JP2019212921A - Piezoelectric element, laminated piezoelectric element, liquid discharging head, liquid discharging device, ultrasonic motor, optical apparatus, and electronic apparatus - Google Patents

Abstract

To provide a non-lead piezoelectric element which is formed by use of non-lead piezoelectric material and is activated stably in a wide practical temperature region.SOLUTION: A piezoelectric element comprises: a first electrode; piezoelectric material; and a second electrode. The piezoelectric material contains, as a primary component, a perovskite metal oxide expressed by the following general formula (1): (BaCa)(TiZr)O(1.00≤a≤1.01, 0.02≤x≤0.30, 0.020≤y≤0.095, and y≤x). The metal oxide contains Mn; the content of Mn is 0.02 pts.wt or more to 0.40 pts.wt. or less relative to 100 pts.wt. of the metal oxide in terms of metal.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a piezoelectric element, a laminated piezoelectric element, a liquid ejection head, a liquid ejection apparatus, an ultrasonic motor, an optical device, and an electronic device. The present invention relates to a liquid discharge head, a liquid discharge device, an ultrasonic motor, an optical device, and an electronic device.

The piezoelectric material is generally an ABO ₃ type perovskite type metal oxide such as lead zirconate titanate (hereinafter referred to as “PZT”). However, since PZT contains lead as an A-site element, its influence on the environment is regarded as a problem. For this reason, a piezoelectric material using a perovskite-type metal oxide not containing lead is desired.

  Barium titanate is known as a perovskite metal oxide piezoelectric material that does not contain lead. Further, for the purpose of improving the characteristics, material development based on the composition of barium titanate has been performed, and an element using the material has been disclosed. Patent Document 1 discloses a piezoelectric element in which part of the A site of barium titanate is replaced with Ca, and Mn, Fe, or Cu is further added. Although these piezoelectric elements are superior in mechanical quality factor compared to barium titanate, there is a problem that a high voltage is required to drive the elements because of low piezoelectric characteristics.

Patent Document 2 discloses an actuator and a liquid discharge head using a material in which Ba and B are added to barium titanate. However, although these materials is advantageous in that the sintering temperature is lowered as low as the piezoelectric constant d ₃₃ is 65 [pC / N], there is a problem that requires a high voltage for driving the element.

  In addition, when the Curie temperature of the piezoelectric material is 80 ° C. or lower, depolarization occurs in a severe environment such as in a car in summer, and the piezoelectricity may be lost. Alternatively, the piezoelectricity may be lost due to heat generated by driving the actuator.

JP 2010-120835 A JP 2011-032111 A

  The present invention has been made to cope with the above-described problems, and provides a lead-free piezoelectric element that can be stably driven in a wide practical temperature range.

A piezoelectric element for solving the above problems is a piezoelectric element having at least a first electrode, a piezoelectric material, and a second electrode, and the piezoelectric material is represented by the following general formula (1):
Formula _{(1) (Ba 1-x} Ca x) a (Ti 1-y Zr y) O 3 (1.00 ≦ a ≦ 1.01,0.02 ≦ x ≦ 0.30,0.020 ≦ y ≦ 0.095 and y ≦ x)
And the metal oxide contains Mn, and the Mn content is 0.02 parts by weight or more in terms of metal with respect to 100 parts by weight of the metal oxide. It is characterized by being 0.40 parts by weight or less.

A laminated piezoelectric element for solving the above problems is a laminated piezoelectric element in which piezoelectric material layers and electrodes including internal electrodes are alternately laminated, and the piezoelectric material layer has the following general formula (1):
General formula (1) (Ba1-xCax) a (Ti1-yZry) O3 (1.00 ≦ a ≦ 1.01, 0.02 ≦ x ≦ 0.30, 0.020 ≦ y ≦ 0.095, And y ≦ x)
And the metal oxide contains Mn, and the Mn content is 0.02 parts by weight or more in terms of metal with respect to 100 parts by weight of the metal oxide. The piezoelectric material is 0.40 part by weight or less.

  A liquid discharge head for solving the above-described problems has at least a liquid chamber including a vibrating portion provided with the above-described piezoelectric element or the above-described laminated piezoelectric element, and an discharge port communicating with the liquid chamber. .

  A liquid ejection apparatus for solving the above-described problems includes a recording medium transport unit and the above-described liquid ejection head.

  An ultrasonic motor for solving the above-described problems includes at least a vibrating body provided with the piezoelectric element or the laminated piezoelectric element, and a moving body that contacts the vibrating body.

  An optical apparatus for solving the above-described problems is characterized in that the drive unit includes the ultrasonic motor described above.

  An electronic apparatus for solving the above-described problems is characterized in that a piezoelectric acoustic component including the piezoelectric element or the laminated piezoelectric element is provided.

  According to the present invention, a lead-free piezoelectric element that can be stably driven in a wide practical temperature range can be provided. In addition, the present invention can provide a liquid discharge head, a liquid discharge apparatus, an ultrasonic motor, an optical apparatus, and an electronic apparatus using the lead-free piezoelectric element.

It is the schematic which shows one embodiment of a structure of the piezoelectric element of this invention. FIG. 3 is a schematic view showing an embodiment of the configuration of the liquid ejection head of the present invention. It is the schematic which shows one embodiment of a structure of the ultrasonic motor of this invention. It is a phase diagram which shows the relationship between x value and y value of the piezoelectric ceramics of the manufacture examples 1 to 73 of this invention. The inside of the dotted line indicates the range of the x value and y value of claim 1. It is a section schematic diagram showing one embodiment of the composition of the lamination piezoelectric element of the present invention. It is the schematic which shows one embodiment of the liquid discharge apparatus of this invention. It is the schematic which shows one embodiment of the liquid discharge apparatus of this invention. It is the schematic which shows one embodiment of the optical instrument of this invention. It is the schematic which shows one embodiment of the optical instrument of this invention. It is the schematic which shows one embodiment of the electronic device of this invention.

  Hereinafter, modes for carrying out the present invention will be described.

  FIG. 1 is a schematic view showing an embodiment of the configuration of the piezoelectric element of the present invention. The piezoelectric element of the present invention includes a piezoelectric material 2, and a first electrode 1 and a second electrode 3 provided for the piezoelectric material 2.

The piezoelectric element according to the present invention is a piezoelectric element having at least a first electrode, a piezoelectric material, and a second electrode, and the piezoelectric material is represented by the following general formula (1):
Formula _{(1) (Ba 1-x} Ca x) a (Ti 1-y Zr y) O 3 (1.00 ≦ a ≦ 1.01,0.02 ≦ x ≦ 0.30,0.020 ≦ y ≦ 0.095 and y ≦ x)
And the metal oxide contains Mn, and the Mn content is 0.02 parts by weight or more in terms of metal with respect to 100 parts by weight of the metal oxide. It is characterized by being 0.40 parts by weight or less.

  The first electrode and the second electrode are made of a conductive layer having a thickness of about 5 nm to 2000 nm. The material is not particularly limited as long as it is usually used for piezoelectric elements. Examples thereof include metals such as Ti, Pt, Ta, Ir, Sr, In, Sn, Au, Al, Fe, Cr, Ni, Pd, Ag, and Cu, and compounds thereof.

  Said 1st electrode and 2nd electrode may consist of 1 type of these, or may laminate | stack these 2 types or more. Further, the first electrode and the second electrode may be made of different materials.

  The manufacturing method of the first electrode and the second electrode is not limited, and may be formed by baking a metal paste, or may be formed by sputtering, vapor deposition, or the like. Further, both the first electrode and the second electrode may be patterned into a desired shape and used.

In the present invention, the perovskite-type metal oxide is an ideal cubic perovskite structure (perovskite structure) as described in Iwanami Physical and Chemical Dictionary, 5th edition (Iwanami Shoten, issued on February 20, 1998). A metal oxide having a structure). A metal oxide having a perovskite structure is generally expressed by a chemical formula of ABO ₃ . In the perovskite type metal oxide, the elements A and B occupy specific positions of unit cells called A sites and B sites in the form of ions, respectively. For example, in the case of a cubic unit cell, the A element is located at the apex of the cube and the B element is located at the body center. O element occupies the center of the cube as an anion of oxygen.

  The metal oxide represented by the general formula (1) means that the metal elements located at the A site are Ba and Ca, and the metal elements located at the B site are Ti and Zr. However, a part of Ba and Ca may be located at the B site. Similarly, some Ti and Zr may be located at the A site.

  In the general formula (1), the molar ratio of the B site element to the O element is 1: 3, but the molar ratio is slightly shifted (for example, 1.00 to 2.94 to 1.00 to 3. 06) However, if the metal oxide has a perovskite structure as a main phase, it is included in the scope of the present invention.

  Whether the metal oxide has a perovskite structure can be determined, for example, from structural analysis by X-ray diffraction or electron beam diffraction.

  The form of the piezoelectric material according to an embodiment of the present invention is not limited and may be any form such as ceramics, powder, single crystal, film, and slurry, but is preferably ceramics. In this specification, “ceramics” represents a so-called polycrystal, which is an aggregate (also referred to as a bulk body) of crystal particles whose basic component is a metal oxide and is baked and hardened by heat treatment. Those processed after sintering are also included.

In the general formula (1), a indicating the ratio between the molar amount of Ba and Ca at the A site and the molar amount of Ti and Zr at the B site is in the range of 1.00 ≦ a ≦ 1.01. If a is less than 1.00, abnormal grain growth is likely to occur, and the mechanical strength of the material is reduced. On the other hand, if a is greater than 1.01, the temperature required for grain growth becomes too high, and sintering cannot be performed in a general firing furnace. Here, “cannot be sintered” indicates that the density does not reach a sufficient value, or that there are many pores and defects in the piezoelectric material.

  In the general formula (1), x indicating the molar ratio of Ca at the A site is in the range of 0.02 ≦ x ≦ 0.30. When x is smaller than 0.02, the dielectric loss (tan δ) increases. When the dielectric loss increases, heat generated when a voltage is applied to the piezoelectric element to drive it increases, which may reduce the driving efficiency. On the other hand, when x is larger than 0.30, the piezoelectric characteristics are not sufficient.

In the general formula (1), y indicating the molar ratio of Zr at the B site is in the range of 0.020 ≦ y ≦ 0.095. When y is smaller than 0.020, the piezoelectric characteristics are not sufficient. On the other hand, if y is greater than 0.095, the Curie temperature (T _c ) is as low as less than 85 ° C., and the piezoelectric characteristics disappear at high temperatures.

  In this specification, the Curie temperature refers to a temperature at which ferroelectricity disappears. In addition to the method of directly measuring the temperature at which the ferroelectricity disappears while changing the measurement temperature, the identification method measures the dielectric constant while changing the measurement temperature using a minute AC electric field, and starts from the temperature at which the dielectric constant shows a maximum. There is a way to ask.

  In the general formula (1), the molar ratio x of Ca and the molar ratio y of Zr are in the range of y ≦ x. When y> x, the dielectric loss increases or the insulation is not sufficient. If the x and y ranges shown above are satisfied simultaneously, the crystal structure phase transition temperature (phase transition point) can be moved from near room temperature to below the practical temperature, and the device can be driven stably over a wide temperature range. It becomes possible to make it.

  The means for measuring the composition of the piezoelectric material in the piezoelectric element according to the present invention is not particularly limited. Examples of the means include X-ray fluorescence analysis, ICP emission spectroscopic analysis, and atomic absorption analysis. In any means, the weight ratio and composition ratio of each element contained in the piezoelectric material can be calculated.

  The piezoelectric material in the piezoelectric element according to the present invention has a Mn content of 0.02 to 0.40 part by weight in terms of metal with respect to 100 parts by weight of the metal oxide. When the piezoelectric material contains Mn in the above range, the insulation and mechanical quality factor are improved. Here, the mechanical quality factor is a coefficient representing elastic loss due to vibration when the piezoelectric material is evaluated as a vibrator, and the magnitude of the mechanical quality factor is observed as the sharpness of the resonance curve in impedance measurement. That is, the constant represents the sharpness of resonance of the vibrator. The improvement in the insulation and the mechanical quality factor is considered to originate from the fact that a defect dipole is introduced by Mn having a different valence from Ti and Zr and an internal electric field is generated. In the presence of an internal electric field, long-term reliability of the device can be ensured when a voltage is applied to the device and driven.

  Here, “metal conversion” indicating the content of Mn means that Ba, Ca, Ti, Zr and Mn measured from the piezoelectric material by X-ray fluorescence analysis (XRF), ICP emission spectroscopic analysis, atomic absorption analysis, etc. From the content of each metal, the element constituting the metal oxide represented by the general formula (1) is converted into an oxide, and the value obtained by the ratio with the Mn weight with respect to the total weight as 100 is obtained. Represent.

  If the Mn content is less than 0.02 parts by weight, the effect of polarization treatment required for driving the device will not be sufficient. On the other hand, if the Mn content is greater than 0.40 parts by weight, the piezoelectric properties are not sufficient, and hexagonal crystals that do not contribute to the piezoelectric properties are manifested.

  Mn is not limited to metal Mn, but may be contained in the piezoelectric material as a Mn component, and the form of inclusion is not limited. For example, it may be dissolved in the B site or included in the grain boundary. Alternatively, the Mn component may be included in the piezoelectric material in the form of a metal, ion, oxide, metal salt, complex, or the like. A more preferable form is to form a solid solution at the B site from the viewpoint of insulation and easy sintering. When dissolved in the B site, if the ratio of the molar amount of Ba and Ca at the A site to the molar amount of Ti, Zr and Mn at the B site is A / B, the resonance of the piezoelectric sensor, piezoelectric transformer, ultrasonic motor, etc. A preferable A / B range in a resonant device (hard device) driven at a frequency is 0.993 ≦ A / B ≦ 0.998. A piezoelectric element having A / B in these ranges has a high piezoelectric constant and a mechanical quality factor, so that a device having excellent durability can be manufactured. A preferable A / B range in a displacement actuator (soft device) driven at a non-resonant frequency such as an optical pickup actuator or a liquid discharge head is 0.996 ≦ A / B ≦ 0.999. A piezoelectric element having A / B within these ranges can achieve both a high piezoelectric constant and a low dielectric loss, and can produce a device having excellent durability.

  The piezoelectric material in the piezoelectric element according to the present invention may contain components other than the general formula (1) and Mn (hereinafter referred to as subcomponents) within a range in which characteristics do not vary. The total amount of the subcomponents is preferably 1.2 parts by weight or less with respect to 100 parts by weight of the metal oxide represented by the general formula (1). If the subcomponent exceeds 1.2 parts by weight, the piezoelectric characteristics and insulation characteristics of the piezoelectric material may be deteriorated. The content of metal elements other than the Ba, Ca, Ti, Zr, and Mn among the subcomponents is 1.0 part by weight or less in terms of oxide relative to the piezoelectric material, or 0.9 in terms of metal. It is preferable that it is below the weight part. In the present specification, the “metal element” includes a metalloid element such as Si, Ge, and Sb. Among the subcomponents, the content of metal elements other than Ba, Ca, Ti, Zr, and Mn is 1.0 part by weight in terms of oxide or 0.9 parts by weight in terms of metal with respect to the piezoelectric material. If it exceeds, the piezoelectric properties and insulation properties of the piezoelectric material may be significantly reduced. Of the subcomponents, the total of Li, Na, Mg, and Al elements is preferably 0.5 parts by weight or less in terms of metal relative to the piezoelectric material. If the total of Li, Na, Mg, and Al elements among the subcomponents exceeds 0.5 parts by weight in terms of metal relative to the piezoelectric material, sintering may be insufficient. Of the subcomponents, the total of Y and V elements is preferably 0.2 parts by weight or less in terms of metal relative to the piezoelectric material. Among the subcomponents, if the total of Y and V elements exceeds 0.2 parts by weight in terms of metal with respect to the piezoelectric material, polarization processing may be difficult.

  Examples of the accessory component include sintering aids such as Si and Cu. Moreover, Sr contained to the extent that it is included as an inevitable component in commercially available raw materials for Ba and Ca may be included in the piezoelectric material of the present invention. Similarly, Nb that is included as an inevitable component in the Ti raw material and Hf that is included as an inevitable component in the Zr commercial material may be included in the piezoelectric material of the present invention.

  The means for measuring the weight part of the subcomponent is not particularly limited. Examples of the means include X-ray fluorescence analysis, ICP emission spectroscopic analysis, and atomic absorption analysis.

  The piezoelectric material in the piezoelectric element according to the present invention preferably has an average equivalent circle diameter of crystal grains constituting the piezoelectric material of 1 μm or more and 10 μm or less. By setting the average equivalent circle diameter within this range, the piezoelectric material of the present invention can have good piezoelectric characteristics and mechanical strength. If the average equivalent circle diameter is less than 1 μm, the piezoelectric characteristics may not be sufficient. On the other hand, if it exceeds 10 μm, the mechanical strength may decrease. A more preferable range is 3 μm or more and 8 μm or less.

  The “equivalent circle diameter” in the present invention represents a “projected area equivalent circle diameter” generally referred to in the microscopic observation method, and represents the diameter of a perfect circle having the same area as the projected area of the crystal grains. In the present invention, the method for measuring the equivalent circle diameter is not particularly limited. For example, a photographic image obtained by photographing the surface of the piezoelectric material with a polarizing microscope or a scanning electron microscope can be obtained by image processing. Since the optimum magnification varies depending on the target particle size, an optical microscope and an electron microscope may be used separately. The equivalent circle diameter may be obtained from an image of a polished surface or a cross section instead of the surface of the material.

  The piezoelectric material in the piezoelectric element according to the present invention preferably has a relative density of 93% or more and 100% or less of the piezoelectric material.

  If the relative density is less than 93%, the piezoelectric characteristics and the mechanical quality factor may be insufficient, or the mechanical strength may be reduced.

  In the piezoelectric material in the piezoelectric element according to the present invention, x and y in the main component of the piezoelectric material are in a range of 0.125 ≦ x ≦ 0.175 and 0.055 ≦ y ≦ 0.090, respectively, and The Mn content is preferably 0.02 parts by weight or more and 0.10 parts by weight or less in terms of metal with respect to 100 parts by weight of the metal oxide.

  A piezoelectric element using a piezoelectric material having this composition range is particularly suitable for a displacement actuator (also referred to as a soft device) such as an optical pickup actuator or a liquid discharge head. When the range of x representing the molar ratio of Ca is smaller than 0.125, durability may be deteriorated. On the other hand, when the range of x is larger than 0.175, the piezoelectric strain may be reduced. Preferably, 0.140 ≦ x ≦ 0.175. Further, if the range of y representing the molar ratio of Zr is smaller than 0.055, the piezoelectric strain may be reduced. On the other hand, when the range of y is larger than 0.09, the Curie temperature is lowered, so that the practical temperature range of the element may be narrowed. Preferably it is 0.055 <= y <= 0.075. Furthermore, if the Mn content is less than 0.02 parts by weight, the polarization treatment may not be sufficient, and if it is greater than 0.10 parts by weight, the piezoelectric strain may be reduced. A preferable range of a is 1.000 ≦ a ≦ 1.005.

  In the piezoelectric material in the piezoelectric element according to the present invention, x and y in the main component of the piezoelectric material are in a range of 0.155 ≦ x ≦ 0.300 and 0.041 ≦ y ≦ 0.069, respectively, and The Mn content is preferably 0.12 parts by weight or more and 0.40 parts by weight or less in terms of metal with respect to 100 parts by weight of the metal oxide.

  A piezoelectric element using a piezoelectric material having this composition range is particularly suitable for a resonant device (also referred to as a hardware device) such as a piezoelectric sensor, a piezoelectric transformer, or an ultrasonic motor. When the range of x representing the molar ratio of Ca is smaller than 0.155, the mechanical quality factor may be decreased. On the other hand, when the range of x is larger than 0.300, the piezoelectric strain may be deteriorated. Preferably, 0.160 ≦ x ≦ 0.300. Further, if the range of y representing the molar ratio of Zr is smaller than 0.041, the piezoelectric strain may be reduced. On the other hand, if the range of y is greater than 0.069, the practical temperature range of the device may be narrowed. Preferably, 0.045 ≦ y ≦ 0.069. Furthermore, if the Mn content is less than 0.12 parts by weight, the mechanical quality factor becomes small, and power consumption may increase when the device is driven at the resonance frequency. On the other hand, when the content of Mn is larger than 0.40 parts by weight, the piezoelectric strain becomes small, and there is a possibility that a higher voltage is required when the device is driven. Preferably, they are 0.20 weight part or more and 0.40 weight part or less. A preferable range of a is 1.004 ≦ a ≦ 1.009.

  The method for producing the piezoelectric material in the piezoelectric element according to the present invention is not particularly limited.

  When manufacturing piezoelectric ceramics, a general method of sintering solid powders such as oxides, carbonates, nitrates and oxalates containing constituent elements at normal pressure can be employed. As a raw material, it is comprised from metal compounds, such as Ba compound, Ca compound, Ti compound, Zr compound, and Mn compound.

  Examples of the Ba compound that can be used include barium oxide, barium carbonate, barium oxalate, barium acetate, barium nitrate, barium titanate, barium zirconate, and barium zirconate titanate.

  Examples of Ca compounds that can be used include calcium oxide, calcium carbonate, calcium oxalate, calcium acetate, calcium titanate, and calcium zirconate.

  Examples of Ti compounds that can be used include titanium oxide, barium titanate, barium zirconate titanate, and calcium titanate.

  Zr compounds that can be used include zirconium oxide, barium zirconate, barium zirconate titanate, calcium zirconate and the like.

  Examples of the Mn compound that can be used include manganese carbonate, manganese oxide, manganese dioxide, manganese acetate, and trimanganese tetroxide.

  In addition, the raw material for adjusting a indicating the ratio of the molar amount of Ba and Ca at the A site of the piezoelectric ceramic and the molar amount of Ti and Zr at the B site in the piezoelectric ceramic according to the present invention is not particularly limited. The effect is the same for any of the Ba compound, Ca compound, Ti compound, and Zr compound.

  The method for granulating the raw material powder of the piezoelectric ceramic in the piezoelectric element according to the present invention is not particularly limited, but the most preferable granulation method is the spray drying method from the viewpoint that the particle size of the granulated powder can be made more uniform. .

  Examples of binders that can be used when granulating include PVA (polyvinyl alcohol), PVB (polyvinyl butyral), and acrylic resins. The amount of the binder to be added is preferably 1 to 10 parts by weight, and more preferably 2 to 5 parts by weight from the viewpoint of increasing the density of the molded body.

  The method for sintering the piezoelectric ceramic in the piezoelectric element according to the present invention is not particularly limited. Examples of the sintering method include sintering with an electric furnace, sintering with a gas furnace, current heating method, microwave sintering method, millimeter wave sintering method, HIP (hot isostatic pressing) and the like. The electric furnace and gas sintering may be a continuous furnace or a batch furnace.

  The sintering temperature of the ceramics in the sintering method is not particularly limited, but is preferably a temperature at which each compound reacts and sufficiently grows crystals. A preferable sintering temperature is 1200 ° C. or higher and 1550 ° C. or lower, more preferably 1300 ° C. or higher and 1480 ° C. or lower from the viewpoint of setting the particle size of the ceramic in the range of 1 μm to 10 μm. Piezoelectric ceramics sintered in the above temperature range exhibit good piezoelectric performance.

  In order to stabilize the characteristics of the piezoelectric ceramic obtained by the sintering process with good reproducibility, it is preferable to perform the sintering process for 2 hours to 24 hours with the sintering temperature kept constant within the above range. A sintering method such as a two-stage sintering method may be used, but a method that does not cause a rapid temperature change is preferable in consideration of productivity.

  The piezoelectric ceramic is preferably heat-treated at a temperature of 1000 ° C. or higher after being polished. When mechanically polished, residual stress is generated inside the piezoelectric ceramic. However, when the heat treatment is performed at 1000 ° C. or higher, the residual stress is relaxed and the piezoelectric characteristics of the piezoelectric ceramic are further improved. In addition, there is an effect of eliminating raw material powder such as barium carbonate deposited at the grain boundary portion. The heat treatment time is not particularly limited, but is preferably 1 hour or longer.

  The piezoelectric element is more preferably one having polarization axes aligned in a certain direction. When the polarization axes are aligned in a certain direction, the piezoelectric constant of the piezoelectric element increases. The polarization method of the piezoelectric element is not particularly limited. The polarization treatment may be performed in the air or in silicone oil. The temperature at the time of polarization is preferably 60 ° C. to 100 ° C., but the optimum conditions differ somewhat depending on the composition of the piezoelectric ceramic constituting the element. The electric field applied for the polarization treatment is preferably 800 V / mm to 2.0 kV / mm.

  The piezoelectric constant and the mechanical quality factor of the piezoelectric element are calculated from the measurement results of the resonance frequency and the antiresonance frequency obtained using a commercially available impedance analyzer, based on the Japan Electronics and Information Technology Industries Association Standard (JEITA EM-4501). It can ask for. Hereinafter, this method is called a resonance-antiresonance method.

(Laminated piezoelectric element)
Next, the laminated piezoelectric element of the present invention will be described.

The laminated piezoelectric element of the present invention is a laminated piezoelectric element in which piezoelectric material layers and electrodes including internal electrodes are alternately laminated, and the piezoelectric material layer has the following general formula (1):
Formula _{(1) (Ba 1-x} Ca x) a (Ti 1-y Zr y) O 3 (1.00 ≦ a ≦ 1.01,0.02 ≦ x ≦ 0.30,0.020 ≦ y ≦ 0.095 and y ≦ x)
And the metal oxide contains Mn, and the Mn content is 0.02 parts by weight or more in terms of metal with respect to 100 parts by weight of the metal oxide. The piezoelectric material is composed of 0.40 parts by weight or less.

  FIG. 5 is a schematic cross-sectional view showing an embodiment of the configuration of the multilayer piezoelectric element of the present invention. The laminated piezoelectric element according to the present invention is composed of a piezoelectric material layer 54 and an electrode including an internal electrode 55, and is a laminated piezoelectric element in which piezoelectric material layers and layered electrodes are alternately laminated, The piezoelectric material layer 54 is made of the above-described piezoelectric material. The electrodes may include external electrodes such as the first electrode 51 and the second electrode 53 in addition to the internal electrode 55.

  FIG. 5A shows a laminate of the present invention in which two piezoelectric material layers 54 and one internal electrode 55 are alternately laminated, and the laminated structure is sandwiched between the first electrode 51 and the second electrode 53. Although the configuration of the piezoelectric element is shown, the number of piezoelectric material layers and internal electrodes may be increased as shown in FIG. 5B, and the number of layers is not limited. In the laminated piezoelectric element of FIG. 5B, nine piezoelectric material layers 504 and eight internal electrodes 505 are alternately laminated, and the laminated structure is sandwiched between the first electrode 501 and the second electrode 503. The configuration includes an external electrode 506a and an external electrode 506b for short-circuiting alternately formed internal electrodes.

  The sizes and shapes of the internal electrodes 55 and 505 and the external electrodes 506a and 506b are not necessarily the same as those of the piezoelectric material layers 54 and 504, and may be divided into a plurality of parts.

  The internal electrodes 55 and 505 and the external electrodes 506a and 506b are made of conductive layers having a thickness of about 5 nm to 2000 nm. The material is not particularly limited as long as it is usually used for piezoelectric elements. Examples thereof include metals such as Ti, Pt, Ta, Ir, Sr, In, Sn, Au, Al, Fe, Cr, Ni, Pd, Ag, and Cu, and compounds thereof. The internal electrodes 55 and 505 and the external electrodes 506a and 506b may be made of one of them, a mixture of two or more kinds or an alloy, or a laminate of two or more of them. It may be a thing. The plurality of electrodes may be made of different materials. From the viewpoint that the electrode material is inexpensive, the internal electrodes 55 and 505 are preferably composed mainly of Ni.

  As shown in FIG. 5B, a plurality of electrodes including the internal electrode 505 may be short-circuited with each other for the purpose of aligning the phases of the drive voltages. For example, the structure which short-circuits the internal electrode 505, the 1st electrode 501, and the 2nd electrode 503 alternately is mentioned. Moreover, the form of the short circuit between electrodes is not limited. An electrode or wiring for short-circuiting may be provided on the side surface of the laminated piezoelectric element, or a through-hole penetrating the piezoelectric material layer 504 may be provided, and a conductive material may be provided inside to short-circuit the electrodes.

  Although the manufacturing method of the multilayer piezoelectric element according to the present invention is not particularly limited, the manufacturing method is exemplified below. As an example, a step (A) of obtaining a slurry by dispersing a metal compound powder containing at least Ba, Ca, Ti, Zr and Mn, and a step (B) of obtaining a molded body by placing the slurry on a substrate. A method including a step (C) of forming an electrode on the molded body and a step (D) of sintering the molded body on which the electrode is formed to obtain a laminated piezoelectric element will be described.

  The powder in this specification intends an aggregate of solid particles. It may be an aggregate of particles simultaneously containing Ba, Ca, Ti, Zr, and Mn, or an aggregate of a plurality of types of particles including an arbitrary element.

  Examples of the metal compound powder in the step (A) include Ba compound, Ca compound, Ti compound, Zr compound and Mn compound. Examples of the Ba compound that can be used include barium oxide, barium carbonate, barium oxalate, barium acetate, barium nitrate, barium titanate, barium zirconate, and barium zirconate titanate.

  Examples of Ca compounds that can be used include calcium oxide, calcium carbonate, calcium oxalate, calcium acetate, calcium titanate, calcium zirconate, and calcium zirconate titanate.

  Examples of Ti compounds that can be used include titanium oxide, barium titanate, barium zirconate titanate, and calcium titanate.

  Zr compounds that can be used include zirconium oxide, barium zirconate, barium zirconate titanate, calcium zirconate and the like.

  Examples of the Mn compound that can be used include manganese carbonate, manganese oxide, manganese dioxide, manganese acetate, and trimanganese tetroxide.

  An example of a method for preparing the slurry in the step (A) will be described. A solvent having a weight 1.6 to 1.7 times that of the metal compound powder is added and mixed. As the solvent, for example, toluene, ethanol, a mixed solvent of toluene and ethanol, n-butyl acetate, or water can be used. After mixing with a ball mill for 24 hours, the binder and plasticizer are added. Examples of the binder include PVA (polyvinyl alcohol), PVB (polyvinyl butyral), and acrylic resins. When PVB is used for the binder, the solvent and PVB are weighed so that the weight ratio of the solvent is, for example, 88:12. Examples of the plasticizer include dioctyl sebacate, dioctyl phthalate, and dibutyl phthalate. When dibutyl phthalate is used as the plasticizer, weigh the same weight as the binder. Then, the ball mill is performed again overnight. The amount of the solvent and binder is adjusted so that the viscosity of the slurry is 300 to 500 mPa · s.

  The molded body in the step (B) is a sheet-shaped mixture of the metal compound powder, binder and plasticizer. As a method of obtaining the molded body in the step (B), for example, there is sheet molding. For the sheet molding, for example, a doctor blade method can be used. The doctor blade method is a method of forming a sheet-shaped molded body by applying the slurry onto the substrate using a doctor blade and drying the slurry. As the substrate, for example, a pet film can be used. For example, fluorine coating on the surface on which the pet film slurry is placed is desirable because it facilitates peeling of the molded product. Drying may be natural drying or hot air drying. The thickness of the molded body is not particularly limited and can be adjusted according to the thickness of the laminated piezoelectric element. The thickness of the molded body can be increased by increasing the viscosity of the slurry, for example.

  The manufacturing method of the electrode in the step (C), that is, the internal electrode 505 and the external electrodes 506a and 506b is not limited, and may be formed by baking a metal paste, or formed by sputtering, vapor deposition, printing, or the like. Good. In order to reduce the driving voltage, the layer thickness and pitch interval of the piezoelectric material layer 504 may be reduced. In that case, after forming the laminated body containing the precursor of the piezoelectric material layer 504 and the internal electrode 505, the process of baking the said laminated body simultaneously is selected. In that case, a material for the internal electrode that does not cause a shape change or deterioration of conductivity due to a temperature necessary for sintering the piezoelectric material layer 504 is required. A metal or an alloy thereof having a lower melting point and lower cost than Pt such as Ag, Pd, Au, Cu, and Ni can be used for the internal electrode 5 and the external electrodes 506a and 506b. However, the external electrodes 506a and 506b may be provided after the laminate is fired. In that case, in addition to Ag, Pd, Cu, and Ni, Al or a carbon-based electrode material can be used.

  A screen printing method is desirable as a method for forming the electrodes. The screen printing method is a method of applying a metal paste using a spatula after a screen plate is placed on a molded body placed on a substrate. A screen mesh is formed at least partially on the screen plate. Therefore, the metal paste in the portion where the screen mesh is formed is applied onto the molded body. The screen mesh in the screen plate is preferably formed with a pattern. By transferring the pattern to the molded body using a metal paste, the electrode can be patterned on the molded body.

  After forming the electrode in the step (C), after peeling from the base material, one or a plurality of the compacts are stacked and pressure-bonded. Examples of the pressure bonding method include uniaxial pressing, cold isostatic pressing, and warm isostatic pressing. Warm isostatic pressing is desirable because it can apply pressure isotropically and uniformly. Heating to near the glass transition temperature of the binder during pressure bonding is desirable because it enables better pressure bonding. A plurality of the compacts can be stacked and pressure-bonded until a desired thickness is reached. For example, after 10 to 100 layers of the molded body are stacked, the molded body can be stacked by thermocompression bonding at a pressure of 10 to 60 MPa at 50 to 80 ° C. for 10 seconds to 10 minutes in the stacking direction. . Moreover, by attaching alignment marks to the electrodes, a plurality of molded bodies can be aligned and stacked with high accuracy. Of course, it is also possible to stack accurately by providing positioning through holes in the molded body.

  Although the sintering temperature of the molded body in the step (D) is not particularly limited, it is preferably a temperature at which each compound reacts and sufficiently grows crystals. A preferable sintering temperature is 1200 ° C. or higher and 1550 ° C. or lower, more preferably 1300 ° C. or higher and 1480 ° C. or lower from the viewpoint of setting the particle size of the ceramic in the range of 1 μm to 10 μm. A laminated piezoelectric element sintered in the above temperature range exhibits good piezoelectric performance.

When a material containing Ni as a main component is used for the electrode in the step (C), the step (D) is preferably performed in a furnace capable of atmospheric firing. After burning and removing the binder at a temperature of 200 ° C. to 600 ° C. in the air atmosphere, the binder is changed to a reducing atmosphere and sintered at a temperature of 1200 ° C. to 1550 ° C. Here, the reducing atmosphere refers to an atmosphere mainly composed of a mixed gas of hydrogen (H ₂ ) and nitrogen (N ₂ ). The volume ratio of hydrogen and nitrogen is preferably in the range of H ₂ : N ₂ = 1: 99 to H ₂ : N ₂ = 10: 90. The mixed gas may contain oxygen. The oxygen concentration is 10 ⁻¹² Pa or more and 10 ⁻⁴ Pa or less. More preferably, it is 10 ⁻⁸ Pa or more and 10 ⁻⁵ Pa or less. The oxygen concentration can be measured with a zirconia oxygen analyzer. By using the Ni electrode, the multilayer piezoelectric element of the present invention can be manufactured at low cost. After firing in a reducing atmosphere, the temperature is preferably lowered to 600 ° C., and the atmosphere is preferably changed to an air atmosphere (oxidizing atmosphere) to perform an oxidation treatment. After taking out from the firing furnace, a conductive paste is applied to the side surface of the element body where the end of the internal electrode is exposed and dried to form the external electrode.

(Liquid discharge head)
The liquid discharge head according to the present invention has at least a discharge port that communicates with a liquid chamber provided with a vibrating portion provided with the piezoelectric element or the laminated piezoelectric element.

  FIG. 2 is a schematic view showing an embodiment of the configuration of the liquid discharge head of the present invention. As shown in FIGS. 2A and 2B, the liquid discharge head of the present invention is a liquid discharge head having the piezoelectric element 101 of the present invention. The piezoelectric element 101 is a piezoelectric element having at least a first electrode 1011, a piezoelectric material 1012, and a second electrode 1013. The piezoelectric material 1012 is patterned as necessary as shown in FIG.

  FIG. 2B is a schematic diagram of the liquid discharge head. The liquid ejection head includes an ejection port 105, an individual liquid chamber 102, a communication hole 106 that connects the individual liquid chamber 102 and the ejection port 105, a liquid chamber partition wall 104, a common liquid chamber 107, a vibration plate 103, and a piezoelectric element 101. In the drawing, the piezoelectric element 101 has a rectangular shape, but the shape may be other than a rectangle such as an ellipse, a circle, or a parallelogram. In general, the piezoelectric material 1012 has a shape along the shape of the individual liquid chamber 102.

  The vicinity of the piezoelectric element 101 included in the liquid discharge head of the present invention will be described in detail with reference to FIG. FIG. 2A is a cross-sectional view in the width direction of the piezoelectric element shown in FIG. The cross-sectional shape of the piezoelectric element 101 is displayed as a rectangle, but may be a trapezoid or an inverted trapezoid.

  In the drawing, the first electrode 1011 is used as a lower electrode, and the second electrode 1013 is used as an upper electrode. However, the arrangement of the first electrode 1011 and the second electrode 1013 is not limited to this. For example, the first electrode 1011 may be used as the lower electrode or may be used as the upper electrode. Similarly, the second electrode 1013 may be used as the upper electrode or the lower electrode. A buffer layer 108 may exist between the diaphragm 103 and the lower electrode. In addition, the difference of these names is based on the manufacturing method of a device, and the effect of this invention is acquired in any case.

  In the liquid discharge head, the vibration plate 103 fluctuates up and down due to expansion and contraction of the piezoelectric material 1012 and applies pressure to the liquid in the individual liquid chamber 102. As a result, liquid is discharged from the discharge port 105. The liquid discharge head of the present invention can be used for printer applications and electronic device manufacture.

  The thickness of the diaphragm 103 is 1.0 μm or more and 15 μm or less, preferably 1.5 μm or more and 8 μm or less. The material of the diaphragm is not limited, but is preferably Si. Boron or phosphorus may be doped into Si of the diaphragm. Further, the buffer layer and the electrode on the diaphragm may be a part of the diaphragm. The thickness of the buffer layer 108 is 5 nm or more and 300 nm or less, preferably 10 nm or more and 200 nm or less. The discharge port 105 has a circle equivalent diameter of 5 μm or more and 40 μm or less. The shape of the discharge port 105 may be circular, or may be a star shape, a square shape, or a triangular shape.

(Liquid discharge device)
Next, the liquid ejection apparatus of the present invention will be described. The liquid discharge apparatus of the present invention has the liquid discharge head.

  As an example of the liquid ejection apparatus of the present invention, the ink jet recording apparatus shown in FIGS. 6 and 7 can be cited. FIG. 7 shows a state where the exteriors 882 to 885 and 887 of the liquid ejection apparatus (inkjet recording apparatus) 881 shown in FIG. 6 are removed. The ink jet recording apparatus 881 includes an automatic feeding unit 897 that automatically feeds recording paper as a recording medium into the apparatus main body 896. Furthermore, a conveyance unit 899 that guides the recording sheet sent from the automatic feeding unit 897 to a predetermined recording position and guides the recording sheet from the recording position to the discharge port 898, a recording unit 891 that performs recording on the recording sheet conveyed to the recording position, And a recovery unit 890 that performs recovery processing on the recording unit 891. The recording unit 891 includes a carriage 892 that houses the liquid ejection head of the present invention and is reciprocated on the rail.

  In such an ink jet recording apparatus, when the carriage 892 is moved on the rail by an electric signal sent from a computer and a driving voltage is applied to the electrodes sandwiching the piezoelectric material, the piezoelectric material is displaced. Due to the displacement of the piezoelectric material, the individual liquid chamber 102 is pressurized through the diaphragm 103 shown in FIG. 3B, and ink is ejected from the ejection port 105 to perform printing.

  In the liquid ejecting apparatus of the present invention, the liquid can be ejected uniformly at a high speed, and the apparatus can be miniaturized.

  Although the above example is illustrated as a printer, the liquid discharge apparatus of the present invention is used as a printing apparatus such as an inkjet recording apparatus such as a facsimile, a multi-function machine, and a copying machine, as well as an industrial liquid discharge apparatus and a drawing apparatus for an object. can do.

(Ultrasonic motor)
The ultrasonic motor according to the present invention includes at least a moving body that contacts a vibrating body provided with the piezoelectric element or the laminated piezoelectric element.

  FIG. 3 is a schematic view showing an embodiment of the configuration of the ultrasonic motor of the present invention. An ultrasonic motor in which the piezoelectric element of the present invention is a single plate is shown in FIG. The ultrasonic motor includes a vibrator 201, a rotor 202 that is in contact with a sliding surface of the vibrator 201 with a pressure spring (not shown), and an output shaft 203 that is provided integrally with the rotor 202. The vibrator 201 is composed of a metal elastic ring 2011, a piezoelectric element 2012 of the present invention, and an organic adhesive 2013 (epoxy, cyanoacrylate, etc.) that bonds the piezoelectric element 2012 to the elastic ring 2011. The piezoelectric element 2012 of the present invention is composed of a piezoelectric material sandwiched between a first electrode and a second electrode (not shown).

  When a two-phase AC voltage having a phase difference of π / 2 is applied to the piezoelectric element of the present invention, a bending traveling wave is generated in the vibrator 201 and each point on the sliding surface of the vibrator 201 performs an elliptical motion. When the rotor 202 is pressed against the sliding surface of the vibrator 201, the rotor 202 receives a frictional force from the vibrator 201 and rotates in a direction opposite to the bending traveling wave. A driven body (not shown) is joined to the output shaft 203 and is driven by the rotational force of the rotor 202. When a voltage is applied to the piezoelectric material, the piezoelectric material expands and contracts due to the piezoelectric lateral effect. When an elastic body such as metal is bonded to the piezoelectric element, the elastic body is bent by expansion and contraction of the piezoelectric material. The type of ultrasonic motor described here utilizes this principle.

  Next, an ultrasonic motor including a piezoelectric element having a laminated structure is illustrated in FIG. The vibrator 204 includes a laminated piezoelectric element 2042 sandwiched between cylindrical metal elastic bodies 2041. The laminated piezoelectric element 2042 is an element composed of a plurality of laminated piezoelectric materials (not shown), and has a first electrode and a second electrode on the laminated outer surface, and an internal electrode on the laminated inner surface. The metal elastic body 2041 is fastened by a bolt, and sandwiches and fixes the piezoelectric element 2042 to form the vibrator 204.

  By applying alternating voltages having different phases to the piezoelectric element 2042, the vibrator 204 excites two vibrations orthogonal to each other. These two vibrations are combined to form a circular vibration for driving the tip of the vibrator 204. A constricted circumferential groove is formed on the top of the vibrator 204 to increase the displacement of vibration for driving. The rotor 205 is brought into pressure contact with the vibrator 204 by a pressure spring 206 to obtain a frictional force for driving. The rotor 205 is rotatably supported by a bearing.

(Optical equipment)
Next, the optical apparatus of the present invention will be described. The optical apparatus according to the present invention is characterized in that the drive unit includes the ultrasonic motor.

  FIG. 8 is a main cross-sectional view of an interchangeable lens barrel of a single-lens reflex camera which is an example of a preferred embodiment of an imaging apparatus of the present invention. FIG. 9 is an exploded perspective view of an interchangeable lens barrel of a single-lens reflex camera which is an example of a preferred embodiment of the imaging apparatus of the present invention. A fixed cylinder 712, a rectilinear guide cylinder 713, and a front group lens barrel 714 are fixed to a detachable mount 711 with the camera. These are fixing members for the interchangeable lens barrel.

  The rectilinear guide tube 713 is formed with a rectilinear guide groove 713a for the focus lens 702 in the optical axis direction. Cam rollers 717a and 717b projecting radially outward are fixed to the rear group barrel 716 holding the focus lens 702 by shaft screws 718, and the cam rollers 717a are fitted in the linear guide grooves 713a.

  A cam ring 715 is rotatably fitted on the inner periphery of the rectilinear guide tube 713. The linear movement guide cylinder 713 and the cam ring 715 are restricted from moving relative to each other in the optical axis direction by the roller 719 fixed to the cam ring 715 being fitted in the circumferential groove 713b of the linear movement guide cylinder 713. The cam ring 715 is formed with a cam groove 715a for the focus lens 702, and the cam roller 717b is fitted into the cam groove 715a at the same time.

  A rotation transmission ring 720 that is held by a ball race 727 so as to be rotatable at a fixed position with respect to the fixed cylinder 712 is disposed on the outer peripheral side of the fixed cylinder 712. In the rotation transmission ring 720, a roller 722 is rotatably held by a shaft 720f extending radially from the rotation transmission ring 720, and the large diameter portion 722a of the roller 722 is in contact with the mount side end surface 724b of the manual focus ring 724. doing. The small diameter portion 722 b of the roller 722 is in contact with the joining member 729. Six rollers 722 are arranged on the outer periphery of the rotation transmission ring 720 at equal intervals, and each roller is configured in the above relationship.

  A low friction sheet (washer member) 733 is disposed on the inner diameter portion of the manual focus ring 724, and this low friction sheet is sandwiched between the mount side end surface 712 a of the fixed cylinder 712 and the front end surface 724 a of the manual focus ring 724. Yes. Further, the outer diameter surface of the low friction sheet 733 has a ring shape and is fitted with the inner diameter 724c of the manual focus ring 724, and the inner diameter 724c of the manual focus ring 724 is fitted with the outer diameter portion 712b of the fixed cylinder 712. Match. The low friction sheet 733 serves to reduce friction in the rotating ring mechanism in which the manual focus ring 724 rotates relative to the fixed cylinder 712 around the optical axis.

  The large diameter portion 722a of the roller 722 and the mount side end surface 724a of the manual focus ring are in contact with each other in a state where pressure is applied by the force of the wave washer 726 pressing the ultrasonic motor 725 forward of the lens. . Similarly, the wave washer 726 is in contact with the small diameter portion 722b of the roller 722 and the joining member 729 in a state where an appropriate pressure is applied by the force that presses the ultrasonic motor 725 forward of the lens. The wave washer 726 is restricted from moving in the mounting direction by a washer 732 that is bayonet-coupled to the fixed cylinder 712, and the spring force (biasing force) generated by the wave washer 726 is the ultrasonic motor 725 and further the roller. 722, the manual focus ring 724 also acts as a pressing force on the mount side end surface 712a of the fixed cylinder 712. That is, the manual focus ring 724 is incorporated in a state of being pressed against the mount side end surface 712 a of the fixed cylinder 712 via the low friction sheet 733.

  Therefore, when the ultrasonic motor 725 is rotationally driven with respect to the fixed cylinder 712 by a control unit (not shown), the joining member 729 is in frictional contact with the small diameter portion 722b of the roller 722, so that the roller 722 is centered on the shaft 720f. Rotate around. When the roller 722 rotates around the axis 720f, as a result, the rotation transmission ring 720 rotates around the optical axis (autofocus operation).

  When a rotational force around the optical axis is applied to the manual focus ring 724 from a manual operation input unit (not shown), the mount side end surface 724b of the manual focus ring 724 is in pressure contact with the large diameter portion 722a of the roller 722. Therefore, the roller 722 rotates around the shaft 720f due to the frictional force. When the large diameter portion 722a of the roller 722 rotates around the axis 720f, the rotation transmission ring 720 rotates around the optical axis. At this time, the ultrasonic motor 725 is prevented from rotating due to the frictional holding force of the rotor 725c and the stator 725b (manual focus operation).

  Two focus keys 728 are attached to the rotation transmission ring 720 at positions facing each other, and the focus key 728 is fitted into a notch 715 b provided at the tip of the cam ring 715. Accordingly, when an autofocus operation or a manual focus operation is performed and the rotation transmission ring 720 is rotated around the optical axis, the rotational force is transmitted to the cam ring 715 via the focus key 728. When the cam ring is rotated around the optical axis, the rear group barrel 716 whose rotation is restricted by the cam roller 717a and the straight guide groove 713a advances and retreats along the cam groove 715a of the cam ring 715 by the cam roller 717b. As a result, the focus lens 702 is driven and a focus operation is performed.

  Here, the interchangeable lens barrel of the single-lens reflex camera has been described as the optical apparatus of the present invention. However, regardless of the type of camera, such as a compact camera or an electronic still camera, a portable information terminal with a camera is also an optical lens of the present invention. Included in the equipment. The present invention can be applied to an optical apparatus having an ultrasonic motor in the drive unit.

(Electronics)
Next, the electronic apparatus of the present invention will be described. According to another aspect of the invention, there is provided an electronic apparatus including a piezoelectric acoustic component including the piezoelectric element or the multilayered piezoelectric element.

  The piezoelectric acoustic component includes a speaker, a buzzer, a microphone, and a surface acoustic wave (SAW) element.

  FIG. 10 is an overall perspective view of a digital camera main body 931 as an example of a preferred embodiment of the electronic apparatus of the present invention as seen from the front. An optical device 901, a microphone 914, a strobe light emitting unit 909, and an auxiliary light unit 916 are disposed on the front surface of the main body 931. Since the microphone 914 is incorporated in the main body, it is indicated by a broken line. A hole shape for picking up sound from the outside is provided in front of the microphone 914.

  On the upper surface of the main body 931, a power button 933, a speaker 912, a zoom lever 932, and a release button 908 for performing a focusing operation are arranged. The speaker 912 is incorporated in the main body 931 and is indicated by a broken line. A hole shape for transmitting sound to the outside is provided in front of the speaker 912.

  The piezoelectric acoustic component of the present invention is used for at least one of a microphone 914, a speaker 912, and a surface acoustic wave element.

  Here, the digital camera has been described as the electronic apparatus of the present invention. However, the electronic apparatus of the present invention is also applied to an electronic apparatus having various piezoelectric acoustic components such as an audio reproduction apparatus, an audio recording apparatus, a mobile phone, and an information terminal. be able to.

  As described above, the piezoelectric element and the laminated piezoelectric element of the present invention are suitably used for a liquid discharge head, a liquid discharge apparatus, an ultrasonic motor, an optical apparatus, and an electronic apparatus.

  By using the piezoelectric element and the laminated piezoelectric element of the present invention, a liquid discharge head having a nozzle density and discharge force equal to or higher than those when a lead-containing piezoelectric element is used can be provided.

  By using the liquid discharge head of the present invention, it is possible to provide a liquid discharge apparatus having a discharge force and discharge accuracy equal to or higher than those when a piezoelectric element containing lead is used.

  By using the piezoelectric element and laminated piezoelectric element of the present invention, it is possible to provide an ultrasonic motor having a driving force and durability equal to or higher than those when a piezoelectric element containing lead is used.

  By using the ultrasonic motor of the present invention, it is possible to provide an optical apparatus having durability and operation accuracy equivalent to or higher than those when a piezoelectric element containing lead is used.

  By using the piezoelectric acoustic component including the piezoelectric element or the laminated piezoelectric element of the present invention, it is possible to provide an electronic device having a sound output equivalent to or higher than that when using a piezoelectric element containing lead.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

  Piezoelectric ceramics used for the piezoelectric element of the present invention were produced.

(Production Example 1)
Barium titanate with an average particle size of 100 nm (manufactured by Sakai Chemical Industry: BT-01), calcium titanate with an average particle size of 300 nm (manufactured by Sakai Chemical Industry: CT-03), calcium zirconate with an average particle size of 300 nm (Sakai Chemical Industry) (Product: CZ-03) was weighed so that the molar ratio was 90.5 to 6.5 to 3.0. Further, 0.008 mol of barium oxalate was added in order to adjust a indicating the ratio between the molar amount of Ba and Ca at the A site and the molar amount of Ti and Zr at the B site. These weighed powders were mixed by dry mixing for 24 hours using a ball mill. In order to granulate the obtained mixed powder, manganese acetate (II) having an Mn weight of 0.08 parts by weight in terms of metal with respect to the mixed powder and a PVA binder having 3 parts by weight with respect to the mixed powder, Each was adhered to the surface of the mixed powder using a spray dryer.

  Next, the obtained granulated powder was filled into a metal mold, and a molding pressure of 200 MPa was applied using a press molding machine to produce a disk-shaped molded body. This molded body may be further pressurized using a cold isostatic pressing machine.

  The obtained molded body was put in an electric furnace, held at a maximum temperature of 1400 ° C. for 5 hours, and sintered in an air atmosphere for a total of 24 hours.

  And the average equivalent circular diameter and relative density of the crystal grains which comprise the obtained ceramic were evaluated. As a result, the average equivalent circle diameter was 6.2 μm, and the relative density was 94.9%. For observation of crystal grains, a polarizing microscope was mainly used. A scanning electron microscope (SEM) was used to specify the grain size of small crystal grains. The average equivalent circle diameter was calculated from the observation result. The relative density was evaluated using the Archimedes method.

  Next, the obtained ceramic was polished to a thickness of 0.5 mm, and the crystal structure was analyzed by X-ray diffraction. As a result, only the peak corresponding to the perovskite structure was observed.

Further, the composition was evaluated by fluorescent X-ray analysis. As a result, 0.08 part by weight of Mn is contained in the composition that can be represented by the chemical formula of (Ba _0.905 Ca _0.095 ) _1.002 (Ti _0.97 Zr _0.03 ) O _3. I understood. This means that the weighed composition matches the composition after sintering. Further, elements other than Ba, Ca, Ti, Zr and Mn were amounts below the detection limit, and were less than 0.1 parts by weight.

  Furthermore, when the crystal grains were observed again, there was no significant difference in the average equivalent circle diameter before and after polishing.

(Production Examples 2 to 52, 72 and 73)
Barium titanate with an average particle size of 100 nm (manufactured by Sakai Chemical Industry: BT-01), calcium titanate with an average particle size of 300 nm (manufactured by Sakai Chemical Industry: CT-03), calcium zirconate with an average particle size of 300 nm (Sakai Chemical Industry) Product: CZ-03) was weighed so as to have a molar ratio shown in Table 1. Further, barium oxalate was weighed so as to have the values shown in Table 1 in order to adjust a indicating the ratio between the molar amount of Ba and Ca at the A site and the molar amount of Ti and Zr at the B site. These weighed powders were mixed by dry mixing for 24 hours using a ball mill. In Production Example 48, Si was mixed as an auxiliary component in a total of 0.8 parts by weight in terms of oxide, and in Production Example 52, Si and Cu were mixed in a total of 1.0 parts by weight in terms of oxides. In order to granulate the obtained mixed powder, manganese (II) acetate is added to the surface so that the weight of Mn is the weight part of Table 1 in terms of metal, and the binder is 3 parts by weight with respect to the mixed powder. As PVA, each was attached using a spray dryer apparatus.

  Next, the obtained granulated powder was filled into a metal mold, and a molding pressure of 200 MPa was applied using a press molding machine to produce a disk-shaped molded body. This molded body may be further pressurized using a cold isostatic pressing machine.

  The obtained molded body was put in an electric furnace, held at a maximum temperature of 1350 ° C. to 1480 ° C. for 5 hours, and sintered in an air atmosphere for a total of 24 hours. The maximum temperature was increased as the amount of Ca increased.

  And the average equivalent circular diameter and relative density of the crystal grains which comprise the obtained ceramic were evaluated. The results are shown in Table 2. For observation of crystal grains, a polarizing microscope was mainly used. A scanning electron microscope (SEM) was used to specify the grain size of small crystal grains. The average equivalent circle diameter was calculated from the observation result. The relative density was evaluated using the Archimedes method.

  Next, the obtained ceramic was polished to a thickness of 0.5 mm, and the crystal structure was analyzed by X-ray diffraction. As a result, only the peak corresponding to the perovskite structure was observed in any sample.

  Further, the composition was evaluated by fluorescent X-ray analysis. The results are shown in Table 3. The subcomponents in the table are elements other than Ba, Ca, Ti, Zr and Mn, and 0 is below the detection limit and means less than 0.1 parts by weight. From this, it turned out that the composition weighed and the composition after sintering corresponded in any sample.

  Furthermore, the crystal grains were observed again, but there was no significant difference in the size and state of the crystal grains after sintering and after polishing.

(Comparative Production Examples 53 to 71)
In addition to the raw material powders similar to those of Production Examples 1 to 52, 72 and 73, barium zirconate having an average particle diameter of 300 nm (manufactured by Nippon Chemical Industry Co., Ltd.) was weighed so as to have the molar ratio shown in Table 1, and a ball mill And dry mixing for 24 hours. In Production Example 65, Y and V were mixed in a total of 2.1 parts by weight in terms of oxide. In order to granulate the obtained mixed powder, manganese (II) acetate was added to the surface so that the Mn weight was Mn weight so that the Mn weight would be the weight part of Table 1 in terms of metal, and 3 wt% with respect to the mixed powder. As a binder, PVA was adhered as a binder using a spray dryer apparatus.

  Using the resulting granulated powder, ceramics were produced under the same conditions as in Production Examples 2 to 52, 72 and 73. And the average equivalent circular diameter and relative density of the crystal grains which comprise the obtained ceramic were evaluated. The results are shown in Table 2. The evaluation of crystal grains and relative density was performed by the same method as in Production Examples 1 to 52, 72, and 73.

  Next, the obtained ceramic was polished to a thickness of 0.5 mm, and the crystal structure was analyzed by X-ray diffraction. As a result, only the peak corresponding to the perovskite structure was observed in any sample.

  Further, the composition was evaluated by fluorescent X-ray analysis. The results are shown in Table 3. From this, it turned out that the composition weighed and the composition after sintering corresponded in any sample.

  FIG. 4 shows the relationship between the x value and the y value of the piezoelectric ceramics of Production Examples 1 to 73. The range of a dotted line shows the range of x and y in General formula (1) showing a perovskite type metal oxide.

(Production of piezoelectric elements and evaluation of static characteristics)
(Examples 1 to 54)
Subsequently, the piezoelectric elements of Examples 1 to 54 were produced using the ceramics of Production Examples 1 to 52, 72, and 73.

  A gold electrode having a thickness of 400 nm was formed on both the front and back surfaces of the disk-shaped ceramic by a DC sputtering method. In addition, 30 nm of titanium was formed as an adhesion layer between the electrode and the ceramic. This electrode-attached ceramic was cut to produce a 10 mm × 2.5 mm × 0.5 mm strip-shaped piezoelectric element.

  The obtained piezoelectric element was subjected to polarization treatment by setting the surface of the hot plate to 60 ° C. to 100 ° C. and applying an electric field of 1 kV / mm on the hot plate for 30 minutes.

As the static characteristics of the piezoelectric element, the Curie temperature of the piezoelectric element in which polarization processing, the dielectric loss was evaluated piezoelectric constant d ₃₁ and the mechanical quality factor (Qm). The results are shown in Table 4. The mechanical quality factor is shown in Table 6 for explanation. The Curie temperature was obtained from the temperature at which the dielectric constant was maximized by measuring the dielectric constant while changing the measurement temperature using a minute alternating electric field having a frequency of 1 kHz. At the same time, dielectric loss was also measured. The piezoelectric constant d ₃₁ was determined by a resonance-antiresonance method, and the absolute value was described in the table.

  Table 4 also shows the ratio of the molar amounts of Ba and Ca to the molar amounts of Ti, Zr and Mn. In addition, “x” in the table means that the evaluation could not be performed.

In all the samples of the examples, the piezoelectric constant d ₃₁ was 55 [pC / N] or more, and the dielectric loss was 0.4% or less. Although not shown in the table, when the piezoelectric constant d ₃₃ was measured using a d ₃₃ meter based on the Berlin coat method, it was 110 [pC / N] or more in any sample.

  Here, Examples 10 and 11, Examples 12 and 13, Examples 19 and 20 in which the range of x is 0.125 ≦ x ≦ 0.175 and the range of y is 0.055 ≦ y ≦ 0.090, and Examples 21 and 22 are compared. In any combination, the x, y and Mn contents were the same, but Examples 11, 13, 19 and 21 having smaller values of a were superior in both piezoelectric constant and dielectric loss. Further, the ratio of the molar amounts of Ba and Ca to the molar amounts of Ti, Zr and Mn in Examples 11, 13, 19 and 21 was 0.996 or more and 0.999 or less.

  Next, Examples 28 and 29, Examples 30 and 31, Examples 38 and 39, in which the range of x is 0.155 ≦ x ≦ 0.300 and the range of y is 0.041 ≦ y ≦ 0.069, and Examples 40 and 41 are compared. In any combination, the x, y, and Mn contents were the same, but the examples 29, 31, 39, and 41 having smaller values of a were superior in both piezoelectric constant and dielectric loss. Further, the ratio of the molar amount of Ba and Ca to the molar amounts of Ti, Zr and Mn in Examples 29, 31, 39 and 41 was 0.993 or more and 0.998 or less.

  Moreover, in all the examples, even if the electrode was changed to baking of the silver paste, the characteristics were the same as those of the gold electrode.

(Comparative Examples 1 to 19)
Next, the piezoelectric elements of Comparative Examples 1 to 19 were fabricated using the ceramics of Production Examples 53 to 71.

  The device was fabricated and evaluated in the same manner as in Examples 1 to 54.

Since Comparative Examples 1 and 15 did not contain Mn, the dielectric loss was as high as 0.9% to 1.1%. Since Comparative Examples 3, 5, 7 and 9 did not contain Zr, the piezoelectric constant d ₃₁ was as low as 41 [pC / N] or less. Since Comparative Examples 4, 6, 8, and 10 contained Zr in a large amount of 15%, the Curie temperature was lowered to 60 ° C., and the temperature that could be used as a piezoelectric element was narrowed. Since Comparative Example 11 contains a large amount of Ca (32% (x = 0.32)), sintering did not proceed sufficiently and grain growth was insufficient, so that the piezoelectric constant was small and the dielectric loss was also large. . In Comparative Example 12, since the value of a was as small as 0.980 and abnormal grain growth in which the grain size grew larger than 30 μm was observed, the static characteristics other than the Curie temperature could not be evaluated. Since the average equivalent circle diameter of the crystal grains constituting the piezoelectric material used in the sample of Comparative Example 12 is considerably larger than the thickness of the formed strip-shaped piezoelectric element (0.5 mm = 500 μm), cleavage occurs in the piezoelectric material. The mechanical strength as a device was remarkably insufficient. Since Comparative Example 13 contained 2.1 parts by weight of Y and V as subcomponents, the piezoelectric constant d ₃₁ was as small as 36 [pC / N]. In Comparative Example 14, the value of a was as large as 1.030, the sintering did not proceed sufficiently, and the grain growth was insufficient. Therefore, the piezoelectric constant d ₃₁ was as small as 20 [pC / N], and the dielectric loss was also low. Increased to 0.9%. Since Comparative Example 16 contained a large amount of Mn at 0.45 parts by weight, the dielectric loss was small, but the piezoelectric constant was small. In Comparative Example 17, the average equivalent circle diameter of the particle diameter was smaller than 1 μm, the piezoelectric constant was small, and the dielectric loss was large. In Comparative Example 18, abnormal grain growth in which the average equivalent circle diameter of the grain size grows larger than 100 μm was observed, and therefore, the static characteristics other than the Curie temperature could not be evaluated for the same reason as in the sample of Comparative Example 12. Since the comparative example 19 had a relative density lower than 93%, the piezoelectric constant was small and the dielectric loss was also large. In addition, the static characteristic of the comparative example 2 was a result inferior to the sample of an Example. In Comparative Example 2, the value of x is 0.05 and the value of y is 0.95. The values of x and y are similar to those of the sample of the example, but the point of y> x is that of the example. Different from the sample.

(Evaluation of dynamic characteristics of piezoelectric elements)
In the following, as a dynamic characteristic of the piezoelectric element, the rate of change of the piezoelectric constant and the power consumption when voltage application was performed for 100 hours under the following conditions were measured.

The dynamic characteristics of Examples 8 to 14, Examples 18 to 22, Examples 25 and 26, and Comparative Examples 1, 4, and 19 were evaluated. As the dynamic characteristics of the piezoelectric element, the piezoelectric constant d ₃₁ after applying an alternating voltage of 100 kHz with a frequency of 110 kHz sufficiently separated from the resonance frequency to the strip-shaped element for 100 hours was evaluated, and the rate of change was calculated. Table 5 summarizes the rate of change in piezoelectric constant before and after application.

  While all the samples of the examples had a change rate of the piezoelectric characteristics of 5% or less, all of the samples of the comparative examples had a change of 10% or more. In Comparative Examples 1 and 19, it is considered that the dielectric loss is large and the electrical loss when a voltage is applied is large. In Comparative Example 4, since the Curie temperature was as low as 60 ° C., it is considered that depolarization occurred due to the effect of heat generation of the element due to application of voltage. That is, if the Curie temperature is 85 ° C. or higher and the dielectric loss is not 0.4% or lower, it can be said that there is not sufficient driving durability as an element.

  Furthermore, as shown below, power consumption was evaluated as dynamic characteristics of the piezoelectric element. Further, for Examples 17, 23, 27 to 32, 34, 38 to 42, 45, 46, 49 to 51 and Comparative Examples 2 and 15, the mechanical quality factor was evaluated using the resonance-antiresonance method. The results are shown in Table 6.

  Subsequently, an alternating voltage having a frequency near the resonance frequency (190 kHz to 230 kHz) was applied to the strip-shaped element, and the relationship between the vibration speed and the power consumption of the element was evaluated. The vibration speed was measured with a laser Doppler vibrometer, and the power consumption was measured with a wattmeter. Table 6 summarizes the power consumption values when the applied voltage and frequency are changed so that the vibration speed is 0.40 m / s.

  All of the samples of the example had a power consumption of 20 [mW] or less, whereas all the samples of the comparative examples had a power consumption of 50 [mW] or more. It is considered that the cause of this difference is that the mechanical quality factor was small as 190 or less in both Comparative Examples 2 and 15, and the value of the mechanical quality factor is important when driving in the vicinity of the resonance frequency. The value of is required.

(Production and evaluation of laminated piezoelectric elements)
(Example 55)
Barium titanate with an average particle size of 100 nm (manufactured by Sakai Chemical Industry: BT-01), calcium titanate with an average particle size of 300 nm (manufactured by Sakai Chemical Industry: CT-03), calcium zirconate with an average particle size of 300 nm (Sakai Chemical Industry) (Product: CZ-03) was weighed to a molar ratio of 84.0 to 10.1 to 5.9. Further, 0.028 mol of barium oxalate was added to adjust a indicating the ratio between the molar amount of Ba and Ca at the A site and the molar amount of Ti and Zr at the B site. To these weighed powders, manganese (IV) oxide having Mn weight of 0.40 parts by weight in terms of metal and PVB binder having 3 parts by weight were added and mixed. Using this mixed powder, a sheet was formed by the doctor blade method to obtain a green sheet having a thickness of 50 μm.

  A conductive paste for internal electrodes was printed on the green sheet. Ni paste was used as the conductive paste. Nine green sheets coated with the conductive paste were laminated, and the laminate was thermocompression bonded.

The thermocompression-bonded laminate was fired in a tubular furnace. Baking is performed in the air up to 300 ° C., and after debinding, the atmosphere is switched to a reducing atmosphere (H ₂ : N ₂ = 2: 98, oxygen concentration 2 × 10 ⁻⁶ Pa), and 1380 ° C. for 5 hours. Retained. In the temperature lowering process, the oxygen concentration was switched from 1000 ° C. or lower to 30 Pa and cooled to room temperature.

  The sintered body thus obtained was cut into a size of 10 mm × 2.5 mm and then the side surfaces were polished, and a pair of external electrodes (first electrode and second electrode) that alternately short-circuit the internal electrodes ) Was formed by Au sputtering to produce a laminated piezoelectric element as shown in FIG.

  When the internal electrode of the obtained laminated piezoelectric element was observed, Ni as an electrode material was alternately formed with the piezoelectric material layer. The obtained laminated piezoelectric element was subjected to polarization treatment by setting the surface of the hot plate to 60 ° C. to 100 ° C. and applying an electric field of 1 kV / mm on the hot plate for 30 minutes.

  When the piezoelectric characteristics of the obtained multilayer piezoelectric element were evaluated, it was possible to obtain satisfactory piezoelectric characteristics having sufficient insulation and equivalent to the piezoelectric element of Example 54.

(Comparative Example 20)
A laminated piezoelectric element was produced in the same process as in Example 55. However, the composition is the same as in Production Example 64.

  When the piezoelectric material layer of the obtained laminated piezoelectric element was observed, a plurality of crystal grains having a particle size of 20 to 30 μm were observed. Therefore, the strength of the element is very fragile, and the piezoelectric characteristics could not be evaluated.

(Device fabrication and evaluation)
(Liquid discharge head according to Example 9)
Using the same piezoelectric element as in Example 9, the liquid ejection head shown in FIG. 2 was produced. Ink ejection following the input electrical signal was confirmed.

(Liquid discharge apparatus using the liquid discharge head according to Example 9)
A liquid discharge apparatus shown in FIG. 6 was produced using the liquid discharge head shown in FIG. 2 using the same piezoelectric element as in Example 9. Ink ejection following the input electrical signal was confirmed on the recording medium.

(Ultrasonic motor according to Example 31)
Using the same piezoelectric element as in Example 31, the ultrasonic motor shown in FIG. The rotation behavior of the motor according to the application of the alternating voltage was confirmed.

(Lens barrel using ultrasonic motor according to Example 31)
The optical apparatus shown in FIG. 8 was produced using an ultrasonic motor using the same piezoelectric element as in Example 31. The autofocus operation according to the application of the alternating voltage was confirmed.

(Electronic device using the piezoelectric acoustic component according to Example 31)
Using the piezoelectric acoustic component using the same piezoelectric element as in Example 31, the electronic apparatus shown in FIG. 10 was produced. The speaker operation according to the application of the alternating voltage was confirmed.

(Liquid discharge head according to Example 55)
A liquid discharge head shown in FIG. 2 was produced using the same laminated piezoelectric element as in Example 55. Ink ejection following the input electrical signal was confirmed.

(Liquid Ejecting Device Using Liquid Ejecting Head According to Example 55)
A liquid discharge apparatus shown in FIG. 6 was produced using the liquid discharge head shown in FIG. 2 using the same laminated piezoelectric element as in Example 55. Ink ejection following the input electrical signal was confirmed on the recording medium.

(Ultrasonic motor according to Example 55)
Using the multilayer piezoelectric element of Example 55, an ultrasonic motor shown in FIG. The rotation of the motor according to the application of the AC voltage was confirmed.

(Lens barrel using ultrasonic motor according to Example 55)
The optical apparatus shown in FIG. 8 was produced using an ultrasonic motor using the same piezoelectric element as in Example 55. The autofocus operation according to the application of the alternating voltage was confirmed.

(Electronic device using the piezoelectric acoustic component according to Example 55)
Using the piezoelectric acoustic component using the same piezoelectric element as in Example 55, the electronic apparatus shown in FIG. The speaker operation according to the application of the alternating voltage was confirmed.

  The piezoelectric element of the present invention is stably driven in a wide practical temperature range, has no load on the environment, and there is no problem even in a device that uses a lot of piezoelectric materials such as a piezoelectric element such as a liquid discharge head and an ultrasonic motor. Can be used.

DESCRIPTION OF SYMBOLS 1 1st electrode 2 Piezoelectric material 3 2nd electrode 101 Piezoelectric element 102 Individual liquid chamber 103 Diaphragm 104 Liquid chamber partition 105 Discharge port 106 Communication hole 107 Common liquid chamber,
108 Buffer layer 1011 First electrode 1012 Piezoelectric material 1013 Second electrode,
201 vibrator 202 rotor 203 output shaft 204 vibrator 205 rotor,
206 Spring 2011 Elastic ring 2012 Piezoelectric element 2013 Organic adhesive,
2041 Metal elastic body 2042 Multilayer piezoelectric element 51 First electrode 53 Second electrode 54 Piezoelectric material layer 55 Internal electrode 501 First electrode 503 Second electrode 504 Piezoelectric material layer 505 Internal electrode 506a External electrode 506b External electrode 701 Previous Group lens 702 Rear group lens (focus lens)
711 Detachable mount 712 Fixed cylinder 713 Straight guide cylinder 714 Front group barrel 715 Cam ring 716 Rear group barrel,
717 Cam roller 718 Shaft screw 719 Roller 720 Rotation transmission ring 722 Roller 724 Manual focus ring 725 Ultrasonic motor 726 Wave washer 727 Ball race 728 Focus key 729 Joining member 732 Washer 733 Low friction sheet 881 Liquid discharge device 882 Exterior 883 Exterior 887 Exterior 890 Recovery unit 891 Recording unit 892 Carriage 896 Device main body 897 Automatic feeding unit 898 Discharge port 899 Conveying unit 901 Optical device 908 Release button 909 Strobe light emitting unit 912 Speaker 914 Microphone 916 Auxiliary light unit 931 Main body 932 Zoom lever button

Claims (11)

A piezoelectric element having at least a first electrode, a piezoelectric material, and a second electrode, wherein the piezoelectric material has the following general formula (1):
Formula _{(1) (Ba 1-x} Ca x) a (Ti 1-y Zr y) O 3 (1.00 ≦ a ≦ 1.01,0.02 ≦ x ≦ 0.30,0.020 ≦ y ≦ 0.095 and y ≦ x)
And the metal oxide contains Mn, and the Mn content is 0.02 parts by weight or more in terms of metal with respect to 100 parts by weight of the metal oxide. A piezoelectric element characterized by being 0.40 parts by weight or less.   2. The piezoelectric element according to claim 1, wherein an average equivalent circle diameter of crystal grains constituting the piezoelectric material is 1 μm or more and 10 μm or less.   The piezoelectric element according to claim 1, wherein a relative density of the piezoelectric material is 93% or more and 100% or less.   X and y in the main component of the piezoelectric material are in the ranges of 0.125 ≦ x ≦ 0.175 and 0.055 ≦ y ≦ 0.09, respectively, and the Mn content is 100 parts by weight of the metal oxide. The piezoelectric element according to any one of claims 1 to 3, wherein the piezoelectric element is 0.02 parts by weight or more and 0.10 parts by weight or less in terms of metal.   X and y in the main component of the piezoelectric material are in the ranges of 0.155 ≦ x ≦ 0.300 and 0.041 ≦ y ≦ 0.069, respectively, and the Mn content is 100 parts by weight of the metal oxide. 4. The piezoelectric element according to claim 1, wherein the piezoelectric element is 0.12 part by weight or more and 0.40 part by weight or less in terms of metal. A laminated piezoelectric element in which piezoelectric material layers and electrodes including internal electrodes are alternately laminated, wherein the piezoelectric material layer has the following general formula (1):
Formula _{(1) (Ba 1-x} Ca x) a (Ti 1-y Zr y) O 3 (1.00 ≦ a ≦ 1.01,0.02 ≦ x ≦ 0.30,0.020 ≦ y ≦ 0.095 and y ≦ x)
And the metal oxide contains Mn, and the Mn content is 0.02 parts by weight or more in terms of metal with respect to 100 parts by weight of the metal oxide. A laminated piezoelectric element comprising a piezoelectric material of 0.40 part by weight or less.   A liquid discharge head comprising: a liquid chamber provided with a vibrating portion in which the piezoelectric element according to claim 1 or the multilayered piezoelectric element according to claim 6 is disposed; and a discharge port communicating with the liquid chamber.   A liquid ejection apparatus comprising: a recording medium conveyance unit; and the liquid ejection head according to claim 7.   An ultrasonic motor comprising: a vibrating body provided with the piezoelectric element according to claim 1 or the laminated piezoelectric element according to claim 6; and a moving body that contacts the vibrating body.   An optical apparatus comprising the ultrasonic motor according to claim 9 in a drive unit.   An electronic apparatus provided with a piezoelectric acoustic component comprising the piezoelectric element according to claim 1 or the multilayered piezoelectric element according to claim 6.

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