JP6646905B2 - Method for producing glass frit covered with collection of fine particles of metal or alloy, and method for producing molded body made of glass frit having properties of metal or alloy - Google Patents

Description

The invention covers the glass frit with a collection of metal or alloy particles. Further, a method of manufacturing a formed body made of glass frit having the properties of a metal or an alloy by a conventional manufacturing method of forming a formed body using the collection of glass frit. The glass frit is a powdered glass produced by melting the prepared glass raw material to vitrify and pulverizing the raw material by water quenching or roll quenching.

The prior art closest to the present invention is a technique for imparting electrical conductivity or thermal conductivity to glass. For example, Patent Literature 1 proposes a method in which carbon nanotubes are mixed with a glass raw material, and the glass raw material is melted to produce a conductive glass in which the carbon nanotubes are dispersed. Further, Patent Document 2 discloses that a SiC powder, which is a thermally conductive filler, is heated to 1500 ° C. or more to form a SiO ₂ film, and the thus-treated SiC powder is mixed with a powdered glass. There has been proposed a method of producing a thermally conductive glass by melting a powdered glass by heating to about ° C.

However, the carbon nanotube described in Patent Document 1 has a volume resistivity of 4.4 × 10 ⁻⁴ −1.2 × 10 ⁻¹ Ωcm, which is smaller than the volume resistivity of copper of 1.68 × 10 ⁻⁶ Ωcm. High resistivity by two digits or more. Further, even when the carbon nanotubes are dispersed in glass, the carbon nanotubes are not directly bonded to each other because the carbon nanotubes are bonded via the non-conductive glass. Therefore, the carbon nanotube does not form a continuous conductive path in the molded body. As a result, an increase in the conductivity of the molded body is restricted. Further, carbon nanotubes are extremely expensive materials compared to metal powder, and the higher the compounding ratio of carbon nanotubes in order to increase conductivity, the more expensive the molded body becomes. Therefore, in the prior art, there is a limit in increasing the conductivity of the glass molded body.
Further, the thermally conductive filler in the patent document 2, the thermal conductivity of SiC has a large value of 200 W / mK, the thermal conductivity of SiO ₂ is small and 1.38 W / mK, the SiO ₂ film is formed The thermal conductivity of the deposited SiC is significantly reduced. On the other hand, even if SiC is directly dispersed in glass as a thermally conductive filler, SiC is not directly bonded to each other because SiC is bonded via non-thermally conductive glass. Therefore, SiC does not form a continuous heat conduction path in the compact. As a result, an increase in the thermal conductivity of the molded body is restricted. In addition, SiC powder is a very expensive material as compared with metal powder, and the higher the compounding ratio of SiC to increase the thermal conductivity, the more expensive the compact becomes. Therefore, in the prior art, there is a limit in increasing the thermal conductivity of the glass molded body.

On the other hand, glass frit is a cheaper material that is lighter and does not corrode than metal. In addition, if a molding machine or a mold is filled with a collection of glass frit and the softened glass frit is joined together, molded bodies of various shapes can be molded at low cost. Therefore, if the glass frit compact has various metal properties, the metal parts can be replaced with transparent and lightweight glass parts.
That is, a glass frit is covered with a substance made of a metal or an alloy, and a collection of glass frit in which the glass frit is joined to each other by a metal bond of a substance made of a metal or an alloy. When a formed body is formed using the collection of glass frit, a glass frit formed body can be formed by bonding the softened glass frit with a metal or alloy material. Furthermore, if the metal material forms a continuous path in the formed body, the formed body has not only conductivity and heat conductivity but also various properties such as magnetism, etc., corresponding to the metal constituting the metal material. In addition, if a continuous path of a substance made of an alloy is formed in the molded body, the molded body has a wider alloy property than the metal property depending on the combination with various metals and the mixing ratio of the metal. As a result, a transparent and lightweight molded body having properties that cannot be considered conventionally can be manufactured at low cost. Therefore, first, the glass frit is covered with a substance made of a metal or an alloy, second, without the metal, the substance made of the alloy is metal-bonded to each other, and third, there is no metal-bonded metal. There is a strong demand for the realization of these three techniques, in which a substance made of an alloy forms a continuous path in a compact.

JP 2008-024540 A JP 2012-111665 A

The glass frit is covered with a material made of a metal or an alloy, and a metal frit of the material made of the metal or the alloy is used to produce a group of glass frit in which the glass frit is joined to each other. Filling the collection of this glass frit into a molding machine or a mold, when softening the glass frit to produce a molded body, a metal or an alloy material, the first metal bonding the softened glass frit, Second, if a continuous path is formed in the compact, a compact having metal or alloy properties can be manufactured at low cost. In other words, since the properties of a metal or alloy are based on the movement of free electrons, if a substance made of a metal or alloy forms a continuous path in a compact, the free electrons move freely in the compact, and the compact becomes a metal or metal. Shows the properties of the alloy.
Furthermore, the raw material for forming the metal or alloy material covering the glass frit is inexpensive. Collected glass frit can be mass-produced at low production cost.
Accordingly, a first object of the present invention is to cover a glass frit with a substance made of a metal or an alloy. The second problem is that such a glass frit can be processed in a large amount by a very simple process using inexpensive raw materials. A third problem is that when a molded body is manufactured using a collection of glass frit that has been subjected to such a treatment, a substance made of a metal or an alloy firstly bonds the softened glass frit to each other, and secondly, It is to form a continuous path in a molded article. The present invention is to solve these three problems.

The manufacturing method of covering the glass frit according to the present invention with a collection of metal fine particles and manufacturing the glass frit collection in which the glass frits are bonded to each other by metal bonding of the metal fine particles includes a first method of depositing metal by thermal decomposition. the nature of the metal compound thermal decomposition temperature combines a lower second nature than the softening point of the glass frit, dispersed in an alcohol, the said metal compound to create the alcohol dispersion was uniformly dispersed in the alcohol One step, the first property of dissolving or mixing with the alcohol, the second property having a higher viscosity than the alcohol, and a boiling point higher than the boiling point of the alcohol, and lower than the thermal decomposition temperature of the metal compound. the organic compound having both a third property, were mixed in the alcohol dispersion, that the organic compound is dissolved or mixed in the alcohol, A second step of serial metal compound and the organic compound to create a liquid mixture uniformly mixed in the alcohol, the collection of glass frit immersed in the mixed solution, the mixed solution on the surface of the glass frit A third step of uniformly adhering the mixed solution with a thickness according to the viscosity, and thereafter taking out the glass frit collection from the mixed solution, and bringing the glass frit collection to a temperature at which the metal compound is thermally decomposed. heated, is first vaporized the alcohol, then vaporizing the organic compound on the surface of the glass frit, it causes precipitation of a collection of fine crystals of the metal compound, further, the metal compound is thermally decomposed, At a temperature lower than the softening point of the glass frit, the thermal decomposition of the metal compound is completed, and on the surface of the glass frit, according to the size of the fine crystals of the metal compound. Collection of granular metal particles are deposited, the metallized bond sites where the metal fine particles are in contact with each other, with collection of the metal bonded metal particles to cover the glass frit, the glass frit covered the metal fine particles and metal binding, 15 by metal bonding of the metal particles, and a fourth step of collection of the glass frit the glass frit to each other bound is manufactured, the collection of the glass frit, the anneal point of the glass frit The fifth step of slowly cooling to room temperature after standing for more than one minute is a method of continuously performing these five steps. A method in which a glass frit is covered with a collection of metal fine particles, and is a manufacturing method for manufacturing a collection of said glass frit frit each other are coupled.

That is, according to the present manufacturing method, the glass frit was covered with the collection of the metal fine particles and the glass frits were bonded to each other by the metal bonding of the metal fine particles only by continuously performing the following five simple steps. A collection of glass frits can be produced in large quantities at low production costs.
The first step is a process of merely dispersing the metal compound in alcohol. The second step is a process of merely mixing an organic compound with the alcohol dispersion. The third step is a process in which a group of glass frit is immersed in the mixed solution, and the group of glass frit is simply taken out. The fourth step is a process in which a group of glass frit is simply heat-treated at a temperature lower than the softening point of the glass frit. The fifth step is a process in which a group of glass frit is left at the annealing point of the glass frit for 15 minutes or more, and then gradually cooled to room temperature. Since both are extremely simple treatments, a mass of glass frit covered with a mass of metal fine particles and having a residual strain caused by heat treatment released can be mass-produced at low production cost.
Further, a metal compound, an alcohol, and an organic compound that precipitate a metal by thermal decomposition are all general-purpose industrial chemicals, and glass frit is a general-purpose industrial material. Further, a metal compound that deposits a metal by thermal decomposition deposits a metal composed of various metal elements. Therefore, a collection of glass frit having a new structure covered with metal fine particles can be mass-produced at a low production cost only by performing an extremely simple treatment using an inexpensive industrial chemical as a raw material. For this reason, according to the present manufacturing method, the first and second problems described in the sixth paragraph are simultaneously solved, and a group of glass frit is manufactured.
That is, according to the present production method, first, the metal compound is uniformly dispersed in the alcohol dispersion. Second, since the organic compound has the property of being dissolved or miscible in alcohol, the metal compound is uniformly dispersed in the mixture. Third, since the organic compound has a higher viscosity than the alcohol, the mixture has a viscosity corresponding to the mixing ratio of the organic compound, and when a group of glass frit is immersed in this mixture, the thickness of the glass frit depends on the viscosity. The mixture adheres. As a result, the metal compound which precipitates the metal by thermal decomposition uniformly adheres to the glass frit.
Thereafter, the collection of glass frit is heat treated. First, the alcohol evaporates, and then the organic compound evaporates. As a result, a collection of fine crystals of the metal compound precipitates on the surface of the glass frit. When the temperature is further increased, the thermal decomposition of the metal compound forming the fine crystals starts, and at a temperature lower than the softening point of the glass frit, the thermal decomposition of the metal compound is completed, and the granular metal corresponding to the size of the fine crystals is formed on the glass frit. Fine particles collect and precipitate. At this time, the metal precipitated by the thermal decomposition of the metal compound is in an active state having no impurities, so that the metal fine particles are metal-bonded at portions where they are in contact with each other, and the collection of metal-bonded metal fine particles covers the glass frit, The glass frit is bonded to each other by the metal bonding of the metal fine particles covering the frit, and a collection of glass frit is manufactured.
The softening point means a lower limit temperature of hot working of the glass frit. Therefore, since the glass frit is processed at a temperature lower than the softening point of the glass frit, the glass frit is not subjected to hot working, and is left at the annealing point of the glass frit for at least 15 minutes to release the strain, and then the room temperature is reduced to room temperature. When gradually cooled, the glass frit returns to the state before the treatment. For this reason, the glass frit after the treatment does not change with time, and can be used as a raw material of a molded body when necessary.
That is, by dispersing the metal compound, which is a raw material of the metal fine particles, in alcohol, the metal compound is liquefied, whereby the mixed liquid of the alcohol dispersion liquid and the organic compound adheres to the glass frit. When the temperature of the glass frit is increased to vaporize the alcohol and the organic compound, the fine crystal of the metal compound is deposited on the surface of the glass frit and covers the glass frit. If the temperature is further increased to thermally decompose the metal compound composed of a collection of fine crystals, metal fine particles corresponding to the size of the fine crystals collect and cover the surface of the glass frit. At this time, since the metal fine particles are metal-bonded to each other at the contact portion, the glass frit is bonded to each other by the metal bonding of the metal fine particles covering the glass frit, and a group of glass frit is manufactured. As described above, in the present production method, first, the metal compound as a raw material of the metal fine particles is liquefied, and the liquefied metal compound is attached to the glass frit. It is characterized in that it precipitates and the fine crystals are thermally decomposed to deposit metal fine particles. As a result, an effect of producing a collection of glass frit in which the glass frit is bonded to each other by the metal bonding of the metal fine particles covering the glass frit is provided.
Further, a metal compound, an alcohol, and an organic compound that precipitate a metal by thermal decomposition are all general-purpose industrial chemicals. A mixture can be obtained simply by mixing such industrial chemicals. In addition, simply raising the temperature of the glass frit immersed in the mixed solution to a temperature lower than the softening point of the glass frit causes the metal compound to thermally decompose, and the glass frit is bonded to each other by metal bonding of metal fine particles covering the glass frit. A mass of bonded glass frit can be produced in large quantities. Therefore, by using inexpensive industrial chemicals as raw materials and carrying out extremely simple processing, a large amount of glass frit can be produced at low production cost. For this reason, according to the present manufacturing method, the first and second problems described in the sixth paragraph are simultaneously solved, and a group of glass frit is manufactured.

Manufacturing method for manufacturing a collection of the glass frit the glass frit to each other are joined by metallic bonds of the fine metal particles described in paragraph 7, the metal compound described 7 paragraph, oxygen ions constituting the carboxyl group of the carboxylic acid A carboxylic acid metal compound having both the first characteristic of covalently bonding to a metal ion and the second characteristic of the carboxylic acid comprising a saturated fatty acid, wherein the organic compound described in paragraph 7 includes carboxylic acid esters, glycols Or any one of organic compounds belonging to any of glycol ethers, wherein the glass frit described in paragraph 7 is a glass frit having a softening point higher than a temperature at which the metal carboxylate is thermally decomposed, and 5 described in paragraph 7 using an acid metal compound, the one kind of organic compound, and the glass frit. One is the production of a collection of the glass frit the glass frit with each other and bonding process with a metal bond of the metal fine particles according to the production method carried out continuously, the glass frit to each other are joined by metallic bonds of the fine metal particles described in paragraph 7 This is a manufacturing method for manufacturing a collection of the glass frit.

In other words, the metal carboxylate compound having the two characteristics completes the thermal decomposition at a temperature of 290 to 430 ° C. in the air atmosphere and precipitates the metal. Accordingly, a collection of granular metal fine particles having a size of 40 to 60 nm precipitates on the surface of the glass frit having a softening point higher than the thermal decomposition temperature of the metal carboxylate. At this time, since the precipitated metal fine particles are in an active state having no impurities, the granular metal fine particles are metal-bonded at a portion where they contact each other, and the glass frit is bonded to each other by the metal bond of the metal fine particles covering the glass frit. A collection of glass frit is produced. After that, if the glass frit is left at the annealing point for at least 15 minutes and then gradually cooled to room temperature, the strain remaining on the glass frit due to the heat treatment is released.
When the temperature of the metal fine particles is raised to a temperature higher than the temperature at which the metal fine particles are precipitated, the adjacent metal fine particles are taken in, grown and coarsened, and the higher the temperature is raised, the larger the metal fine particles become. Become Therefore, when manufacturing a molded body, the glass frit is heated to a temperature exceeding the softening point, so that the metal fine particles are coarsened. When the metal fine particles are excessively coarsened, the softened glass frit protrudes outside the coarsened metal fine particles, and the softened glass frits are directly joined to each other, so that the collection of the metal fine particles does not form a continuous path in the molded body. In some cases, the compact does not show the properties of metal. On the other hand, if the glass frit is covered with a larger collection of metal fine particles, such a situation can be avoided, but the weight reduction characteristic of glass is lost. Therefore, it is desirable to use a glass frit having a softening point higher than 290-430 ° C., which is the thermal decomposition temperature of the metal carboxylate, and close to this thermal decomposition temperature.
That is, among the ions constituting the metal carboxylate compound, the first feature in which the oxygen ion constituting the carboxyl group of the carboxylic acid covalently bonds to the metal ion, and the second feature in which the carboxylic acid is composed of a saturated fatty acid. Where the metal ions are the largest. Therefore, the distance between the oxygen ion and the metal ion constituting the carboxyl group is longer than the distance between the other ions. When a metal carboxylate compound having such a molecular structure is heat-treated in an air atmosphere, when the boiling point of the carboxylic acid is exceeded, the bond between the oxygen ion and the metal ion constituting the carboxyl group is first broken, and the carboxylic acid and the carboxylic acid are separated. Separate from metal. Further, when the carboxylic acid is composed of a saturated fatty acid, the carboxylic acid vaporizes by depriving the heat of vaporization, and the vaporization of the carboxylic acid proceeds in accordance with the molecular weight of the carboxylic acid. When the vaporization is completed, a metal is precipitated. Examples of such a metal carboxylate compound include a metal octylate compound, a metal laurate compound, and a metal stearate compound. Octyl acid has a boiling point of 228 ° C., lauric acid has a boiling point of 296 ° C., and stearic acid has a boiling point of 361 ° C. Therefore, these metal carboxylate compounds are completely decomposed in the air atmosphere at 290-430 ° C.
The carboxylic acid metal compound composed of an unsaturated fatty acid has a carbon atom in excess of a hydrogen atom as compared with the carboxylic acid metal compound composed of a saturated fatty acid. Therefore, a metal oxide such as copper oleate is thermally decomposed. In the case of (1), cuprous oxide Cu ₂ O and cupric oxide CuO are simultaneously precipitated, and a processing cost for reducing cuprous oxide Cu ₂ O and cupric oxide CuO to copper is required. In particular, cuprous oxide Cu ₂ O needs to be once oxidized to cupric oxide CuO in an atmosphere richer in oxygen than the air atmosphere, and further reduced to copper in a reducing atmosphere, which increases the processing cost.
Furthermore, the above-mentioned metal carboxylate compounds are inexpensive industrial chemicals that can be easily synthesized. That is, when a carboxylic acid, which is the most common organic acid, is reacted with a strong alkali, an alkali metal carboxylate compound is generated.When the alkali metal carboxylate is reacted with an inorganic metal compound, a carboxylic acid composed of various metals is obtained. A metal compound is synthesized. Therefore, carboxylic acid metal compounds are the cheapest organometallic compounds.
In the carboxylic acid esters, glycols or glycol ethers, the first property of dissolving or mixing with alcohol, the second property of higher viscosity than alcohol, and the boiling point higher than that of alcohol, carboxylic acid There is an organic compound having the third property lower than the thermal decomposition temperature of the metal compound. Such organic compounds are general-purpose industrial chemicals.
In addition, even if it is the powder glass of low temperature sealing which has the lowest calcination temperature among glass frit, softening point exceeds 300 degreeC. Therefore, many glass frits have a softening point higher than the thermal decomposition temperature of the metal carboxylate.
Therefore, when the organic compound is mixed with the alcohol dispersion of the metal carboxylate, the metal carboxylate and the organic compound are uniformly mixed in a molecular state. When a group of glass frit is immersed in the mixed solution, the mixed solution adheres to the surface of the glass frit with a thickness corresponding to the viscosity. Thereafter, the collection of glass frit is heat-treated in an air atmosphere. First, the alcohol is vaporized, then the organic compound is vaporized, and a collection of fine crystals of the metal carboxylate is deposited on the surface of the glass frit. When the temperature is further increased, the thermal decomposition of the metal carboxylate compound forming the fine crystals starts, and the thermal decomposition of the metal carboxylate compound is completed at a temperature of 290 to 430 ° C. lower than the softening point of the glass frit. The corresponding fine metal particles of 40 to 60 nm collect and precipitate on the surface of the glass frit. At this time, since the metal precipitated by the thermal decomposition is in an active state having no impurities, the granular metal fine particles are metal-bonded at a portion where they contact each other, and the collection of the metal-bonded metal fine particles covers the glass frit, and A collection of glass frits in which the glass frits are joined together by metal bonding is produced.
As described above, using a metal carboxylate compound that is an inexpensive industrial chemical, an organic compound that is a general industrial chemical, and a glass frit that is a general industrial material as raw materials, A mixture of a metal carboxylate compound and an organic compound is adhered to the glass frit, and only heat treatment of the glass frit is performed at a temperature of 290 to 430 ° C. in the air atmosphere. A mass of glass frit to which is coupled is produced in large quantities. For this reason, the present manufacturing method simultaneously solves the first and second problems described in the sixth paragraph, and makes the raw material for manufacturing a collection of glass frit in which the glass frit is bonded to each other by the metal bonding of the metal fine particles described above. Become.

The manufacturing method for manufacturing a molded body made of glass frit having metal properties by using a collection of glass frit in which glass frit is bonded by metal bonding of metal fine particles manufactured according to the manufacturing method described in paragraph 7 is as follows. to produce a collection of the glass frit the glass frit each other are bonded by a metal bond of the metal fine particles according to the production method carried out continuously five steps described in the preceding paragraph, filling the collection of the glass frit into a molding machine or a mold Then, the glass frit is softened and stressed and deformed by the molding machine or the mold, and the metal fine particles covering the deformed glass frit are metal-bonded, whereby the deformed glass frit is bonded to each other. A molded body comprising a collection of the deformed glass frit in the molding machine or the mold; Is formed, and the molded body is left at the annealing point of the glass frit for 15 minutes or more, and then gradually cooled to room temperature, thereby producing a molded body made of glass frit having metal properties.

That is, according to the present manufacturing method, the five processes described in the seventh paragraph are continuously performed on the glass frit group, and the glass frit group is filled into a molding machine or a mold to soften the glass frit. When manufacturing a molded body, the softened glass frit is bonded to each other by a metal bond of metal fine particles, and the metal-bonded metal fine particles form a continuous path in the molded body. The body is manufactured. Therefore, molded articles of glass having various metal properties, lightweight and non-corrosive are manufactured by a conventional molding method, and metal parts can be replaced with glass parts.
That is, since the size of the glass frit is micron-sized and is two orders of magnitude larger than the metal fine particles, the collection of metal-bonded metal fine particles covering the entire glass frit is subjected to stress from the softened glass frit by a molding machine or a mold. When the metal frit is deformed, the collection of metal-bonded metal fine particles follows and deforms similarly, and still covers the deformed glass frit. Further, the deformed glass frit is bonded to each other by the metal bonding of the metal fine particles. For this reason, a compact having metal properties can be produced at low cost by the conventional method for producing a compact.
That is, when the collection of glass frits is subjected to the five treatments described in the seventh paragraph, a collection of glass frits in which the glass frits are bonded to each other by metal bonding of metal fine particles covering the glass frit is manufactured. The collection of the glass frit is filled in a molding machine or a mold, and the softened glass frit is bonded by metal bonding of metal fine particles to form a formed body. At this time, since the metal fine particles covering the glass frit are generated at a temperature lower than the softening point of the glass frit, when the temperature is raised to a temperature exceeding the softening point, the metal fine particles take in adjacent metal fine particles and grow. Coarse. Since the coarse metal particles are in an active state having no impurities, the metal fine particles are metal-bonded to each other at a contact portion. For this reason, the aggregate of coarse metal particles still covers the entire softened glass frit. Further, when the softened glass frit is deformed by receiving a stress from a molding machine or a mold, the collection of metal-bound metal fine particles is also deformed following the deformation of the glass frit, and still covers the deformed glass frit. In addition, the metal fine particles are metal-bonded to each other, so that the deformed glass frit is bonded to each other, and a collection of metal-bonded metal fine particles forms a continuous path in the molded body. Thereafter, the glass frit is left at the annealing point for at least 15 minutes and then gradually cooled to room temperature, and the strain remaining on the glass frit is released by the heat treatment at the time of molding to form a molded article made of glass frit. Further, if the metal fine particles are composed of various metal elements, the molded body has various metal properties, and the molded body that is lightweight and does not corrode replaces metal parts with glass parts.
As described above, the present manufacturing method solves the third problem described in the sixth paragraph, and a molded body having metal properties is manufactured using the collection of glass frit described in the seventh paragraph.

The glass frit according to the present invention covered with a collection of alloy particles, a method of manufacturing a collection of the glass frit the glass frit to each other are joined by metallic bonds of the alloy particles differs pyrolyzed at the same temperature A plurality of metal compounds having both a first property of simultaneously depositing metals and a second property having a thermal decomposition temperature lower than the softening point of the glass frit are dispersed in alcohol, and the plurality of metal compounds are mixed with the alcohol. The first step of preparing an alcohol dispersion uniformly dispersed in, the first property of being dissolved or mixed with the alcohol, the second property having a higher viscosity than the alcohol, the boiling point is higher than the boiling point of the alcohol And mixing an organic compound having a third property lower than the temperature at which the plurality of types of metal compounds are simultaneously thermally decomposed into the alcohol dispersion. And, by organic compound is dissolved or miscible in said alcohol, a second step of the plurality kinds of metal compound and the organic compound to create a liquid mixture uniformly mixed in the alcohol, the glass frit was immersed collect in the mixed solution, uniformly attached to the mixture at a thickness corresponding to the viscosity of the mixed solution on the surface of the glass frit, after this, the take out a collection of the glass frit from the mixture three and step, said collection of said glass frit plurality of metal compounds is heated to thermally decompose the temperature at the same time, to first vaporize the alcohol, then vaporizing the organic compound on the surface of the glass frit causes precipitation a collection of fine crystals of the plurality of types of metal compounds, further, the plurality of types of metal compound is thermally decomposed at the same time, soft of the glass frit Lower than the point temperature, complete pyrolysis of said plurality several metal compounds simultaneously, to the surface of the glass frit, a collection of the plurality of types of granular alloy particles according to the size of the fine crystals of metal compounds precipitated and, and metal binding at sites alloy particles with each other are in contact with each other, with collection of alloy microparticles the metal bond cover the glass frit, the glass frit covered the alloy particles and metal binding, the alloy particles the metal bond, and a fourth step of collection of the glass frit the glass frit to each other bound is manufactured, to room temperature to a collection of the glass frit after standing for more than 15 minutes to anneal point of the glass frit annealing A method of continuously performing these five steps is to cover the glass frit with a collection of alloy fine particles, Said glass frit together with a metal bond of the child is a manufacturing process for producing a collection of the glass frit bonded.

That is, according to this production method, first, a plurality of types of metal compounds are uniformly dispersed in the alcohol dispersion. Second, since the organic compound has the property of being dissolved or miscible in alcohol, a plurality of types of metal compounds are uniformly dispersed in the mixture. Third, since the organic compound has a higher viscosity than the alcohol, the mixed liquid has a viscosity corresponding to the mixing ratio of the organic compound, and when a group of glass frit is immersed in the mixed liquid, the surface of the glass frit corresponds to the viscosity. The mixed solution adheres with the thickness. As a result, a plurality of types of metal compounds that thermally decompose at the same temperature and simultaneously deposit different metals adhere to the surface of the glass frit.
Thereafter, the glass frit is heat-treated. First, the alcohol evaporates, and then the organic compound evaporates. As a result, a collection of fine crystals of a plurality of types of metal compounds is deposited on the surface of the glass frit. When the temperature is further increased, the thermal decomposition of multiple types of metal compounds forming fine crystals starts, and at a temperature lower than the softening point of the glass frit, the thermal decomposition of multiple types of metal compounds is completed at the same time, depending on the size of the fine crystals. The granular alloy fine particles gather and precipitate on the surface of the glass frit. In other words, when multiple types of metal compounds forming fine crystals are thermally decomposed simultaneously, multiple types of metals are simultaneously precipitated, and the multiple types of metals are in an active state having no impurities. An alloy having an appropriate composition is precipitated as granular fine particles corresponding to the size of the fine crystals. In addition, the alloy fine particles do not have impurities, and are metal-bonded at sites where they are in contact with each other. Is manufactured.
The softening point means a lower limit temperature of hot working of the glass frit. Therefore, since the glass frit is processed at a temperature lower than the softening point of the glass frit, the glass frit is not subjected to hot working, and is left at the annealing point of the glass frit for at least 15 minutes to release the strain, and then the room temperature is reduced to room temperature. When gradually cooled, the glass frit returns to the state before the treatment. For this reason, the glass frit after the treatment does not change with time, and can be used as a raw material of a molded body when necessary.
In other words, by dispersing a plurality of types of metal compounds, which are the raw materials of the alloy fine particles, into alcohol, the plurality of types of metal compounds are liquefied, whereby a mixture of the alcohol dispersion and the organic compound adheres to the glass frit. I do. When the temperature of the glass frit is increased to vaporize the alcohol and the organic compound, a collection of fine crystals of a plurality of types of metal compounds is deposited on the surface of the glass frit and covers the glass frit. When the temperature is further increased to thermally decompose a plurality of metal compounds composed of fine crystals, granular alloy fine particles according to the size of the fine crystals gather to cover the surface of the glass frit. At this time, since the granular alloy fine particles are metal-bonded to each other at the contact portion, a collection of glass frit in which the glass frits are bonded to each other by the metal bond of the alloy fine particles covering the glass frit is produced. As described above, the present manufacturing method firstly liquefies a plurality of types of metal compounds that are the raw materials of the alloy fine particles, adheres the liquefied types of metal compounds to the glass frit, and secondly, A feature is that a collection of fine crystals of a plurality of types of metal compounds is precipitated, and the fine crystals are thermally decomposed to precipitate alloy fine particles. This has the effect of producing a collection of glass frit in which the glass frits are joined together by metal bonding of the alloy fine particles covering the glass frit.
Further, a metal compound, an alcohol, and an organic compound that precipitate a metal by thermal decomposition are all general-purpose industrial chemicals, and glass frit is a general-purpose industrial material. A liquid mixture can be formed only by mixing such general-purpose industrial chemicals and industrial materials. Also, simply raising the temperature of the glass frit immersed in the mixed solution to a temperature lower than the softening point of the glass frit causes multiple types of metal compounds to be thermally decomposed simultaneously, and a collection of metal-bonded alloy fine particles covers the glass frit. Then, a collection of glass frits in which the glass frits are bonded to each other by the metal bonding of the alloy fine particles is produced. Therefore, by using inexpensive industrial chemicals and industrial materials as raw materials and performing extremely simple processing, a large amount of glass frits can be produced at low production cost. Further, by changing the combination of metals in a plurality of types of metal compounds, or by changing the ratio of the number of moles of the plurality of types of metal compounds, a collection of alloy fine particles having various compositions covers the surface of the glass frit, A collection of glass frit in which the glass frit is bonded by metal bonding of fine particles is produced at a temperature lower than the softening point of the glass frit.
As described above, a collection of glass frit can be mass-produced at low production cost only by performing extremely simple processing using inexpensive industrial chemicals and industrial materials as raw materials. For this reason, according to the present manufacturing method, the first and second problems described in the sixth paragraph are simultaneously solved, and a group of glass frit is manufactured.

The production method for producing a collection of glass frit in which glass frits are bonded to each other by metal bonding of alloy fine particles described in paragraph 13 includes a method in which a plurality of types of metal compounds described in paragraph 13 form oxygen ions constituting is a plurality of types of carboxylic acid metal compound covalently bonded to a different metal ions, organic compounds described in paragraph 13, carboxylic acid esters, one on either belonging glycols or glycol ethers One kind of organic compound, the glass frit described in paragraph 13 is a glass frit having a softening point higher than a temperature at which the plurality of kinds of carboxylic acid metal compounds are thermally decomposed simultaneously, and the plurality of kinds of carboxylic acid metal compounds and Using the one kind of organic compound and the glass frit, paragraph 13 Five steps to produce a collection of the glass frit the glass frit each other are bonded by a metal bond alloy particles according to the production method carried out continuously, glass frit together with a metal bond alloy fine particles as described in paragraph 13 as described in There is a method of manufacturing a set of combined the glass frit.

That is, when a plurality of types of metal carboxylate compounds are heat-treated in an air atmosphere, the metal carboxylate compounds are composed of the metal carboxylate compounds described in paragraph 10, and are thermally decomposed at 290 to 430 ° C. at the same time. As a result, on the surface of the glass frit having a softening point higher than the thermal decomposition temperature of the metal carboxylate, an alloy comprising fine particles having a size of 40 to 60 nm having a composition corresponding to the mole ratio of the plurality of types of metal compounds. As a collection of granular fine particles. At this time, the precipitated granular alloy fine particles are in an active state having no impurities, so that the granular fine particles are metal-bonded at a portion where they are in contact with each other, and the glass frit is bonded to each other by metal bonding of the alloy fine particles covering the glass frit. A collection of glass frit is produced. After that, if the glass frit is left at the annealing point for at least 15 minutes and then gradually cooled to room temperature, the strain remaining on the glass frit due to the heat treatment is released.
That is, when an oxygen ion constituting a carboxyl group in the same saturated fatty acid is heat-treated in an air atmosphere with a plurality of types of carboxylic acid metal compounds covalently bonded to different metal ions, the same saturated fatty acid is heated at a temperature exceeding the boiling point of the saturated fatty acid. When the fatty acid is simultaneously decomposed into a different metal from the fatty acid and the temperature is further increased, the saturated fatty acid evaporates according to the molecular weight of the saturated fatty acid, and after the vaporization is completed, plural kinds of metals are simultaneously precipitated. An alloy is produced because it is in an active state having no alloy.
Further, in carboxylic acid esters, glycols or glycol ethers, the first property of being dissolved or mixed with alcohol, the second property of higher viscosity than alcohol, and the boiling point is higher than the boiling point of alcohol, and, There is an organic compound having a third property lower than a temperature at which a plurality of types of carboxylic acid metal compounds are simultaneously thermally decomposed. Such organic compounds are all general-purpose industrial chemicals.
In addition, even if it is the powder glass of low temperature sealing which has the lowest calcination temperature among glass frit, softening point exceeds 300 degreeC. Therefore, many glass frits have a softening point higher than the thermal decomposition temperature of the metal carboxylate.
Therefore, when an organic compound is mixed with an alcohol dispersion of a plurality of types of carboxylic acid metal compounds, the plurality of types of carboxylic acid metal compounds and the organic compound are uniformly mixed in a molecular state. When a group of glass frit is immersed in the mixed solution, the mixed solution adheres to the surface of the glass frit with a thickness corresponding to the viscosity. Thereafter, the collection of glass frit is heat-treated in an air atmosphere. First, the alcohol is vaporized, then the organic compound is vaporized, and a collection of fine crystals of a plurality of types of metal carboxylate precipitates on the surface of the glass frit. When the temperature is further increased, the thermal decomposition of the plurality of metal carboxylate compounds forming fine crystals starts, and the thermal decomposition of the plurality of metal carboxylate compounds is simultaneously completed at a temperature of 290 to 430 ° C. lower than the softening point of the glass frit. In addition, particulate alloy fine particles having a size of 40 to 60 nm according to the size of the fine crystals collect and precipitate on the surface of the glass frit. In other words, when fine crystals of a plurality of types of carboxylic acid metal compounds are thermally decomposed simultaneously, a plurality of types of metals are simultaneously precipitated, and the plurality of types of metals are in an active state having no impurities. An alloy having a composition according to the number of moles is precipitated as granular fine particles having a size of 40 to 60 nm according to the size of the fine crystal. In addition, since the alloy fine particles do not have impurities, they are metal-bonded at portions where they are in contact with each other, and a collection of metal-bonded alloy fine particles covers the glass frit. Is manufactured. Therefore, the plurality of types of metal carboxylate compounds and the organic compounds are raw materials for producing the glass frit aggregate described in the fourth characteristic means. Furthermore, when the combination of metals in the plural kinds of metal carboxylate compounds is changed, or when the ratio of the number of moles of the plural kinds of metal carboxylate compounds is changed, the collection of alloy fine particles having various compositions causes the surface of the glass frit to change. In addition to covering, the glass frit is bonded by the metal bonding of the alloy fine particles.
As described above, a plurality of metal carboxylate compounds that are inexpensive industrial chemicals, organic compounds that are general industrial chemicals, and glass frit that is a general industrial material are used as raw materials. A mixture of a metal carboxylate compound and an organic compound is attached to the glass frit, and the glass frit is heat-treated at a temperature of 290 to 430 ° C. in the air atmosphere. A collection of glass frits in which the glass frits are joined together is produced. For this reason, this manufacturing method simultaneously solves the first and second problems described in the sixth paragraph, and forms a collection of glass frits in which the glass frits are bonded to each other by the metal bonding of the alloy fine particles described in the thirteenth paragraph. Become a raw material to manufacture.

The manufacturing method for manufacturing a molded body made of glass frit having properties of an alloy by using a collection of glass frit in which glass frit is bonded by metal bonding of alloy fine particles manufactured according to the manufacturing method described in paragraph 13 includes: to produce a collection of the glass frit the glass frit each other are bonded by a metal bond alloy particles according to the production method carried out continuously five steps described in the preceding paragraph, filling the collection of the glass frit into a molding machine or a mold The glass frit is softened and deformed by applying stress by the molding machine or the mold, and the alloy fine particles covering the deformed glass frit are metal-bonded to each other, whereby the deformed glass frit is bonded to each other. And a collection of the deformed glass frit in the molding machine or the mold. A method for producing a molded body made of glass frit having the properties of an alloy by forming a molded body, leaving the molded body at the annealing point of the glass frit for 15 minutes or more, and then gradually cooling it to room temperature. .

In other words, according to this characteristic means, the five processes described in paragraph 13 are continuously performed on the glass frit collection, and the glass frit collection is filled in a molding machine or a mold, and the glass frit is filled. When producing a molded body by softening, the softened glass frit is bonded to each other by metal bonding of alloy fine particles, and the metal-bonded alloy fine particles form a continuous path in the molded body, so that a molded body having alloy properties Is manufactured. In addition, when the combination of metals in a plurality of types of metal compounds is changed, or the ratio of the number of moles of the plurality of types of metal compounds is changed, the formed body has various alloy properties, and a light-weight, non-corroded formed body can be used. Manufactured by a method of forming a molded body, an alloy part is replaced with a glass part.
In other words, since the size of the glass frit is a micron size and two orders of magnitude larger than that of the alloy fine particles, the aggregate of the metal-bonded alloy fine particles covering the entire glass frit is subjected to stress from the softened glass frit by a molding machine or a mold. When the metal frit is deformed, the collection of metal-bonded alloy fine particles follows and deforms similarly, and still covers the deformed glass frit. Further, the deformed glass frit is bonded to each other by the metal bonding of the alloy fine particles. For this reason, a compact having the properties of an alloy can be produced at low cost by the conventional method of molding a compact.
That is, when the treatment described in paragraph 13 was performed on the collection of glass frit, the glass frit was covered with the collection of metal alloy-bound alloy fine particles, and the glass frit was bonded to each other by the metal bonding of the alloy fine particles covering the glass frit. A collection of glass frit is produced. The collection of the glass frit is filled into a molding machine or a mold, and the softened glass frit is bonded to each other by metal bonding of alloy fine particles to form a formed body. At this time, since the alloy fine particles covering the glass frit were generated at a temperature lower than the softening point of the glass frit, when the temperature was raised to a temperature above the softening point, the alloy fine particles took in adjacent alloy fine particles and grew. Coarse. Since the coarsened alloy fine particles are in an active state having no impurities, the alloy fine particles are metal-bonded to each other at the contact site. For this reason, the aggregate of the coarsened alloy fine particles still covers the entire softened glass frit. Next, when the softened glass frit is deformed by receiving a stress from a molding machine or a mold, the collection of metal-bound alloy fine particles is deformed following the deformation of the glass frit, and still covers the deformed glass frit. In addition, the deformed glass frit is bonded to each other by metal alloying of the alloy fine particles to each other, and the metal bonded alloy fine particles form a continuous path to the molded body, and the molded body has a property of the alloy constituting the alloy fine particles. have. Thereafter, the glass frit is left at the annealing point for 15 minutes or more and then gradually cooled to room temperature, and a heat treatment for forming the molded body is performed to form a molded body made of glass frit from which the strain remaining on the glass frit has been released. For this reason, a compact having the properties of an alloy can be produced at low cost by the conventional method of molding a compact. In addition, if the alloy fine particles are composed of alloys of various compositions, the molded body has various alloy properties, and the lightweight and non-corrosive molded body can replace the alloy part with the glass part.
As described above, according to the present manufacturing method, the molded article having the properties of the alloy is manufactured by solving the third problem described in the sixth paragraph.

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FIG. 3 is a diagram schematically illustrating a state in which a collection of copper fine particles is deposited on the surface of a glass frit. FIG. 4 is a diagram schematically illustrating a state in which a collection of copper fine particles covers a glass frit bonded in a sheet shape, and the glass frit is bonded by metal bonding of the copper fine particles.

Embodiment 1
The present embodiment is an embodiment of the metal carboxylate described in paragraphs 10 and 16. In the present invention, the metal compound which precipitates a metal by thermal decomposition needs to have both properties of firstly dispersing in alcohol and secondly depositing metal by thermal decomposition. Here, copper is used as the metal, and a copper compound will be described as an example.
First, a copper compound having a property of dispersing in alcohol will be described. Inorganic copper compounds such as copper chloride, copper sulfate, and copper nitrate are dissolved in alcohol, and copper ions are eluted, so that many copper ions cannot participate in precipitation of copper fine particles. In addition, inorganic copper compounds such as copper oxide, copper chloride, and copper sulfide do not disperse in alcohols, which are the most common solvents. Therefore, these inorganic copper compounds are not suitable as copper compounds having a property of dispersing in alcohol.
Among the chemical reactions in which copper is produced from an organic copper compound, the simplest chemical reaction is a thermal decomposition reaction. Furthermore, if the synthesis of the organic copper compound is easy, the organic copper compound can be produced at low cost. Among the organic copper compounds having such properties, there is a copper carboxylate compound in which an oxygen ion constituting a carboxyl group of a saturated fatty acid is covalently bonded to a copper ion.
That is, the largest ion among the ions constituting the copper carboxylate compound is a copper ion. Therefore, if the oxygen ion constituting the carboxyl group of the carboxylic acid is covalently bonded to the copper ion, the distance between the copper ion and the oxygen ion constituting the carboxyl group is the longest of the distances between the ions. When the temperature of such a copper carboxylate compound is raised in the air atmosphere, when the temperature exceeds the boiling point of the carboxylic acid, the compound is decomposed into carboxylic acid and copper. When the temperature is further increased, if the carboxylic acid is composed of a saturated fatty acid, the carboxylic acid is vaporized with heat of vaporization, and copper is deposited after the carboxylic acid is vaporized. Note that the thermal decomposition of the copper carboxylate compound in a reducing atmosphere proceeds on a higher temperature side than the thermal decomposition in the air atmosphere, so that the thermal decomposition in the air atmosphere requires less heat treatment cost. If the carboxylic acid is an unsaturated fatty acid, the carbon atom becomes excessive with respect to the hydrogen atom. Therefore, when the copper carboxylate compound composed of the unsaturated fatty acid is thermally decomposed, copper oxide is deposited.
On the other hand, in the copper carboxylate compound, the copper carboxylate in which the oxygen ion constituting the carboxyl group of the carboxylic acid acts as a ligand and approaches and coordinates with the copper ion, the distance between the copper ion and the oxygen ion is increased. On the contrary, the distance between the oxygen ion and the ion bound on the opposite side is longest. In the thermal decomposition reaction of a copper carboxylate compound having such a molecular structure, a bond between an oxygen ion and an ion bonded to the opposite side of the copper ion is first broken, and as a result, copper oxide is deposited.
Furthermore, since a carboxylic acid is the most general-purpose organic acid, a copper carboxylate compound is easy to synthesize and is the cheapest organic copper compound. That is, when the carboxylic acid is reacted in a strong alkaline solution such as sodium hydroxide, an alkali metal carboxylate compound is generated. When this alkali metal carboxylate is reacted with an inorganic copper compound such as copper sulfate, a copper carboxylate is produced. Therefore, it is the cheapest organic copper compound among the organic copper compounds.
The composition formula of the copper carboxylate compound is represented by Cu (COOR) ₂ . R is a hydrocarbon, the composition formula is _C m _{H n} (integer and where m and n). Among the substances constituting the copper carboxylate compound, the copper ion Cu ²⁺ located at the center of the composition formula is the largest. Therefore, when the copper ion Cu ²⁺ and the oxygen ion O ⁻ constituting the carboxyl group are covalently bonded, the distance between the copper ion Cu ²⁺ and the oxygen ion O ⁻ becomes maximum. This is because the covalent radius of the double bond of the copper atom is 115 pm, the covalent radius of the double bond of the oxygen atom is 57 pm, and the covalent radius of the double bond of the carbon atom is 67 pm. . For this reason, in a copper carboxylate compound having such a characteristic molecular structure, when the boiling point of the carboxylic acid is exceeded, the bond between the copper ion having the longest bond distance and the oxygen ion constituting the carboxyl group is first broken. , Separated into copper and carboxylic acid. When the temperature is further increased, if the carboxylic acid is a saturated fatty acid, the carboxylic acid is vaporized with heat of vaporization, and copper is precipitated after the vaporization of the carboxylic acid is completed. Such copper carboxylate compounds include copper octylate, copper laurate, and copper stearate. Many of such copper carboxylate compounds are inexpensive industrial chemicals that are commercially available as metal soaps.
Furthermore, if the boiling point of the saturated fatty acid is low, thermal decomposition starts at a low temperature. When the hydrocarbon constituting the saturated fatty acid has a long-chain structure, the longer the long chain, that is, the larger the molecular weight of the saturated fatty acid, the higher the boiling point of the saturated fatty acid, and the larger the heat of vaporization of the saturated fatty acid, Thermal decomposition temperature increases. Incidentally, the boiling point of lauric acid having a molecular weight of 200.3 is 296 ° C., and thermal decomposition of copper laurate is completed at 360 ° C. in an air atmosphere. The boiling point of stearic acid having a molecular weight of 284.5 is 361 ° C, and the thermal decomposition of copper stearate is completed at 430 ° C.
On the other hand, a saturated fatty acid having a branched chain structure has a shorter chain length than a saturated fatty acid having a straight chain structure, and therefore has a low boiling point and a small heat of vaporization. As a result, the copper carboxylate compound comprising a saturated fatty acid having a branched chain structure has a lower thermal decomposition temperature. In addition, since saturated fatty acids having a branched chain structure have polarities, copper carboxylate compounds also have polarities and are dispersed in a relatively high ratio in polar organic solvents such as alcohols. Octylic acid is a saturated fatty acid having such a branched structure. Octylic acid has a structural formula of CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) COOH, is branched into an alkane of CH ₃ (CH ₂ ) ₃ and C ₂ H ₅ by CH, and a carboxyl group is added to CH. COOH binds. The boiling point of octylic acid at atmospheric pressure is 228 ° C., which is 68 ° C. lower than lauric acid. Copper octylate is thermally decomposed at 290 ° C. in an air atmosphere, and copper is deposited.
On the other hand, when a compact is manufactured using a collection of glass frit covered with a collection of metal or alloy fine particles manufactured at a temperature lower than the softening point of the glass frit, the glass frit rises to a temperature above the softening point. According to the temperature difference between the temperature at which the fine particles are generated and the temperature at which the glass frit is softened, the fine particles take in adjacent fine particles, grow, and become coarse. If the fine particles become excessively coarse, the softened glass frit will protrude outside of the fine particles when subjected to stress from the molding machine or the mold, and the softened glass frit will be directly joined to each other, and the collection of the fine particles will continue to the formed body. There is a case where the formed body does not show the properties of a metal or an alloy without forming a route which is not formed. Therefore, it is desirable to use a glass frit having a softening point close to 290-430 ° C., which is the thermal decomposition temperature of the metal carboxylate.
As described above, a metal octylate compound, a metal laurate compound, and a metal stearate compound are desirable as raw materials for metal fine particles. Further, in these carboxylic acid metal compounds, metal compounds composed of various metal elements exist, and the metal element of the metal fine particles is not limited.
Furthermore, when oxygen ions constituting a carboxyl group in the same saturated fatty acid are heat-treated in an air atmosphere with a plurality of types of carboxylic acid metal compounds covalently bonded to different metal ions, when the boiling point of the saturated fatty acid is exceeded, a plurality of types of carboxylic acid metal compounds are obtained. The acid metal compound is simultaneously decomposed into a saturated fatty acid and a plurality of types of metals, and furthermore, the vaporization of the saturated fatty acid proceeds in accordance with the molecular weight of the saturated fatty acid. After the vaporization is completed, the plural types of metals are simultaneously precipitated. Since each of these metals is in an active state having no impurities, an alloy having a ratio of metals according to the number of moles of the metal carboxylate is produced. Therefore, a plurality of types of metal carboxylate compounds are excellent raw materials for alloy fine particles.

Embodiment 2
In the present embodiment, first, an organic compound having these three properties, which is firstly dissolved or mixed with an alcohol, secondly, has a higher viscosity than alcohol, and thirdly, has a boiling point lower than a temperature at which a metal carboxylate is thermally decomposed. It is an embodiment relating to a compound. Such organic compounds include carboxylic acid esters, glycols, and organic compounds belonging to glycol ethers. The metal carboxylate which precipitates the metal is thermally decomposed at 290-430 ° C.

First, carboxylic esters will be described. Carboxylic esters are classified into a first ester composed of a saturated carboxylic acid, a second ester composed of an unsaturated carboxylic acid, and a third ester composed of an aromatic carboxylic acid.
A carboxylate having a boiling point lower than 290 ° C. is a carboxylate having a molecular weight smaller than that of ethyl myristate having a molecular weight of 256.4 (also referred to as ethyl tetradecanoate). The boiling point of ethyl myristate is 295 ° C.

The second ester, an ester of unsaturated carboxylic acid, which is mixed with methanol, has a higher viscosity than methanol, and has a boiling point lower than 290 ° C. is higher than that of methyl oleate having a molecular weight of 296.6. It is a carboxylic acid ester having a small molecular weight. The boiling point of phenyl methacrylate is 249 ° C, and the boiling point of methyl oleate is 351 ° C.

Among the esters composed of aromatic carboxylic acids, which are the third esters, carboxylic acid esters which are dissolved in methanol and have a higher viscosity than methanol and a boiling point lower than 290 ° C. are dimethyl phthalate having a molecular weight of 194 or less. Is a carboxylic acid ester having a molecular weight of The boiling point of dimethyl phthalate is 284 ° C.
As described above, the carboxylic acid esters include many organic compounds having the three properties described in paragraph 25, and are uniformly mixed with the alcohol dispersion of the metal compound to form a mixture. .

Next, glycols will be described. As the glycols, there are six kinds of glycols consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
Ethylene glycol is a liquid monomer that dissolves in methanol, has a higher viscosity than methanol, and has a boiling point of 197 ° C. Diethylene glycol is a liquid monomer that dissolves in methanol, has a higher viscosity than methanol, and has a boiling point of 244 ° C. Propylene glycol is a liquid monomer that is miscible with methanol, has a higher viscosity than methanol, and has a boiling point of 188 ° C. Dipropylene glycol is a liquid monomer that dissolves in methanol, has a higher viscosity than methanol, and has a boiling point of 232 ° C. Tripropylene glycol is a liquid monomer that is miscible with methanol, has a higher viscosity than methanol, and has a boiling point of 265 ° C. Both are glycols having a boiling point lower than 290 ° C.
As described above, the glycols include the organic compound having the three properties described in paragraph 25, and are uniformly mixed with the alcohol dispersion of the metal compound to form a mixture.

Lastly, glycol ethers will be described. There are three types of glycol ethers: ethylene glycol ethers, propylene glycol ethers, and dialkyl glycol ethers in which each terminal hydrogen of ethylene glycol, diethylene glycol, and triethylene glycol has been substituted with an alkyl group. Both glycol ethers dissolve in methanol and have higher viscosities than methanol.
First, among ethylene glycol ethers, those having a boiling point lower than 290 ° C. include 2-ethylhexyl glycol having a boiling point of 229 ° C., butyl diglycol having a boiling point of 231 ° C., and phenyl glycol having a boiling point of 245 ° C. And methyltriglycol having a boiling point of 249 ° C, benzylglycol having a boiling point of 256 ° C, hexyldiglycol having a boiling point of 259 ° C, butyltriglycol having a boiling point of 271 ° C, and 2-ethylhexylglycol having a boiling point of 272 ° C. Phenyl diglycol having a boiling point of 283 ° C.

Among propylene glycol ethers, those having a boiling point lower than 290 ° C. include butyl propylene diglycol having a boiling point of 231 ° C., methyl propylene diglycol having a boiling point of 242 ° C., and phenyl propylene glycol having a boiling point of 243 ° C. And butyl propylene triglycol at 274 ° C., which has the highest boiling point.

Among the dialkyl glycol ethers, those having a boiling point lower than 290 ° C include diethyldiglycol having a boiling point of 189 ° C, dimethyltriglycol having a boiling point of 216 ° C, and dibutyldiglycol having a boiling point of 255 ° C.
As described above, glycol ethers contain many organic compounds having the three properties described in paragraph 25, and are uniformly mixed with an alcohol dispersion of a metal compound to form a mixed solution.

Embodiment 3
This embodiment is an embodiment relating to a glass frit. The softening point means a lower limit temperature of hot working of the glass frit. Therefore, if the treatment is performed at a temperature lower than the softening point of the glass frit, since the glass frit has not been subjected to hot working, it is left at the annealing point of the glass frit for at least 15 minutes to release the strain caused by the heat treatment, and then the room temperature is reduced to room temperature. When gradually cooled, the glass frit returns to the state before the treatment. For this reason, the glass frit after the treatment does not change with time, and can be used as a raw material of a molded body when necessary. The metal carboxylate which precipitates the metal is thermally decomposed at 290-430 ° C. Further, the softening point of the glass frit has a softening point of more than 300 ° C. even in the case of low-temperature sealing powder glass having the lowest firing temperature. Therefore, there are many glass frit having a softening point higher than the thermal decomposition temperature of the metal carboxylate compound that precipitates the metal.
On the other hand, there is a difference in the coefficient of thermal expansion between the glass frit and the metal or alloy. The glass frit has a micron size, whereas the metal or alloy fine particles have a size of 40-60 nm, which is two orders of magnitude smaller than the glass frit. For this reason, after the thermal decomposition of the metal compound, the volume of the glass frit significantly shrinks as compared with the fine particles, a void is formed between the glass frit and the collection of the fine particles, and the glass frit may fall off. However, if the aggregate of the precipitated fine particles occupies a volume sufficiently larger than the volume shrinkage of the glass frit and precipitates, when the glass frit shrinks in volume and a void is formed, the pressure in the void decreases, so that metal The aggregate of the bound fine particles deforms to fill the void. Therefore, no void is formed due to volume shrinkage of the glass frit.
Glass frit is produced by mixing and mixing a plurality of types of metal oxides as raw materials, thermally melting and vitrifying, and then crushing into fine powder by water quenching or roll quenching. For this reason, it consists of various compositions and composition ratios. On the other hand, a glass frit of lead-free glass is desirable from the viewpoint of the RoHS directive. Examples of the lead-free glass include a phosphate glass mainly containing P ₂ O ₅ , a bismuth glass mainly containing Bi ₂ O ₃ , V ₂ O ₅ and an alkali metal oxide, an alkaline earth metal oxide, Vanadate-based glass composed of zinc oxide, boron oxide, phosphorus pentoxide, tellurium oxide, etc .; borosilicate-based glass composed of SiO ₂ and B ₂ O ₃ and alkali metal oxide or alkaline earth metal oxide; BeF _For example, there is a fluoride-based glass containing ₂ as a main component. Furthermore, the following metal oxides, which are the main raw materials of glass, each have a unique action, and therefore the softening point and the coefficient of linear expansion of the glass frit can be freely changed depending on the ratio of the metal oxides. Silicon oxide SiO _{2 functions} to form a glass network structure, increase the softening point and reduce the thermal expansion. On the other hand, boron oxide B ₂ O ₃ forms a network structure of glass and functions to lower the softening point. Titanium oxide TiO ₂ functions to promote crystallization and increase the softening point. Alumina Al ₂ O ₃ suppresses crystallization, but functions to increase the softening point. In contrast, sodium oxide Na ₂ O lowers the softening temperature and increases the thermal expansion, but is inferior in water resistance. On the other hand, potassium oxide K ₂ O has the same properties as Na ₂ O, but is hard to move because K ⁺ is 1.4 times larger than Na ⁺ , resulting in water resistance. Further, calcium oxide CaO has the same properties as Na ₂ O, but improves the chemical durability of the alkali glass.
The linear expansion coefficients of metal are 239 × 10 ⁻⁷ / ° C. for aluminum, 165 × 10 ⁻⁷ / ° C. for copper, and 117 × 10 ⁻⁷ / ° C. for iron. The linear expansion coefficient of the alloy is, for example, PB permalloy of iron-nickel alloy having a large initial magnetic permeability is 77 × 10 ⁻⁷ / ° C., 42 alloy of iron-nickel alloy having a small thermal expansion coefficient is 42 × 10 ⁻⁷ / ° C., The invar of the iron-nickel alloy with low thermal expansion and high strength is 15 × 10 ⁻⁷ / ° C., which is smaller than the coefficient of thermal expansion of the metal.
As described above, the glass frit according to the present invention has a softening point higher than the thermal decomposition temperature of the metal carboxylate, the first property close to the thermal decomposition temperature, and the linear expansion coefficient of the metal frit. A glass frit having both of these three properties, which is close to the second property, can be appropriately selected and used. The linear expansion coefficient of the alloy is one digit smaller than that of the glass frit. Therefore, when the glass frit is covered with the aggregate of the alloy fine particles, the alloy fine particles are precipitated so that the aggregate of the alloy fine particles occupies a volume sufficiently larger than the volume of the glass frit thermally contracted after the molding of the molded body, and the glass frit is formed. What is necessary is just to fill the volume shrinkage with the deformation of the alloy fine particles.

Example 1
This embodiment is an embodiment in which a glass frit is covered with a collection of copper fine particles. That is, copper has a specific gravity of 8.9, a cross-sectional area of 1 cm ² , a specific conductivity per 1 cm length of 1.00, and a magnetic permeability of 1.00, which is close to the magnetic permeability of vacuum. On the other hand, the degree of the electromagnetic wave reflection loss is proportional to the ratio of the specific conductivity to the relative magnetic permeability. Therefore, the degree of reflection loss of copper is 1.00, which is the second highest after the degree of reflection loss of silver among metals of 1.06. On the other hand, silver has a specific gravity of 1.2 times that of copper and is more expensive than copper. Therefore, if the molded body manufactured by using the glass frit group in the present embodiment shows conductivity close to that of copper, it can be used as a shield sheet or a shield plate excellent in electromagnetic wave reflection performance, and can be used as a metal substrate. Lighter weight and less corrosion.
As a raw material of the copper fine particles, copper octylate Cu (C ₇ H ₁₅ COO) ₂ (for example, a product of Mitsui Chemicals Co., Ltd.) that thermally decomposes at 290 ° C. in the air atmosphere was used. As the organic compound, methyl caprate CH ₃ (CH ₂ ) ₈ COOCH ₃ (for example, a product of Tokyo Chemical Industry Co., Ltd.) having a boiling point of 224 ° C., mixed with methanol and having a viscosity of 2.4 times the methanol was used. . Methyl caprate is a general-purpose industrial chemical used as a raw material for synthetic fiber oils, metal oils, synthetic lubricants, synthetic resins, cosmetics, surfactants and the like. A low-temperature sealing powder glass (product TNS062 of Asahi Glass Co., Ltd.) mainly containing TeO ₂ and V ₂ O ₅ having a softening point of 325 ° C. was used as the glass frit. This glass frit has a specific gravity of 4.2, a coefficient of linear expansion of 132 × 10 ⁻⁷ / ° C., and a particle size characteristic of D50 of 10.0 μm. The coefficient of linear expansion is smaller than the coefficient of linear expansion of copper, 165 × 10 ⁻⁷ / ° C., and no voids are formed after the thermal decomposition of copper octylate due to volume shrinkage of the glass frit.
Here, when the average shape of the glass frit is a square of 8 μm and the thickness is 0.5 μm, the weight of one glass frit is 1.31 × 10 ⁻¹⁰ g. When the copper fine particles covering the surface of the glass frit are spherical fine particles having a diameter of 50 nm, the number of copper fine particles covering one glass frit is 5.76 × 10 ⁴ . The number of copper fine particles precipitated from 1 mol of copper octylate (corresponding to 350 grams) is equal to 10.85 × 10 ¹⁶ . Therefore, when 39.3 g of glass frit (corresponding to 3 × 10 ¹¹ ) is used, a collection of metal-bonded copper fine particles forms an average of 6.3 layers of a multi-layer structure and covers the glass frit. Therefore, the copper fine particles cover the entire glass frit in a multilayer structure including six or seven layers. On the other hand, the surface area per unit mass of copper fine particles is 1.34 × 10 ⁵ cm ² , whereas that of glass frit is 2.43 × 10 ⁻¹ cm ² , and the specific surface area of copper fine particles is smaller than that of glass frit. And about 6 digits larger. For this reason, the collection of metal-bonded copper fine particles forms voids smaller than the fine particles in the gaps between adjacent copper fine particles. For this reason, the apparent specific gravity of the glass frit bonded by the collection of copper fine particles approaches that of the glass frit.
First, 350 g (corresponding to 1 mol) of copper octylate was dispersed in methanol so as to be 10% by weight, and this dispersion was mixed with methyl caprate so as to be 10% by weight. 39.3 g of a glass frit was mixed with the mixture and stirred.
Next, the mixture was placed in a container and fired in an air atmosphere. First, the temperature was raised to 65 ° C. to vaporize methanol, and further to 230 ° C. to vaporize methyl caprate. Next, it was left at 290 ° C. for 1 minute to thermally decompose copper octylate.
Further, the surface of the manufactured sample and a plurality of cut sections were observed with an electron microscope. As the electron microscope, an extremely low accelerating voltage SEM owned by JFE Techno-Research Corporation was used. This device enables surface observation with an extremely low accelerating voltage from 100 V, and allows direct observation of the surface of the sample without forming a conductive film.
First, with respect to reflected electron beams from the surface of the sample and a plurality of cross sections, a secondary electron beam between 900 and 1000 V was taken out and subjected to image processing. In each part of the sample surface, a collection of fine particles having a size of 40 to 60 nm was uniformly formed on the entire surface. In the cross section of the sample, granular fine particles having a thickness of about six layers were laminated on the surface of the glass frit, and the glass frit was bonded by a collection of the granular fine particles.
Next, with respect to the reflected electron beam from the surface of the sample and the plurality of cross sections, image processing was performed by extracting energy between 900 V and 1000 V, and the material of the particles was observed in the density of the image. No shading was observed in any of the particulate fine particles, indicating that they were composed of a single atom.
Further, the energy and the intensity of characteristic X-rays from the surface of the sample and a plurality of cross sections were image-processed to analyze the types of elements constituting the particles. Since the particulate microparticles were composed of only copper atoms, they were copper particulate microparticles.
From the above observation results, it was found that the surface of the glass frit was covered with a large number of copper fine particles, and that the glass frit was metal-bonded by the collection of the copper fine particles. FIG. 1 schematically shows the results. 1 is a glass frit and 2 is copper fine particles.
Further, the surface resistance at a plurality of positions on the sample surface was measured by a surface resistance meter (for example, surface resistance meter ST-4 manufactured by Simco Japan KK). Since the surface resistance value was 1 × 10 ³ Ω / □ less, the sample had a surface resistivity close to copper.
From the above results, the glass frit is covered with the collection of the copper fine particles, and the collection of the glass frit combined by the metal bond of the copper fine particles has a conductivity close to that of copper. This embodiment is only an example. Many glass frits have a softening point higher than the thermal decomposition temperature of the metal octylate compound, and various metals precipitate due to the thermal decomposition of the metal octylate compound. A collection of glass frit can be manufactured.

Example 2
The glass frit group produced in Example 1 was heated to 350 ° C., and a sheet having a thickness of 1 mm was formed by calendering.
The cut surface of the prepared sample was observed with an electron microscope in the same manner as in Example 1. The glass frit was bonded in a thin sheet shape, the surface of which was covered with a collection of copper fine particles, and the glass frit was bonded with a collection of copper fine particles. FIG. 2 schematically shows the cross section of the sample. 3 is a glass frit and 4 is copper fine particles.
Furthermore, the surface resistance of the prepared sample was measured in the same manner as in Example 1. The surface resistance was less than 1 × 10 ³ Ω / □. For this reason, the sheet made of glass frit can be used as a shield sheet having conductivity close to copper and having excellent performance of reflecting electromagnetic waves lighter than copper.
This embodiment is only an example. In other words, a glass molding machine or a mold is filled with a collection of glass frits, and if the temperature is raised above the softening point of the glass frit and a compressive stress is applied, various shapes in which the glass frit softened by the metal bonding of the metal fine particles are bonded together. Can be manufactured.

Example 3
This embodiment is an embodiment in which a glass frit is covered with a collection of aluminum fine particles. Note that aluminum has excellent thermal conductivity and conductivity next to silver, copper, and gold, and has a small specific gravity of 2.70. Therefore, if the molded body manufactured using the collection of glass frit in this embodiment has a conductivity close to that of aluminum, it can be used as a lightweight, non-corrosive, transparent heat dissipation base material.
As a raw material of the aluminum fine particles, aluminum octylate Al (C ₇ H ₁₅ COO) ₃ (for example, a product of Hope Pharmaceutical Co., Ltd.) which thermally decomposes at 290 ° C. in the air atmosphere was used. As the organic compound, methyl caprate of Example 1 was used. As the glass frit, a powder glass for low-temperature sealing (product KP312 of Asahi Glass Co., Ltd.) containing SnO and P ₂ O ₅ having a softening point of 325 ° C. as main components was used. This glass frit has a specific gravity of 3.8, a coefficient of linear expansion of 128 × 10 ⁻⁷ / ° C., and a particle size characteristic of D50 of 6.0 μm. The coefficient of linear expansion is smaller than the coefficient of linear expansion of aluminum, 239 × 10 ⁻⁷ / ° C., and no void is formed due to volume shrinkage of the glass frit after thermal decomposition of aluminum octylate.
Here, if the average shape of the glass frit is a square of 5 μm and the thickness is 0.4 μm, the weight of one glass frit is 3.8 × 10 ⁻¹¹ g. When the aluminum fine particles covering the surface of the glass frit are spherical fine particles having a diameter of 50 nm, the number of aluminum fine particles covering one glass frit is 23,200. Further, the number of aluminum fine particles precipitated from 1 mol of aluminum octylate (equivalent to 457 g) corresponds to 15.2 × 10 ¹⁶ . Therefore, when 38 g of glass frit (corresponding to 10 ¹² ) is used, a collection of metal-bound copper fine particles forms an average of 6.6 layers and covers the glass frit. Therefore, the copper frit covers the entire glass frit in a multilayer structure including six or seven layers.
First, 457 g (corresponding to 1 mol) of aluminum octylate was dispersed in methanol so as to have a concentration of 10% by weight, and this dispersion was mixed with methyl caprate so as to have a concentration of 10% by weight. This mixture was mixed with 38 g of glass frit and stirred.
Next, the mixture was placed in a container and fired in an air atmosphere. First, the temperature was raised to 65 ° C. to vaporize methanol, and further to 230 ° C. to vaporize methyl caprate. Next, it was left at 290 ° C. for 1 minute to thermally decompose aluminum octylate.
Furthermore, the surface of the manufactured sample and a plurality of cut sections were observed with an electron microscope in the same manner as in Example 1.
First, with respect to reflected electron beams from the surface of the sample and a plurality of cross sections, a secondary electron beam between 900 and 1000 V was taken out and subjected to image processing. In each part of the sample surface, a collection of fine particles having a size of 40 to 60 nm was uniformly formed on the entire surface. The cross section of the sample had a thickness of about seven layers in which fine particles were laminated on the surface of the glass frit, and the glass frit was bonded by a collection of fine particles.
Next, with respect to the reflected electron beam from the surface of the sample and a plurality of cross sections, image processing was performed by extracting energy between 900 V and 1000 V, and the material of the particles was analyzed based on the density of the image. No shading was observed in any of the particulate fine particles, indicating that they were composed of a single atom.
Further, the energy and the intensity of characteristic X-rays from the surface of the sample and a plurality of cross sections were image-processed to analyze the types of elements constituting the particles. Since the granular fine particles consisted of only aluminum atoms, they are aluminum granular fine particles.
From the above observation results, it was found that the surface of the glass frit was covered with a large number of aluminum fine particles, and that the glass frit was metal-bonded by the collection of the aluminum fine particles. This result is not shown because it is similar to the result of the first embodiment.
In the same manner as in Example 1, the surface resistance at a plurality of positions on the sample surface was measured with a surface resistance meter. The surface resistance was less than 1 × 10 ³ Ω / □, and the sample had a surface resistance close to that of aluminum.
From the above results, the glass frit was covered with the collection of the aluminum fine particles, and the collection of the glass frit combined with the metal bond of the aluminum fine particles had a conductivity close to that of aluminum. This embodiment is only an example. Many glass frits have a softening point higher than the thermal decomposition temperature of the metal octylate compound, and various metals precipitate due to the thermal decomposition of the metal octylate compound. A collection of glass frit can be manufactured.

Example 4
The glass frit group produced in Example 3 was heated to 350 ° C., and a sheet having a thickness of 2 mm was formed by calendering.
The cut surface of the prepared sample was observed with an electron microscope in the same manner as in Example 1. The glass frit was bonded in a thin sheet, the surface of which was covered with a collection of aluminum fine particles, and the glass frit was bonded with a collection of aluminum fine particles. The result is not shown because it is similar to the sheet of Example 2.
Further, in the same manner as in Example 1, the surface resistance of the prepared sample was measured by a surface resistance meter. The surface resistance was less than 1 × 10 ³ Ω / □. For this reason, the molded body has conductivity close to that of aluminum. Therefore, a sheet made of glass frit can be used as a heat dissipating base material having aluminum properties.
This embodiment is only an example. In other words, a glass molding machine or a mold is filled with a collection of glass frits, and if the temperature is raised above the softening point of the glass frit and a compressive stress is applied, various shapes in which the glass frit softened by the metal bonding of the metal fine particles are bonded together. Can be manufactured.

Example 5
In this example, the glass frit group produced in Example 3 was heated to 350 ° C., and a sheet having a thickness of 1 mm was formed by calendering. If this molded body has a conductivity close to that of aluminum, it can be used as a transparent conductive substrate.
That is, in order for the molded body to be transparent, the incident light must pass through the molded body with a high transmittance. On the other hand, when light enters the molded body, surface reflection occurs due to a difference from the refractive index of air. The surface of the molded body is composed of aluminum fine particles. Therefore, when light enters the molded body, the aluminum fine particles cause surface reflection. The surface reflectance is the square of the value obtained by dividing the difference between the refractive index with air by the sum of the two. Fine particles made of aluminum having a refractive index of 1.48 have a surface reflectivity of 3.7%, and 96.3% of light enters the molded body. The glass frit having a refractive index of 1.51 has a surface reflectance of 4.1%. Further, the ratio of light entering the molded body is represented by the total light transmittance, and the total light transmittance is the square of a value obtained by subtracting the surface reflectance from 1 when the total of the incident light is 1. Therefore, the total light transmittance is 93% for the aluminum fine particles. The total light transmittance of the glass frit is 92%. Since the total light transmittance of a typical float glass having a thickness of 2 mm is 90%, the molded article has a high transmittance for incident light.
Next, the light transmitted through the surface enters the molded body and is scattered. In order for the molded body to be a transparent body, light scattering hardly occurs, that is, it is necessary that the scattering coefficient is small. The light scattering is based on Rayleigh scattering, and if the compact is a form in which a collection of fine particles is dispersed in glass frit, the Rayleigh scattering coefficient is ｛(m ² -1) / (m ² +1)｝ ² . The ratio m becomes 0.98, and {(m ² −1) / (m ² +1)} ² is as small as 4.1 × 10 ⁻⁴ . Further, the scattering coefficient is proportional to the fourth power of the ratio D / λ of the particle diameter D to the wavelength λ of the visible light and the square of the particle diameter D. Assuming that the average particle diameter of the aluminum fine particles is 50 nm, the fourth power of the ratio D / λ to the wavelength of visible light of 380 to 780 nm is 1.3 × 10 ⁻⁵ −2.9 × 10 ⁻⁴ , and the particle diameter D is The square becomes 2.5 × 10 ⁻¹⁵ . Therefore, the scattering coefficient composed of the product of 4.1 × 10 ⁻⁴ , 1.3 × 10 ⁻⁵ −2.9 × 10 ⁻⁴ and 2.5 × 10 ⁻¹⁵ has an extremely small value. As a result, the molded article in this example shows high transparency. Therefore, if the molded body in this embodiment has a conductivity close to that of aluminum, it becomes a transparent conductive molded body.
Next, the cut surface of the formed compact was observed with an electron microscope in the same manner as in Example 1. The glass frit was bonded in a thin sheet, the surface of which was covered with a collection of aluminum fine particles, and the glass frit was bonded with a collection of aluminum fine particles. The result is not shown because it is similar to the sheet of Example 2.
Further, in the same manner as in Example 1, the surface resistance of the prepared sample was measured by a surface resistance meter. Since the surface resistance was less than 1 × 10 ³ Ω / □, the molded body had conductivity close to that of aluminum. Therefore, a sheet made of glass frit can be used as a transparent conductive substrate.

Example 6
The present embodiment is an embodiment of manufacturing a glass frit called permalloy, which is covered with a collection of fine particles of an alloy mainly composed of nickel and iron. Permalloy in this example is PC permalloy having a molar ratio of nickel 80, molybdenum 5 and iron 15. The DC magnetic properties of this PC permalloy are such that the initial permeability is 60,000, the maximum permeability is 180,000, the saturation magnetic flux density is 0.65 Tesla, and the coercive force is 1.2 A / m. The AC inductance is higher as the plate thickness is thinner. A plate thickness of 0.35 mm has an inductance of 15,000 at 0.3 kHz, 8,000 at 1 kHz, and 3,300 at 30 kHz. Therefore, it has a performance of absorbing electromagnetic waves up to around 100 kHz. The thin body made of the conventional PB permalloy or PC permalloy is magnetically annealed at 1100 ° C. in a hydrogen atmosphere to remove an oxide film on the surface of the ingot and an oxide as an impurity present in the inside. After rolling and elongating to a foil shape, a strain relief annealing is performed to remove strain accompanying processing. In contrast, in the present embodiment, nickel, molybdenum, and iron are simultaneously precipitated by thermal decomposition of three kinds of metal compounds, and an alloy having no impurities is generated. Therefore, hydrogen annealing and strain relief annealing in the conventional production of permalloy are performed. Both are unnecessary.
The metal octylate compound, which is a raw material for nickel and iron, is not commercially available and was purified by the following method. When octylic acid (a product of Kyowa Hakko Chemical Co., Ltd.) whose composition formula is represented by C ₇ H ₁₅ COOH is reacted with an aqueous solution of sodium hydroxide NaOH (first-class reagent), a carboxyl group COOH of octylic acid is formed. hydrogen is ionized, sodium ionized carboxyl groups are bonded, sodium _C 7 _H 15 COONa octylate is precipitated. The sodium octylate is washed with water to purify the sodium octylate. Next, when sodium octylate is reacted with an aqueous solution of nickel sulfate (primary reagent) or iron sulfate (primary reagent), nickel octylate Ni (C ₇ H ₁₅ COO) ₂ or iron octylate Fe (C ₇₎ (H ₁₅ COO) ₃ precipitates. The precipitated nickel octylate or iron octylate is washed with water to purify the nickel octylate or iron octylate. Note that molybdenum octylate Mo (C ₇ H ₁₅ COO) ₆ (an industrial chemical having a CAS number of 34041-09-3) cannot be synthesized by the above-mentioned production method, and therefore, an imported product was used. Note that, as the organic compound, methyl caprate was used as in Example 3. As the glass frit, the glass frit of Example 1 was used. The linear expansion coefficient of this glass frit is 132 × 10 ⁻⁷ / ° C., which is close to the linear expansion coefficient of PC Permalloy of 136 × 10 ⁻⁷ / ° C., and the glass frit undergoes volume shrinkage after thermal decomposition of the metal octylate compound. Gaps are not formed due to this.
First, 414 g of nickel octylate (corresponding to 1.2 mol), 72 g of molybdenum octoate (corresponding to 0.075 mol) and 109.5 g of iron octylate (corresponding to 0.225 mol) Was dispersed in methanol so that each of the components became 10% by weight, and these methanol dispersions were mixed. This mixture was mixed so that methyl caprate was 10% by weight. Further, 39.3 g of glass frit was mixed and stirred.
Next, the mixture was placed in a container and fired in an air atmosphere. First, the temperature was raised to 65 ° C. to vaporize methanol, and further to 230 ° C. to vaporize methyl caprate. Next, it was left at 290 ° C. for 1 minute to thermally decompose three kinds of metal octylate compounds.
A plurality of cross sections cut from the surface of the sample were observed with an electron microscope in the same manner as in Example 1. First, with respect to reflected electron beams from the surface of the sample and a plurality of cross sections, a secondary electron beam between 900 and 1000 V was taken out and subjected to image processing. In each part of the sample surface, a collection of fine particles having a size of 40 to 60 nm was uniformly formed on the entire surface. On the cross section of the sample, 9 to 10 layers of fine particles were laminated on the surface of the glass frit.
Next, with respect to the reflected electron beam from the surface of the sample and a plurality of cross sections, image processing was performed by extracting energy between 900 V and 1000 V, and the material of the particles was analyzed based on the density of the image. Since the density of each of the particulate fine particles was recognized, it was found that the particles were composed of a plurality of types of atoms.
Further, the energy and the intensity of characteristic X-rays from the surface of the sample and a plurality of cross sections were image-processed to analyze the types of elements constituting the fine particles. It was composed of a large amount of nickel atoms, a small amount of iron atoms, and a few molybdenum atoms. From the molar ratio of the metal octylate compound used, the particulate fine particles are composed of nickel, molybdenum 5, and iron 15 in a proportion.
From the above observation results, it was found that the glass frit was covered with a large number of PC permalloy fine particles, and the glass frit was bonded by the metal bond of the PC permalloy fine particles. This result is not shown because it is similar to the result of Example 1.
In the same manner as in Example 1, the surface resistance at a plurality of positions on the sample surface was measured with a surface resistance meter. The surface resistance was less than 1 × 10 ³ Ω / □, and the sample had a surface resistance close to PC permalloy. The specific resistance of PC permalloy is 55 μΩcm, which is close to the specific resistance of iron of 10 μΩcm.
From the above results, the sample manufactured in this example has properties close to PC permalloy. This embodiment is only an example. Many glass frits have a softening point higher than the thermal decomposition temperature of the metal octylate compound, and various metals precipitate due to the thermal decomposition of the metal octylate compound. A collection of processed glass frit can be produced.

Example 7
The glass frit group produced in Example 6 was heated to 350 ° C., and a sheet having a thickness of 0.35 mm was formed by calendering.
The cut surface of the prepared sample was observed with an electron microscope in the same manner as in Example 1. The glass frit was bonded in a thin sheet shape, the surface of which was covered with a collection of PC permalloy fine particles, and the glass frit was bonded with a collection of PC permalloy fine particles. The result is not shown because it is similar to the sheet of Example 2.
Further, in the same manner as in Example 1, the surface resistance of the prepared sample was measured by a surface resistance meter. The surface resistance was less than 1 × 10 ³ Ω / □. For this reason, the molded body has conductivity close to that of PC permalloy. Therefore, a sheet made of glass frit can be used as an excellent shield sheet having a performance of absorbing electromagnetic waves.
This embodiment is only an example. In other words, a glass molding machine or a mold is filled with a collection of glass frits, and if the temperature is raised above the softening point of the glass frit and a compressive stress is applied, various shapes in which the glass frit softened by the metal bonding of the alloy fine particles are bonded to each other. Can be manufactured.

The seven embodiments described above are only some examples. That is, as described in paragraph 42, since the softening point of most glass frit is higher than the thermal decomposition temperature of the metal carboxylate, it has a softening point close to the thermal decomposition temperature of the metal carboxylate, Glass frit with expansion coefficient can be selected. For this reason, the glass frit treated at a temperature lower than the softening point is not hot-worked, and is left at the annealing point of the glass frit for at least 15 minutes to release the strain. Returns to the state before the processing. Therefore, the glass frit after the treatment does not change with time, and can be used as a raw material of a molded body when necessary.
Further, the metal carboxylate compound composed of various metal ions described in paragraph 32 can be used as a raw material of the metal fine particles, and the metal carboxylate compound that precipitates the metal or alloy constituting the fine particles can be selected according to the application. In addition, the metal compound is dispersed in alcohol to form a liquid phase, whereby the metal carboxylate adheres to the glass frit, and only heat treatment of the glass frit causes the glass frit to be joined together. Can be produced, and there is no restriction on the carboxylic acid metal compound used. For this reason, it is possible to produce a collection of glass frits in which glass frits made of various components are combined with metal fine particles made of various metals or alloy fine particles made of various alloys.
Furthermore, since the fine particles are two orders of magnitude smaller than the size of the glass frit, when the glass frit is softened or when the softened glass frit is deformed, the collection of fine particles covering the glass frit is reduced to the glass frit. Follow and deform. For this reason, there is no restriction on the manufacturing method of forming a conventional formed body in manufacturing a formed body by bonding the softened glass frit. Therefore, various manufacturing methods for forming a conventional glass molded body can be used.

1 and 3 Glass frit 2 and 4 Copper fine particles

Claims (6)

The glass frit covered with a collection of metal particles, a manufacturing method of the glass frit together with a metal bond of the metal particles to produce a collection of the glass frit is coupled includes a first property of depositing metal by thermal decomposition, a metal compound thermal decomposition temperature combines a lower second nature than the softening point of the glass frit, dispersed in an alcohol, a first step of creating an alcohol dispersion liquid in which the metal compound is uniformly dispersed in the alcohol The first property of dissolving or mixing with the alcohol, the second property having a higher viscosity than the alcohol, and the third property having a boiling point higher than the boiling point of the alcohol and lower than the thermal decomposition temperature of the metal compound. the organic compound having both a, and mixed with the alcohol dispersion, that the organic compound is dissolved or miscible in said alcohol, said metal compound A second step of said organic compound to create a liquid mixture uniformly mixed in the alcohol, the collection of glass frit immersed in the mixed solution, depending on the viscosity of the mixed liquid to the surface of the glass frit uniformly adhered to the mixture at a thickness, after this, a third step of taking out the collection of the glass frit from the mixture, wherein the collection of said glass frit metal compound heated to thermally decompose temperature, first vaporizing the alcohol, then vaporizing the organic compound on the surface of the glass frit, causes precipitation of a collection of fine crystals of the metal compound, further, the metal compound is thermally decomposed, the glass frit At a temperature lower than the softening point, the thermal decomposition of the metal compound is completed, and a granular metal fine particle corresponding to the size of the fine crystal of the metal compound is formed on the surface of the glass frit. Collection of child precipitates, the metallized bond sites where the metal fine particles are in contact with each other, with collection of the metal bonded metal particles to cover the glass frit, the glass frit covered the fine metal particles to metal bond , the metal binding of the metal particles, and a fourth step of collection of the glass frit the glass frit to each other bound is manufactured, the collection of the glass frit, 15 minutes or more to anneal point of the glass frit standing And a method of continuously performing these five steps, wherein the glass frit is covered with a collection of metal fine particles, and the glass frit is bonded to each other by metal bonding of the metal fine particles. it is a combined method of manufacturing a collection of the glass frit. Oxygen production process for producing a collection of the glass frit the glass frit to each other are joined by metallic bonds of the fine metal particles as claimed in claim 1, the metal compound as claimed in claim 1, which constitutes the carboxyl group of the carboxylic acid The first characteristic in which the ion is covalently bonded to the metal ion, and the carboxylic acid is a metal carboxylate compound having the second characteristic of a saturated fatty acid, the organic compound according to claim 1, carboxylic acid esters is an organic compound of any one kind belonging to one of glycols or glycol ethers, glass frit according to claim 1, a softening point of the carboxylic acid metal compound is from thermally decomposed temperature is high glass frit The method according to claim 1, wherein the metal carboxylate, the one kind of organic compound, and the glass frit are used. Glass frit with each other to produce a collection of the glass frit bonded by a metal bond of the metal fine particles according to five of the manufacturing method steps a continuously carried out, the glass frit mutually bonded with a metal bond of the metal fine particles according to claim 1 it is a process for the preparation for producing a collection of the glass frit. A manufacturing method for manufacturing a formed body made of glass frit having metal properties, using a collection of glass frit in which glass frit is bonded by metal bonding of metal fine particles manufactured according to the manufacturing method according to claim 1 , to produce a collection of the glass frit the glass frit each other are bonded by a metal bond of the metal fine particles according to the production method carried out continuously five steps described in claim 1, a molding machine or a die to a collection of the glass frit The glass frit is softened and deformed by applying stress by the molding machine or the mold, and the metal fine particles covering the deformed glass frit are metal-bonded, so that the deformed glass frits are bonded to each other. And formed of a collection of the deformed glass frit in the molding machine or the mold. Body is molded by slow cooling to room temperature after standing for at least 15 minutes to anneal point of the glass frit molded product, a method of manufacturing a molded article comprising the glass frit with the nature of the metal. The glass frit covered with a collection of alloy particles, a method of manufacturing a collection of the glass frit the glass frit to each other are joined by metallic bonds of the alloy particles at the same time deposit a pyrolyzed different metals at the same temperature A plurality of metal compounds having both the first property to be performed and the second property whose thermal decomposition temperature is lower than the softening point of the glass frit are dispersed in alcohol, and the plurality of metal compounds are uniformly dispersed in the alcohol. The first step of preparing an alcohol dispersion, and the first property of dissolving or mixing with the alcohol, the second property having a higher viscosity than the alcohol, the boiling point is higher than the boiling point of the alcohol, and the the organic compound a plurality of types of metal compounds having both a lower third property from thermal decomposition temperature simultaneously mixed with the alcohol dispersion, organic Kika By things dissolved or miscible in said alcohol, said a second step of the plurality kinds of metal compound and the organic compound to create a liquid mixture uniformly mixed in the alcohol, the collection of glass frit mixed immersed in the liquid, uniformly adhere to the mixture at a thickness corresponding to the viscosity of the mixed solution on the surface of the glass frit, thereafter, a third step of taking out the collection of the glass frit from the mixture, wherein the collection of said glass frit plurality of metal compounds is heated to thermally decompose the temperature at the same time, to first vaporize the alcohol, then vaporizing the organic compound on the surface of the glass frit, the plurality of types of causing precipitation of a collection of fine crystals of metal compounds, further, the plurality of types of metal compound is thermally decomposed at the same time, lower than the softening point of the glass frit temperature In, the plurality Several pyrolysis is completed at the same time of the metal compound on the surface of the glass frit, a collection of the plurality of types of granular alloy particles according to the size of the fine crystals of the metal compound is deposited, alloy and metal binding at the site where fine particles contact each other, with collection of alloy microparticles the metal bond cover the glass frit, the glass frit covered the alloy particles and metal bonding, a metal bond of the alloy particles, a fourth step of collection of the glass frit the glass frit to each other bound is manufactured, a fifth slow cooling the collection of the glass frit to room temperature after standing for at least 15 minutes to anneal point of the glass frit A method of continuously performing these five steps is that a glass frit is covered with a collection of alloy fine particles, and the metal frit of the alloy fine particles is bonded. Is a manufacturing method for manufacturing a collection of the glass frit the glass frit to each other are coupled. A method for producing a collection of glass frit in which glass frits are bonded to each other by metal bonding of alloy fine particles according to claim 4, wherein the plurality of types of metal compounds according to claim 4 are characterized in that the carboxyl group in the same saturated fatty acid oxygen ions constituting the group is a plurality of types of carboxylic acid metal compound covalently bonded to a different metal ions, organic compounds according to claim 4, carboxylic acid esters, in any of the glycols or glycol ethers 5. The glass frit according to claim 4, wherein the glass frit according to claim 4 is a glass frit having a softening point higher than a temperature at which the plurality of kinds of carboxylic acid metal compounds are thermally decomposed simultaneously. The method according to claim 4, wherein an acid metal compound, the one kind of organic compound, and the glass frit are used. Glass frit with each other to produce a collection of the glass frit bonded by a metal bond alloy particles according to the manufacturing method for implementing the placing the five steps in succession, the glass frit together with a metal bond alloy particles according to claim 4 There is a method of manufacturing a set of combined the glass frit. A manufacturing method for manufacturing a formed body made of glass frit having properties of an alloy by using a collection of glass frit in which glass frit is bonded by metal bonding of alloy fine particles manufactured according to the manufacturing method according to claim 4 , to produce a collection of the glass frit the glass frit each other are bonded by a metal bond alloy particles according to the production method carried out continuously five steps according to claim 4, the molding machine or a die to a collection of the glass frit The glass frit is softened and deformed by applying stress by the molding machine or the mold, and the alloy fine particles covering the deformed glass frit are metal-bonded to each other, so that the deformed glass frits are bonded to each other. Is composed of a collection of the deformed glass frit in the molding machine or the mold. Form is molded by slow cooling to room temperature the molded product after standing for at least 15 minutes to anneal point of the glass frit is a method of manufacturing a molded article comprising the glass frit having the property of the alloy.

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