JP4946451B2 - Electron emitting device paste, electron emitting device using the same, and method of manufacturing electron emitting device - Google Patents

Description

  The present invention relates to an electron-emitting device paste and an electron-emitting device using the same.

  Carbon nanotubes are not only physically and chemically durable, but also have sharp tip shapes and large aspect ratios suitable for field emission. For this reason, research has been actively conducted on field emission displays (FEDs) using carbon nanotubes as electron-emitting devices, liquid crystal backlights using field emission, illumination, and the like.

  One of the methods for producing the electron-emitting device using the carbon nanotube is a method of producing a film having the carbon nanotube on the cathode electrode by printing the carbon nanotube as a paste (see Patent Document 1). . In this method, a paste containing carbon nanotubes is screen-printed on the cathode electrode, and then the organic components in the paste are decomposed by firing, and further processing such as a laser method, a plasma method, a sandblast method, a tape peeling method, By carrying out on a film having carbon nanotubes, an electron-emitting device in which carbon nanotubes protrude from the surface of the electron-emitting device is produced. However, in this method, the carbon nanotube itself is pulled out of the electron-emitting device due to an external force applied when processing such as tape peeling, or due to the strong adhesion between the inorganic particles and the carbon nanotube in the electron-emitting device, There was a problem that the carbon nanotube did not protrude from the surface of the electron-emitting device.

  As a method for producing an electron-emitting device in which a large number of carbon nanotubes protrude without performing treatments such as a laser method, a plasma method, a sand blasting method, and a tape peeling method, a glass paste in which carbon nanotubes and spherical materials of organic materials are mixed There is a method using (see Patent Document 2). In this method, a PMMA (polymethyl methacrylate) particle having a diameter of 5 to 10 μm mixed with 5 to 10% by weight in a glass paste is screen-printed on a substrate electrode, and then fired to burn out the PMMA particles. A large number of continuous holes leading to the surface are formed in the electron-emitting device, and the tip of the carbon nanotube protrudes from the hole wall by dimensional shrinkage during firing. However, since only the tip of the carbon nanotube protrudes from the hole wall in this method, the large aspect ratio inherent to the carbon nanotube cannot be obtained, and the protruding direction is random and difficult to control. Therefore, there is a problem that the electron-emitting device becomes structurally unstable because it is necessary to form a continuous hole.

Further, an inorganic porous thin film having a large number of pores in which a protruding direction is uniform and a large number of carbon nanotubes are formed has been proposed (see Patent Document 3). In this method, after applying a coating liquid containing inorganic ultrafine particles and organic fine particles on a substrate, an organic porous thin film having a large number of pores is formed by firing the organic fine particles, and then carbon is contained in the pores. In this method, an electron emission source is formed by vapor-phase growing nanotubes. However, in this method, since an inorganic porous thin film having openings on the surface and uniformly arranged must be formed, there is a limitation between the film thickness of the inorganic porous thin film and the particle size of the organic fine particles. There was a problem that there was.
JP-T-2004-504690 (18th paragraph) JP 2004-87304 A (paragraphs 15 to 17) Japanese Patent Laying-Open No. 2005-231966 (11th paragraph)

  The present invention provides an electron emission capable of projecting a large number of electron-emitting materials on the electron-emitting device without damaging the structure of the electron-emitting device even when a process for projecting the electron-emitting material on the surface of the electron-emitting device is performed. Provided are a paste for a device and a method for manufacturing an electron-emitting device using the paste.

  That is, the present invention is an electron-emitting device paste including an electron-emitting material, inorganic particles, and organic fine particles, wherein the average particle size of the organic fine particles is 0.01 to 0.5 μm, and the organic fine particle content is electron emission. An electron-emitting device paste that is 0.1 to 20% by weight of the device paste, and an electron-emitting device using the paste.

  According to the present invention, by containing organic fine particles having an average particle diameter of 0.01 to 0.5 μm in the paste for electron-emitting devices, a large number of fine holes are formed in the fired electron-emitting device. It is possible to obtain an electron-emitting device in which a large number of electron-emitting materials are projected on the electron-emitting device without destroying the structure of the electron-emitting device even if pretreatment for projecting the electron-emitting material on the surface of the emitting device is performed. is there.

  The present invention is an electron-emitting device paste comprising an electron-emitting material, inorganic particles, and organic fine particles, wherein the organic fine particles have an average particle size of 0.01 to 0.5 μm, and the organic fine particle content is The paste for electron-emitting devices is 0.1 to 20% by weight with respect to the paste for electron-emitting devices.

  In general, field emission displays, backlights using field emission, electron emission materials used for illumination, etc. include metal materials such as molybdenum, carbon nanotubes, carbon fibers, carbon nanofibers, carbon nanohorns, carbon nanocoils, There are carbon-based materials typified by carbon nanowalls, fullerenes, diamonds, diamond-like carbon, graphite, and carbon black, and carbon-based materials are preferably used because they can be driven at a low voltage due to low work function characteristics. Among carbon-based materials, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon nanocoils, carbon nanowalls, etc. are preferably used because they have a high aspect ratio and have good electrical emission characteristics. Among them, carbon nanotubes Is more preferable.

When carbon nanotubes are used as the electron emission material, any of single-walled, double-walled, and triple-walled carbon nanotubes may be used, and single-walled or double-walled carbon nanotubes that provide good electrical emission characteristics are preferred. Nanotubes are more preferred. These carbon nanotubes may be used singly or as a mixture of carbon nanotubes having different numbers of layers. The diameter of the carbon nanotube is preferably 0.5 to 20 nm, and more preferably 0.5 to 10 nm. When the diameter of the carbon nanotube is within the above range, electric field concentration tends to occur at the tip of the carbon nanotube, and good electric emission characteristics can be obtained even at a low voltage. In addition, from the viewpoint of electrical emission characteristics and life, carbon nanotubes with few structural defects are preferable. The structural defect of the carbon nanotube can be evaluated by a Raman spectrum measured by laser Raman spectroscopy. There are few structural defects and carbon nanotubes with high crystallinity have a Raman spectrum called G-band peak in the vicinity of 1580 cm ^{−1. The} higher the intensity and the smaller the half width, the fewer the structural defects and the higher the crystallinity. It is known to be a carbon nanotube. On the other hand, it is known that a Raman spectrum called a D-band peak existing in the vicinity of 1360 cm ⁻¹ is seen in carbon nanotubes having many structural defects and low crystallinity. Therefore, the structural defect of the carbon nanotube can be represented by a G / D ratio, which is a ratio of the integrated value (G) of the G band peak and the integrated value (D) of the D band peak, and the larger the G / D ratio, the more the structure defect. It can be seen that the carbon nanotube has few defects and high crystallinity. The G / D ratio of the carbon nanotube used in the present invention is preferably 5 or more, more preferably 10 or more. When the G / D ratio of the carbon nanotube is within the above range, good electric emission characteristics can be obtained.

  Since the carbon nanotube powder may contain impurities such as amorphous carbon and catalytic metal, it can be used by increasing the purity by purification. Further, in order to adjust the length of the carbon nanotube, the carbon nanotube powder may be pulverized by a ball mill, a bead mill or the like.

  The content of the electron-emitting material with respect to the entire paste for electron-emitting devices is preferably 0.1 to 20% by weight. Moreover, it is more preferable that it is 0.1 to 10 weight%, and it is further more preferable that it is 0.5 to 5 weight%. If the content of the electron-emitting material is less than 0.1% by weight, the coating property of the paste is lowered, and a uniform and dense coating film for the electron-emitting device paste cannot be obtained, and pinholes are generated in the coating film. In other cases, the amount of electron emission from the electron-emitting device is reduced, and the luminance is lowered. The pinhole here means a portion where the lower substrate is exposed without being covered by the coating film generated in the coating film of the electron-emitting device paste. When the content of the electron-emitting material exceeds 20% by weight, the dispersibility of the electron-emitting material in the paste for electron-emitting devices is deteriorated, and the coating property of the paste is deteriorated and uniform pattern forming property cannot be obtained. There is a case.

  The paste for electron-emitting devices of the present invention has organic fine particles. The electron-emitting device paste is printed on the cathode electrode and then fired, whereby organic fine particles are burned out, and a large number of holes can be formed in the electron-emitting device. With respect to the electron-emitting device having holes therein, an electron-emitting device in which a large number of electron-emitting materials protrude from the surface of the electron-emitting device can be obtained by raising the electron-emitting material such as a tape peeling method. This is because the release property of the inorganic particles from the electron-emitting device is improved, and the contact point between the electron-emitting material and the inorganic particles is lowered, so that the electron-emitting material can easily protrude from the surface of the electron-emitting device. It is.

  As the organic fine particles used in the paste for electron-emitting devices of the present invention, any organic fine particles can be used as long as they are burned off during firing, and polymer particles are preferably used because the particle diameter can be easily controlled. Specific examples of such organic fine particles include polymethacrylates such as polystyrene and polymethyl methacrylate, polyacrylates such as polymethyl acrylate, polymers such as polyethylene, polypropylene, polybutadiene, polyurethane, polyisobutene, and nylon. , Styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, copolymers such as styrene-butadiene copolymers, and the like, but are not limited thereto.

The average particle diameter of the organic fine particles is 0.01 to 0.5 μm, and more preferably 0.05 to 0.3 μm. If the average particle size of the organic fine particles is less than 0.01 μm, the pore size in the electron-emitting device formed by burning out the organic fine particles becomes too small, and the protrusion of the electron-emitting material by the raising treatment of the electron-emitting material such as a tape peeling method When the average particle size of the organic fine particles is larger than 0.5 μm without increasing the number, the pore size in the electron-emitting device formed by burning out the organic fine particles becomes too large. This is not preferable because the shape of the electron-emitting device may be broken when the process is performed, or the resistance of the electron-emitting device may increase. Here, the average particle diameter of the organic fine particles indicates a cumulative 50% particle diameter (D ₅₀ ). This represents the particle size at which the volume cumulative curve is 50% when the volume cumulative curve is determined with the total volume of one powder group as 100%. This is used as one of the parameters for evaluating the particle size distribution. The particle size distribution of the organic fine particles can be measured by a microtrack method (a method using a microtrack laser diffraction particle size distribution measuring device manufactured by Nikkiso Co., Ltd.).

  The content of the organic fine particles in the paste for electron-emitting devices is 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and further preferably 0.5 to 5% by weight. If the organic fine particle content is less than 0.1% by weight, the porosity in the electron-emitting device formed by burning out the organic fine particles decreases, and the electron emission material protrudes by raising the electron emission material such as tape peeling. If the number of organic fine particles exceeds 20% by weight, the dispersibility of the organic fine particles in the paste for electron-emitting devices may be deteriorated and gelation may occur. This is not preferable because the hole diameter in the electron-emitting device that can be increased is increased, and the shape of the electron-emitting device may be collapsed when raising the electron-emitting material such as a tape peeling method.

When carbon nanomaterials such as carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon nanocoils, and carbon nanowalls are used as the electron emission material, the surface of the organic fine particles used is preferably modified with a functional group. By having a functional group on the surface of the organic fine particles, the dispersibility of the electron-emitting material in the paste for electron-emitting devices is improved, and uniform vacancies can be formed in the electron-emitting devices without unevenness. Specific examples of such functional groups include, but are not limited to, amino groups, carboxyl groups, hydroxyl groups, acrylate groups, glycidyl groups, sulfo groups, alkyl chains such as C ₈ H ₁₇ and C ₁₈ H _37, and the like. Is not to be done. Among these, organic fine particles whose surface is modified with an amino group are preferably used from the viewpoint of good compatibility with the carbon nanomaterial.

  Various shapes such as a spherical shape, a needle shape, a rod shape, a polygonal shape, a flat shape, and a porous shape can be used as the shape of the organic fine particles. From the viewpoint that uniform holes can be formed in the electron-emitting device, the shape of the organic fine particles used in the paste for the electron-emitting device of the present invention is preferably spherical.

  In addition, since the thermal decomposition temperature of the electron emission material is generally 500 ° C. or higher, the thermal decomposition temperature of the organic fine particles used is preferably 500 ° C. or lower, and more preferably 450 ° C. or lower. Use of organic fine particles having a thermal decomposition temperature exceeding 500 ° C. is not preferable because an organic residue tends to remain in the electron-emitting device. The thermal decomposition temperature was set by using a TG measuring device (TGA-50, manufactured by Shimadzu Corporation), a sample of about 5 mg, a flow rate of 20 ml / min in an air or nitrogen atmosphere, and a heating rate of 20-0. The temperature is raised to 500 ° C. at 6 ° C./min. As a result, a chart plotting the relationship between temperature (vertical axis) and weight change (horizontal axis) is printed, and the tangent line between the part before disassembly (part parallel to the horizontal axis) and the part under disassembly is drawn. The temperature can be measured by a method such as the thermal decomposition temperature.

  Examples of inorganic particles contained in the paste for electron-emitting devices of the present invention include metals, metal oxides, ceramics, glass, water glass and the like. In particular, glass powder is preferably included in order to provide adhesion between the electron-emitting device and the cathode electrode.

  Since the thermal decomposition temperature of the electron-emitting material is generally 500 ° C. or higher, the firing temperature of the paste for the electron-emitting device is preferably 500 ° C. or lower. In order to suppress the decomposition of the electron-emitting material, it is 450 ° C. or lower. More preferably it is. Therefore, the softening point of the glass powder contained in the paste for electron-emitting devices is preferably 500 ° C. or less, and more preferably 450 ° C. or less. When the softening point of glass exceeds 500 ° C., the adhesion between the electron-emitting device and the cathode electrode may deteriorate, which is not preferable.

As such glass powder, the glass softening point can be lowered to 450 ° C. or less by containing Bi ₂ O ₃ in an amount of 45 to 86% by weight. Bi can lower the softening point of glass. If Bi ₂ O ₃ is less than 45% by weight, the softening point becomes too high, and if it is more than 86% by weight, the glass tends to become unstable, which is not preferable. More preferably, it is 70 to 85% by weight.

  The softening point of the glass here is a DTA curve obtained by heating 100 mg of a glass sample in air at 20 ° C./min using a differential thermal analysis (DTA) method, and plotting the temperature on the horizontal axis and the amount of heat on the vertical axis. More obtained.

As long as the glass powder contains Bi ₂ O ₃ in an amount of 45 to 86% by weight, the other composition is not particularly limited. Preferably, 45-86 wt% of _Bi 2 _O 3, 0.5 to 8 wt% of _SiO 2, 3 to 25 wt% _B 2 _O 3, glass powder is a glass having 0-25 wt% of ZnO This is preferable in terms of stability and ease of control of the softening point.

By setting the content of SiO ₂ to 0.5 to 8% by weight, the stability of the glass can be improved. If the amount is less than 0.5% by weight, the effect is insufficient. If the amount is more than 8% by weight, the softening point of the glass becomes too high. More preferably, it is 0.5 to 2% by weight.

The stability of the glass can be improved by setting the content of B ₂ O _{3 to 3 to} 25% by weight. If it is less than 3% by weight, the effect is insufficient, and if it is more than 25% by weight, the softening point of the glass becomes too high. More preferably, it is 3 to 10% by weight.

ZnO may not be contained, but the softening point can be lowered by containing up to 25% by weight. If it exceeds 25% by weight, the glass becomes unstable. More preferably, it is 5 to 15% by weight. In addition, Al ₂ O ₃ , Na ₂ O, CaO, MgO, CeO, K ₂ O and the like can be included.

  The electron-emitting device and the cathode electrode need to be firmly bonded, but the ratio of the electron-emitting material and the glass powder contained in the electron-emitting device paste is 50 to 50 parts by weight of the glass powder with respect to 100 parts by weight of the electron-emitting material. When it is 10,000 parts by weight, excellent adhesiveness can be obtained. If it is less than 50 parts by weight, sufficient adhesion cannot be obtained. If it is larger than 10,000 parts by weight, the paste viscosity becomes too high.

  Here, the adhesion between the electron-emitting device and the electrode is evaluated as follows. A solid print of the paste for the electron-emitting device, a tape having a predetermined peel adhesion strength is applied to the electron-emitting device formed by baking, and it is judged whether or not the electron-emitting device is peeled off when it is slowly peeled off. be able to. When many peeling is seen, it is not preferable, and a thing without peeling is preferable.

  The average particle size of the glass powder is preferably 2 μm or less. If it is larger than 2 μm, it may cause a shape defect when a high-definition circular pattern having a diameter of 5 to 50 μm is formed. More preferably, it is 1 μm or less. When the particle size of the glass powder is reduced, the glass powder is easily softened. Therefore, the adhesiveness between the electron-emitting device and the cathode electrode can be obtained with a smaller glass powder content. Therefore, when the average particle diameter of the glass is 1 to 2 μm, the glass powder is preferably 100 to 10,000 parts by weight with respect to 100 parts by weight of the electron emitting material, and when the average particle diameter of the glass is smaller than 1 μm, the electron emitting material 100 is used. The glass powder is preferably 50 to 5000 parts by weight with respect to parts by weight.

  When carbon nanotubes are used as the electron emission material, when the average particle diameter of the glass is 1 to 2 μm, the glass powder is preferably 3000 to 8000 parts by weight with respect to 100 parts by weight of the carbon nanotubes, and the average particle diameter of the glass is smaller than 1 μm. In some cases, the glass powder is preferably 200 to 3000 parts by weight with respect to 100 parts by weight of the carbon nanotubes.

Here, the average particle diameter of the glass powder indicates a cumulative 50% particle diameter (D ₅₀ ). This represents the particle size at which the volume cumulative curve is 50% when the volume cumulative curve is determined with the total volume of one powder group as 100%. This is used as one of the parameters for evaluating the particle size distribution. The particle size distribution of the glass powder can be measured by a microtrack method (a method using a microtrack laser diffraction type particle size distribution measuring device manufactured by Nikkiso Co., Ltd.).

  The electron-emitting device of the present invention contains an electron-emitting material and inorganic particles, and the average pore diameter in the electron-emitting device is preferably 0.01 to 0.5 μm, more preferably 0.05 to 0.3 μm. preferable. When the average hole diameter in the electron-emitting device is less than 0.01 μm, the number of protrusions of the electron-emitting material does not increase by raising the electron-emitting material such as a tape peeling method. This is not preferable because the shape of the electron-emitting device may be collapsed when the raising treatment of the electron-emitting material is performed, and the resistance of the electron-emitting device may be increased. Each hole in the electron-emitting device may exist independently, or may form a continuous hole in which a plurality of holes are connected. By performing napping treatment of the electron emitting material such as a tape peeling method on the electron emitting device having the holes in the above range, it is possible to obtain an electron emitting device having more electron projecting materials than the conventional electron emitting device. The average hole diameter of the holes formed in the electron-emitting device can be controlled by the average particle diameter of the organic fine particles contained in the electron-emitting device paste.

  The porosity in the electron-emitting device is preferably 1 to 50 vol%, more preferably 5 to 40 vol%, and further preferably 10 to 30 vol%. When the porosity in the electron-emitting device is less than 1 vol%, the number of protrusions of the electron-emitting material does not increase by raising the electron-emitting material such as tape peeling, and when it is higher than 50 vol%, the electron emission such as tape peeling occurs. This is not preferable because the shape of the electron-emitting device may be broken when the material is brushed or the resistance of the electron-emitting device may be increased. The porosity of the vacancies formed in the electron-emitting device can be controlled by the content of organic fine particles contained in the electron-emitting device paste.

General methods for measuring the porosity (V) and average pore diameter (R) in the electron-emitting device include mercury intrusion method, gas adsorption method, X-ray small angle scattering method, transmission electron microscope (TEM), and the like. As an example, a mercury intrusion method is used to measure the porosity and hole diameter in the electron-emitting device of the present invention. In this method, evaluation is made on the assumption that the hole shape is cylindrical. In the mercury intrusion method, using the large surface tension of mercury, pressure is applied to cause mercury to enter the vacancies, and the total pore volume (Vt), total The pore surface area (S), the pore diameter distribution, the bulk density (ρv), and the true density (ρr) are obtained, and the porosity (V) and the average pore diameter (R) can be obtained from the following equations.
Porosity: V = (1−ρv / ρr) × 100
Average pore diameter: R = 4 Vt / S.

  Next, the method for manufacturing an electron-emitting device according to the present invention includes a step of baking a paste for an electron-emitting device and burning organic fine particles to form holes in the electron-emitting device, and an electron-emitting material by tape peeling treatment. It is a manufacturing method of the electron-emitting device which has the process of projecting from the surface of an electron-emitting device. Hereinafter, the manufacturing method will be described in detail.

  First, a paste for an electron-emitting device including an electron-emitting material, inorganic particles, and organic fine particles is prepared. The paste for an electron-emitting device can be prepared by preparing various components so as to have a predetermined composition and then uniformly mixing and dispersing the mixture using a kneader such as a three-roller, ball mill, or bead mill. The paste viscosity is appropriately adjusted depending on the addition ratio of glass powder, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is 2 to 200 Pa · s. For example, when the application to the substrate is performed by a spin coating method, a spray method, or an ink jet method other than the slit die coater method or the screen printing method, 0.001 to 5 Pa · s is preferable.

  Next, a pattern of electron-emitting devices is formed on a back substrate on which a cathode electrode, an insulating layer, a gate electrode, and an emitter hole are formed on a glass substrate. The patterning method of the electron-emitting device may be formed by printing the paste for the electron-emitting device directly in the emitter hole by a screen printing method or an ink-jet method and then drying the paste. The pattern of the electron-emitting device may be formed by printing on the back substrate by using a slit die coater method or the like, drying to form a solid film, irradiating with ultraviolet rays through a photomask, and dissolving in a developer. .

  A back substrate having an electron-emitting device pattern made from an electron-emitting device paste is baked at 400 to 500 ° C. to produce an electron-emitting device, and organic fine particles in the electron-emitting device are burned off to emit electrons. Holes are formed in the element. The porosity and the hole diameter of the holes formed in the electron-emitting device can be appropriately adjusted by controlling the content and particle size of the organic fine particles in the electron-emitting device paste. The electron-emitting device can project the electron-emitting material from the surface of the electron-emitting device by performing brushing treatment of the electron-emitting material such as a laser method, a plasma method, and a tape peeling method. As the raising treatment method for the electron-emitting device of the present invention, a tape peeling method is preferably used in that a large number of electron-emitting materials can be projected onto the surface of the electron-emitting device. Here, the projecting direction of the electron-emitting material from the surface of the electron-emitting device is preferably a direction perpendicular to the back substrate because good electrical emission characteristics can be obtained. The number of protrusions of the electron-emitting material on the electron-emitting device can be measured with a scanning electron microscope (SEM).

  The paste for an electron-emitting device of the present invention can contain an organic component such as a binder polymer and an organic solvent in addition to the electron-emitting material, inorganic particles, and organic fine particles, and as necessary, a sensitizer, a sensitization aid, An additive component such as a plasticizer, a thickener, an antioxidant, a dispersant, a coupling agent, a chelating agent, an organic or inorganic suspending agent, or a leveling agent may be included. These organic components are preferably used because they impart shape processability to the paste for electron-emitting devices, and pattern formation of the electron-emitting devices can be performed by a general method such as a screen printing method or an inkjet method. Moreover, since a fine pattern can be formed by photolithography, it is preferable to use a photosensitive organic component obtained by imparting photosensitivity to the organic component. The content of the organic component in the electron-emitting device paste is preferably 20 to 95% by weight, more preferably 30 to 90% by weight. If the organic component content is less than 20% by weight, it is difficult to impart shape processability to the paste for electron-emitting devices, which is not preferable. If the organic component content exceeds 95% by weight, it is not preferable. Good electron emission characteristics of an electron-emitting device manufactured using a paste may not be obtained.

  The photosensitive organic component is a negative photosensitive organic material that is soluble in the developer before UV irradiation but becomes insoluble in the developer after UV exposure due to a chemical change that occurs when irradiated with UV light. Either a positive-type photosensitive organic component that is insoluble in the developer before irradiation with ultraviolet light or that becomes soluble in the developer after exposure can be selected. It can be suitably used when a water-soluble organic component is used. In the case of the negative type, the photosensitive organic component includes a binder polymer, a photocurable monomer, a photopolymerization initiator, an organic solvent, an ultraviolet absorber, a polymerization inhibitor, and the like. If necessary, a sensitizer, a sensitization aid, An additive component such as a plasticizer, a thickener, an antioxidant, a dispersant, a coupling agent, a chelating agent, an organic or inorganic suspending agent, or a leveling agent may be included. Here, as the binder polymer used for the photosensitive organic component, a non-photosensitive binder polymer and a binder polymer imparted with photosensitivity can be used. In the positive type, the photosensitive organic components include a binder polymer, a photoacid generator, an organic solvent, and the like, and as necessary, a sensitizer, a sensitizer, a plasticizer, a thickener, an antioxidant, and a dispersant. Further, an additive component such as an organic or inorganic suspending agent or leveling agent may be included.

  Specific examples of the non-photosensitive binder polymer include cellulose resins (ethyl cellulose, methyl cellulose, nitrocellulose, acetyl cellulose, cellulose propionate, hydroxypropyl cellulose, butyl cellulose, benzyl cellulose, modified cellulose, etc.), acrylic resins Resin (acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl Methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, -Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and other monomers), ethylene-vinyl acetate copolymer resin, polyvinyl butyral, polyvinyl alcohol, propylene glycol, urethane resin , Melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, polyester Examples thereof include lyamide resin, polyimide resin, silicone resin, melamine resin, and phenol resin. These non-photosensitive binder polymers can also be used as the binder polymer of the organic component.

  As the photosensitive binder polymer, a polymer having an acidic group is preferably used. The polymer having an acidic group may be any polymer having an acidic group, but is preferably a polymer having a carboxyl group, more preferably an ethylenically unsaturated group and a carboxyl group in the side chain. It is a polymer having By having an ethylenically unsaturated group in the side chain, pattern formation is improved, and by containing a carboxyl group in the side chain, development with an aqueous alkaline solution is possible. Such polymers include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate or their anhydrides and methacrylic acid esters, acrylic acid esters, styrene , A monomer such as acrylonitrile, vinyl acetate, 2-hydroxyethyl acrylate and the like, polymerized or copolymerized using a radical polymerization initiator to obtain a polymer, and then a mercapto group which is an active hydrogen-containing group in the polymer, It can be obtained by addition reaction of an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, an acrylic acid chloride, a methacrylic acid chloride or an allyl chloride with respect to an amino group, a hydroxyl group or a carboxyl group. is not. Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl crotonic acid, and glycidyl isocrotonic acid. Examples of the ethylenically unsaturated compound having an isocyanate group include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, and methacryloylethyl isocyanate. Further, an ethylenically unsaturated compound having glycidyl group or isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride may be added in an amount of 0.05 to 0.95 mole equivalent to the active hydrogen-containing group in the polymer. preferable. When the active hydrogen-containing group is a mercapto group, an amino group, or a hydroxyl group, the entire amount can be used for introducing a side chain group. However, in the case of a carboxyl group, the acid value of the binder polymer is within a preferable range. It is preferable to adjust the addition amount.

  When using a binder polymer, the content thereof is preferably 1 to 90% by weight, more preferably 10 to 80% by weight, based on the total photosensitive organic component. If the amount of the binder polymer is too small, dispersion of the electron emitting material or inorganic particles is caused. When the amount of the binder polymer is too large, the solubility of the unexposed portion in the developer may be lowered, or the binder may be defective during firing.

  The acid value of the polymer having an acidic group is preferably 50 to 200 mgKOH / g. By setting the acid value to 50 mgKOH / g or more, the solubility of the soluble part in the developer is not lowered, and by setting the acid value to 200 mgKOH / g or less, the development allowable width can be widened. The acid value is measured by dissolving 1 g of the binder polymer in 100 ml of ethanol and then titrating with a 0.1N potassium hydroxide aqueous solution.

  Furthermore, the weight average molecular weight of the binder polymer to be used is preferably 5,000 to 100,000, more preferably 15,000 to 75,000. If the weight average molecular weight is less than 5000, the printability of the paste may be deteriorated. If the weight average molecular weight exceeds 100,000, the solubility in the developer may be deteriorated. The weight average molecular weight of the binder polymer was measured by size exclusion chromatography using tetrahydrofuran as a mobile phase. The column was Shodex KF-803, and the weight average molecular weight was calculated in terms of polystyrene.

  Further, since the thermal decomposition temperature of the electron emitting material is generally 500 ° C. or higher, the thermal decomposition temperature of the binder polymer is preferably 500 ° C. or lower, and more preferably 450 ° C. or lower. Use of a binder polymer having a thermal decomposition temperature of 500 ° C. or higher is not preferable because an organic residue tends to remain in the electron-emitting device. The technique for adjusting the thermal decomposition temperature of the binder polymer can be achieved by selecting a monomer as a copolymerization component. In particular, the thermal decomposition temperature of the copolymer can be lowered by using a monomer that thermally decomposes at a low temperature as a copolymer component. Examples of components that thermally decompose at a low temperature include methyl methacrylate, isobutyl methacrylate, α-methylstyrene, and the like. As the binder polymer having a carboxyl group, a copolymer having (meth) acrylic acid ester and (meth) acrylic acid as a copolymerization component is preferably used because of its low thermal decomposition temperature during firing. In particular, a styrene / methyl methacrylate / methacrylic acid copolymer is preferably used.

  The thermal decomposition temperature was set by using a TG measuring device (TGA-50, manufactured by Shimadzu Corporation), a sample of about 5 mg, a flow rate of 20 ml / min in an air or nitrogen atmosphere, and a heating rate of 20-0. The temperature is raised to 700 ° C. at 6 ° C./min. As a result, a chart plotting the relationship between temperature (vertical axis) and weight change (horizontal axis) is printed, and the tangent line between the part before disassembly (part parallel to the horizontal axis) and the part under disassembly is drawn. The temperature can be measured by a method such as the thermal decomposition temperature.

  As a specific example of the photocurable monomer, a compound containing a carbon-carbon unsaturated bond (ethylenically unsaturated group) having photoreactivity can be used. For example, alcohols (for example, ethanol, propanol, Acrylic acid ester or methacrylic acid ester of hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc., carboxylic acid (for example, propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, Phthalic acid, tartaric acid, citric acid, etc.) and glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidyl methexylylene diamine, amide derivatives (eg, acrylamide, methacrylamide, N-methylo) Acrylamide, methylene bis-acrylamide), reaction products of epoxy compounds with acrylic acid or methacrylic acid. Further, in the polyfunctional photocurable monomer, the unsaturated group may be present by mixing acrylic, methacrylic, vinyl and allyl groups. In the present invention, one or more of these can be used.

  When using a photocurable monomer, the content thereof is preferably in the range of 1 to 50% by weight, more preferably 5 to 30% by weight, based on the total photosensitive organic component. If the amount of the photocurable monomer is too small, the photocuring is likely to be insufficient, and the sensitivity of the exposed portion is lowered or the development resistance is lowered. When the amount of the photocurable monomer is too large, the solubility of the unexposed portion in the developer may be lowered, or the crosslinking density may be too high, which may cause debinding failure during firing.

  When using a photopolymerization initiator, it is selected from those that generate radical species. As photopolymerization initiators, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- (o-ethoxy) Carbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ' , 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-Benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4- Dimethyl Oxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl -1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-bi Imidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bi (Η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2- Dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β -Chloranthra Non, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2 -Phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, N-phenylglycine, tetrabutylammonium (+1) n- Butyltriphenylborate (1-), naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide And combinations of photoreducing dyes such as tribromophenylsulfone, benzoyl peroxide and eosin, methylene blue, and reducing agents such as ascorbic acid and triethanolamine. In the present invention, one or more of these can be used.

  When using a photoinitiator, the content is 0.05-10 weight% with respect to all the photosensitive organic components, More preferably, it is 0.1-10 weight%. If the amount of the photopolymerization initiator is too small, the photosensitivity will be poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed area may be small.

  A sensitizer can be used together with a photopolymerization initiator to improve sensitivity and to expand the effective wavelength range for the reaction.

  Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4 -Dimethylaminophenylvinylene) Isonaphtho Sol, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyl Diethanolamine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, diethylamino Isoamyl benzoate, (2-dimethylamino) ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 2-ethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazo Le, and a 1-phenyl-5-ethoxycarbonyl-thiotetrazole the like. In the present invention, one or more of these can be used.

  Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is contained in the paste of the present invention, the content thereof is usually 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the total photosensitive organic component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be reduced.

  When using an ultraviolet absorber, an organic dye having ultraviolet absorption in the wavelength region of 300 to 550 nm is preferable, and an organic dye having a maximum absorption wavelength (λmax) in the wavelength range of 300 to 550 nm is more preferable. . By using an organic dye having ultraviolet absorption in these wavelength regions, it is possible to suppress light scattering inside the paste for electron-emitting devices during ultraviolet irradiation. Thereby, since photocuring of a non-ultraviolet irradiation part is suppressed, the residue containing the electron emission material in parts other than an electron emission element pattern can be reduced significantly.

  Specific examples of ultraviolet absorbers include azo, benzophenone, benzotriazole, coumarin, xanthene, quinoline, anthraquinone, benzoate, benzoin, cinnamic acid, salicylic acid, hindered amine, A cyanoacrylate type, a triazine type, an aminobenzoic acid type, a quinone type, etc. are mentioned, Although it can use combining 1 type or multiple, it is not limited to these.

  When the carbon nanomaterial as described above is used as the electron emission material, the ultraviolet absorber is preferably a nitrogen-containing compound, and it is burned off when firing the paste for the electron-emitting device. Therefore, the ultraviolet absorber is an organic nitrogen compound. It is more preferable that Furthermore, the organic nitrogen compound has an unshared electron pair possessed by a nitrogen atom, and the organic nitrogen compound easily adheres to the surface of the carbon nanomaterial due to the presence of the unshared electron pair. When organic nitrogen compounds are present on the surface of carbon nanomaterials, the aggregation of carbon nanomaterials can be suppressed, and when organic nitrogen compounds are used, a stable dispersion state of carbon nanomaterials in the paste for electron-emitting devices can be obtained. There is also.

  In addition, since organic nitrogen compounds having an aromatic ring structure have π electrons of the aromatic ring, they have good adhesion to carbon nanomaterials and affinity with photosensitive organic components. Since a stable dispersion state of the material can be obtained, it is preferably used. Furthermore, an organic nitrogen compound having an azo bond is particularly preferably used since it has a wide absorption wavelength absorption range of ultraviolet rays and has good thermal decomposability. Specific examples of the compound having an aromatic ring structure and an azo bond include Sudan I, Sudan Black B, Sudan Red 7B, Sudan II, Sudan IV (all trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), azobenzene, amino Examples thereof include azobenzene, dimethylaminoazobenzene, hydroxyazobenzene, and the like, which can be used alone or in combination.

  The UV absorber preferably has a molecular weight of 500 or less. When the molecular weight exceeds 500, the thermal decomposition temperature may shift to a high temperature side, and cannot be decomposed when the electron-emitting device paste is baked. If undecomposed organic matter remains in the electron-emitting device, the degree of vacuum in the display panel or the backlight panel using the electron-emitting device manufactured by the electron-emitting device paste of the present invention is deteriorated. Deteriorate the life of the.

  The content of the ultraviolet absorber with respect to the total photosensitive organic component in the paste for electron-emitting devices is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. If it is less than 0.001% by weight, the effect of adding an ultraviolet absorber is reduced, and if it exceeds 10% by weight, the transmittance of exposure light may be reduced. In this case, the film thickness is reduced. When the film thickness is reduced, a sufficient amount of electron-emitting material does not remain in the electron-emitting device.

  When a polymerization inhibitor is used, specific examples thereof include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-t- Examples thereof include butyl-p-methylphenol, chloranil, pyrogallol and the like, and one or more can be used in combination, but the invention is not limited to these.

  The molecular weight of the polymerization inhibitor is preferably 500 or less. When the molecular weight exceeds 500, the thermal decomposition temperature may be shifted to a high temperature side as in the case of the ultraviolet absorber, and cannot be decomposed when firing the paste for electron-emitting devices. If undecomposed organic matter remains in the electron-emitting device, the degree of vacuum in the display panel or the backlight panel is deteriorated, and the life of the electron-emitting device is deteriorated.

  The content of the polymerization inhibitor with respect to the total photosensitive organic component in the electron emission source paste is preferably 0.01 to 10% by weight, more preferably 0.02 to 5% by weight. If it is less than 0.01% by weight, the effect of the polymerization inhibitor cannot be obtained, and if it exceeds 10% by weight, photopolymerization may be inhibited.

  By combining the ultraviolet absorber and the polymerization inhibitor, the radical generated by the ultraviolet rays scattered without being absorbed by the ultraviolet absorber can be captured by the polymerization inhibitor to suppress photocuring of the non-ultraviolet irradiation part. This is preferable because residues including the electron-emitting material in portions other than the electron-emitting device pattern can be greatly reduced.

  When the ultraviolet absorber and the polymerization inhibitor are used in combination, the content of the ultraviolet absorber with respect to the total photosensitive organic component in the paste for the electron-emitting device is preferably 0.05 to 5% by weight, more preferably 0.1 to 0.1%. The content of the polymerization inhibitor is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. The total content of the ultraviolet absorber and the polymerization inhibitor with respect to the photosensitive organic component is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and the weight of the ultraviolet absorber and the polymerization inhibitor. A ratio of 1:10 to 10: 1 is preferable because a synergistic effect is obtained.

  A preferable combination of such an ultraviolet absorber and a polymerization inhibitor is a monoester of an azo dye and hydroquinone or hydroquinone from the viewpoint of dispersibility of the electron-emitting material in the paste for electron-emitting devices and good thermal decomposability. Examples thereof include a compound, a combination of an azo dye and phenothiazine. Specific examples of preferable combinations of UV absorbers and polymerization inhibitors include “Sudan IV” (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.) and hydroquinone monomethyl ether, “Sudan IV” and phenothiazine, aminoazobenzene and hydroquinone. Examples include monomethyl ether, aminoazobenzene and phenothiazine.

  The organic solvent is preferably one that dissolves organic components such as a binder polymer. For example, polyhydric alcohols such as diol and triol typified by ethylene glycol and glycerin, compounds obtained by etherification and / or esterification of alcohol (ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, ethylene glycol alkyl ether acetate, diethylene glycol monoacetate) Alkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, propylene glycol alkyl ether acetate) and the like. Specifically, terpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, Ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate Organic solvent mixture containing one or more of such or these butyl Carbitol acetate is used.

  When an organic solvent is used, the content thereof is preferably in the range of 10 to 90% by weight, more preferably 20 to 80% by weight, based on the total photosensitive organic component. If the amount of the solvent is too small, the dispersion stability of the paste for electron-emitting devices is deteriorated and there is a possibility of gelation. When the amount of the solvent is too large, the printing characteristics of the paste for electron-emitting devices are deteriorated, and there is a possibility that a film cannot be formed.

  In order to disperse the inorganic particles and the electron emission material more sufficiently in the paste for the electron emission element, a dispersant may be used. When the carbon nanomaterial as described above is used as the electron emission material, the dispersant is preferably an amine-based comb block copolymer. Examples of the amine-based comb block copolymer include Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 24000SC, Solsperse 24000GR, Solsperse 28000 (all trade names) manufactured by Avicia Co., Ltd., and the like.

  Hereinafter, a method for producing a triode type and a diode type electron emission device for field emission using the paste for an electron emission device of the present invention will be described. Note that other known methods may be used for manufacturing the electron-emitting device, and the method is not limited to the manufacturing method described later.

  First, a method for manufacturing a rear substrate for a triode type electron-emitting device will be described. A conductive film such as ITO is formed on a glass substrate to form a cathode electrode. Subsequently, an insulating material is laminated by 5 to 15 μm by a printing method. Next, a gate electrode layer is formed on the insulating layer by vacuum evaporation. An emitter hole pattern is formed by applying a resist on the gate electrode layer and etching the gate electrode and the insulating layer by exposure and development. Thereafter, an electron-emitting device paste is applied on the emitter hole pattern by screen printing or a slit die coater, and then dried in a hot air oven or the like. When the dried electron-emitting device paste is irradiated with ultraviolet rays from the upper surface (electron-emitting source paste side) through a photomask, or a transparent conductive film such as ITO is used for the cathode electrode, the back surface The electron emission source paste is directly irradiated with ultraviolet rays from the glass substrate side. After the exposure, development is performed with an alkaline aqueous solution or the like, and a pattern of the electron-emitting device is formed in the emitter hole, followed by baking at 400 to 500 ° C. to produce the electron-emitting device. Finally, raising treatment of the electron emission material is performed by a laser irradiation method or a tape peeling method.

  Next, a front substrate is produced. An anode electrode is formed by depositing ITO on a glass substrate. Red, green and blue phosphors are stacked on the anode electrode by a printing method. A triode type electron-emitting device can be manufactured by bonding the back substrate and the front substrate with a spacer glass sandwiched between them and evacuating them with an exhaust pipe connected to the container. In order to confirm the electron emission state, by supplying a voltage of 1 to 5 kV to the anode electrode, electrons are emitted from the electron emission material, and phosphor emission can be obtained.

  When preparing a front plate for a diode-type electron-emitting device, the paste for the electron-emitting device is printed on the cathode electrode in a predetermined pattern by screen printing or a slit die coater, and then heated at a temperature of 400 to 500 ° C. in the atmosphere. Then, an electron-emitting device is obtained, and this is brushed by a tape peeling method or a laser processing method. A phosphor is printed on a glass substrate newly sputtered with ITO, an anode electrode is produced, these two glass substrates are bonded together with a spacer interposed therebetween, and evacuated by an exhaust pipe connected to the container, thereby forming a diode type. An electron-emitting device can be manufactured. In order to confirm the electron emission state, by supplying a voltage of 1 to 5 kV to the anode electrode, electrons are emitted from the electron emission material, and phosphor emission can be obtained.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to this. The electron-emitting material, inorganic particles, organic fine particles, and organic components used in the examples are as follows.

A. Electron emission material Single-walled carbon nanotube (Toray Industries, Inc.)
Carbon nanofiber (manufactured by Showa Denko KK).

B. Glass powders having a composition of Bi ₂ O ₃ (84 wt%), B ₂ O ₃ (7 wt%), SiO ₂ (1 wt%), ZnO (8 wt%) were used. The glass powder having a softening point of 380 ° C. and an average particle diameter of 0.5 μm was used.

C. Organic fine particles Organic fine particles I: Polymethyl methacrylate fine particles having an average particle size of 0.03 μm Organic fine particles II: Polymethyl methacrylate fine particles having an average particle size of 0.1 μm Organic fine particles III: Polymethyl methacrylate fine particles having an average particle size of 0.2 μm Organic fine particles IV: polymethyl methacrylate fine particles having an average particle size of 0.4 μm Organic fine particles V: polymethyl methacrylate fine particles having an average particle size of 1 μm Organic fine particles VI: polystyrene fine particles having amino groups on the surface having an average particle size of 0.2 μm.

D. Organic component Binder polymer: methacrylic acid / methyl methacrylate / styrene = 40/40/30 parts by weight of a copolymer obtained by addition reaction of 0.4 equivalents of glycidyl methacrylate (weight average molecular weight 43000) Acid value 100 mgKOH / g)
Photocurable monomer: Polyethylene glycol diacrylate Photoinitiator: “Irgacure 369” (manufactured by Ciba Specialty Chemicals)
UV absorber: “Sudan IV” (manufactured by Tokyo Chemical Industry Co., Ltd.)
Polymerization inhibitor: Hydroquinone monomethyl ether Dispersant: “Solsperse 24000GR” (manufactured by Avicia)
Organic solvent: Terpineol.

<Evaluation method>
(1) Measurement of glass softening point The glass transition temperature of the used glass powder was measured using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., EXTER6000, TMA / SS). Glass particles were melted at 800 ° C. and processed into a cylindrical shape having a diameter of 5 mm and a height of 2 cm to obtain a measurement sample.

(2) Average particle size measurement of glass powder and organic fine particles The cumulative 50% particle size of the used glass powder and organic fine particles was measured using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrac 9320HRA).

(3) Measurement of porosity and average pore diameter The mercury intrusion method is used to measure the porosity (V) and average pore diameter (R) in the electron-emitting device. After filling the sample cell with about 1 g of the electron-emitting device, fill the mercury, apply pressure in the high-pressure vessel to enter the mercury into the vacancies, and determine the total vacancies from the applied pressure and the amount of mercury injected. Volume (Vt), total pore surface area (S), bulk density (ρv), and true density (ρr) were determined, and porosity (V) and average pore diameter (R) were determined from the following equations.

Porosity (vol%): V = (1−ρv / ρr) × 100
Average pore diameter (μm): R = 4 Vt / S.

(4) Measurement of the number of protrusions of the electron-emitting material The paste for the electron-emitting device is screen-printed on the rear substrate for the triode-type electron-emitting device in which emitter holes of 10 μmφ are arranged at intervals of 40 μm within a 10 mm square. It was printed and dried at 85 ° C. for 15 minutes to obtain a film having a thickness of 2 μm. This film was irradiated with ultraviolet rays from the upper surface through a photomask and then developed with an alkaline aqueous solution to form an electron-emitting device pattern in the emitter hole, and then fired at 450 ° C. to produce an electron-emitting device. . The electron-emitting device was subjected to a brushing process in which an electron-emitting material was projected from the surface using a tape peeling method. The obtained substrate having the electron-emitting device was observed from the side of the substrate with a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.) at an acceleration voltage of 1 kV and a magnification of 30000 times. From this SEM image, the total number of protrusions of the electron-emitting material protruding from the electron-emitting device was measured.

Example 1
Single-walled carbon nanotubes (manufactured by Toray Industries, Inc.) are pulverized by a ball mill using zirconia balls having a diameter of 3 mm, and 0.5 μmφ glass powder, binder polymer, photocurable monomer, UV absorber, dispersant, and organic solvent are added. The composition ratio shown in Table 1 was added and kneaded with three rollers to prepare an electron-emitting device paste.

Next, a paste for an electron-emitting device is printed on a rear substrate for a triode type electron-emitting device in which emitter holes of 10 μmφ are arranged at intervals of 40 μm within a 10 mm square, and dried at 85 ° C. for 15 minutes. did. As a result of measuring the film thickness of the dried electron-emitting device paste with a scanning electron microscope, the film thickness was 2 μm. The dried electron-emitting device paste was irradiated with 1 J / cm ² of ultraviolet light from an upper surface with an ultrahigh pressure mercury lamp with 50 mW / cm ² output using a negative chrome mask (10 μmφ, 40 μm interval). Thereafter, development was performed by applying a 1% by weight aqueous solution of sodium carbonate in a shower for 150 seconds, washing with water using a shower spray to remove the uncured portion, and forming a pattern of the electron-emitting device, followed by 450 ° C. And an electron-emitting device was fabricated. The obtained electron-emitting device had a porosity of 12% and an average pore diameter of 0.036 μm. Further, the number of protrusions of the electron emission material was 91.

Examples 2-11
Similarly to Example 1, an electron-emitting device using the electron-emitting device paste having the composition ratio shown in Table 1 was manufactured, and the porosity, the average hole diameter, and the number of protrusions of the electron-emitting device were measured. The results are shown in Table 1.

Comparative Example 1
Single-walled carbon nanotubes (manufactured by Toray Industries, Inc.) are pulverized by a ball mill using zirconia balls having a diameter of 3 mm, and 0.5 μmφ glass powder, binder polymer, photocurable monomer, UV absorber, dispersant, and organic solvent are added. The composition ratio shown in Table 2 was added and kneaded with three rollers to prepare an electron-emitting device paste. An electron-emitting device was produced in the same manner as in Example 1 using the obtained paste for electron-emitting device. There were almost no vacancies in the obtained electron-emitting device, and the porosity and average vacancy diameter could not be measured.

  The observed number of protruding carbon nanotubes was 32.

Comparative Examples 2-3
Similarly to Example 1, an electron-emitting device using the electron-emitting device paste having the composition ratio shown in Table 2 was manufactured, and the porosity, average pore diameter, and number of protrusions of the electron-emitting material were measured. The results are shown in Table 2.

Comparative Example 4
Similarly to Example 1, an electron-emitting device using an electron-emitting device paste having the composition ratio shown in Table 2 was manufactured, and the porosity and average pore diameter were measured. The results are shown in Table 2. In addition, when the produced electron-emitting device was subjected to raising treatment by a tape peeling method, the structure of the electron-emitting device collapsed and was peeled off from the substrate.

Comparative Example 5
Similarly to Example 1, a paste for an electron-emitting device having the composition ratio shown in Table 2 was produced, but the paste was gelled.

Comparative Example 6
Similarly to Example 1, an electron-emitting device using the electron-emitting device paste having the composition ratio shown in Table 2 was manufactured, and the porosity, the average hole diameter, and the number of protruding electron-emitting materials were measured. The results are shown in Table 2.

Claims (5)

An electron-emitting device paste including an electron-emitting material, inorganic particles, and organic fine particles, wherein the organic fine particles have an average particle size of 0.01 to 0.5 μm, and the organic fine particle content is less than that of the electron-emitting device paste. The paste for electron-emitting devices which is 0.1-20 weight%. The paste for an electron-emitting device according to claim 1, wherein the electron-emitting material is a carbon nanotube. An electron-emitting device including an electron-emitting material and inorganic particles, wherein an average hole diameter in the electron-emitting device is 0.01 to 0.5 μm. The electron-emitting device according to claim 3, wherein the electron-emitting device has a porosity of 1 to 50 vol%. A process for firing the electron-emitting device paste according to claim 1 or 2 to burn away organic fine particles to form vacancies in the electron-emitting device, and projecting an electron-emitting material from the surface of the electron-emitting device by a tape peeling process The manufacturing method of the electron-emitting device which has a process to make.