JP3142261B2 - Ultrafine ceramic oxide powder, method for producing the same, ceramic paste using the same, and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultrafine ceramic oxide powder and a method for producing the same, and a ceramic paste using the ceramic oxide powder produced thereby and a method for producing the same, and more particularly, to burning citric acid. A method of producing an ultra-fine ceramic oxide powder having excellent reactivity in a single step at a low temperature by using it as an auxiliary agent, and a ceramic oxide produced by this method and having extremely fine particles and excellent reactivity The present invention relates to a powder and a ceramic paste using the ultra-fine ceramic oxide powder manufactured as described above.

[0002]

2. Description of the Related Art Ink jet heads, memory chips,
Regarding ceramic oxide powder, which is a raw material in the manufacture of various devices using ceramics such as piezoelectric materials, emphasis is placed on miniaturization of unit particles and uniformization of particle size distribution. this is,
This is because in the case of fine particles, reactivity and applicability can be improved by reducing activation energy by surface treatment or charging the particles.

[0003] Conventional methods used for producing ceramic oxide powder are roughly classified into a solid phase method and a combustion method.

[0004] The solid phase method, also called the oxide method, is a method for producing a ceramic oxide powder using an oxide or a molten salt. In the solid-phase method, raw materials in powder form are mixed and mixed for 1,000
After heat treatment at １，1200 ° C., the mixture is pulverized and sintered to produce a ceramic oxide powder. The production process of the ceramic oxide powder by the solid phase method is shown in FIG.

The particle size of the ceramic oxide powder produced by the solid-phase method varies depending on the particle size of the raw material powder, and the particle size of the produced powder is relatively large at 0.2 to 2 μm.
It is unsuitable for obtaining particles of 0.1 μm or less, and has a disadvantage that heat treatment at a high temperature of 1,000 ° C. or more is required due to the characteristics of the process.

In the combustion method, a combustion aid is added to a raw material and a solvent constituting a ceramic to produce a homogeneous solution, and the produced solution is subjected to a heat treatment at a temperature of 500 ° C. or less to carry out a combustion reaction of the combustion aid. This is a method of producing a ceramic oxide powder by causing additional heat treatment at a temperature of 500 ° C. or more for crystallization of an amorphous primary product generated by a combustion reaction. The manufacturing process of the ceramic oxide powder is shown in FIG.

[0007] In general, combustion aids include acids such as nitric acid and polyacrylic acid, or glycine and urea (u).
rea) is used. The ceramic forming reaction is instantaneously advanced by using the high heat of 1,000 ° C. or more generated by the combustion of the combustion aid.

In order to obtain a ceramic powder having a uniform particle size distribution, metal alkoxides, nitrates,
An acetate or the like is mainly used, and a suitable organic solvent or water is used as a solvent capable of dissolving such a raw material.

Such a conventional combustion method has an advantage that a fine powder of 0.1 μm or less can be obtained at a low temperature of about 500 ° C.

However, there is a disadvantage that the combustion reaction is intense, flames and gases are rapidly generated, whereby powder is scattered, the volume of the combustion product expands, and the volume / weight ratio is too large. .

In general, the combustion reaction product is in the form of an ash containing a large amount of unburned carbon, and is an amorphous body in which particles have not yet been crystallized. The disadvantage is that the material must be additionally heat treated at a temperature of 500 ° C. or higher.

Further, depending on the raw material used, the intermediate product itself aggregates to increase the adhesive strength, so that there is a disadvantage that it is difficult to handle. In particular, when citric acid is added, an intermediate having high adhesive strength is formed.

In addition, when a ceramic oxide powder is produced by a conventional method, the pH should be adjusted by adding a separate base in order to add an excessive amount of an acid. There is a risk of explosion due to excessive heat generated by the reaction.

In the production of various film-type devices using ceramics, conventionally, a method of producing a ceramic paste using a ceramic oxide powder, printing the paste on a diaphragm, or performing a heat treatment after molding is performed. Mainly used.

In particular, considering the recent situation in which miniaturization and sophistication of devices are regarded as important, it is an urgent task to develop a paste having a uniform quality while being capable of printing or molding a fine pattern. is there.

Conventionally, in order to produce a ceramic paste, a binder for securing the inherent properties of the paste,
A vehicle that imparts appropriate fluidity, a plasticizer that enables fine molding, and a dispersion that imparts homogeneity to the paste, in order to uniformly disperse the ceramic particles to make the paste uniform and apply it to printing or molding. A method in which ceramic particles having an average particle diameter of 1 μm produced by a solid phase method are added to a solution in which an agent or the like is dissolved in a solvent, and then mixed and stirred has been used.

FIG. 3 shows a conventional method for producing a ceramic paste as described above.

At this time, cellulose fibers such as ethylcellulose are used as a binder, phthalates are used as a plasticizer, and terpineol is mainly used as a solvent.

When using a ceramic oxide powder produced by a conventional solid-phase method, the above-mentioned organic substance must be added without fail. If no organic substance is added, the viscosity of the ceramic paste is adjusted. In addition, when the ceramic paste is coated on the diaphragm, there is a problem that the coating is not performed.

Further, the ceramic paste produced by such a method cannot be molded at a low temperature due to the large size of the ceramic particles. There are drawbacks that should be dependent on the supplier.

In order to manufacture a ceramic film using the ceramic paste manufactured by the above method, the ceramic paste is printed on a diaphragm, dried at 130 ° C., and heat-treated at 1,000 ° C. or more. Before the heat treatment, there is a problem that another additional heat treatment should be performed at a temperature of 500 ° C. or more for a binder removal operation for removing all the added organic components.

Further, since the heat treatment must be performed at 1,000 ° C. or higher, there is a problem that the range of the diaphragm that can be selected is limited.

[0023]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a method for burning citric acid, which locally generates a high temperature of 1,000 ° C. or more at the time of combustion but does not have a sudden combustion reaction. Ceramic oxide powder having a very fine particle size and a very high reactivity in a single step at low temperature by using it as an agent and producing the ceramic oxide powder by a combustion method, and a method for producing the same The purpose is to provide.

Further, the present invention can be molded at a lower temperature than conventional ceramic pastes by using the ultra-fine ceramic oxide powder, which simplifies the manufacturing process and, at the time of actual application, reduces the inherent characteristics of the ceramic. It is another object of the present invention to provide a ceramic paste that can be reproduced more excellently and a method of manufacturing the same.

[0025]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a method of dissolving or dispersing a ceramic constituent element in a solvent or a dispersion medium by sufficiently dissolving or uniformly dispersing the ceramic constituent material. Producing a mixture; and dissolving or dispersing the ceramic component in the solution or dispersion mixture in an amount or more required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component raw material. Adding an acid to prepare a mixed solution, and heat-treating the mixed solution at 100 to 500 ° C. to evaporate a solvent or a dispersion medium, so that the added citric acid is used as a reducing combustion aid. To cause a non-explosive oxidation-reduction combustion reaction with the anions of the ceramic constituent raw material to be removed, and the reaction heat generated at this time causes the ceramic to be removed. A method for producing an ultrafine ceramic oxide powder which finally obtains an ultrafine ceramic oxide powder having a particle size of 1 μm or less and a uniform particle size distribution by the step of forming the oxide without scattering, and a method for producing the ultrafine ceramic oxide powder by this method The obtained ultra-fine ceramic oxide powder has such characteristics.

Further, the present invention provides a method for producing a solution or dispersion mixture containing ceramic constituent elements by sufficiently dissolving or uniformly dispersing the ceramic constituent raw materials in a solvent or a dispersion medium; To a solution or dispersion mixture in which is dissolved or dispersed, citric acid is added in an amount or more required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component raw material to produce a mixed solution. Heat treating the mixed solution at 100 to 500 ° C. and evaporating the solvent or the dispersion medium, thereby causing the added citric acid to act as a reducing combustion aid,
A non-explosive oxidation-reduction combustion reaction with the anions of the ceramic constituent material is caused to be removed, and the reaction heat generated at this time forms the ceramic oxide without scattering, and finally the particle size is reduced. A step of obtaining an ultrafine ceramic oxide powder having a particle size distribution of 1 μm or less, and dissolving ceramic constituent elements having the same or similar components as the ultrafine ceramic oxide powder based on water or an organic solvent; A step of preparing a sol solution, and a step of mixing the ultra-fine ceramic oxide powder and the ceramic sol solution to produce a ceramic paste, so that the ceramic sol solution reacts on the surface of the ultra-fine ceramic oxide powder. Acts as a powder and improves the reactivity of the powder surface, enabling sintering by only heat treatment at low temperatures. Mick paste preparation and ceramic paste produced in this method has its feature in.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

First, a method for producing an ultrafine ceramic oxide powder as shown in FIG. 2 will be described.

In the method for producing an ultrafine ceramic oxide powder according to the present invention, a ceramic constituent element material is sufficiently dissolved or uniformly dispersed in a solvent or a dispersion medium to produce a solution or a dispersion mixture containing ceramic constituent elements. To do,
To the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, add an amount or more of citric acid required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component material, and mix. The method includes a step of preparing a liquid and a step of heat-treating the mixture at 100 to 500 ° C., and may further include a step of performing additional heat treatment at 700 to 900 ° C. to improve crystallinity.

The raw materials containing the ceramic constituents include:
An oxide of a ceramic constituent element, a salt of a ceramic constituent element such as a carbonate or a nitrate and an organic or inorganic substance, or a complex of a ceramic constituent element is used.

As the ceramic constituent element, lead (P
b) It is preferable to use a piezoelectric / electrostrictive ceramic element having titanium (Ti) as a basic constituent element.

In particular, the ceramic constituent elements include:
Lead (Pb), zirconium (Zr), titanium (Ti),
Or, lead (Pb), zirconium (Zr), titanium (T
i) / lead (Pb), magnesium (Mg), niobium (N
It is preferred to use one consisting of components containing b).

As a solvent or a dispersion medium for dissolving or dispersing the ceramic constituent material, one or more of water or an organic solvent capable of dissolving or dispersing the raw material containing the ceramic constituent is selected. To use. Dimethylformamide (dime
thyl formamide), methoxyethanol (methoxyethan)
ol), acetic acid, alcohols and the like are mainly used.

The reducing combustion aid aids in oxidizing the other party, that is, burning by releasing oxygen itself, that is, being reduced.
As the reducing combustion aid, citric acid which is an organic compound capable of causing a combustion reaction is used. In a conventional method, citric acid is used not as a combustion aid but as a complexing agent, and is used to impart homogeneity to the reaction, and is used in a process such as the Petchini process. And use of the flammability and complexing effects of citric acid to induce a rate-controlled combustion reaction.

Citric acid is added to and mixed with a solution or dispersion mixture in which the ceramic constituents are dissolved or dispersed to produce a mixture. As the amount of citric acid to be added, an amount required to cause an oxidation-reduction combustion reaction with anions of the ceramic constituent raw material or more is added. The progress of the reaction can be controlled by the amount of citric acid added.

A mixed solution containing citric acid and 10
Heat treatment at 0-500 ° C. Although the crystallinity of the ceramic phase is improved as the temperature of the heat treatment increases, the combustion reaction of citric acid can be sufficiently started if the heat treatment temperature is 100 ° C. or higher. Reaction may occur even if heat treatment is performed at 500 ° C. or higher, but heat treatment at a temperature higher than that is meaningless compared to conventional methods.

More preferably, the heat treatment is performed at a temperature of 150 to 300 ° C., and the heat treatment is performed at a considerably low temperature, but the crystallinity of the ceramic phase can be sufficiently secured.

The citric acid is removed during the combustion reaction,
The ceramic oxide is formed without scattering due to the reaction heat of the citric acid generated at this time.

In such a reaction, other components of the ceramic constituent elements are removed by a combustion reaction for a sufficient time, so that a pure form of ceramic oxide powder containing no impurities is formed.

The ceramic oxide powder produced by the above method has a particle size of 1 μm or less, especially 0.01 to 0.1 μm.
m, a very fine powder having a uniform particle size distribution, in which the basic particles are independent or weak aggregates (soft aggregat
Since it is present in the form of e) and is a completely burned ceramic, the additional heat treatment does not reduce the weight.

In addition, since the surface has excellent reactivity and is formed only by heat treatment at a low temperature, the degree of freedom of the diaphragm is high, and various printing methods can be applied to the diaphragm.

In order to improve the crystallinity of the manufactured ultrafine ceramic oxide powder, the method may further include a step of further heat treating the manufactured ceramic oxide powder at 700 to 900 ° C.

FIG. 4 shows a method of manufacturing a ceramic paste using the ultra-fine ceramic oxide powder manufactured as described above.

As a raw material of the ceramic paste, a ceramic oxide powder and a ceramic sol solution produced by dissolving a ceramic constituent element of the same or similar component having an affinity for the ceramic oxide powder are mixed and used.

As a ceramic oxide powder, it is effective to use a fine powder in order to secure a system capable of low-temperature molding in consideration of its own reactivity. The prepared ceramic oxide powder is used.

At room temperature, the surface of the ceramic oxide powder exists in combination with a single layer or more of water. Here, the water bound to the surface affects the acidity and the basicity of the surface of the ceramic oxide powder, and acts as a catalyst when the ceramic oxide powder and the ceramic sol solution are mixed.

The ceramic sol solution is produced by dissolving ceramic constituent elements based on water or an organic solvent. Although various organic solvents can be used as a base, it is preferable to use mainly organic solvents selected from acetic acid, dimethylformamide, methoxyethanol, glycols and alcohols.

The ceramic constituent elements used in producing the ceramic sol solution are lead (Pb), zirconium (Z
r), it is preferable to use a component containing titanium (Ti), and the concentration of the ceramic sol solution used is 0.1 to 5
M is preferable.

When the ceramic oxide powder and the ceramic sol solution are mixed, the content of the ceramic sol solution is preferably 10 to 200 parts by weight based on the ceramic oxide powder. When the content of the ceramic sol solution is 200 parts by weight or more, the viscosity of the mixture is low because the ceramic oxide powder is excessively diluted, and when the content is less than 10 parts by weight, the amount of the ceramic oxide powder is reduced. This is because the viscosity is too high at most.

When both systems of the ceramic oxide powder and the ceramic sol solution are mixed, the liquid-phase ceramic sol solution uniformly coats the surface of the solid-phase ceramic oxide powder and connects the ceramic oxide powder particles to form a powder. The gap between them will be effectively filled.

In the powder-sol mixture thus formed, the ceramic oxide powder having the inherent properties of the ceramic is surrounded by a ceramic sol solution of the same or similar components, so that a suitable fluidity is obtained. The ceramic sol acts as a reaction medium on the surface of the ceramic oxide powder to improve the reactivity of the powder surface.

The organic component contained in the sol ensures the stability of the contact interface when the mixture comes into contact with another organic substance, thereby imparting dispersibility and homogeneity.

In such a system, a sol is thermally decomposed at a low temperature and converted into a composition identical or similar to that of the ceramic oxide powder, so that a ceramic system having improved connectivity between particles even at a low temperature is used. Obtainable.

In order to ensure the stability of the mixture of the ceramic oxide powder and the ceramic sol solution and the fluidity required for molding, an organic solvent for adjusting the physical properties may be added. Various organic solvents for controlling physical properties can be used, but it is preferable to use glycols or alcohols having a certain viscosity and a low vapor pressure at room temperature.

When an organic solvent for adjusting physical properties is added to a mixture of the ceramic oxide powder and the ceramic sol solution, the amount of the organic solvent for adjusting physical properties should be 1 to 100 parts by weight based on the ceramic oxide powder. Is preferred. this is,
When the amount of the organic solvent for adjusting physical properties is less than 1 part by weight,
There is no effect of adding the organic solvent for adjusting physical properties, and the amount added is 1
If the amount is more than 00 parts by weight, the mixture is diluted so that the viscosity cannot be maintained, and the moldability at the time of molding deteriorates.

The addition amount of the organic solvent for adjusting the physical properties is preferably 10 to 40 parts by weight based on the ceramic oxide powder. Can be played.

In order to improve the dispersibility and homogeneity of a mixture obtained by adding a solvent for controlling physical properties to a mixture of a ceramic oxide powder and a ceramic sol solution, a small amount of an organic substance may be added. In this case, it is preferable to use a long-chain alcohol or a polar organic solvent as the organic substance to be added.

It is preferable to use pentanol or hexanol as the long-chain alcohol, and it is preferable to use acetylacetone or methoxyethanol as the polar organic solvent.

The amount of the organic substance to be added is preferably 1 to 50 parts by weight based on the ceramic oxide powder. This means that if the amount of the organic substance is less than 1 part by weight, there is no effect of adding the organic substance, and if the amount exceeds 50 parts by weight,
This is because the mixture cannot maintain the viscosity and is too diluted to deteriorate the moldability.

The addition amount of the organic substance is particularly preferably 10 to 40 parts by weight based on the ceramic oxide powder.
Within the range of the addition amount, the viscosity of the mixture can be appropriately maintained, and the effect of adding an organic substance can be obtained.

The ceramic paste produced by the above method can be heat-treated at 100 to 500 ° C. to form a ceramic film. 100-500 ° C
The reason why the reaction is sufficient only by heat treatment at a low temperature is that the water on the surface of the ceramic oxide powder hydrolyzes the ceramic sol solution, and the ceramic constituent material of the ceramic sol solution released by the hydrolysis is ceramic oxide powder. This is because a reaction equivalent to sintering is performed by a mutual reaction of bonding. Further, the added organic substance is also removed during the heat treatment process.

As described above, since the film can be formed only by heat treatment at a low temperature, the degree of freedom of the diaphragm is high, and not only metals such as nickel and stainless steel, but also ceramics,
An organic compound such as plastic or resin can also be used as the diaphragm, and various methods can be applied at the time of patterning, such as molding using a mold or printing using a screen.

[0063]

The present invention will be described below in detail with reference to examples. However, the following examples are illustrative of the invention and do not limit the scope of the invention.

Example 1 105.3 g of lead nitrate [Pb (NO ₃ ) ₂ ] was dissolved in 300 ml of dimethylformamide to prepare a lead nitrate-DMF solution, and a zirconium peroxide hydroxide [ZrO (N
O ₃₎ a ₂ · 2H ₂ O] _43.1g were prepared peroxide zirconium nitrate aqueous solution was dissolved in water 30 ml.

59.3 g of citric acid was added to the above-mentioned lead nitrate-dimethylformamide solution to completely dissolve it, and then titanium isopropoxide [Ti (i-C ₃ H ₇ O) ₄ ] 44.5 was used.
After adding and stirring to homogenize the mixture, an aqueous solution of zirconium peroxide was gradually added to produce a mixed solution.

The mixed solution thus prepared was heated at 200 ° C. with a heater.
Was heat-treated. After the heat treatment, the solvent water and dimethylformamide were first evaporated, and then the combustion reaction of citric acid was started and gradually expanded to the entire vessel.

At first, the combustion product turned yellow-green, but as the combustion reaction progressed, it became a pale yellow fine powder through a pale orange color. After cooling the container, remove the powder,
Lightly ground in an agate mortar.

The raw powder and the raw powder were placed at 300 ° C., 500 ° C.,
XRD (X-Ray)
Diffraction, X-ray diffraction analysis), SEM (Scanning Elec)
tronMicroscopy, scanning electron microscope, EDS (Energy D
ispersive Spectroscopy, energy dispersive spectroscopy),
The crystallographic structure, microstructure, particle size and components were confirmed by TGA (Thermogravimetric analysis).

As a result of TGA, the powder obtained after the combustion reaction was found to be a completely burned ceramic phase since no further weight loss was observed in the additional heat treatment.

As a result of EDS, all the samples were PZT (52
/ 48).

The crystallinity of the ceramic phase was improved as the heat treatment temperature was increased, but no phase transition phenomenon or peak shift was found.

As a result of SEM, it was found that elementary particles having an average particle diameter of 50 nm of the powder existed in the form of independent or weak aggregates.

Example 2 After dissolving 26.3 g of lead nitrate [Pb (NO ₃ ) ₂ ] in 200 ml of high-purity deionized water, zirconium nitrate hydroxide [ZrO (NO ₃ )] was dissolved. ₂ · 2H
₂ O] 10.8 g was added to dissolve the titanium oxide (Ti
2.9 g of O ₂ ) was added and stirred to produce a solution.

After 14.8 g of citric acid was added to this solution to dissolve it completely, the solution was heated to 200 ° C. using a heater.

The water was first evaporated by the heating, and after the water was evaporated, the combustion reaction of citric acid was started and gradually expanded to the entire vessel. After burning, the container was cooled, the powder was collected and lightly ground in an agate mortar.

Raw powder and raw powder at 300 ° C., 500 ° C.,
XRD, S for the sample heat treated at 700 ° C for 2 hours
EM, EDS, TGA crystallographic structure, fine structure,
When the particle size and components were confirmed, the results were the same as in Example 1.

Example 3 Lead nitrate [Pb (NO ₃ ) ₂ ] was added to 350 ml of DMF.
8 g of magnesium nitrate [Mg (NO ₃ ) ₂ ]
After the was added dissolved 20.8 g, titanium isopropoxide _{[Ti (i-C 3 H} 7 O) 4] was prepared pure sulfuric acid solution was added 50.9 g.

Zirconium peroxide nitrate hydroxide [ZrO
And _{(NO 3) 2 · 2H 2} O] 50.8g of separately prepared a solution dissolved in 100ml of water was added to the solution. 21.5 g of niobium oxide (Nb ₂ O ₁₁ ) and 108.3 g of citric acid were added to this solution, and all were dissolved and heated to 150 ° C. After some solvent evaporation, the temperature was raised to 250 ° C. and maintained.

The completed orange fine powder of the combustion reaction was collected and lightly ground in an agate mortar.

XRD, SEM, and ED were applied to the raw powder and a sample obtained by heat-treating the raw powder at 700 ° C. and 900 ° C. for 3 hours.
When the crystallographic structure, microstructure, particle size and components were confirmed by S, the results were the same as in Example 1.

Example 4 20 g of PZT / PMN fine powder was mixed with 6 g of PZT (52 /
48) Mix with sol. 2 g of trimethylene glycol and 1 g of 1-pentyl alcohol were added and stirred with an automatic mortar.

The obtained paste was subjected to SUS using a fine pattern manufactured on a 250 mesh steel screen.
Screen printing was performed on a 316L diaphragm and a nickel diaphragm.

After drying at 70 ° C. for 10 minutes, heat treatment was performed at 300 ° C. for 2 hours. Aluminum was vacuum-deposited to form an upper electrode, a potential was applied, and the displacement of the diaphragm due to the piezoelectric phenomenon was measured.

As a result of measuring the displacement of the diaphragm, the piezoelectric characteristics appearing as the displacement of the diaphragm were superior to the ceramic paste manufactured by the conventional method. Example 5 5 g of PZT / PMN fine powder was mixed with 3 g of PZT (52/4).
8) The mixture was mixed with the sol, 2 g of 1-pentyl alcohol was added, and the mixture was stirred with an automatic mortar.

The obtained paste was filled with a nickel diaphragm to which a mold formed of a photosensitive film was attached. After drying at room temperature, it was heat-treated at 200 ° C. for 1 hour.

A silver paste was printed by screen printing to form an upper electrode, a potential was applied, and the displacement of the diaphragm due to the piezoelectric phenomenon was measured.

As a result of measuring the displacement of the diaphragm, the piezoelectric characteristics appearing as the displacement of the diaphragm were superior to the ceramic paste manufactured by the conventional method.

[0088]

The present invention described above uses a citric acid as a combustion aid to produce a ceramic oxide powder by a combustion method, so that the particle size can be reduced to a value of 0.3 in a single step at a temperature of 300 ° C. or less. Since it is possible to produce a ceramic oxide powder that is extremely fine and is completely burned and requires no additional heat treatment, the process stability, energy saving and high yield can be ensured. The problems pointed out in the conventional combustion method do not occur.

Further, since the produced ceramic oxide powder has excellent surface reactivity, the viscosity can be adjusted only by additional mixing with a ceramic sol solution having the same or similar composition, and another organic substance can be removed. Coating is possible without addition, and a film can be formed only by heat treatment at a low temperature, so that there is an effect that the applicability is high.

That is, since the diaphragm has a high degree of freedom, not only metals and ceramics such as nickel and stainless steel but also organic compounds such as plastics and resins can be used as the diaphragm. Can be manufactured.

The ceramic paste produced by the method of the present invention has various physical properties such as printability and stability suitable for practical applications, and can be directly heat-treated after printing without a separate binder removal process. Thus, there is an effect that a desired ceramic pattern can be obtained at a much lower temperature than the above.

Also, when a ceramic film is formed using the ceramic paste manufactured according to the method of the present invention, despite the low temperature treatment, the piezoelectric characteristics appearing as the displacement of the diaphragm are superior to the existing results. The constituent components of the paste and the manufacturing process are simple, the process of manufacturing the ceramic film using the paste is energy-saving, and the lead-time of the process is greatly reduced.

[Brief description of the drawings]

FIG. 1A is a process diagram showing a process for producing a ceramic oxide powder by a solid phase method, and FIG. 1B is a process diagram showing a process for producing a ceramic oxide powder by a combustion method.

FIG. 2 is a process chart showing a process for producing a ceramic oxide powder according to the present invention.

FIG. 3 is a process diagram showing a conventional ceramic paste manufacturing process.

FIG. 4 is a process chart showing a process for producing a ceramic paste according to the present invention.

Continuation of the front page (56) References JP-A 64-56320 (JP, A) JP-A 64-24017 (JP, A) JP-A 8-91809 (JP, A) JP-A 8-169715 (JP) JP-A-7-302706 (JP, A) JP-A-9-320888 (JP, A) JP-A-8-169715 (JP, A) Japanese Translation of PCT Application No. 4-507230 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C01B 13/32 C01G 1/02 C01G 25/00 C01G 33/00 H01L 41/187 CA (STN)

Claims (63)

(57) [Claims] 1. A step of fully dissolving or uniformly dispersing a ceramic constituent material in a solvent or a dispersion medium to produce a solution or a dispersion mixture containing a ceramic constituent element, and dissolving or dispersing the ceramic constituent element. Adding to the solution or dispersion mixture the citric acid in an amount required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component material, or more, to produce a mixed solution; The mixed solution is heat-treated at 100 to 500 ° C. to evaporate the solvent or the dispersion medium, so that the added citric acid acts as a reducing combustion aid, and the non-explosive oxidation of the anions of the ceramic component material A step of causing a reduction combustion reaction to be removed, and the reaction heat generated at this time forming the ceramic oxide without scattering, thereby finally Method for producing ultrafine ceramic oxide powder size that there particle size distribution 1μm or less to obtain a uniform ultrafine ceramic oxide powder. 2. The ceramic constituent raw material includes:
2. The ultrafine ceramic according to claim 1, wherein the ceramic is selected from the group consisting of a ceramic constituent element such as an oxide, a carbonate or a nitrate, and a salt of an organic or inorganic substance, or a complex of the ceramic constituent element. A method for producing an oxide powder. 3. The ceramic constituent element is lead (P
3. The method for producing an ultrafine ceramic oxide powder according to claim 2, wherein b) is a piezoelectric / electrostrictive ceramic element containing titanium (Ti) as a basic constituent element. 4. The method according to claim 1, wherein the solvent or the dispersion medium is selected from water or one or more of organic solvents such as dimethylformamide, methoxyethanol, acetic acid, glycols and alcohols. 2. The method for producing an ultrafine ceramic oxide powder according to claim 1. 5. The method according to claim 1, wherein the heat treatment temperature is 150 to 300 ° C. 6. The method according to claim 1, further comprising a step of heat treatment at 700 to 900 ° C. to improve crystallinity. 7. The method for producing an ultrafine ceramic oxide powder according to claim 1, wherein the particle diameter of the ultrafine ceramic oxide powder is 0.01 to 0.1 μm. 8. The method according to claim 1, wherein the citric acid is used as a combustion aid to maintain a non-explosive property while the oxidation-reduction combustion reaction proceeds, thereby enabling mass production. A method for producing ultrafine ceramic oxide powder. 9. A step of dissolving or uniformly dispersing the ceramic constituent materials in a solvent or a dispersion medium to produce a solution or a dispersion mixture containing the ceramic constituent elements; and dissolving or dispersing the ceramic constituent components. Adding the citric acid in an amount or more required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component raw material to the solution or dispersion mixture, thereby producing a mixed solution; The liquid is heat-treated at 100 to 500 ° C. to evaporate the solvent or the dispersion medium, so that the added citric acid acts as a reducing combustion aid, and the anion of the ceramic component material and the non-explosive oxidation— A reduction combustion reaction is caused to be removed, and the reaction heat generated at this time forms the ceramic oxide without scattering, and finally the particle diameter is 1 μm or less. Obtaining an ultra-fine ceramic oxide powder having a uniform particle size distribution, characterized in that the particle size is 1 μm or less, the particle size distribution is uniform, and the surface reactivity is excellent. Ultra fine ceramic oxide powder. 10. The ceramic constituent material is selected from a ceramic constituent element such as an oxide, a carbonate or a nitrate, and a salt of an organic or inorganic substance, or a complex of the ceramic constituent element. 10. The ultrafine ceramic oxide powder according to claim 9, wherein: 11. The ceramic constituent element is lead (P
The ultrafine ceramic oxide powder according to claim 10, wherein b) is a piezoelectric / electrostrictive ceramic element containing titanium (Ti) as a basic constituent element. 12. The ceramic constituent element includes lead (Pb), zirconium (Zr), titanium (Ti) or lead (Pb), zirconium (Zr), titanium (Ti) /
The ultrafine ceramic oxide powder according to claim 11, wherein the powder comprises a component containing lead (Pb), magnesium (Mg), and niobium (Nb). 13. The method according to claim 1, wherein the solvent or the dispersion medium is selected from the group consisting of water and one or more of dimethylformamide, methoxyethanol, acetic acid, glycols and alcohols. 9. The ultrafine ceramic oxide powder according to 9. 14. The ultrafine ceramic oxide powder according to claim 9, wherein the heat treatment temperature is 150 to 300 ° C. 15. The method according to claim 9, further comprising a step of performing heat treatment at 700 to 900 ° C. to improve crystallinity.
An ultrafine ceramic oxide powder as described. 16. The ultrafine ceramic oxide powder according to claim 9, wherein said ultrafine ceramic oxide powder has a particle size of 0.01 to 0.1 μm. 17. The method according to claim 9, wherein the citric acid is used as a combustion aid to maintain a non-explosive property during the oxidation-reduction combustion reaction, thereby enabling mass production. Ultra fine ceramic oxide powder. 18. A non-explosive oxidation-reduction combustion reaction using citric acid as a combustion aid at a low temperature of 100 to 500 ° C., a particle size of 1 μm or less, and a lead (P)
b) Ultrafine ceramic oxide powder characterized by using titanium (Ti) as a basic constituent element. 19. The ceramic constituent element includes lead (Pb), zirconium (Zr), titanium (Ti) or lead (Pb), zirconium (Zr), titanium (Ti) /
19. The ultrafine ceramic oxide powder according to claim 18, wherein the powder comprises a component containing lead (Pb), magnesium (Mg), and niobium (Nb). 20. The ultrafine ceramic oxide powder according to claim 18, wherein said ultrafine ceramic oxide powder has a particle size of 0.01 to 0.1 μm. 21. The ultrafine ceramic oxide powder according to claim 18, wherein the heat treatment temperature is 150 to 300 ° C. 22. A step of fully dissolving or uniformly dispersing the ceramic constituent material in a solvent or a dispersion medium to produce a solution or a dispersion mixture containing the ceramic constituent element, and dissolving or dispersing the ceramic constituent element. Adding to the solution or dispersion mixture the citric acid in an amount or more required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component raw material to produce a mixed solution; The mixed solution is heat-treated at 100 to 500 ° C. to evaporate the solvent or the dispersion medium, so that the added citric acid acts as a reducing combustion aid, and the non-explosive Oxidation-reduction combustion reaction is caused to be removed, and the reaction heat generated at this time forms ceramic oxide without scattering, and finally the particle size becomes 1 m and a step of obtaining an ultrafine ceramic oxide powder having a uniform particle size distribution, and dissolving the same or similar component ceramic constituent element as the ultrafine ceramic oxide powder based on water or an organic solvent to obtain a ceramic. Producing a sol solution; and producing a ceramic paste by mixing the ultra-fine ceramic oxide powder and the ceramic sol solution, wherein the ceramic sol solution is a surface of the ultra-fine ceramic oxide powder. A method for producing a ceramic paste, characterized in that by acting as a reaction medium for improving the reactivity of the powder surface, sintering is enabled only by heat treatment at a low temperature. 23. The method according to claim 22, wherein a component containing lead (Pb), zirconium (Zr), and titanium (Ti) is used as the ceramic constituent element when producing the ceramic sol solution. Manufacturing method of ceramic paste. 24. The method according to claim 2, wherein the organic solvent used as a base in the production of the ceramic sol solution is selected from acetic acid, dimethylformamide, methoxyethanol, glycols or alcohols.
3. The method for producing a ceramic paste according to item 2. 25. The concentration of the ceramic sol solution is 0.5.
The method for producing a ceramic paste according to claim 22, wherein the thickness is 1 to 5M. 26. The method of claim 22, wherein the content of the ceramic sol solution is 10 to 200 parts by weight based on the ceramic oxide powder. 27. The mixture of the ultra-fine ceramic oxide powder and the ceramic sol solution is further added with a solvent for adjusting physical properties, thereby stabilizing the ceramic oxide powder-ceramic sol solution mixture and the flow required for molding. The method for producing a ceramic paste according to claim 22, wherein the property is ensured. 28. The method according to claim 27, wherein a glycol or an alcohol is used as the physical property adjusting solvent. 29. The method according to claim 28, wherein the amount of the solvent for adjusting physical properties is 1 to 100 parts by weight based on the ceramic oxide powder. 30. The method according to claim 29, wherein the amount of the solvent for adjusting physical properties is 10 to 40 parts by weight with respect to the ceramic oxide powder. 31. The method of claim 27, further comprising adding a small amount of an organic substance to improve the dispersibility and homogeneity of the ceramic oxide powder-ceramic sol solution mixture. 32. The method according to claim 31, wherein the organic substance is a long-chain alcohol or a polar organic solvent. 33. The method according to claim 32, wherein pentanol or hexanol is used as the long-chain alcohol. 34. The method of claim 32, wherein acetylacetone or methoxyethanol is used as the polar organic solvent. 35. The method according to claim 31, wherein the amount of the organic substance is 1 to 50 parts by weight based on the ceramic oxide powder. 36. A step of fully dissolving or uniformly dispersing a ceramic constituent material in a solvent or a dispersion medium to produce a solution or a dispersion mixture containing a ceramic constituent element, and dissolving or dispersing the ceramic constituent element. Adding to the solution or dispersion mixture the citric acid in an amount required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component material, or more, to produce a mixed solution; The mixed solution is heat-treated at 100 to 500 ° C. to evaporate the solvent or the dispersion medium, so that the added citric acid acts as a reducing combustion aid, and the non-explosive oxidation of the anions of the ceramic component material A reduction combustion reaction is caused to be removed, and the reaction heat generated at this time forms the ceramic oxide without scattering, and finally the particle diameter is 1 μm; A step of obtaining an ultrafine ceramic oxide powder having a uniform particle size distribution below, and dissolving a ceramic constituent element having the same or similar component as the ultrafine ceramic oxide powder based on water or an organic solvent; Producing a solution; and producing a ceramic paste by mixing the ultrafine ceramic oxide powder and the ceramic sol solution, wherein the ceramic sol solution reacts on a surface of the ultrafine ceramic oxide powder. A ceramic paste characterized in that it acts as a medium and improves the reactivity of the powder surface, so that it can be fired only by a low-temperature heat treatment. 37. The method according to claim 36, wherein a component containing lead (Pb), zirconium (Zr), and titanium (Ti) is used as the ceramic constituent element when producing the ceramic sol solution. Ceramic paste. 38. The method for producing a ceramic sol solution according to claim 3, wherein the organic solvent used as a base is selected from acetic acid, dimethylformamide, methoxyethanol, glycols, and alcohols.
6. The ceramic paste according to 6. 39. The concentration of the ceramic sol solution is 0.5.
The ceramic paste according to claim 37, wherein the thickness is 1 to 5M. 40. The ceramic paste according to claim 36, wherein the content of the ceramic sol solution is 10 to 200 parts by weight based on the ceramic oxide powder. 41. The mixture of the ultrafine ceramic oxide powder and the ceramic sol solution is further added with a solvent for adjusting physical properties, so that the stability of the ceramic oxide powder-ceramic sol solution mixture and the flow required for molding are obtained. 37. The ceramic paste according to claim 36, which secures properties. 42. The ceramic paste according to claim 41, wherein a glycol or an alcohol is used as the physical property adjusting solvent. 43. The ceramic paste according to claim 41, wherein the amount of the solvent for adjusting physical properties is 1 to 100 parts by weight with respect to the ceramic oxide powder. 44. The ceramic paste according to claim 43, wherein the amount of the solvent for adjusting physical properties is 10 to 40 parts by weight with respect to the ceramic oxide powder. 45. The ceramic paste according to claim 41, wherein a small amount of an organic substance is further added to improve the dispersibility and homogeneity of the ceramic oxide powder-ceramic sol solution mixture. 46. The ceramic paste according to claim 45, wherein the organic substance is a long-chain alcohol or a polar organic solvent. 47. The ceramic paste according to claim 46, wherein pentanol or hexanol is used as the long-chain alcohol. 48. The ceramic paste according to claim 46, wherein acetylacetone or methoxyethanol is used as the polar organic solvent. 49. The ceramic paste according to claim 45, wherein the amount of the organic substance is 1 to 50 parts by weight with respect to the ceramic oxide powder. 50. An ultrafine particle produced by a non-explosive oxidation-reduction combustion reaction at a low temperature of 100 to 500 ° C. and having a particle size of 1 μm or less and containing lead (Pb) and titanium (Ti) as basic constituent elements. The ceramic oxide powder is manufactured by mixing a ceramic sol solution of the same or similar component with the ultrafine ceramic oxide powder manufactured based on water or an organic solvent, wherein the ceramic sol solution is the ultrafine ceramic oxide powder. A ceramic paste characterized in that it can be fired only by a low-temperature heat treatment by improving the reactivity of the powder surface by acting as a reaction medium on the surface of the ceramic paste. 51. The method according to claim 50, wherein a component containing lead (Pb), zirconium (Zr), and titanium (Ti) is used as the ceramic constituent element when producing the ceramic sol solution. Ceramic paste. 52. The method for producing a ceramic sol solution, wherein the organic solvent used as a base is selected from acetic acid, dimethylformamide, methoxyethanol glycols, and alcohols.
The described ceramic paste. 53. The concentration of the ceramic sol solution is 0.5.
The ceramic paste according to claim 50, wherein the thickness is 1 to 5M. 54. The ceramic paste according to claim 50, wherein the content of the ceramic sol solution is 10 to 200 parts by weight based on the ceramic oxide powder. 55. The mixture of the ultra-fine ceramic oxide powder and the ceramic sol solution may further include a solvent for controlling physical properties, and the stability of the ceramic oxide powder-ceramic sol solution mixture and the flow required for molding. 51. The ceramic paste according to claim 50, wherein the property is secured. 56. The ceramic paste according to claim 55, wherein a glycol or an alcohol is used as the physical property adjusting solvent. 57. The ceramic paste according to claim 55, wherein the amount of the solvent for adjusting physical properties is 1 to 100 parts by weight with respect to the ceramic oxide powder. 58. The ceramic paste according to claim 57, wherein the amount of the solvent for adjusting physical properties is 10 to 40 parts by weight with respect to the ceramic oxide powder. 59. The ceramic paste according to claim 55, wherein a small amount of an organic substance is further added to improve the dispersibility and homogeneity of the ceramic oxide powder-ceramic sol solution mixture. 60. The ceramic paste according to claim 59, wherein the organic substance is a long-chain alcohol or a polar organic solvent. 61. The ceramic paste according to claim 60, wherein pentanol or hexanol is used as the long-chain alcohol. 62. The ceramic paste according to claim 60, wherein acetylacetone or methoxyethanol is used as the polar organic solvent. 63. The ceramic paste according to claim 59, wherein the amount of the organic substance is 1 to 50 parts by weight based on the ceramic oxide powder.