JPS5132998

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DESCRIPTION JPS5132998
Singh, 49 September 132) Patent Office Secretary-窃 · λ1 Name of invention 門 Address, Osaka
Prefecture Kadoma city Ogata Kadoma address 1006, (582) Representative Matsushita Electric
Industrial Co., Ltd. Shoji Matsushita ■ Japan Patent Office ■ Special Japanese Patent Publication
No. 51-229980. (1976) 3.19. Japanese Patent Application Publication Guar / 〆 q 〆 [phase]
Application date ■ Fermentation 7. (Yooh 197) / P, iJ Office serial number ((f g r / 1/2 / /! Jz //
'λy, tt da? Patent Document 1: Title 1 of the Invention, Title of the Invention Piezoelectric Body
and Method of Manufacturing the Same
4 special applicant
Detailed Description of the Invention The present invention relates to a highly flexible
piezoelectric material comprising an organic polymer material and an inorganic piezoelectric
material, which is a composite material which is made of an organic polymer material and an
inorganic piezoelectric material, and which is polarized and aligned. これまでに。 As a wellknown piezoelectric material. For example, crystals such as quartz crystal, Rochelle salt,
ammonium dihydrogen phosphate and porcelains such as barium titanate. In these materials, a
large piezoelectric 4 has been obtained, but 6 is also hard and brittle, and it is a thin plate of
piezoelectric material because it has been processed. Alternatively, it was extremely painful to
obtain a flexible piezoelectric material. On the other hand, a highly flexible piezoelectric material
is obtained by an organic piezoelectric material such as polyvinyl chloride, polyamide, polyvinyl
alcohol, collagen, carbon fluoride (t, hinil, polyfluorinated vini lyso, etc.). These piezoelectric
properties are small, and the piezoelectric constant of the ln 'c4 length vibration is 6.67 x 10 "-/
VK too much for polyvinylidene fluoride with the largest piezoelectric effect. In the present
invention, it is possible to obtain a novel pressure plate which is easy to be formed and processed
into EndPage: 11 squared into a thin plate and has a large piezoelectricity, while eliminating the
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defects of such conventional inorganic piezoelectric materials and organic piezoelectric materials.
In order to achieve the purpose of the present invention, the present invention is as follows: That
is, 1) In the present invention, a piezoelectric body is constituted by using polyvinylidene fluoride
resin as an organic polymer substance and using a lead zirconate titanate lithium titanate powder
as an inorganic material. That is, a polyvinylidene fluoride resin is dissolved in a solvent to
prepare a 10 car solution, and the particle diameter of this solution is 1 to 6! A certain amount of
lithium tantalate titanate zirconate @ lead porcelain powder is added and mixed uniformly in a
ceramic mail mill to form a film or a molded body. It is necessary to select the ambiguity
condition at the time of thin film formation 15 according to the particle size distribution and
particle diameter of this porcelain powder, and l of the piezoelectric material obtained by that
condition °! Il+! Significant impact on kVkV °. The film obtained in this way! A pair of
electrodes is applied to the bamboo formed body by a method such as steaming or painting. By
applying a voltage of DC 6 to 12 kV / fi to both electrodes while heating for a predetermined
temperature in k, ""-"oil and holding for a predetermined time, cooling in a short time while
applying an electric field An organic-inorganic composite piezoelectric material having
piezoelectricity and dielectricity superior to those of conventional organic piezoelectric materials
is obtained. That is, 1) the present invention is formed of a thin plate-like or thin film-like shaped
polyfluorinated lead resin and lead zirconate titanate lithium tantalate porcelain powder; b.
Composite molding of inorganic porcelain powder The present invention relates to a piezoelectric
material characterized in that a composite molding having a content of 30% to 80% by weight
and polarized by applying a DC voltage of 108 to 165 bits at a temperature of 108 to 165% and
a method of manufacturing the same.
At least this composite molded product, which is composed of polyvinylidene fluoride resin and
lead zirconate titanate lithium tantalate powder, has almost no piezoelectricity until it is oriented
and polarized, and a practically usable book is Not obtained, but after applying a DC voltage of 6
to 12 kV / sw for 24 to 1 hour at a temperature of 10 a to 158 ° C. by raising the electrode to
this molded product, a voltage is applied f or 1! It is not until the temperature has been cooled to
30 ° C. or less within 6 minutes to turn off the voltage and polarization. In addition, when the
content of lithium tank / lead zirconate titanate titanate powder is 30 to 86% by weight of the
total weight, large f piezoelectricity and flexibility were exhibited. If the content of the porcelain
powder is less than this range, the piezoelectricity is small and the practicability is poor, and if
the amount of the porcelain powder is larger than this range when the amount of the porcelain
powder is greater than this range It is not possible to obtain an excellent pressure lO current
collector. The invention is illustrated by the following examples. [Example 1] A solution of 16%
by weight N- [1 di "methyl formamide solution of poly vinylidene fluoride resin and lithium
tantalate 1 '1 lead zirconate porcelain powder in a weight ratio of both components is 18: After
uniformly mixing in a ball mill at 80 ° C, allow to sheet and dry. A composite membrane with a
thickness of 16 t and 5 units was made. Silver paste was applied to the composite membrane and
dried to form an electrode. After applying a direct current voltage of K6kV / sw between upper
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and lower electrodes for 24 hours while heating the sample for 10tS'OK in silicone oil at 20th
order-Replace the temperature of oil with low temperature silicone oil up to t when voltage is
applied Cool down to 30 t 3 for 3 minutes to complete the polarization. By this method. The
piezoelectric constant 1 in the longitudinal direction of the composite piezoelectric film obtained
is 28.8 '× 10−2 m / V). EXAMPLE 2 A solution of polyvinylidene fluoride resin in 16% by
weight N-N dimethylformamide in a solution of lithium mental acid dititanate and lead gluconate
porcelain powder was subjected to ball milling so that the weight ratio of the two components
would be 18: 82 respectively. After mixing uniformly, it is spread into a sheet and dried. A 97 #
thick composite membrane was made. Silver paste was applied to this composite film and dried
to form an electrode. Then, while applying a direct current voltage of K10 kV / W between upper
and lower electrodes while heating the sample for 155 CK in silicone oil in 0, apply the voltage
while applying the voltage The temperature of the silicone oil was cooled to 28 ° C. in 6 minutes
by rapid displacement with silicone oil below room temperature.
Then the voltage was turned off to complete one polarization. One piezoelectric constant of the
composite piezoelectric film in the longitudinal direction obtained by this method EndPage: 2 is
28.5 × 10− ′ ′ m / V value e6 ′ ′) :. In the present invention, the thickness of the film is
limited to this range-not M-shaped. Needless to say, it may be rod-shaped. At the end of the
polarization treatment of Examples 1 and 2, it was found that the number of piezoelectric 'JiL
decreased by about 20% when cooling by substitution of silicone oil was conducted at the end of
polarization treatment. Next, the limit of the polarization temperature will be described with
reference to FIG. Fig. 1 shows the change of the piezoelectric constant in the longitudinal
direction when the polarization temperature is changed and the ellipsing and creasing are
performed on the composite film consisting of polyvinylidene fluoride resin and lithium zirconate
titanate lithium tantalate titanate powder. The component weight ratio shown is 18:82 for
polyvinylidene fluoride resin: lead zirconate titanate lithium tantalate, and the polarization
voltage is 6 kV / one polarization time is 1 hour. As apparent from FIG. 1, the piezoelectric
constant is almost the same at temperatures in the range of Kj 05 to 166 ° C. However, at 0
temperature outside this range, any of Fi is excluded from the scope of the present invention
because the piezoelectric constant decreases. . A stone that explains the reasons for limiting
polarization voltage and polarization time as well. [Example a] Figure 2 shows the piezoelectric
constant in the longitudinal direction when the polarization temperature is changed to 1 osb and
the polarization time is fixed to 1 hour for the composite film prepared by the same method as
Example 2. As is apparent from FIG. 2, when the polarization voltage is lower than 4 kV / m, the
effect on the improvement of the piezoelectricity is small, and when the polarization voltage is
higher than 14 kV / ml, the sample causes dielectric breakdown at the time of polarization to
cause piezoelectricity. For this reason you can not get the elements equipped. The polarization
voltage of the present invention is limited to the range of 6 to 12 kV / a +. [Real m-row 4] FIG. 8
shows the polarization source [piezoelectricity in the case of changing the polarization time by
changing the polarization time to a single pair such as 100 ° C. 1 polarization voltage at 6 kV /
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m for the composite film prepared by the same method as Example 1 As is apparent from FIG. 3,
which shows a change in the constant, when the polarization time is shorter than 30 minutes, the
piezoelectric constant is small, and the piezoelectric constant does not improve over a long time
over 36 hours. It is excluded from the scope of the present invention to waste time and reduce
work efficiency. EXAMPLE 6 15% by weight 1% N-N solution of polyvinylidene fluoride resin in
dimethylformamide dissolved in water [[K lithium zirconate titanate tantalate] ball mill 7 mixing
resin b: resin-porcelain-powder The composite membrane is made by changing the weight
percentage of the sample at a polarization temperature of 1 so'C.
As shown in FIG. 4, the results of measurement of the piezoelectric constant of the piezoelectric
body prepared by the method of cooling while applying a voltage for S minutes after polarization
for 1 hour at a polarization voltage of 10 kV / 鱈 as shown in FIG. The dielectric constant
improves the piezoelectric constant and the dielectric constant when the combination of lithium
zirconate titanate lithium tantalate powder is in the range of 30 to 86% by weight, and when it is
less than 30% by weight, the piezoelectric constant and the dielectric constant The effect of
improving the ratio is small, and when it is more than 86% by weight, the amount of porcelain
powder is too large relative to that of the resin, making it difficult to form and process the
composite molded article. The invention is excluded from the scope of the present invention in
order to obtain a piezoelectric body having aT flexibility. In this way, the ratio of the one-part
ratio of the composite material consisting of polyvinylidene fluoride resin and lithium zirconate
titanate lithium tantalate and the condition at the time of polarization are selected, and a thin film
like film not obtained by barium nitrate ceramic etc. It is a material with great application value
as a piezoelectric element for acoustic devices by making a flexible piezoelectric material.
4. Brief Description of the Drawings FIG. 1 is a view showing the relationship between the
piezoelectric constant and the polarization temperature of a composite film composed of
polyvinylidene fluoride resin and lithium zirconate lithium tantalate titanate powder. FIG. 2 is a
view showing the relationship between the piezoelectric constant and the polarization voltage of
a composite film comprising polyvinylidene fluoride resin and lithium zirconate titanate lithium
tantalate powder. FIG. 3 is a graph showing an EndPage: 3 relationship between the piezoelectric
constant and the polarization time of the fk / ゐ composite film from polyvinylidene fluoride
resin and lithium zirconate titanate lithium tantalate titanate powder. FIG. 4 is a graph showing
the relationship between the content of ceramic powder of poly (vinyl fluoride) resin, lithium
tantalate titanate zirconate, and lead powder-porcelain composite film, and the piezoelectric
constant and the enzyme ratio. . Name Shishio Shio Nakano 7 7 and others 1 1 7 Inventors and
agents other than the above Address and the same place name and f 'f "(2) agent EndPage: 4
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