WO2005091325A1 - 電界放出型の画像表示装置およびその製造方法 - Google Patents
電界放出型の画像表示装置およびその製造方法 Download PDFInfo
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- WO2005091325A1 WO2005091325A1 PCT/JP2005/004823 JP2005004823W WO2005091325A1 WO 2005091325 A1 WO2005091325 A1 WO 2005091325A1 JP 2005004823 W JP2005004823 W JP 2005004823W WO 2005091325 A1 WO2005091325 A1 WO 2005091325A1
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- WIPO (PCT)
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- sealing material
- silicone resin
- material composition
- image display
- refractory filler
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/86—Vessels; Containers; Vacuum locks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J31/00—Cathode ray tubes; Electron beam tubes
- H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
- H01J31/10—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes
- H01J31/12—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes with luminescent screen
- H01J31/123—Flat display tubes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
- H01J9/26—Sealing together parts of vessels
- H01J9/261—Sealing together parts of vessels the vessel being for a flat panel display
Definitions
- the present invention relates to a field emission type image display device such as a field emission display (FED) and a surface conduction electron emission display (SED), and a method of manufacturing the same.
- FED field emission display
- SED surface conduction electron emission display
- Such flat-panel image display devices include a field emission display (FED) in which a phosphor is emitted by an electron beam of a field emission type electron emission device (field emission device), and a phosphor by an electron beam of a surface conduction type field emission device.
- FED field emission display
- SED surface conduction electron emission display
- a field emission type image display device has a front substrate and a rear substrate disposed to face the front substrate, and these substrates are held at a predetermined interval.
- a spacing member spacer
- the joint between the front substrate and the spacing member and the junction between the back substrate and the spacing member are airtightly sealed with a sealing material.
- It has a hermetically sealed container. The interior of the hermetic container is in a high vacuum state, a phosphor screen is formed on the inner surface of the front substrate, and a number of field emission devices ( Hereinafter, referred to as an emitter).
- a plurality of support members are arranged between the substrates in order to support the atmospheric pressure load applied to the rear substrate and the front substrate of the hermetic container in a high vacuum state. Is established. The potential on the back substrate side is almost the ground potential, and an anode voltage is applied to the phosphor screen. Then, the red, green, and blue phosphors constituting the phosphor screen are irradiated with the emitted electron beam, and the phosphors emit light to display an image.
- the thickness is reduced to about several mm. It can be used as a display of current televisions and computers, and can achieve lighter and thinner than CRT.
- a joint between the front substrate and the spacing member and a joint between the rear substrate and the spacing member are formed using an appropriate sealing material.
- the inside of the hermetic container is evacuated to a desired degree of vacuum using the opening or exhaust pipe provided on the front or rear substrate, and then the exhaust pipe is cut and opened.
- a sealing material a glass-based sealing material such as a lead-based low-melting glass is widely used because the sealing portion has excellent airtightness, and the temperature is higher than the softening point of the sealing glass. 400 ° C-Hermetically sealed at 550 ° C.
- the airtight container is particularly high degree of vacuum (10- 6 Torr or less) in which it is necessary SED cases, the evacuation of the exhaust pipe or opening force, the pumping speed is very small sag also reached Since the degree of vacuum that can be obtained is low, there are problems in mass productivity and characteristics.
- Patent Document 1 discloses a method in which a final assembly of a front substrate and a rear substrate constituting an airtight container (envelope) is performed in a vacuum chamber. .
- the front substrate and the rear substrate brought into the vacuum chamber are sufficiently heated. This is to reduce gas emission from the inner wall of the hermetic container (envelope), which is the main cause of deterioration of the degree of vacuum in the hermetic container (envelope).
- a getter film for improving and maintaining the degree of vacuum in the airtight container (envelope) is placed on the phosphor screen. To form.
- the front substrate and the back substrate are cooled to a temperature at which the sealing material,
- the substrate is heated again, and is cooled until the sealing material solidifies in a state where the front substrate and the rear substrate are combined at predetermined positions via the spacing members (side walls).
- the airtight container (vacuum envelope) created by such a method combines the sealing step and the vacuum sealing step, does not require much time for evacuation, and has an extremely good vacuum. You can get a degree.
- the surface conduction type field emission device of the SED is more susceptible to thermal deterioration than the field emission device of the FED.
- Patent Document 1 a low-melting metal material having a melting point of 350 ° C or less, specifically, indium or an alloy containing indium, is used as a sealing material that does not generate foam even when used in a vacuum. ing.
- a low-melting metal material has a low viscosity at the time of melting, so that when sealing an airtight container, there is a possibility that a desired sealing portion force may flow out.
- a metal-based sealing material having a low-melting-point metal material strength does not cause foaming even when used in a high-vacuum atmosphere, but the bonding strength itself of the sealed portion is somewhat inferior.
- the vacuum degree in the hermetic container is equal to or less than 10- 6 T orr, there is a possibility that the adhesive strength of the sealing portion is insufficient. If the bonding strength of the sealing portion is insufficient, the substrate may be bent due to an atmospheric pressure load exerted on the substrate.
- the hermetic container needs to maintain a high degree of vacuum for as long as 10 years or more after sealing. Therefore, the reliability of the sealing portion must be high.
- a low-melting metal material such as indium or an indium-containing alloy is used as the sealing material, if moisture adheres to the sealing portion, the moisture permeates the interface between the low-melting metal material and the substrate, and the inside of the sealing member is not sealed. cavity Force S may occur.
- Patent Document 4 As means for preventing the outflow of the low-melting metal material having a sealing portion force, a modification treatment of the sealing surface and a metal-based sealing material containing other metal components are disclosed in Patent Document 2—Patent Document 4 Is disclosed in Patent Document 5 discloses a metal-based sealing material containing another metal component in order to improve the moisture resistance of the metal-based sealing material. However, even when these means are used, there is a possibility that the adhesive strength of the sealing portion is insufficient. In addition, indium or an alloy containing indium, which is mainly used as a low-melting metal material, is an expensive material, and thus it is preferable to reduce the amount of use as much as possible.
- Patent Document 1 JP 2001-210258 A
- Patent Document 2 JP 2003-197134 A
- Patent Document 3 Japanese Patent Application Laid-Open No. 2004-14460
- Patent Document 4 Japanese Patent Application Laid-Open No. 2004-22189
- Patent Document 5 JP 2004-13067 A
- the present invention provides that the airtight container is sealed at a lower temperature by using a sealing material containing no harmful component such as lead, so that thermal degradation of the phosphor screen and the field emission element is prevented. It is an object of the present invention to provide a field emission type image display device which is reduced and has excellent adhesive strength at a sealing portion, and a method of manufacturing the same.
- the present invention provides a high degree of vacuum condition der airtight container inside the following 10- 6 Torr as SEDconnection also Shi Nag that the adhesive strength of the sealing portion is insufficient force even indium or indium It is an object of the present invention to provide a field emission type image display device capable of reducing the use of expensive low melting point metal materials such as alloys containing the same and a method of manufacturing the same.
- the present invention provides a front substrate, a rear substrate disposed to face the front substrate, and a fixed distance between the front substrate and the rear substrate disposed between the front substrate and the rear substrate. And a gap between the front substrate and the gap holding member and a gap between the rear substrate and the gap holding member using a sealing material.
- the sealing material comprises a sealing material composition containing a curable methylphenol silicone resin and a refractory filler,
- the amount of the refractory filler in the sealing material composition is 10 to 80% by mass relative to the total of the methylphenyl silicone resin and the refractory filler.
- the above methylphenyl silicone resin provides a field emission type image display device characterized in that the molar ratio of the phenol group to the methyl group is 0.1 to 1.2.
- the present invention relates to a field emission type image display device including a hermetically sealed container in which a front substrate, a rear substrate disposed to face the front substrate, and a sealing substrate are sealed with a sealing material.
- the sealing material comprises a sealing material composition containing a curable methylphenol silicone resin and a refractory filler,
- the amount of the refractory filler in the sealing material composition is 10 to 80% by mass relative to the total of the methylphenyl silicone resin and the refractory filler.
- the above methylphenyl silicone resin provides a field emission type image display device characterized in that the molar ratio of the phenol group to the methyl group is 0.1 to 1.2.
- the present invention is directed to a front substrate, a rear substrate disposed to face the front substrate, and a front substrate and a rear substrate disposed between the front substrate and the rear substrate. And a gap holding member configured to hold the gap at a constant interval, and a joint between the front substrate and the gap holding member and a junction between the back substrate and the gap holding member are sealed.
- a field emission type image display device sealed using a material one of a joining portion between the front substrate and the spacing member and a joining portion between the back substrate and the spacing member are provided.
- Low melting point metal material with melting point of 350 ° C or less
- a sealing material comprising a sealing material composition containing a curable methylphenyl silicone resin and a refractory filler.
- the amount of the refractory filler in the sealing material composition is 10 to 80% by mass relative to the total of the methylphenyl silicone resin and the refractory filler.
- the molar ratio of the methyl group to the methyl group is 0.
- a field emission type image display device which is characterized by the following:
- the refractory filler has an average particle size.
- It is preferably a spherical silica having a diameter of 0.1 to 20 m.
- the low melting point metal material also has an alloying power containing indium or indium.
- the present invention provides a method for applying the sealing material composition to a bonding surface between a front substrate and a spacing member and a bonding surface between a rear substrate and a spacing member, A method of manufacturing a field emission type image display device including forming an airtight container by heat curing
- the sealing material composition contains a curable methylphenol silicone resin and a refractory filler
- the amount of the refractory filler in the sealing material composition is 10 to 80% by mass relative to the total of the methylphenyl silicone resin and the refractory filler.
- the molar ratio of phenyl groups to methyl groups in the methylphenyl silicone resin is 0.1-1.2
- the molar ratio of the bifunctional silicon unit to the (total of the bifunctional silicon unit and the trifunctional silicon unit) in the methyl silicone resin is 0.05-0.55,
- the refractory filler is a spherical silica having an average particle diameter of 0.1 to 20 m, and provides a method for manufacturing a field emission type image display device.
- a method for producing a field emission type image display device comprising forming an airtight container by heating and curing the sealing material composition,
- the sealing material composition contains a curable methylphenol silicone resin and a refractory filler,
- the amount of the refractory filler is 10 to 80% by mass relative to the total amount of the methylphenyl silicone resin and the refractory filler in the sealing material composition;
- the molar ratio of phenyl groups to methyl groups in the methylphenyl silicone resin is 0.1-1.2
- the molar ratio of the bifunctional silicon unit to the total of the bifunctional silicon unit and the trifunctional silicon unit in the methylphenol silicone resin is 0.05-0.55,
- the refractory filler is a spherical silica having an average particle diameter of 0.1 to 20 m, and provides a method for manufacturing a field emission type image display device.
- the present invention includes forming a hermetic container by sealing a bonding surface between the front substrate and the spacing member and a bonding surface between the rear substrate and the spacing member using a sealing material.
- a method for manufacturing an electron emission type image display device comprising:
- a metal-based seal made of a low-melting metal material having a melting point of 350 ° C. or lower on one of the joining surface between the front substrate and the spacing member and the joining surface between the rear substrate and the spacing member.
- the amount of the refractory filler is 10 to 80% by mass relative to the total amount of the methylphenyl silicone resin and the refractory filler in the sealing material composition;
- the molar ratio of phenyl groups to methyl groups in the methylphenyl silicone resin is 0.1-1.2
- the molar ratio of the bifunctional silicon unit to the (total of the bifunctional silicon unit and the trifunctional silicon unit) in the methyl silicone resin is 0.05-0.55,
- the refractory filler is a spherical silica having an average particle diameter of 0.1 to 20 m, and provides a method for manufacturing a field emission type image display device.
- a sealing material composition in which the joint between the front substrate and the spacing member and the joint between the rear substrate and the spacing member contains a curable methylphenyl silicone resin and a heat-resistant filler (hereinafter, referred to as a "sealing material").
- a field emission type image display device of the present invention sealed with a sealing material (hereinafter, referred to as “the sealing material composition of the present invention”).
- the front substrate and the rear substrate were sealed with a sealing material comprising the sealing material composition of the present invention (hereinafter, referred to as “the sealing material of the present invention”) without using the spacing member.
- the image display device of the present invention has a lower peeling force (130 ° C-250 ° C) than a conventional lead-based glass sealing material (400 ° C-550 ° C).
- a conventional lead-based glass sealing material 400 ° C-550 ° C.
- One of the joint between the front substrate and the spacing member and the joint between the rear substrate and the spacing member has a low melting point metal material having a melting point of 350 ° C or less.
- the field-emission image display device sealed using the “metal-based sealing material”) and the sealing material of the present invention is excellent in the bonding strength of the sealing portion. Even in a high vacuum state where the internal force of the hermetic container is SlO- 6 To rr or less like SED, the hermetic container is excellent in reliability because the adhesive strength of the sealed portion is not insufficient. In addition, the substrate does not bend due to insufficient bonding strength of the sealing portion.
- the sealing portion has excellent moisture resistance, The reliability of the hermetic container without vacuum leakage is maintained for a long time.
- the sealing material composition of the present invention is applied to the bonding surface between the front substrate and the spacing member and the bonding surface between the back substrate and the spacing member, and the sealing material composition is heat-cured to be airtight.
- the method of manufacturing an image display device of the present invention including forming a container, and applying the sealing material composition of the present invention along at least one peripheral portion of the front substrate and the rear substrate. And the back substrate are laminated, and the sealing material composition is cured by heating.
- the method for manufacturing an image display device of the present invention including forming a container, when forming an airtight container, the temperature is significantly reduced as compared with the case where a conventional glass-based sealing material is used. I have. Thereby, energy consumption and work time are reduced, and energy saving and cost reduction are achieved.
- a metal-based sealing material layer and a sealing material composition layer of the present invention are provided on one of a bonding surface between the front substrate and the spacing member and a bonding surface between the back substrate and the spacing member.
- the method for manufacturing an image display device of the present invention comprising forming and heat-curing the sealing material composition at a temperature equal to or lower than the melting point of the metal-based sealing material, comprises: When the metal-based sealing material is used to heat and cure the sealing material composition of the present invention, the risk of the metal-based sealing material flowing out of the sealing portion, which has been a problem in the past, has been solved. In addition, compared to the case where a conventional glass-based sealing material is used, the sealing is performed at a much lower temperature, so that energy consumption / working time is reduced, thereby saving energy and reducing costs.
- the amount of the expensive metal-based sealing material used can be reduced.
- FIG. 1 is a perspective view showing an image display device according to a first embodiment of the present invention.
- FIG. 2 is a partially enlarged view of the image display device in FIG. 1, showing a state in which a front substrate is removed.
- FIG. 3 is a partial cross-sectional view of the image display device of FIG. 1 cut along line AA.
- FIG. 4 is a partially enlarged plan view of a phosphor screen of the image display device in FIG. 1.
- FIG. 5 is a partial cross-sectional view similar to FIG. 3, in which an opening for evacuation is formed in the rear substrate.
- FIG. 6 is a partial cross-sectional view similar to FIG. 5, showing a state where an opening is sealed using a glass plate and a sealing material.
- FIG. 7 is a partial cross-sectional view illustrating an image display device according to a second embodiment of the present invention.
- FIG. 3 is a partial cross-sectional view of the field emission type image display device of the present invention, which is different from the sealing method.
- FIG. 8 is a partial cross-sectional view similar to FIG. 7, showing a state where only a metal-based sealing material layer is formed at a joint between a front substrate and a spacing member.
- FIG. 9 is a partial cross-sectional view similar to FIG. 7, except for the step of forming a sealing material layer of the present invention.
- FIG. 10 is a plan view of a sample having a force of three glass substrates used for leak evaluation, (a) is a plan view of a lower plate of the sample, and (b) is a plan view of an upper plate of the sample. It is a top view, (c) is a top view of the middle plate of a sample.
- FIG. 11 is a cross-sectional view of the sample shown in FIG.
- FIG. 12 is a perspective view of a sample used for evaluation of adhesion to glass.
- Image display device 2 Eye i ⁇ surface substrate
- Phosphor screen 61 Black light absorbing layer
- FIG. 1 is a perspective view of the image display device according to the first embodiment of the present invention.
- FIG. 2 is a diagram showing the image display device of FIG. 1 with the front substrate removed.
- Fig. 3 shows a section of the image display device of Fig. 1 cut along line A-A.
- FIG. 1 is a perspective view of the image display device according to the first embodiment of the present invention.
- FIG. 2 is a diagram showing the image display device of FIG. 1 with the front substrate removed.
- Fig. 3 shows a section of the image display device of Fig. 1 cut along line A-A.
- the image display device 1 has a general FED configuration. That is, the image display device 1 of the present invention has the front substrate 2 and the rear substrate 3 arranged to face each other.
- a spacing member 4 is arranged between the front substrate 2 and the rear substrate 3.
- the spacing member 4 has a role of a spacer for holding the front substrate 2 and the back substrate 3 at a fixed interval.
- the joining portion between the front substrate 2 and the spacing member 4 and the joining portion between the back substrate 3 and the spacing member 4 are hermetically sealed by the sealing material 51 of the present invention, forming an airtight container 20. I have.
- the inside of the airtight container 20 is kept in a high vacuum state.
- a plurality of plate-shaped support members 14 are provided inside the hermetic container 20 in order to support the atmospheric load applied to the front substrate 2 and the rear substrate 3. ing .
- These support members 14 extend in a direction parallel to the short side of the airtight container 20 and are arranged at predetermined intervals along a direction parallel to the long side.
- the shape of the support member 14 is not particularly limited to this.
- a plurality of columnar support members are provided at predetermined intervals in the long side direction and the short side direction of the airtight container 20. A little.
- a phosphor screen 6 is formed on the inner surface of the front substrate 2.
- FIG. 4 is a partial plan view of the phosphor screen 6, in which the long side of the airtight container 20 is shown in the horizontal direction of the drawing.
- the phosphor screen 6 has striped phosphor layers R, G, and B that emit light in three colors, red, green, and blue, and non-light-emitting portions located between these phosphor layers.
- the black light absorbing layers 61 in the form of stripes are arranged side by side.
- the strip-shaped phosphor layers R, G, and B extend in a direction parallel to the short side of the image display device 1 and are arranged at predetermined intervals along a direction parallel to the long side. be able to.
- a number of field emission field emission devices each emitting an electron beam are provided as an electron emission source for exciting the phosphor layers R, G, and B.
- Element 8 is provided on the inner surface of the rear substrate 3. These field emission elements 8 are arranged in a plurality of columns and a plurality of rows corresponding to each pixel.
- a conductive force sword layer 7 is formed, and a silicon dioxide film 9 having a number of cavities 10 is formed on the conductive force sword layer.
- a gate electrode 12 having molybdenum, niobium and the like is formed.
- a field emission element 8 having a conical shape such as carbon nanotube, molybdenum, silicon or the like, which also has a force.
- a matrix-like wiring (not shown) connected to the electric field emission element 8 and the like are formed.
- a video signal is input to the field emission element 8 and the gate electrode 12.
- a gate voltage of, for example, +100 V is applied in the state with the highest luminance.
- +10 kV is applied to the phosphor screen 6.
- the size of the electron beam emitted from the field emission element 8 is modulated by the voltage of the gate electrode 12, and the electron beam excites the phosphor layer of the phosphor screen 6 to emit light, thereby displaying an image. I do.
- the bonding portion between the front substrate 2 and the spacing member 4 and the bonding portion between the back substrate 3 and the spacing member 4 are described below. It is characterized by being sealed using 51.
- the sealing material of the present invention comprises a sealing material composition (a sealing material composition of the present invention) containing a curable methylphenyl silicone resin and a refractory filler. Since the silanol groups of the curable methylphenol silicone resin have an affinity for the surface of the refractory filler, the mixing of the curable methylphenol silicone resin with the refractory filler can be uniformly and freely controlled. As a result, a semi-cured product that can sufficiently exhibit the properties of both the curable methylphenyl silicone resin and the refractory filler is obtained, and the sealing material, which is a semi-cured product, is particularly suitable for glass members and metal members. It is suitable for sealing.
- glass members can be bonded at a low temperature, bonding strength is high, bonding processability is excellent, mechanical heat resistance is high over a long period of time, gas leak resistance is high, airtightness is high, heat-resistant dimensional stability It has many characteristics such as good properties.
- curable silicone resins have excellent heat resistance, weather resistance, moisture resistance, and electrical characteristics, and are widely used as materials for electric, electronic, and precision equipment. It is also known to improve the strength by blending one. Also, for example, with epoxy resin The denatured curable silicone resin has excellent strength, heat resistance, moisture resistance, and mold release properties.Furthermore, fillers such as silica are blended with this to improve fluidity and mechanical strength of molded products. Further, a composition is known (see JP-A-7-316398). The curable silicone resin or its modified resin has a relatively small elastic modulus, can reduce the stress applied to the glass member to be sealed, and can reduce the strain due to the difference in thermal expansion coefficient. .
- the curable silicone resin is composed of a bifunctional silicone monomer (R Si—X) and a trifunctional silicone.
- R is a carbon atom at the bond end
- R is preferably an alkyl group having 14 to 14 carbon atoms or a monovalent aromatic hydrocarbon having 6 to 12 carbon atoms. More preferably, it is a group, an ethyl group or a phenyl group.
- X is a hydroxyl group or a hydrolyzable group such as an alkoxy group and a chlorine atom.
- X is preferably a hydroxyl group.
- the curable silicone resin is a copolymer obtained by partially hydrolyzing and co-condensing these monomers, and has a silanol group generated by hydrolysis of X.
- This curable silicone resin can be further condensed (curable) by its silanol group, and finally becomes a cured product having substantially no silanol group by curing.
- the cured product is composed of bifunctional silicon units (RSiO) and trifunctional silicon units (RSiO).
- RSiO monofunctional silicon unit
- SiO2 tetrafunctional silicon unit
- Each silicon unit in the curable silicone resin is, together with each silicon unit of the cured product, a silicon unit containing a silanol group that is formed by hydrolysis of X and contributes to the curability of the silicone resin.
- a silicon unit containing a silanol group that is formed by hydrolysis of X and contributes to the curability of the silicone resin.
- a bifunctional silicon unit having a silanol group is represented by (R Si (OH) —)
- a trifunctional silicon unit having a silanol group is represented by (RSi (OH)-
- the curable methylphenol silicone resin has a value of Si—OZSi—R, determined by FT-IR, of which power is 11.1-15. That is, the peak area of Si—O (the peak appearing in the range of 1250—950 cm— 1 ) (a) is changed to the peak area derived from the methyl group (1330—1250 cm— 1). (B) and the product of the peak area derived from the methyl group (b) and the number of moles of the phenyl group determined by the H-NMR force Z (m). It is the value divided by the sum.
- the heat resistance decreases.
- An aromatic hydrocarbon group represented by a phenyl group has mechanical heat resistance equal to or higher than that of a methyl group, which is the shortest alkyl group.
- the resin film becomes harder. Takes on thermoplasticity. Therefore, the mechanical strength of the resin such as heat resistance and bendability can be adjusted by the ratio of the number of filler groups to the total number of R in the resin.
- the curable methylphenol silicone resin in the sealing material composition of the present invention the molar number of the phenyl group and the molar number of the methyl group obtained from 1 H-NMR are 0.1 to 1.2.
- the ratio of the number of fuel groups to the total number of R in the resin is 0.1-0.5, more preferably 0.2-0.5.
- Silicone resins are preferred. Further, Hue was determined from FT IR -.. Peak height from Le group (3074cm- 1) peak height derived from Z methyl group (2996cm- 1) forces SO 1-1 2 of Mechirufue - Le silicone ⁇ also preferable.
- the curable methylphenol silicone resin has a molar ratio of a bifunctional silicon unit to (a total of a bifunctional silicon unit and a trifunctional silicon unit) (simple ratio).
- the molar ratio of the bifunctional silicon units is 0.05-0.55.
- the curable methylphenyl silicone resin is a curable silicone resin containing both a methyl group and a phenyl group as the organic group R.
- the curable methylphenol silicone resin is prepared by, for example, a method of hydrolyzing and co-condensing dichlorodimethylsilane and trichloromethylphenylsilane.
- the molar ratio of the bifunctional silicon units of the curable methylphenyl silicone resin is more preferably 0.2-0.4. Further, the curable Mechirufue - Le silicone resin which becomes a force substantially only the bifunctional Kei-containing units and trifunctional Kei-containing units are preferred. Such a curable methylphenol silicone resin has excellent heat resistance without easily decomposing and discoloring even if it is kept at a high temperature of 250 ° C or more for a long time.
- the molar ratio of the bifunctional silicon unit described above was determined from Si-NMR.
- the curable methylphenyl silicone resin includes curable dialkyl silicone resins such as dimethyl silicone resin, and curable alkyls other than methylphenyl silicone resins such as ethylsilicone resin. Physical properties can be adjusted by adding a small amount of phenyl silicone resin. Usually, it is preferable not to use these curable silicone resins other than the curable methylphenol silicone resin. Also, a curable methylphenol silicone resin can be used after being modified with an epoxy resin, a phenol resin, an alkyd resin, a polyester resin, an acrylic resin, or the like. The amount of the resin that is modified by force is small, and the curable methyl phenyl silicone resin is substantially modified as the preferred one, and the curable methyl phenyl silicone resin is preferred. ,.
- the curable methylphenyl silicone resin is usually handled in a solution (varnish) dissolved in a solvent, such as transportation and storage.
- the sealing material composition of the present invention can be produced by using this varnish and mixing it with a refractory filler.
- the product produced in this way becomes a paste-like sealing material composition having fluidity.
- a solid sealing material composition can be obtained by mixing a curable methylphenol silicone resin with a refractory filler without a solvent.
- the solvent can be removed to obtain a solid sealing material composition.
- a paste-like sealing material composition is obtained by mixing a solvent with the solid sealing material composition.
- the solvent used for the varnishing of the curable methylphenyl silicone resin is not particularly limited, and may be any solvent that dissolves the curable methylphenyl silicone resin.
- aromatic hydrocarbon solvents xylene, toluene, benzene, solvents having a boiling point of 100 ° C or lower, methyl ethyl ketone, ethyl acetate, isopropyl acetate, ethyl ether, dipropyl ether, tetrahydrofuran, acetonitrile, propionitrile , 1-propanol, 2-propanol, aryl alcohol and the like can be used.
- the sealing material composition when used in a paste state in which the sealing material composition is dissolved in a solvent, the sealing material composition is applied, and then heated to volatilize the solvent to remove the solvent.
- the latter is more preferred because of its simplicity. 5-50% by mass of solvent used in varnish Preferably. If the amount is less than 5% by mass, the dissolving effect of the curable methylphenyl silicone resin is insufficient, and it is likely to be difficult to mix homogeneously with the refractory filler. If the content exceeds 50% by mass, when the solvent is mixed with the refractory filler, the solvent causes phase separation with the refractory filler immediately, and after mixing the refractory filler, a large amount of energy is required when removing the solvent. Cost.
- the curable methylphenyl silicone resin is present as a partially polymerized methylphenol silicone resin (also simply referred to as partially polymerized methylphenyl silicone resin) in the sealing material composition.
- Partially polymerized methyl phenyl silicone resin has a higher degree of dehydration and condensation reaction of the curable methyl phenyl silicone resin of the raw material, so that the sealed material is compared with that of the raw material methyl phenyl silicone resin.
- the sealing material composition containing the partially polymerized methylphenylsilicone resin is less likely to generate water during sealing, and therefore, when sealing and curing the material to be sealed, the raw material methylphenylsilicone resin is used.
- the partially polymerized methylphenol silicone resin is a high-viscosity liquid or a solid having a high melt viscosity as compared with the raw material methylphenol silicone resin, and when the sealing material composition of the present invention is used as a molded product. It has properties suitable for For example, when sealing and curing the molded article of the sealing material composition disposed at a predetermined site of the object to be sealed, there is a possibility that the methylphenylsilicone resin flows and the force of the predetermined site protrudes. Less.
- the partially polymerized methylphenyl silicone resin is a curable methylphenyl silicone resin in which the curing of the curable methylphenyl silicone resin as a raw material is partially advanced.
- the curable methyl phenyl silicone resin in the present invention means a curable methyl phenyl silicone resin which is a raw material of the partially polymerized methyl phenyl silicone resin, and also includes the partially polymerized methyl phenyl silicone resin. means.
- a product obtained by partially polymerizing a curable methylphenyl silicone resin is referred to as a partially polymerized methylphenyl silicone resin.
- the partial polymerization of the curable methylphenylsilicone resin is usually stopped to such an extent that the curing reaction of the raw material methylphenylsilicone resin by heating is not completely completed. Is performed by For example, it is obtained by partially curing the raw material methylphenylsilicone resin by a method such as heating at a lower temperature than in the case of normal curing reaction, or heating for a shorter time than required for normal curing. .
- To partially polymerize curable methyl silicone resin for example, polymerize at a temperature of 120 ° C to 180 ° C, and complete the curing reaction based on the viscosity of methyl silicone resin. Stop the reaction to the extent that it does not proceed to the end.
- heating may be stopped when the viscosity of methylphenyl silicone resin reaches OOOcP-60, OOOcP.
- the partial polymerization of the raw material methylphenyl silicone resin can be carried out in the composition in which the refractory filler is present or in the course of the production of the composition.
- the curing of the curable methylphenyl silicone resin by dehydration condensation usually proceeds only by heating, and the dehydration condensation reaction between silanol groups of the resin and the refractory filler by the silanol groups of the resin.
- a dehydrated condensation reaction of silanol groups on one surface forms a cured product insoluble in a solvent.
- the sealing material composition applied to an object to be sealed is cured at a temperature of 140 ° C. or higher, preferably at a temperature of 180 ° C. to 300 ° C. for only 1 to 120 minutes, and the resin hardens and becomes insoluble. Then, it becomes a sealing material.
- the solvent When a solvent is contained in the sealing material composition, it is volatilized and removed at the beginning of heating, and when a non-heat-resistant substance such as an organic substance is present, it is volatilized or removed during curing. Left. However, in order to perform stable curing, it is preferable that the solvent is volatilized and removed at a lower temperature before the sealing material composition is cured. Depending on the type of the solvent, such volatilization removal of the solvent is performed, for example, at a temperature of 100 to 140 ° C for 30 to 60 minutes.
- a curing catalyst may be used to lower the curing temperature of the curable methylphenyl silicone resin.
- Catalysts include organometallic salts such as zinc, cobalt, tin, iron, and zirconium; quaternary ammonium salts; chelates such as aluminum and titanium; and various amines. Is exemplified by salts thereof.
- the refractory filler contained in the sealing material composition is preferably a heat-resistant inorganic powder.
- silica examples include silica, alumina, mullite, zircon, cordierite, ⁇ -Yuk, J-pitite, ⁇ -spodumene, j8-quartz solid solution, forsterite, bismuth titanate, barium titanate and the like. Of course, these can be used in combination.
- the average particle size of the refractory filler is preferably 0.1-130 / zm force S, more preferably 0.1-m force S 0.1-1 20 / zm is more preferable 0.1 One 10 / zm is particularly preferred. If the average particle size exceeds the above upper limit, after curing of the methylphenyl silicone resin, cracks occur at the interface between the refractory filler and the silicone resin, and the gas force S leaks into the internal space of the sealing structure. do it
- the average particle size is less than the above lower limit, the powder will agglomerate and will not be uniformly dispersed in the curable methylphenyl silicone resin. In addition, there is a problem that the amount of the refractory filler is limited due to the increase in viscosity.
- the refractory filler is preferably silica, particularly spherical silica.
- the average particle size of the spherical silica is preferably 0.1 to 130 m, more preferably 0.1 to 90 m, more preferably 0.1 to 20 m, and still more preferably 0.1 to 20 m. — More preferably 10 m.
- a sealing material composition having good coating workability can be obtained. If the average particle size is less than the above range, the particles are aggregated to lower the dispersibility, and a uniform composition cannot be obtained. If the average particle size is more than the above range, precipitation of the particles occurs, resulting in poor dispersibility. A uniform composition cannot be obtained.
- there is a problem that the amount of the refractory filler to be mixed is limited due to the increase in viscosity.
- the blending amount of the refractory filler in the sealing material composition of the present invention is 10 to 80% by mass based on the total amount of the curable methylphenyl silicone resin and the refractory filler. If it is less than 10% by mass, sufficient heat resistance cannot be exhibited. If the content exceeds 80% by mass, dispersibility and affinity with the methylphenyl silicone resin deteriorate, and as a result, cracks are generated in the sealing material (cured product), and gas is introduced into the internal space of the sealing structure. The vacuum or the desired reduced pressure cannot be maintained. Further, the adhesive strength to the sealing site is reduced.
- the preferred amount of refractory filler is 30-70% by mass.
- the amount of the spherical silica in the sealing material composition is determined according to the curable methylphenyl silicone resin and the refractory filler. 10 to 80% by mass, and preferably 30 to 70% by mass, based on the total of If it is less than this range, heat resistance and light resistance will be inferior, and if it exceeds this range, cracks will occur in the sealing material and gas will leak into the hermetic container 20, and the vacuum or the desired pressure reduction will occur. It cannot be maintained.
- the sealing material composition of the present invention can be used to form spherical particles having a larger particle size (more than 130 m) and a narrow particle size distribution.
- a small amount can be blended as a raw material.
- spherical silica or barium titanate glass having a particle size of 300 to 500 m is preferable.
- the compounding amount is preferably 0.1 to 15% by mass (but not more than 50% by mass based on the total amount of the refractory filler) based on the total amount of the curable methylphenol silicone resin and the refractory filler. Particularly preferred is 115% by mass.
- the sealing material composition of the present invention may contain components other than the curable methylphenyl silicone resin and the refractory filler. Such other components are, for example, components other than the component finally functioning as a sealing material, such as the solvent, or components remaining in the sealing material, for example, a sealing material coloring pigment.
- the content of these components in the sealing material composition is not particularly limited, but is an amount that does not impair the properties of the molded article of the sealing material composition of the present invention and the sealing material composition obtained therefrom.
- the former component is preferably 20% by mass or less based on the sealing material composition except for the solvent.
- the amount of the solvent is arbitrary depending on the usage such as using the sealing material composition in a liquid state or using a solid state, and the like, but is usually 50% by mass based on the sealing material composition. The following are preferred.
- Specific examples of the other components and their suitable amounts include the following.
- An amine-based curing agent for accelerating the curing of the methylphenol silicone resin is 5% by mass or less, and a pigment or the like is 15% by mass or less for the purpose of further increasing the mechanical heat resistance of the sealing material or for coloring.
- Improved pot life of adhesive composition, improved dispersibility of refractory filler and methylphenyl silicone resin, and improved sealing property For the purpose of, for example, pine or the like, 5% by mass or less of a tackifier such as rosin and a rosin derivative can be incorporated.
- the sealing material composition of the present invention can be obtained by mixing the curable methylphenyl silicone resin with a refractory filler to form a uniform composition.
- a curable methylphenylsilicone resin solution (varnish) may be used, and the composition may be used as a paste-like composition containing the curable methylphenylsilicone resin, a solvent, and a refractory filler.
- the varnish and the refractory filler may be mixed under heating and stirring, and then the solvent may be volatilized and removed to obtain a solid composition substantially containing no solvent.
- the temperature at which the solvent is volatilized and removed is 100 to 180 ° C, preferably 100 to 140 ° C, depending on the type of the solvent used.
- the sealing material composition of the present invention is preferably used in the form of a paste containing a solvent, preferably containing 10 to 30% by mass of a solvent, because of excellent handling properties.
- its shape is not particularly limited, and it may be formed into a shape such as a sheet, a wire, or a stick.
- a curable methylphenol silicone resin can be partially polymerized to obtain a partially polymerized methylphenol silicone resin.
- the partial polymerization of the curable methyl silicone resin may be performed before mixing with the refractory filler, or may be performed after mixing with the refractory filler.
- a varnish When a varnish is used, it may be carried out in the presence of a solvent or after removing the solvent. Normally, as described above, the varnish and the refractory filler are heated and mixed with stirring to remove the solvent in that state, and then the temperature is further raised in that state to partially remove the methylphenyl silicone resin. It is preferable to carry out a suitable polymerization.
- Partial polymerization of methylphenylsilicone resin stops the reaction before the curing reaction completely progresses, so it is recommended that the viscosity of the composition containing methylphenylsilicone resin be 120-180 ° C. Perform at a temperature of C. When performing partial polymerization at 180 ° C., for example, heating should be stopped when the viscosity of the composition reaches 5000 cP—60, OOOcP !.
- the sealing material composition of the present invention containing the partially polymerized methylphenol silicone resin may be used as a molded article formed into a sheet, wire, stick, or the like.
- a sealing material assembly obtained by heating as described above to obtain a partially polymerized methylphenol silicone resin.
- the resulting composition becomes a clay-like composition, and the clay-like composition in a heated state can be molded into a mold and molded. Specifically, it can be molded into various desired shapes such as a sheet, a wire, and a stick by using a mold made of fluorine resin or the like.
- the obtained molded article of the sealing material composition in the shape of a sheet, a wire, a stick, or the like can be used as a bonding portion between the front substrate and the spacing member, and the back substrate and the spacing member in that shape. It can be applied to the sealing of the joint part.
- the sealing material composition of the present invention containing the partially polymerized methylphenol silicone resin has excellent handleability even when used in the form of a paste dissolved in the above-mentioned suitable solvent. This is rather preferred.
- the amount of the solvent is as described above.
- the layer thickness of the sealing material composition of the present invention at the bonding portion is preferably 300 ⁇ m or less, more preferably 100 ⁇ m or less.
- the front substrate 2 is required to have translucency, and is therefore made of a transparent or translucent material, and is usually made of glass, for example, glass such as soda-lime glass, borosilicate glass, and silica glass. It may be made of transparent or translucent resin.
- the spacing member 4 and the support member 14 may be made of opaque resin or ceramic in addition to the above materials.
- a phosphor of low voltage excitation light emission that is excited at an anode voltage lkV or less is used. Specifically, green light-emitting Zn (Ga, A1)
- Materials constituting the conductive force sword layer 7 include metals such as Pd, Pt, Ru, Ag, Au, Ti, In, Cu, Cr, Fe, Zn, Sn, Ta, W, Pb, and PbO. , SnO, In O, PbO, Sb O, etc.
- SiC silicon carbide such as WC, nitride such as TiN, ZrN, HfN, semiconductor such as Si, Ge, carbohydrate And the like.
- the field emission device 8 formed on the conductive force sword layer 7 is mainly formed of carbon nanotube, molybdenum or silicon.
- a material constituting the gate electrode 12 formed on the silicon dioxide film 9 a general conductor is used.
- metals or alloys such as Ni, Cr, Au, Mo, W, Pt, Ti, Al, Cu, Pd, and Pd, Ag, Au, RuO
- a transparent conductor such as SnO and a semiconductor material such as polysilicon are appropriately selected.
- FIGS. 1 to 4 illustrate a specific configuration of the image display device of the present invention of the first embodiment, and the configuration is not limited to the illustrated configuration.
- the electrode structure may be any of a diode type, a triode type and a tetraode type.
- the Spindt type, Si etching type or transfer mold type may be! /
- the gap (gap width) between the front substrate and the back substrate is small, specifically, when the gap width is about 100 to 500 m, no spacing member is used.
- a desired gap width may be provided only with the sealing material of the present invention, and the front substrate and the rear substrate may be sealed to form an airtight container.
- the layer thickness of the sealing material of the present invention is appropriately selected in the range of 100 to 500 m, corresponding to the gap width. In this case, since the gap width is very small, the support member may not be used.
- the phosphor screen 6 is formed on the front substrate 2.
- a glass sheet having the same size as the front substrate 2 is prepared, and a stripe pattern of the phosphor layer is formed on the glass sheet by a plotter machine.
- the plate glass on which the phosphor stripe pattern is formed and the plate glass for the front substrate are placed on a positioning jig, set on an exposure table, exposed and developed, and the phosphor screen 6 is generated.
- the field emission device 8 is formed on the back substrate 3.
- a matrix-like conductive force sword layer 7 is formed on the rear substrate 3, and the conductive sword layer 7 is formed on the conductive force sword layer 7 by, for example, a thermal oxidation method, a CVD method, or a sputtering method.
- An insulating film 9 is formed.
- a metal film for forming a gate electrode such as molybdenum or niobium is formed on the insulating film 9 by, for example, a sputtering method or an electron beam evaporation method.
- a resist pattern having a shape corresponding to the gate electrode to be formed is formed on the metal film by lithography.
- the metal film is etched by a wet etching method or a dry etching method to form a gate electrode 12.
- the insulating film 9 is etched by wet etching or dry etching to form a cavity 10. Then, after removing the resist pattern, a release layer made of, for example, aluminum or nickel is formed on the gate electrode 12 by performing electron beam evaporation from a direction inclined at a predetermined angle with respect to the rear substrate surface. Thereafter, as a material for forming a cathode, for example, molybdenum or silicon is deposited by an electron beam evaporation method from a direction perpendicular to the surface of the rear substrate.
- a material for forming a cathode for example, molybdenum or silicon is deposited by an electron beam evaporation method from a direction perpendicular to the surface of the rear substrate.
- the field emission device 8 is formed inside each cavity 12.
- the field emission device 8 when the field emission device 8 is formed of carbon nanotubes, the field emission device has a large number of through-holes, and a plate-like metal member serving as a generation nucleus of the carbon nanotube, and a surface of the plate-like metal member and And a carbon nanotube film formed on the through-hole wall.
- the plate-shaped metal member is a metal plate made of iron or an alloy containing iron because it serves as a nucleus for generating carbon nanotubes.
- the through-holes are provided, for example, in a matrix and have a grid shape.
- the shape of the opening of the through-hole may be any shape as long as the distribution of the coating on the plate-like metal member is uniform.
- the shape of the opening may be triangular, square, hexagonal. And the like, a polygon with rounded corners, or a circle or an ellipse.
- the carbon nanotube constituting the coating is a substance composed of fibrous carbon having a thickness of about lOnm or more and less than 1 ⁇ m and a length force of about m or more and less than 100 m.
- Polycarbon nanotubes and multiple graphite layers are stacked in a nested structure, and each graphite layer is cylindrical. Even a carbon nanotube with a coaxial multilayer structure closed in a shape
- a hollow graphite tube having a disordered structure and a defect, or a graphite tube filled with carbon in the tube may be used. Further, these may be mixed.
- One end of these carbon nanotubes is bonded to the surface of the plate-like metal member or the wall of the through-hole, and at the same time, is curled or entangled with each other to cover the metal parts constituting the lattice, and a cotton-like coating is formed.
- the coating covers a plate-like metal member having a thickness of 0.05-0.20 mm with a thickness of 10-30 m and forms a smooth curved surface.
- the sealing material composition of the present invention is applied along the peripheral portion of the back substrate 3.
- a paste-like sealing material composition containing a solvent including a composition containing a partially polymerized methylphenol silicone resin
- a molded product of a sealing material composition such as a sheet (including a molded product containing partially polymerized methylphenylsilicone resin)
- the back substrate 3 has a softening point equal to or higher than the softening point of the sealing material composition.
- the molded body is arranged while being heated to a predetermined temperature.
- the application of the sealing material composition of the present invention may be performed by other methods, for example, by a spray method, a screen printing method, a spin coating method, or the like.
- the spacing member 4 is placed along the periphery of the back substrate 3 so as to cover the sealing material composition of the present invention.
- the sealing material composition is applied to the rear substrate 3 and then heated to a predetermined temperature before the spacing member 4 is placed. It is preferable to volatilize the solvent to remove the solvent.
- the spacing member 4 is placed on the back substrate 3 while the back substrate 3 and the spacing member 4 are heated to a predetermined temperature. .
- a predetermined temperature condition for example, 140 At 120 ° C. or higher, preferably 180 ° C. to 300 ° C., for 1 to 120 minutes to heat and cure the sealing material composition, whereby the joint between the rear substrate 3 and the spacing member 4 is sealed. Is done.
- the support member 14 is placed at a desired position on the back substrate 3 using the sealing material composition of the present invention. Is fixed. Since the time required for the process can be shortened, the fixing of the support member 14 is preferably performed simultaneously with the sealing of the joint between the back substrate 3 and the spacing member 4.
- the sealing material composition of the present invention is applied to the upper surface of the spacing member 4, and the front substrate 2 is placed on the spacing member 4 so as to cover the sealing material composition. I do.
- the front substrate 2 is pressurized from above, it is heated under the above-mentioned predetermined temperature conditions to heat and cure the sealing material composition, so that the joint between the front substrate 2 and the spacing member 4 is sealed.
- the airtight container 20 is formed.
- the upper surface of the support member 14 and the front substrate 2 may be fixed using the sealing material composition of the present invention.
- the sealing material composition of the present invention can be prepared by applying a paste-like sealing material composition containing a solvent so as to have a desired layer thickness, or a sheet having a desired thickness.
- a molded article of the sealing material composition having a shape such as a shape may be arranged. It should be noted that it is not particularly limited which of the back substrate and the front substrate is coated with the sealing material composition of the present invention, and the sealing material composition of the present invention is coated on both the back substrate and the front substrate. May be.
- FIG. 5 is a cross-sectional view of the image display device 1 after the airtight container 20 has been formed.
- an opening 16 for example, ⁇ 2 mm
- a vacuum pump is connected to the opening 16 to evacuate the inside of the airtight container 20 to a predetermined degree of vacuum.
- the opening 16 is sealed with the glass 18 and the sealing material composition 51 of the present invention.
- the sealing material composition 51 of the present invention exists only on the bonding surface between the rear substrate 3 and the glass 18, but the entire surface of the glass 18 has the sealing material of the present invention.
- the back substrate 3 may be bonded with the composition applied.
- the means for evacuating the inside of the airtight container 20 is not limited to the above-described embodiment.
- an exhaust pipe communicating between the inside and the outside of the airtight container 20 is provided, and a vacuum pump is connected to the exhaust pipe to evacuate the inside of the airtight container 20.
- a vacuum pump is connected to the exhaust pipe to evacuate the inside of the airtight container 20.
- the airtight container 20 is sealed by burning off the exhaust pipe.
- the airtight container 20 may be sealed using glass and the sealing material composition of the present invention in the same manner as described above.
- sealing between the back substrate 3 and the spacing member 4 and sealing between the front substrate 2 and the spacing member 4 in a vacuum vessel By performing the attachment, the inside of the airtight container 20 may be maintained at a predetermined degree of vacuum without using the opening 16 and the exhaust pipe.
- FIG. 7 is a partial cross-sectional view showing an image display device according to the second embodiment of the present invention.
- the image display device 1 according to the second embodiment has a configuration of an SED in which a surface conduction type field emission device 8 ′ is formed on a back substrate 3.
- the surface conduction type field emission device 8 ′ is formed so as to span the device electrodes 81, 81 arranged opposite to each other and the device electrodes 81, 81. It comprises a conductive film 82 and a field emission portion 83 which is a crack-shaped portion formed by subjecting a part of the conductive film 82 to an energization forming process.
- a general conductor material can be used as the material of the opposing device electrodes 81, 81.
- a general conductor material can be used.
- Electrodes can be formed easily by using a combination of film-forming techniques such as vacuum evaporation and pattern-junging techniques such as photolithography and etching, but using other methods (for example, printing techniques). It may be formed! / ,.
- the space between the device electrodes 81, 81 can be preferably in the range of several 100 nm in power and several tens of micrometers, and preferably in the range of several tens of micrometers.
- the length of the device electrode 81 can be set to a range of several hundred ⁇ m even with a force of several ⁇ m in consideration of the resistance value of the electrode and the electron emission characteristics. As the thickness of the device electrode 81, an appropriate numerical value is usually selected for both a force of several tens nm and a force in the range of several / zm.
- Examples of the material constituting the conductive film 82 include metals such as Pd, Pt, Ru, Ag, Au, Ti, In, Cu, Cr, Fe, Zn, Sn, Ta, W, and Pb; Acids such as SnO, In O, PbO, Sb O
- Borides such as HfB, ZrB, LaB, CeB, YB, and GdB; TiC, ZrC, HfC, TaC
- nitrides such as TiN, ZrN, HfN
- semiconductors such as Si, Ge, and carbon.
- the method of forming the conductive film 82 when the material forming the conductive film 82 is any of the metals exemplified above, an organic metal solution containing the metal as a main element is applied, Form an organic metal thin film. The formed organic metal thin film is heated and baked, and is patterned by lift-off, etching, or the like, so that the conductive film 82 is formed.
- the method of forming the conductive film 82 is not limited to this, and a vacuum deposition method, a sputtering method, a CVD method, a dispersion coating method, a dive method, a spinner method, or the like can also be used.
- the thickness of the conductive film 82 is appropriately set in consideration of the step coverage to the device electrodes 81, 81, the resistance between the device electrodes 81, 81, forming conditions described later, and the like. It is preferable to set the range of several A to several 100 nm, and more preferable to set the range of 1 nm to 50 nm.
- the conductive film 82 and the device electrodes 81, 81 are electrically satisfactorily connected to each other, and thus have a structure in which a part of each overlaps.
- the manner of overlapping is not limited to the order of the rear substrate 3, the device electrodes 81 and 81, and the conductive film 82 from below, as shown in FIG. 7, but the rear substrate 3, the conductive film 82, and the device electrode 81. , 81 in this order.
- the field emission portion 83 is a crack-like portion formed on a part of the conductive film 82, and has a property that is electrically higher in resistance than the surrounding conductive film 82. Cracks are applied to the conductive film 82 Then, for example, it can be formed by performing the energization forming process.
- the energization forming process is a process in which an electric current is applied to the conductive film 82 so that a part of the conductive film 82 is appropriately destroyed, deformed, or altered to change into a structure suitable for electron emission. is there. In a portion of the conductive film 82 that has been changed to a structure suitable for emitting electrons (that is, the field emission portion 83), an appropriate crack is formed in the thin film. It should be noted that the electric resistance measured between the device electrodes 81, 81 after formation is greatly increased compared to before the field emission portion 83 is formed.
- the field emission portion 83 may be formed by various methods other than the energization forming process, such as using a fine processing technique.
- the formed field emission portion 83 is improved in field emission ability by performing an activation process.
- This activation process is performed by repeatedly applying a voltage pulse in an atmosphere containing a gas of an organic substance. By this treatment, carbon or a carbon compound is converted from the organic substance present in the atmosphere into a conductive form. The element current and emission current are remarkably changed and increased in the gap between the conductive films 82 and on the conductive film 82 around the gap.
- a phosphor excited at an anode voltage of 11 to 10 kV is used as a phosphor constituting the phosphor screen 6, and usually a phosphor for CRT is used.
- usable phosphors include, for example, green light-emitting Y (Al, Ga).
- an aluminum layer (not shown) is deposited as a metal back.
- the image display device of the second embodiment shown in FIG. 7 is different from the image display device of the first embodiment shown in FIG.
- the degree of vacuum in the airtight container 20 is much higher.
- the images display device 1 shown in FIG. 7 a level of vacuum in the hermetic vessel 20 is typically required in SED, specifically less than or equal 10- 6 Torr.
- the image display device 1 of the second embodiment shown in FIG. 7 is different from the image display device 1 of the first embodiment shown in FIG. Between the 2 and the spacing member 4 and between the back substrate 3 The form of sealing at the joint with the spacing member 4 is different. That is, in the image display device 1 shown in FIG.
- one of the joining portions between the front substrate 2 and the spacing member 4 is made of the sealing material 51 of the present invention and the low melting point metal material having a melting point of 350 ° C. or lower. Sealing is performed using a metallic sealing material that is also strong (hereinafter, sometimes simply referred to as “metal-based sealing material”) 52.
- metal-based sealing material a metallic sealing material that is also strong (hereinafter, sometimes simply referred to as “metal-based sealing material”) 52.
- the joint between the front substrate 2 and the spacing member 4 is sealed using the sealing material 51 of the present invention and the metal-based sealing material 52.
- one of the joining portion between the front substrate 2 and the spacing member 4 and the joining portion between the rear substrate 3 and the spacing member 4 are used. It is characterized by being sealed using the sealing material 51 of the invention and a metal-based sealing material 52. Therefore, contrary to FIG. 7, the joint between back substrate 3 and spacing member 4 may be sealed using sealing material 51 of the present invention and metal-based sealing material 52. However, the sealing using the sealing material 51 of the present invention and the metal-based sealing material 52 is performed in a vacuum in a method of manufacturing an image display device according to a second embodiment described later. This is a joining portion, usually a joining portion between the front substrate 2 and the spacing member 4.
- the sealing material 53 used for sealing the other joint that is, the joint between the back substrate 3 and the spacing member 4 is not particularly limited. Instead, a sealing material composed of the sealing material composition of the present invention, which may be a conventional lead-based glass frit!
- the sealing material composition of the present invention has been pointed out to be harmful! Since it does not contain lead, the image display device in which the sealing material 53 is the sealing material composition of the present invention has poor environmental resistance. Are better.
- the image display device 1 of the second embodiment having the structure of general SED is an airtight vessel 20 10- 6 Torr in the following very high vacuum
- the sealing between the front substrate 2 and the spacing member 4 is performed in a vacuum vessel maintained at a predetermined degree of vacuum. Performed at
- the image display device 1 of the second embodiment shown in Fig. 7 has a front substrate sealed in a vacuum vessel.
- the metal-based sealing material 52 has a low-melting-point metal material with a melting point of 350 ° C or lower, the temperature of the bonding portion is much lower than that of conventional sealing using lead-based frit glass. Sealing can be performed. Accordingly, thermal degradation of the components in the hermetic container 20, specifically, the phosphor constituting the phosphor screen 6 and the field emission element 8, which has been a problem when sealing with the conventional lead-based frit glass, occurs. It is reduced.
- the metal-based sealing material 52 has a melting point of 350 ° C or less, and also has a low-melting-point metal material with excellent adhesion and bonding properties.
- a low melting point metal material include indium or an alloy containing indium.
- Indium has excellent characteristics such as low vapor pressure, which is low at 156.7 ° C, soft and strong against impact, and not brittle even at low temperature.
- an alloy containing indium an alloy in which an element such as silver oxide, silver, gold, copper, aluminum, zinc, or tin is added alone or in combination with indium can also be used.
- a eutectic alloy of In97% 7% Ag3% has a lower melting point of 141 ° C and can increase mechanical strength.
- an alloy composed of two or more metals using the expression “melting point” may not have a single melting point.
- the liquidus temperature and the solidus temperature are generally defined in such cases.
- the former is the temperature at which part of the alloy starts to solidify when the liquid state temperature is lowered, and the latter is the temperature at which all of the alloy solidifies.
- the expression “melting point” will be used in such a case, and the solidus temperature will be called the melting point.
- the interface between the metal-based sealing material 52 and the joint is formed of a metal-based material such as Ag, Ni, Co, Au, Cu, or Al.
- the underlayer may be formed using a material having a high affinity for the sealing material 52. By forming such an underlayer, the adhesive strength and airtightness of the portion sealed with the metallic sealing material are further improved.
- the low-melting-point metal material forming the metal-based sealing material 52 has a low viscosity at the time of melting, there is a possibility that a desired sealing portion force may flow out when the airtight container is sealed. Therefore, in the image display device 1 of the second embodiment shown in FIG.
- the sealing material composition 51 of the present invention is heat-cured at a temperature lower than the melting point of the low-melting metal material forming the metal-based sealing material 52. It is necessary to adjust it!
- the curing temperature of the sealing material composition of the present invention is adjusted by using a curing catalyst to lower the curing temperature of the curable methylphenyl silicone resin, such as zinc, cobalt, tin, iron, and zirconium. And quaternary ammonium salts, chelates such as aluminum and titanium, and various amines or salts thereof.
- the curing catalyst may be previously contained in the raw materials when the sealing material composition of the present invention is produced, or may be contained in the sealing material composition after the production according to the use form.
- a curing catalyst When used as a paste-like sealing material composition containing a solvent, it can be mixed with the sealing material composition together with the solvent.
- a curing catalyst When used as a molded article of a sealing material composition such as a sheet, a curing catalyst can be kneaded into the partially cured sealing material composition.
- the curing catalyst is mixed in an amount of 0.1 to 13% by mass based on the mass of the curable methylphenyl silicone resin.
- a curing catalyst When a curing catalyst is contained in the raw material, conditions for partially polymerizing the curable methylphenyl silicone resin are different from those of the image display device of the first embodiment described above.
- a mixture of a curable methylphenol silicone resin from which the solvent has been removed by volatilization, a heat-resistant filler, and a curing catalyst is partially polymerized at 80 ° C to a viscosity of 500 OcP—60, OOOcP. At this point, the heat is stopped.
- the curing temperature of the sealing material composition of the present invention depends on the melting point of the low melting point metal material forming the metal sealing material 52.
- Force appropriately selected Indium or an alloy containing indium suitable as a low-melting metal material has a melting point of about 140 ° C, and is therefore preferably 135 ° C or less.
- the arrangement of the sealing material 51 and the metal-based sealing material 52 of the present invention is not limited to the illustrated one.
- the sealing material composition of the present invention involves a dehydration-condensation reaction during heat curing
- the sealing material 51 of the present invention is disposed outside the metal-based sealing material 52.
- the sealing material 51 of the present invention is located outside the metallic sealing material 52. If arranged, it also serves as a barrier for preventing the metal sealing material 52 from flowing out.
- FIG. 7 illustrates a specific configuration of the image display device 1 according to the second embodiment of the present invention, and the configuration is not limited to the illustrated one.
- a triode type or a tetraode type may be shifted.
- the structure of the surface conduction type field emission device it may be any of a wedge type, a comb tooth type and a star type.
- the joint between the rear substrate 3 and the spacing member 4 is sealed with a sealing material 53.
- This step need not be performed in a vacuum, so it may be performed in the atmosphere.
- the sealing material 53 may be a conventional lead-based frit glass, or may be the sealing material of the present invention.
- frit glass When frit glass is used, a paste-like frit glass containing a solvent and a binder such as -trocellulose is applied along the peripheral edge of the rear substrate 3, dried, and then the frit glass-applied portion is removed.
- the spacing member 4 is placed along the peripheral edge of the rear substrate 3 so as to cover it, and the spacing member 4 is heated to a temperature equal to or higher than the softening temperature of the frit glass while being pressed from above and sealed. .
- the sealing material composition of the present invention is formed along the peripheral portion of the back substrate 3 in the same manner as described for the image display device 1 of the first embodiment. Apply the adhesive composition.
- the sealing material composition of the present invention may be applied as a paste-like sealing material composition containing a solvent, or the back substrate 3 may be heated to a predetermined temperature equal to or higher than the softening point of the sealing material composition.
- the molded article of the sealing material composition such as a sheet may be arranged in a heated state.
- the method may be performed by another method, specifically, for example, a spray method, a screen printing method, a spin coating method, or the like.
- the spacing member 4 is placed along the peripheral portion of the back substrate 3 so as to cover the sealing material composition of the present invention.
- the sealing material composition is applied to the rear substrate 3 and then heated to a predetermined temperature before the spacing member 4 is placed. It is preferable to volatilize the solvent to remove the solvent.
- the rear substrate 3 and the spacing member 4 are required. The spacing member 4 is placed on the rear substrate 3 while being heated to a constant temperature.
- the support member 14 is fixed to a desired position on the rear substrate 3 in the same procedure as in the sealing of the joint between the rear substrate 3 and the spacing member 4.
- conventional lead-based frit glass may be used, or the sealing material composition of the present invention may be used. Since the time required for the process can be shortened, the fixing of the support member 14 is preferably performed simultaneously with the sealing of the joint between the back substrate 3 and the spacing member 4.
- the metal-based sealing material layer 521 and the sealing material composition layer 511 of the present invention are formed on the upper surface of the spacing member 4. Since the metal-based sealing material is a low-melting metal material, it may be heated and melted at a temperature equal to or higher than the melting point and applied to a desired sealing site.
- the sealing material composition of the present invention may be applied to a desired sealing site as described above. That is, it may be applied as a simple sealing material composition containing a solvent, or may be a molded product of a sheet-like sealing material composition on the upper surface of the spacing member 4 heated to a predetermined temperature. May be placed as ⁇ .
- the method may be performed by another method, specifically, a spray method, a screen printing method, a spin coating method, or the like.
- the bonding portion is sealed with the front substrate 2 with the sealing material 53 as described above, and the metal sealing material layer 521 and the sealing material composition of the present invention are further provided on the upper surface of the spacing member 4.
- the assembly of the back substrate 3 on which the layer 511 is formed and the spacing member 4 is placed in a vacuum vessel and evacuated to a predetermined vacuum.
- the degree of vacuum reaches a desired level
- heating is performed to a temperature equal to or higher than the melting point or the softening point of the low melting point metal material forming the metal sealing material layer 521.
- the low melting point metal material forming the metal sealing material layer 521 is melted or softened into a liquid state.
- the upper surface of the spacing member 4 and the peripheral portion of the front substrate 2 are joined, the back substrate 3, the spacing member 4 and the front substrate 2 are laminated in this order, and the front substrate 2 is pressed upward. .
- the sealing material of the present invention Since the composition is adjusted so as to be cured by heating at a temperature equal to or lower than the melting point of the low-melting metal material forming the metal-based sealing material layer 521, the sealing material composition of the present invention is also added during the above-mentioned heating. Thermoset. Therefore, sealing with the metal-based sealing material 52 and the sealing material 51 of the present invention can be performed in one step.
- the metal-based sealing material layer 521 may be formed on the upper surface of the spacing member 4. Good.
- the vacuum vessel is evacuated to a desired degree of vacuum in the same procedure as described above, and then the low-melting-point metal material forming the metal-based sealing material layer 521 is heated and then gradually cooled.
- the joining surface between the front substrate 2 and the spacing member 4 is sealed with the metal sealing material 52.
- FIG. 8 is a partial cross-sectional view of the image display device 1 of the second embodiment at this stage.
- the sealing material composition layer 511 of the present invention is formed in a void outside the metal-based sealing material 52.
- a molded article of the sealing material composition of the present invention in the form of a sheet is applied along the gap.
- the sealing material composition layer 511 of the present invention can be formed.
- the paste is heated to a predetermined temperature and sealed.
- the solvent contained in the dressing composition is volatilized and removed. For example, volatilize the solvent at 40-50 ° C under reduced pressure for 1 hour to remove.
- a predetermined temperature for example, 100 to 120 ° C. for 10 minutes
- it is further heated at a predetermined temperature, for example, 120 to 140 ° C. for 1 to 2 hours to heat and cure the sealing material composition of the present invention. Let it.
- the joint between the front substrate 2 and the spacing member 4 is sealed with the metal-based sealing material 52 and the sealing material 51 of the present invention, and the inside of the hermetic container 20 is maintained at a desired degree of vacuum. It is sealed while being held.
- the sealing material composition of the present invention contains gold. Since it is adjusted so that it is cured by heating at a temperature equal to or lower than the melting point of the low-melting metal material forming the metal-based sealing material 52, there is no danger of the metal-based sealing material 52 flowing out during this heating and curing.
- the interior of hermetic container 20 is evacuated to a desired vacuum in the state of FIG.
- the formation and heat curing of the sealing material composition layer 51 of the present invention may be performed at atmospheric pressure instead of under vacuum, as long as it can be maintained at a high temperature.
- the formation of the sealing material composition layer 51 of the present invention and the heat curing are preferably performed in a vacuum.
- the sealing material composition of the present invention was prepared, and the characteristics were evaluated. (Example 1)
- the applicability when the obtained paste-like sealing material composition was applied on a soda-lime glass substrate using a dispenser was evaluated based on the following evaluation criteria. It will be described later.
- the sealing material composition is a molded body as in Example 6, when the molded body is placed on a glass substrate heated to 180 ° C., the molded body is fluidized to determine whether the force spreads uniformly. It was judged.
- ⁇ The fluidity of the sealing material composition was improved and the coating was able to be applied uniformly.
- the paste-like sealing material composition was applied to an aluminum cup using a dispenser so as to have a thickness of 100 ⁇ m to 200 ⁇ m, and heated at 120 ° C. for 1 hour to volatilize and remove the solvent. . Thereafter, after drying at 200 ° C for 5 minutes, the sealing material composition was heated and cured at 200 ° C for 1 hour and at 250 ° C for 1 hour to obtain a test sample. The mass loss when the sample was heated to 300 ° C. was measured using a differential thermobalance (TG-DTA, manufactured by Mac Science). The measurement was performed in dry air, and the heating rate was 10 ° CZmin.
- the evaluation criteria for the curability evaluation are as follows.
- ⁇ Weight loss of 1% or less when heated to 300 ° C.
- the thickness of the sealing material composition is set to 100 ⁇ m to 200 ⁇ m on an aluminum cup heated to 180 ° C. After drying at 180 ° C for 10 minutes, the sample was cured by heating at 200 ° C for 1 hour and at 250 ° C for 1 hour to obtain a test sample.
- Leakability evaluation was performed using three soda-lime glass substrates of the shape shown in Fig. 10 (lower plate 30: 100 x 100 x 5 mm, upper plate 31: 100 x 100 x 5 mm, and a hole 34 with a diameter of 5 mm at the center). It was carried out using a frame-shaped middle plate 32 having an outer diameter of 100 ⁇ 100 mm, an inner diameter of 70 ⁇ 70 mm, and a thickness of 5 mm.
- a paste-like sealing material composition was applied along the outer edge of the lower plate 30 with a width of 15 mm using a dispenser. After heating at 120 ° C for 1 hour to volatilize and remove the solvent, it was further dried at 180 ° C for 10 minutes. On the other hand, the paste-like sealing material composition is also applied to the upper surface of the middle plate 32 using a dispenser, and is heated at 120 ° C for 1 hour to volatilize the solvent, and then removed at 180 ° C. And dried. Next, while being heated to 180 ° C., as shown in FIG. 11, the lower plate 30, the middle plate 32 and the upper plate 31 were laminated in this order. In FIG. 11, the thickness of the sealing material composition was 100 m. In this state, the sample was cured by heating at 200 ° C. for 1 hour and 250 ° C. for 1 hour while applying an upward force to prepare a test sample for leak property evaluation, and the presence or absence of leak was measured.
- the sealing material composition is a molded body as in Example 6 described below, the sealing material is heated along the outer edge of the lower plate 30 while the lower plate 30 is heated to 180 ° C. The composition was placed and dried at 180 ° C for 5 minutes. On the other hand, the sealing material composition was placed on the middle plate 32 while being heated to 180 ° C, and dried at 180 ° C for 5 minutes. Next, while being heated to 180 ° C, the lower plate 30, the middle plate 32, and the upper plate 31 are laminated in this order as shown in Fig. 11, and pressed at 200 ° C for 1 hour at 250 ° C while pressing from above. The sample was cured by heating at ° C for 1 hour. The thickness of the sealing material composition 511 was 100 ⁇ m.
- a sealing material composition was prepared in the same manner as in Example 1 except that a spherical filler having an average particle size of 3 ⁇ m was used, and the obtained sealing material composition was evaluated. The results are shown in Table 1. In Example 2, ten samples with the same composition were prepared and evaluated. [0140] (Example 3)
- a sealing material composition was prepared in the same manner as in Example 1 except that a spherical filler having an average particle size of 5 ⁇ m was used, and the obtained sealing material composition was evaluated. The results are shown in Table 1. In Example 3, only one sample was evaluated.
- a sealing material composition was prepared in the same manner as in Example 1 except that a spherical filler having an average particle size of 10 m was used, and the obtained sealing material composition was evaluated. The results are shown in Table 1. In Example 4, only one sample was evaluated.
- Example 1 To lower the curing temperature of the sealing material composition to 135 ° C, 1% by mass of an iron-based catalyst (D31, Shin-Etsu Chemical Co., Ltd.) was used as a curing catalyst in the paste-like sealing material composition of Example 1 (curing The sealing material composition was evaluated by mixing (with respect to the weight of the water-soluble methyl silicone resin). The results are shown in Table 1. However, in this example, after applying the sealing material composition, the mixture was heated under reduced pressure at 40 ° C. for 1 hour to volatilize the solvent, and then dried at 100 ° C. for 10 minutes. It was cured by heating at ° C for 1 hour. In Example 5, four samples with the same composition were prepared and evaluated.
- an iron-based catalyst D31, Shin-Etsu Chemical Co., Ltd.
- Example 6 In the same manner as in Example 1, evaluation was performed using the produced sealing material composition. However, in Example 6, after the sealing material composition was partially polymerized by the procedure of Example 1, it was poured into a fluoroplastic mold and molded into a desired shape, and a molded product of the sealing material composition was obtained. Used as In Example 6, two samples with the same composition were prepared and evaluated.
- Example 7 As shown in Table 1, the same operation as in Example 6 was carried out except that 15 parts by mass of a curable methylphenol silicone resin and 85 parts by mass of spherical silica having a particle diameter of 1 ⁇ m were blended. Table 1 shows the results. This composition was inferior in fluidity and poor in applicability since the content of the filler was as large as 85 parts by mass. In addition, the adhesive strength to glass was weak, and the film was peeled off before the evaluation of the leak property and the evaluation of the adhesion to glass, and these evaluations could not be performed. In Example 7, two samples having the same composition were prepared and evaluated. [0145] (Example 8)
- Example 8 The procedure was performed in the same manner as in Example 6, except that a curable methylphenylsilicone resin prepared using only a trifunctional silicon monomer was used. The results are shown in Table 1. This composition was peeled off before the evaluation of the leak property and the evaluation of the adhesion to glass, where the adhesive strength to glass was weak, and it was not possible to carry out these evaluations. In Example 8, two samples having the same composition were prepared and evaluated.
- Example 9 the evaluation was performed in the same manner as in Example 1, except that a conventional lead-based glass sealing material (DT430, manufactured by Asahi Techno Glass Co., Ltd.) was used instead of the sealing composition of the present invention. However, in Example 9, evaluation of the glass adhesiveness was not performed. The sealing temperature is 430 ° C in Example 9. Table 1 shows the results. In Example 9, only one sample is evaluated.
- DT430 manufactured by Asahi Techno Glass Co., Ltd.
- Example 10 the evaluation was performed using a low melting point metal material, a eutectic alloy of In97% -Ag3% (melting point: 141 ° C.), instead of the sealing material composition of the present invention.
- the sealing material is heated to a temperature equal to or higher than the melting point and melt-coated.
- Example 10 only one sample was evaluated, and the hardening evaluation was not performed.
- the image display device of the first embodiment shown in FIG. 3 is manufactured using the sealing material composition prepared in Example 1.
- the specifications of each component are as follows.
- Front substrate 2 Made of soda lime glass, 108mm X 75mm X 2.5mm
- Back substrate 3 Made of soda-lime glass, 108mm x 75mm x 2.5mm, with an opening ( ⁇ 2mm) for evacuation!
- Spacing member 4 Soda-lime glass, width 5mm x height 2mm
- Supporting member 14 Soda-lime glass, width 5mm x height 2mm
- Phosphor screen 6 Using a plotter machine, an RGB pattern (width of 0.3 mm, thickness of 50 ⁇ m, spacing of 50 ⁇ m) and a black light absorbing layer 61 shown in FIG. 4 are formed.
- the used phosphors are as follows.
- Green phosphor Zn (Ga, Al) O: Mn
- Insulating film 9 A silicon dioxide film is formed on conductive force layer 7 by a CVD method.
- Gate electrode 12 A molybdenum film for forming a gate electrode is formed on the insulating film 9 by a sputtering method, and the gate electrode 12 having a desired pattern shape is formed by a dry etching method.
- Field emission device 8 A conical field emission device 8 made of molybdenum is formed by electron beam evaporation.
- the sealing of the joining surface between the back substrate 3 and the spacing member 4 and the fixing of the support member 14 on the back substrate 3 are performed using the paste-like sealing material composition obtained in Example 1. .
- the paste-like sealing material composition obtained in Example 1 is applied to a predetermined site using a dispenser, and heated at 120 ° C. for 1 hour to volatilize and remove the solvent. Then, after drying at 200 ° C for 5 minutes, the spacing member 4 (supporting member 14) is placed on the rear substrate 3 and pressurized from above for 1 hour at 200 ° C and 1 hour at 250 ° C.
- the sealing material composition is heated and cured by heating.
- a paste-like sealing material composition was applied to the upper surface of the spacing member 4 using a dispenser and dried in the same procedure as described above, and then the front substrate 2 was placed on the spacing member 4. Place and heat at 200 ° C for 1 hour and 250 ° C for 1 hour while applying pressure from above to sealant composition. Is cured by heating. At this stage, the image display device 1 is in a state shown in FIG.
- the opening 16 was connected to a vacuum pump, and the inside of the airtight container 20 was evacuated to a desired degree of vacuum. As shown in Fig. 6, the glass plate 18 and the paste obtained in Example 1 were used. The opening 16 is sealed with the sealing material composition of the present invention in a shape.
- the image display device 1 of the second embodiment shown in FIG. 7 is manufactured.
- the specifications of each component are as follows.
- Front substrate 2 soda lime glass, 108mmX75mmX2.8mm
- Back substrate 3 soda lime glass, 108mm X 75mm X 2.8mm
- Spacing member 4 Soda lime glass, width 10mm x height 6mm
- Supporting member 14 Soda-lime glass, width 1 Omm X height 6mm
- Phosphor screen 6 An RGB pattern and a black light absorbing layer 61 shown in FIG. 4 are formed using a plotter machine. The used phosphors are as follows.
- Green phosphor Y (Al, Ga) O: Tb
- Red phosphor Y O: Eu
- an aluminum layer (thickness: 200 nm) is deposited as a metal back.
- the device electrode 81 is formed by combining vacuum evaporation, photolithography and etching. Next, an organic metal solution containing Pd as a main element is applied, heated and baked, and patterned by lift-off and etching to form a conductive film 82. Further, the obtained conductive film 82 is subjected to an energization forming process, and then activated to form a field emission portion 83, thereby forming a surface conduction type field emission device 8 '.
- Example 1 Sealing of the joining surface between the back substrate 3 and the spacing member 4 and fixing of the support member 14 on the back substrate 3 are performed using the paste-like sealing material composition obtained in Example 1. .
- the paste-like sealing material composition obtained in Example 1 is applied to a predetermined site using a dispenser, and heated at 120 ° C. for 1 hour to volatilize and remove the solvent. Then at 200 ° C for 5 minutes After drying, the spacing member 4 (supporting member 14) is placed on the back substrate 3 and heated at 200 ° C for 1 hour and at 250 ° C for 1 hour while applying pressure from above, and the sealing material composition is heated. Is heat-cured.
- a eutectic alloy of In97% —Ag3% (melting point: 141 ° C.) is melt-coated on the upper surface of the spacing member 4 to form a metal-based sealing material layer 521.
- the paste-like sealing material composition obtained in Example 2 is applied using a dispenser to form a sealing material composition layer 511 of the present invention.
- the front substrate 2, the assembly of the rear substrate 3 and the spacing member 4 placed in a vacuum vessel and evacuated to a less degree of vacuum of 10- 6 Torr. Thereafter, the mixture is heated under reduced pressure at 50 ° C for 1 hour to volatilize and remove the solvent.
- the image display device 1 having the same structure as that of the second embodiment is manufactured by the procedure shown in FIGS.
- a metal sealing material 52 is melt-coated on the upper surface of the spacing member 4 in the same procedure as in the second embodiment.
- a front substrate 2 the assembly of the rear substrate 3 and the spacing member 4 placed in a vacuum vessel, becomes less vacuum degree 10- 6 Torr Evacuate until When the degree of vacuum reaches a desired level, the back substrate 3, the spacing member 4 and the front substrate 2 are laminated in this order, and heated at 140 ° C for 1 hour without applying pressure from above, and then gradually cooled.
- the paste-like sealing material composition obtained in Example 2 is applied to a void outside the metal-based sealing material 52 in FIG. 8 using a dispenser. Thereafter, the solvent is volatilized by heating at 50 ° C for 1 hour under reduced pressure to remove the solvent, and further dried at 100 ° C for 10 minutes, and then the rear substrate 3, the spacing member 4 and the front substrate 2 are laminated in this order. Then, the front substrate 2 is heated at 140 ° C. for 1 hour while being pressed from above, and then gradually cooled to obtain the image display device 1 shown in FIG.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)
- Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
- Sealing Material Composition (AREA)
- Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
Description
Claims
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007100016A1 (ja) * | 2006-03-01 | 2007-09-07 | Asahi Glass Company, Limited | ディスプレー用外囲器及びその封着方法 |
JP2012169287A (ja) * | 2012-04-23 | 2012-09-06 | Ulvac Japan Ltd | 表示パネル及びその製造法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001207152A (ja) * | 2000-01-28 | 2001-07-31 | Minoru Yamada | 封着用材料および封着されたガラス構造体 |
JP2002182585A (ja) * | 2000-12-12 | 2002-06-26 | Toshiba Corp | 画像表示装置およびその製造方法 |
JP2004162039A (ja) * | 2002-10-22 | 2004-06-10 | Sophia Product:Kk | 光素子用の封着材組成物、封着構造体および光素子 |
-
2005
- 2005-03-17 JP JP2006511223A patent/JPWO2005091325A1/ja not_active Withdrawn
- 2005-03-17 WO PCT/JP2005/004823 patent/WO2005091325A1/ja active Application Filing
- 2005-03-18 TW TW94108484A patent/TW200539397A/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001207152A (ja) * | 2000-01-28 | 2001-07-31 | Minoru Yamada | 封着用材料および封着されたガラス構造体 |
JP2002182585A (ja) * | 2000-12-12 | 2002-06-26 | Toshiba Corp | 画像表示装置およびその製造方法 |
JP2004162039A (ja) * | 2002-10-22 | 2004-06-10 | Sophia Product:Kk | 光素子用の封着材組成物、封着構造体および光素子 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007100016A1 (ja) * | 2006-03-01 | 2007-09-07 | Asahi Glass Company, Limited | ディスプレー用外囲器及びその封着方法 |
JP2012169287A (ja) * | 2012-04-23 | 2012-09-06 | Ulvac Japan Ltd | 表示パネル及びその製造法 |
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TW200539397A (en) | 2005-12-01 |
JPWO2005091325A1 (ja) | 2008-02-07 |
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