thick, 1000 m as transparent support (D)
Air-cooled tempered glass of mx 600 mm was used.

The adhesive material 1 containing the dye sandwiched between the roll-shaped release films is continuously applied to the surface of the roll-shaped sputtered film 1 where the thin film is not formed, while peeling the release film on one side. Laminated (laminated), thin film /
A roll of PET film / adhesive containing dye / release film was obtained. This was laminated on one main surface of the air-cooled tempered glass while peeling off the release film. Further, an antireflection film 1 with an adhesive material was similarly laminated on the other main surface. Further, the antireflection film 1 was laminated only on the inner side of the sputtered film 1, except that the transparent conductive film having a peripheral portion of 20 mm, that is, the conductive portion was exposed. Further, a silver paste (Mitsui Chemical Co., Ltd. M
SP-600F) is screen printed and dried to a thickness of 1
An electrode of 5 μm was formed to produce an optical filter. FIG. 1 is a plan view of the configuration 1 as viewed from the electrode forming surface, as a plan view showing an example of the display filter of the present invention. FIG. 2 is a cross-sectional view illustrating an example of the configuration of the display filter according to the present invention and a mounted state of the filter.

(Structure 2) PET film (thickness: 75 μm)
m) as a transparent substrate (A), with SnO
_A transparent conductive layer was formed by laminating _two thin films, a silver thin film, and a silver-palladium alloy thin film in multiple layers, and a sputtered film 2 was obtained. The pressure-sensitive adhesive material 2 described in Structure 1 was similarly laminated on the surface of the sputtered film on which the thin film was not formed, to obtain a roll of the sputtered film 2 with the pressure-sensitive adhesive material (E).

As a transparent support (D) serving as a dye layer, an organic dye and an ultraviolet absorber were added to obtain a 3 mm-thick polymethyl methacrylate (hereinafter referred to as PMMA) plate produced by a casting method. On one main surface, a photopolymerization initiator is added to a polyfunctional methacrylate resin, and a coating liquid in which organic silica fine particles (average particle size: 15 μm) is dispersed is applied by a dipping method, ultraviolet-cured, and then subjected to antiglare. Functional transparent layer (F) having properties (haze value measured by haze meter: 2%) and hard coat properties (pencil hardness: 2H)
An anti-glare layer (film thickness: 2 μm) is formed as
A 00 mm × 600 mm anti-glare PMMA plate was produced.

Rolled Sputtered Film 2 with Adhesive
Was laminated on the surface of the PMMA plate on which the anti-glare layer was not formed while peeling off the release film. Further, a photopolymerization initiator is added to the polyfunctional methacrylate resin only on the inner side of the sputtered film 2 except that the conductive portion having a peripheral portion of 20 mm is exposed, and organic silica fine particles (average particle size: 15 μm) Is dispersed, flexographically printed and cured by ultraviolet rays, and has a functional transparent layer (F) having antiglare properties (haze value measured by a haze meter: 5%), anti-Newton ring properties, and hard coat properties (pencil hardness: 2H).
An anti-Newton ring layer was formed. Further, a silver paste was screen-printed and dried in the same manner as in Configuration 1 to form an electrode having a thickness of 15 μm, thereby producing a display filter. FIG. 3 is a cross-sectional view illustrating an example of the configuration 2 of the display filter according to the present invention and a mounted state thereof.

(Structure 3) Air-cooled tempered glass (thickness: 2.5
mm) as a transparent substrate (A), on one of its main surfaces, an IT
A transparent conductive layer was formed by laminating O thin films and silver-gold alloy thin films in multiple layers to obtain a sputtered glass of 1000 mm × 600 mm. A PET film (thickness: 100 μm) is obtained by hydrolyzing alkoxylan on one main surface with glacial acetic acid, and adding a silicone-based surface smoothing agent, an organic dye, or a dithiol complex-based near infrared absorber (SIR manufactured by Mitsui Chemicals, Inc.) -159: center absorption wavelength 850 nm) 0.5 wt% was mixed, and the added coating solution was applied by a gravure coater and cured by heat at 120 ° C. to form a hard coat film containing dye (film thickness: 10 μm).
Is formed, and an ITO thin film (thickness: 70 nm) and S
A two-layer anti-reflection film is formed by sputtering in the order of an iO ₂ thin film (thickness: 90 nm), and is a pigment layer and has a hard coat property (pencil hardness: 3H) and an anti-reflection property (one side of the anti-reflection film surface). Rvis: 0.8%), an anti-reflection film 2 as a functional transparent layer (F) having antistatic properties (surface resistance: 2 × 10 ⁵ Ω / □) and antifouling properties. In the same manner as in Configuration 1, a roll of the antireflection film 2 with the adhesive (E) was obtained. As in the case of the configuration 1, the antireflection film 2 was laminated on the main surface on which the thin film of the sputtered glass was not formed. Further, a silver paste was screen-printed and dried in the same manner as in Configuration 1 to form an electrode having a thickness of 15 μm, thereby producing a display filter. FIG. 4 shows a cross section of Configuration 3 as a cross-sectional view showing an example of the display filter of the present invention and its mounted state.

[Example 1] In the structure 1, in order from the PET film, an ITO thin film (thickness: 40 nm), a silver thin film (thickness: 11 nm), an ITO thin film (thickness: 95 nm),
Silver thin film (thickness: 14 nm), ITO thin film (thickness: 90 n)
m), silver thin film (thickness: 12 nm), ITO thin film (thickness:
(40 nm) to produce a total of seven transparent conductive layers. The dye-containing pressure-sensitive adhesive that is the dye layer is dye PS-V manufactured by Mitsui Chemicals, Inc.
Acrylic adhesive to be coated using iolet-RR /
The diluents containing the dyes were prepared and prepared so as to be 1760 (wt) ppm. The cross section of the PET film / transparent conductive layer is shown in FIG. 5 as a cross-sectional view showing one example of the transparent conductive layer in the present invention.

[Example 2] A transparent conductive layer was produced in the same manner as in Example 1 except that the dye-containing pressure-sensitive adhesive serving as the dye layer was dye PS-Violet- manufactured by Mitsui Chemicals, Inc.
RC and pyromethene dye (maximum absorption wavelength 497nm)
Acrylic pressure-sensitive adhesive / dilution-containing diluents were prepared and prepared so as to be 1640 (wt) ppm and 1900 (wt) ppm, respectively.

Comparative Example 1 A transparent conductive layer was produced in the same manner as in Example 1 except that the adhesive contained no dye, and a display filter having no dye layer was produced.

Comparative Example 2 A transparent conductive layer was prepared in the same manner as in Example 1 except that the dye-containing pressure-sensitive adhesive used as the dye layer was dye MS-Red-G and PS manufactured by Mitsui Chemicals, Inc. -Violet-RC is 380 (wt) ppm,
A acryl-based adhesive / dilution-containing diluent was prepared at 530 (wt) ppm.

Example 3 In the structure 2, in order from the PET film, a SnO ₂ thin film (thickness: 40 nm), a silver thin film (thickness: 9 nm), a SnO ₂ thin film (thickness: 80 nm),
Silver-palladium alloy thin film (thickness: 11 nm), SnO ₂
A total of five transparent conductive layers of a thin film (thickness: 40 nm) were produced. The PMMA plate as the dye layer is made of PS-Violet-
The pigments were prepared so as to contain 12 (wt) ppm and 15 (wt) ppm of RC and pyromethene dye (maximum absorption wavelength 497 nm), respectively.

Comparative Example 3 A transparent conductive layer was produced in the same manner as in Example 3 except that no dye was contained in the PMMA plate, and a display filter having no dye layer was produced.

Example 4 In the structure 3, an ITO thin film (thickness: 40 nm), a silver-gold alloy thin film (thickness: 12 nm), and an ITO thin film (thickness: 40 n) in order from the tempered glass.
m) to produce a total of three transparent conductive layers. The hard coat film of the antireflection film 2 which is a dye layer is made of a coating solution containing a near-infrared absorber SIR-159 (center absorption wavelength: 850 nm) manufactured by Mitsui Chemicals, Inc., and PS-Violet-RR.
Were prepared to contain 4000 (wt) ppm and 4500 (wt) ppm, respectively.

[Comparative Example 4] In the structure 3, a transparent conductive layer was formed in the same manner as in Example 4, and the hard coat film of the antireflection film 2 as the dye layer was coated with PS-Mitsui Chemicals Co., Ltd. Brilli. Red-HEY is 600 (w
t) It was prepared and prepared to contain ppm.

Example 5 A transparent conductive layer was produced in the same manner as in Example 1 except that the dye-containing pressure-sensitive adhesive as the dye layer was formed of tetra-t-butyl of the formula (3) -The tetraazaporphyrin / copper complex is 1350 (wt) p
pm so as to prepare a diluent containing an acrylic pressure-sensitive adhesive / dye.

[0090]

Embedded image

Example 6 A transparent conductive layer was produced in the same manner as in Example 1 except that the dye-containing pressure-sensitive adhesive, which is a dye layer, was formed by a dye PS-Red-G manufactured by Mitsui Chemicals, Inc. The tetra-t-butyl-tetraazaporphyrin / copper complex of (3) was 430 (wt) ppm and 980, respectively.
An acrylic pressure-sensitive adhesive / dye-containing diluent was prepared and prepared so as to be (wt) ppm.

Example 7 A transparent conductive layer was produced in the same manner as in Example 1 except that the dye-containing pressure-sensitive adhesive, which is a dye layer, was a dye PS-Red-G manufactured by Mitsui Chemicals, Inc. (4) The tetra-t-butyl-tetraazaporphyrin / vanadyl complex of [Chemical Formula 5] is 820 (wt) each.
Acrylic pressure-sensitive adhesives / dilution-containing diluents were prepared and prepared to be in ppm and 1000 (wt) ppm.

[0093]

Embedded image

The total light transmittance, near-infrared light transmittance, visible light reflectance, and transparent conductivity of the display filters of the present invention of Examples 1 to 7 and the display filters of Comparative Examples 1 to 4 prepared as described above. Layer resistance, chromaticity of emission (x,
y), image quality such as contrast, and chromaticity (x,
y) Image quality such as contrast and contrast was evaluated by the following methods.

In each of Examples 1-2 and 5-7 and Comparative Examples 1-2, the display filter was mounted in parallel with the electrode forming surface at a distance of 2 mm from the plasma display panel screen with the human side. Example 3 and Comparative Example 3
In Example 4, the electrode forming surface was on the plasma display panel side, and the light-transmitting portion of the display filter was placed in close contact with the screen of the plasma display panel.
In Comparative Example 4, the electrode forming surface was on the side of the plasma display panel, and was placed 2 mm away from the plasma display panel screen in parallel.

1) Total light transmittance of filter for display In Examples 1 to 7 and Comparative Examples 1 to 4, the light-transmitting portion of the object to be measured was cut out into small pieces, or a small piece sample having the same configuration was prepared. 3.) A sample was fixed to the sample-side entrance of a reflection integrating sphere (light incident angle 6 °) of a spectrophotometer (U-3400) manufactured by Hitachi, Ltd., and the total light transmittance of the measurement object at 300 to 800 nm was measured.

2) Near-infrared transmittance of display filter (T850 nm, T950 nm) In Examples 1 to 7 and Comparative Examples 1 to 4, the light-transmitting part of the object to be measured was cut out into small pieces, or a small piece sample having the same configuration was used. Prepared and measured with a spectrophotometer (U-3400) manufactured by Hitachi, Ltd. at 850 nm and 950 nm near-infrared transmittances T850 nm and T95.
0 nm was measured.

3) Visible light reflectance (Rvis) of display filter In Examples 1 to 7 and Comparative Examples 1 to 4, the light-transmitting portion of the object to be measured was cut out into small pieces, or a small piece sample having the same structure was prepared. Using a spectrophotometer (U-3400, manufactured by Hitachi, Ltd.) using a reflection integrating sphere (ray incident angle 6 °).
The total light reflectance on both surfaces of the object to be measured at -800 nm was measured. Rvis was calculated from the transmittance determined in accordance with JIS R3106.

4) Sheet Resistance of Transparent Conductive Layer In Examples 1 to 7 and Comparative Examples 1 to 4, before manufacturing a display filter, the sheet resistance of the transparent conductive layer provided on the substrate was measured by a four-step method. Needle measurement method (probe interval 1m
m).

5) Visibility The visibility when the display filters of Examples 1 to 7 and Comparative Examples 1 to 4 were mounted was determined by the reflection of external light and the Newton ring in Example 3 and Comparative Example 3. Judgment was made based on whether or not the visibility of the image was reduced. ○ indicates good, Δ indicates no problem, and × indicates inferior.

6) Luminance (Highest Luminance) and Contrast Ratio (Highest / Lowest Luminance Ratio) The case where no display filter is mounted on the plasma display, and the case where the display filters of Examples 1 to 7 and Comparative Examples 1 to 4 are mounted Was measured. The maximum luminance (cd / m ² ) at the time of white display and the minimum luminance (cd / m ² ) at the time of black display of a plasma display panel at the time of light with an ambient brightness of 100 lx are measured by a luminance meter (LS) manufactured by Minolta Co., Ltd. -110), and the ratio (highest luminance / lowest luminance) was determined. The contrast ratio at the time of light is preferably 30 or more, and more preferably 40 or more.

7) Color Purity of Emitted Color Measurements were made for the case where the display filter was not mounted on the plasma display and the case where the display filters of Examples 1 to 7 and Comparative Examples 1 to 4 were mounted.

In red (R) display, green (G) display, and blue (B) display, a CRT color analyzer (CA100) manufactured by Minolta Co., Ltd.
y) was measured. It is preferable that the three primary colors of PDP emission be determined by the NTSC system and be closer to the chromaticity range of RGB colors. The above results are shown in Tables 1 and 2 and FIG.

[0104]

[Table 1]

In Table 1, the value A is the wavelength 6 of the minimum transmittance at the wavelength of 580 to 605 nm of the display filter.
As a percentage of the maximum transmission at 15-640 nm,
Preferably it is 20 to 85%. In Table 1, the B1 value is the maximum transmittance of the display filter at a wavelength of 450 to 480 nm, the B2 value is the maximum transmittance of the display filter at a wavelength of 510 to 535 nm, and the B3 value is the maximum transmission of the display filter at a wavelength of 615 to 640 nm. And preferably 45% or more. In Table 1, the C value is the wavelength 51 of the minimum transmittance at the wavelength of 540 to 580 nm of the display filter.
As a percentage of the maximum transmission at 0-535 nm, 4
Preferably it is 0-90%. In Table 1, D indicates ○ (preferred) when the transmittance of the display filter monotonically decreases as the wavelength becomes longer at wavelengths of 520 to 540 nm, and x (unfavorable) when the transmittance does not decrease monotonically. In Table 1, the E1 value is the wavelength 4 of the minimum transmittance at the wavelength of 480 to 5210 nm of the display filter.
As a percentage of the maximum transmission at 50-480 nm,
Preferably it is 50 to 90%. In Table 1, E2 values are wavelengths 480 to 5210 of the display filter.
The minimum transmittance at nm is preferably 50 to 90% as a percentage of the maximum transmittance at wavelengths of 510 to 535 nm.

[0106]

[Table 2]

As is clear from Tables 1 and 2, and FIG.
When the display filters of Examples 1 to 7 of the present invention, which are excellent in near-infrared cut ability and low resistance for electromagnetic wave shielding, are used, the color purity is superior to that of the plasma display panel alone and is determined by the NTSC method. A display close to the chromaticity range is obtained. Example 2
And the use of 5 to 7 display filters, the most problematic red emission is particularly improved. In the display filters of Examples 5 to 7 using the tetraazaporphyrin compound, red emission was improved, and the decrease in the luminance of the plasma display was reduced in Example 2.
Fewer. The display filters of Comparative Examples 1 to 4 are excellent in near-infrared cut ability and low resistance for electromagnetic wave shielding, but the chromaticity range cannot correct the emission of the plasma display panel, and the color reproduction range is equal to or less than that. Can only have. They do not reduce or cannot sufficiently reduce the light emission that causes the reduction in color purity, they do not significantly reduce external light reflection, and cannot shift the emission wavelength peak to improve color purity. , Etc. For the same reason, it can be seen that the contrast ratio can be improved without significantly deteriorating the luminance by using the display filters of the present invention of Examples 1 to 7. Even when the display filters of Comparative Examples 1 to 4 were used, only the improvement of the contrast ratio by reducing the overall light emission luminance was not at a sufficient level.

The display filter of the present invention is excellent in low reflectivity, and the display filter of the present invention of Example 3 does not generate Newton rings even when it is brought into close contact with the screen by the anti-Newton ring layer. , Visibility is not inferior or excellent. The low reflectivity also contributes to the improvement of the contrast ratio. The sheet resistance increases when the number of layers is small and an alloy containing silver instead of silver is used. Although the near-infrared transmittance is also increased, the filter for display of the present invention of Example 4 uses a near-infrared absorber in combination, so that the number of layers is small and the near-infrared cut ability is reduced even when an alloy is used. Are better. Furthermore, the display filter of the present invention is characterized in that the functional transparent layer has various functions, whereby the transparent conductive layer has excellent weather resistance, environmental resistance and / or abrasion resistance, and has excellent abrasion resistance and / or abrasion resistance. Or antifouling properties and / or
Or it has excellent antistatic properties. The display filters of Examples 1 to 7 did not show significant changes in optical characteristics even when left in air at 80 ° C. for 200 hours or more, and even when irradiated with 50 million lx · hour of visible light. .

[0109]

As described above, according to the present invention, as a filter for a plasma display, it is possible to improve the color purity and contrast of the emission color of a color plasma display, and at the same time, to obtain excellent transmission characteristics without significantly impairing luminance and visibility.
It has transmittance and visible light reflectance, and also shields electromagnetic waves generated from the plasma display, which are said to be harmful to health, and blocks near infrared rays that may cause erroneous operation of peripheral electronic devices. The present invention can provide a filter for a display having near-infrared cut ability and excellent weather resistance, environmental resistance, antistatic property, abrasion resistance and stain resistance.

[Brief description of the drawings]

FIG. 1 is a plan view showing an example of a display filter of the present invention.

FIG. 2 is a cross-sectional view showing an example (configuration 1) of the display filter of the present invention and a mounted state thereof.

FIG. 3 is a cross-sectional view showing an example (configuration 2) of the display filter of the present invention and a mounted state thereof.

FIG. 4 is a cross-sectional view illustrating an example (configuration 3) of the display filter of the present invention and a mounted state thereof.

FIG. 5 is a cross-sectional view showing one example (Example 1) of the transparent conductive layer in the present invention.

FIG. 6 shows a triangle indicating a preferred chromaticity range with the chromaticity determined by the NTSC system as a vertex, a triangle indicating a color reproduction range of a plasma display panel (PDP) connecting the chromaticities of RGB light emission of a PDP, and the embodiment. R when the display filters of the present invention of Examples 1 to 4 and the display filters of Comparative Examples 1 to 4 were installed in a plasma display.
FIG. 2 is a diagram in which chromaticity of GB emission is plotted on a chromaticity x-chromaticity y coordinate system determined by CIE.

FIG. 7 shows a triangle indicating a suitable chromaticity range with the chromaticity determined by the NTSC method at the top, a triangle indicating the color reproduction range of a plasma display panel (PDP) connecting the chromaticities of RGB light emission of a PDP, and FIG. When the display filters of the present invention of Examples 5 to 7 were installed in a plasma display, the chromaticity of the RGB emission was determined by the chromaticity x− defined by the CIE.
It is the figure plotted on the chromaticity y coordinate system.

[Explanation of symbols]

00 Display screen 01 Transparent portion of display filter 10 Transparent conductive layer 11 High refractive index transparent thin film layer 12 Metal thin film layer 20 Transparent substrate (A) 21 Transparent substrate containing dye (A) (dye layer) 30 Adhesive material ( E) 31 Dye-containing pressure-sensitive adhesive (E) (dye layer) 40 Transparent support (D) 41 Transparent support (D) containing dye (dye layer) 50 Electrode 60 Anti-reflective property, hard coat property, gas barrier Functional transparent layer (F) 61 having antistatic, antistatic and antifouling properties 61 Antireflection film having antifouling properties 62 Hard coat film 63 having antistatic properties 63 Transparent substrate on which 62, 61 is formed 70 Antiglare Layer (functional transparent layer (F) having anti-glare property and hard coat property) 80 Unnewton ring layer (function having anti-glare property, anti-Newton ring property and hard coat property) (Transparent layer (F)) 90 A functional transparent layer (F) having an antireflection property, a hard coat property, an antistatic property and an antifouling property as a dye layer 91 An antireflection film having an antistatic property and an antifouling property 92 Dye -Containing hard coat film

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shin Fukuda 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Taizo Nishimoto 580 Nagaura, Sodegaura-shi, Chiba 32 32 Mitsui Chemicals, Inc. Inventor Megumi Misawa 32, 580 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals, Inc.

Claims (11)

[Claims] 1. A color filter comprising at least a transparent conductive layer having a sheet resistance of 1 to 10 Ω / □ and a dye layer, and having a wavelength of 580 to 605 nm.
A display filter, wherein the minimum transmittance at m is 10 to 85% of the maximum transmittance at a wavelength of 615 to 640 nm. 2. The maximum transmittance at a wavelength of 450 to 480 nm, the maximum transmittance at a wavelength of 510 to 535 nm, and the maximum transmittance at a wavelength of 615 to 640 nm are 45% to 85%, respectively. Display filters. 3. The minimum transmittance at a wavelength of 540 to 580 nm is one of the maximum transmittance at a wavelength of 510 to 535 nm.
The filter for a display according to claim 1, wherein the filter is 0 to 90%. 4. The display filter according to claim 1, wherein at a wavelength of 520 to 540 nm, the transmittance monotonously decreases as the wavelength becomes longer. 5. The minimum transmittance at a wavelength of 480 to 510 nm is 50 to 90% of the maximum transmittance at a wavelength of 450 to 480 nm and / or the maximum transmittance at a wavelength of 510 to 535 nm. A display filter according to claim 4. 6. The high refractive index transparent thin film layer (B) and the metal thin film layer (C) wherein the transparent conductive layer is formed on at least one principal surface of the transparent substrate (A). From (B) / (C) as a repeating unit, and is a transparent conductive film obtained by repeating lamination one to four times, and further laminating at least the high-refractive-index transparent thin film layer (B) thereon. The display filter according to any one of claims 1 to 5, wherein 7. The display filter according to claim 1, wherein the transparent support (D) is formed via an adhesive (E). 8. An anti-reflection property, an anti-glare property, an anti-reflection anti-glare property,
A functional transparent layer (F) having at least one function selected from an antistatic property, an anti-Newton's ring property, a gas barrier property, a hard coat property, and an antifouling property is formed directly or via an adhesive (E). The display filter according to any one of claims 1 to 7, wherein: 9. A dye layer comprising a dye-containing transparent substrate (A), a dye-containing transparent support (D), a dye-containing adhesive (E), and a dye-containing functional transparent layer (F). 9. The display filter according to claim 1, comprising at least one of the following. 10. The display filter according to claim 1, wherein the dye is one or more dyes, at least one of which is a tetraazaporphyrin compound. 11. The display filter according to claim 10, wherein the tetraazaporphyrin compound is a dye represented by the formula (1). Embedded image [In the formula (1), A ^{1 to} A ⁸ each independently represent a hydrogen atom,
Halogen atom, nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, 1-2 carbon atoms
An alkyl group, a halogenoalkyl group, an alkoxy group,
Alkoxyalkoxy group, aryloxy group, monoalkylamino group, dialkylamino group, aralkyl group, aryl group, heteroaryl group, alkylthio group, or
Represents an arylthio group, A ¹ and A ² , A ³ and A ⁴ , A
⁵ and A ⁶ , A ⁷ and A ⁸ may each independently form a ring other than an aromatic ring via a linking group, and M is two hydrogen atoms, a divalent metal atom, or a trivalent one. Represents a substituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom. ]