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Specification 1 and title of the invention Piezoelectric or company pyroelectric element Polymer
Silane coupling agent layer having a general formula YR8iX + on the surface of a film having
piezoelectricity or pyroelectricity, provided that chlorine bonded to silicon silicon atom, A
piezoelectric or pyroelectric element characterized in that a metal thin film electrode is formed
through an alkoxy group, an acetoxy group, and Y represents a vinyl group,-.
2,% claim scope
3. Detailed Description of the Invention The present invention relates to a piezoelectric or
pyroelectric element. Polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyvinyl
fluoride, polyvinyl chloride, polymethyl methacrylate, large nylon 11, etc. and those having a
ferroelectric powder filled in a resin matrix are polarized In these materials, great piezoelectricity
and pyroelectricity are observed. These piezoelectric and pyroelectric substances are used as
piezoelectric elements and pyroelectric elements by providing electrodes. The properties
required for the electrode are: (1) good electrical conductivity, (2) excellent moisture resistance,
(3) excellent adhesion to piezoelectric and pyroelectric substances, and by external contact (4)
inexpensive and easy to install, etc. In addition to the above four conditions, the electrode of the
piezoelectric element is durable against vibration for a long time (5). There is a demand for (6) a
small mass. It is known that, as an electrode satisfying such conditions, it is made by palladium,
gold, complex, nickel, zinc, aluminum or other 9 metals or their mixture t's, sputtering, plating or
thermocompression bonding. However, contact with the outside can not be avoided when the
piezoelectric or pyroelectric element is incorporated into the system, and if the polymer
piezoelectric pyroelectric material is If! When using a thin film with a large area of Im, it is not
possible to avoid shaking and working at the time of handling, and the 4iFK piezoelectric element
necessarily involves mechanical vibration due to the expansion and contraction of the element
itself. It is necessary to satisfy the condition of (5) in order to provide the durability against the
above. Furthermore, the environmental impact used EndPage: 1 can not be ignored. Since
electrodes used for piezoelectric and pyroelectric elements are generally extremely thin films,
they necessarily accompany deterioration of the electrodes due to oxidation and corrosion in
high temperature and humidity, and the condition of (2) is set to give moisture resistance thereto.
The adhesion and moisture resistance of the electrode used in the prior art, which is required to
be satisfied 9, have not been sufficient. In addition, in the case of a smooth oriented film with a
highly crystalline surface such as polyvinylidene fluoride film, for example, the adhesion to metal
is poor, and in some cases, it may peel off when rubbed with a finger and does not withstand
long-time vibration. There is a disadvantage that only an unstable electrode can be obtained. In
addition, when trying to form a fine 'pattern on the electrode of polymer piezoelectric material or
pyroelectric material by etching etc., the electrode formed by the conventional evaporation,
sputtering, plating etc. remarkably promotes the deterioration of the electrode, for example, the
adhesion deterioration 1 In order to compensate for such defects, there are corona treatment,
surface treatment with organic and inorganic chemicals, and sand blasting, but the effect is not
sufficient even in the treatment of this town, and this is still the case. It is not preferable that a
high-performance piezoelectric material or a non-electric material can not be obtained because a
high voltage can not be applied at the time of the reduction of the withstand voltage, for example,
the polarization due to the treatment such as, for example.
As a method to compensate for other adhesive defects, an adhesive layer of epoxy resin, acrylic
resin, etc. is provided on the surface of a film or sheet of polymeric piezoelectric material or
pyroelectric material, and metal thin film electrodes are deposited and sputtered through this
adhesive layer. The method of providing by plating etc. is also known. However, this method has
stress loss due to the adhesive layer and ignores the influence of dielectric constant and Young's
modulus, and further, the drop of the 8 / N ratio is not prevented at the output side of the signal.
Moreover, when it is used for a pyroelectric element, the heat conduction between the electrode
and the non-electrostatic film is deteriorated, so that the response is slow9, and the electrical loss
due to the dielectric constant of the adhesive layer can not be ignored. In this crying, by applying
a metal thin film electrode to the surface of a film or sheet having high polymer piezoelectricity
or pyroelectricity through a silane coupling agent layer, the piezoelectric pyroelectricity is hardly
deteriorated and it is extremely effective. An object of the present invention is to provide a nine
piezoelectric or pyroelectric element which is durable without causing peeling even for a long
time operation and which is excellent in moisture resistance. The piezoelectric element or the
pyroelectric element of the present invention will be described with reference to the drawings,
wherein l is, for example, polyfluorinated vinyl IJ den or composite piezoelectric material
(polymer piezoelectric and piezoelectric inorganic particles, or polymer matrix and piezoelectric
inorganic particles A polymer film or composite film which exhibits extremely high
piezoelectricity and pyroelectricity by applying a positive electrode operation such as the
following A thin film electrode 3 is provided. The silane coupling agent in the present invention
can be of the general formula YR81X3 and X is a hydrolyzable ρ group (eg chlorine, alkoxy
group, acetoxy group etc.) bonded to a silicon atom, Y Examples of the rubber-bonding agent
include vinyl, epoxy, methacrylic, amino, mercapto and the like, which may be, for example,
vinyltrichlorosilane, vinyltriethoxysilane, vinyltris2β-methoxyethoxynosilane, r- Glycidoxypropyl
trimethoxysilane, r-methacroxyloxy brovir trimethoxysilane, N-β (aminoethyl) γaminopropyltrimethoxy 7silane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane , R-W9
tritrimethoxysilane, γ-aminopropyltriethoxysilane Include emissions they may be mixed and
used alone or two or more kinds of silane coupling agents. The formation of the silane coupling
agent layer in the present invention can be performed by any method, for example, by immersing
a polymer film or composite sheet exhibiting piezoelectricity or pyroelectricity in a solution in
which the silane coupling agent is dissolved in alcohol or the like. Or by spray application or the
Cover of silane coupling agent! [The thickness of the film may be appropriately selected
depending on the thickness, material, etc. of the polymer film or composite sheet exhibiting
piezoelectricity and pyroelectricity, but in the case of a thin film piezoelectric element, there is no
stress loss due to the covering film. It is desirable to be as thin as possible within the required
limits, taking into account the influence of the dielectric constant and the EndPage: 2 ratio. In the
case of the pyroelectric element, the thickness should be the minimum necessary to improve the
heat conduction between the metal thin film electrode and the pyroelectric film, to make the
response K quickly, and to avoid the electrical loss due to the dielectric constant of the coating
film. desirable. The piezoelectric or non-electric element according to the present invention is
manufactured, for example, as follows. After applying a piezoelectric treatment to a polymer film
that exhibits piezoelectricity in advance by applying a polarization treatment such as polyvinyl
chloride fluoride, etc. K, apply an ethanol solution in which a silane coupling agent is dissolved,
dry it, and deposit it in metal film By providing the electrodes, it is possible to obtain a
piezoelectric or pyroelectric element. When a composite of a polymer piezoelectric material and
piezoelectric inorganic particles is used as a polymer piezoelectric material, a metal thin film
electrode is provided via a silane coupling agent before the polarization treatment is detected,
and this metal thin film electrode is used. The element can also be obtained by using a
polarization treatment. Examples of metal thin film electrode materials used in the present
invention include gold, platinum, copper, lead, nickel, chromium, zinc, aluminum, palladium and
the like, and any material may be used. Hereinafter, the present invention will be described in
detail by way of examples. Example 1 80 weight leaf parts of titanium and lead zirconate powder
having strong electric conductivity and polyvinylidene fluoride powder powder additives are
switched by a mixed wire roll heated to 165 ° C. and repeated 250 μm thickness The
composite sheet was taken out as a composite sheet of a certain degree and then biaxially
stretched by a multi-stage calender roll of 150 to 160 ° C. to form a composite sheet of about
100 μm. This composite sheet was subjected to a solution of 0.1% ethanol in γaminopropyltriethoxysilane, 0.1% ethanol solution in vinyltriethoxysilane, and 0.1% ethanol
solution in γ-glycidoxyprovirto's “lymethoxysilane”, respectively. After immersion, it was
dried at room temperature and a silane coupling agent was applied. (A sample person. B, C) This
was vapor-deposited under a vacuum of 5XIF'torr. The thickness of the deposited film was about
1 μ. When this steaming ip was subjected to a peeling test with an adhesive tape, the peeling of
the deposited film was completely ignored. On the other hand, as a comparative example, the
composite sheet was subjected to complex deposition in exactly the same manner as before sand
blasting with No. 1000 sandpaper, and was easily peeled off by an adhesive tape (sample, E).
A DC voltage of 140 KV /-is applied between the lower electrodes in a constant temperature bath
at 120 ° C. for 2 hours using the vapor deposition film as an electrode for 2 hours, and then the
room temperature is reached for 10 minutes with the voltage applied. It cooled, polarization was
completed and the piezoelectric element was obtained. The piezoelectric constant of this
piezoelectric element is d3, = 5.7 to 6.3 XI (r "C / N, d, = 21.9 to 228XIF" C / N, and the
piezoelectric element according to the present invention is not to be subjected to undercoating.
There was nothing worse than in comparison. Example 2 A piezoelectric film was obtained in
which three types of silane coupling agents were coated in the same manner as in Example 1
with an oblique axis stretched film (thickness 60 μm) of polyvinylidene fluoride. (Sample 1, 2.3)
This was vacuum deposited with aluminum under 5XIF '1 or vacuum. The thickness of the
deposited film was about 1 μ. Similarly, as a comparative example, a polyfluorinated vinylity film
as it was or this film surface / surface was sandblasted with a No. 1000 sandpaper, and
aluminum was vapor deposited just as before. (Samples 4 and 5) A resist was printed on the
vapor-deposited film of 5 f ¥ j (φ 13 su) 1 and etching of the electrode with nitric acid was
carried out. It peeled off. Next, apply a DC voltage of 600 KVAx to the upper and lower electrodes
n11 for 2 hours in an isothermal bath at 100 ° C. using the aluminum deposition film as an
electrode for the deposited film of 4ef and cool it to room temperature for 10 minutes while
applying the voltage. To obtain a piezoelectric element. This piezoelectric element has the
characteristics '31' '87 to 9.4 X IF 12 C / N, d' = 18, 5-19. As a result, the piezoelectric device of
the present invention was not inferior to the sample 5 at all. The piezoelectric element of the
present invention was replaced with a piezoelectric element in a pickup of a commercial record
player, and used for record performance, and was used for a total of 1000 hours or more, but no
change in voice and shape was observed. On the other hand, in the case of the sample 5 which
had EndPage: 3 and which had not been coated with an ani coat, the sensitivity decreased in
about a half hour, and in the case where it was used for 100 hours, the deposited film peeled off
in places.
4 is a cross-sectional view V of the piezoelectric or pyroelectric element according to the present
invention. 1: Piezoelectric or pyroelectric substance, 2: silane coupling agent liquid coating, 3:
metal thin film electrode. Attorney Patent Attorney General Kensuke Chika (1 other) EndPage: 4
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