WO2011132554A1 - 耐火性フィラー粉末、封着材料及び耐火性フィラー粉末の製造方法 - Google Patents
耐火性フィラー粉末、封着材料及び耐火性フィラー粉末の製造方法 Download PDFInfo
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- WO2011132554A1 WO2011132554A1 PCT/JP2011/058941 JP2011058941W WO2011132554A1 WO 2011132554 A1 WO2011132554 A1 WO 2011132554A1 JP 2011058941 W JP2011058941 W JP 2011058941W WO 2011132554 A1 WO2011132554 A1 WO 2011132554A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1003—Pure inorganic mixtures
Definitions
- the present invention relates to a method for producing a refractory filler powder, a sealing material and a refractory filler powder, and relates to a plasma display panel (hereinafter referred to as PDP), an organic EL display, a field emission display (hereinafter referred to as FED), a fluorescent display tube (hereinafter referred to as The present invention relates to a fireproof filler powder, a sealing material, and a method for producing a fireproof filler powder suitable for sealing a display device such as a VFD, and sealing electronic parts such as a piezoelectric vibrator package and an IC package.
- PDP plasma display panel
- FED field emission display
- FED field emission display
- the present invention relates to a fireproof filler powder, a sealing material, and a method for producing a fireproof filler powder suitable for sealing a display device such as a VFD, and sealing electronic parts such as a piezoelectric vibrator package and an IC package.
- sealing material a composite powder material containing glass powder and refractory filler powder is used. This sealing material is excellent in chemical durability and heat resistance as compared with a resin-based adhesive, and is suitable for ensuring airtightness.
- Patent Document 1 As the glass powder used for the sealing material, PbO—B 2 O 3 based glass has been used (see Patent Document 1, etc.). However, from the environmental point of view, it is required to remove PbO from the glass composition, and Bi 2 O 3 —B 2 O 3 based glass has been developed. In Patent Document 2 and the like, Bi 2 O 3 —B 2 O 3 glass has a low melting point and has the same chemical durability as PbO—B 2 O 3 glass. It is disclosed.
- the refractory filler powder used for the sealing material has been added to reduce the thermal expansion coefficient and improve the mechanical strength.
- low expansion lead titanate has been used. It was. However, it is required to remove PbO from the composition of the refractory filler powder in the same manner as the glass powder. For this reason, willemite, cordierite, tin dioxide, ⁇ -eucryptite, mullite, silica, ⁇ -quartz solid solution, aluminum titanate, zircon and the like have been studied as refractory filler powders.
- Patent Document 3 willemite has low expansion and good compatibility with Bi 2 O 3 —B 2 O 3 glass (it is difficult to devitrify Bi 2 O 3 —B 2 O 3 glass during sealing). Therefore, it attracts attention (see Patent Document 3 and Non-Patent Document 1).
- Willemite has low expansion, but is less effective in increasing the mechanical strength of the sealing part than other refractory filler powders. If the mechanical strength of the sealing portion is low, the sealing portion is likely to be damaged due to mechanical impact or the like, and it is difficult to maintain the airtightness of the display device or the like.
- willemite is generally produced by a solid phase reaction method.
- a solid phase reaction method in order to complete the solid phase reaction, it is necessary to bake the raw material at a high temperature (specifically, 1440 ° C. or higher).
- a high temperature specifically, 1440 ° C. or higher.
- the firing temperature is too lower than the solid phase reaction temperature, a part of the raw material tends to be unreacted. If unreacted raw material remains in the sealing material, unintentional crystals are likely to be deposited on the glass during sealing, which tends to cause poor sealing.
- the melting point of willemite is about 1510 ° C., which is close to the above solid-phase reaction temperature (see Non-Patent Document 1).
- the present invention aims to reduce the cost of the sealing material by creating a refractory filler powder having low expansion, high strength, and capable of solid-phase reaction at a low temperature, and a method for producing the same. It is a technical problem to prevent sealing failure due to breakage and unreacted raw materials.
- the present inventor has found that the above technical problem can be solved by using refractory filler powder precipitated with willemite and garnite as the main crystal, and proposes as the present invention. That is, the refractory filler powder of the present invention is characterized in that willemite and garnite are precipitated in the same particle.
- the firing temperature can be lowered, and as a result, the fired product is hardly fused and the production efficiency of the refractory filler powder is improved.
- the refractory filler powder of the present invention is characterized in that the ratio of willemite to garnite is 99: 1 to 70:30 in molar ratio. If it does in this way, the mechanical strength of a sealing part can be raised, maintaining the effect of reducing a thermal expansion coefficient.
- the refractory filler powder of the present invention contains, as a composition, mol%, ZnO 60 to 79.9%, SiO 2 20 to 39.9%, and Al 2 O 3 0.1 to 10%. It is characterized by that. If it does in this way, it will become easy to optimize the ratio of willemite and garnite, and it will become easy to raise the mechanical strength of a sealing part, maintaining the effect of reducing a thermal expansion coefficient.
- the refractory filler powder of the present invention is produced by a solid phase reaction method.
- the solid phase reaction method first, raw materials such as oxides are prepared so as to have a desired composition, and after firing this, the obtained fired product is crushed, pulverized, and classified to produce a refractory filler powder. Is the method. According to this method, since it is not necessary to melt the raw material, the manufacturing cost of the refractory filler powder can be reduced.
- the sealing material of the present invention is characterized in that the sealing material containing glass powder and refractory filler powder contains the above refractory filler powder as the refractory filler powder.
- the sealing material of the present invention is characterized in that the content of the refractory filler powder is 0.1 to 70% by volume. If it does in this way, it will become easy to match the thermal expansion coefficient of sealing material with the thermal expansion coefficient of to-be-sealed material, and the mechanical strength of sealing material can also be raised.
- the sealing material of the present invention is characterized in that the glass powder is Bi 2 O 3 —B 2 O 3 glass.
- Bi 2 O 3 -B 2 O 3 glass has a low melting point and good thermal stability and water resistance, so that it is easy to seal at low temperatures and to ensure airtightness of a display device or the like. It has properties.
- Bi 2 O 3 —B 2 O 3 glass has good compatibility with the refractory filler powder of the present invention.
- the term “to glass” refers to a glass containing an explicit component as an essential component and having a total amount of 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more (hereinafter the same) ).
- the sealing material of the present invention further includes one or two kinds selected from cordierite, zircon, ⁇ -eucryptite, quartz glass, alumina, mullite, and alumina-silica ceramics as a refractory filler powder. It contains more than seeds.
- the sealing material of the present invention is characterized by further containing an inorganic pigment.
- the sealing material of the present invention is characterized by substantially not containing PbO.
- substantially does not contain PbO refers to a case where the content of PbO in the sealing material is 1000 ppm (mass) or less.
- the method for producing a refractory filler powder according to the present invention comprises ZnO 60 to 79.9%, SiO 2 20 to 39.9%, Al 2 O 3 0.1 to 10 in terms of mol% as a composition. After the raw materials are prepared so as to contain a%, willemite and garnite are precipitated by a solid phase reaction method.
- the refractory filler powder of the present invention has a composition of mol% of ZnO 60 to 79.9% (preferably 63 to 70%), SiO 2 20 to 39.9% (preferably 28 to 35%), Al It is preferable to contain 0.1 to 10% of 2 O 3 .
- the batch composition for producing the refractory filler powder also preferably contains, in mol%, ZnO 60 to 79.9%, SiO 2 20 to 39.9%, and Al 2 O 3 0.1 to 10%. .
- ZnO and SiO 2 are constituents of the crystal.
- Al 2 O 3 is a constituent component of the crystal and functions as a reaction accelerator, and is a component that lowers the firing temperature.
- the content of Al 2 O 3 is preferably 0.1 mol% or more, 1 mol% or more, and particularly preferably 3 mol% or more. If the content of Al 2 O 3 is less than 0.1 mol%, it will be difficult to function as a reaction accelerator. On the other hand, when the content of Al 2 O 3 is too large, it becomes difficult to generate the willemite.
- the refractory filler powder of the present invention is preferably produced by a solid phase reaction method. According to this method, since it is not necessary to melt the raw material, the manufacturing cost of the refractory filler powder can be reduced. Moreover, it is preferable to grind and mix the raw materials before firing. In this way, since the raw materials are mixed in a fine powder state while receiving mechanical impact, the specific surface area of the raw materials is increased, and as a result, the solid phase reaction is promoted. In this way, the firing time can be shortened.
- the firing temperature is preferably a temperature at which desired crystals are sufficiently precipitated without causing fusion of the fired product, and specifically, 1400 to 1460 ° C. is preferable.
- the average particle diameter D 50 of the refractory filler powder is 20 ⁇ m or less, especially 2 ⁇ 15 [mu] m is preferred. If it does in this way, it will become easy to narrow a sealing thickness, without raising the manufacturing cost (crushing cost, classification cost) of a refractory filler powder.
- the average particle diameter D 50 of the refractory filler powder is preferably at least 0.5 [mu] m.
- the “average particle diameter D 50 ” refers to a value measured by the laser diffraction method, and in the volume-based cumulative particle size distribution curve when measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle.
- the particle diameter is 50%.
- the maximum particle diameter D max of the refractory filler is preferably 100 ⁇ m or less, particularly preferably 10 to 75 ⁇ m. If it does in this way, it will become easy to narrow down sealing thickness, without raising the manufacturing cost of sealing material.
- the “average particle diameter D max ” refers to a value measured by the laser diffraction method. In the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle. The particle diameter is 99%.
- the sealing material of the present invention includes glass powder and refractory filler powder, and includes the above refractory filler powder as the refractory filler powder.
- the content of the refractory filler powder is preferably 0.1 to 70% by volume, 15 to 50% by volume, and particularly preferably 20 to 40% by volume.
- the content of the refractory filler powder is more than 70% by volume, the content of the glass powder is relatively decreased, so that the fluidity of the sealing material is lowered, and as a result, the sealing strength is easily lowered.
- the content of the refractory filler powder is less than 0.1% by volume, the effect of the refractory filler powder becomes poor.
- the content of the refractory filler powder of the present invention is 0.1 to 70% by volume, 15 to 50% by volume, 20 to 40% by volume is particularly preferable.
- Various glass-based glass powders can be used as the glass powder.
- Bi 2 O 3 —B 2 O 3 series glass, V 2 O 5 —P 2 O 5 series glass, and SnO—P 2 O 5 series glass are suitable in terms of low melting point characteristics, and Bi 2 O 3 — B 2 O 3 glass is particularly preferred from the viewpoints of thermal stability and water resistance.
- Bi 2 O 3 —B 2 O 3 glass has a glass composition of mol% in terms of the following oxides: Bi 2 O 3 15-50%, B 2 O 3 15-50%, ZnO 0-45% ( The content is preferably 1 to 40%. In this way, both thermal stability and low melting point characteristics can be achieved at a high level. In addition, in order to improve thermal stability, it is preferable to add 0.1 mol% or more of BaO, Fe 2 O 3 , or CuO.
- the average particle diameter D 50 of the glass powder less than 15 [mu] m, 0.5 ⁇ 10 [mu] m, particularly 1 ⁇ 5 [mu] m is preferred.
- the average particle diameter D 50 of the glass powder is smaller than 15 [mu] m, and reduced the softening point of the glass powder, thereby improving the flowability of the sealing material.
- the sealing material of the present invention further contains one or more kinds selected from cordierite, zircon, ⁇ -eucryptite, quartz glass, alumina, mullite, and alumina-silica ceramics as a refractory filler powder.
- a refractory filler powder is useful from the viewpoint of adjusting the thermal expansion coefficient and fluidity and improving the mechanical strength.
- the total content of these refractory filler powders is preferably 0 to 30% by volume, particularly preferably 0 to 10% by volume.
- the sealing material of the present invention preferably further contains an inorganic pigment. If it does in this way, the appearance defect of a sealing part can be reduced.
- the content of the inorganic pigment is preferably 0 to 10% by volume, 0.1 to 5% by volume, particularly 0.5 to 3% by volume. If the content of the inorganic pigment is more than 10% by volume, the amount of the inorganic pigment dissolved in the glass at the time of sealing increases, so that the thermal stability of the sealing material tends to be impaired.
- the inorganic pigment Cu-based oxides, Fe-based oxides, Cr-based oxides, Mn-based oxides, and spinel complex oxides thereof are preferable.
- the average particle diameter D 50 of the inorganic pigment is preferably 0.01 to 5 ⁇ m, 0.5 to 5 ⁇ m, particularly preferably 1 to 3 ⁇ m.
- the average particle diameter D 50 of the inorganic pigment is larger than 5 ⁇ m, it becomes difficult to uniformly disperse the inorganic pigment in the sealing material, and there is a possibility that poor sealing occurs locally.
- the average particle diameter D 50 of the inorganic pigment is 0.01 ⁇ m smaller, since the inorganic pigment is easily dissolved into the glass during the sealing, easily thermal stability of the sealing material is impaired.
- the sealing material of the present invention may further contain glass fiber, glass beads, silica beads, resin beads, etc. up to 10% by volume as a spacer in order to make the sealing thickness uniform.
- the thermal expansion coefficient is preferably 80 ⁇ 10 ⁇ 7 / ° C. or less, particularly preferably 75 ⁇ 10 ⁇ 7 / ° C. or less.
- the “thermal expansion coefficient” refers to a value measured with a push rod type thermal expansion coefficient measurement (TMA) apparatus in a temperature range of 30 to 300 ° C.
- the softening point is preferably 475 ° C. or less, particularly preferably 460 ° C. or less. If it does in this way, the fluidity
- the “softening point” refers to a value measured with a differential thermal analysis (DTA) device, and is measured with a macro-type DTA device in the atmosphere, at a heating rate of 10 ° C./min, at room temperature, and at the start of measurement. be able to.
- DTA differential thermal analysis
- Ts the temperature at the fourth bending point shown in FIG. 1 corresponds to the softening point.
- the crystallization temperature is preferably 550 ° C. or higher, 570 ° C. or higher, particularly 600 ° C. or higher. This makes it difficult for crystals to precipitate on the glass in the primary firing step (glazing step, binder removal step) and secondary firing step (sealing step), and it is easy to ensure the airtightness of the display device and the like.
- the “crystallization temperature” refers to the crystallization peak temperature measured with a DTA apparatus, and is measured with a macro DTA apparatus in the atmosphere, at a temperature rising rate of 10 ° C./min, under conditions such as starting measurement from room temperature. Can do.
- the sealing material of the present invention may be used in a powder state, but is preferably kneaded uniformly with a vehicle and made into a paste for easy handling.
- a vehicle usually includes a solvent and a resin.
- the resin is added for the purpose of adjusting the viscosity of the paste.
- surfactant, a thickener, etc. can also be added as needed.
- the produced paste is applied to the surface of an object to be sealed using an applicator such as a dispenser or a screen printer.
- acrylic acid ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used.
- acrylic acid esters and nitrocellulose are preferable because they have good thermal decomposability.
- Solvents include N, N′-dimethylformamide (DMF), ⁇ -terpineol, higher alcohol, ⁇ -butyllactone ( ⁇ -BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, water, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Tripropylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO), - methyl-2-pyrrolidone or the like can be used.
- ⁇ -terpineol is preferable because it is highly viscous and
- the sealing material of the present invention is preferably sintered into a predetermined shape and used as a tablet.
- Tablets press frit, glass sintered body, glass molded body
- molded into a ring shape are used for sealing exhaust pipes such as PDPs.
- the tablet has an insertion hole for inserting the exhaust pipe.
- the exhaust pipe is inserted into the insertion hole, and the tip of the exhaust pipe is aligned with the position of the exhaust hole of the panel and fixed with a clip or the like. .
- an exhaust pipe is attached to a panel by softening a tablet by a secondary baking process.
- the sealing material of the present invention is processed into a tablet, when the exhaust pipe is attached, it becomes easy to connect to the exhaust equipment, the inclination of the exhaust pipe can be reduced, and further, while maintaining the light emission capability such as PDP, It becomes easy to install so that airtight reliability is maintained.
- Tablets are produced by multiple heat treatments. First, a resin and a solvent are added to the sealing material to prepare a slurry. Thereafter, this slurry is put into a granulator such as a spray dryer to produce granules. At this time, the granules are dried at a temperature at which the solvent volatilizes (about 100 to 200 ° C.). Further, the produced granules are put into a mold designed to have a predetermined size, and then dry press-molded into a ring shape to produce a pressed body. Next, the resin remaining in the press body is decomposed and volatilized in a heat treatment furnace such as a belt furnace, and then sintered at a temperature about the softening point of the sealing material. In this way, a tablet having a predetermined shape can be produced. Also, the number of times of sintering may be multiple. In this way, the strength of the tablet is improved and it is easy to prevent the tablet from being broken or broken.
- the sealing material of the present invention is preferably used as a tablet-integrated exhaust pipe by making it into a tablet and attaching it to the tip of the exhaust pipe further expanded in diameter. In this way, it is not necessary to align the exhaust pipe and the tablet with the exhaust hole as a starting point, and the work of attaching the exhaust pipe can be simplified.
- the tablet-integrated exhaust pipe it is necessary to first heat-treat the tablet in contact with the tip of the exhaust pipe, and to bond the tablet to the tip of the exhaust pipe in advance.
- the jig for fixing the exhaust pipe is preferably made of a material to which the tablet is not fused, such as a carbon jig.
- the adhesion between the exhaust pipe and the tablet may be performed in the vicinity of the softening point of the sealing material for a short time, for example, about 5 to 10 minutes.
- SiO 2 —Al 2 O 3 —B 2 O 3 glass containing a predetermined amount of an alkali metal oxide is suitable, and FE-2 manufactured by Nippon Electric Glass Co., Ltd. is particularly suitable.
- This exhaust pipe has a thermal expansion coefficient of 85 ⁇ 10 ⁇ 7 / ° C., a heat resistant temperature of 550 ° C., and has dimensions of, for example, an outer diameter of 5 mm and an inner diameter of 3.5 mm.
- the diameter of the tip of the exhaust pipe is increased, the self-supporting stability can be improved. In that case, the flare shape or the flange shape is preferable for the tip of the exhaust pipe.
- FIG. 2 shows an example of the tablet-integrated exhaust pipe having this configuration. That is, FIG. 2 is a cross-sectional view of the tablet-integrated exhaust pipe, in which the tip of the exhaust pipe 1 is enlarged in diameter, and the tablet 2 is bonded to the tip of the exhaust pipe on the panel side.
- a tablet and a high melting point tablet are attached to the tip of the expanded exhaust pipe, and the tablet is attached to the tip of the enlarged exhaust pipe, A structure attached to the rear end side of the tablet is preferable.
- the area in contact with the panel or the like becomes larger than in the case of the exhaust pipe alone, so that it becomes easy to attach the panel vertically to the panel.
- a high melting point tablet can be placed between the tablet and the jig, eliminating the need for a special jig and, as a result, simplifying the manufacturing process of the tablet-integrated exhaust pipe be able to.
- the tablet is bonded to the outer peripheral surface of the distal end portion of the exhaust pipe, the tablet is bonded only to the outer peripheral surface of the distal end portion of the exhaust pipe, In other words, a configuration in which the surface is not bonded to the panel or the like is more preferable. If it does in this way, it will become easy to prevent the situation where the component of a tablet flows into an exhaust hole in a vacuum exhaust process.
- the high melting point tablet is not directly bonded to the exhaust pipe, but is fixed to the exhaust pipe through the tablet, the exhaust pipe can be pressure-sealed with the high melting point tablet portion being fixed with a clip in the secondary firing step. Therefore, it is preferable.
- FIG. 3 shows an example of the tablet-integrated exhaust pipe having this configuration. That is, FIG. 3 is a cross-sectional view of the tablet-integrated exhaust pipe, in which the distal end portion of the exhaust pipe 1 is enlarged, and the tablet 2 is bonded to the distal end portion on the outer peripheral surface side of the flange portion 1a of the exhaust pipe 1. is doing.
- the high melting point tablet 3 is not bonded to the outer peripheral surface side of the exhaust pipe 1.
- the tablet 2 is attached to the front end side of the flange portion 1 a, and the high melting point tablet 3 is attached to the rear end portion side of the flange portion 1 a than the tablet 2.
- ST-4 and FN-13 manufactured by Nippon Electric Glass Co., Ltd. are preferable as the high melting point tablet.
- the method for producing the high melting point tablet is the same as the method for producing the tablet when the material is glass.
- ceramics, metal, etc. can also be used as a high melting point tablet.
- Table 1 shows examples (samples Nos. 1 to 4) and comparative examples (samples Nos. 5 to 7) of the refractory filler powder of the present invention.
- the refractory filler powder in the table was prepared by a solid phase reaction method. First, various oxide raw materials were prepared so as to have the composition shown in the table, and pulverized and mixed for 10 minutes to 3 hours using a ball mill. This pulverized mixture was put in an alumina crucible and baked for 20 hours at the calcination temperature in the table. Finally, the obtained fired product was pulverized and pulverized with a ball mill, and then classified with a 250 mesh pass sieve to obtain a refractory filler powder having an average particle diameter D 50 of 12 ⁇ m. For each refractory filler, the presence or absence of fusion of the fired product and the presence or absence of unreacted raw material (mainly ZnO) were evaluated. The results are shown in Table 1.
- sample No. Nos. 1 to 4 contain Al 2 O 3 in the composition, so that willemite and garnite are precipitated as main crystals, and there are no unreacted substances even when the firing temperature is 1420 to 1440 ° C. Was completed.
- Sample No. Since 5 and 6 do not contain Al 2 O 3 in the composition no garnite is precipitated, and when the firing temperature is 1430 ° C., unreacted raw materials remain, and the firing temperature is 1470 ° C. In this case, fusion of the fired product occurred, and it was difficult to crush the fired product.
- Sample No. No. 7 is considered to have little effect of reducing the thermal expansion coefficient because no willemite is precipitated.
- Table 2 shows a glass composition example and characteristics of Bi 2 O 3 —B 2 O 3 based glass.
- Bi 2 O 3 —B 2 O 3 series glasses described in Table 2 were prepared as follows. First, a glass batch in which raw materials such as various oxides and carbonates were prepared so as to have the glass composition in the table was prepared, and the glass batch was put in a platinum crucible and melted at 1100 ° C. for 1 hour. Next, the molten glass was formed into a thin piece with a water-cooled roller. Finally, after grinding the flaky glass ball mill, and classified with a sieve of 200 mesh, the average particle diameter D 50 was obtained glass powder 10 [mu] m.
- the glass transition point and softening point are values measured with a DTA apparatus in an air atmosphere. Note that the measurement was started from room temperature, and the rate of temperature increase was 10 ° C./min.
- the thermal expansion coefficient is a value measured with a TMA apparatus.
- the measurement temperature range was 30 to 300 ° C.
- a dense sintered glass powder was processed into a predetermined shape.
- Table 3 shows examples (samples A to D) and comparative examples (samples E and F) of the sealing material of the present invention.
- Each sample in the table was prepared by mixing the refractory filler powder described in Table 1 and the glass powder described in Table 2 at a volume ratio described in the table. About each sample, the glass transition point, the softening point, the thermal expansion coefficient, and the bending strength were evaluated. The results are shown in Table 3.
- the glass transition point and softening point are values measured with a DTA apparatus in an air atmosphere. Note that the measurement was started from room temperature, and the rate of temperature increase was 10 ° C./min.
- the thermal expansion coefficient is a value measured with a TMA apparatus.
- the measurement temperature range was 30 to 300 ° C.
- a sintered body of a dense sealing material processed into a predetermined shape was used as a measurement sample.
- the bending strength is a value measured by a three-point bending test based on the bending strength test method of JIS R1601: fine ceramics.
- Samples A to D had a low coefficient of thermal expansion and a high bending strength.
- sample E had a lower bending strength than samples A to D.
- Sample E is considered to have a higher manufacturing cost than Samples A to D because the manufacturing cost of the refractory filler powder is high.
- Sample F had a higher coefficient of thermal expansion than Samples A to D.
- the refractory filler and sealing material using the same according to the present invention are (1) sealing of display devices such as PDP, organic EL display, FED, VFD, etc., and (2) electronic components such as piezoelectric vibrator packages and IC packages. (3) Sealing between cores of magnetic head or between core and slider, (4) Sealing of solar cells such as silicon solar cells and dye-sensitized solar cells, (5) Lighting such as organic EL lighting Suitable for sealing devices.
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Abstract
Description
Claims (11)
- 同一粒子中にウイレマイト及びガーナイトが析出していることを特徴とする耐火性フィラー粉末。
- ウイレマイトとガーナイトの割合が、モル比で99:1~70:30であることを特徴とする請求項1に記載の耐火性フィラー粉末。
- 組成として、モル%で、ZnO 60~79.9%、SiO2 20~39.9%、Al2O3 0.1~10%を含有することを特徴とする請求項1または2に記載の耐火性フィラー粉末。
- 固相反応法により作製されてなることを特徴とする請求項1~3のいずれかに1項に記載の耐火性フィラー粉末。
- ガラス粉末と耐火性フィラー粉末を含む封着材料において、
耐火性フィラー粉末が、請求項1~4のいずれかに1項に記載の耐火性フィラー粉末であることを特徴とする封着材料。 - 耐火性フィラー粉末の含有量が0.1~70体積%であることを特徴とする請求項5に記載の封着材料。
- ガラス粉末がBi2O3-B2O3系ガラスであることを特徴とする請求項5または6に記載の封着材料。
- 更に、耐火性フィラー粉末として、コーディエライト、ジルコン、β-ユークリプタイト、石英ガラス、アルミナ、ムライト、アルミナ-シリカ系セラミックスから選ばれる一種又は二種以上を含むことを特徴とする請求項5~7のいずれかに1項に記載の封着材料。
- 更に、無機顔料を含むことを特徴とする請求項5~8のいずれかに1項に記載の封着材料。
- 実質的にPbOを含有しないことを特徴とする請求項5~9のいずれかに1項に記載の封着材料。
- 組成として、モル%で、ZnO 60~79.9%、SiO2 20~39.9%、Al2O3 0.1~10%を含有するように、原料を調合した後、固相反応法により、ウイレマイト及びガーナイトを析出させることを特徴とする耐火性フィラー粉末の製造方法。
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CN201180019327.8A CN102844271B (zh) | 2010-04-22 | 2011-04-08 | 耐火性填料粉末、密封材料和耐火性填料粉末的制造方法 |
US13/642,656 US8853111B2 (en) | 2010-04-22 | 2011-04-08 | Refractory filler powder, sealing material, and method for producing refractory filler powder |
KR1020127027312A KR101441598B1 (ko) | 2010-04-22 | 2011-04-08 | 내화성 필러 분말, 봉착 재료 및 내화성 필러 분말의 제조 방법 |
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JP2010-098440 | 2010-04-22 | ||
JP2010098440A JP5605748B2 (ja) | 2010-04-22 | 2010-04-22 | 耐火性フィラー粉末、封着材料及び耐火性フィラー粉末の製造方法 |
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WO2011132554A1 true WO2011132554A1 (ja) | 2011-10-27 |
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JP (1) | JP5605748B2 (ja) |
KR (1) | KR101441598B1 (ja) |
CN (1) | CN102844271B (ja) |
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JP5605748B2 (ja) * | 2010-04-22 | 2014-10-15 | 日本電気硝子株式会社 | 耐火性フィラー粉末、封着材料及び耐火性フィラー粉末の製造方法 |
JP5779922B2 (ja) * | 2011-03-16 | 2015-09-16 | 日本電気硝子株式会社 | 耐火性フィラー及びこれを用いた封着材料 |
KR101464996B1 (ko) * | 2010-05-10 | 2014-11-25 | 니폰 덴키 가라스 가부시키가이샤 | 내화성 필러 및 이것을 사용한 밀봉 재료, 및 내화성 필러의 제조 방법 |
JP7075033B2 (ja) * | 2017-08-29 | 2022-05-25 | 日本電気硝子株式会社 | フィラー粉末の製造方法 |
KR102522821B1 (ko) * | 2017-09-04 | 2023-04-18 | 니폰 덴키 가라스 가부시키가이샤 | 유리 물품의 제조 방법 및 제조 장치 |
Citations (3)
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JPH04114930A (ja) * | 1990-09-05 | 1992-04-15 | Nippon Electric Glass Co Ltd | 低融点封着用組成物 |
JPH06171980A (ja) * | 1992-12-04 | 1994-06-21 | Sumitomo Metal Mining Co Ltd | 低温焼成基板用組成物 |
JP2009062257A (ja) * | 2006-10-24 | 2009-03-26 | Nippon Electric Glass Co Ltd | ビスマス系ガラス組成物およびビスマス系材料 |
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JPH07102982B2 (ja) | 1987-06-16 | 1995-11-08 | 日本電気硝子株式会社 | 低温封着用フリット |
JP3424219B2 (ja) | 1994-08-17 | 2003-07-07 | 日本電気硝子株式会社 | 低融点封着用組成物 |
WO2001028943A1 (en) * | 1999-10-18 | 2001-04-26 | Corning Incorporated | Transparent glass-ceramics based on alpha- and beta-willemite |
JP5413562B2 (ja) | 2007-12-06 | 2014-02-12 | 日本電気硝子株式会社 | 封着材料 |
JP5605748B2 (ja) * | 2010-04-22 | 2014-10-15 | 日本電気硝子株式会社 | 耐火性フィラー粉末、封着材料及び耐火性フィラー粉末の製造方法 |
KR101464996B1 (ko) * | 2010-05-10 | 2014-11-25 | 니폰 덴키 가라스 가부시키가이샤 | 내화성 필러 및 이것을 사용한 밀봉 재료, 및 내화성 필러의 제조 방법 |
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- 2011-04-08 KR KR1020127027312A patent/KR101441598B1/ko active IP Right Grant
- 2011-04-08 US US13/642,656 patent/US8853111B2/en active Active
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH04114930A (ja) * | 1990-09-05 | 1992-04-15 | Nippon Electric Glass Co Ltd | 低融点封着用組成物 |
JPH06171980A (ja) * | 1992-12-04 | 1994-06-21 | Sumitomo Metal Mining Co Ltd | 低温焼成基板用組成物 |
JP2009062257A (ja) * | 2006-10-24 | 2009-03-26 | Nippon Electric Glass Co Ltd | ビスマス系ガラス組成物およびビスマス系材料 |
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US8853111B2 (en) | 2014-10-07 |
US20130102453A1 (en) | 2013-04-25 |
KR101441598B1 (ko) | 2014-09-22 |
CN102844271A (zh) | 2012-12-26 |
JP5605748B2 (ja) | 2014-10-15 |
CN102844271B (zh) | 2016-02-03 |
JP2011225402A (ja) | 2011-11-10 |
KR20120131220A (ko) | 2012-12-04 |
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