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Patent Office Secretary 3 inventor address Osaka Hidakamon city Ogata Kadoshin name 1002
Name (882) Matsushita Electric Industrial Co., Ltd. Representative company Shoji Matsushita 6th
Shiosuke 571 address Osaka Hikado Shin city Ojado Kado Shin 1oo 6 * 6 eyes of documents
attached ̶ [Phase] Japan Patent Office ■ JP-A-51-32992 @ (1976) 3.19 ■ 昭 V / / ρ / り 7 /
■ Application date 、,, 7. (197,2: ') 7', /, F in the agency number medal P gu \ / 2 / / / ”71 j" r
<t, f da specification 1, the title of the invention 2, special 1 Ffl '11 request (1) at least
polyvinylidene fluoride resin and two. 2. A piezoelectric body comprising: titanium cheltallate
zirconate lead zirconate porcelain powder; and 2, a system containing 30% to 86i [1% by volume]
of cheltantalunium zirconate titanate # lead porcelain powder. (2) containing at least 4
polyvinylidene fluoride resin and lead zirconate titanate powder of nickel tantalate, and having a
lead ratio of lead zirconate butyric acid of liquer tantalate of 30 to 86 TLIl [% The am object is
kept at 106 ° C. to 165 ° C. and the I of 6 to 12 kV Z! (1) A method of manufacturing a
piezoelectric body characterized in that the voltage is applied for 4 to 1 hour, the temperature is
rapidly cooled to 30 ° C. or less within 6 minutes while the voltage is applied, and the
polarization is performed.
Piezoelectric body and method of the same
3. Detailed Description of the Invention The present invention relates to a flexible, large
piezoelectric material having flexibility and an electric field arranged and polarized composite
material consisting of an organic polymer material and an inorganic piezoelectric material, and a
method of manufacturing the same. According to the known piezoelectric materials, for example,
nine crystals of quartz, N'el salt, ammonium dihydrogen phosphate and the like after all, and
barium titanate and the like tend to occur. A large piezoelectric material is found in these
materials, but ft is a hard, brittle, and difficult-to-process material, so a thin plate piezoelectric
material or a flexible piezoelectric material is obtained. That was extremely hard and done.
Although one piezoelectric material with high sinterability is beaten by horns, piezoelectric
materials such as vinyl chloride, polyamide, polyvinyl alcohol, collagen, vinyl fluoride,
polyvinylidene fluoride, etc. The piezoelectric property of the piezoelectric element is small, and
the pressure IE constant of the wedge length vibration is 6.6 Tx1 o ′ ′ m / VK and fz · in the
polyvinylidene fluoride having the largest piezoelectric effect. The present invention eliminates
the disadvantages of the conventional inorganic piezoelectric material and the organic
piezoelectric material, and it is easy to form and process EndPage: 1 into 4 / II plates, and the
#Tm piezoelectric material has large piezoelectricity. For the purpose of obtaining the invention,
the present invention has been accomplished by variously examining the method of welding the
material to each material 'b' for the purpose of obtaining it. That is, in the present invention, the
piezoelectric body is constructed using polyvinylidene fluoride resin as the organic polymer
substance and nickel tantalum / titanium bustle zirconate vessel as the inorganic material. A
solution of Sinawarapo IJ polyvinylidene fluoride in a solvent is prepared by adding each solution
of 1 to 6 μK particle size to this solution and adding lead tantalum zirconate titanate zirconate
porcelain 扮 に to this solution The mixture is uniformly mixed in an outlet ball bowl to form a
film or a molded body. At this time, it is S * to select IIk-dissipation conditions at the time of
forming four films depending on the particle size distribution and particle diameter of the
porcelain powder, and the characteristics of the obtained piezoelectric material have a personal
influence on the characteristics. A pair of electrodes are applied to the skin W14t bamboo
molding thus obtained by heating or m # e, respectively, and heated to a predetermined
temperature in silicone oil. A voltage of V / ss is applied and held for a predetermined time, and
after cooling for a short time while applying an electric field, a stop inorganic composite
piezoelectric having superior piezoelectricity and dielectricity than conventional stop
piezoelectric materials. The body is obtained. That is, the present invention is a composite formed
product of polyvinylidene fluoride resin and lead zirconate titanate ceramic powder which is
formed into a thin plate or thin film shape, and the ratio of the weight of the inorganic porcelain
powder is large. It is a book related to a piezoelectric material and polarization method
characterized by applying 30% to 86% of a composite molded product at a temperature of 106 to
156 "C by applying a direct at pressure and using a hundred percent army.
A composite molded product composed of at least a polyvinylidene fluoride resin and a nickel
zirconate titanate tantalate ceramic powder has almost no piezoelectricity without orientation
polarization, and practically usable ones can not be obtained. 0 After providing an electrode on
this molded product and applying a temperature of 106 to 165 ° CF) temperature [m voltage 6
to 12 hVl for 24 to 1 hour, the temperature is cooled to 30 ° C. or less within 6 minutes while
the voltage is applied. It is not until the voltage is turned off that the piezoelectricity is excellent.
In addition, when the content ratio of lead zirconate titanate 2 tantalate is “30 ′ to 85i 31% of
the total weight, large piezoelectricity and flexibility are exhibited. When M'it of the porcelain
powder is less than this range, the piezoelectricity is small and practical, and on the contrary,
when the number of the porcelain powder is more than this range, it becomes difficult to form
and process the composite molded article, and 5 'J flexibility It is impossible to obtain an
excellent piezoelectric body. The invention will now be described by way of example. [Example 1]
Poly! 11) The amount of 15fi quantity% hN dimethyl formamide of the effect of vinylidene
fluoride, a solution of lead zirconate titanate oxalate powder, and a solution of borate in a ball
mill so that the in ratio of both parts is 18: 82 respectively. After mixing uniformly, a sheet of
arsenide was dried to form a composite membrane of 159 μm thickness. 0 This composite
membrane was coated with silver paste and dried to form a IIc electrode. Then, between the top
and bottom electrodes while heating the sample to 106 ° C. in silicone oil. After applying a
direct current voltage of v / sws for 24 hours, the temperature of the oil was cooled to 30 ° C. in
3 minutes by substitution of low temperature silicone oil until voltage t was applied, and
polarization was induced. The piezoelectric constant in the longitudinal direction of the
composite piezoelectric film obtained by this method is 29.3 × 1 o −2 m / V (046 te h −) ft
knee. EXAMPLE 2 16% Polyvinylidene Fluoride Resin in an Amount of N-N Dimethylformamide
(Doped with a solution of lead zirconate titanate zirconate at a weight ratio of 18:82) The mixture
was uniformly mixed with a ball mill, and then it was abraded to dryness and dried. A 93 μm
thick composite, membrane was made. The paste was paste-dried on this composite film to form
an electrode. Next, apply a DC voltage of 10 * V '/ m between the upper and lower electrodes for
1 hour while heating the sample to 166 ° C. in silicone oil, and then the temperature of the
silicone oil is room temperature until t when the voltage is applied. The solution was cooled to 29
° C. in 6 minutes by rapid substitution with silicone oil.
Then the voltage was turned off and the polarization ended. This EndPage: Piezoelectric constant
tit 28.9 XIQ- "m / V (D @ te; b-zft-) in the longitudinal direction of the combined pressure tm
obtained by the 2 method. In the embodiment, the composite film having a thickness of 9s to
169μ was used, but in the present invention, the thickness of the composite is not limited to the
thickness of this range, and is plate-like. It may not be a rod-shaped one, as it is not a beta one. In
addition, it was found that when cooling by direct conversion of silicone oil was not performed at
the end of the labor treatment of Examples 1 and 2 in piezoelectric constant, the piezoelectric
constant was reduced by about 20%. Next, the reason for limitation of the engineering
polarization temperature will be described with reference to FIG. FIG. 41 shows the change of the
piezoelectric constant in the longitudinal direction of 5 when electretization is carried out by
changing the polarization temperature for a composite film composed of polyvinylidene fluoride
resin and lead zirconate titanate ceramic powder. This component weight ratio is 1 in 1a: B2 of
polyfluorovinylidene resin: titanium lead tantalate lead zirconate powder and the polarization
voltage is ehV / s @ polarization time L1 hour from FIG. 1 As apparent, the temperature in the
range of 105 to 165 ° C. produces about 10 piezoelectric constants, but any temperature
outside this range is excluded from the scope of the present invention as the piezoelectric
constants decrease. Similarly, the polarization voltage and the polarization time t (the reasons for
limitation are explained. [Example 3] FIG. 2 shows the longitudinal direction piezoelectricity of
the composite film prepared by the same method as in Example 2 when the polarization
temperature is changed to a polarization temperature of 105 "C1 polarization time of 1 hour and
-k. Indicates a change in constant. As clearly shown in FIG. 2, when the volume voltage is lower
than 4 × V / ms, the effect on the improvement of the piezoelectricity is small, and the sample
has observed the leading edge fracture at the time of delivery at polarization voltage C lower
than 14 kv / 1 @ 1. Thus, it is impossible to obtain a piezoelectric element. For this reason, the
polarization voltage of the present invention is limited to a range of 6 to 12 kV / 訃. [Do? I14!
FIG. 3 shows the change in the piezoelectric constant in the longitudinal direction when the
polarization time is changed to a constant polarization temperature of 106 ° 01 and the
polarization voltage is fixed to 6 mV / am for the composite film prepared by the same method as
in Example 1. Show. As apparent from the s3 figure, when Y'c polarization time is more than 30
minutes, the piezoelectric W number is small, and the piezoelectric constant does not improve
even if it takes longer than 86 hours. It is excluded from the scope of the present invention in
order to waste the work and reduce the work efficiency. [Implementation f @ 6] 16% by weight
N-N / of polyvinylidene fluoride resin. A composite film is made by changing the percentage of
coercivity of # powder powder by method of mixing the powder form titanium lead ホ ル ム ア ミ
ド lead zirconate porcelain powder with methyl formamide bath solution and making a
polarization temperature of 130 "C.
FIG. 4 shows the measurement results of the piezoelectric constant of the piezoelectric body
prepared by the method of applying a voltage for 10 minutes after polarization with a
polarization voltage of 10 kv / sml and cooling it while applying a voltage for 6 minutes. As
apparent from FIG. 4, the piezoelectric constant and the dielectric constant are two, and when the
inclusion ratio of lead zirconate titanate lead tantalate is in the range of aO to 86 wt%, the
improvement of the piezoelectric constant and the dielectric constant is slow . When it is less
than 30 鴫, there is little improvement in the piezoelectric constant and dielectric constant. When
the amount exceeds 86 weight, organ powder is damaged to the resin, and it becomes difficult to
process composite and synthetic cedar. In this way, a composite of polyvinylidene fluoride resin
and lead-aluminium-zirconate-titanate-zirconate-titanate magnetic powder is included in the
scope of the present invention. By selecting and controlling the component ratio of the substance
and the conditions at the time of polarization, the piezoelectric constant and the dielectric wheel
are superior to the conventional piezoelectric body. Moreover, it is a material which can make a
thin and flexible piezoelectric body which can not be obtained with conventional quartz crystal,
barium titanate porcelain, etc., and has a large application 10I + value as a piezoelectric
confection for acoustic devices.
4. Brief description of the drawings FIG. 1 shows the relationship between the piezoelectric
constant and polarization temperature of a double valley film composed of polyvinylidene
fluoride resin and nickel zirconate titanate zirconate titanate powder. Fig. 2 shows borated
vinylidene fluoride resin and two. It is a figure which shows the relationship of the piezoelectric
constant and polarization voltage of the composite film which consists of a lead zirconate titanate
ceramic powder. FIG. 3 is a diagram showing the EndPage: 3 relationship between the
piezoelectric constant and the polarization time of a composite film composed of polyfluorinated
biphenyl 313 den resin and titanium zirconate lead zirconate powder containing nickel tantalate,
and FIG. The compound is composed of polyfluorinated vigny lyso, n-resin and di-V kel tantalum
1-titanium lead dilunate aS powder! It is a figure which shows the relationship between the
soiling rate, piezoelectric v number, and dielectric constant of IfDll device powder. Name of agent
Attorney Nakao Toshio et al. 14 哩 mus / [i ′ ′ 峰 憾 愈-叫 com) com W-- 7 Inventors and
Agents Other Than Above (1) Inventor's Address Same Location (2) Agent EndPage: 4
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