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Patent application (1) Jan. 20, 1975 General Secretary of the Patent Office Representative
Masaharu Matsushita [Fa] Japan Patent Office-Japanese Patent Laid-Open No. 51-840980
Published Japanese Patent No. 51. (1976) 7.23 Japanese Patent Application No. 50-3821
internal serial number 11 1 、 Name of invention
Non-molecular piezoelectric material
3. Detailed Description of the Invention The present invention relates to a polymer pressure used
in the diaphragm portion of a turtle noise noise converter: to a material, a polymer piezoelectric
excellent in flexibility and exhibiting a high pressure ratio together It is a material providing
material, and as the piezoelectric material of one polymer is β-type polyfluorinated vinyl
chloride, it is a ** crystal material or a general material, and a single crystal with quartz crystal,
Rochelle salt, etc. is known from old times It was In recent years, ceramic strong @ integral
magnetism such as barium titanate, zircon, and lead titanate-based has become mainstream.
Although these inorganic piezoelectric materials can be obtained with high piezoelectricity, they
are difficult to process, and thin and flexible piezoelectric materials can not be obtained.
Recently, it has been confirmed that polymers also have piezoelectricity, and the piezoelectric
coefficients of various polymer films are flat. For example, polyvinyl fluoride, polyvinylidene
fluoride, polyvinyl chloride, polyvinylidene, nylon 11. ナイロン12. ポリカーボネート1. It is
a thermoplastic resin with polymethyl methacrylate. When a direct current high voltage is
applied to these polymer films, a piezoelectric effect can be obtained. Furthermore, a polymer
film such as polyvinylidene fluoride, which has a 菫 and β type molecular structure and can be
converted to β type with spontaneous separation by stretching treatment etc., has a large
piezoelectric effect when electretized with a base of 8 厘It has been found to have. A piezoelectric
body obtained by electretizing a polymer film or sheet has a disadvantage that its piezoelectricity
is higher than that of an inorganic piezoelectric body and it has a small size. However, since a
thin and flexible film is obtained by EndPage: 1, which is easy to form and process, applications
different from inorganic piezoelectric materials can be expected. Note that we say electretization
here, and after raising sF # in the condition that high voltage is applied to the polymer film, it is
said to cool down to -11. In order to maintain the flexibility of the polymer and improve the
piezoelectricity of W, research has been conducted on a composite piezoelectric material in
which an inorganic piezoelectric material powder is mixed with a base resin and molded. That is,
barium titanate, lead titanate. After grinding inorganic piezoelectric materials such as lead
zirconate, titanium and lead zirconate with an M horizontal machine, etc., they are kneaded into
the base resin using a heat roll etc. and made into a film or sheet by press molding etc. .
Electretization is equivalent to that of one molecule alone. However, in the composite
piezoelectric material, since the material is a composite material for improving the characteristics
or the ceramic after specific gravity 7 #, it has many disadvantages when it is composited in a
large amount.
For example, it is impossible to form a film-like thickness (less than 1 ωμ), and it can only be
formed into a sheet of a size of at most μ. Mechanical characteristics such as pulling strength
become stupid. The other effective means of improving the piezoelectricity, the stretching
process, becomes unusable. As electretization becomes difficult, the applied voltage can not be
stabilized sufficiently. Etc. The present invention improves the disadvantages of the above P by 4
and provides a polymer piezoelectric material having very high piezoelectric properties
maintaining the formability as a fully-powerable resin. Polymer pressure by 1. The material is sixband construction coated with β-type polyvinylidene fluoride and 70 · Table 1j #. Although βpoly-poly-twill vinylidene is generally obtained by further forming an α-form-poly (7-vinylidene
fluoride) by a rolling process such as roll processing, it can also be obtained from film forming by
a solution method. It is. From the viewpoint of layer compounding and lamination, polyurethane
plasticizers which are good in solubility and adhesiveness with polyvinylidene difluoride are most
suitable. The means for laminating the above-mentioned engineering polymer compound is a
method in which the engineering polymer compound is made into a single sheet in advance, and
a method of heat fusion by overlapping with a press and the like, a solvent is coated on the resin
film surface, The method of making a laminated film by removing etc. is utilized. On the O
piezoelectric property, β-type polyvinylidene fluoride film for the present invention Molecular
Piezoelectric Material Co., Ltd. is a polymer compound, so all are composite compounds of
inorganic piezoelectric materials. Compared to the converted materials, the formability is not
impaired at all, the mechanical properties are not steeped, and electretization conditions can be
performed without any problem. In the following, examples of the present invention are shown in
comparison with other types of polymeric piezoelectric materials. [Example 1] 80 μm thick
polyvinylidene fluoride (hereinafter referred to as FVF) on one surface of which film is formed
into a β-type by roll stretching after film-forming, polyurethane using tetra-human tetrafuran
(hereinafter 'ng) as a solvent Coating plastic (PU) solution, and? An electrode is formed by A2
vapor deposition on one surface of a sample having a thickness of 100 μm by dry removal of HF
to form an electrode, and the voltage is applied at 90 ° C. and 6 KV (sωKV, 4 m) in the
thickness direction to keep 7 辱It took 1 hour to perform cooling and electretization. da1-16-63
× 10-· · / tension [Conventional example 1] A single pole is formed on the surface of the 30 μthick β-type pvy 2 sample used in Example 1 in A16 size and its thickness direction The
temperature was kept at 90 ° C. for 7 hours by applying aKV (667 KV, Aa) (1) voltage for 1
hour, followed by cooling for 1 hour.
The obtained pressure% characteristics were as follows. ds, -6, 511 × 1012 C / N [Conventional
Example 2] 8 mpvy used in Example 1 The electrode was deposited on one surface of a 100 μm
thick lid PvF2 sample before roll stretching EndPage: 2 ulffi L, -t-no In the thickness direction, 90
° C., s, es KV (ag. The pressure tW property which was maintained for 7 hours by applying a
voltage i of Kv / & and subjected to electretization for 1 hour after cooling was 0 t, the pressure t
W property was the following value: 012 ds, (), 51 × 10 C / N [conventional example 3) vl pole
is formed with A1 # 'on both surfaces of the sample formed into a thickness of 400 p by titanium
zircon molding in amIPvF 2 used in the conventional example 2, 90 K, 12 KV (aoo KV, A- The
electretization was carried out by keeping the voltage applied for 7 hours and cooling for 1 hour,
and the obtained pressure characteristics were as follows. In the example of d51m4-5C) x 10 C /
N or more, supplementing the experimental result is possible to apply a voltage of about P'v] F2
base material h1ooox n i, the ferroelectric ceramic composite is One sail or almost limit. On the
other hand, the sample according to the present invention is also capable of 1000 generations.
On the other hand, as the conditions for electretization, although the S degree is optimal for all 3
# s at 90 to 100 ° C, the time approaches the saturation in about 2 hours in the conventional
method, If the sample according to the invention is long! # Sleep good. Also, although the larger
the applied voltage, the better the larger the voltage applied, "the ferroelectric ceramic composite
is extremely reduced particularly in the case of drawing because of the limit of dielectric
breakdown, and sufficient electret formation is achieved. Is not represented. In other words, the
implementation of the present invention is expected to be improved by the fist which further
increases the voltage application because of the relative softness with the conventional method.
As described above, the polymeric piezoelectric material according to the present invention is
approximately equal to the material obtained by electretizing β-type poly (7-vinyl divinylitrine)
obtained by subjecting a single polyvinylidene difluoride to drawing by subjecting the remains to
electretization. The piezoelectric characteristics of 2621 G can be improved. Moreover, since the
obtained polymeric piezoelectric material has excellent piezoelectric properties without any
deterioration in the mechanical properties of the thermoplastic resin, it has a stab that enables a
transducer of an entirely new structure to be obtained. It is. Name of the agent Attorney Nakao
Toshio Nakao has one person 6 other than the address mentioned above Address address in
Osaka Prefecture Kadoma city 1006 Address End Page: 3 Procedure amendment document
1101151 240 Patent Office Secretary's case Show case 1960 patent Application No. 8821, Title
of the Invention Title of the Invention Polymer Piezoelectric Material Three-Sleeved Case 1 の 係
Patent Applicant Address Osaka Prefecture Kadoma City Ogata Kadoma 1006 Address Name 41 ·
(582) Matsushita Electric Industrial Co., Ltd. Representative Masaharu Matsushita 4 Agent 〒
517 Address Kadoma City Ogata Kamon Shinkan 1006, Matsushita Electric Industrial Co., Ltd.
[Contact telephone (coming call) 柘 鼾 丑 赫 Patent office] Target of 4117-11H6 correction
Non-molecular piezoelectric material
Item 6 of the detailed description of the invention in the description, the contents of the
correction 1 “Method and” on page 4 line 4 of the specification is corrected to “J in the
method. 2MjfE ') [line 20) rIiiPVF2 sample] is corrected to-"αmpvy2 trial". ・)EndPage:
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