JP3522929B2 - Image display device - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a field emission display and an image display device having an electron-emitting device having a structure similar to that of the field emission display.
More specifically, by providing an antireflection layer on the conventional FED, higher quality image display is possible while maintaining the excellent characteristics originally possessed by the FED such as viewing angle, gradation and brightness. Regarding FED.

[0002]

2. Description of the Related Art Conventionally, a liquid crystal display has been widely used as a flat panel display. However, this liquid crystal display requires many steps and strict quality control in its manufacture, and has a large power consumption. However, the FED is attracting attention as an alternative to these liquid crystal displays.

As shown in FIG. 10 , the above-mentioned conventional FED is as follows.
An electron emitting substrate 100 including a glass substrate 1, a wiring layer 2, an electron emitting element 3, an insulating layer 4, and an extraction electrode 5, and a light emitting substrate 200 including a glass substrate 6, an anode 7, and R, G, and B phosphor layers. Has a basic structure in which they are opposed to each other in a vacuum state and electrically connected. In this FED, a voltage is applied to the electron emission element 3, the extraction electrode 5, and the anode 7, the extraction electrode 5 extracts electrons from the electron emission element 3, and the electrons are collided with the anode 7 to cause the phosphor to emit light.

Then, by controlling the combination of the voltages applied to the extraction electrode 5, the anode 7 and the electron-emitting device 3, the amount and direction of the electrons emitted from the electron-emitting device 3 are controlled, and the electron beam is desired. The phosphor layer (the phosphor layer of B in FIG. 10 ) is irradiated, and the energy causes the phosphor layer B to emit blue light. The blue light emitted from the phosphor layer B is radiated to the outside through the transparent anode 7 and the glass substrate 6 and is observed as blue light. In this way, a desired image is displayed on the surface of the glass substrate 6 by causing the R, G, and B phosphor layers to emit light in any combination and in any order.

As the FED to which the present invention is applied,
A cold cathode (field emission array) whose electron-emitting device emits electrons by an electric field concentration effect, or a MIM structure (metal / insulator / metal / insulator / metal insulator)
Metal), MIS structure (metal / insulator / semiconductor), MSM
Structure (metal / semiconductor / metal) Including an electron-emitting device having a micro electron source. In 1965, "Radio Engineering Electro Physics (Radio Eng. Electro
n Phys.) ”Volume 10, 1290-1296”
Some reports have been made since reported by MI Elinson et al. There is an FED having a planar electron-emitting device having fine particles between electrodes, and a newly developed micro-electron-emitting device. The FED is also included in the FED targeted by the present invention.

Further, as the FED targeted by this patent,
It is not always necessary to have the structure of FIG. 1. For example, the electron-emitting substrate 100 having a bipolar structure without the extraction electrode 5 or an insulator layer on the extraction electrode 5 and an electron beam converged thereon /
The FED having various structures such as a quadrupole structure having a converging electrode for deflecting, and a planar electron-emitting device having a structure different from that of FIG. 1 are also included. For example, there are various methods of irradiating the phosphors with electron beams from these electron-emitting devices, and the combination of the electron-emitting devices and the phosphors is shown as a many-to-many combination in FIG. 1, but is not limited to this. not,
For example, any of one-to-one, one-to-many, many-to-one, and many-to-many may be used.

[0007]

When a mono or full-color image is displayed and observed by the above FED, external light is reflected on the display surface and the reflected light enters the eyes of the observer depending on the angle of observation. There is a problem that the displayed image is difficult to see. In particular, the FED is a self-luminous thin display, and since it is particularly used for a portable terminal or the like, it is often used under natural light or strong illumination light, and the above-mentioned problem becomes prominent. Therefore, the object of the present invention is to provide a conventional FED.
It is an object of the present invention to provide an FED which has an excellent antireflection effect and can display a clear and excellent quality image while maintaining the excellent properties such as the viewing angle, gradation and brightness.

[0008]

The above object can be achieved by the present invention described below. That is, according to the present invention, an electron-emitting substrate including a glass substrate, a wiring layer, an electron-emitting device, an insulating layer, and an extraction electrode, and a light-emitting substrate including a glass substrate, an anode, and a phosphor layer are placed in a vacuum state. In the FED, which is laminated and electrically connected to and facing each other, an antireflection layer composed of at least one low refractive index layer and at least one high refractive index layer is formed on the glass substrate surface of the light emitting substrate , Anti-reflection
The stop layer has a refractive index lower than that of the adhesive layer and the adhesive layer.
Low refractive index layer having a refractive index, the adhesive layer and the low refractive index layer
Has a higher refractive index than the adhesive layer above.
Which has a high refractive index layer,
The FED is characterized by having a hard coat layer between it and the coating layer .

According to the present invention, the FED is formed by forming an antireflection layer composed of at least one low refractive index layer and at least one high refractive index layer on the glass substrate surface of the FED on the light emitting substrate side. It is possible to display a clear and excellent quality image having an excellent antireflection effect while maintaining the original excellent characteristics such as viewing angle, gradation and brightness.
That is, by applying an antireflection technique and forming an antireflection layer on the display surface of the FED, the reflected light is reduced and the light generated in the phosphor layer is efficiently radiated to the outside to provide a clear and excellent quality. It is possible to display the image of. Also, FE
When D is a color display having R, G, and B phosphor layers, it is possible to display a clear and excellent quality full-color image together with the above characteristics.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments. The following description will be made on the case where the FED is a color display having R, G and B phosphor layers, but it goes without saying that the present invention also includes a single-layer phosphor layer, that is, an FED for monochrome display. is there.

The example shown in FIG. 1 is an antireflection layer composed of at least one low refractive index layer and at least one high refractive index layer on the surface of the glass substrate 6 on the light emitting substrate 200 side of a conventionally known FED. 8 shows an embodiment in which 8 is provided. In the present invention, high refraction or low refraction means a relative high or low refractive index. In the example shown in FIG. 2, an adhesive layer 9 for adhering the glass substrate 6 and the low refractive index layer 10 is formed of an adhesive having a high refractive index, and a layer above the adhesive layer 9 is used for refracting the adhesive layer 9. The antireflection layer 8 made of the low refractive index layer 10 having a refractive index lower than the refractive index was formed.

The example shown in FIG. 3 corresponds to the example shown in FIG.
A high refractive index layer 11 having a refractive index higher than that of the adhesive layer is provided between the adhesive layer 9 and a low refractive index layer 10 having a refractive index lower than that of the adhesive layer. It is an example. The example shown in FIG. 4 is an example in which the hard coat layer 12 is provided between the adhesive layer 9 and the high refractive index layer 11 in the example shown in FIG.

Next, F shown in FIG. 1 which is a basic form of the present invention
The details of the ED will be described. In addition, FIG. 1 shows R of the display,
Only a structure for driving one unit pixel portion of G and B is shown,
The actual dimensional ratio of each part is disregarded and drawn. The glass substrate 1 has a sufficient thickness to support the formed FED, and the wiring layer 2 is formed thereon. An electron-emitting device 3 and an insulating layer 4 are formed on the wiring layer 2,
The extraction electrode 5 is formed on the insulating layer 4.

As the glass substrate 1, soda lime glass, low expansion glass (for example, Corning 7059, etc.),
High strain point glass or the like is used, and the wiring layer 2 supplies a voltage to the electron-emitting device 3. For example, ITO, Sn
Transparent conductive films such as O ₂ , ZnO: Al, Al, Au,
It is formed from a material such as W, Mo, Ti, Ta, Nb, Cr, or Pt to a thickness of about 0.02 to 200 μm by a method such as vapor deposition and photography, or printing and firing.

There are various methods for forming the electron-emitting device. As a typical manufacturing method, a method combining etching of a Si substrate with deposition of an insulator or a metal, or Spin
There is a metal deposition method such as dt type. The shape of the electron-emitting device is various, such as a conical shape, a caldera shape, a cross shape, and a flat shape. Further, there is a micro electron source having a MIM, MIS, or MSM structure that emits thermoelectrons without utilizing the electric field concentration effect. These materials also vary depending on the structure.

On the side of the light emitting substrate 200, an anode 7 and RGB phosphor layers are formed on the lower surface of the glass substrate 6. The anode 7 is formed of, for example, a transparent conductive film of ITO, SnO ₂ , ZnO: Al or the like with a thickness of about 0.3 to 200 μm by a method such as vapor deposition and photography, or printing and firing. The phosphor layers are usually R, G and B, respectively.
The phosphor that emits light is dispersed in a solvent and a resin binder that can be baked at a low temperature (eg, ethyl cellulose, nitrocellulose, acrylic resin, etc.), and a phosphor paste is applied and baked into a mosaic shape. It is formed.

Phosphors which emit R color by electron irradiation include Y ₂ O ₃ : Eu, Y ₂ O ₂ S: Eu, Y ₂ SiO ₅ :
Eu, Y ₃ Al ₅ O ₁₂ : Eu, ScBO ₃ : Eu, Zn
_{3 (PO 4) 2: Mn} , YBO 3: Eu, SnO 2: Eu,
(Y, Gd) BO ₃ : Eu, GdBO ₃ : Eu, LuB
There is O ₃ : Eu, etc., and as a phosphor that emits B color,
ZnMgO, ZnGa ₂ O ₄ , ZnS: Ag, Y ₂ Si
O ₅ : Ce, CaWO ₄ : Pb, BaMgAl ₁₄ O ₂₃ : E
Examples of a phosphor that emits G color, such as u, include ZnO:
Zn, Gd ₂ O ₂ S: Tb, ZnGa ₂ O ₄ : Mn, Zn
S: Cu, Al, Zn ₂ SiO ₄ : Mn, BaAl
₁₂ O ₁₉ : Mn, BaAl ₁₂ O ₁₉ : Mn, YBO ₃ : T
b, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, G
bBO ₃ : Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ O ₃ C
l ₄ : Eu and the like can be mentioned.

These phosphor layers are RGBRG vertically and horizontally.
It is provided in a plane by repeating B ...
The size of one pixel of R, G, and B colors is about 1 to 250.
0 μm ² and the spacing between the phosphor layers of each color is about 2
It is about 70 μm. About 0.5 for each color by vapor deposition and photography, electrodeposition, printing, or printing and baking.
It is formed to have a thickness of about 200 μm.

The electron emitting substrate 100 and the light emitting substrate 200 as described above are the electron emitting substrate 1 as a completed FED.
00 and the light emitting substrate 200 are arranged so as to face each other as shown in FIG. 1, and have a space of about 100 μm to 10 mm by using a spacer, a sealant, etc., and the space is in a vacuum state. To be laminated.

The FED configured as described above is, for example,
In the case of an electron-emitting substrate having a three-pole structure, the same operation as that of a vacuum tube is performed, and a predetermined voltage is applied to each electrode by using the electron-emitting device 3 as a cathode, the anode 7 as an anode, and the extraction electrode 5 as a grid to emit electrons. Electrons are extracted from the element 3, emitted to the anode 7 and collided with each other to cause the phosphor layer to emit light of each color. At this time, the electron-emitting device 3 and the anode 7
And, depending on the on / off of the voltage applied to the extraction electrode 5 and the level of the voltage, each color is made to emit light individually or simultaneously, and the anode 7,
A color image is observed from above in the drawing through the glass substrate 6.

In the present invention, as shown in FIGS. 1 to 4, the FED as described above includes at least one low refractive index layer and at least one high refractive index layer on the surface of the glass substrate 6 of the light emitting substrate 200. It is characterized in that an antireflection layer 8 composed of a layer is formed. In the illustrated FED, the antireflection layer 8
The adhesive layer 9 for forming the film is the antireflection layer 8 and the glass substrate 6
Any of known adhesives having such a function can be used. However, in order to impart sufficient hardness and durability to the antireflection layer 8, it is preferable to increase the crosslink density of the adhesive, increase the adhesion between the layers, and form the adhesive layer 9 having high hardness. For that purpose, it is preferable to use an adhesive having a glass transition temperature of 20 ° C. or higher after solidification (or curing).

As an example of the adhesive having such a glass transition temperature, there is a urethane adhesive. Examples of urethane-based adhesives include moisture-curable (1-liquid type), thermosetting (2-liquid type) and other reactive curable urethane-based adhesives. The moisture-curing type is mainly composed of an oligomer and a prepolymer of a polyisocyanate compound, and the thermosetting type is mainly composed of a monomer, an oligomer and a prepolymer of a polyisocyanate compound and an oligomer and a prepolymer of a polyol compound. When these reaction-curable urethane-based adhesives are used, it is preferable to perform an aging treatment at a temperature of from room temperature to about 80 ° C. after laminating with other layers, since the entire antireflection layer 8 is not adversely affected by heat. .

The glass transition temperature after aging is 20 ° C. by further containing 10% by weight or more of the polyisocyanate of the adhesive as a crosslinking agent in the urethane adhesive.
The above can be done. Examples of the polyisocyanate compound that can be contained in the adhesive include tolylene diisocyanate (TFI), 3,3′-tolylene-4,4′-diisocyanate, diphenylmethane-
4,4'-diisocyanate (MDI), triphenylmethane-p, p'p "-triisocyanate (TM),
2,4-tolylene dimer (TT), naphthalene-1,
5-diisocyanate, tris (4-phenylisocyanate) thiophosphate, TDI trimer, cyclohexamethane-4,4'-diisocyanate, hydrogenated TD
I (HTDI), meta-xylylene diisocyanate (X
DI), hexahydrometa-xylene diisocyanate (HXDI), hexamethylene diisocyanate, trimethylpropane-1-methyl-2-isocyano-4-carbamate, polymethylene polyphenyl polyisocyanate, 3,3'dimethoxy-4,4'-diphenyl Isocyanate, diphenyl ether-2,4,1'-triisocyanate, m-xylylene diisocyanate (M
XDI), polymethylene polyphenyl polyisocyanate (PAPI) and the like.

Another preferred adhesive is an ionizing radiation curable adhesive. The adhesive is a relatively low molecular weight polyester resin having an acrylate-based functional group,
Polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin, polythiol polyene resin, polyfunctional alcohol such as polyfunctional compounds (meth) acrylate oligomer or prepolymer as a main agent, As the reactive diluent to the main agent, for example, ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene,
Monofunctional and polyfunctional monomers such as methylstyrene and N-vinylpyrrolidone, for example, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth). Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. It was added. The above reactive diluent is
In addition to the above urethane-based adhesive, the urethane-based adhesive can also be used as an ionizing radiation curable adhesive.

When the above-mentioned ionizing radiation-curable adhesive is cured by ultraviolet rays, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, as a photopolymerization initiator in the adhesive,
Tetramethyl thiuram monosulfide, thioxanthones, n-butylamine, triethylamine, tri-n-butylphosphine and the like as a photosensitizer are mixed and used. Particularly in the present invention, an adhesive in which urethane acrylate is mixed as the oligomer and dipentaerythritol hexaacrylate is mixed as the monomer is preferable.

In the present invention, the above-mentioned adhesive is the above-mentioned F
It is applied on the surface of the glass substrate 6 of the ED and a low refractive index layer having a refractive index lower than that of the adhesive layer 9 made of the adhesive is formed on the surface of the glass substrate 6, or the release paper surface is preliminarily formed. The low-refractive index layer 10 and the adhesive layer 9 are laminated in this order, and the adhesive layer 9 is laminated so that the adhesive layer 9 is in contact with the glass substrate 6, the release paper is peeled off, and then the adhesive layer 9 is heated or ionized. The radiation forms an antireflective coating for curing, for example as shown in FIG.

The material for forming the low refractive index layer 10 may be an inorganic material or an organic material, but the lower layer (the adhesive layer 9 in FIG. 2 and the high refractive index in FIGS. 3 and 4) in direct contact with the layer. It is necessary to have a refractive index lower than that of the index layer 11). Examples of the low refractive index material include LiF
(Refractive index 1.4), MgF ₂ (refractive index 1.4), 3Na
F · AlF ₃ (refractive index 1.4), AlF ₃ (refractive index 1.
4), Na ₃ AlF ₆ (cryolite, refractive index 1.33), Si
O _x (x: 1.50 ≦ x ≦ 2.00, refractive index 1.35 to
1.48) and other inorganic materials. A film formed of a low-refractive-index inorganic material has high hardness, and plasma CVD
A film formed of SiO _x (x is 1.50 ≦ x ≦ 4.00, preferably 1.70 ≦ x ≦ 2.20) by the method has a good hardness and a lower layer (for example, hard coat). Excellent adhesion to layer 12). The method of forming the low refractive index layer 10 using an inorganic material having a low refractive index is, for example, forming the coating into a single layer or a multilayer by vapor deposition, sputtering, ion plating, plasma CVD or other vapor phase method of the inorganic material. Alternatively, a low refractive index resin composition containing a low refractive index inorganic material or a low refractive index organic material is applied to form a single-layer or multi-layer coating film.

As the low-refractive-index organic material, an organic material such as a polymer having a fluorine atom introduced therein is preferable because its refractive index is as low as 1.45 or less. As a resin that can be used as a solvent, polyvinylidene fluoride (refractive index 1.40) is mentioned as a preferable organic material because it is easy to handle.
When this polyvinylidene fluoride is used as the low-refractive index organic material, the low-refractive index layer 10 has a refractive index of approximately 1.40, but in order to further lower the refractive index of the low-refractive index layer 10. Is trifluoroethyl acrylate (refractive index 1.
A low refractive index acrylate such as 32) may be added in an amount of 10% by weight to 300% by weight, preferably 100% by weight to 200% by weight.

Since this trifluoroethyl acrylate is a monofunctional type and therefore the film strength of the low refractive index layer 10 is not sufficient, a polyfunctional acrylate such as, for example,
It is desirable to add dipentaerythritol hexaacrylate (abbreviation: DPHA, 4 functional type) which is an ionizing radiation curable resin. The film strength of the DPHA increases as the added amount increases, but from the viewpoint of lowering the refractive index of the low refractive index layer 10, the added amount is preferably small, for example, 1
It is recommended to add in a proportion of ˜50% by weight, preferably 5 to 20% by weight.

To further improve the antireflection performance, FIG.
It is preferable to form a high refractive index layer 11 having a refractive index higher than that of the low refractive index layer 10 below the low refractive index layer 10 as shown in FIG. It is advantageous in terms of antireflection effect that the high refractive index layer 11 is formed of a thin film having a thickness of about 0.1 μm. For example, the high refractive index layer 11 can be easily formed by using a high refractive index metal or metal oxide. For the film formation, a thin film may be formed by a vacuum forming method or the like. Alternatively, fine particles having a high refractive index listed below may be dispersed and used in the binder resin. Alternatively, a resin containing molecules or atoms of a high refractive index component may be used as the binder resin itself used for the high refractive index layer. For example, a resin in which fine particles having a high refractive index are dispersed is used as the resin for the hard coat layer 12. As a molecule or atom forming the resin for the hard coat layer 12, a resin having a high refractive index containing atoms into which many components having a high refractive index are introduced is used.

Examples of the ultrafine particles having a high refractive index include ZnO (refractive index 1.90) and TiO ₂ (refractive index 2.
3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅
(Refractive index 1.71), SnO ₂ , ITO (refractive index 1.9
5), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ O
₃ (refractive index 1.63) and the like. Further, as the molecule and atom of the component for improving the refractive index, an aromatic ring,
Examples thereof include halogen atoms other than F, S, N, and P atoms.

In the present invention, as shown in FIG. 4, a hard coat layer 12 can be provided between the adhesive layer 9 and the high refractive index layer 11. In the present invention, “hard coat layer” or “having hard property” means JIS K54.
A pencil hardness test represented by 00 indicates a hardness of H or higher. As the material forming the hard coat layer 12, any material may be used regardless of whether it is an inorganic material or an organic material. When an inorganic material is used as the material of the hard coat layer 12, for example, metal oxide is vacuum-deposited, ion-plated,
It can be formed by a known method such as sputtering or (plasma) CVD. Alternatively, a composite oxide film may be formed by a sol-gel method. When the material of the hard coat layer 12 is an organic material, the binder resin may be any transparent resin (for example, a thermoplastic resin, a thermosetting resin, an ionizing radiation curing resin, etc.). But it can be used. In order to impart the hard performance, the thickness of the hard coat layer 12 is set to 0.5 μm or more, preferably 3 μm or more so that the hardness can be maintained and the antireflection layer 8 is imparted with the hard performance. You can

In order to further improve the hardness of the hard coat layer 12, the binder resin used in the hard coat layer 12 is a reaction curable resin, that is, a thermosetting resin and / or an ionizing radiation curable resin. Preference is given to using. Considering productivity, energy efficiency, heat damage to the release film, and the like, it is optimal to use the ionizing radiation curable resin as the binder resin of the hard coat layer 12.
The thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicon resin, poly Siloxane resin etc. are used,
If necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. may be added to these resins before use.

In order to give the hard coat layer 12 particularly flexibility, 1 part by weight or more and 100 parts by weight or less of the solvent drying type resin may be contained with respect to 100 parts by weight of the ionizing radiation curing type resin. A thermoplastic resin is mainly used as the solvent-drying resin. The type of solvent-drying thermoplastic resin added to the ionizing radiation-curable resin is usually used, especially when a mixture of polyester acrylate and polyurethane acrylate is used as the ionizing radiation-curable resin, As the solvent-drying resin used, polymethacrylic acid methyl acrylate or polymethacrylic acid butyl acrylate can keep the hardness of the coating film high. Moreover, in this case, since the refractive index is close to that of the main ionizing radiation curable resin, the transparency of the coating film is not impaired, and the transparency,
In particular, it is advantageous in terms of low haze value, high transmittance, and compatibility.

When an ionizing radiation curable resin is used as the binder resin in the hard coat layer 12, the curing method is a usual curing method for ionizing radiation curable resins, that is, curing by irradiation with electron beams or ultraviolet rays. be able to. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used, and in the case of ultraviolet curing, ultraviolet rays or the like emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, carbon arc, xenon arc, and a metal halide lamp are used. it can.

In order to improve the antireflection performance of the antireflection layer 8, the hard coat layer 12 preferably has a higher refractive index than the glass substrate 6. In order to make the hard coat layer 12 have a high refractive index, the method described for the high refractive index layer 11 can be used. Further, in order to prevent reflection at the interface between the layers, it is preferable that the high refractive index layer 11 has a higher refractive index than the hard coat layer 12.
Although the present invention has been described above with reference to an example in which the antireflection layer 8 is directly provided on the glass substrate 6 of the FED, in addition to this, an antireflection sheet is separately prepared, and the antireflection sheet is formed on the glass substrate 6 of the FED.
The FED of the present invention can be obtained by laminating the FED on any layer by any method. This example will be described below.

FIG. 5 is a process diagram showing an example of a method for producing a type I antireflection sheet used in the present invention. FIG. 5A shows a state in which the low refractive index layer 10 is formed on the release film 13. The low refractive index layer 10 is formed by a vacuum forming method or coating. FIG. 5B shows a state in which the low refractive index layer 10 is about to be laminated with the transparent base film 14 via the adhesive layer 9 made of an adhesive. The adhesive layer 9 can be formed by applying an adhesive to the transparent substrate film 14 side or the low refractive index layer 10 side. The adhesive is used as it is or after being dissolved and dispersed in a solvent. FIG. 5C shows a state in which the release film 13 is peeled from the laminate and the coating film on the release film 13 is transferred to the transparent substrate film 14 side, and the transferred sheet is the present invention. It becomes a type I antireflection sheet used in.

FIG. 6 is a process diagram showing an example of the first method of manufacturing the type II antireflection sheet used in the present invention. In FIG. 6A, the low refractive index layer 10 is formed on the release film 13, and the high refractive index layer 1 is further formed on the low refractive index layer 10.
1 shows a state in which 1 is formed. FIG. 6B shows a state in which the transparent base film 14 is about to be laminated on the release film 13 via the adhesive layer 9 made of various adhesives formed in the above process. The adhesive layer 9 can be formed by applying an adhesive to the transparent substrate film 14 side or the low refractive index layer 10 side. The adhesive is used as it is or after being dissolved and dispersed in a solvent. FIG. 6C shows a state in which the release film 13 is peeled off from the laminate and the coating film on the release film 13 is transferred to the transparent substrate film 14 side, and the transferred sheet is the present invention. It becomes the type II anti-reflection sheet used.

FIG. 7 is a process diagram showing an example of a second method of manufacturing the type II antireflection sheet used in the present invention. FIG. 7A shows a state in which the high refractive index layer 11 is formed on the release film 13. FIG. 7B shows a state in which the high refractive index layer 11 is about to be laminated with the transparent base film 14 via the adhesive layer 9 made of an adhesive. The adhesive layer 9 can be formed by applying an adhesive to the transparent substrate film 14 side or the high refractive index layer 11 side. The adhesive is used as it is or after being dissolved and dispersed in a solvent. FIG. 7C shows a state in which the release film 13 is peeled off from the laminate and the coating film on the release film 13 is transferred to the transparent substrate film 14 side.
FIG. 7D shows a state in which the low refractive index layer 10 is further formed on the exposed high refractive index layer 11, which is a type II antireflection sheet used in the present invention.

FIG. 8 is a process diagram showing an example of the first method of manufacturing the type III antireflection sheet used in the present invention. In FIG. 8A, a low refractive index layer 10 is formed on a release film 13, a high refractive index layer 11 is further formed on the low refractive index layer 10, and a hard coat layer 12 is further formed thereon. Shows the state. FIG. 8B shows an adhesive layer 9 made of an adhesive layer formed on the release film 13 in the above process.
1 shows a state in which the transparent base film 14 is going to be laminated via. The adhesive layer 9 can be formed by applying an adhesive to the transparent substrate film 14 side or the hard coat layer 12 side. The adhesive is used as it is or after being dissolved and dispersed in a solvent. FIG. 8C shows the release film 13 obtained by peeling the release film 13 from the laminate.
The state in which the above coating film is transferred to the transparent substrate film 14 side is shown, and the transferred sheet is the type II used in the present invention.
It becomes the antireflection sheet of I.

FIG. 9 is a process diagram showing an example of the second method of manufacturing the type III antireflection sheet used in the present invention. In FIG. 9A, a high refractive index layer 11 is formed on a release film 13, and a hard coat layer 12 is further formed thereon.
The state in which the is formed is shown. FIG. 9B shows a release film 1
3 shows a state in which each layer formed in the above step is to be laminated on the transparent base film 14 via the adhesive layer 9 made of an adhesive. The adhesive layer 9 can be formed by applying an adhesive to the transparent substrate film 14 side or the hard coat layer 12 side. The adhesive is used as it is or after being dissolved and dispersed in a solvent. FIG. 9C shows
The figure shows a state in which the release film 13 is peeled from the laminate and the coating film on the release film 13 is transferred to the transparent substrate film 14 side. FIG. 9D shows a state in which the low refractive index layer 10 is further formed on the exposed high refractive index layer 11, which is a type II antireflection sheet used in the present invention.

In each of the methods for producing the antireflection sheet used in the present invention described above, when a urethane adhesive is used as the adhesive, the urethane adhesive is coated with a solution and the solvent is removed. Since it shows tackiness at the time of lamination, it has a certain degree of adhesive strength immediately after lamination, but the roll for lamination is 40 to 8
Heating at 0 ° C. is preferable because the adhesive strength immediately after lamination can be further improved. Further, in order to obtain sufficient adhesive strength between the transparent base film of the antireflection sheet and the hard coat layer, the adhesive layer 9 has a dry thickness of 0.
It is necessary to be 5 to 20 μm, preferably 1 to 10 μm.

As the release film used above, a release film such as silicon, fluorine or acryl-melamine, or an untreated release film is generally used. The surface may have unevenness, and in this case, since unevenness is formed on the surface of the final product, it is possible to further impart an antiglare effect to the surface of the obtained antireflection sheet.

The transparent base film suitable for the antireflection sheet used above may be a transparent film, for example, triacetyl cellulose film, diacetyl cellulose film, acetate butyrate cellulose film, poly film. Ether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, trimethylpentene film, polyetherketone film, (meth) acrylonitrile film, etc. can be used, but especially , Triacetyl cellulose film, and uniaxially stretched polyester are preferably used because they are excellent in transparency and have no optical anisotropy. Its thickness is usually 8 μm
Those having a thickness of about 1000 μm are preferably used.

[0045]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples. In addition, unless otherwise specified, "parts" and "%" in the text are based on weight. Example 1 Formation of Electron Emission Substrate First, a Si substrate was introduced into a chamber kept in vacuum,
This was heated to 300 ° C and exposed to water vapor at the same time
An oxide film of 0.1 μm is formed on the surface of the substrate. Next, SiN, which is an inorganic insulator layer, is formed on the Si substrate to a thickness of 0.3 μm by sputtering. Then, a resist agent (ORM85 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated with a spinner and left to dry in an oven at 80 ° C. for 30 minutes. After cooling, the desired pattern is exposed, the resist phenomenon and water washing are carried out, and then the product is placed in an oven at 135 ° C. for 3 hours.
Leave for 0 minutes. After air cooling, the SiN layer is etched with hydrofluoric acid. Then, the substrate was left in a resist stripping solution (Clean Stop manufactured by Tokyo Ohka Kogyo Co., Ltd.) held at 120 ° C. for 5 minutes, and further immersed in a strip rinse solution at room temperature for 1 minute and in isopropyl alcohol at room temperature for 1 minute. Strip the resist. The substrate is washed with water and then dried.

Next, the SiO ₂ layer is patterned on this substrate by reactive ion etching using CHF ₃ + O ₂ as an etchant, using the SiN patterned by the above operation as a mask. This completes the patterning of the surface oxide film. Anisotropic etching of Si is performed using a potassium hydroxide aqueous solution on the substrate on which the patterning of the surface oxide film has been completed. Next, this substrate is introduced into a chamber kept in vacuum, and this substrate is heated to 300 ° C. and at the same time exposed to water vapor for surface oxidation to form an oxide film of 0.1 μm on the Si surface. On this substrate, an insulator layer having a mixed composition of SiO ₂ and Al ₂ O ₃ is deposited with a film thickness of 400 μm by a sputtering method. Further, a Mo layer having a film thickness of 100 μm is deposited thereon by a sputtering method. Finally, this substrate is treated with a hydrofluoric acid / nitric acid mixed solution to remove SiO ₂ . The substrate thus obtained is introduced into a vacuum chamber and placed on a glass substrate on which a Cr electrode placed on a heater heated to 350 ° C. is patterned. With the glass substrate side as the cathode, the glass substrate and Si
By applying a voltage of 400 V between the substrate and the substrate, electrostatic adhesion was performed to form an electron emission substrate.

Example 2 Formation of Light-Emitting Substrate A three-color (light-emitting color: red, green, blue) phosphor paste prepared by forming an electrode of ITO on a glass substrate and forming a paste on the electrode by a binder that is burned off by firing. Was used for screen printing on the electrode and baking at 450 ° C. for 15 minutes to burn off the organic binder in the phosphor paste to form a phosphor layer. Here, a phosphor paste having the following composition, that is, a phosphor and a binder dissolved in a solvent were kneaded with a three-roll and then diluted to 30,000 cps with the solvent.

(Phosphor paste for green light emission) Phosphor: Zn ₂ SiO ₄ : Mn (P1-G1S manufactured by Kasei Optonix Co., Ltd.) 50.0% by weight Binder: Ethylcellulose (N-50) 4.2 wt% solvent: BCA 45.8 wt% (the phosphor paste for red color) _{phosphor: (Y, Gb) BO 3} : Eu ( Kasei Optonix Co., KX-504A) 51.0 wt%, Binder: Ethyl cellulose (N-50) 4.5 wt% -Solvent: BCA 44.4 wt% (Phosphor paste for blue color development) -Phosphor: BaMgAl ₁₄ O ₂₃ : Eu (KX- manufactured by Kasei Optonix KK) 501A) 51.0 wt% -Binder: Ethyl cellulose (N-50) 4.1 wt% -Solvent: BCA 44.9 wt%

Example 3 5 which has been treated with acrylic-melamine which is a release film
0 μm polyester film (MC-19: trade name,
36 parts by weight of ZnO ultrafine particle toluene dispersion (Sumitomo Osaka Cement Co., Ltd.) and carboxyl group-containing (meth) acrylate (Mitsubishi Chemical Co., Ltd.) on Reiko Co., Ltd.
A high-refractive-index resin consisting of 9 parts by weight was applied so as to have a film thickness of 7 μm. 320m on the coating film formed in the above process
After irradiating ultraviolet rays of j, 175Kv, 7.5M
The coating film was cured by irradiating with an electron beam at rad to form a high refractive index layer. Next, 4 parts by weight of a thermosetting two-component urethane adhesive [LX660: manufactured by Dainippon Ink and Chemicals], and K
W75: an aromatic polyisocyanate, an adhesive consisting of 1 part by weight of Dainippon Ink and Co., Ltd. and 16 parts by weight of ethyl acetate] on the high refractive index layer, the thickness of the adhesive is 3 to 10 μm.
The adhesive layer 9 was formed by coating so as to have a thickness of m. This adhesive had a Tg (glass transition temperature) after curing of 43 ° C.

Then, a TAC film (FT-UV-80: film thickness 80 μm, manufactured by Fuji Photo Film Co., Ltd.) was laminated through the adhesive layer 9 and aged at 40 ° C. for 3 days or more. Then, the release film was peeled off and the high refractive index layer was transferred to a TAC film to form a high refractive index layer. On the obtained high-refractive index layer, a SiO _x film, which is a low-refractive index layer, was formed to a thickness of 100 nm by a vacuum deposition method to obtain an antireflection sheet. After the antireflection sheet is attached to the surface of the light emitting substrate of Example 2, this and the electron emitting substrate are attached to each other by a conventional method, and the FED of the present invention is then attached.
It was created. Operate this FED to display an image,
When the image was observed from the front under a fluorescent lamp, a good antireflection effect was obtained, and there was no angle at which the image was difficult to see due to the reflected light. The pencil hardness, durability and adhesion of the obtained antireflection sheet are shown in Table 1 below, and the refractive index and reflectance are shown in Table 2 below.

Example 4 In the method for producing an antireflection sheet of Example 3, the adhesive was changed to a thermosetting two-pack type urethane adhesive to replace a moisture-curing one-pack type urethane adhesive (an adhesive having the following composition). ) Was used, and an antireflection sheet was produced in exactly the same manner as in Example 3 except that it was humidified when the adhesive was applied. This adhesive had a Tg of 53 ° C. after curing. The antireflection sheet is attached to the light emitting substrate surface of an FED produced by pasting the light emitting substrate surface of the second embodiment and the electron emitting substrate of the first embodiment by a conventional method to produce the FED of the present invention. did. When this FED was operated to display an image and the image was observed from the front under a fluorescent lamp, a good antireflection effect was obtained, and there was no angle at which the image was difficult to see due to reflected light. Incidentally, the pencil strength, durability of the obtained antireflection sheet,
The adhesion is shown in Table 1 below, and the refractive index and reflectance are shown in Table 2 below. Moisture-curing 1-pack urethane adhesive A270L: Polyester aromatic isocyanate, Takeda Pharmaceutical Co., Ltd. 5 parts by weight Ethyl acetate 7 parts by weight

Table 1 Evaluation results

Durability: A ... 100 ° C. dry × 1000 h
Heat resistance test. The number is the time when the crack occurred. Durability: B ... Moisture and heat resistance test of 40 ° C. × 90% RH × 1000 h. The number is the time when the crack occurred. Durability: Moisture and heat resistance test of C ... 65 ° C. × 90% RH × 1000 h. The number is the time when the crack occurred. Adhesion: A ... Adhesion before heat and humidity resistance test of 65 ° C. × 95% RH × 1000 h. Adhesion: B ... Adhesion before heat and humidity resistance test of 65 ° C. × 95% RH × 1000 h.

Table 2 Characteristics of antireflection film According to Table 1 above, the antireflection sheet used in the present invention having Tg of the adhesive layer of 20 ° C. or higher is excellent in scratch resistance because of its high pencil hardness, and also exhibits excellent coating resistance even after long-term storage. It can be seen that the durability and the adhesion are excellent.

[0055]

According to the present invention as described above, an antireflection layer comprising at least one low refractive index layer and at least one high refractive index layer is formed on the glass substrate surface of the FED on the light emitting substrate side. As a result, it is possible to display a clear and excellent quality image having an excellent antireflection effect while maintaining the excellent characteristics such as the viewing angle, gradation and brightness that the FED originally has. Further, when the FED is a color display having R, G and B phosphor layers, a clear and excellent quality color image can be displayed in addition to the above characteristics.

[Brief description of drawings]

FIG. 1 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 2 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 3 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 4 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 5 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 6 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 7 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 8 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 9 is a diagram schematically illustrating an embodiment of the present invention.

FIG. 10 is a diagram schematically illustrating a conventional FED.

[Explanation of symbols]

1: Glass substrate 2: Wiring layer 3: Electron emitting device 4: Insulation layer 5: Extraction electrode 6: Glass substrate 7: Anode 8: Antireflection layer 9: Adhesive layer 10: Low refractive index layer 11: High refractive index layer 12: Hard coat layer 13: Release film 14: Transparent base film 100: electron emission substrate 200: Light emitting substrate

Continuation of the front page (56) Reference JP-A-4-155731 (JP, A) JP-A-7-56004 (JP, A) JP-A-6-56478 (JP, A) JP-A-5-343007 (JP , A) JP 64-80904 (JP, A) JP 64-70701 (JP, A) JP 62-215202 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB) Name) H01J 29/89 H01J 29/88

Claims (6)

(57) [Claims] 1. An electron-emitting substrate including a glass substrate, a wiring layer, an electron-emitting device, an insulating layer, and an extraction electrode, and a light-emitting substrate including a glass substrate, an anode, and a phosphor layer are placed in a vacuum state between them. In an image display device, which is laminated and electrically connected to each other, an antireflection layer including at least one low refractive index layer and at least one high refractive index layer is formed on a glass substrate surface of a light emitting substrate , The antireflection layer is an adhesive layer
And a low refractive index having a refractive index lower than that of the adhesive layer
Layer, and between the adhesive layer and the low refractive index layer, the contact
A high refractive index layer having a refractive index higher than that of the adhesive layer
And further includes a hard coat between the adhesive layer and the high refractive index layer.
An image display device having a coat layer . 2. The image display device according to claim 1, wherein the phosphor layer is composed of red (R) light emitting, green (G) light emitting, and blue (B) light emitting phosphor layers. 3. The glass transition temperature of the adhesive layer is 20 ° C. or higher.
The image display device according to claim 1 or 2. 4. A glass substrate, a wiring layer, an electron-emitting device and an insulating layer.
An electron emission substrate including an edge layer and an extraction electrode, and a glass substrate
And the light emitting substrate consisting of the anode and the phosphor layer,
Image table formed by stacking and facing electrically in an empty state
In the device shown, at least the glass substrate surface of the light emitting substrate is
From one low refractive index layer and at least one high refractive index layer
Is formed, and the antireflection layer is an adhesive layer.
And a low refractive index having a refractive index lower than that of the adhesive layer
The adhesive layer has a glass transition temperature of 20 ° C. or higher.
An image display device characterized by being above. 5. The phosphor layer comprises red (R) emission and green.
(G) luminescent and blue (B) luminescent phosphor layers
The image display device according to claim 4. 6. The antireflection layer comprises an adhesive layer and the adhesive layer.
Between the low refractive index layer having a refractive index lower than the refractive index,
High refractive index having a refractive index higher than that of the adhesive layer
The image display device according to claim 4, comprising an index layer.