JPS5132996

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DESCRIPTION JPS5132996
1 、 Name of invention
Piezoelectric body and method of manufacturing the same
3. Detailed Description of the Invention The present invention relates to a highly flexible
piezoelectric material having an electrical field orientation and polarization composed of an
organic polymer material and an inorganic piezoelectric material, and a method of manufacturing
the same. The piezoelectric materials well known to date include, for example, quartz, Rochelle's
salt, crystals of dihydrogen phosphate diimmonium, which crystals, and porcelains such as
barium titanate. Among these materials, large piezoelectric materials can be obtained, but
because they are hard and brittle and difficult to process, it is difficult to obtain thin plate
piezoelectric materials or large flexible piezoelectric materials. The On the other hand, although
large piezoelectric materials are obtained by organic piezoelectric materials such as polyvinyl
chloride, polyamide, polyvinyl alcohol, collagen, yt'l J 1 'nyl, polyvinylidene fluoride, etc., these
piezoelectrics are obtained. The body is small, and even with the largest piezoelectric effect
polyvinylidene fluoride, the number of piezoelectric chambers 12 with length oscillation is only
6-6 TX 10 m / v. In order to obtain a novel piezoelectric material which is easy to be formed and
processed into EndPage: 1 as well as having a large piezoelectricity as well as the defects of the
present invention or other conventional inorganic piezoelectric materials and organic
piezoelectric materials. Material composition K and its production method were studied in detail,
and the present invention was completed. That is, in the present invention, the piezoelectric body
is constructed using polyvinylidene fluoride resin as the organic polymer substance, and zinc
antimonic acid titanate and lead zirconate porcelain powder as the inorganic material. That is, it
is dissolved in a polyfluorinated vini lysoan h1 fr solvent to make a lacquer solution, and this
solution + lead C of zinc antimonate titanate zirconate titanate powder having a C% radius of
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about 1 to 6 μm is added and uniformly mixed in a porcelain peel mill (( Mix and make a film or
a company sentence. At this time, it is necessary to carry out a suitable sales room during Px-Fu
generation depending on the particle size distribution and particle diameter of the porcelain
powder, and is it remarkable for many cases of piezoelectric materials obtained under the
conditions? およほす。 A film or a film obtained in this way-or vapor deposited on a molded
body or a method such as painting or the like! Since the pole is exposed and heated to a constant
temperature change in silicone oil; DC 6 to 12 kV / af) 1iB for both electrodes! The mark 7XI is
held for a fixed period of time M. By cooling in a short time while applying an electric field, an
organic non-contact composite piezoelectric having superior piezoelectricity and dielectricity
than conventional organic piezoelectric materials can be obtained. It is. That is, the present
invention is a composite formed product of a polyfluorinated vini lyso / resin formed in a thin
plate or thin film and a lead zirconate titanate zinc antimonate powder, and the content of non-p)
porcelain powder The present invention relates to a piezoelectric body equivalent to applying
30% to 86% of a composite molded product at a temperature of 106 ° C. to 165 ° C. by
applying pressure directly to the pressure R 1 F and dividing it, and a method of manufacturing
the same.
A composite molded product composed of at least this polyvinylidene fluoride resin and zinc
zirconate titanate zirconate powder has almost no piezoelectricity in the absence of orientation
polarization, and one which can be used for * is not obtained, but After providing an electrode on
this molded product and applying 1 o δ to 166 ′ ′ Cf) fll AWT [@ t EE 6 to 12 kV / aid 2 a to
1 hour, apply a voltage and cool it to 30 ° C. or less within 9 ttia degrees t δ minutes to apply a
voltage Turning off and polarization t-termination K only leads to excellent piezoelectricity. In
addition, when the content of zinc antimonate titanate zirconate porcelain powder is 30 to 86%
by weight of the total weight, large piezoelectricity and flexibility are exhibited. If the content of
the porcelain powder is less than this range, the piezoelectricity is small and practical, and
conversely, if the amount of the porcelain powder is more than this size), it is difficult to form
and process composites, moldings, It is not possible to obtain a flexible piezoelectric material.
The invention will now be described by way of example. EXAMPLE 1 A mixture of 15 wt% N-N
dimethylformamide solution of polyvinylidene fluoride resin and zinc-zirconate titanate lead-free
porcelain powder in a weight ratio of both components of 18: 82 respectively. He was uniformly
mixed, spread into a sheet and dried to form a composite membrane of 166 μ in thickness. The
paste was applied to the composite film and dried to form an electrode. Then apply a DC voltage
of 6kV / II between the upper and lower electrodes for 24 hours while heating the sample t106
° CK in silicone oil, change the temperature of the oil until the voltage is applied, 3 by replacing
the low temperature silicone oil The polarization was completed by cooling to 30 ° C. in one
minute. The piezoelectric constant in the longitudinal direction of the nine composite
piezoelectric films obtained by this method was 29.1 × 10-12 rn / V. [Exemplary Example 2] 1eS
weight% N-N dimethyl formamide solution of poly (vinylidene fluoride) resin lead zirconate
titanate zirconate porcelain powder is uniformly mixed with Darnul so that the weight ratio of
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both components is 1sHsz The solution was mixed and fc, and then stretched into a sheet and
dried 112 to form a 92 μ thick composite membrane. This composite #Kil paste is coated and
dried to form an electrode. Then, it is heated to a sample H11 sa ° C in silicone oil while being
heated to a test H11 sa ° C, and a direct current voltage of 1 okV / ■ between upper and lower
electrodes! After applying for 1 hour, the voltage is applied to 11 and the temperature H1 of
silicone oil! Cooled at 28 ° CK in 6 minutes by rapid replacement with silicone oil below 1 ° C.
Then the voltage was turned off and the polarization ended. This method EndPage: 2i-shows that
the piezoelectric constant -12 · number in the longitudinal direction of the composite
piezoelectric film is 28.9 × 10! ! value of l / V). In the embodiment, the composite film having a
thickness of 92 to 186 μm was used, but in the present invention, the thickness of the film is not
limited to this range, and plate-like or rod-like Needless to say, the piezoelectric constant may be
reduced by about 20% when the cooling of the silicone oil by fk 先 is not performed at the end of
the polarization treatment. all right. Next, the reasons for limitation of the polarization
temperature will be described with reference to FIG. Fig. 1 shows a composite J [lI [K consisting
of polyvinylidene fluoride resin and lead zinc zirconate titanate borate powder and changing the
polarization temperature for Electrification in the longitudinal direction Piezoelectric constant
150: 會會重量 This component weight ratio is polyfluorinated vinylidene resin: zinc antimonate
titanate zirconate lead porcelain powder is 1a: s2, polarization II! π is eskV ° / m 1 polarization
time is 1 hour. As is apparent from FIG. 1, at temperatures in the range of 10δ to 1158 ° C, the
piezoelectric constant of about -St is exhibited, but at temperatures outside this range, the
piezoelectric constant falls in any range of the present invention Excluded from Similarly, the
reasons for limitation of the polarization voltage and the polarization time will be described.
[Embodiment 3] FIG. 2 shows an object 1 made by the same method as Embodiment 2. About iK
Polarization temperature is 10δ ° C 1 polarization time! As is apparent from FIG. 2, when the
polarization voltage is lower than akV / l, the effect on improving the piezoelectricity is small. In
addition, polarization-voltage t higher than 1 akV / m causes breakdown of the sample at the
time of polarization, making it impossible to obtain a piezoelectrically biased stack. Therefore, the
polarization voltage of the present invention is in the range of 6 to 12 kV / ν. Limited to
[Example 4] FIG. 3 shows the same polarization temperature [(-106 ° C., 1 mE pressure t-6 kV /
ff constant) and the polarization time of the composite film prepared by the same method as
Example 1]. If the polarization time is shorter than 8a minutes as shown in Fig. 3, the change of
the piezoelectric constant in the longitudinal direction of the case is small, the piezoelectric
constant is small t · · ·, and the length exceeds 36 hours. Even if it takes time, the improvement of
the piezoelectric constant does not occur, and it is time-consuming and is excluded from the
scope of the present invention in order to lower the working efficiency. [Example 6] In a method
of mixing lead-zinc antimonate titanate zirconate powder with 166 wt% N-N dimethylformamide
solution of polyfluorinated vinyl resin, a resin: weight percentage of resin: tfak The piezoelectric J
was prepared by a method of preparing a composite J [and preparing a sample with a stem
temperature of 1 sec. C1 polarization voltage of 10 kV / aFI for 1 hour, and applying a voltage
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for 6 minutes to cool it. The results of measurement of the piezoelectric constant are shown in
FIG. 4. As is apparent from FIG. 4 °, the piezoelectric constant and the dielectric constant of the
zinc zirconate titanate lead zirconate titanate ceramic powder are 3 ° to 86 °. When it is in the
range of 10%, the improvement of the piezoelectric constant and the dielectric constant is
remarkable. When it is less than 30% by weight, the improvement effect of the piezoelectric
constant and the dielectric constant is small. In contrast to 1. However, it is excluded from the
scope of the present invention because it is not possible to obtain a flexible piezoelectric material,
unless it is too large and it is difficult to form and process a composite molding.
In this way, the component ratio of the composite material consisting of polyvinylidene fluoride
resin and lead zirconate titanate zirconate titanate powder and the conditions for polarization
thereof are selected and the thin film form which can not be obtained by barium titanate acid and
the like. Flexible piezoelectric, can be made into a body, and is made of a material with high value
of response value as a piezoelectric device of sound device back,-
4. Brief Description of the Drawings FIG. 1 is a view showing the eg of the piezoelectric constant
and the polarization temperature of a composite film composed of polyvinylidene fluoride resin
and titanium lead antimonate-lead zirconate porcelain powder. FIG. 2 is a view showing the
relationship between the piezoelectric constant and the analysis voltage of a composite film
which contains polyvinylidene fluoride resin and lead zirconate titanate zirconate titanate. Fig. 8
is a diagram showing the end of the PA retention of the piezoelectric constant and the
polarization time of the composite film made of polyvinylidene fluoride resin and lead zirconate
titanate zirconate powder, and Fig. 4 is a diagram showing poly FIG. 11 is a view showing the
relationship between the content ratio of a composite film consisting of vinylidene fluoride-fat
and zinc anti-succinic acid I'll lead zirconate porcelain powder, the piezoelectric constant, and the
dielectric constant. Name of agent Attorney Nakao Toshio Nakano 1 person # Jl Figure 1 μ Fig.
2 Polarization 'jL! (° C.) heat (oJl polarization voltage-1) Fig. 3 xl D 42 Fig. 4 polarization a8
cabinet (tr) 瑳 Ministry 1P 竿 (wt%) 7 Inventors and agents other than the above (1) Inventors
Address Dougaya Hayakawa Name Hayakawa (2) Substitute ° EndPage: ４
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