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Patent Office Secretary 2 Inventor Name-"wv't Pan (other 2) 3 Patent Applicant Address ° Osaka
Prefecture Kadoma City Ogata Kamon Shinkan Address 1002 Name (582) Matsushita Electric
Industrial Co., Ltd. Representative Masaharu Matsushita 4th, reason Person 、 571. HousingOsaka Prefecture Kadoma City Oza Kadoma 1006 ■ Japan Patent Office 0 JP 50-148 9900 JPN
50. (1975) 11.28 ■ Japanese Patent Application No. 4 '? -5'l / 47 [phase] Japanese Patent
Application No. 41 (197 to t) r, "6466466.5" 76g2454, specification 1, title of the invention
Method of manufacturing piezoelectric material
a1 Detailed description of the invention and 8 inventions: 黴 強 ′ ′ ・ ・ ′ ′ ′ ′ ′ kl kl kl
kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl kl. Method of manufacturing a
piezoelectric material characterized in that the composite resin is molded with an insulating resin
and then electretized. According to the manufacturing method of the present invention, a
piezoelectric material which is rich in flexibility and exhibits a very high piezoelectric 皐It's
something you can get. As a conventional piezoelectric material, an inorganic crystal material is
generally used. A crystal was known. In recent years, barium titanate. Ceramic ferroelectric
ceramics such as zircon and lead titanate are the mainstream. -These inorganic piezoelectric
materials have high piezoelectricity and can be obtained from turtle butterflies! The lt-shaped
processing is a surrounding motion, and a thin and flexible piezoelectric body can not be
obtained, and the shape is often limited in application. However, recently, it has been confirmed
that even polymers have piezoelectric properties, and 1 The various polymers 74 have been
investigated for their piezoelectric constants 1 For example, polyvinyl fluoride, polyvinylidene
fluoride, polyvinyl chloride , Polyvinylidene chloride, nylon 11. ナイロン12. Thermoplastic
resin such as polycarbonate and polymethyl methacrylate. When a direct current high voltage is
applied to these polymer films, the piezoelectric effect is obtained, and it is further found that, in
specific trees and oils, if the film stretched in advance is electretized, it has a large piezoelectric
effect. -. The term "electretization" as used herein refers to raising the temperature in a high
electric field applied to the polymer film and then cooling to room temperature, and electretizing
the polymer film or the control sheet to exit the US9 piezoelectric body # i. EndPage: 1 There is a
drawback that the piezoelectric coefficient is extremely small compared to the inorganic
piezoelectric material. However, it is easy to form and process. Since a thin and flexible film is
obtained, it can also be expected in applications different from inorganic piezoelectric materials.
Therefore, research on composite piezoelectric materials having both of these characteristics is
being carried out. No. 1 By mixing and molding mechanical piezoelectric powder in resin. It is a
composite piezoelectric material in which the improvement of the piezoelectricity is shown in
FIG. V, and the flexibility of the polymer is maintained. Conventionally, as inorganic piezoelectric
powders, ceramics and fine powders such as barium titanate, lead titanate, lead zirconate, and
titanium zirconate have been used. However, two-component, three-component inorganic
piezoelectric materials can be used as ceramic fine powder, i-composition, ceramic composition
with various composition ratios, and a-composition to show high piezoelectricity at 9 o'clock The
The present invention provides a method of producing a piezoelectric material which is superior
to compounding a ceramic fine powder of an appropriate or compositional range with a
thermoplastic resin. The thermoplastic resin according to the present invention refers to
polyvinyl difluoride; polyvinyl chloride, polyvinyl chloride, polyvinylidene chloride, polystyrene,
polycarbonate, polymethyl methacrylate, and the like. The ternary system of the present
invention-a ferroelectric * 9 fy is Pb (Mi; r $ bH)! TiyZrzO3 Pb(CofbH)!
TiyZxzOs, Pb (Sb $ bH), TiyZrzOs, Pb (CdfbH), TlyZrzO3, & Tono-k9iy / are mentioned. (However,
x-1-y-)-gxl) By using a ceramic fine powder in the vicinity of the oxortropic phase transition
composition of a ferroelectric ceramic like one. It has been found that a composite piezoelectric
material having a higher piezoelectricity than before can be obtained. In addition, it was found
that, in particular, when it is within the range shown in FIG. Ceramics with compositions near the
morphotropic phase transition exhibit high piezoelectricity when they are composites because
they are sensitive to external stress. 'Especially, electro mechanical coupling? It was found to be
effective when combined with a large number of ceramics. Examples of the present invention will
be described below. [Example 1] Inducer 1-body ceramic Pb (Mg, / ib,)! Between the composition
of TiyZrgO3, (where x-)-y dew point 1) @ tx = 0.12 to O, 't 4.7 = 0.46 to 0.4 T, 寞 mO, 41 to 0.43
(see 11121 m) ) 0 composition range where x is a sample obtained by compound molding of
ceramic fine powder and polyvinylidene fluoride (hereinafter referred to as PVF2) taken at K 0 as
xxamp 1 · x 0, 37 to 0.40, y = o, ss to 0.41 ,! No. 22 to 0.26 (see FIG. A) l1 cND PvF2 cross IK
synthetic shape 9 trial shaping molding amp 1 · 2. Similarly, one composition range 8 is X =
0.1δ to 0.20, 7zO, 60− + 0.62, E =, 0.80 to 0.38 (see 11112) and nine samples? 8amp1、
3とする。 Samples 1 to 34 are Pb (hitsfb-t, h), TiyZr dewpoint '03 powder no less than 20 pl! After kneading the PVF2 (L'z ') 20 pt with a hot roll and performing press molding. , And heated
to ˜ 86 ° C., 2501 cIII> -direct current 1. A voltage was applied in the thickness direction, and
was maintained for 3 hours in the condition of the dimension and cooled for 30 minutes.
The piezoelectric coefficients of the samples obtained above were measured, and the order of
Tatokoro, jE electrode size pi, Sample 1> 8 ampl + 2) Sample 3 was obtained. Assuming that the
value of Sample 3 is 1, 8 ampl · 2 is 1.6 times of that and 8 ampl · 1 is 3 times that. EXAMPLE 2
After grinding barium titanate in a ball mill. A sample composite-molded with Pvv2 in the same
manner as Example 1 is referred to as Sample A. The same conditions as in Example 1 were
applied to Samplea No forming condition 3 polarization conditions. When the magnitude of the
piezoelectric coefficient is set to 1 (SampleAn), Sample 1 kx is δ, Sample 2 is 3 times that,
Sample 3 u is 01.6 times. e1に
Pb(F@44TaH)03. Pb(Mi4Jbq)Oa。 Pb (Nif%) 03-fk E no strong tlj II
body 'e indication f. It is possible to show morphotropiophas @ boundaτy smoothly from the
composition of PbTiO3: PbZr0a-48: 8F5% Luo, but it changes according to the kind of A. In the
case of FIG. 1, A shows the morphotropic phase boundary in the case of Pb (rain f1) O 3 busy. In
the figure, a large-scaled piezoelectric tube is shown at 41% in combination with a ceramic fine
powder having one composition ratio of one black portion in the figure. 11E2 BxPb (Mf $%) OsyPbTio, dew point PbZr0. It is a phase diagram of Sansei EndPage: 2 degree distribution yarn.
The curved line morphotropiapha @ eboundary is indicated by a solid line. In the S2 diagram, the
composition ratios of the ceramic powder at the end of 1.2, 3 usample-1 and sample 2 ° sampl ·
3 are shown. The manufacturing method of the present invention is configured as described
above, and according to the present invention, it is possible to obtain a piezoelectric material
which is rich in flexibility and has a high piezoelectric book.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a ternary diagram of three-component
ferroelectric ceramics according to an embodiment of the present invention. Name of agent
Attorney Nakao et al. 1 person 1111 Figure 2 Figure 6 Inventors and agents other than those
mentioned above End address: 3