TW201018647A - Method for synthesizing powder and method for fabricating electronic part and component - Google Patents

Abstract

This invention provides a method for synthesizing a powder for reducing corrosion of a reaction container, decreasing impurity which mixes with a product due to corrosion, or increasing a choice of materials of which the reaction container is made. The method of this invention is to provide a power material which stays at a reaction field for a predetermined period of time to produce powder microparticles so as to be able to moderate critical condition for generating a subcritical or supercritical state in a manner that is even more preferable than the case where only water exists. Achieving the objective entails heating and/or pressurizing a mixture of water and a solvent under a supercritical state, at temperature and pressure lower than the ones required to achieve the same supercritical state for only water, creating a reaction environment for the subcritical or supercritical state, and treating the reaction environment created for the subcritical or supercritical state as the reaction field.

Description

201018647 % VI. Description of the invention: - Technical field to which the invention pertains The invention relates to the field of powder synthesis for the production of metal oxide powders and the manufacturing technology of electronic parts; in particular, regarding - m ^ PTCCPositive Temperature

Coefficient, positive temperature coefficient) dielectric material for electronic components such as components, piezoelectric material, semiconductor material, and other materials for the production of barium titanate fine particles, and methods for producing electronic components. © [Prior Art] It has been known that tetragonal barium titanate (BaTi〇3) has a very high relative dielectric constant. Therefore, it is possible to suppress the thickness of the dielectric layer to a few Mm by applying to a multilayer ceramic capacitor. The capacitor can be made small and large. Then, as the capacitor is miniaturized, the thickness of the dielectric layer is also becoming thinner and thinner. Therefore, there is a barium titanate powder as a dielectric material used for the dielectric layer as a nanometer. Various proposals have been made for particles and microparticles to become nm-level. ❹ As a method for producing such barium titanate microparticles, various proposals such as a solid phase reaction method, an oxalic acid method, and a sol-gel method are proposed. In addition, temperature and pressure are important parameters of the chemical reaction, that is, there is a liquid reaction in which the reaction temperature is raised above the boiling point of the liquid medium to increase the system's repeated force above atmospheric pressure to cause the liquid phase to react. Examples of such a liquid phase reaction include a hydrothermal synthesis method, a solvothermal method (reaction), and a supercritical hydrothermal method. In addition, when the reaction temperature is raised above the boiling point of the liquid medium to raise the pressure of the system above atmospheric pressure to react the liquid phase in the liquid phase, the use of water 3 321544 201018647 is called "hydrothermal anti-library" ^ t ~ 'if When another organic solvent is used as the reaction medium, it is called "solvent heat reaction". Further, the solvothermal method can produce nano particles of several nanometers, but it is often seen that it takes hours to days to produce nanobes. Therefore, it is not easy to produce fine particles of several cuts or so. ^ If the supercritical hydrothermal method exceeds the critical temperature and critical pressure of the liquid, the ion reaction speed is fast and it is easy to produce nano particles, and it is also suitable for the flow-through manufacturing process for mass production: super-sleeping The boundary water t method is produced by mixing a titanium compound aqueous solution and a hydrazine salt aqueous solution/4, adding a water supply solution, and then performing a hydrothermal reaction in water of a subcritical or supercritical state: The cubic crystal or 5 〇 (10) is a [first-party-locked Nylon particle (for example, refer to Patent Document H). [Patent Document 1] JP-A-2003-261329 (Patent Document 2) JP-A-2005-289737 [Summary of the Invention] [Problems to be Solved by the Invention] The conventional supercritical hydrothermal method of 2, etc. is carried out in the low temperature condition of the hot material village, but it still needs to exceed the critical temperature of water (374. The above high temperature conditions. This ^ in order to get the subcritical Water or supercritical water state, the silk force, also needs to exceed the high pressure condition of 3 MPa or more of the critical pressure of water (22 MPa). Wire, corrosion of reaction vessel or pipeline, etc. or caused by corrosion 321544 4 201018647 - Impurity The problem of mixing into the target product. That is to say, the material can be used under the conditions of the critical temperature and the critical pressure of the supercritical water. The material that can be used is a HaseU〇y material with sus or anti-corruption. ❹ ^品名), etc. 'But there is a rot under the conditions of high temperature and high pressure, and Fe'Cr, such as Fe'Cr, is a mixture of impurities in the production of titanium dioxide. Further, Ti which is excellent in corrosion resistance is in the order of 35 generations or more: the strength is weakened at a high temperature, and therefore it is not possible to produce a material such as a reaction vessel or a pipeline which is disclosed in a conventional supercritical hydrothermal method such as Patent Document 2. In addition to the super-critical hydrothermal method of pure water, it is possible to synthesize the number (10) of the size of the 〇1〇 and the specific surface area of green 〇 〇 MVg and very high ^ rice particles, but 'because it will lower the overall Gibbs (Gibbs) Free two Γ, there are also problems that easily cause agglutination between particles. The agglomeration of nanoparticles reduces the quality of the powder. = In addition, in the _ thermal method of not using water at all, even if it is raised to a solvent like water 2 = and above the critical pressure, the decomposition power of hiding organic matter will not be 'so' in order to synthesize fine particles, it is necessary to be relative to the supercritical ruler... Long reaction time. Further, when the powder is synthesized by a conventional hydrothermal method disclosed in Patent Document 2, etc., in order to rapidly heat the room temperature: the original: slurry and the critical state 'requires a large amount of high-temperature water. For example, in the case of a high temperature water of about 5 〇〇C at room temperature, in order to exceed the critical temperature of water 374, the supercritical water of the slurry flow rate is more than 4 times. Therefore, it becomes lower and the synthesis efficiency is lowered. On the other hand, there is a problem that hydrothermal synthesis occurs during heating when it is mixed, and the critical reaction of super 321544 5 201018647 cannot be achieved. However, the batch processing in which the time is concentrated into one device or the processing is divided according to the operation of each unit and the raw materials are concentrated and processed according to the division is suitable for mass production. When the reaction conditions of the conventional hydrothermal synthesis are applied to the supercritical reaction environment, the aqueous solution of the aqueous compound and the aqueous solution of the cerium salt are mixed, and the alkaline aqueous solution is put into the reaction vessel together, and the temperature and pressure are raised by heating, and finally Become supercritical. Therefore, the temperature and pressure at the initial stage of the reaction are more greatly reduced than the temperature and pressure in the latter half of the reaction. Further, since the reaction is continuously performed during the temperature rise and the pressure rise, the conditions of temperature and pressure are changed. As a result, the particles to be produced are coarsened, the uniformity is deteriorated, or the crystallinity is lowered. As such, batch mode has the potential to achieve a reaction in a supercritical environment.

The present invention has been made in view of the above, and it is an object of the present invention to provide a method for synthesizing a powder which can reduce corrosion of a reaction container or the like, or a mixture of impurities due to corrosion, or a material which can expand the reaction volume. And methods of manufacturing electronic parts. Further, an object of the present invention is to provide a powder which can be used as a powder which can be used as a raw material which is low in content of impurities such as Fe, Cr, Ni, etc., specifically, a content of 200 ppm or less and which is used for the production of electronic parts. A method of synthesizing and a method of producing an electronic component using the powder. Further, an object of the present invention is to provide a method for synthesizing a ruthenium which can synthesize a small amount of aggregated particles (nanoparticles) with high dispersibility in a short time, and a method for producing an electronic component using the same. . 321544 6 201018647 The present invention has been made in view of the foregoing, and it is an object of the present invention to provide a larger amount of raw material concentration (e.g., about one digit) which is higher in the reaction zone than in the conventional flow-through supercritical hydrothermal synthesis. A method of nanoparticle and a method of producing an electronic component using the powder. The present invention is directed to a method for synthesizing a powder of a powder having a small particle size and good crystallinity by generating a subcritical reaction environment or a supercritical reaction environment by batch processing. And methods of manufacturing electronic parts. ® [Means for Solving the Problem] In order to solve the problem and achieve the object, the first aspect of the method for synthesizing the powder of the present invention uses water and lower temperature and lower in comparison with water alone. a mixed solvent which becomes a solvent of a supercritical state under pressure, and generates a reaction environment of a subcritical or supercritical state by at least one of heating and pressurization to generate a reaction environment of the subcritical or supercritical state as a reaction field 'The powder raw material is retained in the reaction field for a predetermined time Φ to generate powder fine particles. In order to solve the above problems and achieve the object, the "second aspect of the method for synthesizing the powder of the present invention" has the following steps: the raw material and the lower pressure and lower temperature when compared to the presence of water alone The first step of pressurizing and heating the raw materials prepared by mixing the supercritical state agents. The pressurized and heated raw material slurry and the reaction accelerator containing water are respectively supplied to the reaction path' and a second step of generating a reaction environment in which the reaction path generates a subcritical or supercritical state in the reaction path; and using the aforementioned reaction environment in the subcritical or supercritical state as a reaction field, the slurry of the raw material 321544 7 201018647 is subjected to the reaction. The third step of generating the powder fine particles after the predetermined time has elapsed, and the fourth step of cooling the generated fine powder particles to stop the growth of the fine powder particles. Further, the method for synthesizing the powder of the present invention is the above invention, wherein the second step comprises: pressurizing and heating the raw material slurry at a higher volume ratio than water contained in the reaction accelerator. Supply to the reaction path. Further, the method for synthesizing the powder of the present invention has the step of heating the reaction accelerator, and the second step of supplying the reaction accelerator heated by hydrazine to the reaction path. Further, in the method of synthesizing the powder of the present invention, the solvent is a solvent which becomes a supercritical state at a lower pressure than when water alone exists. The second step is formed by pressurization. Subcritical or supercritical state. Further, the method for synthesizing the powder of the present invention is the above invention, and the solvent includes an organic solvent which can be continuously dissolved in a supercritical state and water. Θ In order to solve the above problems and achieve the object, the third aspect of the method for synthesizing the powder of the present invention has the following steps: the raw material and the lower pressure and lower temperature in the presence of water alone a first step of heating at least a slurry prepared by mixing a solvent in a supercritical state; mixing the heated slurry with a reaction accelerator containing water to generate a subcritical state or a supercritical state by at least heating The second step of the reaction environment; θ and the first $ music: the body is retained in the reaction environment for a predetermined time to generate the powder 8 321544 201018647 particles, and after the predetermined time elapses, the third growth of the powder particles is stopped. step. Preferably, in the preferred embodiment of the present invention, in the method of synthesizing the powder, at least the slurry fed to the reaction vessel is heated in the first step, and at least heated in the second step. The reaction accelerator is added to the slurry, and in the third step, the growth of the powder particles is stopped by decompressing at least one of the slurry in the reaction vessel and cooling the slurry in the reaction vessel. . Preferably, in the preferred embodiment of the present invention, in the method of synthesizing the powder, in the first step, the slurry is pressurized. Preferably, in the preferred embodiment of the present invention, in the method of synthesizing the powder, the growth of the above-mentioned powder particles is stopped by cooling and depressurizing the slurry in the reaction environment. At this time, the slurry system of the above reaction environment was rapidly cooled and depressurized. As a preferred aspect of the present invention, a method of synthesizing the powder in the above-mentioned powder is preferred, and the heated reaction accelerator is mixed in the polymer. Further, when the reaction accelerator is in a small amount, it may not be heated, for example, a mixture of room temperature water and a high temperature slurry. As a preferred aspect of the present invention, it is preferred to synthesize the powder, and to stir the slurry while adding the aforementioned reaction accelerator. As a preferred aspect of the present invention, it is preferred that the powder is synthesized in such a manner that the precursor is in a subcritical or supercritical state before the addition of the reaction accelerator. As a preferred aspect of the present invention, it is preferred to synthesize the above powder 9 321 544 201018647 Method 'The foregoing solvent is a supercritical state and an organic solvent in which water is continuously dissolved. The preferred embodiment of the present invention is preferably a method for synthesizing the powder. The reaction accelerator comprises water. In addition, in order to solve the above problems and achieve the object, the method for producing an electronic component according to the present invention is to manufacture an electronic component including an electron (four) obtained by slurrying powder fine particles generated by the above-described method of production as a two-component element. . [Effects of the Invention] According to the present invention, a subcritical or supercritical state of a mixed solvent is produced by using water and a mixed solvent of a solvent which becomes a supercritical state at a lower temperature and a lower pressure than when water alone exists. The reaction environment, therefore, can reduce the critical temperature and/or critical pressure used to generate the subcritical or supercritical state, so that the corrosion of the reaction vessel or the like can be reduced by the relaxation of the critical conditions or the impurities due to the corrosion The effect of blending the product or expanding the selection range of the material of the reaction container or the like. Further, by performing gold plating on the surface of the reactor, the impurities of the mixed product can be reduced. In addition, by increasing the proportion of the alcohol in the mixed solvent, the reaction trapping of the pure water synthesis can be greatly suppressed, and the synthesized particles rapidly diffuse due to the solvent and the party to the Brownian motion, thereby obtaining a better dispersion. status. Further, according to the second aspect of the present invention, the slurry is not subjected to the reaction even if the slurry of the shoulder prepared by using a solvent such as an alcohol is not subjected to the reaction, and the raw material slurry is pressurized and heated. To the reaction path, the raw material slurry can be heated without a large amount of reaction accelerator to generate a subcritical or 321544 10 201018647 - superb boundary (four). By this, the ratio of the mixing ratio of the critical water (4) slurry can be read, that is, the amount of the raw material can be increased more than that of the reaction accelerator, and the number of digits can be increased even more than the supercritical hydrothermal synthesis. The concentration of the raw material in the anti-f region enables a larger amount of nanoparticle to be produced. In addition, :: the reaction is added to the reaction path by using high temperature fines plus temperature. For example, when the temperature after mixing is said, it is not necessary to add ❹ = body and water preheating temperature to 3 〇. . 〇 Above. In particular, the ratio of water is /. Room temperature water can also be used. The reaction accelerator is to the shed. The ci-like" does not require preheating of the rotted money containing water, and (4) increases the height to reduce the safety of the powder of the third aspect of the present invention due to the high temperature water::::: domain. The manufacturing method is capable of achieving results by means of electronic components. ～ The effect of the powder having a small diameter and good crystallinity is exemplified. [Embodiment] The following is a detailed description of the production of a synthetic material for carrying out the powder of the present invention. The present invention = various changes are made. In addition, in the case of / invented, it is possible that the person with ordinary knowledge in the technical field can easily think about it and the real person: the same person, that is, in the range of equals and so on. And the permeate phase (summary of the present invention) ^Inventive read synthesis method, when the time of hiding (4) is compared with the solvent at a lower temperature and a lower pressure in the presence of a water single sheet, which is a supercritical solvent, 321544 11 201018647 The reaction environment of the subcritical or supercritical state is generated by heating and/or pressurization, and the powder is synthesized in the reaction environment. Thereby, the critical condition for generating a subcritical or supercritical state is more relaxed than when water alone exists. As such a solvent, there is a polar organic solvent which is lower than the critical temperature and critical pressure of pure water. The polar organic solvent which can be used in the present invention is, for example, ethanol (about 241 ° C, 6 MPa), methanol (about 239 ° C, 8 MPa), isopropyl alcohol (about 235 ° C, 4.8 MPa), methyl ether ( 127 ° C, 5.3 MPa), acetone (235 ° C, 4. 6 MPa). Here, the use of ethanol as a solvent is exemplified. Fig. 1-1 and Fig. 1-2 are characteristic diagrams showing the critical conditions of a mixed solvent of mixed water and ethanol. In addition, Figure 1-1 shows the relationship between critical temperature and ethanol agronomy. Figure 1-2 shows the relationship between non-critical pressure and ethanol concentration. Further, in Figs. 1-1 and 1-2, the measurement results of the examples described later (i.e., part of the experimental data) are also displayed. In addition, the critical conditions are described in the literature "AA Abdurashidova, AR Bazaev, E. A. Bazaev and IM Abdulagatov, "The thermal properties of water-ethanol system in the near-critical and supercritical states" 'High Temperature Vol. 45 No 2,2007, pl78-186" (hereinafter referred to as Reference 1) is calculated as a critical condition. First, the critical temperature Tw when the water is alone is about 374 ° C, and the critical pressure Pw is about 22 MPa. On the other hand, in the presence of ethanol alone, the decomposition power of supercritical ethanol is slightly lower than that of supercritical water, the critical temperature Te is about 241 ° C, and the critical pressure Pe is about 6. IMPa, which has a critical condition lower than water. . Here, 12 321544 201018647 mixed solvents of mixed water and ethanol, such as Dibu > m, a diagram and 1-2, the temperature of the £s boundary Tm and the critical pressure Pm with the E + a · The weight ratio changes. In other words, by mixing ethanol in water and lowering the critical temperature and critical pressure than when water is present alone, the weight ratio of ethanol is higher and the critical temperature and critical pressure are further lowered. Then, by adjusting the ratio of the composition of the mixed solvent (water and ethanol) to adjust the critical temperature Tra and the critical pressure pm of the mixed solvent, the reaction rate, the particle growth rate, the control of the crystallinity, and the dispersibility of the resultant powder can be achieved. The control of the cockroach. For example, when the oxalic acid titanium oxide is placed on the surface of the human body and kept at a supercritical state of 300 ° C and 20 MPa for more than 丨 hours, almost no decomposition reaction occurs, and barium titanate BaTi 〇 3 cannot be synthesized. On the other hand, when supercritical water of 400 〇C and 30 MPa is added, yttrium yttrium is formed in only i seconds. By increasing the ratio of water by this characteristic, the decomposition rate of the organic substance can be increased, and barium titanate fine particles and the like can be produced at a high speed. In addition, the ion product [H+][〇H—] of the two warm waters is at 2〇〇. (: The temperature of the temperature to 300 °C is about 10-11, and the decomposition ability of water is also the largest. At the same time, the ion reaction can also be promoted. In addition, as shown in the figure 丨-丨 and 卜2, if When the molar fraction of ethanol is about 30% or more, the mixed solvent of water and ethanol can have sufficient decomposition power, and at the same time, it is about 3 〇〇〇c or less, and the critical condition of 10 MPa is very lower than that of pure water. In addition, if the ratio of ethanol is increased, the mixing temperature can be further reduced: the critical temperature Tm of the grain, the critical pressure pm, and the decomposition rate (reaction speed) or the rate of formation of the fine particles can be alleviated. In addition, by further reducing the critical temperature and critical pressure, and slowing down the temperature and pressure conditions, the corrosion in the reactor can also be reduced. For example, the ratio of the mixed solvent can be increased by increasing the ratio of ethanol. The temperature is reduced from 374t: down to about 260°C, and the critical pressure is reduced from 22MPa to 6MPa to 7MPa. The result is, for example, even if it is used by SUS or sulphur

When Hastel loy material is used as a reaction vessel or pipeline of material, k also weakens its corrosivity and reduces the content of impurities relative to the product. Alternatively, the critical temperature and the critical pressure of the mixed solvent can be drastically reduced. For example, the critical temperature can be lowered to 30 (TC or less. Therefore, the material selection range of the reaction container or the like can be expanded to use Ti having good corrosion resistance. Even if it is a ratio of sputum and ethanol, it must be adjusted to contain water. Because it does not contain Jc, it has the effect of reducing the decomposition power or the ionic reaction rate is insufficient. ❹ Because the mixed solvent of water and ethanol 'even It is the same temperature, =, and also maintains the decomposition power of the subcritical water environment, which is the same as the supercritical reaction environment of the early-phase. Therefore, := in the manufacture of barium titanate The synthesis of the powder of the present invention is carried out without cutting into a uniformity of barium titanate, and it is possible to produce high-crystallity barium titanate nanoparticles even after the event of post-temperature sintering. Help: Dispersion of raw materials and products. For example, when TTMt has: sub-, the number of sub-particles is a block of submicron relative to η. Production of supercritical energy by adding a mixed solution of ethanol' Brother, (4) _ 钡 钡 钡 钡 钡 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321

St = = said 'in the super solvent produced by the addition of ethanol, ~ should be the environment, can make the block of barium titanate particles disappear, human. Titanic acid depends on the full dispersion of the slit ten nm _ microparticles / materials and The nuclear (4) system is not limited to ethanol, as long as it can lower the critical temperature, the critical pressure, and the organic solvent soluble in water as compared with pure water. For example, an alcohol which is inexpensive and low in toxicity (methanol, propanol, IPA (isopropanol), butanol, etc.) or a propionate or the like can be used. : a reaction environment generated by a subcritical mixed solvent or a supercritical mixed solvent state generated as described above, that is, by using mixed water and becoming supercritical under lower temperature and lower pressure than when water alone exists The reaction environment composed of the subcritical or supercritical state of the mixed solvent of the solvent is applicable to a synthesis method of a powder, for example, a scorpion. As an example thereof, for example, it is applied to Patent Document 2, etc., by mixing an aqueous solution of a titanium compound and an aqueous solution of cerium salt, and after adding an alkaline aqueous solution, in a mixed solvent of a subcritical or supercritical critical state, a mixed solvent is used. Thermal synthesis is carried out to produce barium titanate microparticles. Specifically, the raw material titanium oxide and barium hydroxide may be added to an alcohol, dispersed in a supercritical alcohol state, and then mixed with a reaction accelerator containing water by a subcritical or supercritical state. The solvent is mixed to produce barium titanate fine particles. If necessary, an alkaline aqueous solution containing NaOH or an organic pH adjuster TMAH (tetramethylammonium oxide) may also be added. The Ti〇2 powder of the raw material is not dissolved in water, but it is easy to produce a powder of the order of nm, so that the slurry can be directly prepared without pulverization. The Ba(〇H) 2 system of the raw material is easily ionized when it is mixed with high-temperature and high-pressure water. Therefore, it is not necessary to pulverize 321544 15 1 201018647. Further, in order to ensure a more uniform reaction, it is preferred to disperse the raw material slurry in the supercritical alcohol before the water and the raw materials are filled. Further, in order to adjust the Ba:Ti in the barium titanate of the product, it is possible to adjust Ba: Ti in the starting genus to be about 1:1. Further, the method for synthesizing the powder of the present embodiment is not limited to a system suitable only for metal vapors and hydroxides, and is also applicable to vapors, nitrates, carbonates, organic acid salts, and composite metal compounds. Original oblique. For example, it is not limited to the application of Patent Documents 1, 2, etc., and can be applied to a novel method for producing bismuth citrate fine particles. Novel method for producing barium titanate microparticles® is schematically provided by using a composite metal complex comprising ruthenium and titanium as a starting material to supply a composite metal complex to a subcritical supercritical state formed by a mixed solvent. In the reaction environment, it is retained for a predetermined time to form barium titanate microparticles. Specifically, the bismuth oxalate oxime system has ruthenium and titanium in a ratio of 1: 近 at a close distance in the same molecule, and can be reacted by an equimolar ratio when decomposed into a supercritical mixed solvent. Crystallization produces barium titanate microparticles. In more detail, the composite metal complex is completely decomposed by utilizing the decomposition force of the subcritical or supercritical mixed solvent, and at the same time, by reacting in a reaction environment of a subcritical or supercritical state generated by the mixed solvent. The thermal synthesis of the supercritical mixed solvent of the field causes the ion of the decomposed complex & metal complex to be crystallized into small-sized and highly crystalline barium titanate microparticles of the order of nm. As described above, in the present embodiment, by using titanium oxide + cerium hydroxide and a composite metal complex containing cerium and titanium as a starting material, it is possible to use it in a slurry state without being dissolved in a solvent. At the same time, such as 321544 16 201018647 - Li Wenbi 2, etc., can be achieved without the limitation of solubility, achieve a high degree of supersaturation, to achieve the formation of barium titanate. Further, the composite metal complex containing the powder of cerium and lanthanum is present in the ratio of 1:1 between the close distances in the originally identical molecules, and therefore, by decomposition of the composite metal complex Immediately, it is crystallized by a reaction at a molar ratio to produce barium titanate having a high conversion rate. In addition, the composite metal complex as a raw material is in a reaction environment in a subcritical mixed solvent or a supercritical mixed solvent state, the mantle is subjected to a decomposition treatment and a two-stage treatment by synthesis treatment of crystallization, so When the state is directly input, the no-treatment speed is excessively rapid, and the reaction time for increasing the crystallinity can be ensured. Here, the composite metal complex containing ruthenium and titanium as a starting material includes a buffer of bismuth and titanium (particularly a bismuth oxychloride) or a titanium oxyhydroxide. In the titanium oxyhydroxide, it is preferable that Ba: Ti = 1 ·· i of bismuth oxalate, titanium oxyhydroxide. In view of the easiness of obtaining, the cost of raw materials, and the low content of c〇2, etc., it is most suitable as titanium oxyhydroxide BaTi〇(C2〇4)2 · 4H2〇. In this embodiment, titanium oxalate oxalate is used. Further, in order to adjust the Ba: Ti in the product: barium titanate (BaTi〇3), Ba: Ti in the starting material can be appropriately adjusted to about 1:1. For example, when the titanium oxalate oxalate is supplied to the reaction environment of the subcritical mixed solvent or the supercritical mixed solvent state and retained, it can be completely decomposed together with the organic component of the titanium oxalate raw material within a few seconds to several minutes. The barium titanate microparticles are produced by subsequent synthesis. As a result, the efficiency of the manufacturing steps of the barium titanate microparticles 321544 17 201018647 can be greatly improved not only by the batch manufacturing process using the autoclave but also by the continuous flow type manufacturing process by which the yield is good. (Embodiment 1) 1 stroke threshold The present embodiment 1 shows the application of the method of manufacturing a general-purpose pear sister-in-law of a barium titanate which is applied to a continuous flow type manufacturing process by a state of a rush method. example. Fig. 2 is a schematic diagram showing the schematic configuration of a continuous flow type manufacturing apparatus to which the present invention is applied. The speed is as follows: i, the pipe 3 and the apparatus are provided with a slurry which is supplied from the valve 2 by stirring the slurry containing the slurry of the raw material as a room temperature high-pressure slurry, and supplies I soil water, the reaction tube of the field The slurry pump 4 of 3; the liquid supply pump which is supplied by the tank 5 through the valve 6 for 'heating by the heater 7 to become high temperature water' mixed with the high temperature slurry at room temperature 8; a cooling tank 9 disposed on the discharge side of the y; and a recovery tank 11 connected to the side of the sag by the valve 10. The inside of the reaction tube 3 is also provided with a heating 12 in which the inside of the furnace is heated to a supercritical state (or a subcritical state). In addition, the continuous flow manufacturing shock mounting shown in Fig. 2 causes the fluid to flow from the lower side to the upper side, but it is also possible to use two of the shell warm water and the room temperature high pressure slurry on the upstream side. The line is disposed above the reaction tube 3 to allow fluid to flow from the upper side to the lower side. Further, the thickness of the reaction tube 3 is, for example, a pipe having an inner diameter of 8 mm in the second embodiment to be described later. However, a commercially available pipe having a diameter of 1/32 inch to several (10) may be used. Further, in the example shown in Fig. 2, the flow path arrangement for mixing the line between the warm water line and the room temperature high-pressure slurry is formed. However, when the reaction time is as long as several minutes, the line on the warm water side can be omitted. , a flow path configuration in which only the prepared water or solvent and the reactants are deposited in the reaction tube 3 by the slurry of 18 321 544 201018647. In addition, the manufacturing equipment is designed to make the raw material polymerization line become the south temperature and south pressure and mix with the surface temperature and the south pressure water. In this way, by also making the slurry high temperature and high pressure, it is not necessary or necessary to heat the slurry by water or a mixed solvent of water and a solvent, so that the mixing ratio of the raw material slurry: water can be made 1: 1 or more. Thereby, the raw material concentration of the reaction portion can be increased, and productivity can be improved. Next, a method of producing the barium titanate fine particles of the first embodiment will be described. Fig. 3 is a schematic flow chart showing a method of producing barium titanate using the continuous flow type manufacturing apparatus shown in Fig. 2. A. Raw material preparation step First, a raw material preparation step is carried out. In the raw material preparation step, the raw materials are prepared, and various treatments such as pulverization of the raw materials, preparation of the slurry, and dispersion of the slurry are sequentially performed. In the pulverization treatment of the raw material, in order to facilitate the discharge from the slurry pump 4, the raw material particles are pulverized by a ball mill, a pellet mill, and a planetary pulverization to a size of about several +/- m. In order to reduce the inconsistency of the product, it is preferred to pulverize to a submicron size. Here, in the first embodiment, the Ti〇2 powder which is commercially available as a submicron is used as the raw material, and therefore, the pulverization treatment is not required. Further, in the state in which titanium oxynitrate is used as a raw material, the raw material particles are pulverized by the following treatment. As the pulverization method, a wet ball mill method in which zirconia is used as a sphere, ion exchanged water in a solvent, and ethanol in a polar solvent can be used. The pulverization time is 24 hours, the volume ratio is as follows: Sphere: Solvent = 1: 4: 8, the cylinder volume of the ball mill is 700 mL, and the volume ratio of the contents of the cylinder is 70% or more, and the size of the raw material is 19 321544 201018647. 5以上。 The average size of the raw material powder is about 0.5. The preparation of the slurry of bismuth oxalate titanate is such that the powder concentration in the slurry is, for example, 25 g/L. As a stable condition for the acidity lock, it must be an environment of pH > 12, therefore, adjust the pH by adding an aqueous test solution (adding electrolyte or water test or ammonia). In the first embodiment, NaOH was added. The specific addition amount of NaOH is determined by the amount of C〇2 contained in the raw material. However, when, for example, bismuth oxalate is used as a raw material, the ratio of NaOH: C〇2 is set as an index to be greater than 2: Prevent the formation of BaC〇3. Further, when Ti 2 and Ba (0H) 2 are used as raw materials, a pH adjusting agent such as NaOH or TMAH may be added without adding a test. The dispersion treatment in the slurry is carried out by ultrasonic waves for 5 minutes to 10 minutes before the reaction. Next, at the time of the reaction treatment, the slurry is stirred by the slurry mixer 1 and sent to the slurry pump 4 side. B. Reaction Environment Formation Step The reaction environment formation step is a step of generating a reaction environment in a subcritical mixed solvent or a supercritical mixed solvent state, and various treatments for adjusting the critical conditions of the mixed solvent, heating and pressurizing, and mixing. The adjustment treatment as a critical condition of the mixed solvent adjusts the ratio of water to solvent (ethanol). Here, the amount of water is made 5 wt% to 95 wt% in terms of % by weight. Thereby, the critical temperature of the mixed solvent is adjusted between 260 ° C and 370, and the critical pressure is adjusted between 8 MPa and 22 MPa. In the heat treatment, the pure water is heated by the heater 7 to become a state of high temperature water. Further, the reaction tube 3 containing the slurry containing the high-temperature water and the organic solvent 2013018, 201018647 (ethanol, etc.) is heated by the heater 12 to a temperature higher than the critical temperature of the mixed solvent to be prepared. In the pressurization treatment, the raw material containing the raw material supplied from the slurry mixer 1 and the organic solvent (ethanol, etc.) is pressurized to a mixed mixture by the slurry crucible 4, and the raw material is near the critical pressure of the solvent. The polymer was supplied to the reaction tube 3 side as a room temperature high pressure polymer. In the mixing treatment, high temperature and high pressure water and a room temperature high pressure slurry are mixed and supplied to the reaction tube 3. In the mixed state, the reaction environment in the reaction tube 3 is preferably a condition close to the critical condition of the mixed solvent, and becomes a supercritical state exceeding the critical temperature and the critical pressure. In particular, the lowest temperature system capable of synthesizing tetragonal barium titanate is greater than 215 C, and the lowest pressure system is greater than 5 MPa'. When titanium oxalate is used as a raw material, the pH of the alkaline environment is greater than 12 to 14. Therefore, in order to improve the squareness, the reaction environment in the reaction tube 3 is preferably a temperature and a pressure higher than the critical condition of the mixed solvent. ❹C. Powder Formation Step The private formation step is to reserve the slurry containing the titanium oxalate oxalate in the reaction tube 3 in the reaction environment which is formed into a supercritical mixed solvent-like bear (or subcritical mixed solvent state). The step of generating barium titanate microparticles in time 'continuously performs the decomposition or dissolution step and the crystallization step. C-1·Decomposition or Dissolution Step In the decomposition or dissolution step, supercritical mixing by supplying a slurry containing a reactant (metal oxide, hydroxide or composite metal complex, etc.) to the reaction tube 3 The solvent state (or subcritical mixed solvent state) reaction 321544 21 201018647 environment, and the supercritical solvent decomposition decomposition to decompose or dissolve the components of the reactants. More specifically, for example, if T i 〇 2 + Ba (0H) 2 is used as a raw material, it is dissolved into Ba+2, Ti〇2 hydrate, Ti(0H)4 hydrate,

Ions of Ti(0H)3+1, TiCOHV1, and the like. Further, if oxalate is used as an example, the complicated molecular structure is completely destroyed by the decomposition force generated by the intense collision of the molecular and subcritical mixed solvent or supercritical mixed solvent. For example, titanium oxide is Ti(0H)4(aq) or

Ti(0H)3+1 or ΤΚΟΗ), etc., the organic component of the oxalate is completely decomposed to a simple molecular grade such as C0, C〇2, Η2〇. Next, the components such as Ti and Ba which are decomposed and dissolved are dissolved in a subcritical mixed solvent or a supercritical mixed solvent. As a result, the decomposed inorganic component achieves high saturation (supersaturation). That is to say, the powder of Ti〇2, Ba(0H)2, and bismuth oxalate is used as a raw material, and therefore, when it is decomposed into a subcritical mixed solvent or a supercritical mixed solvent, it can be partially realized in a simple manner. High supersaturation, and suitable for nanocrystallization of the formed barium titanate particles. The time required for the decomposition or dissolution step varies with temperature, pressure, and type of reactant. ^ ❹ C-2. Crystallization step In the crystallization step, after decomposing the titanium oxysulfate, in the reaction tube 3, the reaction environment in the state of the subcritical mixed solvent or the supercritical mixed solvent is used as the reaction field and then retained. The reaction time is to thermally synthesize a supercritical mixed solvent containing the decomposed Ba or Ti ions to form a nucleus of barium titanate for crystallization to form a high crystalline nanometer size titanate lock. . At this time, the time (reaction time) which is retained in the reaction tube 3 constituting the reaction field 22 321544 201018647 is adjusted and controlled. The treatment in the crystallization step must be carried out for a minimum of several seconds at the same time as the temperature and pressure conditions of the above-mentioned subcritical mixed solvent or supercritical mixed solvent state. Then, in order to obtain higher crystallinity, it is preferably retained in a subcritical mixed solvent or a supercritical mixed solvent for several seconds or more to stably crystallize. In order not to be limited by the length of the reaction tube (i.e., the length is not too long), and it does not grow to a particle size of a desired size or more, the reaction time is preferably within several tens of seconds. Thereby, the most suitable size of about 50 nm to 150 nm and the highly crystalline barium titanate are produced. Regarding the titanate lock, it is known that the optimum size of the highest relative dielectric constant from 5Onm to 15Onm is excessively smaller or excessively larger than this size, and the relative dielectric constant of the barium titanate powder tends to decrease. Here, the reaction time which is retained in order to control the crystallinity and particle diameter of barium titanate is adjusted by the diameter or length of the reaction tube 3, or by adjusting the flow rate of the pump 4, 8 or the valves 2, 6. The adjustment and the adjustment of the timing of the rapid cooling of the reaction are stopped. The stoppage of the growth of barium titanate (BaTi〇3) particles is carried out by rapid cooling using the cooling bath 9. The cooling rate is, for example, a rapid cooling rate of about 30 ° C /sec or more, and is cooled to room temperature. Further, the formed barium titanate particles rapidly flow and diffuse in the supercritical mixed solvent by the good dispersion characteristics of the organic solvent in the supercritical mixed solvent to disperse the barium titanate particles. In this way, aggregation of the particles can be suppressed by reducing the contact between the newly generated particles. Further, when the particle aggregation prevention after the crystallization step is emphasized, the mixing ratio can be adjusted to increase the ratio of the organic solvent of the mixed solvent. 23 321544 201018647 D. Recovery step In the recovery step, the gas is released by depressurization to atmospheric pressure with a valve 10, and gas-liquid separation is carried out to recover the slurry to the recovery tank U. In the case of the recovered body, 'the removal of the additive Na' is washed by ion-exchanged water. Further, barium titanate powder and liquid are separated by centrifugation by rotation at a high speed of at least several thousand rpm or more. Further, the pH adjustment was repeated until it became neutral, and then, by a dryer at about 1 Torr. The crucible is dried and finally the barium titanate microparticles are obtained. In the present embodiment, ethanol and ion-exchanged water constituting the mixed solvent are mixed into the slurry. However, the present invention is not limited thereto. For example, ethanol or water may be mixed in the supply path of the high-temperature water, or by separately. Ethanol is supplied to the reaction tube 3 instead of water, and on the other hand, water is mixed into the slurry to be supplied to the reaction tube 3, and becomes a mixed solvent in the reaction tube 3. In any case, it is sufficient to know the mixing ratio of water and ethanol. Further, at least the mixed solvent in the reaction tube 3 may be in a subcritical or supercritical state. According to the aforementioned reference 1, if it is about 35{rc#, the ethanol itself does not decompose due to supercritical water. In the actual experiment, the hydrolysis rate of ethanol is also very slow at a temperature of from 400 ° C to 500 ° C, and therefore, the mixed solvent of the present invention can be produced. (Embodiment 2) Here, the raw material slurry system prepared by water undergoes a hydrothermal reaction in the flake slurry during preheating. Therefore, in the conventional flow-through supercritical reaction, the supercritical reaction environment is rapidly achieved by mixing the warm water with the raw material slurry at room temperature. However, in order to mix high-temperature water like this and become supercritical, 321544 24 201018647 requires high-temperature water of several times the room temperature slurry. That is to say, in order to become a supercritical state, there is a limit to the ratio of the raw material slurry that can be mixed with high-temperature water. Therefore, it is limited by the amount of materials that can be synthesized. On the other hand, the raw material slurry system prepared by an organic solvent such as an alcohol does not contain water, and even if it is supercritical, the reaction speed of the raw material slurry is very slow, compared with the high-speed reaction of high-temperature high-pressure water and raw materials. In the present invention, the raw material slurry containing no water is heated and pressurized to a target temperature and a target pressure by the difference in the reaction rate, and then reacted with a water-containing reaction to accelerate the reaction. By preheating the raw material slurry as described above, it is not necessary or necessary to heat the raw material slurry with high-temperature water, so that the feeding of the raw material slurry can be more greatly improved than in the conventional supercritical flow-type reaction. Involvement. As a result, it is possible to apply a continuous flow type production step with good mass productivity, and it is possible to greatly improve the efficiency of the production steps of the barium titanate fine particles. In the second embodiment, an application example of a method for producing barium titanate fine particles suitable for use in a rapid flow-through manufacturing process in which a supercritical state is easily produced by the present invention is shown. Fig. 4 is a schematic plan view showing a continuous flow type manufacturing apparatus according to a second embodiment of the present invention. The continuous flow type manufacturing apparatus includes: a heater 13 that heats a slurry supplied from a slurry aggregator 1 that mixes a slurry containing a raw material via a valve 2 to generate a high-temperature slurry; The high-temperature slurry generated by the heating is supplied as a high-pressure high-temperature slurry to the slurry pump 4 constituting the reaction tube 3 of the reaction field; and the heated state 7 of the high-temperature water is generated by heating the pure water supplied from the tank 5 via the valve 6; a liquid supply pump 8 that is supplied to the reaction tube 3 by mixing 25 321544 201018647 high-temperature water and high-temperature high-pressure slurry generated by heating by the heater 7; and a cooling tank 9 disposed on the discharge side of the reaction tube 3; And a recovery tank u connected to the discharge side of the cooling tank 9 via a valve. Further, the continuous flow crucible manufacturing apparatus is provided with a heating heater for heating the portion of the reaction tube 3 in a supercritical state (or a subcritical state) around the reaction tube 3, and is also shown in Fig. 4 In the example of the continuous flow type manufacturing apparatus, the fluid flows from the lower side to the upper side. However, two lines of the warm water and the high-temperature high-pressure slurry which are the upstream side may be disposed on the upper portion of the reaction tube 3 to make the fluid. Flow from the upper side to the lower side. Further, as the thickness of the reaction tube 3, a commercially available pipeline of 1/32 inch to several (10) in diameter can be used. Here, when the raw material slurry is not heated, in order to make the mixed fluid become the commercial temperature surface pressure, it is necessary to preheat the supercritical water to a temperature higher than the critical condition (for example, at a critical temperature of 2 〇〇. 〇 to 300) (: high temperature), the ratio of the mixture of supercritical water and raw material slurry is more than that of supercritical water, that is, the supercritical water mixed with preheating is more than the raw material slurry. For example, in order to exceed the supercritical water Condition 'Supercritical water: The mixing ratio of the raw material slurry must be about 4:1 or more. Therefore, the concentration of the raw material in the fluid after mixing is lowered. In contrast, by supplying the reaction to the heater 13 The slurry of the tube 3 becomes high temperature and high pressure', and it is not necessary or necessary to heat the polymer by water (supercritical water), so that the mixing ratio of the raw material slurry: water can be 1:1 or more, that is, the raw material slurry In addition, when the mixed solution of water and the solvent is supplied from the liquid supply pump 8 side, the mixing ratio of the raw material slurry: the mixed solution can be similarly set to 1:1 or more. Raw material (metal salt raw material The volumetric flow rate (cc/min) of the whole body of the crucible is not included in the raw material water 26 321544 201018647, and the volume flow rate of the reaction (or mixed solution) can be increased to be more than 丨. Further, in the example shown in Fig. 4, the heater 7 is used to heat the water, and the present invention is not limited thereto, and the water may be maintained in the chamber π, that is, the room temperature water is supplied to the reaction tube. 3. The raw material_ can be made into a high dish temperature and the proportion of mixed water can be reduced. Therefore, even if the water supplied to the reaction tube 3 is used as room temperature water, the inside of the reaction tube 3 can be made subcritical or supercritical. Here, the method for producing the barium titanate fine particles of the second embodiment can be basically produced by the same production method as that of the first embodiment except for the step of heating the slurry. 5 brothers in the second embodiment of the method of manufacturing the chitin-staple microparticles. In the case of the continuous flow-through manufacturing apparatus shown in Fig. 4, first, the raw material preparation step is prepared as the raw material preparation step. The pulverization of the raw material, the preparation of the slurry, and the dispersion of the slurry are performed. Next, the reaction environment of the reaction state is generated as a subcritical mixed solvent or a supercritical mixed solvent. Here, various processes of heating, twisting, and mixing are performed. Here, the heat treatment "heats the body to a high temperature slurry by the heater 13." The pure water is heated by the heater 7 to be in a state of high temperature water. Further, the reaction tube 3 containing the slurry containing the high-temperature water and the organic solvent (ethanol, etc.) is kept at a critical temperature of the mixed solvent to be prepared by the heater 12. Further, in the pressurization treatment, by the slurry The body pump 4 pressurizes a slurry containing a raw material supplied from a slurry stirrer 27 321544 201018647 and an organic solvent (ethanol, etc.) to a critical pressure of the aforementioned organic solvent, and, as described above, by a heater 13 is heated to supply the raw material slurry to the reaction tube 3 side as a high-temperature high-pressure slurry. Further, the pure water system is also pressurized by the liquid feeding pump 8 and heated by the heater 7, and pure water is supplied to the λ reaction tube 3 side as high-temperature high-pressure water. Further, the pure water system can be used as room temperature high pressure water without heating. In the mixing treatment, the high temperature and high pressure water and the high temperature and high pressure slurry are mixed, or the room temperature high pressure water and the high temperature and high pressure slurry are mixed and supplied to the reaction tube 3. In the mixed state, the reaction environment in the reaction tube 3 is preferably close to the condition of the mixed solvent © critical conditions, and becomes a supercritical state exceeding the critical temperature and the critical pressure. As described above, in the reaction environment generating step to generate the reaction environment, the barium titanate fine particles can be produced by performing the above-described powder forming step and recovery step. Here, in the present embodiment, the liquid system in which the reaction tube (reaction region) 3 and the slurry are mixed may contain at least a reaction accelerator for accelerating the water of the powder synthesis, and as described above, it may be an ethanol (organic solvent). The mixed solvent may also be a mixed solvent with other solvents which are not related to the reaction. Further, in the reaction tube 3 in which the slurry and the reaction accelerator are mixed, a subcritical or supercritical state must be generated. Further, the slurry system may be in a state containing a liquid as long as it does not contain water. In the present embodiment, the raw material slurry is preferably in a state in which the crystal water contained in the raw material slurry or the water contained in the alcohol is less, and for example, Ba(0H)2 · 2H2〇, Ba(0H)2 can be used. 8Η2〇 of the reactants with crystal water, about 99% of the alcohol sold in the market. 28 321544 201018647 . As such, the slurry supplied by the slurry mixer 1 which agitates the slurry containing no water is supplied as a high-temperature high-pressure package via the valve 2, the slurry chest 4, and the heater 13 to constitute a reaction field. Reaction tube 3. By thus, the slurry is supplied to the reaction field at a south temperature, and the slurry can be subcritical or supercritical even if the slurry is not heated by the mixed water. Thereby, the synthesis of the powder can be carried out in a ratio of a solvent or a condition in which the concentration of the raw material is high, that is, a condition in which the ratio of water to the slurry is small. Further, basically, it is not necessary to heat the slurry by the hydrophobic water, and therefore, it is not necessary to make the water high temperature. In addition, it is not necessary to heat the slurry by a large amount of high temperature water to become a subcritical or supercritical state. Thereby, the temperature of the water supplied to the reaction tube can be lowered, and the official line capable of heating the supply water becomes a high temperature, which can suppress the occurrence of rot. In addition, even if the slurry system is heated to a subcritical or supercritical state, the reaction rate in the state where water is not contained (the rate at which the raw material decomposes to form particles) is still slow, so the reaction (the decomposition of the raw material or the formation of particles) does not occur. get on. On the other hand, P is heated first, and basically, the synthesis of the powder is not carried out. When the reaction tube 3 and water are mixed and become a subcritical or supercritical state, they are synthesized to form a powder. Further, in the above embodiment, the synthesis of barium titanate is described, but in the present embodiment, in addition to barium titanate, a synthesis method of various metal vapor nanoparticles may be used; for example, ferrous salt , a method of synthesizing a positive electrode material of a primary battery of a battery material, a phosphor, and the like. For example, a dielectric material, a ferrous salt, a positive electrode material of a lithium secondary battery, a phosphor, or the like can be obtained by using a conventional supercritical hydrothermal synthesis method, but various kinds of these are synthesized. In the case of microparticles, the above-mentioned more excellent characteristics of the nanoparticles are also produced by applying the method of the present invention to 29321544 201018647. More specifically, as a synthesis example of dielectric nanoparticles, except _

In addition to BaTi〇3, SrTi〇3, (Ba, Sr)Ti〇3, (Ba, Ca)Ti〇3, (Ca〇.25CUD.75) Ti〇3 are also listed. As the positive electrode material of the lithium secondary battery, synthesis of LiCo〇2 or LiFeP〇4 can also be used, and as a synthesis system of ferrous salt nanoparticles, synthesis of BaO·6Fe2〇3 or the like can also be used. (Embodiment 3) In the third embodiment, an application example of a method for producing barium titanate fine particles which is applied to a batch manufacturing process using a high-volume pressure cooker having a high mass productivity is shown. In the case of the circulation type, when it is large, it is limited by the capabilities of the slurry pump 4, the liquid supply pump 8, the heater 7, and the like. Therefore, in the case of mass production, it is suitable for the batch type of the third embodiment. Fig. 5 is a schematic diagram showing the schematic configuration of a batch type manufacturing apparatus according to a third embodiment of the present invention. This batch type manufacturing apparatus is constituted as a main body by a pressure cooker 21 which supplies a reaction vessel containing a slurry of a raw material to generate a reaction environment. The pressure cooker 21 includes a stirrer 22 for stirring the supplied slurry, and a heater 23 for performing a reaction environment in which the inside of the pressure cooker 21 is supercritical (or subcritical) by applying heat and pressure. . Further, a valve 24 that communicates with the atmosphere is provided on the upper side of the pressure cooker 21, and the recovery groove 26 is connected to the bottom side via the valve 25. The recovery tank 26 has an exhaust port 27. Next, a method of producing the barium titanate fine particles of the third embodiment will be described. Fig. 6 is a schematic flow chart showing a method for producing barium titanate using the batch type production apparatus shown in Fig. 5. Further, the detailed description of the steps of the state of the manufacturing method described with reference to Fig. 3 will be omitted. 30 321544 201018647 庸 A. Raw material preparation step ' The raw material preparation step is the same as in the third drawing. However, the dispersion of the slurry is dispersed by ultrasonic waves for 5 minutes to 10 minutes before the reaction, and the slurry containing the raw material is supplied to the pressure cooker 21, and then dispersed by the stirring of the mixer 22. . B. Reaction environment generation step The reaction environment generation step is a step of generating a reaction environment in a subcritical mixed solvent or supercritical mixed solvent state, and is subjected to heating, pressure treatment, and adjustment of the critical conditions of the mixed solvent. This heating and pressurization treatment is carried out in the pressure cooker 21 by heating the slurry containing the raw material and the organic solvent (ethanol or the like) into the pressure cooker 21 by the heater 23 to a critical temperature or higher of the mixed solvent. The reaction environment of the subcritical mixed solvent or supercritical mixed solvent state. The pressurization at this time is pressurized by heating, and is pressurized to a critical pressure of the mixed solvent. This pressure is adjusted by the heating temperature and the filling rate of the slurry. The filling rate of the slurry is about 10% or more of the volume of the pressure cooker 21. In addition, the adjustment of the critical conditions of the mixed solvent is the same as that described in the flow-through reaction environment generation step. C. Powder Formation Step The powder formation step is carried out by using a slurry containing niobium oxalate in a pressure vessel 21 of a reaction vessel which is formed in a reaction environment of a supercritical mixed solvent state (or a subcritical mixed solvent state). The step of generating barium titanate microparticles for a predetermined period of time consists of a decomposition or dissolution step and a crystallization step. The decomposition or dissolution step at this time is the same as that in the flow pattern described in Fig. 3, 31 321 544 201018647. In the crystallization step, after decomposing the titanium oxalate titanate, the reaction environment in the state of the subcritical mixed solvent or the supercritical mixed solvent is used as the reaction field to retain the predetermined reaction time in the pressure cooker 21 to synthesize the decomposed oxalic acid The thermal synthesis treatment of the supercritical mixed solvent of titanium ions forms a nucleus of titanium 'acid strontium to form a high crystalline nanometer titanate. At this time, the temperature increase rate is 1 〇 or more, and the temperature rise time is within a few ten minutes to reach the state of the supercritical mixed solvent of the most temperature and pressure. Further, by causing the generated particles to rapidly flow and diffuse in the supercritical mixed solvent, the contact between the newly formed particles is reduced to suppress aggregation of the particles. The growth of the barium titanate particles is stopped after the reaction field reaches the highest temperature and pressure, and the barium titanate or the like is not maintained in the reaction field in the pressure cooker 21, and the open valves 24, 25' are sharply reduced by the injection of the pressure cooker 21. Press it on. The decompression speed at this time is reduced to atmospheric pressure within a few seconds to several minutes (e.g., 1 MPa / sec). In addition, the cooling temperature is below about 10 °C. D. Recovery step In the recovery step, the pressure is released from the pressure cooker 21 to atmospheric pressure to release the helium gas, and the gas-liquid separation is carried out to recover the slurry to the recovery tank 26. The washing, drying, solid-liquid separation, and flow-through of the recovered slurry were carried out in the same manner. Thereby, barium titanate fine particles are finally obtained. (Embodiment 4) In the following, the batch manufacturing apparatus shown in Fig. 7 is used as the fourth embodiment, and the application of the batch-type manufacturing microparticles suitable for the batch manufacturing process of the autoclave having good mass productivity is shown. An application example of the manufacturing method. 32 321 544 201018647 ❹ This FIG. 7 is a schematic view showing a schematic configuration of a batch type manufacturing apparatus according to a fourth embodiment of the present invention (that is, a method for realizing the synthesis method of the powder of the present embodiment). Schematic diagram of a configuration example of a manufacturing apparatus). The sub-contracting manufacturing system shown in Figure 7 implements a batch-type manufacturing process, which is suitable for mass production of titanium lag particles. The batch type manufacturing apparatus supplies a reaction valley containing a starting surface (4) to generate a reaction environment. η 101 is constructed as a center. The reaction container has a reaction environment of a stirrer 1G2 for mixing the slurry, and heating to cause the reaction vessel 101 to generate a supercritical m critical state, and by: Γ: Heater (heating means) 105; cooling reactor vessel Τ: slurry cooler 118: and measuring reaction vessel 〇2 =: 104. Reaction vessel Pressure cooker, pressure vessel in a face pressure. In addition, 1 can be set. One device 118 is connected to the injection channel in response to the need for the reaction. The rapid agent is passed through the injection path (10) to the reaction vessel. _ The person who is away from the powder: the pressure, and monitor the reaction conditions of the oral form of the embodiment. Further, the predetermined pressure is maintained in the reaction vessel iQi while the reaction accelerator is being injected by the back pressure valve 112. In the tank 110, a reaction accelerator used in the method for synthesizing the powder of the present embodiment is stored. In the present embodiment, the reaction accelerator is pure water or an aqueous alkaline solution containing water. The groove 11 is connected to the injection path 103 via the pump 1〇9, the i-th valve VI, and the 321544 33 201018647 2 wide V2. When the first valve VI and the second valve V2 are opened to drive the pump 109, the reaction accelerator (hereinafter referred to as water) in the tank 110 is supplied into the reaction vessel 1〇1 through the injection path 1〇3. The pressure of the back pressure valve 112 is adjusted to the aforementioned target value so that the pressure in the tank 110 does not exceed the target value during operation of the pump 109. Further, a heater 108 is provided as a heating means for the reaction accelerator in the supply path of the reaction accelerator. After heating the reaction accelerator supplied to the reaction vessel 101 by the heater 108, the warmed water is supplied into the reaction vessel 1〇1. In the injection path 103, the compressed gas cylinder 116 is connected via the second valve V2. The compressed gas cylinder 116 is filled with an inert gas (for example, a〇g. The inert gas G in the compressed gas cylinder 116 is supplied to the reaction vessel ι1 as needed when the raw material and the solvent are charged into the reaction vessel 101. The reaction vessel 1〇1 is connected to the discharge path 119. The gas or liquid in the reaction vessel 101 or the slurry after the reaction is discharged from the discharge path π9. The third valve V3 and the fourth valve V4 are connected to the discharge path 119. The fifth valve V5 is connected to the recovery container 115 via the fourth valve "and the filter ι 3" in the discharge path 119. The recovery container 115 is recovered from the slurry after the reaction by the method of synthesizing the powder of the present embodiment. The container of the produced product (powder particles) pw is provided with an exhaust path 114 in the recovery container U5, and the gas in the recovery container 115 is discharged to the outside. The third valve V3 is connected to the discharge path 119 on one side, and the other The side is connected between the outlet of the filter 113 and the inlet of the recovery container 115. When the reaction in the reaction container 101 is stopped, the third valve is opened, and the pressure in the reaction container 101 is drastically lowered, thereby causing the reaction container 1 to be closed. The polymer in the crucible 1 is rapidly ejected into the recovery container 115 by 321544 34 201018647. Further, when the reaction is stopped, the fourth valve V4 can be opened, or after decompressing in the reaction vessel 101, by the cooler 118. Cooling is carried out to recover the powder of the product to the reaction vessel 101. The fifth valve V5 is connected to the discharge path 119 on one side and to the inlet of the vacuum pump 117' on the other side. The vacuum pump 117 is supplied to the reaction vessel 101 in the raw material and solvent. In the meantime, the air in the reaction vessel 101 is discharged to the outside. At this time, as described above, the inert gas G in the compressed gas cylinder 116 can be supplied to the reaction vessel 101 as needed. ❹ Next, the use of Fig. 7 will be described. A method for producing barium titanate microparticles in the case of a batch-type manufacturing apparatus. Here, the method for producing barium titanate described above can be realized by the method for synthesizing the powder of the present embodiment. When the batch type manufacturing apparatus 100 is used to produce barium titanate by the method of synthesizing the body, the same as the manufacturing method of the third embodiment shown in the sixth embodiment, the A. raw material preparation step and the B. reaction environment are generated. Step C, powder formation step, D. recovery step to produce a powder of barium titanate. @ A. Raw material preparation step First, a raw material preparation step is performed. The raw material preparation step is the same as the production method of the third embodiment. The raw materials are prepared, and various treatments such as pulverization of the raw materials, preparation of the slurry, and dispersion of the slurry are sequentially performed. Here, the dispersion of the slurry is dispersed by ultrasonic waves for 5 minutes to 10 minutes before the reaction. After the slurry containing the raw material is placed in the reaction container 101 included in the batch type production apparatus 100 shown in Fig. 7, the dispersion treatment is performed by stirring by the agitator 102. Further, in the raw material preparation step, the pulverized raw material and the slurry may be placed in the reaction vessel 101, and the two may be mixed and dispersed in the reaction vessel 35 321544 201018647 101. Here, when the slurry is put into the container 101, the air to the reaction container is discharged by the vacuum pump 117, and if necessary, the compressed gas cylinder 116 is filled with an inert gas such as Ar into the reaction container 101. Further, the pulverization treatment can use the aforementioned method. Further, the aforementioned pH adjusting agent may be added as needed. Here, in the raw material preparation step, the slurry is subjected to dispersion treatment, and after the slurry is introduced into the reaction vessel 101, it is made into a solvent, for example, a critical condition of ethanol before the reaction accelerator is introduced, thereby achieving low surface tension. The supercritical state of supercritical ethanol. The raw material powder before the reaction is maintained in a well dispersed state by stirring of the supercritical alcohol. ❹ Reaction environment generation step The reaction environment generation step is a reaction of generating a reaction accelerator water and a subcritical state or a supercritical state of a mixed solvent of a solvent which becomes a supercritical state at a lower pressure than when water alone exists. The steps of the environment. The slurry in the reaction vessel 101 which is heated and pressurized by at least heating is supplied with water (pure water) which is rapidly reacted with the raw materials in the slurry by the tank 110 to form a mixed solvent of water and solvent. In the critical state or the supercritical state, in the present embodiment, the pressure in the reaction vessel 101 is increased by heating the slurry in the reaction vessel 1〇1, and as a result, the slurry is pressurized. That is to say, both the temperature rise and the pressure increase of the slurry present in the reaction vessel 101 are achieved by heating. However, the present embodiment is not limited thereto, and the slurry may be pressurized by means of forcibly pressurizing the slurry. For example, the slurry in the reaction vessel 101 can be forcibly pressurized by a pump pressurizing means to raise the 36 321 544 201018647 slurry, and the slurry is heated by the heater 105 to be warmed. If this is the case, the pressure can be changed without changing the temperature, and therefore, the reaction conditions can be easily controlled. As described above, in the present embodiment, the slurry in the reaction vessel 101 can be pressurized by heating, and the slurry can be lifted by forced pressurization, and can also be heated and forcedly added. In the meantime, the slurry is raised. ❹ The reaction accelerator contains at least water or water alone. Further, the reaction accelerator adjusts the pH, and therefore, the test agent can be added to the water. Further, the scrambler 102 can be used to carry out the scrambling, and the reaction accelerator can be supplied to the entire body if the reaction accelerator is supplied to the polymer. Therefore, the reaction can be started quickly. Although the liquid supply capacity of the pump 109 and the heating capacity of the heater 1〇8 are different from the amount of water of the reaction container 1〇1, the water present in the reaction container 1Q1 can be realized within a few seconds. The energy of the solvent: the agent's critical state or supercritical state. Further, in the present embodiment, the device 控制η is controlled to supply the water I to the reaction & 260 by the liquid supply speed and the injection time of the pump 1〇9. In order to supply water into the reaction vessel 101, the pressure in the thief 1 is set to the target value, and the back pressure cooler m is set. In addition, a safety valve 1〇7 is provided to allow the reaction to be carried out without exceeding the safety pressure. Thereby, the pressure in the reaction vessel 101 in which the supply water is reacted is at a predetermined pressure. It is a solvent which dissolves the scorpion scorpion (in this embodiment, ethanol) alone, and does not perform the reaction of the secondary steel, or even if it is carried out, even if the reaction environment of the missing-human critical state or the supercritical state is generated. It is also extremely slow ' 321544 37 201018647 Therefore, in the method of synthesizing the powder of the present embodiment, the temperature is raised and boosted by at least heating the slurry of the starting material and the solvent (the third step), and the preparation is prepared. After the reaction environment, water having a fast reaction rate with the starting material in the slurry is supplied to the slurry to form a reaction environment in a subcritical state or a supercritical state (second step). In this case, by supplying water, the subcritical state or the supercritical state of the mixed solvent is generated. Next, the slurry containing the reactants is allowed to remain in the reaction environment for generation for a predetermined period of time, whereby the reaction of producing barium titanate from the reactants can be carried out. As described above, in the present embodiment, the water is supplied to the slurry by starting the reaction of generating barium titanate from the reactants (or starting the reaction very slowly) in the preliminary reaction environment. The subcritical state or the supercritical state of the mixed solvent of water and solvent starts the above reaction (or the above reaction is carried out abruptly). Therefore, in the method for synthesizing the powder of the present embodiment, the reaction environment in which the subcritical state or the supercritical state is generated at the desired timing can start the reaction of generating barium titanate from the reactants. Therefore, it is easy and accurate. The time of the reaction is well controlled. As a result, a powder having a small particle diameter (in the present embodiment, barium titanate) can be produced. ❹ Fig. 8-1 is a conceptual diagram showing pressure and temperature changes in the method of synthesizing the powder of the fourth embodiment. Fig. 8-2 is a conceptual diagram showing pressure and temperature changes of a method for producing a powder by a conventional batch hydrothermal synthesis method. When the mixed solvent of water and solvent is heated and pressurized to form a reaction environment in a subcritical state or a supercritical state, as shown in Fig. 8-2, the formation of titanic acid from the reactants starts in the rise of temperature and pressure. "The reaction. In addition, the temperature and pressure at the beginning of the reaction are significantly lower than the temperature of the latter half of the reaction 38 321544 201018647 degrees and the pressure. As a result, the temperature or pressure variation in the reaction is large, resulting in the formation of <0 phthalate microparticles In the case of growth, coarsening of the particles or reduction in crystallinity is caused. It is easy to produce fine particles such as nanoparticles. ❹ On the other hand, the method for synthesizing the powder of the fourth embodiment is as described above, after the preparation of the preliminary reaction environment. Supplying water to the slurry and starting the reaction of generating barium titanate from the reactants. Thereby, as shown in FIG. 8A, the reaction can be started after the slurry=temperature and pressure are stabilized, and therefore, The above reaction is carried out at a stable temperature and pressure. Therefore, it is possible to produce a particle having a small variation, and it is possible to suppress the growth of the generated barium titanate microparticles. Therefore, for example, a nanoparticle can be produced. In addition, since the reaction described above can be started by the supply of water, the control of the reaction time is also easy, and the control of the powder granules produced is also relatively easy. A preliminary reaction environment is formed in the reaction vessel 1 () 1 to supply the ruthenium containing the starting material and the solvent (ethanol) to the canned core state in the reaction vessel 101 to be heated by the heater 105 to constitute a slurry. The subcritical γ of the solvent of the body is more than Α, thereby making the solvent supercritical. The pressure of the slurry is boosted by heating, and the slurry is pressurized to the critical pressure of the solvent. ^ ^ ^ Knife above. The pressure is by heating the temperature and the slurry

The fill rate is adjusted. The filling rate of the 唠 A A body is, for example, about 10% or more of the volume of the reaction vessel 101. ^ The preliminary pressure in the reaction vessel 101 in the reaction environment of the reaction preparation is determined by the amount of water, the amount of reaction accelerated and the ratio of the solvent, and the temperature, which are filled in the reaction vessel 101. The agitator 102 provided in the container 101 is uniformly public and private, and the glutinous agent and the raw material are produced. In order to generate a better temperature, the temperature (preparation temperature) and the preparation pressure of the reaction environment prepared for the preparation of the knife are satisfactory. In addition, in the present embodiment, after the water is supplied to the body in the preliminary reaction environment, the subcritical state of the mixed solvent of water and the agent is rapidly generated or The reaction in the supercritical state. Therefore, in the reaction environment forming step, it is preferred to adjust the slurry/pressure and the pressure close to the target reaction conditions, thereby allowing the reaction to be carried out rapidly and rapidly. The environment generating step is preferably supplied to the polymer in the reaction vessel 101 after the water in the tank 110 is heated by the heater 108. ❹ In this case, the temperature of the body is suppressed. When the degree is lowered, the body/m degree can be increased by the water temperature, so that the subcritical state or the supercritical state of the mixed solvent of water and the solvent can be formed more quickly, and the reaction can be easily controlled. Preferably, the temperature of the water is raised at the target reaction temperature, whereby the water and the slurry 'tb S substance can be quickly brought into a subcritical state or a supercritical state after the water is supplied to the slurry. The environment generating step, as described above, preferably the mixture of water and slurry becomes a condition close to the critical condition of the mixed solvent, more preferably a supercritical state exceeding the critical temperature and critical pressure of the mixed solvent, especially capable of being synthesized into The minimum temperature of the tetragonal barium titanate is greater than 215 l, and the lowest pressure system is greater than 5 MPa. Therefore, in order to improve the squareness of the produced barium titanate, the reaction environment in the reaction vessel 101 is preferably higher than the criticality of the mixed solvent. The temperature and pressure of the condition. In addition, the critical condition of the mixed solvent can be changed by adjusting the ratio of water and solvent (ethanol). In this embodiment, the weight is The amount of water is 321544 40 201018647 is 5wt% to 95wt%. Thereby, the critical temperature of the mixed solvent is adjusted between 260 ° C and the critical pressure is adjusted between 8 MPa and 22 MPa. In this embodiment It is preferred that the crystal water contained in the raw material or the water contained in the alcohol is small, but in practice, it is also possible to use, for example, Ba(〇H) 2 · 8H2 具. Qin. Crystallized water reactant or commercially available About 99% alcohols C. Powder formation step The powder formation step is carried out by a reaction environment in which a subcritical state or a supercritical state is generated by supplying a reaction accelerator to the slurry and mixing a step of retaining a slurry of a metal oxide, a hydroxide or a complex metal complex, etc. for a predetermined time to form barium titanate microparticles (particles of powder) (step 3), by a decomposition or dissolution step and The crystallization step and the dispersion step are constituted. C-1. Decomposition or Dissolution Step In the decomposition or dissolution step, supercritical mixing is carried out by supplying a slurry containing a reactant (metal oxide, hydroxide or composite metal complex, etc.) to the reaction vessel 10101. The reaction state of the solvent state (or subcritical mixed solvent state) is decomposed by supercritical solvent addition to dissolve or dissolve the components of the reactant. As a result, the inorganic components such as Ti and Ba which are decomposed achieve high saturation (supersaturation). C-2. Crystallization step In the crystallization step, after decomposing the titanyl oxalate, the reaction environment in the state of the subcritical mixed solvent or the supercritical mixed solvent is used as the reaction field in the reaction grid 101 to re-stay the predetermined reaction. At a time, by synthesizing a thermal synthesis treatment of a supercritical mixed solvent containing ions of decomposed Ba or Ti, 321544 41 201018647 forms a nucleus of barium titanate for crystallization to form a highly crystalline nanometer-sized barium titanate. . The resulting particles rapidly flow in the supercritical mixed solvent and are 'diffused, reducing the contact between the newly formed particles and suppressing the aggregation of the particles. When the generated nm-sized barium titanate particles are kept in this state for a long period of time, particles may grow. In order to stop the growth of barium titanate, the temperature and pressure in the reaction vessel 101 can be made lower by holding the barium titanate or the like in the reaction field in the reaction vessel 101 after reaching the target reaction time. It is realized by the value of the supercritical condition. In the present embodiment, by opening at least one of the third valve V3 and the fourth valve V4, the high-temperature high-pressure fluid is injected from the reaction vessel 101, and the inside of the reaction vessel 101 is rapidly decompressed, thereby lowering the temperature in the reaction vessel 101. And stress. By cooling and decompressing the slurry in the reaction environment by the third valve V3 and the fourth valve V4, the reaction environment can be easily eliminated and the growth of the barium titanate particles can be stopped. The decompression speed at this time is a speed which is decompressed from the subcritical or supercritical pressure to the atmospheric pressure within a few seconds to several minutes. In the present embodiment, the reaction can be stopped only by opening the third valve V3 and the fourth valve V4 of the batch-type manufacturing apparatus 100. Therefore, the reaction time can be freely controlled in units of seconds, minutes, and hours. It is particularly easy to achieve the advantages of high speed reaction control. Further, when the growth of the barium titanate particles is stopped, the temperature and pressure in the reaction vessel 101 can be made lower than the value which is a subcritical or supercritical condition by cooling the inside of the reaction vessel 101 with the cooler 118. The temperature in the reaction vessel 101 is lowered by a pressure reduction to about 100 °C. However, when the next recovery step is carried out, it is preferred to lower the temperature in the reaction vessel 101 to lower the temperature of the slurry. Therefore, in the embodiment of the present application, 42 321544 201018647, the temperature of the slurry in the reaction vessel 101 is lowered by using the cooler 118. Thereby, it is possible to shift to the recovery step more quickly than when the temperature of the slurry in the reaction vessel 101 is naturally lowered, so that the manufacturing step can be shortened and the production efficiency can be improved. The formed particles rapidly flow and diffuse in the supercritical mixed solvent by the good dispersion characteristics of the organic solvent in the supercritical mixed solvent, thereby reducing the contact between the newly formed particles and suppressing aggregation of the particles. If the prevention of particle agglomeration after the crystallization step is emphasized, it is preferred to increase the proportion of the organic solvent in the mixed solvent. D. Recovery Step In the recovery step, the fourth valve V4 is opened, and only the fluid (liquid and gas) of the reaction vessel 101 is discharged through the filter 113 into the recovery container 115, and the recovery container 115 is discharged from the exhaust path 114. Gas. When the fluid passes through the filter 113, a part of the powder smaller than the size filtered by the filter 113 is moved into the recovery container 115, and the large-part product powder remains in the reaction container 101 by the valve operation. After the reaction vessel 101 was cooled to room temperature, the powder of the product was recovered. Here, in order to remove the additive, the recovered powder is washed by ion-exchanged water. Further, solid (barium titanate fine particles) and a liquid are separated by centrifugal separation at a high speed of a few thousand rpm or more. Further, the adjustment of the pH was repeated until it became neutral, and then, by drying in a dryer at about 100 ° C, finally, barium titanate fine particles were obtained. As described above, the method for synthesizing the powder of the present embodiment and the batch type production apparatus 100 can realize the reaction environment of the subcritical state or the supercritical state by the set temperature, pressure, reaction time, and reaction concentration. A fine particle such as barium titanate is obtained. Further, in order to rapidly recover the barium titanate particles, the flow system of the reaction vessel 1〇 may not pass through the filter crucible 3. At this time, most of the inner grain in the reaction state 101 is discharged to the recovery container 115 by opening the third valve V3, and only a part remains in the reaction cell 1 〇 1. At this time, it is possible to separate the solid and the liquid by washing and moving into the recovery container 115 and remaining in the reaction container 101, thereby obtaining particles such as barium titanate. Further, by these embodiments i to 4, the size limitation of the starting materials can be relaxed. Most of the conventional manufacturing methods are carried out by the bottom-to-bottom method. Therefore, in order to produce a number of (10) feet of barium titanate, it is necessary to use Ti〇^ of 1〇11111 to 3〇11111 in the raw material stage. Nanoparticles such as tBaC〇3 or bismuth oxalate are used as raw materials, and in order to manufacture or pretreat the raw materials of the nanoparticles, there is a problem in the complexity of the steps or the cost. In this respect, if by these implementations! In the case of the method for producing barium titanate microparticles of 4, the starting material of ceric acid cerium oxide (IV) is decomposed by the secondary critical or supercritical mixed solvent, and therefore, a smaller powder. Therefore, even if a raw material of about _ is used, the following barium titanate can be produced as a primary particle, and it is not necessary to finely pulverize it to several tens of ηπ or less in the raw material stage. Yu Zhili said that in order to make the age of the Nai, f must be higher than the preparation. * When these embodiments 1 to 4 are mixed with a powder of oxalic acid oxalate, they can be mixed in a critical (four) or supercritical H. A higher degree of supersaturation is achieved in the daytime without being limited by, for example, solubility. Further, the obtained solid fraction product 321544 44 201018647 is a single-phase barium titanate, and the Ba and Ti content of the waste liquid is not more than ppm, which is the ICP detection limit. That is, the oxalate starting material can be converted to barium titanate at a conversion rate of almost 100%. In addition, according to the first to fourth embodiments, oxalic acid oxalate which contains a powder of bismuth and titanium in a ratio of 1:1 in one molecule is used as a raw material. Therefore, it is possible to greatly reduce the mixing practice. The importance of the reaction components. As a result, in the flow-through type, the production of barium titanate is not affected even without using a fine mixer or a fine line. For example, it is possible to use a rough reaction tube 3 with an inner diameter of 8 mm and a 1/4 inch Y-shaped mixer, and a Reynolds number (Re=UL/v, U: fluid velocity) by a continuous flow manufacturing apparatus. , L: characteristic length, >: kinematic viscosity coefficient) 4 〇〇〇 to 7000 range 'The flow of the fluid is mixed and turbulent, and the barium titanate fine particles having an average particle diameter of 50 nm and a maximum particle diameter of 90 nm are synthesized. It is also possible to synthesize barium titanate fine particles having a particle diameter of 100 nm to 150 nm at a low scrambling speed of 300 rpm in a 300 cc autoclave. Therefore, the improvement step is practical, and no clogging occurs, and the mass productivity is good. Further, it is known that the crystal of the barium titanate fine particle powder obtained by the conventional hydrothermal synthesis has a 0H group, but if it is carried out by these embodiments, then as shown in Fig. 9, the formed barium titanate is formed. At the time, the amount of holes (voids) is so small that it is almost impossible to detect by TEM observation. In addition, Fig. 9 shows a transmission electron microscope image (HAADF-STEM image, high-angle annular dark-field scanning transmission electron microscopy image) observed by the atomic arrangement of the synthesized powder, high angle annular dark field scanning penetration Schematic illustration of a type of electron microscope image). 45 321544 201018647 (Embodiment 5) The present embodiment 5 shows an electron suitable for manufacturing an electronic component including an electronic material produced by using barium titanate which is a powder produced by the production methods of the first to fourth embodiments as a constituent element. An example of the method of manufacturing a part. In the fifth embodiment, an example of a laminated ceramic capacitor is shown as an electronic component. Fig. 10 is a cross-sectional view showing a configuration example of the multilayer ceramic capacitor 30. The multilayer ceramic capacitor 30 is a capacitor element body 40 having a dielectric layer 31 and an internal electrode layer 32 alternately laminated. At both ends of the capacitor element body 40, an internal electrode layer 32 that is alternately disposed inside the capacitor element body 40 and an external electrode 33 that is electrically connected to each other are formed. The internal electrode layer 32 is laminated so that the respective end faces are alternately exposed on the surfaces of the opposite end portions of the capacitor element body 40. The conductive material contained in the internal electrode layer 32 is not particularly limited, and a noble metal or a noble metal (for example, Ni or Ni alloy) can be used. Further, a pair of external electrodes 33 are connected to the exposed end faces of the electrode layers 32 which are alternately arranged to constitute a capacitor circuit. The conductive material contained in the external electrode 33 is not particularly limited, and inexpensive Ni, Cu or an alloy thereof can be used. The dielectric layer 31 is a thin film layer of a dielectric material using barium titanate fine particles produced by the production method of the first or second embodiment as a raw material. The multilayer ceramic capacitor 30 configured as described above is manufactured by a usual printing method or a sheet method using a paste to form a low-cost wafer (GreenChip), and after calcination, the external electrode 33 is printed or transferred for forging 46. 321544 201018647 Made and burned. In the case of the printing method, the dielectric layer paste and the internal electrode layer paste are printed and laminated on a substrate such as PET, and cut into a predetermined shape, and then peeled off from the substrate to form a low-cost wafer. Further, when the sheet method is used, a soft sheet is formed by using a paste for a dielectric layer, and after the paste for an electrode layer is printed on the flexible sheet, these are laminated to form a low-cost wafer. Also. De-bonding treatment of low-cost wafers before simmering. The environment in which the wafer is used in the paste can be appropriately determined in accordance with the type of the internal electrode layer paste: However, when a soap metal such as Ni or gold is used as the conductive material, it is preferably a reduction calcination environment. Further, the temperature at which the calcination is maintained is preferably (10) 叱 to just. C. The capacitor obtained as described above is subjected to end surface grinding by the body 40, and the paste for external electrodes is applied and calcined to form an external electrode button. The coating layer is formed on the surface of the external electrode 33 by electric ore or the like. ❹ 匕 3 is a dielectric material of a dielectric material containing barium titanate fine particles as a dielectric layer 31, and a laminated ceramic capacitor 3 manufactured as described above. Second, it is mounted on a printed circuit board or the like by Tan Xi or the like, and is used in various electronic devices and the like. Further, in the fifth embodiment, a description will be given of a method of manufacturing an electronic component which is applied to a capacitor using a bismuth silicate fine particle manufactured by any one of the manufacturing methods of the following: Secondly, the present invention is not limited thereto, and the same applies to the use of the sister acid steel fine particles as the electric material such as a piezoelectric material or a semiconductor. Further, the manufacturing apparatus is preferably a gold-plated surface of the 321544 47 201018647 region in which the raw material is reacted to form a particle, that is, the surface which is in contact with the raw material. For example, in the case of a continuous flow type manufacturing apparatus, it is preferred to apply gold plating to at least the reaction tube; in the case of a batch type manufacturing apparatus, it is preferred to apply gold plating to at least the inside (inner surface) of the pressure cooker. In this way, by ion-plating the flow paths of the particles and the raw material, impurities mixed in the particles can be reduced. Further, it is more desirable to apply gold to the raw material or the region through which the particles pass, the pipeline, and the like. Further, the treatment of the region in which the raw material is reacted to synthesize the particles or even the region through which the raw material or the particles pass is not limited to gold plating, and the reactivity can be further reduced, and the contact with the raw material can be formed by platinum or gold. The face. Further, when the titanate © 合成 is synthesized in the present embodiment, the surface in contact with the raw material can be formed of titanium. By forming the surface in contact with the raw material with titanium of the same element as barium titanate, it is possible to prevent impurities from being mixed into the generated particles. Further, in the above-described embodiment, an application example of a method of manufacturing an electronic component which is applied to a capacitor using a barium titanate fine particle manufactured by a method for synthesizing a powder as a dielectric material is described, but is not limited thereto. Here, an electronic component using an electronic material such as a piezoelectric material or a semiconductor material such as a PCT element using barium titanate fine particles can be similarly applied. Further, in the above embodiment, the synthesis and formation of barium titanate are described. However, the method of the present invention may be used as a synthesis method of various metal oxide nanoparticles, in addition to barium titanate, such as ferrous salt. , a piezoelectric material, a positive electrode material for a lithium secondary battery, a phosphor, and the like. As an example, an example of a method for synthesizing the powder of the fourth embodiment in the synthesis of potassium citrate will be described. As a method for synthesizing particles of orthorhombic potassium citrate 48 321544 201018647 There has been a report on the use of hydrothermal synthesis (Japanese Patent Laid-Open No. 2-5_257957). However, in the conventional synthesis method, the reaction time is about 24 hours and is very long. By applying the method for synthesizing the powder of the embodiment i, it is possible to obtain nano particles of potassium citrate smaller than the reported particles in a very short time and at a lower temperature and pressure than the conventional synthesis method. ❹ Select Nb2〇5, K〇H as the starting material, adjust this to a ratio of 1:3·4 in terms of stoichiometric ratio... Put the adjusted starting material and solvent methanol 250CC into Figure 7 In the reaction vessel of the batch type manufacturing apparatus shown, after the temperature is raised and the pressure is raised to the boot, and the enthalpy is introduced, the water is introduced into the reaction snail 101 by the pump 1〇9, and the reaction is carried out for 15 minutes. After the reaction, (4) the powder contained in the reaction is confirmed to confirm the product and the particle size. The product is lithium niobate, and the particle size is approximately the same as that of the powder of the first embodiment. If the method is used, it is possible to obtain about 150 nm of square orthorhombic lithium niobate particles in a very short time. (4) The method for synthesizing the powder is suitable for use in the synthesis of a positive electrode material of a mesogen, a ferrous salt, or a chain secondary battery, and can be used as a synthesis example of the dielectric nano particles having more excellent characteristics. In addition to the titanate face πt lift SrTi〇3, (Ba, Sr) Ti〇3, (Ba, ca) Ti〇3, visit month L _ . ^ ^ V^^〇.25Cu〇.75) Ti as lithium two The positive material of the 3-person battery can also be used in .LlC〇〇2 or

Synthesis of LiFeP〇4 'as a ferrous salt nanoparticle. Synthesis of BaO. 6Fe2〇3, ZnO·Fe2〇3, etc. (Example) 321544 49 201018647 (Example 1) In Example 1, the solvent-based decomposition of titanyl oxalate and titanic acid were carried out by a supercritical mixed solvent using the batch type production apparatus shown in Fig. 5 When the synthesis of 钡. For example, by adding 200 cc of slurry (20 g/L of bismuth oxalate powder, 10% of ethanol, 10% of water, and 10 g of NaOH for pH adjustment) to the autoclave 21 of 300 cc, by means of a heater 23 is heated to raise the temperature and pressure in the high vessel, and the reaction environment of the supercritical mixed solvent is generated at a critical temperature lower than the critical temperature and the critical pressure at the critical pressure, and the oxalate is completely decomposed. Next, a tetragonal white barium titanate is produced by a single supercritical phase synthesis. The analysis results when the experiment was carried out by changing the ratio of ethanol or heating temperature, pressurization pressure and the like are shown in Table 1. Further, "BT0" in Table 1 indicates BaTiO(Ba2O2O4H2O2) oxalate titanate. Further, the relationship between experimental conditions and critical conditions of each experiment is shown in Fig. 1-1 and Fig. 1-2. In addition, in the first and third figures, the experimental conditions are shown by the experiment number. ❹ 50 321544 201018647 [Table 1] Table 1 Experimental No. ΒΤ 0 size um Ethanol mol% Final pressure MPa Final temperature. Heating time minute mixed solvent critical pressure reference value MPa mixed solvent critical temperature reference value 乞FWHM (111) d50(BET) Nm TG weight loss rate 200 to 1000 °C 1 0.5 843⁄4 20 301 55 7.2 252 0.128 434 -0.3 2 1.2 82% 16 278 42 7.3 254 0.142 238 -0.2 3 0.5 74% 24 334 55 8.1 259 0.149 169 -0.5 4 0.5 743⁄4 20 308 48 8.1 259 0.119 NA -0.6 5 0.5 74% 21 269 39 8.1 259 0. 231 118 - 1.0 6 0.5 74% 8 303 50 8.1 259 0.157 223 -1.2 7 0.5 543⁄4 10 275 40 10.1 277 0.172 97 -0.4 8 0.5 39% 24 320 52 12.2 296 0.147 180 -0.4 9 1.3 43⁄4 20 350 58 20.7 365 0.155 364 - 3.3

From the results shown in Table 1, it was found from the FWHM (lll) showing the half-value width of the XRD (111) peak that all the samples obtained above the critical conditions of the mixed solvent and in the vicinity of the critical conditions showed high crystallinity. In particular, it is known that the crystallinity of the barium titanate microparticles synthesized under the conditions exceeding the critical conditions of the mixed solvent (both the critical pressure and the critical temperature) becomes higher than the temperature of the reaction. In any case, the FWHM (lll) is about 0.23 or less, and exhibits higher crystallinity than the conventional example disclosed in Patent Document 2 and the like. On the other hand, 220 cc of a raw material slurry of titanium oxalate, water and NaOH was added to a 500 cc autoclave 21, and after raising the temperature to about 200 ° C, it was about 4 MPa to 5 MPa. Then, for about 30 seconds, the sample cooled and recovered was decomposed to a certain extent, but a single crystal of barium titanate could not be formed. It was found that, in such a state that the reaction environment did not become a critical strip 51 321544 201018647 and a critical condition, a single crystal of barium titanate could not be produced. (Example 2) In Example 2, the solvent-decomposed decomposition of titanyl oxalate and the synthesis of barium titanate by a supercritical mixed solvent using the continuous flow type production apparatus shown in Fig. 2 will be described. The prepared raw material slurry (25 g/L of oxalate titanate, 40 g/L of NaOH added, ethanol) at a flow rate of 10 cc/min was used as a slurry of raw material: high temperature water = about 1:5. The mixture was mixed with high-temperature water of about 480 ° C to a ratio of 8 and introduced into a reaction tube 3 having a length of 5 cm and an inner diameter of 8 mm. Next, the temperature and pressure are set to be higher than the critical conditions of the estimated mixed solvent, and a reaction environment of the supercritical mixed solvent is generated in the reaction tube 3. The passage time of the mixed solvent containing the slurry through the reaction tube 3 is about 5 seconds to 8 seconds. Next, the product is cooled by the cooling bath 9 for a few seconds to room temperature. The results of analysis in the case where the ratio of ethanol, the heating temperature, the pressurization pressure, and the like were changed to carry out the production of barium titanate fine particles of 100 rpm or less are shown in Table 2. Further, the relationship between the experimental conditions and the critical conditions of each experiment is shown in Fig. 1-1 and Fig. 1-2. Further, in Sections 1-1 and 1-2, the experimental conditions are shown by experiment numbers. Further, the average particle diameter and standard deviation obtained from about 200 particles were calculated from SEM photographs as d50 and sd, which are shown in Table 2. The average particle diameter and standard deviation were calculated by measuring the size of about 250 to 300 particles using the SEM photographs shown in Figs. 11-1 and 11-2. Here, Fig. 11-1 shows a schematic explanatory view of an SEM photograph obtained by photographing the generated particles of the sample A, and Fig. 11-2 shows an illustration of the SEM photograph obtained by photographing the particles generated as the sample B. Illustrating. 52 321544 201018647 ^ , In addition, by the SEM photographs shown in Figures 11-1 and H-2, the size distribution of the analyzed samples of about 250 to 300 particles of sample A and sample B, respectively, is displayed. In Figures 12-1 and 12-2. Here, the $12-1 chart shows the measurement of the particle size distribution of the powder shown in the figure, and the Fig. 12-2 shows the measurement result of the powder particle distribution shown in Fig. 11-2. . Such as the 12th one! As shown in Figure 12 and Figure 2, both the sample and the sample have a sharp size distribution. In addition to the sample VIII and the sample ,, the results of the measurement of the logarithmic types are shown in Table 2. [Table 2] Table 2 Experiment No. Ethanol mol% Pressure MPa Reaction tube outlet temperature X: Flow rate cc/min Reaction tube passage time sec d50 (SEM) nm sd (SEM) nm sd/d50 BET m2/g FWHM (111) A 74% 20 270 55 8 50 10 0.20 27.1 0.312 B 20% 35 333 75 6 50 14 0.28 24.5 0.303 C 19% 20 250 68 7 70 20 0.30 19.8 0.337 D 6% 30 375 55 8 50 15 0.30 21.8 0.250 E 43⁄4 30 390 88 5 60 12 0.20 17.3 0.172 F Methanol 33⁄4 33 360 100 5 50 13 0.26 37.7 -丨— 0.321 The results shown in Table 2 show the fwhm (111) of the xRD(m) peak half-value width. From the left and right, it is higher in crystallinity than the conventional examples disclosed in Patent Document 2 and the like. Further, the specific surface area S measured by BET is, for example, about 20 m2/g, and the granule kneaded by the density of 5.9 g/cc is about 50 ηιη. In addition, it was found that the sharpness of the size distribution of sd/d50 < 3 53 321544 201018647 was obtained in all experiments. In addition, it is known that, as shown in Figures 11-1 and 11-2, both Sample A and Sample B generate regular tetragonal particles. In addition, f is the square of c/a=1.003 by the analysis of the Rietveld method. Even when sterol is used instead of ethanol, highly crystalline nanopicic acid-locked particles are obtained. From the above, it was found that Example 2 can simultaneously establish high crystallinity and nanocrystallization. (Example 3) Next, as a third embodiment, a device (manufactured by 0M LAB Co., Ltd.) which performs gold plating of about 5/zm on the inner surface of a SUS-made pressure cooker MMJ-500 was used, and barium titanate was carried out in the same manner as in the third embodiment. Synthesis experiment. The synthesized barium titanate powder was completely characterized by ICP-AES, and the detected element was quantitatively analyzed by a calibration curve method. In addition, for comparison, a barium titanate synthesis experiment was also performed on a device that did not perform gold plating, and the synthesized barium titanate powder was completely characterized by ICP-AES, and the detected element was further subjected to a calibration curve method. Quantitative analysis was carried out and the results were shown at 54 321544 201018647 [Table 3] Table 3 Reactor material pressure MPa Reaction temperature °c ET ratio wt% Fe content ppm Cr content ppm Ni content ppm SUS 20 400 90% 1352 3532 3151 SUS 20 308 88% 1419 854 488 SUS 18 356 pure water 884 447 Γ 866 SUS 12 313 pure water 2222 601 820 gold plated 20 300 88% 186 55 200 gold plated 17 233 93% 156 25 170 As shown in Table 3, it is known that the comparison is made by clock When the amount of impurities of barium titanate synthesized by a batch process and a barium titanate synthesized by a SUS material is gilded, the content of the SUS constituent elements Fe, Cr, and Ni is made 200 ppm by gold plating the reactor. the following. It was found that by performing mineral gold as described above, particles having less impurities can be synthesized. Further, in the same manner as in Example 3 except that TAP was used instead of NaOH as a pH adjuster using an organic pH adjuster, the reactor was subjected to gold plating to carry out the same titanic acid.钡 Synthesis experiments. The measurement results at this time are shown in Table 4. 55 321544 201018647 [Table 4] Table 4 Reactor material pressure MPa Reaction temperature t: ET ratio wt% Fe content ppm Cr content ppm Ni content ppm Gold plating 11 270 69% 36 0 172 In addition, without using pH adjuster to T i When ruthenium 2 and Ba (0H) 2 were used as raw materials and methanol was used as the solution, the same barium titanate synthesis experiment was carried out under the same conditions as in Example 3, that is, the reactor was subjected to gold plating. The measurement results at this time are shown in Table 5. [Table 5] Table 5 Reactor Pressure Reaction Temperature MT Ratio Fe Content Cr Content Ni Content Material MPa degree. C Example wt% ppm ppm ppm Mineral gold 10 272 92% 0 0 0 Mineral gold 10 270 84% 2. 9 0 0 Gold plating 14 280 84% 0 0 0 Learned as shown in Tables 3 to 5, by pH The modulation agent and the modulation of the raw materials and the solvent change the corrosion mechanism to further reduce the content of impurities. (Example 4) Next, a description will be given of the use of the continuous flow type production apparatus shown in Fig. 4, after mixing the raw material polymer and mixing with a reaction accelerator containing water to carry out barium titanate synthesis. In addition, the diameter of the pipeline is 1/8 inch. In Example 4, the prepared room temperature raw material slurry (the feed of decyl alcohol, Ti〇2 and Ba(0H)2, 56 321544 201018647, 2 g/L) was first pressurized to 20 MPa, and heated to about 400 ° C. It was supplied to the reaction tube 3 side at a flow rate of 20 cc/min. Further, a room temperature NaOH (4 g/L) aqueous solution and a slurry which flowed into the reaction tube 3 side at a flow rate of about 4 cc / min were mixed. That is, the mixing is carried out in a mixed condition of a raw material slurry: an aqueous solution = about 5:1. The temperature of the mixed fluid introduced into the reaction tube 3 was 295 °C. Next, the mixed flow system of the reaction tube 3 becomes a value higher than the critical condition of the mixed solvent obtained by estimating the temperature and pressure, and a reaction environment for generating a supercritical mixed solvent in the reaction tube 3 is formed. Further, the passage time of the mixed solvent containing the slurry through the reaction tube 3 is about 3 seconds. Then, the mixed fluid (the product formed in the reaction tube 3) that has passed through the reaction tube 3 is cooled by the cooling bath 9 for several seconds to room temperature. The mixing ratio of the slurry to the water is about 5:1, and therefore, the synthesis of the acid block can be carried out under a mixing ratio (ratio of slurry to water) which is about 10 times higher than that of the embodiment 2. It is known that it is possible to synthesize a titanium acid sour pot having the same high crystallinity and an average size of several tens of nanometers, which can improve the mass productivity, and can increase the amount of raw materials relative to the supply to the reaction tube. The ratio of water is about one digit. (Example 5) In the same manner as in Example 4, the continuous flow type production apparatus shown in Fig. 4 was used in the same manner as in Example 4, and the measurement of the mixing ratio of the high-temperature water was 6: i. Specifically, the prepared raw material slurry (feeding amount of oxalic acid-oxygen-titanium 2g/L, Na0H added amount uw, methanol) is heated to 3, at a flow rate of 18 cc/min, at a ratio of 6: 和 and room temperature. The water was mixed and introduced into the reaction tube 3. Next, 'the temperature and pressure are 275 which is higher than the critical condition of the estimated mixed solution 321544 57 201018647. 〇, 15 MPa, a reaction environment for generating a supercritical/mixed solvent in the reaction tube 3. Further, the passage time of the mixed solvent containing the slurry through the counter-tube 3 is about 3 seconds. Next, the product is cooled by the cooling bath 9 for a few seconds to room temperature. The generation was carried out by the above conditions, and as a result, the average size of the particles was about 3,111,111, the title (111) was 35, and the specific surface area ssa was -42.4 m2/g. In this manner, when the mixing ratio of the synthesized particles is 6: 丄, the particles can be appropriately synthesized and formed. By this, it is possible to synthesize titanium β-antimonate having the same high crystallinity and an average size of several tens of nanometers even at a high mixing ratio, which can improve mass productivity and increase the amount of raw materials relative to the supply to the reaction tube. The ratio of water is about one digit. (Embodiment 6) Next, an embodiment of the present invention will be described. Example 6 is a barium titanate powder produced by using the batch type apparatus of Fig. 7 and having the following experimental conditions. 5克的。 The experimental conditions are 2.6 g of Ti 〇 2 powder is added to about 25. 8g

Ba(OH)2 . 8H2 〇 (purity 98%) was mixed with 270 cc of methanol and about 28 g of NaOH' to make a slurry. At this time, it becomes Ba : Ti = l : 1. The slurry of the production ® was placed in a reaction vessel (pressure cooker) having a volume of 500 cc, and after heating to 280 ° C, the preliminary pressure of the reaction vessel was about i3 MPa, which exceeded the critical condition of methanol to form a supercritical state. In the process, the mixer was rotated at a rotation speed of about 1000 rpm to agitate the slurry, and the slurry was well dispersed. The slurry in the reaction vessel was poured into room temperature water at 20 cc/min for 2 minutes. The methanol concentration of the injected slurry was reduced to 84% by weight. The temperature in the reaction vessel was lowered to 277. (:, after 58 321544 201018647, immediately returned to 28 by heating with a heater (TC. Start the reaction by water injection) The pressure in the reaction vessel is still 13 MPa without change. Direct After the reaction for 30 seconds, the valve was opened to release the fluid in the reaction vessel to the recovery vessel. Thereby, the pressure in the reaction vessel was drastically lowered within 2 minutes, and the reaction was stopped. The slurry in the reaction vessel was completely cooled. After the body, the product remaining in the reaction vessel was recovered by about 14.8 g. When the product was observed by SEM, the average particle size was about 76 coffee. Further, when the product was subjected to xrd analysis, the composition was FWHM(lll)=〇. 286, c/a=l.007. Thus, in Example β, nanocrystalline particles having high crystallinity were obtained. (Example 7) Example 7 was obtained by using the distribution shown in Fig. 7 The device was prepared by the following experimental conditions. The experimental conditions were mixed with pulverized bismuth oxalate titanate powder 36g, sterol 271cc and NaOH large & 9β.. body. After adding to a volume of 4 = 10280 C, in the reaction vessel The pressure is about 13 ^Pa ..., inside, to 2 hearts. Injecting 2 hours of room temperature water. The reaction is started by water injection, and the concentration of sterol is reduced to 84% by weight, and The change becomes . After the direct reaction for 30 seconds, the internal solution = 2, and the product injected into the recovery container is recovered 2 g. The residue remaining in the reaction container (4) is directly and naturally (four) about 2 to room temperature, and is recovered. The material is about 13.3g. It is known by XRD analysis that both of them are titanate. ' By the jet, the urgency is 321544 59 201018647 The average particle size of the cold barium titanate is about 4〇ηιη, which becomes FWHM(lll) 〇, 291, c / a = i. 〇〇 5. In addition, the average particle size of barium titanate naturally cooled in the reaction vessel is about 6 〇 ηηη, which becomes FWHM (lll) = 〇. 232, c / a = 1. 005. In Example 7, the nano-sized barium titanate microparticles were obtained, and it was found that the particle size of the barium titanate microparticles dried by the residual heat of the reaction vessel was slightly larger, but the crystallinity was also higher. The quencher is further improved. (Example 8) Example 8 is an example in which no NaOH is used. ❹ For the batch device, add about 22.94 g of Ba(OH)2 · 8汛0 (purity 98%) to 6.4 g of Ti〇2 powder, and mix 271 cc of IPA to prepare a slurry. The reaction vessel (pressure cooker) having a volume of 500 cc is heated to 280 ° C, and the preliminary pressure of the reaction vessel is about 12. 5 MPa 'The critical condition of IPA is exceeded to generate a supercritical state. In the process, the mixer is made to be about 1000 rpm. The rotation speed is rotated to stir the body, and the slurry is well dispersed. The slurry in the reaction vessel was poured into room temperature water at 20 cc/min for 2 minutes. The methanol concentration of the injected slurry was reduced to © 84 wt%. The temperature in the reaction vessel was lowered to 276 ° C. Then, it was immediately returned to 280 C by heating with a heater. The reaction was started by the pressure of the water in the reaction vessel rising to 17. 5 MPa'. After 30 seconds of direct reaction, the mixture was opened to release the fluid in the reaction vessel to the recovery vessel. Thereby, the pressure in the reaction vessel was drastically lowered within 2 minutes, and the reaction was stopped. The product remaining in the reaction vessel was recovered by about 14.3 g after the slurry in the reaction vessel was completely cooled. Viewed by SEM 321544 60 201018647 • When the product is inspected, the average particle size is about 50 nm. Further, when XRD analysis is performed on the product, FWHM(lll)=〇.322, c/a=l.006. Thus, in Example 8, a titanate-locking particle which does not contain high purity and high crystallinity of Na was obtained. (Comparative Example 1) In Comparative Example 1, 220 cc of a slurry of titanyl oxalate, water and NaOH was placed in a reaction vessel of 500 cc, and the temperature was raised to about 2 Torr (Tc, and then it was about 4 MPa to 5 MPa. After about 3 seconds, the cooled ruthenium and the recovered sample were decomposed to a certain extent by the titanium oxalate oxalate, but no single crystal of barium titanate was formed. (Comparative Example 2) Comparative Example 2 was obtained by using titanium oxalate, ethanol and The slurry of Na〇H was poured into a reaction vessel of 500 cc, and after raising the temperature to about 2 ° C, water was poured into water: ethanol = 1: 1, and it became about 4 sen & to 5 MPa. After holding for 30 seconds, the slurry was released from the reaction vessel and the product was recovered. The cerium product was decomposed to a certain extent, but no single crystal of barium titanate was formed. Comparative Examples 1, 2 In addition, in order to obtain a sufficient reaction rate, it is preferably a critical pressure of a mixed solvent and a critical temperature or more. [Industrial Applicability] As described above, the method for synthesizing the powder of the present invention and the method for producing the electronic component are Used to make powder particles (metal oxide powder) One example is a powder of barium titanate)' is particularly suitable for producing a powder having a small particle size and a good crystal structure. [Illustration of the drawings] 321544 201018647 Figure 1-1 is a view showing the present invention. Summary of the critical temperature conditions of the mixed solvent of water and ethanol and the characteristic diagram of one part of the experimental data. Figure 2 shows the critical pressure conditions and experimental data of the mixed solvent of water and ethanol for illustrating the outline of the present invention. Fig. 2 is a schematic view showing a schematic configuration of a continuous flow type manufacturing apparatus according to a first embodiment of the present invention. Fig. 3 is a view showing a titanic acid of the first embodiment of the present invention using a continuous flow type manufacturing apparatus. Fig. 4 is a schematic view showing a schematic configuration of a continuous flow type manufacturing apparatus according to a second embodiment of the present invention. Fig. 5 is a view showing a batch type which is applied to the third embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 6 is a schematic view showing a step of manufacturing a barium titanate according to a third embodiment of the present invention using a batch type manufacturing apparatus. The figure shows a schematic configuration diagram of a batch type manufacturing apparatus to which the fourth embodiment of the present invention is applied. Fig. 8-1 is a conceptual diagram showing pressure and temperature changes in the method for synthesizing the powder of the fourth embodiment. Fig. 8-2 shows a conceptual diagram of the pressure and temperature change of the method for producing a powder by a conventional batch type hydrothermal synthesis method. Fig. 9 is a transmission electron microscope showing the arrangement of atoms of the synthesized powder. Fig. 10 is a cross-sectional view showing a configuration example of a multilayer ceramic capacitor to which the fifth embodiment of the present invention is applied. 62 321544 201018647 , Fig. 11_1 shows photographs taken as particles of sample A. Schematic illustration of the SEM photo. Fig. 11-2 is a schematic explanatory view showing an SEM photograph obtained by photographing the particles generated as the sample b. Fig. 12-1 is a view showing the measurement results of the particle size distribution of the powder shown in Fig. 11-1. Fig. 12-2 is a view showing the measurement results of the particle size distribution of the powder shown in Fig. 11-2. [Explanation of main components] 1 Slurry mixer 2, 6, 10, 24, 25 Valve 3 Reaction tube 4 Slurry pump 5, 11 boring tank 7, 13, 23, 105, 1 〇 8 Heater 8 Liquid supply pump 9 Cooling tanks 11, 26 Recovery tank 12 Heating heater Q 21 Pressure cooker 11, 102 Mixer 27 Exhaust port 30 Laminated ceramic capacitor 31 Dielectric layer 32 Internal electrode layer 33 External electrode 40 Capacitor element body 100 Batch manufacturing apparatus 101 Reaction vessel 103 Injection path 104 Thermometer 106 Pressure gauge 107 Safety valve 109 Pump 111, 118 Cooler 112 Back pressure valve 113 Filter 63 321544 201018647 114 Exhaust path 115 Recovery container 116 Compressed gas cylinder 117 Vacuum pump 119 Discharge path G Inert gas PW product (powder particles) VI First valve V2 Second valve V3 Third valve V4 Fourth valve V5 Fifth valve

321544

Claims (1)

201018647 seven The scope of application for patents: The method for synthesizing powders is the use of water and a solvent in the presence of a mixed solvent compared to water alone. Qi 1 and generate at least a sub- or super-critical reaction environment by heating and pressurizing, " using the subcritical or supercritical bears and the 雍俨~' The secret is generated between the pre- (four) 2. If you apply for a patent scope! Method for synthesizing powder of the item 3. The solvent contains an organic solvent which is soluble in water in a supercritical state. The manufacturing method of the month a = zero: manufactures an electronic component including the electronic material produced by using the synthetic method of the powder of the first aspect of the patent application. The method for synthesizing the powder of the sub-process has the following steps: adding the raw material and the raw material polymer which is formed into a supercritical state at a lower pressure and a lower temperature in the presence of water alone. The first step of pressing and heating; supplying the pressurized and heated raw material slurry and the reaction containing water to the reaction path separately, and generating a subcritical or supercritical state in the reaction path by pressurization The second step of the reaction environment; the third reaction step of generating the powder fine particles by leaving the raw material slurry in the reaction field for a predetermined period of time in the reaction environment of the subcritical or supercritical state; The powder fine particles are generated to stop the powder microparticles from forming the third step of 321544 65 201018647. 5. The method for synthesizing a powder according to item 4 of the patent application, wherein the first step 2 comprises: pressurizing and heating the above-mentioned volume ratio of water contained in the reaction accelerator; The raw material slurry is supplied to the reaction path. 6. The method for synthesizing a powder according to claim 4, wherein the stomach further comprises the step of heating the reaction accelerator, and the second step is to supply the heated reaction accelerator to the reaction path. 7. The method for synthesizing a powder according to the fourth aspect of the invention, wherein the second step is to cause the raw material slurry to be in a supercritical state before mixing the raw material polymer and the reaction accelerator. 8. The method for synthesizing a powder according to the fourth aspect of the invention, wherein the solvent comprises an organic solvent which is soluble in water in a supercritical state. 9. The method of synthesizing a powder according to claim 4, wherein the reaction accelerator comprises water. 10. A method of producing an electronic component, comprising: manufacturing an electronic component comprising an electronic material produced by using the powder fine particles produced by the method for synthesizing the powder of the fourth aspect of the patent application; 11. A method for synthesizing a powder, comprising the steps of: heating a slurry prepared by mixing a raw material and a solvent which becomes a supercritical state at a lower pressure and a lower temperature than when the water alone is present; The first step; mixing the heated slurry with a reaction accelerator containing water, at least by heating to generate a subcritical state or a supercritical state of the reverse 66 321544 201018647 to the second step of the environment; The third step of stopping the growth of the powder particles after the predetermined time has elapsed after the body is retained in the reaction environment for a predetermined period of time to form powder particles. 12. The method for synthesizing a powder according to claim 11, wherein in the first step, at least the slurry introduced into the reaction vessel is heated, and in the second step, at least heated The reaction accelerator is added to the slurry, and in the third step, the growth of the powder particles is stopped by depressurizing at least one of the slurry in the reaction vessel and cooling the slurry in the reaction vessel. 13. The method for synthesizing a powder according to the above aspect of the invention, wherein in the first step, the slurry is pressurized. 14. A method of synthesizing a powder according to the scope of claim U, wherein the growth of the powder particles is stopped by cooling and depressurizing the slurry in the reaction environment. The method for synthesizing a powder according to the item n of the patent application, comprising: mixing the heated reaction accelerator in the slurry. 16. The method for synthesizing a powder according to the item U of the patent application, comprising: stirring the slurry and simultaneously adding the aforementioned reaction accelerator. The method for synthesizing a powder according to the eleventh aspect of the invention, wherein the slurry is made supercritical before the reaction accelerator is added. 8. The method for synthesizing a powder according to the eleventh aspect of the invention, wherein the solvent comprises an organic solvent which is soluble in water in a supercritical state. 19. The method for synthesizing a powder according to claim 11, wherein the reaction accelerator of the first embodiment 321544 67 201018647 comprises water. 20. A method of producing an electronic component, comprising: manufacturing an electronic component comprising an electronic material produced by using the powder fine particles produced by the method for synthesizing the powder of claim 11; 68 321544