JP2001206769A - Piezoelectric body porcelain composition and its manufacturing method, piezoelectric body element and its manufacturing method and ink-jet printer head and ultrasonic motor using the element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a piezoelectric body porcelain composition that can be sintered at a comparatively low temperature while keeping excellent piezoelectric characteristics. SOLUTION: This piezoelectric body porcelain composition contains PZT shown by the chemical formula: Pb(Zr1-xTix)O3, wherein 0.2<x<=1 as the principal component, 0.01-10 wt.% GeO2 and 0.01-10 wt.% Bi2O3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ink jet printer head, a micropump, an ultrasonic motor, an ultrasonic vibrator, a piezoelectric transformer, a frequency filter, a piezoelectric sensor, a piezoelectric speaker, a piezoelectric relay, a micromachine, a micromirror device, and the like. Piezoelectric ceramic composition to be used and method of manufacturing the same, piezoelectric element including piezoelectric member formed of piezoelectric ceramic composition, method of manufacturing the same, and ink jet printer configured using piezoelectric element It relates to a head and an ultrasonic motor.

[0002]

2. Description of the Related Art Lead zirconate titanate (Pb (Zr
_{1-x Ti x) O 3} (0.2 <x ≦ 1, preferably 0.
3 <x ≦ 1); when x = 1, that is, PbTiO
₃ and below, or a piezoelectric porcelain composition containing PZT as a main component (hereinafter referred to as a “PZT porcelain composition”) has excellent piezoelectric properties. It is used for various piezoelectric elements in various technical fields. For example, in an ink jet printer head, a piezoelectric element having a piezoelectric film made of a PZT-based porcelain composition is used as an actuator that changes the volume of an ink chamber in order to eject ink filled in the ink chamber from an ink nozzle. ing.

[0003] Ink jet printer heads include various types and configurations of printer heads in addition to the printer head having the configuration shown in FIG.
No. 12138, JP-A-4-1052, JP-B-4-52213, JP-B7-33089,
U.S. Pat. No. 4,845,590, JP-B-6-6375, JP-B-6-61936, JP-A-10-86
369). FIG. 1 schematically shows the configuration of a printer head, which is one of the various types of ink jet printer heads, in a partially enlarged manner. It is composed of a diaphragm 3 and an actuator 4. The head base 1 is formed with a number of ink nozzles for ejecting ink, a number of ink paths individually communicating with the respective ink nozzles, and a number of ink chambers 2 individually communicating with the respective ink paths. (Figure 1
In FIG. 1, only one ink chamber 2 is shown, and illustration of ink paths and ink nozzles is omitted. A vibration plate 3 is attached so as to cover the entire upper surface of the head base 1, and the upper surfaces of all the ink chambers 2 of the head base 1 are closed by the vibration plate 3. Piezoelectric elements 5 for applying a vibration driving force to the vibration plate 3 are formed on the vibration plate 3 at positions individually corresponding to the respective ink chambers 2.
An actuator 4 having a large number of piezoelectric elements 5
By applying a voltage to the desired selected piezoelectric element 5 by controlling the power supply 9, the piezoelectric element 5 is expanded and contracted in a direction parallel to the diaphragm 3. However, since the piezoelectric element 5 is restrained by the diaphragm 3 on the surface on the lower electrode 6 side, as a result, the diaphragm 3 and the piezoelectric element 5
Is deflected and displaced in a direction perpendicular to the surface of the diaphragm 3. The volume of the ink chamber 2 changes due to the bending displacement of the vibration plate 3, and ink is ejected from the ejection nozzles communicating via the ink path.

In the piezoelectric element 5, a piezoelectric film 7 is formed on a lower electrode 6, an upper electrode 8 is formed on the piezoelectric film 7, and a piezoelectric film 7 is formed by the lower electrode 6 and the upper electrode 8. Are sandwiched between them. The piezoelectric film 7 is generally formed of a PZT-based porcelain composition. The piezoelectric film 7 is formed by forming a film using a screen printing method, a sol-gel method, or the like, and then heating and firing the film.

[0005] PZT-based porcelain compositions have excellent piezoelectric properties.
The ink jet printer head described above.
In addition to tutors, micro pumps, ultrasonic motors,
Sound transducer, piezoelectric transformer, frequency filter, piezoelectric sensor
Sensors, piezoelectric speakers, piezoelectric relays, micromachines,
It is widely used as a constituent material for chrome mirror devices, etc.
However, it is necessary to add trace components to PZT-based materials.
Many attempts have been made to further improve the physical properties
Is being done. For example, Japanese Patent No. 2841911 discloses
Adds bismuth sodium titanate to PZT material
PZT system without impairing piezoelectric characteristics
An invention for improving the mechanical strength of a porcelain composition has been disclosed
I have. Japanese Patent Publication No. 5-25831 discloses a PZT-based material.
MnO ₂The mechanical quality characteristics, pressure
P whose electric constant and temperature characteristics are all above a certain level
A technique for obtaining a ZT-based porcelain composition is disclosed. JP
No. 5-116947 discloses that PZT-based materials include MnO,
NiO and La₂O₃By adding
Mechanical coupling coefficient K_pLarge relative permittivity ε_rTemperature change rate
PZT-based porcelain composition having small and uniform grain size
Have been disclosed. Paraziu for PZT material
Add metal powder to increase the dielectric constant and piezoelectric strain constant.
A technique for obtaining a PZT-based porcelain composition having high mechanical strength is disclosed
Have been. Also, Japanese Patent Application Laid-Open No. 8-319159 discloses
Is a solid solution of Sb and Mn in a PZT-based material,
PZT-based porcelain having both piezoelectric distortion constant and low dielectric loss
Composition, also with high piezoelectric strain constant and large mechanical quality
A technique for obtaining a PZT-based porcelain composition having a number
ing. In addition, the Journal of the European
・ Ceramic Society (Journal of
the EuropeanCeramic Society
ty),19, 999-1002 (1999)
Pb for ZT fine particles₅Ge₃O₁₁By adding
Thus, a method for lowering the firing temperature of PZT fine particles has been disclosed.
Have been.

[0006]

By the way, for example, the above-mentioned piezoelectric element of the ink jet printer head is formed on the lower electrode by using a paste or a coating solution containing a PZT material or its precursor composition. In this case, the lower electrode and the substrate (diaphragm) are simultaneously heated at a high temperature in the process of firing the PZT-based material.
However, the firing temperature of PZT-based materials is very high,
For example, PZT requires a firing temperature of about 1,150 ° C. A lower electrode made of Pt or the like, zirconia,
The substrate made of ceramics such as alumina was selected as a material having excellent heat resistance, but even in that case, it was damaged during the firing process, and deterioration of the characteristics was inevitable. Therefore, it is necessary to lower the firing temperature in order to reduce damage to the electrodes and the substrate during the firing process, and to increase the range of selection of materials such as the electrodes and the substrate. This is a common requirement for all piezoelectric elements, not limited to ink jet printer heads.

As described above, many techniques have been proposed for improving the physical properties of a PZT porcelain composition by adding a trace component to the PZT material, but sintering at a relatively low temperature is possible. There have been few proposals for certain PZT-based porcelain compositions. This is because the conventional method of producing a piezoelectric element involves preparing a piezoelectric ceramic composition, cutting it out, and attaching electrodes to the processed product. Is not so expensive. The only journal of
The European Ceramic Society, 19 ,
999-1002 (1999) reports a method of lowering the firing temperature of PZT fine particles using a Pb-Ge-based composition. In this method, calcination is performed at 750 ° C. to 800 ° C. to provide the same piezoelectric characteristics as that of a normal PZT-based porcelain composition.
The PZT fine particles coated with the b-Ge-based composition are special, require a complicated process for their production, and are not suitable for general use. Further, it is very difficult to stably produce the special raw material fine particles.
Further, this method has a drawback that firing at a temperature of 950 ° C. or more causes a decrease in the piezoelectric characteristics. It is known that when a glass component such as SiO ₂ or B ₂ O ₃ is added to a PZT-based material, it is possible to lower the sintering temperature.
Since the piezoelectric properties of the porcelain composition are significantly reduced, it is not preferable when the composition is used as a piezoelectric body.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel piezoelectric ceramic composition having excellent piezoelectric properties equivalent to or better than ordinary PZT. It is in. At the same time, without deteriorating the excellent piezoelectric properties, using special raw materials,
Provided is a PZT-based porcelain composition that can be fired at a low temperature without requiring a complicated manufacturing process, and a method that can suitably manufacture such a PZT-based porcelain composition. Providing the above PZT
Provided is a piezoelectric element having a piezoelectric film formed from a ceramic composition, and a method for suitably manufacturing the piezoelectric element by forming a piezoelectric film on a lower electrode formed on a substrate. And an inkjet printer head in which the piezoelectric element is used in an actuator, and an ultrasonic motor in which the piezoelectric element is used in a drive unit.

[0009]

As a result of investigations to solve the above problems, the present invention has a piezoelectric property equal to or higher than that of a conventional PZT porcelain composition, and is a completely new one which has not been disclosed before. As a result, the present invention was completed. Also, in addition, the obtained porcelain composition,
The ordinary PZ without deteriorating its excellent piezoelectric properties
It has also been found that firing at a temperature several hundred degrees lower than that of the T porcelain composition is possible. The invention according to claim 1, in a PZT-based ceramic composition, the GeO ₂ 0.01 wt% to 10
Wt% and _Bi 2 _{O 3} 0.01 wt% to 10 wt%
It is characterized by including. The invention according to claim 2 is
In claim 1 ceramic composition according to characterized in that the content of the content of GeO ₂ is 0.01 wt% to 5 wt% _Bi 2 _{O 3} was 0.01 wt% to 5 wt% .

[0010] The PZT-based porcelain composition of the present invention is preferably composed of GeO ₂
And Bi ₂ O ₃ simultaneously, PZT
This enables firing at a low temperature during production without losing the excellent piezoelectric properties of the porcelain composition. The mechanism by which the present invention exerts its effects is not clear, but during firing, the lead component, GeO ₂ and Bi ₂ O ₃ react to form some low-melting substance, which contributes to sintering at low temperatures. I think that the. Further, it is considered that the excellent piezoelectric properties of the PZT-based porcelain composition of the present invention are caused by the constituent elements in the porcelain composition being in a specific composition balance.

If the content of GeO ₂ or Bi ₂ O ₃ is too small, sintering does not proceed sufficiently during low-temperature firing, and a dense PZT-based porcelain composition cannot be obtained. On the other hand, G
If the content of eO ₂ or Bi ₂ O ₃ is too large, PZ
The composition balance of the T-based porcelain composition is lost, and its piezoelectric characteristics are reduced. The PZT-based porcelain composition of the present invention, which can simultaneously provide a sufficiently dense structure and excellent piezoelectric characteristics even when firing in a low temperature range, is composed of GeO ₂ and Bi.
₂ O ₃ , each containing preferably 0.01% to 10% by weight, more preferably 0.01% to 5% by weight.
contains.

[0012] The invention according to claim 3 is the invention according to claim 1 or
3. The porcelain composition according to claim 2, wherein₂O₃/ GeO
₂Characterized in that the weight ratio is 0.05 to 2.5.
You. The invention according to claim 4 is the porcelain composition according to claim 3.
In, Bi₂O₃/ GeO ₂Weight ratio of 0.1 to
0.8.

[0013] The porcelain composition according to the third aspect of the present invention is characterized in that Bi is
_When the weight ratio of ₂ O ₃ / GeO ₂ is in the range of 0.05 to 2.5, a denser PZT-based porcelain composition is obtained, and the piezoelectric characteristics are further improved. The porcelain composition of the invention according to claim 4 has a more dense structure and possesses more excellent piezoelectric properties.

According to a fifth aspect of the present invention, there is provided a porcelain composition according to any one of the first to fourth aspects, wherein La ₂
O ₃ and / or Nb ₂ O ₃ at 0.01% by weight to 10% by weight
% By weight. According to a sixth aspect of the present invention, there is provided the porcelain composition according to the fifth aspect, wherein La ₂ O _{3 is used.}
And / or the content of Nb ₂ O ₃ is from 0.01% by weight to
It is characterized by being 5% by weight.

Since the porcelain composition contains La ₂ O ₃ and / or Nb ₂ O ₃ , the piezoelectric properties are stabilized and the leak resistance is improved.

Note that La ₂ O ₃ and / or Nb ₂ O
Other than ₃ , as long as the properties are not deteriorated, other metal components may be contained in the porcelain composition.

The invention according to claim 7 is the invention according to claims 1 to
A method for producing the PZT-based porcelain composition according to claim 6
In the method, the raw material is represented by the chemical formula Pb (Zr_1-x
Ti _x) O₃Composite of composition represented by (0.2 <x ≦ 1)
It is made of oxide and has an average particle size of 0.05 μm to 0.5 μm.
It is characterized by using certain particles.

The invention according to claim 8 is the manufacturing method according to claim 7, wherein the particles have a chemical formula (Zr _1-x Ti
_x ) ₂ O ₄ (0.2 <x ≦ 1), comprising a composite oxide having a perovskite structure obtained using PbO and an oxide having a composition represented by 0.2 <x ≦ 1.

According to a ninth aspect of the present invention, in the method for producing a PZT-based porcelain composition according to the fifth or sixth aspect, as a raw material, a chemical formula of Pb (Zr _1-x Ti _x ) O ₃
-YLa ₂ O ₃ (0.2 <x ≦ 1), Pb (Zr _{1-x
Ti x) O 3 -yNb 2 O} 5 (0.2 <x ≦ 1) or _{Pb (Zr 1-x Ti x} ) O 3 -yLa 2 O 3 -zNb
₂ O ₅ (0.2 <x ≦ 1), composed of a composite oxide having a composition expressed by 0.2 <x ≦ 1 and having an average particle diameter of 0.05 μm to 0.5 μm and N
It is characterized by using particles in which b and La are dissolved. In the above chemical formulas, y and z are values (molar ratio to PZT) corresponding to the content ratio of La ₂ O ₃ or Nb ₂ O ₅ in the PZT-based porcelain composition according to claim 6 or 7. .

According to a tenth aspect of the present invention, in the manufacturing method according to the ninth aspect, the particles have a chemical formula (Zr _1-x T)
having _{i x) 2 O 4 (0.2} <x ≦ 1) oxide having a composition represented by the PbO and _La 2 _{O 3} and / or _Nb 2 _{O 5} and the resulting perovskite structure as a starting material It is characterized by comprising a composite oxide.

In the production method according to each of the seventh and ninth aspects of the present invention, a PZT-based material is prepared by using particles having an average particle size of 0.5 μm or less (more preferably, 0.3 μm or less) as a raw material. The firing of the porcelain composition is facilitated. In particular, when a paste is prepared using the raw material particles to form a film, the packing density is improved.
Note that it is not preferable to use particles that are too small, such as an average particle diameter of less than 0.05 μm, as the raw material becomes difficult to synthesize and handle.

In the production method according to each of the eighth and tenth aspects of the present invention, particles of the above-described complex oxides are used as raw materials, and the raw material particles are synthesized at a relatively low temperature by a solid-phase reaction. It is also possible
Raw material particles having a small particle size can be obtained, a pulverizing step for obtaining raw material particles having a desired particle size is easy, and contamination (contamination) during the pulverization can be reduced.

According to an eleventh aspect of the present invention, there is provided the manufacturing method according to any one of the seventh to tenth aspects, wherein
And a step of preparing a slurry or paste in which the component and the Bi component are added to the particles as an alkoxide or a metal salt or a solution thereof, respectively.

In the production method of the present invention, the Ge component and the Bi component are added separately from the particles serving as the raw materials.
The liquid phase is well formed, which results in the Ge component and Bi
The component can be present in the PZT-based porcelain composition so that it functions efficiently and effectively. As described above, in order to favorably generate a liquid phase, it is preferable that the Ge component and the Bi component are not previously present in the perovskite crystal.

According to a twelfth aspect of the present invention, there is provided the slurry according to the seventh or eighth aspect, wherein the Ge component, the Bi component, the La component and the Nb component are added as alkoxides or metal salts or their solutions, respectively. Alternatively, the method is characterized by passing through a step of preparing a paste.

In the production method of the present invention, since the Ge component and the Bi component are added together with the La component and the Nb component separately from the particles serving as the raw materials, a liquid phase is favorably formed. The Bi component can be present in the PZT-based porcelain composition so that it functions efficiently and effectively. As described above, in order to favorably generate a liquid phase, it is preferable that the Ge component and the Bi component do not exist in the perovskite crystal in advance, but the La component and the Nb component exist in the perovskite crystal in advance. It may be left in advance, or may be added to the raw material particles later.

According to a thirteenth aspect of the present invention, in the piezoelectric element comprising at least a piezoelectric member and a plurality of electrodes, the PZT system according to any one of claims 1 to 6, wherein It is characterized by being formed of a porcelain composition.

The piezoelectric element of the present invention is formed of a PZT-based porcelain composition that can be fired at a low temperature while maintaining excellent piezoelectric characteristics as described above. The excellent piezoelectric properties are useful for various piezoelectric elements, but particularly when the piezoelectric element is manufactured by forming or forming a piezoelectric member and then firing it with other components. This is more preferable because the temperature can be reduced.

According to a fourteenth aspect of the present invention, in the piezoelectric element according to the thirteenth aspect, the piezoelectric member is a piezoelectric film,
An upper electrode and a lower electrode are provided so as to sandwich the piezoelectric film.

In the piezoelectric element of the present invention, the firing temperature can be reduced when the piezoelectric element is formed by a method of forming a film on the lower electrode and then firing to form a piezoelectric film. Therefore, it is possible to reduce damage to the lower electrode and the substrate (diaphragm) that are received during the firing process, and it is possible to increase the range of choice of materials such as the electrode and the substrate.

According to a fifteenth aspect of the present invention, in the piezoelectric element according to the fourteenth aspect, the thickness of the piezoelectric film is 1 μm or more.
The thickness is set to 25 μm.

When the thickness of the piezoelectric film is less than 1 μm,
A sufficient force cannot be obtained to displace the piezoelectric element. When the film thickness exceeds 25 μm,
It is not preferable because a high voltage is required for driving the piezoelectric element. Further, in the case of bending displacement, the film thickness is 25 μm
If the value exceeds, the strength of the piezoelectric film itself increases, and the amount of displacement of the element decreases, which is not preferable.

According to a sixteenth aspect of the present invention, in the piezoelectric element according to the thirteenth aspect, the piezoelectric member is a polarized piezoelectric thin plate, and electrodes are provided on both surfaces of the piezoelectric thin plate in a predetermined pattern. It is characterized by being arranged.

According to the piezoelectric element of the present invention, it is possible to lower the firing temperature in the process of firing after molding when manufacturing the piezoelectric element used for the drive unit of the ultrasonic motor.

According to a seventeenth aspect of the present invention, a step of forming a lower electrode on a surface of a substrate;
A method for manufacturing a piezoelectric element, comprising: a step of forming a piezoelectric film made of the piezoelectric ceramic composition according to claim 6; and a step of forming an upper electrode on the piezoelectric film. Te, formula _{Pb (Zr 1-x Ti x} ) O 3 (0.
2 <x ≦ 1) forming a film on the lower electrode using a composition containing a composite oxide having a composition represented by 2 <x ≦ 1), and then heating the composition film to form the piezoelectric film. It is characterized by.

The invention according to claim 18 is a step of forming a lower electrode on the surface of the substrate, and forming the lower electrode on the lower electrode.
7. A method for manufacturing a piezoelectric element, comprising: a step of forming a piezoelectric film made of the piezoelectric ceramic composition according to claim 6; and a step of forming an upper electrode on the piezoelectric film. _{(Zr 1-x Ti x)} O 3 -yLa 2 O
_{3 (0.2 <x ≦ 1)} , Pb (Zr 1-x Ti x) O 3
-YNb ₂ O ₅ (0.2 <x ≦ 1) or Pb (Zr
_{1-x Ti x) O 3} -yLa 2 O 3 -zNb 2 O
₅ After forming a film on the lower electrode using a composition containing a composite oxide having a composition represented by (0.2 <x ≦ 1), the composition film is subjected to a heat treatment to form the piezoelectric film. Is formed. In the above chemical formulas, y and z are as defined in claim 6.
Or La in the PZT-based porcelain composition according to claim 7
(PZ) corresponding to the content ratio of ₂ O ₃ or Nb ₂ O ₅
Molar ratio to T).

According to a nineteenth aspect of the present invention, in the manufacturing method according to the seventeenth aspect or the eighteenth aspect, the particles comprising the composite oxide and each alkoxide or metal salt of Ge and Bi or a solution thereof are used. And preparing the composition.

According to a twentieth aspect of the present invention, in the method according to the seventeenth aspect, the particles comprising the composite oxide and each alkoxide or metal salt of Ge, Bi, La and Nb, or a solution thereof are used, The method is characterized in that the composition is prepared.

According to a twenty-first aspect of the present invention, in the manufacturing method according to any one of the seventeenth to twentieth aspects, a photosensitive composition further containing at least a photosensitive organic polymer is used as the composition. After the film formation, a predetermined pattern is baked on the photosensitive composition film and developed to form a photosensitive composition film having a predetermined pattern, and then heat treatment is performed.

The invention according to claim 22 is characterized in that, in the manufacturing method according to any one of claims 17 to 21, the heat treatment of the composition film is performed at a temperature of 600 to 950 ° C.

According to the manufacturing method of each of the seventeenth to twenty-second aspects of the present invention, the piezoelectric element of the fourteenth aspect of the present invention can be obtained by a simpler manufacturing process than the conventional one. Further, as in the piezoelectric element according to the fifteenth aspect, a thin piezoelectric film having a thickness of 1 μm to 25 μm can be advantageously formed.

According to a twenty-third aspect of the present invention, a step of forming a piezoelectric thin plate made of the piezoelectric ceramic composition according to any one of the first to sixth aspects and a step of forming predetermined piezoelectric plates on both surfaces of the piezoelectric thin plate A method for manufacturing a piezoelectric element, comprising: a step of forming an electrode of a pattern; and a step of performing a polarization process on the piezoelectric thin plate, wherein a chemical formula Pb (Zr _1-x Ti _x )
After forming a thin plate using a composition containing a composite oxide having a composition represented by O ₃ (0.2 <x ≦ 1), the thin plate is subjected to a heat treatment to form the piezoelectric thin plate. It is characterized by doing.

The invention according to claim 24 is the invention according to claim 5 or
A piezoelectric thin plate comprising the piezoelectric ceramic composition according to claim 6.
Forming step, and predetermined on both sides of the piezoelectric thin plate, respectively.
Forming an electrode in a pattern of
Performing a polarization process; and
And the chemical formula Pb (Zr_1-xTi_x) O₃-YLa
₂O₃(0.2 <x ≦ 1), Pb (Zr_1-xTi_x)
O₃-YNb₂O₅(0.2 <x ≦ 1) or Pb (Z
r_1-xTi_x) O₃-YLa₂O₃-ZNb ₂O
₅(0.2 <x ≦ 1)
After forming a sheet material using the composition, the sheet material is
Heat-treating to form the piezoelectric thin plate,
I do. The y and z in each of the above chemical formulas are defined in claim 6 or
La in the PZT-based porcelain composition according to claim 7.₂O₃
Or Nb₂O₅(Corresponding to PZT)
Molar ratio).

According to the manufacturing method of each of the inventions according to claims 23 and 24, the piezoelectric element of the invention according to claim 16 can be obtained by a simpler manufacturing process than the conventional one.

According to a twenty-fifth aspect of the present invention, one or two
An ink jet printer head having at least two ink nozzles, wherein the volume of an ink chamber communicated with the ink nozzle is changed by an actuator, and the ink is ejected from the ink nozzle. A piezoelectric element according to claim 15 is used.

The ink-jet printer head according to the present invention may be used as an actuator.
5 is provided with the piezoelectric element having the above characteristics according to any one of the inventions.

According to a twenty-sixth aspect of the present invention, there is provided an ultrasonic motor including a stator for generating a traveling vibration wave by a driving unit, and a moving body moved by the traveling vibration wave. Item 13 or Claim 1
6 is characterized by using the piezoelectric element described in 6.

The ultrasonic motor according to the present invention includes the piezoelectric element having the above characteristics according to the invention of claim 13 or 16 as a drive unit of the stator.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.

The PZT-based porcelain composition according to the present invention has G
eO ₂ 0.01 wt% to 10 wt%, preferably 0.
0.01% to 5% by weight, and 0.01% by weight of Bi ₂ O ₃
% By weight, preferably 0.01% to 5% by weight. G in PZT porcelain composition
Content ratio of eO ₂ and Bi ₂ O ₃ Bi ₂ O ₃ / GeO
₂ is 0.05 to 2.5 by weight ratio, preferably 0.1 to 2.5
0.8.

The PZT-based porcelain composition contains GeO ₂ and Bi ₂ O ₃ , and is therefore made of ordinary PZT porcelain.
It has the same or better piezoelectric properties than the porcelain composition. In the case of manufacturing the same, the firing temperature can be lowered to a range of, for example, 600 ° C. to 950 ° C. On the other hand, in the PZT-based porcelain composition, the piezoelectric characteristics do not deteriorate due to the coexistence of GeO ₂ and Bi ₂ O ₃ . Since the content of GeO ₂ and Bi ₂ O ₃ is in the range of 0.01% by weight to 10% by weight, and preferably 0.01% by weight to 5% by weight, this PZT-based porcelain composition has It has a dense structure and retains excellent piezoelectric properties. Further, the weight ratio of Bi ₂ O ₃ / GeO ₂ is 0.05 to 2.5, preferably 0.1 to 0.8, so that the PZT-based porcelain composition has a dense structure. Maintains excellent piezoelectric properties.

The PZT porcelain composition contains La ₂ O ₃
Or Nb ₂ O ₃ , or La ₂ O ₃ and Nb ₂ O
₃ can be contained in an amount of 0.01% by weight to 10% by weight, preferably 0.01% by weight to 5% by weight. Thereby, the piezoelectric characteristics of the PZT-based porcelain composition are stabilized, and the leak resistance is improved.

Note that La ₂ O ₃ and / or Nb ₂ O
_In addition to P3, as long as the characteristics do not deteriorate, this P
Other metal components may be contained in the ZT-based porcelain composition.

The PZT-based porcelain composition having the composition described above can be used, for example, to form a piezoelectric film constituting a piezoelectric element which is one of the components of the above-described ink jet printer head (see FIG. 1). Used as material. As described above, in addition to the printer head having the configuration shown in FIG. 1, there are various types and configurations of printer heads in the inkjet printer head. The PZT-based porcelain composition according to the present invention The present invention can be used for a piezoelectric element used in a printer head of a system and a configuration.

For example, the piezoelectric element used in the ink jet printer head having the structure shown in FIG. 1 has a structure in which the piezoelectric film is sandwiched between the lower electrode and the upper electrode as described above. The material of the lower electrode is not particularly limited,
Any element that is generally used in a piezoelectric element may be used, for example, platinum (Pt), gold (Au), or the like. Also, the material of the upper electrode is not particularly limited as long as it is a material generally used in a piezoelectric element, and for example, Au, Pt, or the like is used. The thickness of these electrodes is not particularly limited, either.
m. Further, an adhesion layer formed of, for example, titanium, chromium, titanium oxide, or the like may be provided between the lower electrode and the piezoelectric film and / or between the piezoelectric film and the upper electrode. The thickness of the piezoelectric film formed of the PZT-based porcelain composition is, for example, about 1 μm to 25 μm. The reason why the thickness of the piezoelectric film is set to this level is that the magnitude of the driving force of the piezoelectric film depends on the bulk amount of the piezoelectric film, and if the piezoelectric film is too thin, the driving force becomes insufficient and the piezoelectric element becomes insufficient. This is because effective vibration cannot be obtained, and if the piezoelectric film is too thick, a large voltage is required to displace the piezoelectric element.

The PZT-based porcelain composition having the above composition is
It is used as a material for forming a piezoelectric element used in a drive unit for generating a progressive vibration wave for rotating a rotor or reciprocating a sliding body in an ultrasonic motor. Ultrasonic motors have various drive systems and configurations, and the PZT-based porcelain composition according to the present invention is:
The piezoelectric elements used in the ultrasonic motors of these various types and configurations can be used.

FIG. 2 is a schematic longitudinal sectional view showing an example of the configuration of one type of ultrasonic motor (surface acoustic wave motor) among the various types of ultrasonic motors. This ultrasonic motor
The stator 10 includes a piezoelectric element 11 and an elastic ring 12, a slider 13 disposed on the elastic ring 12 side of the stator 10, and a rotor 14 disposed on the slider 13.

As shown in FIG. 3, a plan view of the piezoelectric element 11 as viewed from the back side thereof is formed by forming electrodes on both the front and back surfaces of a piezoelectric thin plate 15 formed in an annular shape. The piezoelectric thin plate 15 is formed of a PZT-based porcelain composition. The electrode on the front surface side (joint surface side with the elastic ring 12) of the piezoelectric thin plate 15 is (1/2) λ in the circumferential direction.
A plurality of divided electrodes 16 are formed so as to be independently arranged in a line for each (λ: wavelength of vibration wave).
The electrodes on the back surface side of the piezoelectric thin film 15 are separated from each other by (3/4) λ and (1/4) λ in the circumferential direction to divide the entire back surface into two, and A pair of partially divided electrodes 17 is formed to correspond to the formation region of the divided electrodes 16 on the front surface side. Although not shown, in the piezoelectric element of the rod-shaped ultrasonic motor, divided electrodes are formed on the front surface side of the piezoelectric thin film so as to divide the entire surface into two in the circumferential direction, and the whole surface electrode is formed on the back surface side. Is formed. The piezoelectric thin film 15 corresponds to each of the divided polarizations 16 so that the polarization direction in the thickness direction is alternately changed (the polarity (+) of the adjacent divided electrodes 16,
(So that (−) is different), a polarization process is performed.

The thickness of the piezoelectric thin film 15 formed of the PZT-based porcelain composition is not particularly limited as long as polarization in the thickness direction is possible, but is, for example, about 0.5 mm.
The materials and methods for forming the electrodes 16 and 17 are not particularly limited. For example, the electrodes are formed by applying and baking a paste of a metal such as silver, depositing or plating a metal such as nickel.

The ultrasonic motor having such a configuration has two types of AC driving voltages V ₀ si having phases different from each other by 90 °.
By applying nωt and V ₀ cosωt to the respective partially divided electrodes 17, the piezoelectric element 11 bends and vibrates, generating a vibration wave traveling in the circumferential direction on the elastic ring 12, and the traveling vibration wave As a result, the rotor 14 pressed against the elastic ring 12 via the slider 13 moves orbitally, and the rotor 14 rotates.

Further, the PZT-based porcelain composition having the above composition can be used in addition to the above-described actuator of the ink jet printer head and the drive section of the ultrasonic motor, as well as a micropump, an ultrasonic transducer, a piezoelectric transformer, a frequency filter, It can be widely used as a constituent material for sensors, piezoelectric speakers, piezoelectric relays, micromachines, micromirror devices, and the like.

Next, a method for producing the above-described PZT-based porcelain composition will be described. The PZT-based porcelain composition is, for example, a PZT particle, a raw material of a trace component such as Ge, Bi, La, and Nb, and an organic binder added to a solvent,
It is manufactured by preparing a slurry or paste, mixing and shaping them, and then firing the obtained formed body. PZT particles are obtained by a solid-phase reaction of raw material particles, a sol-gel method using a metal alkoxide or a metal salt as a starting material, a coprecipitation method,
It is manufactured by a known method such as a hydrothermal method or a spray decomposition method. As the PZT particles serving as the base material, it is preferable to use easily sinterable particles, and the average particle diameter is 0.5%.
Those having a size of not more than μm, more preferably not more than 0.3 μm are used. In particular, when a paste is prepared by adding and mixing a raw material of trace components such as PZT particles, Ge, Bi, and the like and an organic binder in a solvent to form a paste and forming a film using the paste, the packing density is improved. Also, it is desirable to use particles having a small particle size. However, if the particle size is too small, raw material synthesis and handling become difficult,
Generally, particles having an average particle size of 0.05 μm or more are used. As raw material particles in the case of producing PZT particles by a solid-phase reaction, the chemical formula (Zr _1-x Ti
_x ) ₂ O ₄ (0.2 <x ≦ 1, preferably 0.3 <x ≦
Fine particles of oxide having the composition represented by 1) and PbO are used. According to the method of producing PZT particles by such a solid phase reaction, PZT particles having a perovskite structure can be obtained at a low temperature, and particles having a small particle size can be obtained, and particles having a desired particle size can be obtained. Crushing work is also simple, and the intrusion of contaminants during crushing is reduced.

As raw materials for trace components such as Ge and Bi,
The respective alkoxides or metal salts or their solutions are used. Particularly, the Ge component and the Bi component are added as raw materials separate from the PZT particles so that the Ge component and the Bi component are present so as to function efficiently and effectively in the PZT-based porcelain composition, so that the liquid phase is favorably formed. Is desirable. As the organic binder, for example, a homopolymer or copolymer of hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, nylon, (meth) acrylic acid, and the like are used. As the solvent, for example, an alcohol such as methanol or ethanol is used. The firing temperature of the molded body is, for example, about 600 ° C. to 950 ° C.

Further, regarding the La component and the Nb component
As described above, the alkoxide or metal salt
May be added to the solvent together with the PZT particles.
Is a complex oxide perovska containing PZT as a main component.
With the chemical formula Pb (Zr
_1-xTi_x) O₃-YLa₂O₃, Pb (Zr_1-x
Ti _x) O₃-YNb₂O₅Or Pb (Zr_1-xT
i_x) O₃-YLa₂O₃-ZNb₂O₅(In each formula,
0.2 <x ≦ 1, preferably 0.3 <x ≦ 1)
La and / or Nb having a composition of
Solid-solved particles (hereinafter referred to as “PZT-based particles”)
And the PZT-based particles and Ge and Bi
Add sid or metal salt and organic binder to solvent
To prepare a slurry or paste.
Thus, a PZT-based porcelain composition may be manufactured.
Y and z in each of the above chemical formulas represent the PZT-based porcelain composition.
La ₂O₃Or Nb₂O₅Content ratio (0.0
1% by weight to 10% by weight, preferably 0.01% by weight to 5% by weight
% By weight) (molar ratio to PZT).
You. PZT-based particles also have an average particle size of 0.05 μm to 0.5 μm.
μm, more preferably 0.05 μm to 0.3 μm
Things are used. In addition, PZT-based particles
When manufacturing a child, the chemical formula (Zr_1-xTi_x)₂
O₄(0.2 <x ≦ 1, preferably 0.3 <x ≦ 1)
Fine particles of oxide having the composition shown, PbO and La₂O₃You
And / or Nb₂O₅And are used as starting materials
You.

Next, a method for manufacturing a piezoelectric element will be described. The following description shows one example of a method for manufacturing a piezoelectric element, and a piezoelectric element used as an actuator of an ink jet printer head and a piezoelectric element used for a driving unit of an ultrasonic motor are described below. It can be manufactured by various methods other than the following manufacturing methods.

When the piezoelectric element of the present invention is used as an actuator of an ink jet printer head as shown in FIG. 1, for example, a piezoelectric film is formed on a lower electrode, and the piezoelectric film is formed on the piezoelectric film. It is manufactured by forming an upper electrode. The lower electrode is preferably formed on a substrate such as a vibration plate by a conventional method such as a screen printing method, a sputtering method, and an evaporation method. Further, the lower electrode may also function as a substrate such as a diaphragm. Further, after the piezoelectric element is formed, the piezoelectric element may be fixed on a substrate such as a diaphragm. The material of the lower electrode is not particularly limited, and for example, platinum, gold, palladium and the like are used. The material of the diaphragm is not particularly limited, but is selected from, for example, ceramic, glass, metal, and the like. Specifically, zirconia, alumina, magnesia,
Examples include silicon nitride, aluminum nitride, silicon carbide, silicon oxide, silicon, and the like. The piezoelectric film is formed on the lower electrode by using a composition containing PZT particles or PZT-based particles (hereinafter, representatively referred to as “PZT particles”) prepared as described above. It is formed. The solvent used when preparing the composition is used for improving workability such as coatability of the composition, and may be appropriately selected from various solvents and used, such as ethyl cellosolve. Is used as a solvent. In addition,
The PZT particles have good dispersibility even when blended at a high concentration in the composition.

When a composition containing PZT particles is obtained, the composition is applied on the lower electrode formed on the diaphragm, and, if necessary, dried to remove the solvent and to remove the solvent. Apply until the film thickness is reached. The method for applying the composition is not particularly limited, and a conventional coating method, for example, a screen printing method, a spin coating method, a dipping method, a casting method, a doctor blade method, or the like is used. After the application step, the composition film is fired. The sintering may be performed at an appropriate temperature.
Firing at a low temperature such as 50 ° C. is possible. In addition, firing is performed in an inert gas atmosphere, an oxygen-containing atmosphere (such as in air),
What is necessary is just to carry out under arbitrary atmospheres, such as PbO atmosphere, and it can carry out under normal pressure or reduced pressure. Usually, the temperature is raised from room temperature to about 600 to 950 ° C. in air,
The firing is performed for several minutes to 24 hours. Moreover, you may make it raise a temperature stepwise at the time of baking. By such calcination, organic components are almost completely eliminated, and sintering further proceeds to obtain a piezoelectric film having a dense structure. When the piezoelectric film is formed on the lower electrode, the piezoelectric film is formed on the piezoelectric film by a conventional method.
For example, an upper electrode is formed by a screen printing method, a sputtering method, a vapor deposition method, or the like, to obtain a piezoelectric element. The material of the upper electrode is not particularly limited, and for example, platinum, gold, palladium and the like are used.

The piezoelectric element used in the drive unit of the ultrasonic motor is manufactured by forming a piezoelectric thin film, forming electrodes on both sides of the piezoelectric thin film, and subjecting the piezoelectric thin film to a polarization treatment. . The piezoelectric thin film is formed by molding using the composition containing the PZT particles described above, firing the obtained molded body under the same firing conditions as described above, and then processing the fired body into an annular thin plate. . When the piezoelectric thin film is obtained, electrodes are formed on both surfaces of the piezoelectric thin film in a predetermined pattern as shown in FIG. 3 by applying and baking a conductive material such as a silver paste in a conventional manner. I do. Also,
According to a known method, a DC voltage is applied between the electrodes on both surfaces of the piezoelectric thin film to apply an electric field, and the piezoelectric thin film is subjected to a polarization treatment in a predetermined pattern to obtain a piezoelectric element.

Next, a method for producing a patterned piezoelectric film by imparting photosensitivity to a composition containing PZT particles will be described. In this manufacturing method, a photoreactive group, for example, a negative-acting type photoreactive group is introduced into at least a part of the surface of the PZT particle, and the PZT having the photoreactive group is introduced.
A photosensitive composition containing T-particles, Ge and Bi component raw materials, a negative photosensitive organic polymer, and if necessary, a sensitizer and / or a photopolymerizable monomer is used. Note that the PZT particles themselves and Ge, Bi
Since trace components such as are described above, their description is omitted below.

First, PZT particles having a photoreactive group on at least a part of the surface will be described. The PZT particles are produced by the method as described above. However, since a functional group such as a hydroxyl group is present on the surface of the PZT particles,
By reacting the functional group with a compound having a photoreactive group, a photoreactive group is introduced to the surface of the PZT particle. In order for PZT particles to have appropriate photosensitivity, it is desirable that a photoreactive group be uniformly introduced over the entire surface of the particles. The type of the photoreactive group to be introduced is not particularly limited, but is selected from, for example, a (meth) acryloyl group and a vinyl group.

The compound having a photoreactive group to be reacted with the PZT particles includes, for example, a silane coupling agent and a titanium coupling agent having a photoreactive group. Examples of such a silane coupling agent include divinyldimethoxysilane, divinyldi-β-methoxyethoxysilane, vinyltriethoxysilane, vinyltri-β-methoxyethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and the like. Among them, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane and the like are easily available. Also,
Examples of the titanium coupling agent include Ajinomoto Co., Ltd.
Commercially available from Prenact KR-55 (trade name)
What is used.

The reaction between the silane coupling agent or titanium coupling agent having a photoreactive group and the PZT particles is as follows:
Usually, they are mixed in an alcohol such as methanol and stirred at room temperature. With this reaction,
The alkoxy group of the silane coupling agent or the titanium coupling agent is hydrolyzed to form a bond between a hydroxyl residue on the surface of the PZT particle and Si or Ti.

In addition to the above, as the compound having a photoreactive group to be reacted with PZT particles, for example, a compound having a double bond, for example, (meth) acrylic acid or its ester compound is used. More specifically, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Acrylate and the like are used. Such a reaction between (meth) acrylic acid or (meth) acrylate and PZT particles is usually performed by mixing them in an alcohol such as methanol and stirring the mixture at room temperature. By this reaction, a (meth) acryloyl group is introduced into a hydroxyl residue on the surface of the PZT particle.

The reaction for introducing a photoreactive group into the PZT particles depends on the type of the PZT particles, the average particle size (surface area per unit weight), the type of the photoreactive group-containing compound, and the like. The group-containing compound is used in an amount of usually 1% by weight to 10% by weight, preferably 2% by weight based on the PZT particles.
Mix at a ratio of about 7% by weight. When the mixing ratio of the photoreactive group-containing compound is less than 1% by weight, the effect of introducing the photoreactive group tends to be small. Is introduced. For example, PZT particles having an average particle size of 0.5 μm by the BET method are provided with a silane coupling agent such as 3-methacryloxypropyltrimethoxysilane and a compound such as (meth) acrylic acid and (meth) acrylate at 2% by weight.
It is preferable to mix and react at a ratio of about 7% by weight.

Further, a method using surface graft polymerization, C
A photoreactive group can be introduced into the surface of the PZT particles also by the method using VD.

As described above, PZ having a photoreactive group on its surface
T particles can be dispersed in the photosensitive composition at a high concentration,
Since the particles themselves have photosensitivity, there is no problem of sensitivity reduction and resolution reduction due to the use of the particle filler.

Next, the negative photosensitive organic polymer will be described. In the case of a negative photosensitive organic polymer, the exposed portion becomes hardly soluble or hydrophobic.

The photosensitive organic polymer may be an organic polymer having sufficient photosensitivity by itself or an organic polymer having sufficient photosensitivity depending on a combination with a photosensitizer. Usually, an organic polymer having sufficient photosensitivity in combination with the latter photosensitizer is used. In this specification, the term “organic polymer” is used to include both organic polymers and organic oligomers.

Examples of the organic polymer having sufficient photosensitivity include an azide group-containing polymer, a polymer having a photodimerization type functional group such as a cinnamoyl group and a cinnamylidene group such as polyvinyl cinnamate, and the like. .

As the organic polymer having sufficient photosensitivity depending on the combination with the photosensitizer, various polymers having a polar group or a non-polar group can be used. Preferred photosensitive organic polymers include polar groups such as hydroxyl, alkoxy, carboxyl, ester, ether groups,
It contains a carbonate group, an amide group or an N-substituted amide group (such as -NHC (O)-,> NC (O)-), a nitrile group, a glycidyl group or a halogen atom.
The photosensitive organic polymer may be a polymerizable oligomer or polymer having a polymerizable group such as a (meth) acryloyl group, an allyl group, and a vinyl group.

Examples of the hydroxyl group-containing polymer and derivatives thereof include polyvinyl alcohol-based polymers,
Polyvinyl acetal, hydroxyethyl cellulose,
Examples include hydroxypropyl cellulose, ethylene-vinyl alcohol copolymer, phenolic resin, novolak resin, methylolmelamine and derivatives thereof (for example, acetalized product and hexamethoxymethylmelamine). Examples of the carboxyl group-containing polymer and derivatives thereof include homopolymers or copolymers containing polymerizable unsaturated carboxylic acids such as (meth) acrylic acid, maleic anhydride, and itaconic acid, and esters thereof, and carboxyl group-containing cellulose derivatives. (Carboxymethyl cellulose or a salt thereof). As the ester group-containing polymer, for example, a homo- or copolymer (for example, polyvinyl acetate, ethylene-vinyl acetate copolymer) containing monomers such as vinyl esters such as vinyl acetate and (meth) acrylates such as methyl methacrylate , (Meth) acrylic resins, etc.), saturated polyesters, unsaturated polyesters, vinyl ester resins, diallyl phthalate resins, cellulose esters and the like. Examples of the polymer having an ether group include polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether, and silicon resin. Examples of the carbonate group-containing polymer include bisphenol A-type polycarbonate.

Examples of the polymer having an amide group or a substituted amide group include polyoxazolines and N-acylated polyalkyleneimines (polymers corresponding to the above polyoxazolines, such as N-acetylamino group and N-polypropionylamino group). Such as polymers having an N-acylamino group), polyvinylpyrrolidone and its derivatives, polyurethane-based polymers, polyureas, nylon or polyamide-based polymers, polymers having burette bonds, polymers having allohanate bonds, and proteins such as gelatin. Is mentioned.

The polyoxazoline monomer includes:
2-oxazoline, 2-substituted-2-oxazoline having a substituent at the 2-position of the oxazoline ring (for example, haloalkyl group such as alkyl group, dichloromethyl, trichloromethyl, pentafluoroethyl group, phenyl group, 4-methylphenyl, A phenyl group having a substituent such as 4-chlorophenyl, or an oxazoline having a substituent such as an alkoxycarbonyl group). The polyoxazoline may be a homopolymer or a copolymer, and the polyoxazoline may be used alone or as a mixture of two or more. Further, the polyoxazoline may be a copolymer in which oxazoline is graft-polymerized to another polymer.

The polyurethane-based polymers include, for example, polyisocyanates (for example, tolylene diisocyanate,
Hexamethylene diisocyanate, isophorone disissocyanate, etc.) and polyols (polyhydric alcohols such as ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, etc., polyether polyols such as diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, etc.), polyesters (Polyols and the like). Further, the polyurea includes a polymer formed by a reaction between a polyisocyanate and a polyamine (for example, ethylenediamine, diethylenetriamine, or the like).

The above-mentioned nylon or polyamide-based polymer includes a polyamide (nylon 66, nylon 6, nylon 610, nylon 611, nylon 612 or a modified nylon thereof) using a lactam component, a dicarboxylic acid component or a diamine component. (Meth) acrylamide polymers, polyamino acids and the like are included.

The polymer having a buret bond is formed by the reaction between the polyisocyanate and the compound having a urethane bond, and the polymer having an allonate bond is formed by the reaction between the polyisocyanate and the compound having a urea bond. The resulting polymer is included.

The polymer having a nitrile group includes an acrylonitrile polymer, and the polymer having a glycidyl group includes, for example, an epoxy resin and a homopolymer or copolymer of glycidyl (meth) acrylate. Examples of the halogen-containing polymer include polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a vinylidene chloride-based polymer, and chlorinated polypropylene.

Other organic polymers include, for example, polyolefin resins such as polyethylene, polypropylene, carboxyl-modified polyolefin, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-
A styrene-based resin such as a butadiene-styrene block copolymer can be used. These may be used alone or in combination of two or more.

The polymerizable oligomer having a polymerizable group includes:
Polyvinylphenol derivative, epoxy (meth) acrylate (for example, resin formed by reaction of epoxy resin with (meth) acrylic acid), polyester (meth)
Acrylates, unsaturated polyester resins, polyurethane (meth) acrylates [for example, a diol component (polyalkylene glycol, polyester diol, etc.), a diisocyanate (2,4-tolylene diisocyanate, etc.) and a hydrokisyl group-containing polymerizable monomer (2- Reaction products with hydroxyethyl methacrylate, N-methylol acrylamide, etc., compounds having a hydroxylosilyl group and a polymerizable unsaturated group (hydroxyethyl phthalyl (meth) acrylate, trimethylol propane diallyl ether, etc.) and diisocyanate (xylylene isocyanate) , 2,4-tolylene diisocyanate)
A urethane reaction product with a polymerizable polyvinyl alcohol-based polymer (for example, polyvinyl alcohol and N
A reaction product with methylol acrylamide), a polyamide-based polymer [for example, a polycarboxylic acid or an acid anhydride thereof (such as pyromellitic dianhydride) and a hydroxyl group-containing polymerizable monomer (such as allyl alcohol)]
A carboxyl group-containing ester produced by the reaction of
If necessary, a prepolymer formed by the reaction of a halogenating agent (such as thionyl chloride) for converting a carboxyl group into an acid halide group with a diamine (such as p, p'-diaminodiphenyl ether), and a carboxyl group-containing polymer (poly) Reaction products of (meth) acrylic acid or maleic acid copolymer, ethylene-maleic anhydride copolymer, etc.) and amino group-containing polymerizable monomers (allylamine, etc.), and silicone resin type polymers. Is exemplified.

The photosensitive organic polymer or oligomer as described above may be used alone or in combination of two or more. Preferably, polyvinyl alcohol, hydroxyethylcellulose, hydroxypropylcellulose, nylon and (meth) acrylic acid alone are used. Polymers and copolymers are used.

In this photosensitive composition, a photopolymerizable monomer or oligomer may be used in combination with the photosensitive organic polymer, if necessary. The photopolymerizable monomer or oligomer includes a monofunctional or polyfunctional photopolymerizable compound. Examples of the photopolymerizable group include a (meth) acryloyl group, an acrylamide group, an allyl group, a vinyl ether group, a vinyl thioether group, a vinyl amino group, a glycidyl group, and an acetylenically unsaturated group.

Examples of the monofunctional photopolymerizable compound include alkyl (meth) acrylic acid, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) methacrylate. ) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl ( Meth) acrylates,
(Meth) acrylamide, N-methylol (meth) acrylamide, N-diacetone (meth) acrylamide,
N, N'-methylenebis (meth) acrylamide, styrene, (meth) acrylonitrile, vinyl acetate, N-vinylpyrrolidone, and the like.

Examples of the polyfunctional photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like. Further, tetramethylolmethanetetra (meth) acrylate, (meth) acrylate of 2,2,5,5-tetrahydroxymethylcyclopentanone, (meth) acrylate of diglycidyl phthalate, N, N, N ′ , N'-tetrakis (β-
(Hydroxyethyl) ethylenediamine (meth) acrylate, transesterification reaction product of triglycerin with methyl acrylate, urethane type (meth) acrylate, unsaturated ester of polycarboxylic acid, unsaturated acid amide, inorganic acid Esters and metal salts, monomers having an acetylenically unsaturated group, monomers having a glycidyl group, and the like can also be used.

Examples of the urethane type acrylate include a reaction product of a polyisocyanate (eg, 2,4-tolylene diisocyanate) and a hydroxyl group-containing monomer (eg, 2-hydroxyethyl methacrylate), and a polyisocyanate (eg, 2,4 -Tolylene diisocyanate) and a hydroxyl group-containing monomer (such as 2-hydroxyethyl methacrylate), and then the remaining isocyanate group is reacted with an alkanolamine (such as triethanolamine). The reaction product, benzoin and polyisocyanate (2,
Reaction products obtained by reacting a hydroxyl group-containing monomer (such as 2-hydroxyethyl methacrylate) with 4-tolylene diisocyanate).

Examples of unsaturated esters of polycarboxylic acids include polycarboxylic acids (phthalic acid, trimetic acid, pyromellitic acid, etc.) and hydroxyl group-containing monomers (allyl alcohol, 2-hydroxyethyl methacrylate, etc.). Multifunctional monomers esterified with, for example, diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl chlorendate, diallyl adipate, diallyl diglycolate, triallyl cyanurate, diethylene glycol bisallyl carbonate, 2
-Phthalic acid ester of hydroxyethyl methacrylate, trimellitic acid ester of allyl alcohol, p-
Compounds obtained by esterifying hydroxybenzoic acid with (meth) acryloyl chloride and further adding an epoxy-containing monomer (glycidyl methacrylate) are exemplified.

As the unsaturated acid amide, for example, N,
In addition to alkylenebisacrylamides such as N'-methylenebisacrylamide and hexamethylenebisacrylamide, condensates of polyamines with unsaturated acids, unsaturated acid amides having a hydroxyl group (for example, N-methylolacrylamide) and polycarboxylic acids, Reaction products with a bivalent epoxy are exemplified. Further, the reaction product in the presence of an acidic compound of N-methylolacrylamide,
3,3-trimethyl-1-acryloylaminomethyl-
5-acryloylaminocyclohexane, hexahydro-1,3,5-triacryl-5-triazine, N-acryloylhydroxyethylmaleimide, and an oligomer obtained by reacting ε-caprolactam with tetramethylenediamine are reacted with acrylic acid chloride. Bisacrylamide, N, N′-bis (ε-acryloylhydroxyethyl) aniline, a reaction product of N-methylolacrylamide with diethylene glycol diglycidyl ether, and the like.

Examples of the ester or metal salt with an inorganic acid include zinc acrylate and an alcohol-soluble polyamide resin, and bis (2-hydroxyethyl methacrylate) ester of phosphoric acid.

Examples of the monomer having an acetylenically unsaturated group include 9- (ω-methoxybutenyl) anthraquinol synthesized from anthraquinone and 1-methoxybuten-3-yne, and 2,4-hexadiyne-1,6- Urethane obtained by reacting a diol with hexyl isocyanate is exemplified. Examples of the monomer having a glycidyl group include bisphenol-A-diglycidyl ether.

The amount of the photopolymerizable monomer or oligomer is, for example, selected from the range of 5 to 500 parts by weight, preferably about 10 to 300 parts by weight based on 100 parts by weight of the photosensitive organic polymer. Is done.

In this photosensitive composition, various photosensitizers and photopolymerization initiators can be used as a photosensitizer depending on the type of the photosensitive organic polymer. Depending on the type of the photosensitive organic polymer, the photosensitizer is a conventional photosensitizer or sensitizer, for example, an azide compound, a pyrylium salt, a thiapyrylium salt, a photodimerization sensitizer, a photopolymerization initiator [for example, ketones (acetophenone, Propiophenone, anthraquinone, thioxanthone, benzophenone or a derivative thereof), benzoin ether or a derivative thereof (eg, benzoin methyl ether), acylphosphine oxide, or the like.

The amount of the photosensitive agent used is selected, for example, from the range of about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, based on 100 parts by weight of the photosensitive organic polymer.

In this photosensitive composition, the photosensitive organic polymer (A1) and a photosensitive agent (A
2) and / or a photopolymerizable monomer (A3), and PZ
The blending ratio with the T particles (B) may be determined in view of the use of the photosensitive composition and required performance. From the viewpoint of improving the pattern shape after firing and the adhesion to the lower electrode, 0.5 <[B / (A1 + A2 + A)
3 + B)] <0.99, preferably 0.8 <
More preferably, [B / (A1 + A2 + A3 + B)] <0.95. When this compounding ratio becomes 0.5 or less,
The sinterability and the adhesion to the lower electrode tend to decrease. On the other hand, when the compounding ratio is 0.99 or more, the photosensitive characteristics tend to decrease and the resolution tends to deteriorate. PZT in the photosensitive composition
Even when the particles are blended at such a high concentration, the dispersibility is good.

If necessary, various known additives such as a polymerization accelerator, a dissolution accelerator, an antioxidant, a dye, and a pigment may be appropriately added to the photosensitive composition.
Further, the photosensitive composition usually contains a solvent in order to improve workability such as applicability. The solvent is appropriately selected from various known solvents.

The photosensitive composition can be prepared by a conventional method, for example, by mixing each component of the composition with an appropriate solvent (eg, a hydrophilic solvent such as an alcohol). The photosensitive organic polymer, the photosensitizer and / or photopolymerizable monomer and / or various additives used as required, and the PZT particles may be mixed simultaneously, or may be mixed in an appropriate order. Is also good.

The photosensitive composition thus obtained is applied on the lower electrode to form a photosensitive composition film. The lower electrode is formed on the diaphragm by a conventional method such as screen printing, a sputtering method, and a vapor deposition method, and the materials of the lower electrode and the diaphragm are not particularly limited as described above. The diaphragm may be subjected to an appropriate surface treatment in advance, for example, may be subjected to a surface treatment with a silane coupling agent or the like.

The coating method is not particularly limited, but is performed by a conventional coating method, for example, a spin coating method, a dipping method, a casting method, a screen printing method, a doctor blade method and the like. After the coating treatment, if necessary, the photosensitive composition film may be formed by removing the solvent by performing a drying treatment.

The formed photosensitive composition film is irradiated or exposed to light through a predetermined mask to perform pattern exposure. As the light beam, halogen lamp, high pressure mercury lamp, UV
Light emitted from a lamp, excimer laser, electron beam, X-ray, or the like is used, and light having a wavelength of about 100 to 500 nm, particularly ultraviolet light, is effective. Exposure time is optional, but depending on the photosensitive characteristics of the photosensitive composition and the type of light,
Usually, it is good to select from the range of about 0.1 second to 20 minutes. After the exposure, if necessary, heat treatment may be performed at a temperature of, for example, about 80 ° C. to 120 ° C. By such exposure, photo-curing occurs in the exposed portion, and the photosensitive composition film becomes hardly soluble (water resistant).

After pattern exposure, the photosensitive composition film is developed by a known method to form a high-resolution negative pattern. For development, depending on the type of photosensitive composition,
Various developers such as water, an aqueous alkali solution, an organic solvent, and a mixture thereof can be used. Further, the developing method is not particularly limited. For example, a paddle (meniscus)
Method, a dipping method, a spray method, or the like may be employed.

The pattern formed by the development is heated and baked. The firing may be performed at an appropriate temperature, depending on the type and blending amount of the PZT particles, the use of the piezoelectric film, and the like. In the present invention, firing at a low temperature of 600 ° C. to 950 ° C. is possible. The firing may be performed in an arbitrary atmosphere such as an inert gas atmosphere, an oxygen-containing atmosphere (such as in air), or a PbO atmosphere, and may be performed under normal pressure or reduced pressure.
Usually, it is good to bake in air by raising the temperature from room temperature to about 600 ° C. to 950 ° C. over 2 hours to 24 hours. Further, the temperature may be increased stepwise. By such baking, organic components are almost completely eliminated, and a dense piezoelectric film is obtained.

An upper electrode is formed on the piezoelectric film by an ordinary method, for example, by a screen printing method, a sputtering method, an evaporation method, etc., to obtain a piezoelectric element. The material of the upper electrode is
There is no particular limitation as described above.

[0111]

EXAMPLES <Synthesis of PZT Particles> A predetermined amount of each of ZrTiO ₄ fine particles (manufactured by Sakai Chemical) and PbO was weighed, and
After mixing them in a ball mill for 10 hours, dry them,
A mixed powder was obtained. After calcining the obtained mixed powder at a temperature of 650 ° C. for 2 hours, the calcined powder is ball-milled for 16 hours to obtain PZT particles (PZT-0.2) having an average particle diameter of 0.2 μm. Was.

The calcined powder was ball-milled for 24 hours to obtain a powder having an average particle size of 0.15 μm.
ZT particles (PZT-0.15) were obtained.

A predetermined amount of ZrTiO ₄ fine particles (manufactured by Sakai Chemical)
, A predetermined amount of PbO, and La ₂ O ₃ so as to be 0.5% by weight with respect to PZT.
After ball mill mixing for an hour, the mixture was dried to obtain a mixed powder. After calcining the obtained mixed powder at a temperature of 650 ° C. for 2 hours, the calcined powder is ball-milled for 16 hours to obtain La-containing PZT particles (PZT-La) having an average particle diameter of 0.2 μm. Was.

Also, a predetermined amount of ZrTiO ₄ fine particles (manufactured by Sakai Chemical), a predetermined amount of PbO, and Nb ₂ O ₅ were weighed so as to be 0.5% by weight with respect to PZT. After ball mill mixing for an hour, the mixture was dried to obtain a mixed powder. After calcining the obtained mixed powder at a temperature of 650 ° C. for 2 hours, the calcined powder was ball-milled for 16 hours to obtain Nb-containing PZT particles (PZT-Nb) having an average particle size of 0.2 μm. .

For comparison, commercially available PZT particles (PZT-LQ, manufactured by Sakai Chemical Co., Ltd., average particle size: 0.5 μm) were used.

<Manufacture of PZT-based porcelain composition> [Examples 1 to 21] PZT particles in ethanol, respectively predetermined amounts of Ge (OEt) ₄ (tetraethoxygermanium) and Bi (OBu) ₃ (tributoxybismuth)
After adding an organic binder (hydroxypropylcellulose), they were mixed in a ball mill for 16 hours and then granulated. Subsequently, using a mold having a diameter of 15 mm, the granulated material was primarily formed, and then C at 1.4 t / mm ² was used.
IP (cold isostatic pressing) treatment was performed to form a molded body having a thickness of 3 mm. After the obtained molded body was subjected to a binder removal treatment at a temperature of 400 ° C. for 1 hour, it was baked at a predetermined temperature for 2 hours.

After cutting the obtained fired body into a size of 0.5 mm, a silver electrode was baked on the surface. The obtained sample was polarized at a voltage of 3 kV / mm and a temperature of 120 ° C. for 15 minutes, and then an electromechanical coupling coefficient (Kp) was measured at room temperature using a network analyzer. Table 1 summarizes the sample preparation conditions and evaluation results.

[0118]

[Table 1]

[Comparative Examples 1 to 5] PZT-0.15, PZT
T-0.2, PZT-LQ, PZT-La and PZT
Using each PZT particle of -Nb, a molded body containing neither Ge nor Bi was prepared in the same manner as in the above-described example, and the obtained molded body was subjected to binder removal treatment.
Baking was performed at a temperature of 0 ° C. for 2 hours. However, each of the obtained fired bodies had a relative density of 85% or less, sintering did not proceed sufficiently, and was not suitable as a piezoelectric material.

[Comparative Examples 6 and 7] By the same method as in the above-described example, only 1% by weight of Ge (OEt) ₄ or Bi (OBu) ₃ was added to PZT-0.2 powder to obtain a molded product. The formed body was subjected to a binder removal treatment and then fired at a temperature of 900 ° C. for 2 hours. However,
Each of the obtained fired bodies had a relative density of 85% or less, sintering did not proceed sufficiently, and was not suitable as a piezoelectric material.

[Comparative Examples 8 to 10] Comparative Examples 6 and 7 described above
Were molded at 980 ° C. for 2 hours, and samples were prepared in the same manner as in the above Examples (Comparative Examples 8 and 9). Also, Ge (OEt) ₄ and Bi were added to the PZT-0.2 powder by the same method as in the above-described example.
(OBu) ₃ was added in an amount of 15% by weight to form a molded body, and the obtained molded body was subjected to a binder removal treatment.
The sample was fired at a temperature of 00 ° C. for 2 hours, and a sample was prepared in the same manner as in the above example (Comparative Example 10). The electromechanical coupling coefficient (Kp) of the obtained sample was measured in the same manner as in the example. Table 1 shows the sample preparation conditions and evaluation results at this time. The electromechanical coupling coefficient (Kp) of each sample was 47%, 46% and 39%, respectively.
Which was smaller than the sample according to the example of the present invention.

[Comparative Example 11] The same conditions as those of the above-described embodiment.
To PZT-0.2 powder as SiO2₂
2% by weight to make a fired body and make a sample
did. By firing at the same level of temperature of 900 ° C as in the example
Means that the density of the obtained fired body is 7.63 g / cm ³Becomes
However, the electromechanical coupling coefficient (Kp) of the sample was 32%.
The characteristics of the piezoelectric ceramics are very poor.
Was.

From Table 1, according to the embodiment of the present invention, P
It can be seen that the novel porcelain composition obtained by adding Bi and Ge to ZT exhibits piezoelectric properties equal to or higher than that of a normal PZT porcelain composition. Further, according to the present invention, it is possible to produce a piezoelectric ceramic composition having a Kp of about 60% at a firing temperature of 950 ° C. or less. In particular, the use of PZT-0.15 powder was effective.

When the Bi ₂ O ₃ / GeO ₂ ratio is 0.5
When, the material was well-balanced in terms of synthesis conditions and physical properties.

In Comparative Examples 8 and 9, in which Bi ₂ O ₃ or GeO ₂ was solely added to the PZT particles, the Kp value of the obtained sample was higher than that of the Example, despite firing at a higher temperature than in the examples. It was considerably smaller than the example.

In this example, the results obtained by using PZT powders having two particle diameters are exemplified. However, if a PZT powder having finer and excellent sinterability is used, it is possible to fire the piezoelectric material at a lower temperature. Needless to say.

<Preparation of Photosensitive Paste> (1) Preparation of Organic Component 2 g of hydroxypropylcellulose, 8 g of pentaerythritol triacrylate, 0.5 g of a photopolymerization initiator (Irgacure 18000, manufactured by Cibagaiki) and 8 g of ethyl cellosolve were mixed. The mixture was stirred until homogeneous and clear.

(2) Addition of Photosensitivity to PZT Particles To 20 g of each of the above PZT particles, 0.6 g of hydroxyethyl methacrylate and 40 g of methanol were added, and the mixed solution was stirred at room temperature for 2 hours. Thereafter, the solution was dried under reduced pressure at a temperature of 40 ° C. to remove methanol, and photoreactive groups were introduced on the surfaces of the PZT particles.

(3) Preparation of Organic Component / PZT Particle Mixture (Photosensitive Paste) 9 g of the PZT particles obtained in (2) and a trace component were added to 1.5 g of the solution of the organic component obtained in (1). Were mixed at room temperature to prepare a photosensitive paste.

<Preparation of Piezoelectric Element> [Examples 22 to 30] In order to prepare a piezoelectric element for an ink jet printer head having the configuration shown in FIG. 1, zirconia having a thickness of 10 μm serving as a diaphragm was prepared. A Pt film having a thickness of 0.5 μm was formed as a lower electrode on the substrate by a sputtering method, and the above-mentioned photosensitive paste was applied on the lower electrode by a screen printing method. At this time, the paste film thickness was adjusted so that the thickness of the fired piezoelectric film was 5 μm. Then, the paste film is heated at 70 ° C. for 30 minutes.
And dried. The photosensitive paste film containing the PZT particles was exposed for 20 seconds using a mask aligner exposure apparatus (M-2L, manufactured by Mikasa) having a 250 W ultra-high pressure mercury lamp. The paste film after the exposure was spray-developed with methanol for 15 seconds to form a 200 μm × 3 mm pattern.

The obtained PZT particle-containing paste film was heated under predetermined firing conditions to obtain a piezoelectric film having a dense structure. On the obtained piezoelectric film, Au was formed by a sputtering method through a metal mask as an upper electrode to form a piezoelectric element.

The obtained piezoelectric element was evaluated by measuring the vibration width of the element when a voltage of 30 V was applied, using a Tencor step meter. The type of PZT particles used for making the piezoelectric element, the type and amount of trace components,
Table 2 summarizes the firing conditions and the evaluation results.

[0133]

[Table 2]

[Comparative Examples 12 to 16] PZT-0.15,
PZT-0.2, PZT-LQ, PZT-La and P
Using each PZT fine particle of ZT-Nb, an attempt was made to produce a piezoelectric element having a piezoelectric film containing neither Ge nor Bi in the same manner as in the above-described embodiment. However, in the firing at a temperature of 950 ° C. or lower as in the example,
A vibrating piezoelectric element could not be produced.
In order to advance the densification of the piezoelectric film, the firing temperature was further increased, and an attempt was made to produce a piezoelectric element. However, an intended displaceable piezoelectric element could not be obtained. This is considered to be due to the fact that the zirconia substrate (vibrating plate) and the lower electrode material deteriorated due to the reaction with PZT during the firing process, resulting in breakage of the piezoelectric element.

As can be seen from Table 2, according to the embodiment of the present invention, it is possible to obtain a piezoelectric element having a sufficiently large amplitude width at a firing temperature of 950 ° C. or lower.

An ink jet printer head having 50 nozzles was prepared by using 50 piezoelectric elements formed in parallel on a zirconia substrate (diaphragm) under the same conditions as in Example 24 described above. FIG. 4 is a longitudinal sectional view showing a schematic configuration of the printer head. In FIG. 4, reference numeral 18 denotes a nozzle plate on which the nozzle 19 is formed,
Reference numeral 20 denotes a flow path plate in which an ink chamber 21 communicating with the nozzle 19 and an ink supply path 22 communicating with the ink chamber 21 are formed. Reference numeral 23 denotes a zirconia substrate.
Indicates a piezoelectric element that is formed by the lower electrode 25, the piezoelectric film 26, and the upper electrode 27 and constitutes an actuator. Stainless steel was used for the material of the nozzle plate 18, and silicon was used for the material of the flow path plate 20. The ink is supplied to the ink chamber 21 from an ink tank (not shown) through an ink supply path 22. When an ink ejection test was performed using this ink jet printer head, ink ejection at an average ejection speed of 8.2 m / sec was confirmed under driving conditions of 30 V and 3 kHz. This proved that the piezoelectric element of the present invention was useful as an ink jet printer head.

<Preparation of Piezoelectric Element for Ultrasonic Motor> Example 31 The fired body obtained in Example 3 was used
After processing into a ring plate having an outer diameter of 80 mm, an inner diameter of 60 mm, and a thickness of 0.5 mm, polarization processing was performed in the pattern shown in FIG. Then, as shown in FIG. 3, A
An electrode and a B electrode (E electrode is a ground electrode) were formed.
An AC voltage of V ₀ sinωt was applied to the A electrode of the obtained piezoelectric element, and a V ₀ cosωt with a phase delay of 90 ° was applied to the B electrode. As a result, it was confirmed that an elastic wave was generated in the element. Thereby, it turned out that the piezoelectric element of the present invention is useful as a drive unit for an ultrasonic motor.

[0138]

According to the first aspect of the present invention, a PZT which is obtained by firing at a low temperature and maintains excellent piezoelectric characteristics.
A porcelain composition can be provided. Claim 2
According to the invention according to the invention, PZ having more excellent piezoelectric properties
A T-based porcelain composition can be provided.

The porcelain composition according to the third aspect of the present invention has a denser structure and retains more excellent piezoelectric characteristics. The porcelain composition of the invention according to claim 4 has a more dense structure and possesses more excellent piezoelectric properties.

The porcelain composition of the invention according to claim 5 has stable piezoelectric properties and excellent leak resistance. Also,
The porcelain composition of the invention according to claim 6 has more stable piezoelectric properties and more excellent leak resistance.

According to the manufacturing method of each of the inventions according to the seventh to twelfth aspects, a PZT-based porcelain composition having the above characteristics can be suitably manufactured. According to the manufacturing method of each of the inventions according to claims 7 and 9, the firing of the porcelain composition is facilitated, and the packing density is improved particularly when a paste is prepared and formed into a film.

According to the production method of each of the eighth and tenth aspects of the present invention, PZT particles or PZT-based particles can be synthesized at a low temperature by a solid-phase reaction, and particles having a small particle size can be synthesized. PZT of desired particle size
The pulverization step for obtaining particles or PZT-based particles is also facilitated, and contamination during the pulverization is reduced.

According to the manufacturing method of each of the eleventh and twelfth aspects of the present invention, the Ge component and the Bi component can be present in the PZT-based porcelain composition so that they function efficiently and effectively.

The piezoelectric element according to the thirteenth aspect of the present invention is capable of lowering the firing temperature when a piezoelectric member is formed by firing after forming or forming a film, and the piezoelectric member has an excellent piezoelectric member. Maintain characteristics.

The piezoelectric element according to the fourteenth aspect of the present invention forms a piezoelectric film by forming a film on the lower electrode and then firing the film.
In this case, the lower electrode and the substrate (diaphragm) receive less damage during the firing process, and the choice of materials for the electrode and the substrate is expanded, and the piezoelectric film retains excellent piezoelectric characteristics. I do.

In the piezoelectric element according to the fifteenth aspect,
Effective vibration can be reliably obtained, and the drive voltage does not need to be so large.

The piezoelectric element of the invention according to claim 16 is used as a drive unit of an ultrasonic motor, and can reduce the firing temperature in the process of forming a piezoelectric thin plate by firing after molding, The body plate retains excellent piezoelectric properties.

According to the manufacturing method of each of the seventeenth to twenty-second aspects of the invention, the piezoelectric element having the above-described characteristics of the fourteenth aspect of the present invention is manufactured by a simpler manufacturing process as compared with the related art. The thickness is 1 μm to 25 μm as in the piezoelectric element of the invention according to claim 15.
Thus, a thin piezoelectric film can be formed.

According to the manufacturing method of the twenty-third and twenty-fourth aspects of the present invention, the piezoelectric element having the above-mentioned characteristics of the sixteenth aspect of the present invention is manufactured by a simpler manufacturing process than the conventional one. can do.

The ink jet printer head according to the twenty-fifth aspect of the present invention has a high performance by being provided with a piezoelectric element having the above characteristics as an actuator.

The ultrasonic motor according to the twenty-sixth aspect of the present invention
By providing a piezoelectric element having the above characteristics as a drive unit that generates ultrasonic vibration, high performance can be achieved.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view schematically showing an example of a configuration of an ink-jet printer head in which a piezoelectric element is used for an actuator, and schematically shows a partially enlarged view.

FIG. 2 is a schematic vertical cross-sectional view showing one configuration example of an ultrasonic motor in which a piezoelectric element is used for a drive unit.

FIG. 3 is a plan view of a piezoelectric element of the ultrasonic motor shown in FIG. 2 as viewed from a back surface side.

FIG. 4 is a longitudinal sectional view showing a schematic configuration of an ink jet printer head produced in an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Head base 2, 21 Ink chamber 3, 23 Vibrating plate 4 Actuator 5, 24 Piezoelectric element 6, 25 Lower electrode 7, 26 Piezoelectric film 8, 27 Upper electrode 9 Power supply 10 Stator 11 Piezoelectric element 12 Elastic ring 13 Slider 14 Rotor 15 Piezoelectric thin plate 16 Divided electrode 17 Partially divided electrode 18 Nozzle plate 19 Nozzle 20 Flow path plate 22 Ink supply path

[Procedure amendment]

[Submission date] March 8, 2000 (200.3.8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

The invention according to claim 18 is a step of forming a lower electrode on the surface of the substrate, and forming the lower electrode on the lower electrode.
7. A method for manufacturing a piezoelectric element, comprising: a step of forming a piezoelectric film made of the piezoelectric ceramic composition according to claim 6; and a step of forming an upper electrode on the piezoelectric film. _{(Zr 1-x Ti x)} O 3 -yLa 2 O
_{3 (0.2 <x ≦ 1)} , Pb (Zr 1-x Ti x) O 3
-YNb ₂ O ₅ (0.2 <x ≦ 1) or Pb (Zr
_{1-x Ti x) O 3} -yLa 2 O 3 -zNb 2 O
₅ After forming a film on the lower electrode using a composition containing a composite oxide having a composition represented by (0.2 <x ≦ 1), the composition film is subjected to a heat treatment to form the piezoelectric film. Is formed. In the above chemical formulas, y and z are as defined in claim 5.
Or La in the PZT-based porcelain composition according to claim 6.
(PZ) corresponding to the content ratio of ₂ O ₃ or Nb ₂ O ₅
Molar ratio to T).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 41/187 H01L 41/22 A 41/24

Claims (26)

[Claims] 1. A chemical formula _{Pb (Zr 1-x Ti x} ) O
₃ (0.2 <x ≦ 1) In a piezoelectric ceramic composition containing a complex oxide as a main component, 0.01% to 10% by weight of GeO ₂ and Bi ₂ O
_3. A piezoelectric ceramic composition containing 0.01 to 10% by weight of No. ₃ . 2. The piezoelectric ceramic composition according to claim 1, wherein the composition contains 0.01% to 5% by weight of GeO _{2 and} 0.01% to 5% by weight of Bi ₂ O ₃ . 3. The weight ratio of Bi ₂ O ₃ / GeO ₂ is 0.0
3. The piezoelectric ceramic composition according to claim 1, wherein the composition is 5 to 2.5. 4. The weight ratio of Bi ₂ O ₃ / GeO ₂ is 0.1.
4. The piezoelectric ceramic composition according to claim 3, wherein the ratio is from 0.8 to 0.8. 5. The piezoelectric ceramic composition according to claim 1, wherein La ₂ O ₃ and / or Nb ₂ O ₃ are contained in an amount of 0.01% by weight to 10% by weight. 6. The piezoelectric ceramic composition according to claim 5, wherein La ₂ O ₃ and / or Nb ₂ O ₃ are contained in an amount of 0.01 to 5% by weight. 7. The method for producing a piezoelectric ceramic composition according to claim 1, wherein the raw material is a chemical formula of Pb (Zr _1-x Ti _x ) O.
_3. Production of a piezoelectric ceramic composition characterized by using particles composed of a composite oxide having a composition represented by (0.2 <x ≦ 1) and having an average particle diameter of 0.05 μm to 0.5 μm. Method. 8. The method according to claim 1, wherein the particles have a chemical formula (Zr _1-x T)
_{i x) 2 O 4 (0.2} < according to claim 7, wherein a complex oxide having the resulting perovskite structure as a starting material and oxide and PbO having a composition represented by x ≦ 1), piezoelectric A method for producing a body porcelain composition. 9. A method of making a claim 5 or claim 6 piezoelectric ceramic composition according, as a raw material, chemical formula _{Pb (Zr 1-x Ti x} ) O 3 -y
La ₂ O ₃ (0.2 <x ≦ 1), Pb (Zr _1-x Ti
_{x) O 3 -yNb 2 O 5} (0.2 <x ≦ 1) or Pb
_{(Zr 1-x Ti x)} O 3 -yLa 2 O 3 -zNb 2 O
_5. Production of a piezoelectric ceramic composition, characterized by using particles composed of a composite oxide having a composition represented by (0.2 <x ≦ 1) and having an average particle diameter of 0.05 μm to 0.5 μm. Method. 10. The method according to claim 1, wherein the particles have a chemical formula (Zr _1-x Ti
_{x) 2} O ₄ (0.2 <composite including an oxide and PbO and _La 2 _{O 3} and / or _Nb 2 _{O 5} and the resulting perovskite structure as a starting material represented by the composition by x ≦ 1) The method for producing a piezoelectric ceramic composition according to claim 9, comprising an oxide. 11. The method according to claim 7, further comprising a step of preparing a slurry or a paste in which the Ge component and the Bi component are added to the particles as an alkoxide or a metal salt or a solution thereof, respectively. A method for producing a piezoelectric ceramic composition. 12. The method according to claim 7, which comprises a step of preparing a slurry or a paste in which the Ge component, Bi component, La component and Nb component are added as alkoxides or metal salts or their solutions, respectively.
A method for producing a piezoelectric ceramic composition. 13. A piezoelectric element comprising at least a piezoelectric member and a plurality of electrodes, wherein the piezoelectric member is
A piezoelectric element formed of the piezoelectric ceramic composition according to any one of claims 1 to 6. 14. The piezoelectric element according to claim 13, wherein the piezoelectric member is a piezoelectric film, and an upper electrode and a lower electrode are provided so as to sandwich the piezoelectric film. 15. The thickness of the piezoelectric film is 1 μm to 25 μm.
The piezoelectric element according to claim 14, wherein m is m. 16. The piezoelectric element according to claim 13, wherein the piezoelectric member is a polarized piezoelectric thin plate, and electrodes are provided on both surfaces of the piezoelectric thin plate in a predetermined pattern. 17. A step of forming a lower electrode on a surface of a substrate, and a step of forming a piezoelectric film made of the piezoelectric ceramic composition according to claim 1 on the lower electrode. When a method for manufacturing a piezoelectric element comprising a step, the forming an upper electrode on the piezoelectric film, the chemical formula _{Pb (Zr 1-x Ti x} ) O 3 (0.2 <x ≦
After forming a film on the lower electrode using a composition containing a composite oxide having the composition represented by 1), the composition film is subjected to a heat treatment to form the piezoelectric film. And a method for manufacturing a piezoelectric element. 18. A step of forming a lower electrode on a surface of a substrate; a step of forming a piezoelectric film made of the piezoelectric ceramic composition according to claim 5 on the lower electrode; forming an upper electrode on the body layer, a method of manufacturing a piezoelectric element comprising the chemical formula _{Pb (Zr 1-x Ti x} ) O 3 -yLa 2 O
_{3 (0.2 <x ≦ 1)} , Pb (Zr 1-x Ti x) O 3
-YNb ₂ O ₅ (0.2 <x ≦ 1) or Pb (Zr
_{1-x Ti x) O 3} -yLa 2 O 3 -zNb 2 O
₅ After forming a film on the lower electrode using a composition containing a composite oxide having a composition represented by (0.2 <x ≦ 1), the composition film is subjected to a heat treatment to form the piezoelectric film. Forming a piezoelectric element. 19. The piezoelectric material according to claim 17, wherein the composition is prepared using particles made of the composite oxide, alkoxides or metal salts of Ge and Bi, or a solution thereof. Method for manufacturing a body element. 20. The piezoelectric body according to claim 17, wherein the composition is prepared using particles of the composite oxide, and alkoxides or metal salts of Ge, Bi, La, and Nb, or a solution thereof. Device manufacturing method. 21. A photosensitive composition containing at least a photosensitive organic polymer is used as the composition. After forming the film, a predetermined pattern is printed on the photosensitive composition film and developed to have a predetermined pattern. 21. A heat treatment is performed after forming the photosensitive composition film.
The method for producing a piezoelectric element according to any one of the above. 22. The heat treatment of the composition film is performed at 600 ° C. to 9 ° C.
22. The method for manufacturing a piezoelectric element according to claim 17, which is performed at a temperature of 50 ° C. 23. A step of forming a piezoelectric thin plate made of the piezoelectric ceramic composition according to claim 1, and forming electrodes in a predetermined pattern on both surfaces of the piezoelectric thin plate. a step, a method of manufacturing a piezoelectric element comprising the steps of applying a polarization treatment to the piezoelectric sheet, the chemical formula _{Pb (Zr 1-x Ti x} ) O 3 (0.2 <x ≦
Forming a thin plate using a composition containing a composite oxide having a composition represented by 1), and then heating the thin plate to form the piezoelectric thin plate; Device manufacturing method. 24. A step of forming a piezoelectric thin plate made of the piezoelectric ceramic composition according to claim 5, or a step of forming electrodes in a predetermined pattern on both surfaces of the piezoelectric thin plate. Subjecting the piezoelectric thin plate to a polarization process, comprising the steps of: chemical formula Pb (Zr _1-x Ti _x ) O ₃ -yLa ₂ O
_{3 (0.2 <x ≦ 1)} , Pb (Zr 1-x Ti x) O 3
-YNb ₂ O ₅ (0.2 <x ≦ 1) or Pb (Zr
_{1-x Ti x) O 3} -yLa 2 O 3 -zNb 2 O
₅ After forming a thin plate using a composition containing a composite oxide having a composition represented by (0.2 <x ≦ 1), the thin plate is heated to form the piezoelectric thin plate. A method for manufacturing a piezoelectric element, comprising: 25. An ink jet printer head having one or two or more ink nozzles, wherein the volume of an ink chamber connected to the ink nozzle is changed by an actuator to eject ink from the ink nozzle. An ink jet printer head, wherein the actuator uses the piezoelectric element according to any one of claims 13 to 15. 26. An ultrasonic motor including a stator that generates a progressive vibration wave by a driving unit, and a moving body that is moved by the traveling vibration wave. An ultrasonic motor using the piezoelectric element according to any one of the preceding claims.