KR20060029233A - Glass paste and method for production thereof - Google Patents

Abstract

A glass paste containing an inorganic oxide glass powder and an organic component, characterized in that said glass paste contains the foreign substance having an outer size of 10 mum or more in an amount of 30 pieces/100 g or less. The glass paste can be used for preventing the reliability of a gas-tight sealing from being lost due to the generation of a gas form a foreign substance during firing.

Description

Glass paste and its manufacturing method {GLASS PASTE AND METHOD FOR PRODUCTION THEREOF}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass paste for forming an airtight seal structure and a method for manufacturing the same, and more particularly, to a glass paste suitable for a partition forming material such as a plasma display panel and a method for producing the same.

The glass paste used for forming the airtight sealing structure contains an inorganic oxide glass powder and an organic component, and the desired performance can be realized by forming and firing a complex structure by using each forming method. Applications and electronic parts are also widely used in image display devices. Among them, in order to form a particularly precise and dense structure, a precise array structure is formed by glass paste, for example, for forming barrier ribs (barrier ribs and barriers) constituting a plasma display panel (hereinafter abbreviated as PDP). There is a glass paste used as.

PDP is a self-luminous image display device, which is a flat display having excellent characteristics such as light weight, high viewing angle, etc., but the front glass substrate 11 and the rear glass substrate are shown in FIG. The partition 13 for partitioning between two board | substrates of (12) by several gas discharge parts is provided. On the glass substrate 11, a transparent electrode 16 made of a pair of ITO or the like is formed, and a plasma discharge is generated by applying a voltage between the transparent electrodes 16. On the transparent electrode 16, a protective film 4 made of a dielectric layer 17 and MgO or the like is formed to cover the substrate glass. The address electrode 18 is formed on the back glass 12, and the fluorescent substance 21 is apply | coated so that it may be coat | covered. The voltage is applied between the transparent electrodes 16 and the plasma is generated in the discharge space 20 partitioned by the partition wall 13. The ultraviolet light is irradiated onto the phosphor 21 by the plasma discharge and the phosphor 21 emits light. This is the basic operation principle of this PDP.

As a method of forming the partition wall of the said PDP panel, the resist film which has a desired pattern is formed on the rib layer formed in layer form as described in patent document 1, and a unnecessary part is removed by sandblasting after that, As described in the sand blast method for forming a film and Patent Document 2, there are a printing method for forming a partition by repeating screen printing and firing of a thick film paste a plurality of times, and also there is a photosensitive paste method, a press method, a transfer method, and the like. Even if any method is adopted, the size of the partition 13 is about 50 to 120 µm in width, and its height is a fine barrier structure of 70 to 300 µm. If for some reason the barrier ribs cannot maintain or ensure airtightness, gas purity inside the apparatus, structural strength, etc., plasma discharge cannot be performed and the phosphors do not emit light, thereby impairing the function of the PDP.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-283938

Patent Document 2: Japanese Patent Application Laid-Open No. 05-101776

As described above, when the glass paste is used in the PDP, in the glass paste used for the partition wall having a precise and fine structure, the glass paste is not intentionally added as a constituent component of the glass paste, that is, after the formation of bubbles or partition walls. If defects such as residues due to processing methods such as wounds and sandblasts are present in the partition walls, there is a risk of problems such as deterioration of airtightness, deterioration of gas purity inside the apparatus, and weakening of structural strength after assembling the PDP. There is this. In addition, due to the residue, the degree of vacuum in the discharge space 20 cannot be maintained, and even if a voltage is applied between the electrodes, a sufficient plasma discharge is not obtained, and as a result, the function as a PDP panel may not be sufficiently exhibited.

For this reason, in order to precisely adjust the particle diameter of the powder glass to be used, and to prevent segregation of powder glass, etc., the adjustment method by various apparatuses was used as a mixing method and a dispersion method of a glass powder and an organic solvent. Further, the various barrier rib forming methods described above have been further improved, so that a method capable of forming a barrier rib of higher dimensional accuracy has been adopted. In addition, in order to damage the vacuum degree, sufficient consideration is also required in adsorption gas, moisture, etc. in the material which comprises a partition, under reduced pressure, and invention, such as heat processing of a partition material, and heat processing by specific gas atmosphere, was also performed.

However, despite various efforts as described above, when a partition is formed using glass paste by a facility that produces PDP largely, a sufficient vacuum state is not realized in the quality inspection for the assembled molded article, There was a case where the desired performance could not be achieved with the PDP. This problem has been a major obstacle in order to build a high-yield manufacturing state with high quality and to realize production in accordance with demand by stable production.

In view of such a situation, the inventors of the present invention provide a glass paste for use in a hermetic sealing structure such as a PDP, and in addition to various properties that have been requested so far, a glass paste having a high sealing strength property and a reliable sealing state, and The object of this invention is to provide a manufacturing method.

The glass paste of the present invention is a glass paste containing an inorganic oxide glass powder and an organic component, characterized in that the number of organic foreign matters having an external dimension present in the glass paste of 10 µm or more is 30/100 g or less.

In the glass paste of this invention, in order to form a more stable structure, the quantity of organic foreign material is 30 / 100g or less, More preferably, it is more preferable that it is 20 / 100g or less and 10 / 100g or less. And more preferably, less than 5 / 100g.

Herein, the organic foreign material is an organic compound composed of C (carbon), H (hydrogen), O (oxygen) as a main element, halogen elements such as {Cl (chlorine), S (sulfur), N (nitrogen), P (phosphorus), etc., may also contain trace metals such as magnesium and iron}, and the organic compound is characterized by covalent bonding of C atoms, and intentionally added to the glass paste. It means not.

The said organic foreign material is an apparatus, a tool, etc. which are normally used in the manufacturing process of a glass paste as a generation source, and are unavoidably mixed from a use jig | tool etc. in each step of a process in the middle of manufacturing. The type and amount of these organic foreign matters differ depending on which device, tool, etc. are used. Some examples of such organic foreign matters are as follows. For example, a part called a squeegee mounted on three rolls used for crushing agglomerates has a role of removing a glass paste treated with three rolls from a roll, but is worn over time by a glass powder or a filler powder. . And this wear powder becomes an organic foreign material. In addition, tools such as a spatula and a storage container used when handling the paste may cause organic foreign matter. Or in the manufacturing process of a glass powder, an organic foreign material may generate | occur | produce by the inner wall of a container etc. which hold temporarily stored glass temporarily with time.

The external dimension of an organic foreign material means the long axis diameter with respect to each organic foreign material particle, not an average particle diameter or a maximum or minimum particle diameter. This long axis diameter is the interval when the projection image of the particles is sandwiched by two parallel lines orthogonal to the short axis diameter, and the short axis diameter is the interval when the projection image is sandwiched by the two parallel lines to represent the minimum distance.

In addition, the inorganic oxide glass powder of the present invention is an inorganic oxide glass powder for mixing glass with organic components to form a glass paste, and the number of organic foreign substances having an external dimension of 10 µm or more in the inorganic oxide glass powder is 20/100 g or less. It features.

The number of organic foreign matters having an outer dimension of 10 µm or more in the inorganic oxide glass powder is preferably 20 or less in 100 g of the glass powder, so that the desired fluidity can be obtained after adjustment as a glass paste, and it is preferable because it realizes stable strength after firing. . In order to obtain higher firing strength, the number of organic foreign matters is preferably 13 / 100g or less, and more preferably 6 / 100g or less. And more preferably, it is 4 or less than 100g.

In addition, the method of manufacturing the glass paste of the present invention is a method of manufacturing a glass paste in which the inorganic oxide glass powder and the organic components are mixed and dispersed, wherein the inorganic oxide glass powder having the number of organic foreign matters of 20/100 g or less is mixed with the organic components. Dispersion treatment is characterized in that the number of organic foreign matters is 30 / 100g or less glass paste.

1 is a partial cross-sectional view showing the structure of a plasma display panel.

The glass paste of the present invention is a glass paste containing an inorganic oxide glass powder and an organic component, wherein the number of organic foreign substances having an external dimension of 10 µm or more in the glass paste is 30/100 g or less, It is preferable to have an external dimension larger than 10 times the average particle diameter of the inorganic oxide glass.

Here, the fact that the organic foreign matter other than the organic component has an external dimension larger than 10 times the average particle diameter of the inorganic oxide glass means that the external dimension of the organic foreign substance is 10 times or more with respect to the average particle diameter of the powder by the inorganic oxide glass. It means. The external dimension of the organic foreign material means the major axis diameter of the individual organic foreign material particles as described above.

In addition to the above structure, the glass paste of the present invention preferably contains an organic foreign material containing at least one component selected from polypropylene, polyethylene, polyamide, tetrafluoroethylene polymer, cellulose, and rayon.

Preferably, polypropylene (polymer of propylene C ₃ H ₆ Polypropylen (CH ₃ CH ₂ CH) _n ), polyethylene (Polyethylene (CH ₂ CH ₂ ) _n ), polyamide, tetrafluoroethylene CF ₂ CF ₂ or more components selected from the polymer of ₂ (Polytetrafluoroethylene (CF ₂ CF ₂ ) _n ), cellulose (Cellulose (C ₆ H ₁₀ O ₅ ) _n ), and rayon are contained in a mass percentage of 1% or more.

In addition to the above components, the organic foreign material may be acetate, acrylic, azlon, polyester, polystyrene, polytetrafluoroethylene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, manila hemp, flax, jute , Sisal, wool, cotton, silk, mohair, ramie, linen, vicugna, kapok, ginseng, poly (1-butene), poly (3-methyl-1butene), Poly (1-pentene), natural rubber, polyisoprene, polybutadiene, diene styrene copolymer, ethylene propylene copolymer, and polyurethane may contain 2% or more by mass percentage.

Moreover, it is preferable that the glass paste of this invention is 2.0 mm or less in external dimension in addition to said structure.

Here, the external dimension of an organic foreign material is the long axis diameter of each organic foreign material particle as mentioned above. Organic foreign matters having an external dimension of less than 10 μm are often difficult to detect and cannot be removed. However, organic foreign matters having an external dimension of 2.0 mm (2000 μm) or more are sufficiently removed by a classification operation or the like. Is possible.

In addition, in the glass paste of this invention, it is preferable that organic foreign material is a fibrous form, flaky form, or a bulk form in addition to said structure.

Here, the organic foreign matter does not necessarily need to be seen only in the form of fibrous, flaky, or bulky alternatively, and two or more or all of the above three forms may be in a mixed state. Among the above three forms, the problem of forming a particularly precise and fine array structure is an organic foreign matter having a fibrous or flake form, but in the case of a bulk, it is heated to a high temperature to cause foaming. have.

Moreover, it is preferable that the glass paste of this invention is 40-85 mass% and inorganic component 15-60 mass% of an inorganic oxide glass powder in addition to said structure.

The content ratio of the inorganic oxide glass powder and the organic component greatly affects the properties of the glass paste, such as viscosity, flow characteristics, and moldability, and is important for producing a hermetic sealing structure by a desired molding method. When the ratio of the inorganic oxide glass powder is less than 40% by mass, it is difficult to form a densified structure when firing the hermetic sealing structure. When the content of the inorganic oxide glass powder exceeds 85% by mass, the formability of the glass paste is different. It becomes difficult to adjust by conditions. Therefore, the mixing ratio of the inorganic oxide glass powder is preferably in the range of 40% by mass to 85% by mass. For example, when glass paste is used for the purpose of forming a fine arrangement such as PDP, this condition becomes more stringent, and the mixing ratio of the inorganic oxide glass powder is better to be in the range of 45% by mass to 70% by mass.

Moreover, when it contains more than 60 mass% about the content rate of an organic component, since the viscosity of a glass paste becomes small too much and also requires time for the degassing process at the time of baking from the dough of the glass paste after shaping | molding, 60 mass% It is better to do as follows. On the other hand, when the content ratio of the organic component is less than 15% by mass, the flowability of the glass paste becomes too small, so that the moldability of the glass paste is inhibited and it is difficult to form a structure having a fine shape or the like. And when the glass powder which has an average particle diameter of 20 micrometers or less is employ | adopted, since this tendency becomes more remarkable, the content rate of an organic component is preferably 18 mass% to 50 mass%, More preferably, 20 mass% It is better to set it to the range of 45 mass% at.

Moreover, it is preferable that the softening point of the glass paste of this invention is 620 degrees C or less in addition to said structure.

Here, the softening point is 620 ° C. or lower, which is a necessary condition in order to prevent obstacles in the parts constituting other hermetic structures such as glass substrates by firing of the glass paste. There may be a problem such as a decrease in function. Moreover, when it has a softening point higher than 620 degreeC, the rinse property at the time of baking may deteriorate. More preferably, the softening point is lower than 570 ° C. In addition, the softening point here is measured using the powder of a product particle diameter with respect to glass powder, and is measured using a macro type differential thermal analyzer (MacroDTA).

Moreover, it is preferable that the glass paste of this invention contains a crystallized glass powder and / or an inorganic crystalline powder in addition to said structure.

The crystallized glass powder is a powder made of glass ceramics, and the inorganic crystalline powder is a powder made of ceramics or the like.

Here, crystallized glass means that the crystal phase is precipitated in the glass phase by heat treatment or the like, and the inorganic crystal powder is a powder of only the crystal phase containing no glass. And even if it contains any powder, if the function required for a filler is satisfied, it will not interfere.

Moreover, it is preferable that the glass paste of this invention contains at least 1 mass% or more of any one of titania, alumina, zirconia, silica, magnesia, and mullite in a filler in addition to said structure.

Namely, among the above fillers, TiO ₂ (titanium oxide) called titania, Al ₂ O ₃ (aluminum oxide) called alumina, ZrO ₂ (zirconium oxide) called zirconia, SiO ₂ (silicon dioxide) called magnesia, and magnesia At least 1 mass% of MgO (magnesium oxide) and Al ₂ O ₃ -SiO ₂ -based compound (often referred to as 3Al ₂ O ₃ · 2SiO ₂ ) called mullite are contained.

Although a filler is added in order to realize the function mentioned above, what is especially preferable as a filler of the glass paste which comprises an airtight structure is what contains titania, alumina, zirconia, silica, magnesia, and mullite. Moreover, when forming a precise and fine arrangement structure by glass paste, it is preferable to use the filler containing zirconia and alumina. In the glass paste of the present invention, in addition to the above fillers, one or two kinds of fillers such as zircon, barium zirconate, cordierite, lead titanate, barium titanate, zinc oxide, iron oxide, silicon carbide, and uremanite The above may be added and a part thereof may be replaced with an inorganic pigment or the like as necessary. In addition, about the shape of a filler particle, it may be a crushed thing, or what was shape | molded to predetermined shape by processing, such as granulation, may be sufficient. That is, it is possible to appropriately select powder particles of a shape such as a spherical body, a polyhedron or a filamentous body. In addition, as a method of adjusting a filler, it is possible to use various grinding | pulverization and mixing apparatuses, such as a ball mill, as needed.

It is preferable to use the glass paste of this invention for airtight sealing of a display display element.

For example, the glass paste of the present invention can be applied to hermetic sealing of a CRT, that is, a representative display display element, that is, a face and a funnel of a CRT.

In particular, the glass paste of the present invention is suitable for a plasma display panel (PDP), an electron emitting device (FED), and a fluorescent display tube (VFD).

The glass paste of the present invention has a remarkable effect by being applied to applications that need to form very fine micron order structures such as partition walls of plasma displays.

In addition, the inorganic oxide glass powder of the present invention is an inorganic oxide glass powder which is mixed with an organic component to form a glass paste. The number of organic foreign substances having an external dimension of 10 µm or more in the inorganic oxide glass powder is 20/100 g. In addition to the following, it is preferable to contain a crushed product.

Since the crushed material is pulverized into a plurality of particles by any mechanical impact force, and the resulting surface is highly reactive, has an active state, and has a large surface area, it is rapidly eutectic with other surrounding crushed materials by heating to a high temperature state. It is preferable because it is easy.

Incidentally, the inclusion of the crushed product does not prevent the addition of the molded granules, granulated granules, gaseous phase or liquid powder. In order to realize the required performance, it is possible to add a predetermined amount having these properties.

In addition, the method of manufacturing the glass paste of the present invention is a method of manufacturing a glass paste in which the inorganic oxide glass powder and the organic components are mixed and dispersed, wherein the inorganic oxide glass powder having the number of organic foreign matters of 20/100 g or less is mixed with the organic components. In addition to the glass paste having the number of organic foreign matters of 30 / 100g or less by dispersing, the inorganic oxide glass powder is prepared by using an oxidation-resistant metal material for lining the storage container during grinding and preservation of the glass powder. It is desirable to obtain.

The oxidation-resistant metal material is not particularly limited as long as it can be used as a storage container in air at room temperature. For example, it can be used if it is comprised from stainless materials, such as SUS304, and the container which can ensure airtightness.

The mixing and dispersing treatment of the glass paste can be performed by a general kneading apparatus such as a roll mill, bead mill, ball mill, or the like.

The roll mill here is an agglomeration device for agglomerated particles represented by three rolls and an application device thereof, and the bead mill is a medium stirring mill having a bead driven as a medium. In addition, the ball mill includes not only a so-called narrow ball mill, which functions to disintegrate aggregate particles by rolling ceramic balls or the like in a container, but also includes a vibration ball mill, a medium planetary mill, and the like.

In addition, in the case where the desired characteristics can be realized unless the glass to the glass composition of the glass frit constituting the glass paste of the present invention is not particularly limited, containing PbO, for example, PbO-B ₂ O ₃ -SiO ₂ based Glass etc. can be employ | adopted. In addition, it is also possible to employ a BaO-ZnO-B ₂ O ₃ system, a ZnO-Bi ₂ O ₃ -B ₂ O ₃ system, or the like. Examples of the PbO-B ₂ O ₃ -SiO ₂ -based glass include, by mass percentage, PbO 50 to 75%, B ₂ O ₃ 0 to 20%, SiO ₂ 10 to 30%, Al ₂ O ₃ 0 to 6%, ZnO 1~10%, can be preferably used with CaO + MgO + SrO + BaO 0~10 %, SnO 2 + TiO 2 + ZrO composition of _20-6%. In addition, for example, BaO-ZnO-B ₂ O ₃ -based glass, the composition of BaO 5-40%, ZnO 20-55%, B ₂ O ₃ 15-50%, SiO ₂ 0-2% in molar percentage What has can be used preferably. _{Further, ZnO-Bi 2 O 3 -B} 2 O 3 based glass ZnO is 25~45%, in mass _{percentage, 15~35% Bi 2 O 3,} B 2 O 3 10~30%, SiO 2 0.5~8% , CaO + SrO + BaO What has a composition of 8 to 24% can be used preferably.

Moreover, it is possible to add Cu, Fe, Ni, Mn, Co, Cr, Ag, Au, Te etc. as a coloring component to the glass of the above composition system suitably within the range according to necessity. These additive components can be melted in glass as oxides, carbonates, metals, nitrates, sulfates, and the like to satisfy a predetermined function, and as specific amounts of addition, these additives are represented as oxides and have a content of 0.5% by mass or less. By doing so, the object can be achieved.

In addition, the glass paste of this invention can add a thermoplastic resin, a plasticizer, a solvent, etc. as needed as said organic component. Thermoplastic resin is a component which raises the intensity | strength after drying of a paste, and gives flexibility, It is preferable that the range of content is 0.1 to 20% by mass percentage. As the thermoplastic resin, polyvinyl butyral, polybutyl methacrylate, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose and the like can be used alone or in a predetermined compounding ratio. Moreover, a plasticizer is a component which can also provide flexibility while adjusting a drying rate, and it is preferable that the content is 0 to 10% by mass percentage. As the plasticizer, dioctyl phthalate, diisooctyl phthalate, butyl benzyl phthalate, dibutyl phthalate, dicapryl phthalate and the like can be used, and they can be used alone or in combination in a predetermined compounding ratio. In addition, a solvent is a component which is necessary in order to paste a material, and it is preferable that the content is 5 to 30% by mass percentage. Examples of the solvent include diethylene glycol monobutyl ether acetate (alias butyl carbitol acetate), terpineol (alias terpineol), 2,2,4-trimethyl-1,3-pentadiol monoisobutylate, and dibutyl phthalate. (Alias dibutyl phthalate), dioctyl phthalate (alias dioctyl phthalate), polyethyleneglycol, etc. can be used individually or in mixture at a predetermined compounding ratio.

In addition, when providing photosensitivity to the glass paste of this invention, at least 1 sort (s) of photosensitive monomer, photosensitive oligomer, photosensitive polymer, etc. are contained, and if necessary, a photoinitiator, a ultraviolet absorber, a sensitizer, a sensitizer, a polymerization inhibitor A predetermined function can also be provided by adding suitably.

In order to prepare a paste using the above-mentioned various materials and various components, each material, namely, glass powder, filler powder, resin, plasticizer, solvent, and the like, is prepared, and then each is weighed by an appropriate amount suitable for the compounding ratio. This is done by mixing. At this time, the order of mixing, the mixing device, and the like can be selected as necessary, and specially limited, if it can be managed so as not to cause agglomerates in the paste by inadvertently drying or inadequate mixing operation. It doesn't happen.

As described above, the glass paste of the present invention is a glass paste containing an inorganic oxide glass powder and an organic component, and since the number of organic foreign substances having an external dimension of 10 μm or more in the glass paste is 30/100 g or less, it is calcined. It is possible to prevent the sealing body from deteriorating the reliability of the hermetic sealing by the gas generated from the foreign matter at the time, and contribute to the improvement of the yield of the hermetic structure using the glass paste.

The organic foreign material has an external dimension larger than 10 times the average particle diameter of the inorganic oxide glass, or contains polypropylene, polyethylene, polyamide, Teflon, cellulose or rayon, or has an external dimension of 2.0 mm or less, Or by having any form of fibrous, flaky, or block shape, the organic foreign material in a glass paste can be easily distinguished from an organic component or an inorganic oxide glass, and an organic foreign material can also be easily specified also in quality inspection. Therefore, it is possible to detect and remove foreign matters at an early stage, and to promptly remove defective products in the process.

40-40 mass% of organic-inorganic oxide glass powder and 60-15 mass% of organic components employ | adopt the liquid separation ratio which satisfy | fills the optimal flow characteristic which is needed when manufacturing an airtight structure, and it is strong and high airtightness It is possible to easily manufacture a structure having a structure.

The softening point of 620 DEG C or lower does not reduce a large load on structural members such as plate glass constituting an airtight structure at the time of firing, and also delays deterioration over time such as equipment that performs heat treatment and the like, thereby reducing equipment cost. It becomes possible to suppress the periodic maintenance cost burden etc. concerning.

By incorporating the crystallized glass powder and / or the inorganic crystalline powder as a filler, a filler capable of realizing appropriate properties can be adopted according to the use of the glass paste or the like, thereby imparting desired performance to the hermetic structure after firing. have.

By containing at least 1% by mass or more of titania, alumina, zirconia, silica, magnesia and mullite in the filler, the glass paste can be provided with properties such as required strength, chemical resistance, shape retention, and the like required for the airtight structure. .

The glass paste of the present invention is used for hermetically sealing of display display elements, thereby greatly contributing not only to hermeticity but also to the shape of the sealed portion after sealing, thereby improving the properties such as strength, chemical durability, insulation and the like. Contribute to. Therefore, the high post-sealing characteristic which is not influenced by the magnitude | size of the airtight sealing body can be implement | achieved, and it becomes possible to respond easily to future enlargement of the airtight sealing body. For example, when used in a display device such as a PDP, the display area can be adapted to increase.

In particular, the glass paste of the present invention is applied to a plasma display panel, an electron-emitting device, and a fluorescent display tube, so that a stable sealing structure can be maintained for a long time and the performance required for the sealing structure can be exhibited for a long time.

The inorganic oxide glass powder of the present invention is an inorganic oxide glass powder which is mixed with an organic component to form a glass paste, and the number of organic foreign substances having an external dimension of 10 µm or more present in the inorganic oxide glass powder is 20/100 g or less. When used as a glass paste used for forming a microstructure, defects in the fired product obtained by firing the glass paste can be reduced, and the structural strength of the fired product can be stabilized.

Since the inorganic glass powder contains a crushed material, it is possible to easily adjust the inorganic glass powder having a desired particle size and particle size distribution by changing the crushing method or the crushing device, and the inorganic glass powder having an optimum particle size according to the use and performance. By selecting and using appropriately, it becomes possible to form the structure which implements high performance.

The manufacturing method of the glass paste of this invention is a manufacturing method of the glass paste which mix-disperses an inorganic oxide glass powder and an organic component, and mixes and disperse | distributes the inorganic oxide glass powder and the said organic component whose number of organic foreign substances is 30 / 100g or less Since it is to be processed, the stress characteristic inside the enclosure caused by external force applied to the sealing portion of the sealing structure after sealing is not likely to be concentrated locally, and the strength characteristic that is important in the quality inspection after assembling the product. Can be secured.

In addition, when the glass powder is crushed and preserved, the inorganic oxide glass powder is obtained by using an oxidation-resistant metal material in the interior of the storage container, so that foreign matters generated by abrasion of the inner wall of the container by the glass powder are not organic. It can be made of a metal material, and it becomes possible to suppress the gas which arises from organic foreign material in sealing operation etc. That is, by eliminating the generation source of organic foreign matter, the reliability of the glass paste can be improved and a stable product can be manufactured.

Hereinafter, the glass paste of this invention and its manufacturing method are demonstrated based on an Example.

Example 1

The glass paste which concerns on an Example is produced in the following procedure. First, the glass powder weighs various inorganic raw materials so as to have a predetermined composition of A to J shown in Table 1, and mixes a predetermined amount by a small rocking mixer for 4 hours to prepare a batch of raw material mixing. The raw material mixture batch is heated to a temperature of 1000 ° C. or higher in a platinum crucible or a quartz crucible to promote chemical reactions between the raw materials, to cause a vitrification reaction, to melt for at least 5 hours, and to be homogenized by using a homogenizing means such as stirring. It is made into a molten state. Subsequently, the molten glass flows out from the molten glass outlet provided in the bottom of this crucible, roll-molded into a film shape of about 1 mm, and the film glass which is still high temperature after shaping | molding is put into the container made from SUS which stocked water. It is thrown in, and coarsely pulverized by thermal shock in a state in which mixing of organic foreign matter is prevented. In order to remove the adhered moisture, the obtained coarse ground glass is dehydrated for 10 hours in a heating furnace to obtain a dry coarse ground glass. The obtained glass is temporarily stored in a container formed of stainless steel as the oxidation resistant metal material. And this dry coarse ground glass is thrown into the ball mill made from alumina, and it grind | pulverizes for 6 hours. About the obtained glass powder, the average particle size (D50) was measured using SALD-2000J by Shimadzu Corporation, and the softening point of glass was measured by a macro type differential thermal analyzer, and the corresponding temperature of an inflection point was measured. It was set as the softening point. Table 1 summarizes the results of the above series of measurements. In addition, when the measurement of the organic foreign material in the obtained glass powder was performed at this stage, it was zero pieces per 100 g of powders, and it had a state with sufficiently high cleanliness.

Moreover, about the filler, the thing of the compounding ratio shown in Table 2 was used. The average particle size of the alumina was measured in the same manner as described above. As a result, D50 = 2.1 µm, D50 = 0.6 µm for titania, D50 = 2.0 µm for α-quartz, D50 = 1.7 µm for zirconia, and magnesia. It was about D50 = 2.2 μm.

Next, the obtained glass powder was mixed in the ratio as shown in Table 3 as a compounding ratio in the final glass paste. Specifically, 7-21 mass% equivalent of the filler which suitably distributed alumina, titania, zirconia, etc. as 71-51 mass% as a glass powder, and a filler was first weighed and prepared, respectively. As the organic component, an appropriate amount of butylcarbitol acetate and terpineol is used as a solvent, and an appropriate amount of dioctylphthalate, butylbenzyl phthalate and dibutyl phthalate is used as a plasticizer, and sorbitan sesquioleate and glycerol monooleate are used as dispersants. An appropriate amount was adjusted, and 22-30 mass% was added at the compounding ratio with respect to a glass paste, and it mixed homogeneously with the homogenizer, and the said glass powder and the filler were added there. And the crude mixing paste of the obtained inorganic powder and organic component was previously adjusted finely by using a gap gauge, and kneading operation was performed using the three roll mill provided with the squeegee made from SUS304, and the glass paste was obtained. In addition, in the series of manufacturing processes described above, by employing a tool, an apparatus, a storage container, or the like, which avoids the intervening organic matter as much as possible, the manufacturing is realized under an environment that can eliminate the possibility of organic foreign matter being mixed during manufacturing.

In order to perform the evaluation which measures the number of organic foreign material in a sealed state using the obtained glass paste, it screen-prints on the surface of the alkali free plate glass which has a dimension of 200 mm x 200 mm x 1 mm using a screen printing apparatus. To form a laminated structure having a thickness of 1100 µm. After the structure was subjected to sandblasting, the surface of the formed partition (rib) structure was irradiated at a magnification of 200 times with a scanning electron microscope to measure the number of organic foreign matters per 100 g of the glass paste. As a result, as shown in Table 3, as for the glass paste of this invention, when the number of organic foreign substances was not detected at all, or even if it detected, it was confirmed that it was in the state which has a high cleanliness as it is small in 1-2 pieces / 100g. Moreover, when the major axis diameter of these organic foreign material was measured, the dimension was 31-68 micrometers. In the table, the notation ND means no detection. In addition, as a result of evaluating the structural strength such as cracking defects on the surface of the (rib) structure, defects caused by lowering the strength such as cracking or cracking were not confirmed, and it was confirmed that it had a high strength. there was.

Comparative Example 1

In the manufacturing process, the glass paste similar to Example 1 was produced in the same procedure as Example 1, without any special measures against organic foreign matter. That is, it produced without the measures, such as a container and a tool which hold | maintain glass powder, and the thing used as a generation source of organic foreign materials, such as a tool and squeegee used in a roll mill, etc. And the same evaluation was performed using this glass paste, and the result as shown in Table 4 was obtained. That is, it turned out that the glass paste of the comparative example 1 is 31-110 piece / 100g of organic foreign material, and it is the quality which is difficult to provide for actual use.

Example 2

Next, the leakage property after forming a sealing structure using the glass paste of an Example was evaluated in the following procedures.

First, the glass powder, the filler, and the organic component were prepared, the weighing and the combination were performed in the same procedure as Example 1, and the glass paste of the samples No. 1-10 of Example 1 was produced. Subsequently, screen printing is used for the plate glass (dimensions 10x10x0.7mm) for PDP which prepared these glass pastes beforehand, and the dimension of width 100micrometer and height 100micrometer along the edge on the one side of the transmissive surface of plate glass was measured. In order to form the structure which shows the letter-shaped external appearance so that it might become the printing cross section similar to the partition wall which has, the multiple layer printing was performed several times. Subsequently, the PDP plate glass is plasticized in a state where the printed sample surface is faced upwards, and a separate PDP plate glass having the same size is mounted so as to sandwich a structure made of a glass paste formed by printing. The heating firing was performed as it is performed. The test fired structure thus obtained was subjected to a gross leak test and a fine leak test using 400 samples (40 samples were prepared for each paste of Sample Nos. 1 to 10). . As a result, when the glass paste of the Example was used, the leak was not confirmed also in any of the gross leak test and the fine leak test, and it turned out that it is the quality which a problem does not produce.

Comparative Example 2

On the other hand, 400 specimens of a test fired structure were produced by the same preparation procedure as in Example 2 using the glass pastes of Sample Nos. 11 to 20 as Comparative Examples. Using this test fired structure, a gross leak test and a fine leak test were performed in the same manner as in Example 2. As a result, in the gross leak test, leak was confirmed to 6 out of 400 samples. Moreover, in the fine leak test performed after the gross leak, it turned out that the leak is confirmed by three of 400 samples. As a result of the cause trace investigation by the microscope with respect to the leak generating sample, traces of organic foreign matter and deformation of the partition wall due to foaming of the organic foreign matter were confirmed in 8 samples of the 9 leaked samples. In addition, it was confirmed that the remaining one sample was not caused by organic foreign matter, but was caused by cracks caused by mishandling during firing after printing. And by evaluating such Example 2 and the comparative example 2, it turns out that the airtight structure created by the glass paste (sample No. 1-10) of an Example has the grade which can fully endure various leak tests. It became.

Claims (15)

A glass paste containing an inorganic oxide glass powder and an organic component, wherein the number of organic foreign matters having an external dimension present in the glass paste of 10 µm or more is 30/100 g or less. The glass paste according to claim 1, wherein the organic foreign material has an outer dimension of at least 10 times the average particle diameter of the inorganic oxide glass. The glass paste according to claim 1, wherein the organic foreign material contains at least one component selected from polypropylene, polyethylene, polyamide, tetrafluoroethylene polymer, cellulose, and rayon. The glass paste according to claim 1, wherein an external dimension of the organic foreign material is 2.0 mm or less. The glass paste according to claim 1, wherein the organic foreign material is in the form of fibrous, flaky, or bulky forms. The glass paste according to claim 1, wherein the inorganic oxide glass powder is 40 to 85% by mass and the organic component is 15 to 60% by mass. The glass paste according to claim 6, wherein the softening point is 620 ° C. or less. The glass paste according to claim 6, wherein the glass paste contains crystallized glass powder and / or inorganic crystalline powder as a filler. The glass paste according to claim 8, wherein the filler contains at least 1% by mass of any one component selected from titania, alumina, zirconia, silica, magnesia and mullite. The glass paste according to claim 1, which is used for hermetic sealing of a display display element. The glass paste according to claim 10, wherein the display display element is any one of a plasma display panel, an electron emitting element, and a fluorescent display tube. An inorganic oxide glass powder which is mixed with an organic component to form a glass paste, wherein an inorganic oxide glass powder having an outer dimension of 10 µm or more present in the inorganic oxide glass powder has 20/100 g or less. The inorganic oxide glass powder according to claim 12, wherein the inorganic glass powder contains a crushed product. A method of manufacturing a glass paste for mixing and dispersing an inorganic oxide glass powder and an organic component, the method comprising mixing and dispersing an inorganic oxide glass powder having an organic particle number of 20/100 g or less and the organic component therein to obtain 30 organic impurities. A method for producing a glass paste, wherein the glass paste is 100 g or less. The method for producing a glass paste according to claim 14, wherein an inorganic oxide glass powder is obtained by using an oxidizing metal material in the interior of the storage container during the crushing and preservation of the glass powder.

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