TW201137061A - Paste for electron emitting source, electron emitting source using the same and method for producing them - Google Patents

Abstract

By means of using a paste composition capable of generating cracks on a surface of electron emitting source, an activating treatment step for exposing carbon nanotubes on the surface of electron emitting source can be omitted, while, an electron emitting source capable of emitting electron under low voltage and emitting light uniformly can be obtained.

Description

[Technical Field] The present invention relates to a paste for an electron source, an electron source using the same, an electron emitting element, and a method for producing the same. [Prior Art] Carbon-based materials typified by carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon nanotube coils, and carbon nanowalls are not only excellent in physical and chemical durability, but also suitable for The sharp tip shape of the electric field radiates with a large aspect ratio. Therefore, various types of application systems such as an electric field radiation type display (FED) using a carbon-based material as an electron emission source, a liquid crystal backlight unit (LCD-BLU) using an electric field emission, an illumination device, and an X-ray source are used. Exuberant. As one of methods for producing an electron source using a carbon-based material, there is a method of pasting a carbon-based material (for example, a carbon nanotube) onto a cathode substrate. As an example of such a method, a coating film of a paste containing a carbon nanotube is formed on a cathode electrode, and after heat treatment, the surface of the film is subjected to activation treatment such as a tape peeling method or a laser irradiation method. The paste material used in this method is known to contain glass powder in a paste containing a carbon nanotube (for example, refer to Patent Document 1), a carbonate-containing one (for example, refer to Patent Document 2), or a metal carbonate (for example). For example, refer to Patent Document 3) and the like. Further, when a paste using a binder resin is used, the binder resin is removed by baking. For this reason, there has been proposed a technique in which a residue is less likely to remain and a relatively low-temperature heat-eliminating material is used (for example, see Patent Document 4). Further, in the above-described step, in order to obtain good electron emission characteristics, the carbon nanotubes are exposed to the surface of the electron source to be exposed. However, if the activation treatment can be omitted, the cost can be reduced more greatly. In the case where a good electron emission characteristic is obtained without performing the raising treatment, a porous electron emitting source is proposed, and the electron emitting material protrudes from the pore wall (see, for example, Patent Document 5). The electron source is a plastic particle such as polymethyl methacrylate mixed in a paste containing a carbon nanotube, and the plastic particles are burned in the heat treatment step, and a continuous gap is formed in the region where it exists to form a continuous shape. Hole. Since the carbon nanotubes protrude from the pore walls, no activation treatment is required. CITATION LIST Patent Literature Patent Literature No. JP-A-2007-124789 (Patent Document 3): JP-A-2008-243789 [Problem to be Solved by the Invention] However, in the method described in Patent Document 5, there is a problem that the voltage required for electron emission increases. Further, there is a problem that the uniformity of light emission is poor. The present invention has been made in view of the above problems, and an object thereof is to provide an activation treatment step which can omit the surface of the electron nanotube from being uncovered by 201137061, and can perform electron emission at a low voltage. A paste for an electron emission source that uniformly emits light, and an electron emission source using the same. Means for Solving the Problem The present invention relates to a paste for an electron emission source comprising (A) an electron emitting material, (B) a thermally decomposable foaming agent, and (C) a component which generates a shrinkage stress upon thermal decomposition. Further, another aspect of the present invention is a paste for an electron source comprising a (A) electron emitting material and (D) a thermal polymerization initiator having a function as a thermally decomposable foaming agent and having an ethylenically unsaturated group. . Advantageous Effects of Invention According to the present invention, since the activation step of exposing the carbon nanotube to the surface of the electron emission source can be omitted, the cost of the apparatus, materials, and the like necessary for the activation treatment step in the production of the electron emission source can be reduced. Further, according to the present invention, electron emission can be obtained at a low voltage, although activation treatment is not required, and an electron emission source capable of obtaining uniform illumination can be obtained. [Embodiment] The paste for electron emission source of the present invention contains (A) an electron emitting material, (B) a thermally decomposable foaming agent, and (C) a component which generates shrinkage stress during thermal decomposition. Further, another aspect of the paste for an electron source according to the present invention comprises (A) an electron emitting material and (D) a thermal polymerization initiator having a function as a thermally decomposable foaming agent and having an ethylenically unsaturated group. Further, the present invention relates to an electron emission source and an electron emission element obtained by using the same, and a method of manufacturing the same. In the case of using the paste for an electron emission source of the present invention, it is possible to perform electronization at a low voltage without performing an activation treatment such as a tape peeling method or a laser irradiation method, and it is excellent in adhesion to a cathode electrode, and can be obtained. A uniform source of electron emission. The reason why electron emission can be performed at a low voltage without performing activation treatment is presumed as follows. Further, in the following description, a carbon nanotube is exemplified as the f (A) electron emitting material. However, as will be described later, the electron emitting material is not limited thereto, and other materials are also applicable. When the paste for electron source of the present invention is applied to a substrate and the electron source obtained by heat treatment is observed, it is understood that cracks occur in the electron source, and the carbon nanotubes protrude from the crack. Therefore, it is considered that electron emission can be obtained from a carbon nanotube protruding from a crack even without activation treatment. In the course of cracking, it is considered that the force of pulling out the carbon nanotube in a slightly vertical direction in the cross section (crack surface) generated by the crack inside the electron source is effective. Therefore, the protruding length of the carbon nanotubes becomes long, and the aspect ratio becomes large. As a result, electric field concentration in the carbon nanotubes is easy, and the voltage required for electron emission can be kept low. In order to carry out electron emission at a practically low voltage, the length of the carbon nanotube protruding from the crack surface is preferably 0.5 μm or more, more preferably 1.0 μm or more, particularly preferably 3.0 μm or more, and particularly preferably 4.0 μm or more. The best is 5.0 μιη or more. This can be achieved by using the paste for an electron emissive source of the present invention. The length of the protruding carbon nanotubes is long as long as it is short-circuited without contact with the gate electrode or the anode electrode, and the longer the protruding length of the carbon nanotubes, the lower the voltage required for electron emission. There is also a prominent carbon naphthalene 201137061 meter tube will exist in the cracked bridge, but can contain that. In the occurrence of cracks, it is considered that (B) thermal decomposition type foaming agent has a large amount of help. The thermally decomposable foaming agent in the present specification is a substance which is thermally decomposed to emit a gas and which generates bubbles in the paste film of the electron source. It is believed that this bubble is the starting point of the crack and is prone to many cracks. If the number of cracks increases, the exposed electron-emitting material increases, so that the uniformity of light emission increases. Further, in the occurrence of the above-mentioned cracks, it is considered that (C) a component which generates shrinkage stress at the time of thermal decomposition also contributes greatly. It is considered that due to the influence of the component (C), a large contraction stress is applied to the electron source during thermal decomposition, and the generated crack grows. An example of the component (C) which causes shrinkage stress at the time of thermal decomposition is, for example, a compound such as a metal salt, an organometallic compound, a metal complex, a decane coupling agent or a titanium coupling agent. These are decomposed by heating. However, these are not characterized in that the plastic particles described in the above Patent Document 5 are completely burned by combustion or decomposition, but have a characteristic of eventually remaining as a metal oxide or a ruthenium compound. In the following description of the present specification, the substance having the feature that the component (C) does not completely disappear even when heated to the paste baking temperature is collectively referred to as "residual compound". Since this residual compound shrinks during thermal decomposition, shrinkage stress is generated in the paste film for electron source, and cracks can be formed in the electron source after firing. Since the shrinkage stress is large, if the width of the crack is increased, a carbon nanotube having a long protruding length can be obtained in the electron source, and the voltage required for electron emission is lowered. Further, as another example of the component (C) which causes shrinkage stress during thermal decomposition, a combination of a thermal polymerization initiator and a compound containing an ethylenically unsaturated group may be mentioned. The thermal polymerization initiator generates a radical due to decomposition by heating, and is used for crosslinking a double bond portion of a compound containing an ethylenically unsaturated group. Since the double bond portion is crosslinked, a large shrinkage stress is applied to the electron source during thermal decomposition. It is considered that in this case, if there is a defect in the electron source, cracking occurs as a starting point and growth is performed. As a result, as in the case of the above-mentioned "residual compound", the voltage required for electron emission can be reduced. Further, it is recognized that these components are decomposed and disappeared after the baking of the paste for electron source. In this case, the substance which disappears when the component (C) is heated to the paste baking temperature is collectively referred to as a "disappearing crack generating agent". Further, specific examples of the vanishing cracking agent are not limited thereto, and any one of the same properties may be used. Further, each of the above-mentioned components may have a property of releasing a gas, promoting crosslinking, and containing a plurality of ethylenically unsaturated groups in one substance. Thereby, the type of the substance to be mixed can be reduced, and the system can be simplified. Specifically, as another aspect of the component (C) which generates shrinkage stress at the time of thermal decomposition, a thermal polymerization initiator containing an ethylenically unsaturated group may be mentioned. This is also included in the vanishing cracking agent. In addition, in place of the component (B) and the component (C), a thermal polymerization initiator containing (D) as a thermal decomposition type foaming agent and containing an ethylenically unsaturated group may be used. In this case, the same effect is obtained because the above three elements are contained in each paste. In addition, (D) a thermal polymerization initiator which is a function of a thermal decomposition type foaming agent and which contains an ethylenic non-201137061 saturated group, is a thermal polymerization initiator containing an ethylenically unsaturated group, and serves as (B) thermal decomposition. The task of the type of foaming agent. In addition, as another example of the disappearing crack generating agent, a substance having a property of a thermal decomposition type foaming agent and a thermal polymerization initiator, a compound containing an ethylenically unsaturated group, or a use-containing compound may be used. The case of a thermally decomposable foaming agent having an ethylenically unsaturated group and a thermal polymerization initiator. Since these have the task of thermally decomposing a foaming agent, they can be used together with the component (B), or the component (B) can be omitted. Further, in the component (C) which generates shrinkage stress at the time of thermal decomposition, a cerium oxide material or a polyfluorene oxide material may be contained. The component (C) is preferably one in which shrinkage stress is generated at a temperature below the baking temperature of the paste for an electron source. In the use of a light-emitting device such as a general display or illumination, since the inexpensive soda lime glass is used as the substrate, the component (C) preferably has a shrinkage stress at a temperature of 100 ° C or more and 500 ° C or less. Further, the lower limit is more preferably 150 ° C or more, and particularly preferably 200 ° C or more. Further, the upper limit is more preferably 450 ° C or less, and particularly preferably 400 ° C or less. It may be a combination of any of the preferred lower limits or any preferred upper limit. When the temperature at which the component (C) causes a shrinkage stress is within the above range, a good crack can be formed due to the synergistic effect with the starting point of the thermally decomposable foaming agent. Since the above-mentioned vanishing cracking agent disappears after firing of the paste for electron source, it is equivalent to a component which generates shrinkage stress at a temperature within the above range. The details of the residual compound will be described later. Further, in the present specification, when a component is subjected to a contraction stress at a temperature of, for example, 100 ° C or more, and the temperature is less than or equal to the following, it means that the following conditions are satisfied. First, for this component, TGA (Thermogravimetric) was carried out under an inert gas atmosphere at a temperature increase rate of 10 ° C / min.

Analysis) Thermogravimetric analysis. The point at which the slope of the TGA curve obtained as a result becomes negative is taken as the thermal decomposition temperature of the component. Further, when the temperature after the thermal decomposition temperature is negative and the temperature region is in the range of 100 ° C or more and 500 ° C or less, the component is subjected to shrinkage stress at a temperature of 100 ° C or more and 500 ° C or less. This is because the slope of the TGA curve after the thermal decomposition temperature is negative, that is, when the weight is decreased, it indicates that the material continues to thermally decompose. In addition, when any of the "residual compound" or the "disappearing cracking agent" is used as the component (C), almost no organic residue remains in the electron source, and good electron emission can be obtained. Features are preferred. As described above, in the present invention, it is presumed that the occurrence of bubbles by the thermally decomposable foaming agent and the occurrence of shrinkage stress by the residual compound or the vanishing cracking agent are in the step of heat treatment or in parallel at the same time. Occurrence occurs to promote the occurrence and growth of cracks. Among the above, a more preferable aspect of the paste for an electron emissive source of the present invention is as follows. (I) A paste for an electron source comprising (A) an electron emitting material, (B) a thermally decomposable foaming agent, and (C) as a component selected from the group consisting of a metal salt, an organometallic compound, a metal complex, and decane At least one or more of the group consisting of a coupling agent and a titanium coupling agent. -10- 201137061 (II) A paste for electron source, which comprises (A) an electron emitting material, (B) a thermally decomposable foaming agent, and a thermal polymerization initiator as component (c) and an ethylenic property. An unsaturated group of compounds. (III) A paste for an electron emissive source comprising (A) an electron emitting material, (B) a thermally decomposable foaming agent, and a thermal polymerization initiator containing an ethylenically unsaturated group as the component (C). (IV) A paste for an electron emission source comprising (A) an electron emitting material and (D) a thermal polymerization initiator having a function as a thermally decomposable foaming agent and having an ethylenically unsaturated group. On the other hand, as described in the above Patent Document 5, when the carbon nanotubes are protruded from the pore walls of the continuous pores formed by the plastic particles, the shrinkage stress due to the burning of the plastic particles is weak, so the carbon nanotubes are weak. The protruding length becomes shorter and the aspect ratio becomes smaller. As a result, electric field concentration is less likely to occur at the tip end of the carbon nanotube, and the voltage required for electron emission increases. The crack of the electron emission source of the present invention means a crack formed in an electron emission source as shown in Fig. 1, and has a width of 〇·5 μm or more. Further, the width of the crack is the width of the crack in the surface portion of the electron source as measured by the reference numeral 3 in Fig. 1 . The depth of the crack can also reach the cathode substrate or not. As an example, Fig. 2 shows an electron micrograph of the crack of the surface of an electron source using carbazolyl as a residual compound and azomethamine as a thermal decomposition type foaming agent, Fig. 3 An electron micrograph showing a carbon nanotube protruding from the crack surface. Further, in Fig. 4, it is shown that -11 - 201137061 uses t-butyl peroxylaurate and tetrapropylene glycol dimethacrylate as a vanishing cracking agent, and uses azomethicamine as a thermal decomposition type. An optical micrograph of the crack of the surface of the electron emitting source of the foaming agent, and an electron micrograph of the carbon nanotube protruding from the cracked surface is shown in Fig. 5. The paste for an electron emissive source of the present invention will be described in more detail below. Generally, in the (A) electron emitting material used for an electric field radiation type display or the like, there is a metal material represented by molybdenum, or a carbon nanotube, a carbon nanofiber, a carbon nanohorn, a carbon nano coil, or Carbon-based materials such as carbon nanotwist, such as needle carbon, diamond, diamond-like carbon, graphite, carbon black, fullerene, and graphene. In the present invention, any of these may be used, and it is preferable to use needle-shaped carbon from the viewpoint of low voltage function due to low work function characteristics. Among the acicular carbons, carbon nanotubes are more preferred because of their high electrical and solar characteristics. Hereinafter, a paste for an electron radiation source using a carbon nanotube as a representative of acicular carbon will be described as an example. Among the carbon nanotubes, a single layer or a multilayer of two or three layers can be preferably used. Mixtures of carbon nanotubes with different layers can also be used. Since the unrefined carbon nanotube powder contains impurities such as amorphous carbon or catalytic metal, it can be used by purifying by acid treatment or the like to improve the purity. Further, in order to adjust the length of the carbon nanotubes, the carbon nanotube powder can be pulverized by an ultrasonic 'ball mill or a bead mill. The amount of the (A) electron emitting material is preferably from 0.1 to 2% by weight based on the entire paste for the electron source. Further, it is preferably 〇. 1 to 1% by weight, particularly preferably 0.1 to 5.0% by weight. When the content of the electron emitting material is within the above range -12 - 201137061, good dispersibility, printability, and pattern formation property of the paste for an electron source can be obtained. (B) The thermally decomposable foaming agent is preferably one which decomposes in the range of 50 to 300 ° C to release gas, more preferably decomposes at 100 to 250 ° C to release gas, and more preferably 150 to 250 ° C. Decompose and release gas. By using a gas generated in the above temperature range, bubbles are not generated in the drying step in the production of the paste film for electron source, and cracking can be sufficiently caused in the heat treatment step at the time of crack formation. In the present specification, for example, the decomposition in the range of 50 to 300 ton means that the thermal decomposition temperature obtained by the TGA measurement is in the range of 50 to 300 ° C. (B) A specific example of the thermally decomposable foaming agent. For example, an azo compound such as azodimethylamine or azobisisobutyronitrile, dinitrosopentamethylenetetramine, N,N'-dinitroso-N,N'-dimethyl a nitroso compound such as p-xylyleneamine, p-toluenesulfonate, p,p'-oxybis(phenylsulfonate), anthracene dimethylamine or the like, p-toluene An azide compound such as a mercapto azide, an anthracene compound such as acetone or sulfonylhydrazine, melamine, urea, dicyanamide or the like is not limited thereto. Among these, it is particularly preferable to use an azo compound, a nitroso compound, or a ruthenium compound because no bubbles are generated in the drying step at the time of preparation of the paste film for electron source, and the amount of gas released during thermal decomposition Since there are many, the effect of sufficiently generating cracks in the heat treatment step at the time of crack formation is large. (B) The thermally decomposable foaming agent is preferably used as a particle in the paste for an electron source to promote the formation of cracks. The thermal decomposition type foaming-13-201137061 agent particle system has a lower limit of the average particle diameter of preferably 1. Ομηη or more, more preferably 3·0 μmη or more, and particularly preferably 6.8 μm or more. Further, the upper limit is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less. It may be a combination of any of the preferred lower limits or any preferred upper limit. When the average particle diameter of the thermally decomposable foaming agent particles is at least the above lower limit 値, the formation of cracks is further promoted, and the voltage required for electron emission can be reduced. Further, when the upper limit is less than or equal to the above, the surface unevenness of the electron emission source can be reduced, and uniform cracks can be formed, so that excellent light emission uniformity can be obtained. The average particle diameter referred herein means the cumulative 50% particle diameter (D5Q). In this case, the total volume of a group of powders is taken as 100%, and when the volume accumulation curve is obtained, the particle diameter at which the volume cumulative curve becomes 50% is used as the cumulative average diameter, which is used as a general evaluation of the particle size distribution. One of the parameters. Further, the measurement of the particle size distribution of the thermally decomposable foaming agent particles can be carried out by the microtrack method (method of a micro-track laser diffraction type particle size distribution measuring apparatus manufactured by Nikkei Co., Ltd.). The lower limit of the content of the (B) thermally decomposable foaming agent is preferably 1.0% by weight or more, more preferably 2.0% by weight or more, and particularly preferably 3% by weight or more, based on the entire paste for electron source. It is particularly preferably 5.0% by weight or more, and particularly preferably 1% by weight or more. Further, the upper limit is preferably 30% by weight or less, more preferably 25 % by weight or less. It can be any preferred lower limit or any combination of preferred upper limits. In addition, the lower limit of the content of the thermally decomposable foaming agent is preferably 1.0% by weight or more, more preferably 3.0% by weight, and particularly preferably 5.0% by weight based on the total solid content of the solvent removed from the paste for electron source. On -14-201137061, the best is 1% and more than %. Further, the upper limit is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 35% by weight or less. When the content of the thermally decomposable foaming agent is within the above range, the coating film can be applied to an electron source. A uniform bubble is formed inside. (C) A specific example of a residual compound which is one example of a component which generates shrinkage stress at the time of thermal decomposition. Further, since the residual compound differs in thermal decomposition temperature depending on the species, it is preferred to suitably select a compound which is blended with the temperature to be used. The term "metal salt" means carbonate, sulfate, nitrate, hydroxide salt, hydrogencarbonate, acetate, halide salt and the like. As the metal carbonate, for example, potassium carbonate, calcium carbonate, sodium carbonate, cesium carbonate, magnesium carbonate, lithium carbonate, copper (II) carbonate, iron (II) carbonate, silver carbonate (I), nickel carbonate, hydrotalcite, or the like can be used. . Examples of the metal sulfate include zinc sulfate, aluminum sulfate, potassium sulfate, calcium sulfate, silver sulfate, potassium hydrogen sulfate, barium sulfate, iron (II) sulfate, iron (III) sulfate, copper (I) sulfate, and sulfuric acid. Alum such as copper (II), sodium sulfate, nickel sulfate, barium sulfate, magnesium sulfate, potassium alum, and iron alum. Examples of the metal nitrate include magnesium nitrate, zinc nitrate, aluminum nitrate, uranyl nitrate, chlorine nitrate, potassium nitrate, calcium nitrate, silver nitrate, cerium nitrate, cobalt nitrate, cobalt (II) nitrate, and cobalt (III) nitrate. , nitric acid planing, ammonium cerium nitrate, ferric nitrate, iron (II) nitrate, iron (III) nitrate, copper (II) nitrate, sodium nitrate, lead nitrate (II), barium nitrate, barium nitrate and the like. Examples of the metal hydroxide salt include calcium hydroxide, magnesium hydroxide, manganese hydroxide, iron hydroxide (strontium), zinc hydroxide, copper (II) hydroxide, barium hydroxide, aluminum hydroxide, and hydrogen. 15- 201137061 Iron (III) oxide, etc. Examples of the metal hydrogencarbonate include sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydrogencarbonate. The metal halide salt is a salt formed between a metal such as an alkali metal or an alkaline earth metal and a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include sodium fluoride, potassium fluoride, calcium fluoride, and lithium fluoride. , sodium chloride, potassium chloride 'magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, potassium iodide, sodium iodide and the like. Examples of the metal acetate include sodium acetate, potassium acetate, calcium acetate, and magnesium acetate. As the metal salt, any of an anhydrate or a hydrate can be used. As the organometallic compound, a compound having a metal-carbon bond can be mentioned. Examples of the metal element constituting the organometallic compound include tin (Sn), indium (In), antimony (Sb), zinc (Zn), gold (Au), silver (Ag), copper (Cu), and palladium (Pd). ), aluminum (A1), titanium (Ti), nickel (Ni), platinum (Pt), manganese (Mn), iron (Fe), cobalt (Co), chromium (Cr), zirconium (Zr), and the like. Further, as a group contained in the organic chain in which an organometallic compound is bonded to a metal element, there are an ethyl fluorenyl group, an alkyl group, an alkoxy group, an amine group, a decylamino group, an ester group, an ether group, and a ring. An oxy group, a phenyl group, a halogen group or the like. Specific examples of the organometallic compound include trimethylindium, triethylindium, tributoxide indium, trimethoxyindium, triethoxyindium, tetramethyltin, tetraethyltin, and tetra. Butyltin, tetramethoxytin, tetraethoxytin, tetrabutoxytin, tetraphenyltin, triphenylsulfonium, triphenylphosphonium diacetate, triphenylsulfonium oxide, triphenylsulfonium Halogen and the like. The metal complex is a structure in which a ligand is coordinated around the metal element exemplified as the organometallic compound. Examples of the ligand forming the metal complex include an amine group, a phosphino group, a carboxyl group, a carbonyl-16 - 201137061-based 'thiol group, a hydroxyl group, an ether group, an ester group, a decyl group, a cyano group, and a halogen group. An isolated electron pair such as thiocyano, pyridyl or phenanthryl. Specific examples of the ligand include triphenylphosphine, nitrate ion, halide ion ' hydroxide ion, cyanide ion, thiocyanate ion, ammonia'-oxygen carbon, acetoacetate, pyridine, and B. Diamine, bipyridyl, phenanthroline, BINAP, catecholate, tripyridin, ethylenediaminetetraacetic acid, porphyrin, cyc Um, and crown ether. Specific examples of the metal complex include an indoleacetone indium complex, an indium ethylenediamine complex, an indium ethylenediaminetetraacetate complex, an indoleacetone tin complex, and a tin ethylenediamine. The complex compound, tin ethylenediamine tetraacetic acid, and the like. The decane coupling agent may, for example, be a hydrolyzable alkyl group having an alkoxy group, a halogen or an ethoxy group. Alkoxy groups, especially methoxy or ethoxy groups, are generally preferred. Further, examples of the organic functional group of the decane coupling agent include an amine group, a methacryl group, an acryl group, a vinyl group, an epoxy group, a decyl group, and an alkyl group. Base 'allyl and the like. Specific examples thereof include N-β (aminoethyl) γ-aminopropyltrimethoxydecane, Ν-β(aminoethyl)γ-aminopropylmethyldimethoxydecane, and fluorenyl-phenylene. - γ-aminopropyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-dibutylaminopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, hydrazine -β-(Ν-vinylbenzylaminomethylaminopropyltrimethoxydecane. hydrochloride, γ-methylpropenyloxypropyltrimethoxydecane, γ-methylpropenyloxy Propyltriethoxydecane, γ-methacryloxypropylmethyldimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane-17- 201137061, vinyltriethylhydrazine Oxydecane, vinyl trichlorodecane, (β-methoxyethoxy)decane 'γ·glycidoxypropyltrimethyl, γ-glycidoxypropylmethyldiethoxydecane, --(3,4-hexyl)ethyltrimethoxydecane, γ-mercaptopropyltrimethoxyphosphonium propyltrimethoxydecane, methyltrimethoxydecane, methyltrioxane, dimethylformene Oxydecane, dimethyldiethoxy oxime Trimethoxydecane, isobutyltrimethoxydecane, n-hexyltrioxane, n-decyltrimethoxydecane, n-hexadecyltrimethoxyphosphonium trimethoxydecane, diphenyldimethoxydecane, etc. In the present invention, one type selected from the above-mentioned coupling agents may be used alone or in combination of two or more kinds. The above-mentioned one coupling agent or a combination of two or more kinds of heterogeneous condensates may be used. The decane moiety titanium of the decane coupling agent is used. Among them, the metal salt is preferably used. The electron source obtained by using the paste containing the metal source is a large crack size in the electron source, and the carbon nanotube The length of the protrusion is also long. Moreover, the behavior is good, and the uniformity of illumination is good. It is presumed that the shrinkage stress generated when the inorganic salt is thermally decomposed is larger than the shrinkage stress generated when the organic solution is formed. From the viewpoint of thermal decomposition at a low temperature region of 100, a metal carbonate or a metal sulfate is preferred. Among them, a metal carbonate is more likely to occur. Further, if a metal carbonate containing magnesium is used, 'ene Trimethylnonane epoxy cycloalkane, γ-chloroethoxy hydrazine, n-propyl methoxy fluorene, phenylamine, a low voltage that can be combined with two kinds of electrons which are self-condensed to replace a salt The gold content of the component is divided into 5/00 °C salt and metal, and the MgO system generated by the decomposition of heat -18-201137061 acts as a secondary electron emitting material, and the electron source can be driven by a low voltage. Preferably, the average particle diameter of the residual compound is 0.5 to 10 μm. When the average particle diameter of the residual compound is 〇.5 μm or more, cracking may occur due to shrinkage stress generated during thermal decomposition. From 10 μmη or less, the surface unevenness of the emitter can be reduced to obtain good luminescence uniformity. Here, the average particle diameter means a cumulative 50% particle diameter (D5Q), which can be measured by the same method as in the case of the thermally decomposable foaming agent particles. The lower limit of the content of the residual compound is preferably 1.0% by weight or more, more preferably 5.0% by weight or more, and still more preferably 10% by weight or more based on the entire paste for electron source. Further, the upper limit is preferably 30% by weight or less, more preferably 25% by weight or less. It can be any preferred lower limit or any combination of preferred upper limits. In addition, the lower limit of the content of the residual compound is preferably 1.0% by weight or more, more preferably 5.0% by weight or more, and still more preferably 10% by weight or more based on the total solid content of the solvent removed from the paste for electron source. Further, the upper limit is preferably 60% by weight or less, more preferably 50% by weight or less, still more preferably 40% by weight or less, and particularly preferably 35% by weight or less. When the content of the residual compound is within the above range, uniform cracks can be formed in the electron source coating film. (C) A specific example of the destructive crack generating agent which is one example of a component which generates shrinkage stress at the time of thermal decomposition. Examples of the thermal polymerization initiator include 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), and 1,1' in the azo system. -Azobis(cyclohexyl-19-201137061 alkene-1-carbonitrile), 1-[(1·cyano-1-methylethyl)azo]carbamamine (2_(aminocarbamimidyl)) Butyronitrile), 2,2'-azobis{2-methyl-indole-[2-(dihydroxybutyl)]propanamine}, 2,2'-azobis[2-methyl-indole -(2-hydroxyethyl)-propionamide], 2,2'-azobis[Ν-(2-propenyl)-2-methylpropionamide], 2,2'-azobis ( N-butyl-2-methylpropanamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (2,4, 4-trimethylpentane) (azobistrioctane) and the like. Further, examples of the peroxide system include tert-butylperoxytrimethylacetate, third hexylperoxy-2-ethylhexanoate, and 1,1-bis(t-butylperoxy). -2-methylcyclohexane, 1,1-bis(Third hexylperoxy)·3,3,5-trimethylcyclohexane, 1,1-bis (trihexylperoxy)cyclohexane Alkane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2- Bis(4,4-dibutylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, third hexylperoxyisopropylmonocarbonate, tert-butyl Peroxymaleic acid, tert-butylperoxy_3,5,5-trimethylhexanoate, tert-butylperoxylaurate, benzhydryl peroxide, 2,5·2 Methyl 2,5-di(m-tolylperylperoxy)hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, third Hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzimidyl peroxy)hexane, tert-butyl peroxyacetate, 2,2-double (third Butyl peroxy)butane, tert-butylperoxybenzoate Acid ester, n-butyl-4,4-bis(t-butylperoxy)valerate, di-tert-butylperoxyisophthalate, α,α'_bis (t-butyl) Oxygen) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, tert-butyl cumene Oxide, etc. -20- 201137061 As a component containing an ethylenically unsaturated group, a propyl group, a acryloyl group, and a propylene group or a methyl methacrylate group as a propylene group or a methyl group Examples of the acrylonitrile group include methyl acrylate, ethyl acrylate, isopropyl propionate, n-butyl acrylate, second acrylate, tert-butyl acrylate, n-amyl acrylate, benzyl acrylate, butoxy acrylate. Ethyl ethyl ester, butoxy group, cyclohexyl acrylate, 2-cyclopentyl acrylate 2-ethylhexyl acrylate, tetrapropylene glycol dimethyl propyl, and, as an ethylenically unsaturated group, have one ethylene The monofunctional polyfunctional monomer of the unsaturated group, for example, a bifunctional monomer, a 4-functional monomer, a 5-functional monomer, and a 6-functional decomposability are preferably used.

SB carcass. As a specific example of the monofunctional monomer, a methyl group acrylate is used. Specific examples thereof include acrylic acid, crotonic acid, maleic acid, fumaric acid, acetic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-amyl acrylate, dibutyl acrylate, and n-butyl acrylate. Examples of the tert-butyl acrylate, the butylene glycol acrylate, and the butoxy-triethylene group include a vinyl methacryl fluorenyl group. Specific examples of the ruthenium compound are n-propyl acrylate, butyl acrylate, isobutyl acrylate, propylene glycol acrylate, dicyclopentenyl enoate, enoate, and the like. The fraction may be one molecule, two or three functional monomers, a monomer, etc., but from a thermofunctional or bifunctional (meth)acrylic acid or ('methacrylic acid, Ib An ester or such an anhydride propyl ester, isobutyl acrylate, propylene 2-n-butoxyethyl ester, alcohol acrylate, propylene-21 - 201137061 2-ethylhexyl acrylate, glycerin acrylate, acrylic acid Heptafluorodecyl ester, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, methoxy ethylene glycol acrylate , methoxy diethylene glycol acrylate, octafluoroethyl acrylate, trifluoroethyl acrylate, octadecyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentoxide, 贰 three Hydroxymethylpropane tetraacrylate, glycerin acrylate, neopentyl glycol acrylate, propylene glycol acrylate, acrylamide, aminoethyl acrylate, styrene, α-methyl styrene, allyl acrylate, benzyl acrylate Ester, cyclohexyl acrylate, bicyclic acrylate The ester, the dicyclopentenyl acrylate, and a compound in which a part or all of the acrylate in the molecule of the above-mentioned compound is a methacrylate compound, and the like. Specific examples of the bifunctional monomer include divinylbenzene and the like. Aromatic divinyl monomer, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate' 1,6-hexanediol Alkanediol di(meth)acrylate such as di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetrapropylene glycol di(methyl) a polyalkylene glycol di(meth)acrylate such as an acrylate, a urethane di(meth)acrylate, or a polyester di(meth)acrylate, etc. The ethylenic unsaturation in the present invention The component of the group is not limited to these. One or two or more types may be used. Examples of the thermal polymerization initiator containing an ethylenically unsaturated group include a vinyl group of -22-201137061. Thermal polymerization of allyl, acrylonitrile and methacryl Specific examples thereof include diallyl peroxydicarbonate, bis(2-methyl-2-propenyl)peroxydicarbonate, and bis(2-ethyl-2-propenyl). Peroxydicarbonate, bis(1-methyl-2-propenyl)peroxydicarbonate, bis(2-methyl-2-butenyl)peroxydicarbonate, bis(2-methyl-) 2-propenyloxyethyl peroxy)dicarbonate, etc. A substance having both the properties of a thermally decomposable foaming agent and a thermal polymerization initiator, and a thermally decomposable foaming agent which promotes crosslinking by heat The azo-based thermal polymerization initiator is exemplified as such a component. Specific examples thereof include 2,2'-azobis(2-methylpropionitrile) and 2,2'-azo. Bis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), Bu [U-cyano-1-methylethyl)azo]carbamamine ( 2-(Aminomethylmercapto)isobutyronitrile) 2,2'-azobis{2-methyl-N-[2-(l-hydroxybutyl)]-propanamide}, 2,2' -azobis[2-methyl-N-(2-hydroxyethyl)-propanamide], 2,2'-azobis[Ν-(2·propenyl)-2-methylpropionamide ], 2,2'-azobis(N-butyl-2-methylpropionamidine) ), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis(2,4,4.trimethylpentane) (azo) Third octane) and so on. Examples of the thermally decomposable foaming agent containing an ethylenically unsaturated group include an azo compound containing a vinyl group, an allyl group, an acrylonitrile group, or a methacryl fluorenyl group, or a nitroso compound or an anthracene compound. . Specific examples thereof include phenyl azo acrylonitrile, N-methyl-N-nitrosoallylamine, and high allylic hydrazine. (D) as a thermal decomposition type foaming agent and containing an ethylenic unsaturated -23-201137061-based thermal polymerization initiator, preferably in the range of 50 to 300 t, and the gas is released, preferably at 100. Those who decompose at ~250 °C to release gas, especially those that decompose at 150~250 °C and release gas. Such a compound is an azo compound, a nitroso compound, an anthracene compound, an azide compound or a ruthenium compound, and is preferably a thermal polymerization initiator containing an ethylenically unsaturated group. Specifically, for example, an azo-based thermal polymerization initiator which is an 2,2'-azobis[N-(2-propenyl)-2-methylpropanamide containing an ethylenically unsaturated group is mentioned. ] Wait. (D) The thermal polymerization initiator which is a function of a thermal decomposition type foaming agent and contains an ethylenically unsaturated group, and the lower limit of the average particle diameter is preferably Ι.Ομηι or more, more preferably 3.0 μmη or more, and particularly preferably 6.0. Ιιη or more. Further, the upper limit is preferably 25 μm or less, more preferably 20 μm or less, and particularly preferably 15 μm or less, which may be any combination of a preferred lower limit or any preferred upper limit. When the average particle diameter of the thermal polymerization initiator containing the ethylenically unsaturated group as the function of the thermal decomposition type foaming agent is at least the above lower limit ,, the formation of cracks is further promoted, and the electron emission can be reduced. Voltage. Further, if it is less than or equal to the above upper limit 値, the surface unevenness of the electron emission source can be reduced, and the crack of the uniform sentence can be formed, so that good luminescence uniformity can be obtained. As the component (C), a vanishing cracking agent and a residual compound can also be used. It is particularly preferred to use one or a combination of ones selected from the group consisting of metal salts, organometallic compounds, metal complexes, decane coupling agents, and titanium coupling agents. By further containing these components, the cracking system generated when the paste for heat treatment of the electron source is heat-treated is increased, and the carbon nanotubes having a long protruding length are increased. Therefore, a source having better electron emission characteristics is obtained. The lower limit of the vanishing crack yield is preferably 1.0% by weight or more, more preferably 3.0% by weight or more, and 5.0% by weight or more based on the entire paste for electron source. Further, the upper limit is preferably 50% by weight, more preferably 40% by weight or less, and particularly preferably 30% by weight or less. A preferred lower limit 値 or a combination of any of the preferred upper limits 。. In addition, the lower limit of the content of the crack generating agent is preferably 1% by weight or more, 1% by weight or more, and particularly preferably 1% by weight, based on the entire solid content of the solvent for removing the solvent. /〇 above. Further, the upper limit weight is not more than 50% by weight, more preferably 50% by weight or less, even more preferably 40% by weight, particularly preferably 30% by weight or less. In the above range of the disappearing crack generating agent, the coating film can be applied to the electron source. The paste for electron emission source of the present invention may be uniformly contained therein. It can be used as long as it is a role as an adhesive. When the heat resistance of the test is 500 to 600 ° C and the soda lime glass (softening or so) is used as the substrate glass or the like, the sintering temperature of the inorganic powder is 500 ° C or less, more preferably 45 ° C or less. By using an inorganic powder having a temperature, it is possible to suppress the burning of the carbon nanotubes and the inexpensive substrate glass such as calcium glass. Examples of such inorganic powders include silver, copper, nickel, alloys, metal powders such as solder, and the like. Since the metal powder may cause the burning of the carbon nanotubes, the content of the electron-electronic radioactive agent of the present invention is: % or more, % or less, and may be any one with respect to the disappearing turtle. The cross is preferably 60: The amount of the content is less than or equal to the crack. The inorganic powder is considered to have a carbon nano-dots 5.0 (the TC degree is preferably a specific example of the use of sodium for the above-mentioned sintering, and glass pulverization is used for the radioactive source - 25-201137061. It is preferable to use a glass powder in the paste. Since the glass softening point differs depending on the glass composition, it can be controlled by the selection of the glass composition. As the glass powder contained in the paste for electron emission sources of the present invention, Bi2〇3-based glass is preferably used. Glass, S11O-P2O5-based glass, SnO-B2〇3-based glass, etc. If the glass powder is used, it is preferable to control the softening point of the glass in the range of 300 ° C to 450 ° C. The ratio of the electron emitting material (A) to the inorganic powder contained in the (A) is preferably 200 to 8000 parts by weight based on 100 parts by weight of the electron emitting material, and is sufficient if it is 200 parts by weight or more. When the adhesiveness is 8,000 parts by weight or less, the paste for the electron source is moderately viscous. The average particle diameter of the inorganic powder is preferably 2. Ομηη or less, more preferably 1.0 μηη or less. When the average particle diameter of the final layer is 2.0 μm or less, the formability of the fine electron source pattern and the adhesion between the electron source and the cathode electrode can be obtained. Here, the average particle diameter means the cumulative 50% particle diameter (D50). In the same manner as in the case of the thermally decomposable foaming agent particles, the paste for an electron source of the present invention preferably contains conductive particles. The paste for electron source contains conductive particles and an electron source. The internal resistance 値 is lowered, and electron emission can be performed at a low voltage by the electron emission source. The conductive particles are not particularly limited as long as they are electrically conductive, and are preferably particles containing a conductive oxide or a part of the surface of the oxide. Or all of the particles coated with the conductive material -26-201137061. Since the metal has high catalytic activity and is heated to a high temperature by firing or electron emission, the electron emitting material is deteriorated. Indium oxide, tin (IT0), tin oxide, oxidized, etc. Further, it is preferably coated on part or all of the oxide surface of titanium oxide, cerium oxide or the like. ΙΤΟ, tin oxide, zinc oxide, gold, platinum, silver, copper, palladium, nickel, iron, cobalt, etc. In this case, as a coating material for the conductive material, bismuth, tin oxide, zinc oxide is preferred. When the conductive particles are contained in the paste for electron source, the content of the conductive particles is preferably 0.1 to 100 parts by weight, more preferably 0.5, based on 1.0 part by weight of the electron emitting material. When the content of the conductive particles is within the above range, the electrical contact between the electron emitting material and the cathode electrode is preferably changed. The average particle diameter of the conductive particles is preferably 0.1 to Ι.Ομιη, more preferably It is 0.1~0·6μπι. When the average particle diameter of the conductive particles is within the above range, the uniformity of the electric resistance in the electron source is good, and surface flatness is obtained, so that uniform electron emission can be obtained from the surface at a low voltage. Here, the average particle diameter means a cumulative 50% particle diameter (D 5 Q ), which can be measured by the same method as in the case of the thermally decomposable foaming agent particles. In order to impart patterning performance by a general printing method such as screen printing or inkjet coating, the paste for an electron source of the present invention may contain an organic binder, a solvent, and a dispersant. Further, in order to improve the paste characteristics, a plasticizer, a tackifier, an antioxidant, an organic or inorganic precipitation preventive agent, or an additive such as a -27-201137061 flat agent may be contained. Further, when the pattern is formed by lithography, it can be imparted by containing a resin having an ethylenically unsaturated group, a photocurable monomer, a photopolymerization initiator, an ultraviolet absorber, a polymerization inhibitor, a sensitizer, or the like. Photosensitive. Examples of the organic binder include cellulose resins (ethyl cellulose, methyl cellulose, nitrocellulose, acetaminophen, cellulose propionate, hydroxypropyl cellulose, butyl cellulose, Benzyl cellulose, modified cellulose, etc.), acrylic resin (from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, methacrylic acid Propyl ester, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, methyl 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, acrylic acid Isobornyl ester, isobornyl methacrylate, glycidyl methacrylate, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, acrylamide, methyl Acrylamide, acrylonitrile 'methacrylonitrile a polymer formed by at least one of the monomers), an ethylene-vinyl acetate copolymer resin, polyvinyl butyral, polyvinyl alcohol, propylene glycol, a urethane resin, a melamine resin, a phenol resin Alkyd resin, etc. As the solvent, it is preferred to dissolve an organic component such as a binder resin. For example, a poly--28-201137061 alcohol such as a glycol or a triol represented by ethylene glycol or glycerin, and a compound which etherifies and/or esterifies an alcohol (ethylene glycol monoalkyl ether) Glycol dialkyl ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkane acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene dialkyl ether, propylene glycol Ethyl ether acetate) and the like. More specifically, an alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol is used. Diether, ethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl fumarate 'ethyl cellosolve acetate, propyl cellosolve acetate, butyl acetate Ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ester, propylene glycol monopropyl ether acetate, 2,2,4-trimethyl-1,3-pentane monoisobutyrate A carbamide alcohol acetate or the like or a mixture of organic solvents on the one of these. The method for producing the paste for an electron emission source of the present invention may be an electron-emitting material, a thermally decomposable foaming agent, and a component which generates and contracts stress during thermal decomposition, and optionally an inorganic powder or an organic binder powder. After the various components such as a solvent are brought into a predetermined composition, they are uniformly dispersed by a kneader such as a mill, a planetary ball mill, a bead mill, a super honing machine, a mixer roll, a homogenizer, or the like using ultrasonic waves. The paste viscosity is adjusted according to the addition ratio of the glass powder, the tackifier, the solvent, the plasticizer, and the preventive agent. However, depending on the printing method, the viscosity range of the paste is different, so the paste viscosity is appropriately adjusted. For example, when the pattern is formed by a die coater or a screen printing method, the viscosity is preferably 2 〇〇 Pa * s. Further, a spin coating method, a spray method, or an inkjet method is used to form a graph, and an ethyl ether alcohol bis-ethyl ether ethyl ethane lysine acetate diol is precipitated in a raw, divided, and precipitated manner. It is required by the seam 2~ case -29-201137061, the viscosity is preferably 0.001~5Pa*s. Hereinafter, a method of producing an electron emission source and an electron emitting element using the paste for an electron emissive source of the present invention will be described. Further, the electron radiation source and the electron emitting element can be produced by other well-known methods and are not limited by the production method described later. First, a method of fabricating an electron radiation source will be described. The electron emission source is obtained by calcining a pattern in which the pattern of the paste for an electron emission source of the present invention is formed on a substrate. First, using the paste for an electron emission source of the present invention, a pattern of an electron source is formed on a substrate. As the substrate, any of the electron emitting sources can be fixed, and examples thereof include a glass substrate, a ceramic substrate, a metal substrate, and a film substrate. It is preferred to form a film having conductivity on the substrate. As a method of forming a pattern of an electron emission source on a substrate, a general printing method such as a screen printing method or an inkjet method is preferably used. Further, when a paste for electron source which has been provided with photosensitivity is used, it is preferable to form a pattern of a fine electron source in a batch by lithography. Specifically, the photosensitive electron source paste of the present invention is printed on a substrate by a screen printing method or a slit die coater, and then dried by a hot air dryer to obtain a paste for an electron source. membrane. The coating film is irradiated with ultraviolet rays from the upper surface (on the side of the paste for electron source) through a mask, and then developed by an alkali developing solution or an organic developing solution to form an electron source pattern. Next, the pattern of the electron source is fired. The calcination atmosphere is in an atmosphere of an inert gas such as the atmosphere or nitrogen, and the calcination temperature is calcined at a temperature of 400 to 500 °C. Next, a method of fabricating an electron emitting element will be described. Electron emitting element-30-201137061 The electron emitting source formed by the paste for electron emissive source of the present invention can be formed on a cathode electrode to form a back surface plate so as to be opposite to a front panel having an anode electrode and a phosphor. Relatively. Hereinafter, a method of fabricating a diode-type electron emitting element and a method of fabricating a triode-type electron emitting element will be described in detail. In the method of fabricating a diode-type electron emitting device, first, a cathode electrode is formed on a glass substrate. In the cathode electrode, a conductive film such as ITO or chromium can be formed on a glass substrate by a sputtering method or the like. On the cathode electrode, an electron-emitting source was produced by using the paste for an electron source of the present invention on the cathode electrode to obtain a back sheet for a diode-type electron emitting element. Next, an anode electrode is formed on the glass substrate. In the anode electrode, a transparent conductive film of ITO or the like can be formed on a glass substrate by a sputtering method or the like. A phosphor is printed on the anode electrode formed on the glass substrate to obtain a front panel of the diode-type electron emitting element. In the back panel and the front panel of the diode-type electron emitting device, the spacer is sandwiched so that the electron emitting source and the phosphor face each other, and the vacuum is exhausted by the exhaust pipe connected to the container. The vacuum degree is melted in a state of 1 X 10_3 Pa or less, and a diode-type electron emitting element is obtained. 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 carbon nanotubes and collide with the phosphor, whereby the phosphor is emitted. In the method of fabricating a triode-type electron emitting device, a cathode electrode is first formed on a glass substrate. The cathode electrode can be formed into a film of a conductive film such as ITO or chromium by a sputtering method or the like. Next, an insulating layer is formed on the cathode electrode -31 - 201137061. The insulating layer can be made of an insulating material at a film thickness of about 3 to 2 μm by a printing method, a vacuum deposition method, or the like. Next, a gate electrode layer is formed on the insulating layer. The gate electrode layer is formed by forming a conductive film such as chromium by a vacuum deposition method or the like. Next, an emission hole is formed in the insulating layer. In the method of producing the emission hole, the photoresist is applied to the gate electrode by spin coating or the like, dried, and the pattern is transferred by irradiation with ultraviolet rays through the mask, and then developed with an alkali developing solution or the like. An emission hole can be formed in the insulating layer by developing the gate electrode and the insulating layer by the developing portion. Then, an electron source is formed inside the emission hole by using the paste for electron emission source of the present invention by the above method, and a back sheet for a triode-type electron emitting element is obtained. Next, an anode electrode is formed on the glass substrate. In the anode electrode, a transparent conductive film such as I TO can be formed on a glass substrate by a sputtering method or the like. A phosphor is printed on the anode electrode formed on the glass substrate to obtain a front panel of the triode-type electron emitting element. The back panel and the front panel of the triode-type electron emitting device are bonded to each other with the electron source and the phosphor facing each other, and are vacuum-exhausted by an exhaust pipe connected to the container. The vacuum degree is 1.0 XI (the viscosity is less than T3Pa, and a diode-type electron emitting element is obtained. In order to confirm the electron emission state, a voltage of 1 to 5 kV is supplied to the anode electrode, and the gate electrode is supplied with 20 to 150 V. The electrons are emitted from the carbon nanotubes and collide with the phosphor to obtain the luminescence of the phosphor. The electron source prepared by using the paste for electron source of the present invention is, for example, a scanning electron microscope (S-4). The energy dispersive X-ray analyzer (EMAX ENERGY EX-250) combined in 8 00 can be analyzed as -32-201137061. As a specific analysis method using the above method, first, a scanning electron microscope is used to observe electrons. The source of the radiation greatly identifies, for example, an electron emitting material having a fibrous structure, a particulate conductive oxide, and a glass component as a matrix. The composition can be identified by elemental analysis of each component using an energy dispersive X-ray analyzer. However, the analysis of the electron source may be any method as long as it is a component of the identifiable electron source. In addition, when the paste for an electron emission source of the present invention is used, for example, an electron source such as the following can be produced, which is an electron emission having a crack and protruding inside the electronic emission material of the crack. The source, the shortest length of the electron source is 1.0 mm or less, and the crack source accounts for an electron source of 10% or more of the electron source. Thus, the electron source having a small but high density crack is formed. When used as a device, it is an electron radiation source that can coexist with high resolution and good electron emission characteristics. The planar shape of the electron radiation source is not particularly limited, and it is preferable from the viewpoint that the uniformity of the light emission is good. Use square, rectangle, parallelogram, trapezoid, circle, triangle 'tetragonal, ellipse, fan, positive η angle (η is an integer of 5 or more) The shape of the electron emitter is determined by the following method. First, when viewing the electron source in a direction slightly perpendicular to the substrate, a plane pattern slightly parallel to the substrate is considered. According to the method of finding the center of gravity of the general plane pattern, the center of gravity of the electron source is determined. Furthermore, the distance between the straight line of the center of gravity and the plane of the electron source is 2 points, and the shortest line is selected. The length between the intersections at that time is taken as the shortest length of the electron source. The shortest length of the electron source obtained by this method is equal to the length of one side when the plane figure is square, and equal to the short side when the plane is rectangular. The length is equal to the length of the diameter in the case of a circle. The shortest length of the electron source is preferably 1.0 mm or less, more preferably 0.5 mm or less, and particularly preferably 0.3 mm or less. If the shortest length of the electron source is within the above range, a device having a higher resolution can be obtained. Next, the proportion of the cracked portion to the electron source is obtained by the following method. In the same manner as the above-described method, when the electron source is imaged as a plan view, the area where the crack occurs is the area of the entire flat pattern as "the ratio of the crack to the electron source", expressed as a percentage (%). As an example of the calculation method of the above-described area, the planar pattern of the electron emission source is input as image data of a scanning electron microscope or an optical microscope, and is calculated using a general image processing software such as MATLAB (manufactured by MathWorks Co., Ltd.). The proportion of the cracked portion to the electron source is preferably 1% or more, more preferably 15% or more, and particularly preferably 2% or more. When the proportion of the cracked portion to the electron source is within the above range, the voltage required for electron emission is low, and an electron source having excellent light emission uniformity can be obtained. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited by the terms. Electron radiation materials used in the respective examples and comparative examples 'Inorganic powders and organic components, and evaluations in the respective examples and comparative examples, the evaluation methods are as follows. (A) Component <Electron Radiation Material> Carbon Nanotube 1: Two-layer carbon nanotube (manufactured by Shenzhen Nano Port Co., Ltd.) Carbon nanotube 2: Multi-layer carbon nanotube (Dongli Co., Ltd.) ). (B) component <thermal decomposition type foaming agent> Thermal decomposition type foaming agent 1: azomethicin decomposition temperature 200 ° C (San Xiehuacheng (share) ''Cellmic C 1 2 1 ” 'Average Particle size 1 2μπ〇 Thermal decomposition type foaming agent 2: Dinitrosopentamethylenetetramine decomposition temperature 20 5 °C (San Xiehuacheng (share) "CelImic Α" by Nissin Engineering Co., Ltd." Turbo Classifier" dry centrifugal grader, average particle size 15 μm) Thermally decomposable foaming agent 3 : p,p'-oxybis(phenylsulfonate) decomposition temperature 1 60 ° C (San Xiehuacheng (share)" Cellmic S", average particle size 13μπι) The average particle size of the thermally decomposable foaming agent 1 Ι.Οηηι品(三协化成(股)"Cellmic C-2" by the Nissin Engineering Co., Ltd. "Turbo Classifier" dry type Centrifugal grader) The average particle size of the thermally decomposable foaming agent 1 is 6·0 μηη (San Xiehuacheng (share) ''Cellmic CE') The average particle size of the thermally decomposable foaming agent 1 is 18 μπι (San Xiehuacheng ( Share), 'C e 11 mic C -1 9 1 ”) The average particle size of the thermally decomposable foaming agent 1 is 25 μηη (Yonghe Chemical Industry Co., Ltd., Vinyfor AC#K3 -35- 201137061 (C) Component <Residual compound> Metal carbonate 1 : Basic magnesium carbonate, heavy (Wako Pure Chemical Industries, Ltd.) (thermal decomposition temperature: 25 0 ° C, 400 ° C) Metal carbonate 2: sodium carbonate decahydrate (Wako Pure Chemical Industries, Ltd.) (thermal decomposition temperature: 200 ° C) Metal carbonate 3 : sodium bicarbonate (Wako Pure Chemical Industries, Ltd.) (thermal decomposition) Temperature: 3 00 ° C) Metal nitrate: Magnesium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) (thermal decomposition temperature: 400 ° C) Metal sulfate: magnesium sulfate heptahydrate (Wako Pure Chemical Industries Co., Ltd. )) (thermal decomposition temperature: 200 ° C) Metal hydroxide salt: magnesium hydroxide (Wako Pure Chemical Industries, Ltd.) (thermal decomposition temperature: 350 ° C) Organometallic compound: Nikka Octhix tin ( Japanese chemical industry (shares)) (thermal decomposition temperature: 305 °C) Metal complex 1 : Nacem tin (Japan Chemical Industry Co., Ltd.) (thermal decomposition temperature: 200 ° C) Metal complex 2: double (acetonitrile) zinc (11) (Japan Chemical Industry Co., Ltd.) (thermal decomposition temperature: 150 ° C) Agent: "KBE-04" (Shinjuku Polyoxane (stock)) (thermal decomposition temperature: 15 〇 °C) Titanium coupling agent: "Orgatix TA30" (MATSUMOTO Precision Chemicals (Fe-36-201137061)) (thermal decomposition Temperature: 1 50 °c). <Thermal polymerization initiator>

Thermal polymerization initiator 1: tert-butylperoxylaurate 10 hour half-life temperature 9 8 °C

Thermal polymerization initiator 2: Third ethyl peroxy-2-ethylhexanoate 10 hour half-life temperature 72 ° C Thermal polymerization initiator 3: benzoyl hydrazine peroxide 10 hour half life Temperature 7 4 °C. <Compound containing ethylenically unsaturated tomb> Compound containing ethylenically unsaturated group 1: Tetrapropylene glycol dimethacrylate Compound containing ethylenically unsaturated group 2: Cyclohexyl acrylate containing ethylenically unsaturated group Compound 3: n-butyl acrylate. <Thermionic polymerization initiator containing an ethylenically unsaturated group>

Thermal polymerization initiator containing ethylenically unsaturated group 1: bis(2-methyl-2-propenyl)peroxydicarbonate 10 hour half-life temperature 39 ° C

Thermal polymerization initiator containing ethylenically unsaturated group 2: diallyl peroxydicarbonate 10 hour half-life temperature 39 ° C Thermal polymerization initiator containing ethylenically unsaturated group 3: bis(2-methyl-2 - propyleneoxyethyl peroxy) dicarbonate 1 hour half-life temperature 44 °C. (D) Component &lt; Thermal polymerization initiator containing an ethylenically unsaturated group as a thermally decomposable foaming agent&gt; -37- 201137061 2,2-Azobis[N-(2-propylidene)-2 -Methylpropionamine] hour half-life temperature 96 it. Other components &lt;Inorganic component&gt; Glass powder: SnO-P2〇5-based glass "KF9079," (made by Asahi Glass Co., Ltd.), softening point 3 40 ° C, average particle diameter 〇.2 μιη Conductive particle: white conductivity Powder "ET-500W, (coated with spherical titanium oxide as the core 'coated with SnC^/Sb conductive layer, manufactured by Ishihara Sangyo Co., Ltd.) 'Specific surface area 6.9m2/g' density 4.6g/cm3, average particle Trail 〇.2μιη. &lt;Organic ingredients&gt; Adhesive: poly(methyl propylene succinic acid) fine powder, [h] = 0.60 (made by Wako Pure Chemical Industries, Ltd.) Polystyrene particles: Megabeads NIST traceable particle size Standard particle, 1 0 · 0 μιη Solvent: Terpineol (Wako Pure Chemical Industries, Ltd.). Evaluation method &lt;Observation of surface crack width of electron emission source&gt; Using an optical microscope, it was confirmed whether or not the surface of the electron emission source was cracked. Further, the electron emission source was observed at a magnification of 1, 〇〇〇 to 20,000 times by a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.), and the crack width was measured. The crack width is the widest part of the crack observed. &lt;Looking at the protruding length of the carbon nanotube by the crack surface generated by the electron source-38-201137061 degree&gt; By a scanning electron microscope (S4800 manufactured by Hitachi, Ltd.), the magnification is 1,000~ When the temperature was 20,000 times, the length of the carbon nanotubes protruding from the crack surface was measured at any 20 points, and the average protruding length 〇 was measured. <Measurement of electric field strength> In a vacuum chamber having a degree of vacuum of 5.0 x 10 4 Pa, a vacuum chamber was formed. A substrate of an electron emission source and a phosphor layer (P22, manufactured by OPTONIX Co., Ltd.) having a thickness of 5 μm formed on a soda lime glass substrate on which an ITO thin film is formed, and a spacer sandwiching the ΙΟΟμηι The voltage was applied at 10 V/sec by a voltage application device (Chrysanthemum Electronics Industrial Co., Ltd. to withstand voltage/insulation resistance tester TOS920 1 ). From the obtained current-voltage curve (maximum current 値l mA/cm 2 ), the electric field intensity at which the current density reaches a predetermined current 求出 is obtained. The specified current is the enthalpy described in each of the examples and the comparative examples. &lt;Performance of uniformity of light emission&gt; The back surface of an electron emitting element having an Icm x 1 cm square was formed on the ITO substrate in a vacuum chamber of 〇xl (T4Pa), and a thickness of 5 μm was formed on the ITO substrate. The front substrate of the phosphor layer (P22) is sandwiched by a spacer of 1 μm in the opposite direction, and is applied by a voltage application device (tolerance voltage/insulation resistance tester TOS9201 manufactured by Kikusui Electronics Co., Ltd.). The voltage of the current 値 is specified so that the front substrate emits light. The specified current is the enthalpy described in each of the examples and the comparative examples. The light-emitting area is -39-201137061 The luminescence image is input by the CCD camera, and the electron emission of 1 cm x 1 cm square is measured. The proportion of the light-emitting portion in the device is digitized. In this case, the light-emitting area is 80% or more as the best (A), and 50% or more and less than 80% is regarded as good (B), and 30 is used. % or more and less than 50% are considered as (C), and those below 30% are regarded as not (D). &lt;Particle size adjustment of residual compound&gt; Used in paste for electron emission source of the present invention Metal salt is obtained by the following method In a container of zirconia having a volume of 50,000 ml, 20 g of a metal salt and 80 g of a solvent are added, and 0.3 mm (|) of oxidized pin (TorayCeram (trade name) manufactured by Toray Co., Ltd.) is added thereto. The planetary ball mill (FRITSCH Japan planetary ball mill P-5) was pulverized. The pulverized solution from which the oxidized pin beads had been removed was dried to obtain a metal salt having an average particle diameter of 1 to 3 μm. A 3 mm diameter chrome ball ball mill pulverizes two carbon nanotube tubes, and adds an organic binder, a solvent, a glass powder, a conductive particle, a residual compound, a thermally decomposable foaming agent at a composition ratio shown in Table 1. The mixture was kneaded by three rolls to prepare a paste for an electron source. Next, ITO was formed on the glass substrate by sputtering to form a cathode electrode. On the cathode electrode, a mesh using SUS200 mesh was used. In the screen printing method, the paste for electron source is printed into a coating film of 1 cm X 1 cm square, and then dried in a hot air dryer at 100 ° C for 5 minutes. The obtained electron source is used in a paste film at atmospheric atmosphere. Roasting at 450 °C, and getting -40- 201137061 To the electron source. The obtained electron source has a crack width of 1 0.5 μm, and the carbon nanotube has a protrusion length of 2.9 μm. Further, the electric field intensity of ImA/cm2 is 3.5 ν/μηι, and the luminous area at that time. In the same manner as in the first embodiment, the paste for electron emission source and the electron emission source shown in Tables 1 to 2 were prepared. The crack width and carbon are shown in Tables 1 and 2. The protruding length of the nanotube, the electric field strength of lmA/cm2, and the measurement result of the illuminating area. In the examples 2 to 10, the type of the residual compound was changed, and the examples 11 and 12 were changed in the type of the thermally decomposable foaming agent, and the examples 13 and 14 were used to change the content of the residual compound. Example I5 A plurality of residual compounds are used with the 16 series. In either case, cracks and carbon nanotubes with a length of 〇.5μπι or more protruding from the crack surface can be seen on the surface of the electron source, and electron emission can be seen without the activation step. In addition, good results were obtained regardless of the type of (Β) thermally decomposable foaming agent particles or (C) components, but the results were better when a metal salt was used as the residual compound of the component (C). The results when using metal carbonates were particularly good. Comparative Example 1 Two layers of carbon nanotubes were pulverized by using a ball mill having a diameter of 3 mm of zirconia balls, and organic binder, solvent, glass powder, conductive particles, and thermally decomposable hair were added at a composition ratio shown in Table 3. The foaming agent was kneaded by three rolls to prepare a paste for an electron source. Next, ITO was formed on the glass substrate by a ruthenium plating method, and a shape of -41 - 201137061 was used as a cathode electrode. On the cathode electrode, the paste for electron source was printed into a coating film of 1 cm X 1 cm square by a screen printing method using a screen of SUS200 mesh, and then dried at 100 ° C in a hot air dryer. 5 minutes. The obtained electron source was baked at 450 ° C in the atmosphere to obtain an electron source. No cracks in the obtained electron source and protrusion of the carbon nanotubes were observed. Further, the electric field intensity at which ImA/cm2 was reached was more than 15 ν/μηη, and the illuminating area at that time was 3%. Comparative Examples 2 to 5 In the same manner as in Comparative Example 1, the paste for an electron emission source and the electron emission source having the composition ratios shown in Table 3 were prepared. Table 3 shows the measurement results of the crack width, the protruding length of the carbon nanotubes, the electric field strength up to ImA/cm2, and the illuminating area. In Comparative Examples 2 to 4, when a thermal decomposition type foaming agent was not added and only a residual compound was used, the width of the crack was small, and the protruding length of the carbon nanotube was also short. Further, the electric field intensity of 1 mA/cm2 is high, and the uniformity of luminescence is also not good. Further, in Comparative Example 5, in which polystyrene particles were added, voids in which pores were continuously connected were formed in the electron source. Therefore, the crack width of Comparative Example 5 is a measure of the width of the void. It appears that the crack width is large, but the carbon nanotubes have a short protruding length. Moreover, the uniformity of light emission is also not good even when the electric field strength cylinder of ImA/cm2 is reached. Example 1 7 A paste for an electron source was produced in the following manner. After weighing lg multi-layer carbon nanotubes, 8 g of glass powder, 6 g of conductive particles, 20 g of binder, and 65 g of solvent in a chrome oxide container having a volume of 500 ml, a chromium oxide bead of 42-201137061 0·3πιηιφ was added thereto. Torayceram (trade name) manufactured by Toray Industries Co., Ltd. was preliminarily dispersed at 100 rpm in a planetary ball mill (FRITSCH Japan planetary ball mill P-5). The mixture of zirconia beads has been removed by three rolls. Then, the thermal decomposition type foaming agent 1, the thermal polymerization initiator 1, and the ethylenically unsaturated group-containing compound 1' were added in a manner of the composition ratio shown in Table 4, and then mixed by a three-roller to become an electron emission. Source paste. These were combined in a paste for an electron source to be 6 wt%. Next, the prepared paste for an electron source was printed on a soda lime glass substrate on which an ITO film was formed, and a square pattern of 5 mm x 5 mm was printed using a screen of SUS3 25 mesh. After drying at 100 ° C for 10 minutes, it was baked at 450 ° C in the atmosphere to obtain an electron source. On the surface of the obtained electron emission source, a carbon nanotube having a length of 0.5 μm or more protruding from the crack surface can be seen, and electron emission can be seen without an activation step. Further, the electric field intensity of 0.1 mA/cm2 was 6.6 V/μm, and the uniformity of light emission at that time was the best (A). [Example 1] 8 to 2 3 In the same manner as in the case of Example 1, the preparation and evaluation of the paste for an electron source and the electron source of the composition ratio shown in Table 4 were carried out. In the examples 18 to 19, (B) a thermal decomposition type foaming agent, a thermal polymerization initiator of the component (C), and a compound containing an ethylenically unsaturated group are used. Example 2 0 to 2 2 A thermal polymerization initiator containing (B) a thermally decomposable foaming agent and an ethylenically unsaturated group of the component (C) was used. In Example 23, an ethylenically unsaturated group-containing thermal polymerization initiator which is a thermally decomposable foaming agent of the component (D) is used. The content in these pastes for the electron-emitting source was 6 wt%. In either case, the surface of the electron radioactive source -43- 201137061 can be seen on the surface of the carbon nanotubes with a length of 〇·5μιη or more protruding from the crack surface, and the electron emission can be seen without the activation step. The evaluation results of electric field strength and uniformity of luminescence are shown in Table 4. Examples 24 to 38 In the same manner as in Example 1-7, the preparation and evaluation of the paste for an electron source and the electron source of the composition ratios shown in Tables 5 to 7 were carried out. In Examples 24 to 28, (B) a thermally decomposable foaming agent and a thermal polymerization initiator of the component (C), a compound containing an ethylenically unsaturated group, and a residual compound were used. In Examples 29 to 33, (B) a thermally decomposable foaming agent and a thermopolymerization initiator containing an ethylenically unsaturated group of the component (C) and a residual compound were used. In Examples 34 to 38, a residual polymer of the component (C) and a thermal polymerization initiator containing an ethylenically unsaturated group as a thermally decomposable foaming agent of the component (D) were used. Among these, the content of the component other than the residual compound in the paste for electron source is 6 wt%. Further, the residual compound was added so that the content in the paste was 9 wt%. In either case, a carbon nanotube having a length of 0.5 μm or more protruding from the crack surface can be seen on the surface of the electron source, and electron emission can be seen without the activation step. The evaluation results of electric field strength and uniformity of luminescence are shown in Tables 5 to 7. Comparative Example 6 A paste for an electron source was produced by the following method. In a container of chromic oxide having a volume of 500 ml, weigh lg multi-layer carbon nanotubes, 8 g of glass powder, 6 g of conductive particles, 20 g of binder, and 65 g of solvent, and then add 0·3πιηηφ of oxidized beads. (Torayceram (trade name) of Toray Co., Ltd.), in -44-201137061 Planetary ball mill (FRITSCH Japan Co., Ltd. planetary type ϊ Pre-dispersion at 100 rpm. Mixing the mixture with three rolls. Second, add The thermally decomposable foaming agent 1 was pulverized to a content of 6 wt%, and then kneaded in a three-roller to form a source paste. Then, the produced electron source was used on a soda lime glass substrate of an ITO film. It is printed in a square pattern of 5mm x 5mm using SUS325. It is baked at 45 °C in the atmosphere at 100 °C to obtain an electron source. The surface of the source is only visible from the wall of the void. The length of the protrusion is less than 0.1 μηι. Further, the electric field strength was 12.5 ν / μηη. Comparative Examples 7 to 1 0 In the same manner as in Comparative Example 6, the preparation and evaluation of the group source paste and the electron source shown in Table 8 were performed. More than (Β) thermal decomposition foaming And (D) In Comparative Examples 9 and 10 which are thermal decomposition initiators having a thermal decomposition energy and having an ethylenically unsaturated group, only the carbon nanotubes protruding from the surface of the calcined surface were observed to have a protruding length of less than 0.1 μm. In the electric comparative examples 7 and 8 in which the electron emission was obtained, the electric field of 16 ν/μηη was applied to the electron emission. In the same manner as in the first embodiment, the number is shown in Table 9~ In the mill Ρ-5), the oxidized pin was removed, and the electron source was turned into an electron paste. After the screen was formed with a mesh, it was dried for 10 minutes. The resulting electron carbon nanotubes have a ratio of 0·1 m A/cm2 of electrons compared to any of the examples 7 to 1 0 medium-sized foaming agents. The wall of the gap is made of carbon nanotubes, although the field strength is large. The strength is also not shown in the composition ratio -45- 201137061 Electronic source paste and electron source. Tables 9 to 10 show the measurement results of the crack width, the protruding length of the carbon nanotubes, the electric field strength at which ImA/cm2 was reached, and the light-emitting area. Example 3 9 to '43 are those in which (B) the thermally decomposable foaming agent and the residual compound of the component (C) are changed, and the examples 44 to 45 are those in which the component (C) is changed, and Example 46~ The 49 system changes (B) the average particle diameter of the thermally decomposable foaming agent particles. In either case, a crack and a carbon nanotube having a length of 〇.5 μm or more protruding from the crack surface can be seen on the surface of the electron source, and electron emission can be seen without an activation step. Further, good results were obtained regardless of the average particle diameter of the (Β) thermally decomposable foaming agent particles, but the results were better when the ratio was 6.0 μm or more and 20 μπι or less. Example 5 The paste for an electron source used in Example 42 was printed on a soda lime glass substrate on which a tantalum film was formed, and printed into a fine pattern of 200 μm to 1000 μm using a screen of SUS325 mesh. At 1〇〇. (3) After drying for 1 minute, it was calcined at 450 ° C in the atmosphere to obtain an electron source. The electron source was observed by SEM at a magnification of 500 times from the substrate 'Fig. 6'. Photograph. From the above photograph, using MAT LAB, the ratio of the crack portion in the electron source corresponding to 200 μm&gt;&lt;200 μm was calculated as '12.6%» Further, the electric field intensity reaching 1 mA/cm 2 was 1 · 7 V / μ m, good electron emission characteristics can be obtained even in fine patterns. -46- 201137061 φ__ [16 Example 10 〇Η 1000 3000 850 200 〇in Example 9 〇1000 3000 850 i 200 500 Example 8 ο Η 1000 3000 850 | 200 500 Example 7 ο 1000 3000 850 | 200 500 Example 6 ο Η 1000 3000 850 200 500 Example 5 ο 1000 3000 〇〇 200 500 Example 4 Ο 1000 1 3000 850 200 〇 Example 3 Ο 1000 3000 850 | 200 500 Example 2 Ο 1000 3000 850 200 500 Example 1 ο 1000 3000 〇〇〇200 500 2-layer carbon nanotube. I organic binder solvent glass powder conductive particles metal carbonate 1 metal carbonate 2 metal carbonate 3 metal sulfate metal nitrate metal hydroxide salt organometallic compound metal complex 1 decane coupling agent titanium coupling agent Sub Radical Material Organic Compound Inorganic Powder (C) Residual Compound -/, inch, 201137061 200 &lt;N ψ· &lt; VO B(59) 200 m (N inch v〇B(60) 200 On ν〇2 B(62) 200 〇〇 VO inch · m B(63) 200 2 o (N vi B(70) 200 (N od CN &lt;N On — B(71) 200 〇\ &lt;NB(70) 200 o 〇\ (N p — B(74) 200 uo (N as — B(75) 200 10.5 On CN cn A(82) Thermal decomposition type foaming agent 1 Thermal decomposition type foaming agent 2 Thermal decomposition type foaming agent 3 Crack (μηι) Carbon nanotube protruding length (μηι) m -tni flap S «Ν a ο 1 mm Luminous uniformity (%) (B) Thermal decomposition type foaming agent 201137061 Φ&gt;Μ [3S Example 16 〇 1000 3000 850 200 500 500 Example 15 〇1000 3000 〇〇〇200 〇〇Example 14 Ο1000 3000 850 | 200 2000 Implementation Example 13 Ο *-Η 1 1000 3000 ! i 850 j 200 1000 Example 12 Ο 1000 3000 850 200 500 Example 11 Ο 1000 3000 850 200 500 2 layers of carbon nanotube organic binder solvent glass powder conductive particles metal carbonate Salt 1 metal carbonate 2 metal carbonate 3 metal sulfate metal nitrate 1 i metal hydroxide salt - organometallic compound 1 ____ _ . _ metal complex 1 decane coupling agent 駄 coupling agent (Α) electron radioactive material organic Residual compound in the inorganic powder (C)-6 inch - 201137061

201137061 φ__ [i Comparative Example 5 〇1000 3000 850 200 Comparative Example 4 〇1000 3000 850 | 200 500 Comparative Example 3 〇1000 3000 00 〇CN 500 Comparative Example 2 〇1000 3000 850 200 500 Comparative Example 1 〇1000 3000 00 〇CS 2 layers of carbon nanotubes organic binder solvent glass powder conductive particles metal carbonate 1 metal carbonate 2 metal carbonate 3 metal sulfate metal nitrate i metal hydroxide salt organometallic compound metal complex 1 decane coupling agent Titanium coupling agent (A) Electron radiation material Organic component Inorganic powder (C) Residual compound 丨Ις _ 201137061 1300 (Ν CN C(30) 口 10.3 C(33) rn — ν〇od ! C(39) οο C (45) 200 灭1 &gt;15 D(3) Thermal decomposition type foaming agent 1 Thermal decomposition type foaming agent 2 Thermal decomposition type foaming agent 3 Polystyrene particle cracking (μτη) Carbon nanotube protruding length ( Ιηη) N i έ m KTVf 缌s &lt;N 6 1 M paste luminescence uniformity (%) (8) Thermal decomposition type foaming agent 201137061

[Inch luminescence uniformity &lt;&lt; C &lt;&lt;&lt;&lt; ΓΜ I u 1 forging? 〇n &gt; mg shed VO 〇6 00 〇0 00 VO 〇〇〇〇〇 substance name / paste concentration azo dimethyl hydrazine / 2 wt% t-butyl peroxy laurate / 2 wt% tetrapropylene glycol Acrylate/2wt% dinitrosopentamethylenetetramine/2wt% third hexylperoxy-2-ethylhexanoate/2wt% -1 cyclohexyl acrylate / 2wt% 叩'-oxyl double (Benzene sulfonium)/2^^% Dibenylhydrazine peroxide/2wt% n-butyl acrylate/2wt% bis(2-methyl-2-propenyl)peroxydicarbonate/3wt% Nitromime/3 wt% diallyl peroxydicarbonate/3 wt% dinitrosopentamethylenetetramine/3 wt% bis(2-methyl-2-propoxyethyl peroxyl) Dicarbonate/3wt% ρ,ρ'-oxybis(benzene dilatide)/3wt% 2,2'-azobis[1^(2-propenyl)-2-methylpropionamide] /6 evaluation [% type (B) thermal decomposition type blowing agent (C) in the thermal polymerization initiator (C) containing ethylenically unsaturated group-containing compound (B) thermal decomposition type blowing agent (C) Thermal polymerization initiator-1 (C) ethylenically unsaturated group-containing compound (B) thermal decomposition type blowing agent (C) thermal polymerization initiator (C) containing ethylenically unsaturated group Compound (C) Thermal polymerization initiator containing ethylene 14 unsaturated group (B) Thermal decomposition initiator containing ethylenic unsaturated group in thermal decomposition type foaming agent (C) (B) Thermal decomposition type foaming agent (C) Thermal polymerization initiator containing ethylenically unsaturated group (B) Thermal decomposition type foaming agent (D) Thermal reaction initiator containing ethylenically unsaturated group as thermal decomposition type foaming agent Example 00 〇\ ( N — e1? 201137061 【5嗽】 Uniformity of luminescence&lt;&lt;&lt;&lt;&lt; . ΐ| iu SI s» as 〇 — — 〇 00 — substance name / paste concentration azo dimethyl hydrazine Amine / 2 wt% T-butyl peroxylaurate / 2 wt% Tetrapropylene glycol dimethacrylate / 2 wt% Bis (acetamidine) Word (H) / 9 Wt% Azodimethylamine / 2 wt% Third Butylperoxylaurate/2wt% tetrapropylene glycol dimethacrylate/2wt% basic magnesium carbonate, heavy/9wt% azomethicamine/2wt% tert-butylperoxylaurate/2wt % Tetrapropylene glycol dimethacrylate/2wt% Magnesium nitrate hexahydrate / 9wt% azo dimethyl hydrazine / 2wt% ! Third butyl peroxylaurate / 2wt% i tetrapropylene di P methacrylic acid Ester/2wt% magnesium sulfate heptahydrate / 9wt% Nitromimeamine/2wt% Tert-butylperoxylaurate/2wt°/〇tetrapropylene glycol dimethacrylate/2wt% Magnesium hydroxide/9wt°/〇 type (B) Thermal decomposition type foaming agent Residual compound in the ethylenically unsaturated group-containing compound (C) in the thermal polymerization initiator (C) (B) Thermal polymerization initiator in the thermal decomposition type blowing agent (C) (C) Residual compound in the ethylenically unsaturated group-containing compound (C) (B) The ethylenically unsaturated group-containing compound in the thermal polymerization initiator (C) in the thermally decomposable foaming agent (C) Residual compound in (C)! (B) Residual compound (C) in the ethylenically unsaturated group-containing compound (C) in the thermal polymerization initiator (C) in the thermal decomposition type foaming agent /C) Residual compound in the ethylenically unsaturated group-containing compound (C) in the thermal polymerization initiator (C) in the thermal decomposition type foaming agent (C) Example 00 &lt;s 201137061 [9® Uniform luminescence Sex &lt;&lt;&lt;&lt;&lt;&lt;&lt; s fN a OO Face-cut electric field strength (ν / μΙΏ) uS Os P inch ·, Bu inch substance name / paste concentration bis (2-methyl-2-propenyl) Oxydicarbonate / 3wt% azomethamine / 3wt% bis (acetamidine acetone II) / 9wt% bis (2_methyl^_peroxydicarbonate / 3wt% azomethine / 3 wt% basic magnesium carbonate, heavy/9wt% bis(2-methyl-2-propyl)peroxydicarbonate/3wt% azomethicamine/3 wt% magnesium nitrate hexahydrate/ 9wt% bis(2-methyl-2-propenyl)peroxydicarbonate/3wt% azomethicamine/3wt% magnesium sulfate heptahydrate/9wt% bis(2-methyl-2-propenyl) Peroxydicarbonate/3wt% azomethicamine/3wt% Magnesium hydroxide/9wt% Thermal polymerization initiator containing ethylenically unsaturated group in type (C) (B) Thermal decomposition type foaming agent The ethylenic unsaturated group-containing thermal polymerization initiator in the residual compound (C) (B) The ethylenic property in the residual compound (C) in the thermally decomposable foaming agent (C) Thermal polymerization initiator of saturated group (B) Thermal polymerization initiator containing ethylenically unsaturated group in residual compound (C) in thermal decomposition type foaming agent (C) (B) Thermal decomposition type foaming agent ( Residue in the thermal decomposition-type foaming agent (C) containing an ethylenically unsaturated group in the residual compound (C) in C) Compound of Example 3 &lt; N m ώ- 201137061

[Bu® uniformity of luminescence &lt;&lt;&lt;&lt;&lt; S 2 1 1 &gt; 5 Jg ϋ in 〇 00 ΓΟ 寸 · ν〇rS substance name / paste concentration 2,2'-azo Bis[^2-propenyl]-2-methylpropanamide]/6 research % bis(acetonitrile)zinc(II)/9wt% 2,2'-azobis[N-(2-propenyl) )-2-methylpropionamide]/6wt% basic magnesium carbonate, heavy/9wt% 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide]/ 6wt% magnesium nitrate hexahydrate/9wt% 2,2'-azobis[Ν-(2-propenyl)-2-methylpropionamide]/6wt% magnesium sulfate heptahydrate/9wt% 2,2 '-Azobis[N-(2-propenyl)-2-methylpropionamide]/6wt% Magnesium hydroxide/9wt% Species · S Slightly &lt;55 Κ~ m Hub K) Distillation to 5 m δ π ϊ &lt;ίπ 赞度 w ^ (C) Residual compound S Slightly &lt;5S K- KI 蘅饀 to Φ | More than UJ on $ (C) Residual compound S &lt;5s If K ) Derivative distillation to |1 mountain on 2 4q change and 0/ ^ (C) Residual compound S 拍&lt;to κ~ Κ] &lt;(rn retort to 11 t跋(C) Compound S JSD tv a Κ] &lt;ra 蘅m deputy mountain nr> ϊ| implementation of residual compounds in w green (C) «Ο m v〇 00 CO -9ς- 201137061

Si? QQQU ο ϋ ϋ s (N a O &gt; 5. &gt; (N &gt; 16 IT) VO rn im ^H Λ ί—&lt; o • ίΠί SR face deletion &gt; VO ε _ ο ο 屮 &amp; %% VO Sf m 1 iwm Ό i 氍域砮% mi 氍氍遐53 K助 K ti E v〇尔 m disk secret &amp; g secret a- m 11 ΚΛ 11 E- I | 鮏1 1 S m U&gt ; \ \ 臧ΠΙ 1 1 r CO HI II E mI7&gt; TO. She a 濉a 松4π &lt;ίπ 骏 timil 蘅4β Slightly W 蘅蘅J5Q &lt;5ϊ Distillation an &lt;55 m κ~ to Κ- HF 毖&lt;Π迪&lt;Sn 褰Φ Ν3 i= K) m &lt;ffl 镒 〇〇 OS Ο J_J 201137061 φ__ [6^] Example 45 〇1000 3000 〇〇〇200 1000 〇900 1000 19.9 (Ν Α( 93) Example 44 〇1000 3000 00 200 1000 〇1—^ 〇σ\ 18.6 Os inch·oo Α(90) Example 43 〇1000 3000 〇00 200 2000 〇17.9 — (Ν CN Α(90) Example 42 Ο 1000 i 1 3000 沄00 2 00 2000 2000 22.5 Os inch (96) Example 41 Ο 1000 3000 850 j 200 1500 1500 20.1 々Α (94) ! Example 40 ο 1000 3000 〇〇200 1000 1000 1 19.3 Ο oi Α (93) Example 39 ο ψ-^ 1000 3000 850 200 500 1000 17.8 — m &lt;Ν Α(91) 2 layers of carbon nanotubes organic binder solvent glass powder conductive particles thermal decomposition type foaming agent 1 12μπι thermal polymerization initiator 1 Ethylene-unsaturated compound 1 metal carbonate 1 crack (μιη) carbon nanotube protrusion length (μτη) /—Ν ί -tni ϋ1 £ &lt;Ν ε ο 1 face-cut uniformity (%) (Α Residual compound in the disappearing crack generating agent (C) in the organic component of the electron-emitting material without the end-cracking (Β) thermal decomposition type foaming agent (C) 201137061 iw01 s Example 49 〇1000 3000 850 200 200 500 29.1 OO CN cn C(47) Example 48 〇1000 3000 850 l 200 200 500 21.4 卜&lt;N ν〇ΓΛ B(72) Example 47 〇1000 3000 oo 200 200 〇cn σ; CN Ο — A(81 Example 46 〇1000 3000 850 200 200 500 κη OO A(80) 2-layer carbon nanotube organic Peptide solvent glass powder conductive particles thermal decomposition type foaming agent 1 Ι.Οηηι thermal decomposition type foaming agent 1 6.0μη thermal decomposition type foaming agent 1 18μηι thermal decomposition type foaming agent 1 25μηι metal carbonate 1 Crack (μηι) Carbon nanotube protrusion length (μιη) /—Ν ί Ε mm 豳ns ΓΊ BO ί Emission uniformity (%) (A) Electron radiation material ί I 1 1 (Β) Thermal decomposition type Residual compound in the foaming agent (C)-6W-I-201137061 [Simplified description of the drawings] Fig. 1 is a cross-sectional model diagram of the electron emitting source of the present invention. Fig. 2 is an electron micrograph of an electron emission source in which cracks have occurred. Fig. 3 is an electron micrograph showing a carbon nanotube of a crack surface generated by the electron emission source of the present invention. Fig. 4 is an optical micrograph of an electron emission source in which cracking has occurred. Fig. 5 is an electron micrograph showing a carbon nanotube which protrudes from a crack surface generated by the electron emission source of the present invention. Fig. 6 is an electron micrograph of an electron source that has cracked. [Key element symbol description] 1 Crack generated in an electron source 2 Carbon nanotubes protruding 3 Crack width 4 Electron source 5 Cathode Substrate 6 Crack 7 protruding carbon nanotube _ · -60-

Claims (1)

201137061 VII. Patent application scope: 1. A paste for an electron source comprising (A) an electron emitting material, (8) a thermally decomposable foaming agent, and (C) a component which generates a shrinkage stress upon thermal decomposition. 2. The paste for an electron source according to the first aspect of the patent application, wherein the component (C) is a compound which is thermally decomposed at a temperature above 100 ° C and below 500 ° C. 3. The paste for an electron source according to claim 1 or 2, wherein the component (C) contains a group selected from the group consisting of a metal salt, an organometallic compound, a metal complex, a decane coupling agent, and a titanium coupling agent. At least one or more substances in the group. 4. The paste for an electron emissive source according to claim 1 or 2, wherein the component (C) contains a thermal polymerization initiator and a compound containing an ethylenically unsaturated group. 5. The paste for an electron source according to claim 1 or 2, wherein the component (C) contains a thermal polymerization initiator containing an ethylenically unsaturated group. A paste for an electron source comprising (A) an electron emitting material and (D) a thermal polymerization initiator having a function as a thermally decomposable foaming agent and having an ethylenically unsaturated group. 7. The paste for an electron source according to any one of claims 1 to 6, which is used for producing an electron source having cracks. 8. The paste for an electron source according to any one of claims 1 to 7, which further contains an inorganic powder. 9. The paste for an electron emissive source according to any one of claims 1 to 5, 7 or 8, wherein the thermal decomposition temperature of the (B) thermally decomposable foaming agent is 50 to 300 ° C ° - The paste for an electron source according to any one of claims 1 to 5 or 7 to 9, wherein the (Β) thermally decomposable foaming agent has an average particle diameter of 1.0 to 25 μm. The paste for an electron source according to any one of claims 1 to 5 or 7 to 10, wherein the (Β) thermally decomposable foaming agent is selected from the group consisting of an azo compound, a nitroso compound, and an anthracene. One or more of the group consisting of a ruthenium compound, an azide compound, an anthraquinone compound, melamine, urea, and dicyanamide. 12. The paste for an electron source according to claim 6, wherein the thermal decomposition temperature of the thermal polymerization initiator having the function of the thermal decomposition type foaming agent and containing an ethylenically unsaturated group is 50 to 3 00 °C. 1 3 . The paste for an electron source according to claim 6, wherein the (D) is a thermal decomposition type foaming agent and the average particle diameter of the thermal polymerization initiator containing an ethylenically unsaturated group is 1.0 to 1. 25μηι. 14. The paste for an electron emissive source according to claim 6, wherein the (D) is a thermal decomposition type blowing agent and the thermal polymerization initiator containing an ethylenically unsaturated group is selected from the group consisting of an azo compound, and a sub One or two or more substances selected from the group consisting of a nitro compound, an acid hydrazine compound, an azide compound, and an oxime compound. 15. The paste for an electron emission source according to any one of claims 4 to 4, which further comprises a metal salt, an organometallic compound, a metal complex, a squalane coupling agent and a titanium coupling agent. At least one or more substances in the group. -62- 201137061 The paste for electron source of the present invention is a paste of the electron source of the group of 16. The metal salt of the metal salt is contained in the metal salt of the metal salt. 1 7. As claimed in the patent scope 3, 1 5 $ wherein the metal salt contains magnesium. 18· An electron radiation source' is a method for preparing an electron emission source by using an electron emission source according to any one of the first to second pages of the patent application range, having a crack, and the electron emission material protrudes from the crack surface. . 1 9 . An electron emitting element which is characterized in that the electron emitting element of the electron emitting source of any one of claims 1 to 17 of the patent application has an irregularity. The neon electrons protrude from the cracked surface of the radioactive material. 2 0. A method for manufacturing an electron-emitting radioactive card source, which is heat-treated with a paste for an electron source according to any one of claims 1 to 17 of the patent application, and has cracks and electron-emitting materials from the turtle The crack is prominent. -63-