JP2011211140A - Method of manufacturing piezoelectric material, piezoelectric element, liquid ejecting head, and liquid ejecting apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a piezoelectric material in which a piezoelectric layer is manufactured which has superior durability and a small load on an environment, a piezoelectric element, to provide a liquid ejecting head, and to provide a liquid ejecting apparatus.SOLUTION: The method of manufacturing the piezoelectric material includes the processes of: forming a composite oxide containing sodium, potassium, lithium, niobium and tantalum by mixing and calcining a powder of metal oxides or metal carbonates of sodium, potassium, lithium, niobium and tantalum; and forming a piezoelectric material composed of a solid solution containing a perovskite oxide containing sodium, potassium, lithium, niobium and tantalum, and bismuth manganate by adding a metal oxide or metal carbonate containing manganese and bismuth to the composite oxide containing sodium, potassium, lithium, niobium and tantalum, and mixing and then calcining them.

Description

  The present invention relates to a method for manufacturing a piezoelectric material, a piezoelectric element, a liquid ejecting head, and a liquid ejecting apparatus.

  As a typical example of a liquid ejecting head, for example, a part of a pressure generation chamber communicating with a nozzle opening for ejecting ink droplets is configured by a vibration plate, and the vibration plate is deformed by a piezoelectric element so that the ink in the pressure generation chamber is There is an ink jet recording head that pressurizes and ejects ink droplets from nozzle openings. As a piezoelectric element used in an ink jet recording head, there is a piezoelectric material having an electromechanical conversion function, for example, a piezoelectric material layer composed of piezoelectric ceramics sandwiched between two electrodes. Such a piezoelectric element is mounted on a liquid ejecting head as an actuator device in a flexural vibration mode.

A liquid jet head using lead zirconate titanate (PZT) having high displacement characteristics is known as a piezoelectric ceramic (see Patent Document 1). However, from the viewpoint of environmental pollution, there is a demand for piezoelectric ceramics that suppress the content of lead, which is a harmful substance. Here, conventionally, as a piezoelectric ceramic not containing lead, for example, a so-called KNN-based material having potassium, sodium and niobium such as (K, Na) NbO ₃ (potassium sodium niobate) having a perovskite structure represented by ABO ₃ Is known (see, for example, Patent Document 2).

JP 2001-223404 A JP 2008-50206 A

  However, KNN-based materials have a problem that dielectric loss (tan δ) is relatively high and durability is insufficient. Such a problem is not limited to a piezoelectric material used for a liquid ejecting head typified by an ink jet recording head, and similarly exists in a piezoelectric material used for a piezoelectric element or the like mounted in another apparatus.

  In view of such circumstances, the present invention provides a piezoelectric material manufacturing method, a piezoelectric element, a liquid ejecting head, and a liquid ejecting apparatus capable of manufacturing a piezoelectric layer that is excellent in durability and has a low environmental load. With the goal.

  An aspect of the present invention that solves the above problems includes sodium, potassium, lithium, niobium and tantalum by mixing and pre-baking powders of metal oxide or metal carbonate of sodium, potassium, lithium, niobium and tantalum. Forming a composite oxide, and adding and mixing a metal oxide or metal carbonate containing manganese and bismuth to the composite oxide containing sodium, potassium, lithium, niobium and tantalum, followed by sintering. Thus, there is provided a method for producing a piezoelectric material, comprising a step of forming a piezoelectric material comprising a solid solution containing a perovskite oxide containing sodium, potassium, lithium, niobium and tantalum and bismuth manganate.

  In such an embodiment, a piezoelectric material having a small tan δ and excellent durability and a small environmental load can be easily manufactured. In addition, the piezoelectric material has excellent water resistance.

  Further, when a metal oxide or metal carbonate containing manganese and bismuth is added to the composite oxide containing sodium, potassium, lithium, niobium and tantalum, a metal oxide or metal further containing zirconium and calcium It is preferable to form a piezoelectric material made of a solid solution containing perovskite oxide containing sodium, potassium, lithium, niobium and tantalum, bismuth manganate and calcium zirconate by adding carbonate. According to this, it is possible to manufacture a piezoelectric material having excellent durability, high dielectric constant, and excellent temperature stability.

  In addition, a piezoelectric element of the present invention includes a piezoelectric layer made of the above piezoelectric material and an electrode for applying a voltage to the piezoelectric layer. According to this, a piezoelectric element having a piezoelectric material having excellent durability can be provided.

  According to another aspect of the invention, there is provided a liquid ejecting head including the piezoelectric element and a pressure generating chamber communicated with a nozzle opening for ejecting droplets. According to this, it becomes a liquid jet head excellent in durability.

  According to another aspect of the invention, there is provided a liquid ejecting apparatus including the liquid ejecting head. In this aspect, the liquid ejecting apparatus is excellent in durability.

FIG. 3 is an exploded perspective view of the recording head according to the first embodiment. FIG. 3 is a cross-sectional view of the recording head according to the first embodiment. 3 is a flowchart illustrating an example of a method for manufacturing a piezoelectric material according to the first embodiment. It is a figure which shows the X-ray-diffraction pattern of the sample 3 and the sample 7. Is a diagram showing the temperature change in the _{d 33} of the sample 15. 3 is a SEM observation photograph of Sample 3. 4 is a SEM observation photograph of Sample 7. 3 is a SEM observation photograph of Sample 15. It is a perspective view of the liquid ejecting apparatus according to another embodiment.

(Embodiment 1)
FIG. 1 is an exploded perspective view showing a schematic configuration of an ink jet recording head which is an example of a liquid jet head according to Embodiment 1 of the present invention, and FIG. 2 is a cross-sectional view of the ink jet recording head.

  As illustrated, the ink jet recording head 10 includes an actuator unit 20, one flow path unit 30 to which the actuator unit 20 is fixed, and a wiring board 50 connected to the actuator unit 20.

  The actuator unit 20 is an actuator device including a piezoelectric element 40, and includes a flow path forming substrate 22 in which a pressure generation chamber 21 is formed, a vibration plate 23 provided on one surface side of the flow path forming substrate 22, And a pressure generation chamber bottom plate 24 provided on the other surface side of the path forming substrate 22.

The flow path forming substrate 22 is made of, for example, a ceramic plate such as alumina (Al ₂ O ₃ ) or zirconia (ZrO ₂ ) having a thickness of about 150 μm. In this embodiment, the plurality of pressure generating chambers 21 have their widths. Two rows arranged in parallel along the direction are formed. A vibration plate 23 made of, for example, a zirconia thin plate having a thickness of 10 μm is fixed to one surface of the flow path forming substrate 22, and one surface of the pressure generating chamber 21 is sealed by the vibration plate 23.

  The pressure generation chamber bottom plate 24 is fixed to the other surface side of the flow path forming substrate 22 to seal the other surface of the pressure generation chamber 21, and is provided in the vicinity of one end of the pressure generation chamber 21 in the longitudinal direction. A supply communication hole 25 for communicating the generation chamber 21 with a reservoir described later, and a nozzle communication hole 26 provided near the other end in the longitudinal direction of the pressure generation chamber 21 and communicating with a nozzle opening 34 described later.

  And the piezoelectric element 40 is provided in each area | region facing each pressure generation chamber 21 on the diaphragm 23, for example, in this embodiment, since the row | line | column of the pressure generation chamber 21 is provided in two rows, it is piezoelectric Two rows of elements 40 are also provided.

  Here, each piezoelectric element 40 includes a first electrode (electrode layer) 43 provided on the vibration plate 23, and a piezoelectric layer (piezoelectric ceramic layer) 44 provided independently for each pressure generating chamber 21. And a second electrode (electrode layer) 45 provided on each piezoelectric layer 44. In the present embodiment, the piezoelectric layer 44 is generally a piezoelectric material having a large film thickness (for example, 10 to 1000 μm). For example, powder of metal oxide or metal carbonate is physically mixed and pulverized. A so-called bulk piezoelectric layer 44 produced by a solid phase method such as firing after forming. The first electrode 43 is provided across the piezoelectric layers 44 arranged side by side and serves as a common electrode for each piezoelectric element 40 and functions as a part of the diaphragm. Of course, the first electrode 43 may be provided for each piezoelectric layer 44.

  The flow path forming substrate 22, the vibration plate 23, and the pressure generation chamber bottom plate 24, which are each layer of the actuator unit 20, are formed of a clay-like ceramic material, a so-called green sheet, to a predetermined thickness, for example, a pressure generation chamber. After drilling 21 and the like, they are laminated and fired to integrate them without requiring an adhesive. Thereafter, the piezoelectric element 40 is formed on the vibration plate 23.

In this embodiment, the piezoelectric layer 44 formed on the first electrode 43 is manufactured by a predetermined manufacturing method to be described later. Sodium (Na), potassium (K), lithium (Li ), A piezoelectric material made of a solid solution containing a perovskite oxide containing niobium (Nb) and tantalum (Ta) and bismuth manganate (for example, BiMnO ₃ ). Note that the perovskite oxide is a compound having a perovskite structure. In the perovskite structure, that is, the A site of the ABO ₃ type structure, oxygen is 12-coordinated, and the B site is 6-coordinated of oxygen to form an octahedron. In addition, Na, K, Li and Ca contained if necessary in the A site are located, and Nb, Ta and Zr contained if necessary in the B site are located. The piezoelectric material constituting the piezoelectric layer 44 contains bismuth manganate. In this bismuth manganate, Bi is located at the A site of the perovskite oxide and Mn is located at the B site. Thus, the A site may be Na, K, Li, Bi, or Ca contained if necessary, and the B site may be Nb, Ta, Mn, or Zr that is optionally contained Zr. .

  In this way, a piezoelectric material made of a solid solution containing a perovskite oxide containing Na, K, Li, Nb, and Ta and bismuth manganate is used as the piezoelectric layer 44, as shown in the examples described later. , Tan δ is small (for example, tan δ is 2.0 or less), and the piezoelectric element 40 having the piezoelectric layer 44 with excellent durability is obtained. Moreover, it is excellent also in water resistance. Furthermore, since the content of lead and antimony can be lowered or not substantially contained, adverse effects on the environment can be reduced.

The piezoelectric layer 44 preferably further contains calcium zirconate (for example, CaZrO ₃ ). Further, by containing calcium zirconate, the dielectric constant is increased and the temperature stability is excellent.

  The molar ratio of each element of the perovskite oxide containing Na, K, Li, Nb and Ta is not particularly limited. For example, K is 42 mol% or more with respect to the total molar amount of Na, K, and Li. 48 mol% or less, Na may be 47.5 mol% or more and 52 mol% or less, and Nb may be 80 mol% or more and 85 mol% or less with respect to the total molar amount of Nb and Ta.

Moreover, the ratio of the perovskite type oxide containing Na, K, Li, Nb and Ta, bismuth manganate, and calcium zirconate to be contained as required is not particularly limited, and includes Na, K, Li, Nb and Ta. A small amount of bismuth manganate or calcium zirconate may be added to the perovskite oxide. For example, bismuth manganate may be 0.25 mol% or more and 1 mol% or less with respect to a perovskite oxide containing Na, K, Li, Nb, and Ta. The calcium zirconate may be 1 mol% or more and 4 mol% or less with respect to the perovskite oxide containing Na, K, Li, Nb, and Ta. The piezoelectric material having such a composition ratio is represented by the following formula (1), for example. Of course, when CaZrO ₃ is not contained, n is zero in the following formula (1).
(K _x , Na _y , Li _1-xy ) (Nb _z , Ta _1-z ) O ₃ -m [BiMnO ₃ ] -n [CaZrO ₃ ] (1)
(0.420 ≦ x ≦ 0.480, 0.475 ≦ y ≦ 0.520, 0.80 ≦ z ≦ 0.85, 0.0025 ≦ m ≦ 0.01, 0.01 ≦ n ≦ 0.04)

  Here, such a piezoelectric element 40 contains sodium, potassium, lithium, niobium and tantalum by mixing and pre-baking powders of metal oxide or metal carbonate of sodium, potassium, lithium, niobium and tantalum. Forming a composite oxide, and adding and mixing a metal oxide or metal carbonate containing manganese and bismuth to a composite oxide containing sodium, potassium, lithium, niobium and tantalum, followed by sintering Can be manufactured. An example of the manufacturing method will be described with reference to FIG. FIG. 3 is a flowchart showing a method for manufacturing a piezoelectric element.

As shown in FIG. 3, first, as the main starting material for obtaining the piezoelectric layer 44, for example, Na ₂ CO ₃ , K ₂ CO ₃ , Li ₂ CO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ These powders are prepared and weighed to a predetermined ratio in a dried state, and then, for example, pure water, ethanol, etc. are added and mixed and pulverized with a ball mill to obtain a raw material mixture. Furthermore, after this raw material mixture is dried, a composite oxide powder containing K, Na, Li, Nb and Ta is formed by synthesis (preliminary firing) at 700 to 1000 ° C.

Next, Bi ₂ O ₃ powder, MnO ₂ powder and, if necessary, CaZrO ₃ powder are added to this powder and mixed with a ball mill or the like. After the mixture is dried, a predetermined amount of binder is added thereto. And granulated by a die press or the like at a predetermined pressure (for example, 1000 to 2000 kg / cm ² ). And what is called bulk piezoelectric material represented by the said Formula (1) is formed by degreasing what was shape | molded at the temperature of about 600-700 degreeC, and sintering at the temperature of about 1000-1250 degreeC.

  Thereafter, the piezoelectric material is polished, the first electrode 43 and the second electrode 45 are formed on both surfaces thereof, and further, the above-described piezoelectric element 40 is formed by performing poling and various measurements. The formed piezoelectric element 40 is mounted on the flow path forming substrate 22 to form the ink jet recording head of this embodiment. That is, by forming the piezoelectric element 40 by such a method, it is possible to realize an ink jet recording head that is environmentally friendly and excellent in durability as described above.

In particular, in the present embodiment, Bi ₂ O ₃ , MnO _2, and CaZrO ₃ are added to powders formed from Na ₂ CO ₃ , K ₂ CO ₃ , Li ₂ CO ₃ , Nb ₂ O ₅ , and Ta ₂ O ₅ powders. Powder is added. That is, Bi ₂ O ₃ , MnO ₂ and CaZrO ₃ powders are added during the production of the piezoelectric material. Thereby, the piezoelectric layer 44 can be made denser and excellent in piezoelectric characteristics. Here, since KNN-based materials such as (K _x , Na _y , Li _1-xy ) (Nb _z , Ta _1-z ) O ₃ have a high crystal grain growth rate, the piezoelectric material produced is a grain boundary. The density of the pores on the upper side becomes relatively low due to entering the crystal grains. In the present embodiment, Bi ₂ O is used during the production, that is, after calcining a KNN-based material such as (K _x , Na _y , Li _1-xy ) (Nb _z , Ta _1-z ) O _3. By simultaneously adding ₃ and MnO ₂ or the like, it is possible to produce a dense piezoelectric layer 44 having excellent piezoelectric characteristics.

  On the other hand, the flow path unit 30 includes an ink supply port forming substrate 31 joined to the pressure generating chamber bottom plate 24 of the actuator unit 20 and a reservoir forming substrate on which a reservoir 32 serving as a common ink chamber of the plurality of pressure generating chambers 21 is formed. 33 and a nozzle plate 35 in which nozzle openings 34 are formed.

  The ink supply port forming substrate 31 is made of a zirconia thin plate having a thickness of 150 μm. The nozzle communication hole 36 connecting the nozzle opening 34 and the pressure generation chamber 21, and the reservoir 32 and the pressure generation chamber 21 together with the supply communication hole 25 described above. The ink supply port 37 is connected to each other, and an ink introduction port 38 that communicates with each reservoir 32 and supplies ink from an external ink tank is provided.

  The reservoir forming substrate 33 receives a supply of ink from an external ink tank (not shown) on a plate material having corrosion resistance such as 150 μm stainless steel, which is suitable for forming an ink flow path. And a nozzle communication hole 39 for communicating the pressure generating chamber 21 and the nozzle opening 34 with each other.

  The nozzle plate 35 is formed, for example, by forming nozzle openings 34 in a thin plate made of stainless steel at the same arrangement pitch as the pressure generating chambers 21. For example, in the present embodiment, since the flow path unit 30 is provided with two rows of the pressure generating chambers 21, the nozzle plate 35 is also formed with two rows of nozzle openings 34. The nozzle plate 35 is bonded to the opposite surface of the reservoir forming substrate 33 to the flow path forming substrate 22 to seal one surface of the reservoir 32.

  Such a flow path unit 30 is formed by fixing the ink supply port forming substrate 31, the reservoir forming substrate 33, and the nozzle plate 35 with an adhesive, a heat welding film, or the like. In the present embodiment, the reservoir forming substrate 33 and the nozzle plate 35 are formed of stainless steel. However, for example, the reservoir forming substrate 33 and the nozzle plate 35 are formed of ceramics, and the flow path unit 30 is integrally formed in the same manner as the actuator unit 20. You can also.

  And such a flow-path unit 30 and the actuator unit 20 are joined and fixed through the adhesive agent and the heat welding film.

  In addition, as shown in FIG. 2, a terminal portion 46 that conducts to the piezoelectric element 40 is provided in a region opposite to the peripheral wall of the pressure generating chamber 21 at one end in the longitudinal direction of each piezoelectric element 40. The terminal part 46 is provided for each piezoelectric element 40 and is electrically connected to the terminal part 46 that is electrically connected to the second electrode 45 of the piezoelectric element 40 and the first electrode 43 that is drawn to both ends of the piezoelectric element in the parallel direction. (Not shown) are juxtaposed in the direction in which the piezoelectric elements 40 are juxtaposed. In the present embodiment, two rows of the terminal portions 46 arranged in parallel between the rows of the piezoelectric elements 40 arranged in parallel are provided.

  Such a terminal portion 46 is formed such that the height from the flow path forming substrate 22 (vibrating plate 23), that is, the upper end surface is higher than the height of the piezoelectric element 40 from the flow path forming substrate 22 (vibrating plate 23). ing. This is to prevent the displacement of the piezoelectric element 40 from being lowered by the contact of the wiring board 50 with the piezoelectric element 40 when the terminal portion 46 and the wiring layer 51 of the wiring board 50 are connected. In the present embodiment, the height of the terminal portion 46 from the flow path forming substrate 22 (the vibration plate 23) is 20 μm.

  In addition, such a terminal part 46 can be formed by screen printing using metal materials with high electroconductivity, such as silver (Ag), for example.

  A wiring layer 51 provided on the wiring board 50 is electrically connected to a terminal portion that is electrically connected to each of the second electrode 45 and the first electrode 43 of the piezoelectric element 40. A drive signal from a drive circuit (not shown) is supplied to each piezoelectric element 40. The drive circuit is not particularly illustrated, but may be mounted on the wiring board 50 or may be mounted on other than the wiring board 50.

  The wiring substrate 50 is formed of, for example, a flexible printing circuit (FPC), a tape carrier package (TCP), or the like, which is provided across the two rows of piezoelectric elements 40. Specifically, the wiring substrate 50 is formed by forming a wiring layer 51 having a predetermined pattern on the surface of a base film 52 made of polyimide or the like by performing tin plating or the like using a copper thin base as a base, and is connected to the terminal portion 46 of the wiring layer 51. A region other than the edge portion is covered with an insulating material 53 such as a resist.

  Further, the wiring substrate 50 is provided with through holes 54 in regions facing each other between the rows of the piezoelectric elements 40 arranged side by side. The wiring layer 51 has a terminal portion at the end on the through hole 54 side. 46 is connected. The through holes 54 of the wiring substrate 50 are formed on the surface of the base film 52 where the through holes 54 are not provided, on the wiring layer 51 connected to the piezoelectric elements 40 in one row and on the piezoelectric elements 40 in the other row. After the wiring layers 51 to be connected are formed so as to be continuous, the conductive wiring layers 51 connected to the two rows of piezoelectric elements 40 are provided on the base film 52 so as to be cut.

  The wiring layer 51 of the wiring substrate 50 and the terminal portion that is electrically connected to the piezoelectric element 40 are electrically and mechanically connected via an adhesive layer 55 made of an anisotropic conductive material.

  In the ink jet recording head 10 having such a configuration, ink is taken into the reservoir 32 from the ink cartridge (reserving means) through the ink introduction port 38, and ink is passed through the liquid flow path from the reservoir 32 to the nozzle opening 34. Then, a recording signal from a drive circuit (not shown) is supplied to the piezoelectric element 40 via the wiring substrate 50, whereby a voltage is applied to each piezoelectric element 40 corresponding to each pressure generating chamber 21 to thereby apply the piezoelectric element 40. At the same time, the diaphragm 23 is bent and deformed to increase the pressure in each pressure generating chamber 21 and eject ink droplets from each nozzle opening 34.

  Characteristics such as durability of the piezoelectric layer 44 obtained by the manufacturing method described above will be described in more detail in the following experimental examples.

(Sample 1)
After weighing Na ₂ CO ₃ , K ₂ CO ₃ , Li ₂ CO ₃ , and Nb ₂ O ₅ powders dried at 120 ° C., ethanol and the like are added and mixed and pulverized with a ball mill, did. Furthermore, after drying this raw material mixture, the composite oxide powder containing K, Na, Li and Nb was formed by calcining at 800 ° C.

Next, 7% by weight of a polyvinyl alcohol (PVA) aqueous solution was added to the powder and granulated, and molded at 1500 kg / cm ² by a mold press. And what was shape | molded was sintered at 1060 degreeC for 2 hours, and the piezoelectric material layer represented by the said Formula (1) of x, y, z, m, and n shown in the sample 1 of Table 1 was produced.

  The surface of the piezoelectric layer thus formed is polished, a silver paste is applied to the polished surface by printing, and baked at 700 ° C. for 20 minutes, so that a pair of electrode layers are formed on both sides in the thickness direction of the piezoelectric layer. A piezoelectric element was formed by forming (first electrode 43 and second electrode 45).

  Then, in the state in which the formed piezoelectric element is immersed in silicon oil at 130 to 160 ° C., a piezoelectric element is subjected to polarization treatment (polling) by applying an electric field of 3 to 5 kV / mm for 5 to 15 minutes. A piezoelectric element was obtained.

(Samples 2-3)
A powder of complex oxide containing K, Na, Li, Nb and Ta is obtained by further mixing Ta ₂ O ₅ powder with Na ₂ CO ₃ , K ₂ CO ₃ , Li ₂ CO ₃ , Nb ₂ O ₅ powder. Except that it was formed and the sintering temperature was 1120 ° C. for 2 hours, the same operations as in Sample 1 were performed, and the above x, y, z, m, and n shown in Sample 2 and Sample 3 in Table 1 A piezoelectric layer represented by the formula (1) was produced, and piezoelectric elements of Sample 2 and Sample 3 were obtained.

(Samples 4 to 10)
Na ₂ CO ₃ , K ₂ CO ₃ , Li ₂ CO ₃ , Nb ₂ O _5, and Ta ₂ O ₅ powders are weighed in a state of being dried at 120 ° C., then added with ethanol or the like and mixed and pulverized by a ball mill. Thus, a raw material mixture was obtained. Furthermore, after this raw material mixture was dried, a composite oxide powder containing K, Na, Li, Nb and Ta was formed by calcination at 850 ° C.

Next, Bi ₂ O ₃ powder and MnO ₂ powder were added to this powder, mixed with a ball mill, and the mixture was dried. Then, 7 wt% aqueous solution of polyvinyl alcohol (PVA) was added to the powder in the same manner as in Sample 1. It was added and granulated, and molded at 1500 kg / cm ² by a mold press. And what was shape | molded was sintered at 1160 degreeC for 2 hours, and the piezoelectric material layer represented by the said Formula (1) of x, y, z, m, and n shown to the samples 4-10 of Table 1 was produced.

  The surface of the piezoelectric layer thus formed is polished, a silver paste is applied to the polished surface by printing, and baked at 700 ° C. for 20 minutes, so that a pair of electrode layers are formed on both sides in the thickness direction of the piezoelectric layer. A piezoelectric element was formed by forming (first electrode 43 and second electrode 45).

  Then, in the state where the formed piezoelectric element is immersed in silicon oil at 25 ° C., an electric field of 3 to 4 kV / mm is applied for 5 to 15 minutes to polarize the piezoelectric element (polling), and samples 4 to 10 A piezoelectric element was obtained.

(Samples 11-16)
When Bi ₂ O ₃ powder and MnO ₂ powder were added, CaZrO ₃ powder was further added, and the sintering temperature was 1130 ° C. for Sample 11 and Sample 14 for 2 hours, and Sample 12 and Sample 13 were 1160 ° C. 2 hours, except for Sample 15 and Sample 16 at 1150 ° C. for 2 hours, the same operations as in Samples 4 to 10 were performed, and x, y, z, m, and n shown in Samples 11 to 16 in Table 1 A piezoelectric layer represented by the above formula (1) was produced, and piezoelectric elements of Samples 11 to 16 were obtained.

(Samples 17-18)
A composite containing K, Na, Li, Nb, Ta and Sb by further mixing Sb ₂ O ₅ with powder of Na ₂ CO ₃ , K ₂ CO ₃ , Li ₂ CO ₃ , Nb ₂ O ₅ and Ta ₂ O ₅ Except that the oxide powder was formed, the same operation as in Samples 4 to 10 was performed, and x, y, z, and m shown in Sample 17 and Sample 18 in Table 1 and w = 0.03 A piezoelectric layer represented by (2) was prepared, and piezoelectric elements of Samples 17 to 18 were obtained. Note that the formula in _{(2), (K x,} Na y, Li 1-x-y) (Nb z, Sb w Ta 1-z-w) O 3: ratio of m (mole ratio): BiMnO ₃ = 1 It is.
(K _x , Na _y , Li _1-xy ) (Nb _z , Sb _w Ta _1-zw ) O ₃ -m [BiMnO ₃ ] (2)

(Test Example 1)
The piezoelectric constants d ₃₃ (displacement characteristics), dielectric loss (tan δ), density, and dielectric constant ε _r in the polarization direction of the samples 1 to 18 thus formed were measured. The results are shown in Table 1. D ₃₃ was measured with a Piezo d ₃₃ meter manufactured by UK PIEZOTEST, tan δ was measured with HP 4294A manufactured by Hewlett-Packard, and the density was measured at 25 ° C. by the ARCHIMIDES method. Further, the dielectric constant epsilon _r was measured at 25 ° C. with a Hewlett-Packard HP4294A. Also, the samples 1 to 10, also measured _{d 33} after immersion in water for three days, to determine the rate of decrease of _{d 33} after immersion for previous _{d 33} dipping. The results are shown in Table 2.

  As a result, bismuth manganate and calcium zirconate were added to the perovskite oxide composed of K, Na, Li, Nb, and Ta, and in samples 4 to 16 within the scope of the present invention, tan δ was small and durability It was confirmed to be excellent. And it was highly insulating and could be easily polled. On the other hand, Samples 2 to 3 that do not contain bismuth manganate and Sample 1 that is a perovskite oxide composed of K, Na, Li, and Nb have larger tan δ and poor durability compared to Samples 4 to 16. It was. In addition, when the same operation was performed for each sample a plurality of times and tan δ was measured, the values of Samples 4 to 16 were not different from those of Samples 1 to 3, and the reproducibility was good.

In addition, bismuth manganate and further calcium zirconate were added to perovskite type oxides composed of K, Na, Li, Nb and Ta, and in samples 4 to 7 and 9 to 16 within the scope of the present invention, manganic acid was used. compared with samples 1-3 without the addition of bismuth or calcium zirconate, piezoelectric constant d ₃₃ is high, was 180 or more. Incidentally, the sample 8 of m = 0.01, the piezoelectric constant _{d 33} or because it is generous amount of bismuth manganate was comparable with the sample 1-3.

  Bismuth manganate and calcium zirconate are added to the perovskite oxide composed of K, Na, Li, Nb, and Ta. Samples 4 to 16 within the scope of the present invention have small tan δ and excellent durability. Was confirmed.

  And the samples 4-10 which added bismuth manganate to the perovskite type oxide which consists of K, Na, Li, Nb, and Ta had a high dielectric constant. And in the samples 11-16 which further added calcium zirconate, the dielectric constant was remarkably high even compared with the samples 4-10.

Further, from the results of Sample 17 and Sample 18, Na of the present invention, K, Li, Nb, In the perovskite-type oxide and systems by adding bismuth manganate containing Ta, when is added antimony d ₃₃ is substantially I also found that it decreased.

The powder X-ray diffraction patterns of Samples 1 to 18 were also obtained at room temperature by using “D8 Discover” manufactured by Bruker AXS, using CuKα rays as the X-ray source. As an example of the results, an X-ray diffraction pattern showing a correlation between diffraction intensity and diffraction angle 2θ is shown in FIG. 4 (Sample 3 and Sample 7). As a result, in all samples 1 to 18, an ABO ₃ type structure was formed, and no peaks due to other heterogeneous phases were observed.

(Test Example 2)
Samples 11~16, 25 ℃, 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, at each temperature of 450 ° C., even the measurement _{d 33} after heating for 5 minutes and _to examine the change in temperature of the _{d 33.} An example of the result is shown in FIG. 5 (Sample 15). As a result, _{d 33} of Samples 11 to 16, even when heated to 200 ° C., hardly changed and before heating, the samples 11 to 16 was confirmed that the temperature stability is excellent.

(Test Example 3)
The surfaces of Samples 1 to 18 were observed with a 5000-times scanning electron microscope (SEM). An example of the results is shown in FIG. 6 (a) (surface of sample 3), FIG. 6 (b) (cross section of sample 3), FIG. 7 (a) (surface of sample 7), FIG. Cross section), shown in FIG. 8 (sample 15). As shown in Figures 6-8, Sample 7 with added BiMnO _3, rather than sample 3 without added BiMnO _3, small particle size, porosity has been reduced, it had dense.

(Other embodiments)
The exemplary embodiments of the present invention have been described above. However, the basic configuration of the present invention is not limited to the above. For example, in the above-described embodiment, the ceramic plate is exemplified as the flow path forming substrate 22, but the present invention is not particularly limited thereto. For example, a material such as a silicon single crystal substrate, an SOI substrate, or glass may be used. .

  Furthermore, in the above-described embodiment, the piezoelectric element in which the first electrode, the piezoelectric layer, and the second electrode are sequentially laminated on the substrate has been illustrated. However, the present invention is not particularly limited thereto, and for example, a piezoelectric material and an electrode forming material are used. The present invention can also be applied to a longitudinal vibration type piezoelectric element that is alternately stacked and expands and contracts in the axial direction.

  In addition, the ink jet recording head of these embodiments constitutes a part of a recording head unit including an ink flow path communicating with an ink cartridge or the like, and is mounted on the ink jet recording apparatus. FIG. 9 is a schematic view showing an example of the ink jet recording apparatus.

  In the ink jet recording apparatus II shown in FIG. 9, the recording head units 1A and 1B having the ink jet recording head 10 are detachably provided with cartridges 2A and 2B constituting the ink supply means, and the recording head units 1A and 1B. Is mounted on a carriage shaft 5 attached to the apparatus main body 4 so as to be movable in the axial direction. The recording head units 1A and 1B, for example, are configured to eject a black ink composition and a color ink composition, respectively.

  The driving force of the driving motor 6 is transmitted to the carriage 3 via a plurality of gears and timing belt 7 (not shown), so that the carriage 3 on which the recording head units 1A and 1B are mounted is moved along the carriage shaft 5. The On the other hand, the apparatus body 4 is provided with a platen 8 along the carriage shaft 5, and a recording sheet S that is a recording medium such as paper fed by a paper feed roller (not shown) is wound around the platen 8. It is designed to be transported.

  In each of the above-described embodiments, the ink jet recording head has been described as an example of the liquid ejecting head. However, the present invention is widely intended for all liquid ejecting heads, and is a liquid ejecting liquid other than ink. Of course, the present invention can also be applied to an ejection head. Other liquid ejecting heads include, for example, various recording heads used in image recording apparatuses such as printers, color material ejecting heads used in the manufacture of color filters such as liquid crystal displays, organic EL displays, and FEDs (field emission displays). Examples thereof include an electrode material ejection head used for electrode formation, a bioorganic matter ejection head used for biochip production, and the like.

  In addition, the present invention is not limited to a liquid jet head typified by an ink jet recording head, but is also applied to an ultrasonic device such as an ultrasonic transmitter, a piezoelectric element mounted on other devices such as a pressure sensor and an ultrasonic motor. can do.

  DESCRIPTION OF SYMBOLS 10 Inkjet recording head (liquid ejecting head), 21 Pressure generation chamber, 22 Flow path formation substrate, 23 Vibration plate, 24 Pressure generation chamber bottom plate, 30 Flow path unit, 31 Ink supply port formation substrate, 32 Reservoir, 33 Reservoir formation Substrate, 34 nozzle opening, 35 nozzle plate, 36 nozzle communication hole, 40 piezoelectric element, 43 first electrode (electrode layer), 44 piezoelectric layer, 45 second electrode (electrode layer), 50 wiring board, 51 wiring layer, 52 Base film, 53 Insulating material

Claims (5)

  A step of forming a composite oxide containing sodium, potassium, lithium, niobium and tantalum by mixing and calcining powders of metal oxide or metal carbonate of sodium, potassium, lithium, niobium and tantalum; and By adding a metal oxide or metal carbonate containing manganese and bismuth to a composite oxide containing sodium, potassium, lithium, niobium and tantalum, mixing and then sintering, sodium, potassium, lithium, niobium and A method for producing a piezoelectric material comprising a step of forming a piezoelectric material comprising a solid solution containing a perovskite oxide containing tantalum and bismuth manganate.   When the metal oxide or metal carbonate containing manganese and bismuth is added to the composite oxide containing sodium, potassium, lithium, niobium and tantalum, the metal oxide or metal carbonate further containing zirconium and calcium A piezoelectric material comprising a perovskite oxide containing sodium, potassium, lithium, niobium and tantalum, and a solid solution containing bismuth manganate and calcium zirconate is formed by adding The manufacturing method of the piezoelectric material of description.   A piezoelectric element comprising a piezoelectric layer made of the piezoelectric material according to claim 1 and an electrode for applying a voltage to the piezoelectric layer.   A liquid ejecting head comprising: the piezoelectric element according to claim 3; and a pressure generating chamber communicating with a nozzle opening for ejecting liquid droplets. A liquid ejecting apparatus comprising the liquid ejecting head according to claim 4.