WO2010106924A1 - 有機圧電材料の延伸処理方法、有機圧電材料の製造方法、超音波振動子、超音波探触子および超音波医用画像診断装置 - Google Patents
有機圧電材料の延伸処理方法、有機圧電材料の製造方法、超音波振動子、超音波探触子および超音波医用画像診断装置 Download PDFInfo
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- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
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- H—ELECTRICITY
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
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- the present invention relates to an organic piezoelectric material stretching method and a manufacturing method for manufacturing an organic piezoelectric material constituting an ultrasonic vibrator suitable for high frequency and wide band, and ultrasonic waves using the organic piezoelectric material manufactured thereby.
- the present invention relates to a transducer, an ultrasonic probe, and an ultrasonic medical image diagnostic apparatus.
- Ultrasound is generally referred to as a sound wave of 16 kHz or higher, and can be examined non-destructively and harmlessly, so that it is applied to various fields such as defect inspection and disease diagnosis.
- an ultrasonic diagnosis that scans the inside of a subject with ultrasound and images the internal state of the subject based on a reception signal generated from a reflected wave (echo) of the ultrasound from the inside of the subject.
- a device In this ultrasonic diagnostic apparatus, an ultrasonic probe that transmits and receives ultrasonic waves to and from a subject is used.
- a transducer that generates a received signal by receiving a reflected wave of an ultrasonic wave generated by a difference in acoustic impedance inside a subject is generated by mechanical vibration based on a transmission signal.
- An ultrasonic transmitting / receiving element configured to be provided is used.
- harmonic imaging that forms an image of the internal state in the subject using the harmonic frequency component, not the frequency (fundamental frequency) component of the ultrasound transmitted from the ultrasound probe into the subject
- Harmonic Imaging technology has (1) a low sidelobe level compared to the level of the fundamental frequency component, an improved S / N ratio (signal to noise ratio) and improved contrast resolution, and (2) frequency Increasing the beam width narrows and the lateral resolution is improved. (3) Since the sound pressure is small and the fluctuation of the sound pressure is small at a short distance, multiple reflections are suppressed. (4) Focus It has various advantages such as a greater depth speed compared to the case where the further attenuation is the same as the fundamental wave and the high frequency is the fundamental wave.
- This ultrasonic probe for harmonic imaging requires a wide frequency band from the frequency of the fundamental wave to the frequency of the harmonic, and its lower frequency range is used for transmission to transmit the fundamental wave. Is done.
- the frequency region on the high frequency side is used for reception for receiving harmonics (see, for example, Patent Document 1).
- the ultrasonic probe disclosed in Patent Document 1 receives an ultrasonic wave that is applied to a subject, transmits an ultrasonic wave into the subject, and is reflected and returned within the subject. It is an acoustic probe.
- the ultrasonic probe transmits a fundamental wave composed of ultrasonic waves having a predetermined center frequency, which is composed of a plurality of arranged first piezoelectric elements having a predetermined first acoustic impedance, into the subject. , And a first piezoelectric layer responsible for receiving the fundamental wave of the ultrasonic waves reflected back within the subject.
- a higher harmonic wave of ultrasonic waves reflected and returned from the subject which includes a plurality of second piezoelectric elements arranged with a predetermined second acoustic impedance smaller than the first acoustic impedance.
- a second piezoelectric layer responsible for receiving waves is provided.
- the second piezoelectric layer is overlaid on the entire surface of the first piezoelectric layer on the side where the ultrasonic probe is applied to the subject. Therefore, the ultrasonic probe can transmit and receive ultrasonic waves in a wide frequency band with such a configuration.
- the fundamental wave in harmonic imaging is preferably a sound wave having the narrowest possible bandwidth.
- the piezoelectric element responsible for this is a so-called polarization treatment of a single crystal such as quartz, LiNbO 3 , LiTaO 3 , KNbO 3 , a thin film such as ZnO or AlN, or a sintered body such as Pb (Zr, Ti) O 3. Ceramic inorganic piezoelectric materials are widely used. Piezoelectric elements that detect received waves on the high frequency side require a wider bandwidth sensitivity, and these inorganic materials are not suitable.
- an organic piezoelectric body using an organic polymer material such as polyvinylidene fluoride (hereinafter also abbreviated as “PVDF”) is known (see, for example, Patent Document 2).
- PVDF polyvinylidene fluoride
- this organic piezoelectric material has greater flexibility, and can be made into any shape and form, making it easier to reduce the thickness, area, and length. Have.
- This organic piezoelectric element cannot be said to have sufficient piezoelectric properties as compared to an inorganic piezoelectric element, and in order to increase the molecular orientation and the amount of polarization, It is known that it is effective to perform an additional treatment such as a heat treatment below the melting point or a polarization method combining them (see, for example, Patent Documents 2 and 3).
- Patent Document 4 when a piezoelectric body mainly composed of PVDF is produced by these known methods, although the piezoelectric characteristics are surely improved, the crystallinity is high (see Patent Document 4), which may be an advantage as an organic piezoelectric body. Not only is flexibility lost, but it becomes fragile.
- PVDF has a glass transition temperature below room temperature, so even if it is cooled from the heat treatment temperature to room temperature, the molecular motion is not sufficiently frozen, and even if the residual stress hidden inside is removed, the film deforms with time. End up.
- the ultrasonic probe's reception sensitivity is lowered or the dielectric breakdown strength is lowered. A new problem specific to the child was found (see Patent Documents 5 and 6).
- the present invention has been made in view of the above-described problems and situations, and the solution is to produce an organic piezoelectric material that is excellent in flatness, processing characteristics, and piezoelectric characteristics, and suitable for high frequency and wideband. It is an object to provide an organic piezoelectric material stretching method and manufacturing method, an ultrasonic transducer using the organic piezoelectric material manufactured thereby, and an ultrasonic medical diagnostic imaging apparatus.
- a primary stretching process for first stretching an unstretched organic piezoelectric material a heat treatment process for heat treating the first stretched organic piezoelectric material, and a cooling for second stretching while cooling the heat treated organic piezoelectric material to room temperature
- An organic piezoelectric material stretching method that sequentially performs the steps, From the primary stretching step to the cooling step, tension is not applied to the organic piezoelectric material so that the tension is not released, and the heat treatment is a heat treatment while keeping the tension within the range of 0.1 to 500 kPa.
- the primary stretching is biaxial stretching or uniaxial stretching, the stretching ratio is 2 to 10 times, and the secondary stretching treatment is a stretching treatment of stretching 10% or less in the longitudinal direction of stretching.
- An organic piezoelectric material stretching method is used.
- the organic piezoelectric material is made of a copolymer of vinylidene fluoride and trifluoroethylene, and the content ratio of the vinylidene fluoride is 95 to 60 mol% and the trifluoroethylene is 5 to 40 mol%. 4. The method for stretching an organic piezoelectric material according to any one of 1 to 3, wherein:
- a method for producing an organic piezoelectric material comprising subjecting an organic piezoelectric material produced by the method for stretching an organic piezoelectric material according to any one of 5.1 to 4 to polarization treatment.
- An ultrasonic vibrator having an organic piezoelectric material and an electrode manufactured by the method for manufacturing an organic piezoelectric material according to 6.5.
- An ultrasonic probe comprising the ultrasonic transducer according to 7.6.
- Ultrasound in which a means for generating an electrical signal and a plurality of transducers for receiving the electrical signal and transmitting an ultrasonic wave toward the subject and generating a reception signal corresponding to the reflected wave received from the subject are arranged
- the ultrasonic medical image diagnostic apparatus comprising: an ultrasonic probe; and an image processing unit that generates an image of the subject according to the reception signal generated by the ultrasonic probe.
- Comprising both a transmitting ultrasonic transducer and a receiving ultrasonic transducer, and one or both of the ultrasonic transducers is the ultrasonic transducer according to 6, Ultrasonic medical diagnostic imaging device.
- An ultrasonic transducer using the organic piezoelectric material and an ultrasonic medical image diagnostic apparatus can be provided.
- the present invention provides a primary stretching step for primary stretching of an unstretched organic piezoelectric material, a heat treatment step for heat-treating the first stretched organic piezoelectric material, and 2 during cooling the heat-treated organic piezoelectric material to room temperature.
- An organic piezoelectric material stretching method that sequentially performs a cooling process for performing a subsequent stretching process, From the primary stretching step to the cooling step, tension is not applied to the organic piezoelectric material to release the tension, and the heat treatment is a heat treatment while keeping the tension within the range of 0.1 to 500 kPa.
- the heat treatment is performed for 30 minutes within a temperature range of 100 to 140 ° C. while maintaining a tension so as to be within a range of 0.1 to 500 kPa. It is preferable that the heating process is performed within a time period of ⁇ 10 hours.
- the secondary stretching process performed while cooling to room temperature is a stretching process in which stretching is performed within a range of 10% or less in the stretching longitudinal direction. Preferably there is.
- the organic piezoelectric material is made of a copolymer of vinylidene fluoride and trifluoroethylene, and has a content ratio of 95 to 60 mol% for vinylidene fluoride and 5 to 40 mol% for trifluoroethylene. Is preferred. Furthermore, it is preferable that the organic piezoelectric material has an electromechanical coupling constant of 0.3 or more.
- the organic piezoelectric material stretching method of the present invention is an organic piezoelectric material stretching treatment method in which an unstretched organic piezoelectric material is first stretched and then heat treated, and the organic piezoelectric material is subjected to a primary stretching step. Without releasing the tension (without setting the tension to 0), the tension continues to be applied, and the tension along the stretching longitudinal direction is 0.1 to 500 kPa from the end of the primary stretching process to the end of the heat treatment.
- the heat treatment is preferably performed within a temperature range of 100 to 140 ° C. within a time period of 30 minutes to 10 hours while maintaining a tension so as to be within a range of 0.1 to 500 kPa. Subsequently, it is preferable to perform a stretching treatment of 10% or less in the stretching longitudinal direction while the heat-treated organic piezoelectric material is cooled to room temperature.
- the organic piezoelectric material according to the present invention is used for an ultrasonic vibrator
- the organic piezoelectric material is produced so that the long side direction of the ultrasonic vibrator and the stretched direction are perpendicular to each other. It is preferable. It is also preferable that the organic piezoelectric material is produced so that the long side direction of the ultrasonic vibrator is parallel to the stretched direction.
- the ultrasonic transducer can be suitably used for an ultrasonic medical image diagnostic apparatus.
- the ultrasonic medical image diagnostic apparatus comprising: an ultrasonic probe that has been performed; and an image processing unit that generates an image of the subject in accordance with the reception signal generated by the ultrasonic probe.
- the probe includes both an ultrasonic transducer for transmission and an ultrasonic transducer for reception, and either one or both of the ultrasonic transducers is the ultrasonic transducer of the present invention. preferable.
- the ultrasonic transducer of the present invention is an ultrasonic transducer that is used in a probe for an ultrasonic medical image diagnostic apparatus that includes an ultrasonic transmission transducer and an ultrasonic transmission transducer.
- the ultrasonic vibrator of the present invention is configured by arranging a pair of electrodes with a layer (or film) (hereinafter referred to as a piezoelectric layer) or a “piezoelectric film” made of a film-like piezoelectric material interposed therebetween,
- a layer or film
- piezoelectric film made of a film-like piezoelectric material interposed therebetween.
- An ultrasonic probe is configured by, for example, arranging a plurality of transducers one-dimensionally.
- a predetermined number of transducers in the major axis direction in which a plurality of transducers are arranged is set as the aperture, and the plurality of transducers belonging to the aperture are driven to converge the ultrasonic beam on the measurement site in the subject. And has a function of receiving reflected echoes of ultrasonic waves emitted from the subject by a plurality of transducers belonging to the aperture and converting them into electrical signals.
- Organic piezoelectric material as the constituent material of the piezoelectric material constituting the ultrasonic vibrator of the present invention can be adopted regardless of whether it is a low molecular material or a high molecular material.
- a high molecular organic piezoelectric material for example, polyvinylidene fluoride, a polyvinylidene fluoride copolymer, a polyvinylidene cyanide or a vinylidene cyanide copolymer, an odd-numbered nylon such as nylon 9 or nylon 11, or an aromatic Aromatic nylon, alicyclic nylon, polylactic acid, polyhydroxycarboxylic acids such as polyhydroxybutyrate, cellulose derivatives, polyurea and the like. From the viewpoint of good piezoelectric properties, processability, availability, etc., it is necessary to be a polymer organic piezoelectric material, particularly a polymer material mainly composed of vinylidene fluoride.
- the former copolymerization ratio is 60 to 99 mol%. Furthermore, it is preferably 85 to 99 mol%.
- a polymer containing 85 to 99 mol% of vinylidene fluoride and 1 to 15 mol% of perfluoroalkyl vinyl ether, perfluoroalkoxyethylene, perfluorohexaethylene, etc. is composed of an inorganic piezoelectric element for transmission and an organic piezoelectric element for reception. In combination with the element, it is possible to suppress the transmission fundamental wave and increase the sensitivity of harmonic reception.
- the organic piezoelectric material is advantageous in that it can be formed into a thin film as compared with an inorganic piezoelectric material made of ceramics, so that it can be a vibrator corresponding to transmission and reception of higher frequencies.
- the organic piezoelectric material preferably has a relative dielectric constant of 10 to 50 at the thickness resonance frequency, and the relative dielectric constant is adjusted by adjusting the CF 2 group or CN of the compound constituting the organic piezoelectric material. It can be carried out by adjusting the quantity, composition, polymerization degree, etc. of polar functional groups such as groups, and polarization treatment described later.
- the organic piezoelectric material constituting the ultrasonic vibrator of the present invention may be configured by laminating a plurality of polymer materials.
- the polymer material to be laminated the following polymer material having a relatively low relative dielectric constant can be used in addition to the above polymer material.
- the numerical value in parentheses indicates the relative dielectric constant of the polymer material (resin).
- the polymer material having a low relative dielectric constant is preferably selected according to various purposes such as adjusting the piezoelectric characteristics or imparting the physical strength of the organic piezoelectric material.
- the organic piezoelectric material according to the present invention has the above-described polymer material as a main constituent, and is a film that can be stretched at a temperature not lower than room temperature and not higher than 10 ° C. from the melting point. Uniaxial stretching treatment (primary stretching) is performed. And it can heat-treat, maintaining the tension
- an organic piezoelectric material containing a copolymer having vinylidene fluoride as a copolymerization component is used as a vibrator, it is formed into a film and then a surface electrode for inputting an electric signal is formed.
- a general method such as a melting method or a casting method can be used.
- a polyvinylidene fluoride-trifluoroethylene copolymer it is known that it has a crystal form with spontaneous polarization only when it is formed into a film.
- a solution obtained by dissolving the above polymer material in an organic solvent such as ethyl methyl ketone (MEK) is cast on a substrate such as a glass plate, and the solvent is dried at room temperature to obtain a film having a desired thickness.
- the film is stretched to a predetermined length at room temperature.
- the stretching can be performed in a uniaxial or biaxial direction so that the organic piezoelectric material having a predetermined shape is not destroyed.
- the draw ratio is 2 to 10 times, preferably 2 to 6 times.
- the melt flow rate at 230 ° C. is 0.03 g / min or less. More preferably, a high-sensitivity piezoelectric thin film can be obtained by using a polymer piezoelectric material of 0.02 g / min or less, more preferably 0.01 g / min or less.
- the organic piezoelectric material subjected to the primary stretching treatment is not released from the tension (the tension is not reduced to 0) after the primary stretching step, and the tension is continuously applied.
- the heat treatment is carried out while keeping the tension along the range of 0.1 to 500 kPa.
- the tension is continuously applied without releasing the tension, and the tension at that time is preferably 0.1 kPa or more.
- the organic piezoelectric material is heat-treated by supporting the end with a chuck, clip, etc. in order to efficiently and uniformly heat the film surface, and the temperature around 10 ° C lower than the melting point of the film. It is preferable to place it below.
- the melting point is 150 ° C. to 180 ° C.
- the tension along the stretching longitudinal direction is a tension along a direction parallel to the tension applied in the stretching process in the stretching process.
- the tension during the heat treatment needs to be in the range of 0.1 to 500 kPa from the viewpoint of finished flatness.
- the cooling step is a step of cooling the organic piezoelectric material by lowering the temperature of the heat-treated organic piezoelectric material to room temperature, and a secondary stretching process is performed while the organic piezoelectric material is cooled to room temperature.
- the secondary stretching process is a relaxation process.
- the relaxation treatment is to change the stress at both ends of the film while following the shrinkage or expansion force applied to the film in the process of cooling to room temperature after the heat treatment. As long as the film is not loosened and the flatness cannot be maintained, or the stress increases and breaks, the relaxation treatment can be expanded to the extent that it will not stretch in the direction of applying tension, even if it is shrunk so as to relieve stress. Also good.
- the stretched direction when the stretched direction is defined as plus, the length is about 10%, and when the film stretches during cooling, the second stage stretching is performed at most about 10% so as to follow the slack.
- secondary stretching treatment second-stage stretching
- FIG. 2 shows an example of a change in tension applied in each process of the present invention.
- the vertical axis represents tension
- the horizontal axis represents time
- a represents a primary stretching step
- b represents a heat treatment step
- c represents a cooling step.
- the organic piezoelectric material according to the present invention is polarized and used for an ultrasonic vibrator.
- a polarization treatment method in the polarization treatment a conventionally known method such as a DC voltage application treatment, an AC voltage application treatment, or a corona discharge treatment is used. Can be applied.
- the corona discharge treatment can be performed by using a commercially available apparatus comprising a high voltage power source and electrodes.
- the voltage of the high voltage power source is preferably ⁇ 1 to ⁇ 20 kV, the current is 1 to 80 mA, the distance between the electrodes is preferably 1 to 10 cm, and the applied voltage is preferably 0.5 to 2.0 MV / m. .
- electrodes needle-like electrodes, linear electrodes (wire electrodes), and mesh electrodes conventionally used are preferable, but the invention is not limited thereto.
- the selection of the substrate differs depending on the use and usage of the organic piezoelectric material according to the present invention.
- a plastic plate or film such as polyimide, polyamide, polyimide amide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate resin, or cycloolefin polymer is used. Can do.
- the surface of these materials may be covered with aluminum, gold, copper, magnesium, silicon or the like.
- a single crystal plate or film of aluminum, gold, copper, magnesium, silicon simple substance, or rare earth halide may also be used.
- An ultrasonic vibrator having an organic piezoelectric material according to the present invention is manufactured by forming electrodes on both sides or one side of a piezoelectric film (layer) having an organic piezoelectric material, and polarizing the piezoelectric film. Is.
- the electrode is formed using an electrode material mainly composed of gold (Au), platinum (Pt), silver (Ag), palladium (Pd), copper (Cu), nickel (Ni), tin (Sn), or the like. .
- a base metal such as titanium (Ti) or chromium (Cr) is formed to a thickness of 0.02 to 1.0 ⁇ m by sputtering.
- Electrodes can also be formed by screen printing, dipping, or thermal spraying using a conductive paste in which fine metal powder and low-melting glass are mixed, other than by sputtering.
- an ultrasonic transducer can be obtained by supplying a predetermined voltage between the electrodes formed on both sides of the piezoelectric film to polarize the piezoelectric film.
- the ultrasonic transducer of the present invention is used for an ultrasonic probe.
- the ultrasonic probe of the present invention preferably includes an ultrasonic transmission transducer and an ultrasonic reception transducer, and the ultrasonic transducer of the present invention is preferably used as an ultrasonic reception transducer.
- both transmission and reception of ultrasonic waves may be performed by a single transducer, but more preferably, the transducer is configured separately for transmission and reception in the probe.
- the piezoelectric material constituting the transmitting vibrator may be a conventionally known ceramic inorganic piezoelectric material or an organic piezoelectric material.
- the ultrasonic probe can arrange an ultrasonic receiving transducer on or in parallel with the transmitting transducer.
- a structure in which an ultrasonic wave receiving vibrator constituted by the ultrasonic vibrator of the present invention is laminated on an ultrasonic wave transmitting vibrator is preferable.
- the vibrator is laminated on the transmission vibrator in a form of being bonded onto another polymer material (a polymer (resin) film having a relatively low relative dielectric constant as a support, such as a polyester film). May be.
- the film thickness of the receiving vibrator and the other polymer material be matched to a preferable receiving frequency band in terms of the probe design.
- the film thickness is preferably 40 to 150 ⁇ m.
- the probe may be provided with a backing layer, an acoustic matching layer, an acoustic lens, and the like as described later.
- a probe in which vibrators having a large number of piezoelectric materials are two-dimensionally arranged can be used. A plurality of two-dimensionally arranged probes can be sequentially scanned to form a scanner.
- FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an ultrasonic probe.
- the ultrasonic probe 10 includes an ultrasonic vibrator having electrodes 5 on both sides of the transmitting piezoelectric material 1 and an ultrasonic vibrator having electrodes 5 on both sides of the receiving piezoelectric material 3 with the support 2 interposed therebetween. And an acoustic lens 6 and a backing layer on the outside of each ultrasonic transducer.
- the acoustic lens is arranged to focus the ultrasonic beam using refraction and improve the resolution.
- the acoustic lens converges ultrasonic waves and is in close contact with the living body to match the acoustic impedance of the living body (density ⁇ sound speed; (1.4 to 1.6) ⁇ 10 6 kg / m 2 ⁇ sec), It is a necessary condition that the reflection of ultrasonic waves can be reduced and that the ultrasonic attenuation amount of the lens itself is small.
- an acoustic lens conventionally made on the basis of a polymer material such as rubber is provided at a portion in contact with the human body to focus the ultrasonic beam.
- the lens material used here it is desirable that the sound velocity is sufficiently smaller than that of the human body, the attenuation is small, and the acoustic impedance is close to the value of the human skin.
- the lens material has a sound velocity sufficiently smaller than that of the human body, the lens shape can be made convex, and slipping can be performed safely when making a diagnosis, and if the attenuation is reduced, sensitivity is improved. If the ultrasonic impedance can be transmitted and received and the acoustic impedance is close to the value of the skin of the human body, the reflection will be small, in other words, the transmittance will be large. Because.
- a material constituting the acoustic lens as a material constituting the acoustic lens, conventionally known homopolymers such as silicon rubber, fluorosilicone rubber, polyurethane rubber, epichlorohydrin rubber, ethylene-propylene copolymer rubber obtained by copolymerizing ethylene and propylene Copolymer rubber etc. can be used. Of these, it is preferable to use silicon rubber.
- Examples of the silicon rubber used in the present invention include silicon rubber and fluorine silicon rubber.
- Silicon rubber is an organopolysiloxane having a molecular skeleton composed of Si—O bonds, and having a plurality of organic groups mainly bonded to the Si atom.
- the main component is methylpolysiloxane, and the entire organic 90% or more of the groups are methyl groups.
- a material in which a hydrogen atom, a phenyl group, a vinyl group, an allyl group or the like is introduced instead of the methyl group can also be used.
- the silicone rubber can be obtained, for example, by kneading a curing agent (vulcanizing agent) such as benzoyl peroxide with an organopolysiloxane having a high degree of polymerization, followed by heat vulcanization and curing.
- a curing agent vulcanizing agent
- benzoyl peroxide with an organopolysiloxane having a high degree of polymerization
- organic or inorganic fillers such as silica and nylon powder, and vulcanization aids such as sulfur and zinc oxide may be added.
- butadiene rubber examples include butadiene alone or a copolymer rubber mainly composed of butadiene and copolymerized with a small amount of styrene or acrylonitrile.
- butadiene rubber refers to a synthetic rubber obtained by polymerization of butadiene having a conjugated double bond.
- the butadiene rubber can be obtained by 1,4 or 1.2 polymerization of butadiene having a conjugated double bond alone.
- a butadiene rubber vulcanized with sulfur or the like can be used.
- An acoustic lens can be obtained by mixing silicon rubber and butadiene rubber and curing them.
- a vulcanizing agent such as benzoyl peroxide
- vulcanizing by heating and crosslinking (curing).
- Zinc oxide can accelerate vulcanization and shorten the vulcanization time without deteriorating lens characteristics.
- the mixing ratio of the silicone rubber and the butadiene rubber is preferably 1: 1 in order to obtain a material whose acoustic impedance is close to that of the human body and whose sound speed is smaller than that of the human body and less attenuated.
- the mixing ratio can be changed as appropriate.
- inorganic fillers such as silica, alumina, titanium oxide, and organic resins such as nylon are blended according to the purpose of sound speed adjustment, density adjustment, etc. You can also
- the ultrasonic probe is provided on the back surface of the ultrasonic transducer and includes a backing layer for the purpose of suppressing propagation of ultrasonic waves to the rear. Thereby, the pulse width can be shortened.
- the acoustic matching layer (also referred to as “ ⁇ / 4 layer”) is arranged in multiple layers in order to reduce the difference in acoustic impedance between the transducer and the living body and efficiently transmit and receive ultrasonic waves.
- the above-mentioned ultrasonic probe of the present invention can be used for various types of ultrasonic diagnostic apparatuses.
- an ultrasonic probe probe
- piezoelectric transducers that transmit ultrasonic waves to a subject such as a patient and receive ultrasonic waves reflected by the subject as echo signals is arranged
- An ultrasonic medical image diagnostic apparatus is preferred.
- an electric signal is supplied to the ultrasonic probe to generate an ultrasonic wave, and a transmission / reception circuit that receives an echo signal received by each piezoelectric vibrator of the ultrasonic probe, and transmission / reception control of the transmission / reception circuit It is preferable that a transmission / reception control circuit for performing the above is provided.
- the display control unit includes an image data conversion circuit that converts the echo signal received by the transmission / reception circuit into ultrasonic image data of the subject, and controls and displays the monitor with the ultrasonic image data converted by the image data conversion circuit.
- An ultrasonic medical image diagnostic apparatus including a circuit and a control circuit that controls the entire ultrasonic medical image diagnostic apparatus is preferable.
- a transmission / reception control circuit, an image data conversion circuit, and a display control circuit are connected to a control circuit, and the control circuit controls operations of these units.
- the transmission / reception circuit corresponds to “means for generating an electric signal”
- the image data conversion circuit corresponds to “image processing means”.
- the image quality and its reproduction / reproduction are compared with the prior art by making use of the characteristics of the ultrasonic transducer excellent in piezoelectric characteristics and heat resistance of the present invention and suitable for high frequency and wide band. An ultrasonic image with improved stability can be obtained.
- Example 1 Ethyl methyl ketone (hereinafter MEK) obtained by heating polyvinylidene fluoride copolymer powder (weight average molecular weight 290,000) having a molar ratio of vinylidene fluoride (hereinafter VDF) and trifluoroethylene (hereinafter 3FE) of 75:25 to 50 ° C. ), A solution dissolved in a 9: 1 mixed solvent of dimethylformamide (hereinafter DMF) was cast on a glass plate.
- MEK Ethyl methyl ketone
- the film was stretched 3.8 times at room temperature by a uniaxial stretching machine with a load cell capable of measuring the load applied to the chuck.
- the chuck was moved until the stress at the film edge reached 20 kPa. Subsequently, heat treatment was performed at 135 ° C. for 1 hour while controlling the distance between the chucks so that the stress was maintained at 100 kPa without removing the chuck. Then, it cooled to room temperature, performing the relaxation process (secondary extending
- the secondary stretching amount (relaxation amount) calculated from the chuck position was determined to be 9% stretching based on the length of the film after the heat treatment.
- the film thickness of the obtained heat-treated film was 43 ⁇ m.
- Gold / aluminum was vapor-deposited on both surfaces of the obtained film so that the surface resistance was 20 ⁇ or less to obtain a sample with a surface electrode.
- the electrode was subjected to polarization treatment while applying an AC voltage of 0.1 Hz at room temperature.
- the polarization treatment was performed from a low voltage, and the voltage was gradually applied until the electric field between the electrodes finally reached 100 MV / m.
- the final polarization amount was obtained from the residual polarization amount when the piezoelectric material was regarded as a capacitor, that is, the film thickness, the electrode area, and the charge accumulation amount with respect to the applied electric field, and Sample 1 of the present invention was obtained.
- Table 1 summarizes the primary stretching ratio of the sample, the tension immediately after the primary stretching, the heat treatment temperature, the heat treatment time, the tension during the heat treatment, and the secondary stretching amount (relaxation amount) in the cooling step.
- the electromechanical coupling constant kt was obtained by the following equation .
- an electromechanical coupling constant 0.3 or more is a practically favorable range.
- Example 2 (Preparation and evaluation of ultrasonic probe) Component raw materials CaCO 3 , La 2 O 3 , Bi 2 O 3 and TiO 2 , and subcomponent raw materials MnO are prepared.
- the final composition of the components is (Ca 0.97 La 0.03 ) Weighed to be Bi 4.01 Ti 4 O 15 .
- the obtained mixed powder was temporarily molded and calcined in the air at 800 ° C. for 2 hours to prepare a calcined product.
- piezoelectric ceramic raw material powder having a particle diameter of 100 nm was obtained by changing the pulverization time and pulverization conditions.
- the final sintered body had a thickness of 20 ⁇ m.
- the firing temperature was 1100 ° C.
- An electric field of 1.5 ⁇ Ec (MV / m) or more was applied for 1 minute to perform polarization treatment.
- an ultrasonic probe was prototyped by laminating a laminated receiving transducer on the above-described piezoelectric material for transmission, and installing a backing layer and an acoustic matching layer.
- a laminated resonator for reception using only a polyvinylidene fluoride copolymer film (organic piezoelectric film) was laminated on the above laminated resonator.
- a probe similar to the above-described ultrasonic probe was produced.
- the reception sensitivity is originating the fundamental frequency f 1 of 5 MHz, to determine the received relative sensitivity of 20MHz as 15 MHz, 4 harmonics as received second harmonic wave f 2 as 10 MHz, 3 harmonic.
- an acoustic intensity measurement system Model 805 (1 to 50 MHz) of Sonora Medical System, Inc. (Sonora Medical System, Inc: 2021 Miller Drive Longmont, Colorado (0501 USA)) was used.
- the dielectric breakdown strength was measured by multiplying the load power P by 5 times, testing for 10 hours, and then returning the load power to the standard to evaluate the relative reception sensitivity.
- the probe including the receiving piezoelectric (body) laminated vibrator according to the present invention has a relative receiving sensitivity about 1.2 times that of the comparative example, and the dielectric breakdown strength is It was confirmed to be good.
- the ultrasonic transducer of the present invention can be suitably used for an ultrasonic probe used in an ultrasonic medical image diagnostic apparatus.
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Abstract
Description
該1次延伸工程から冷却工程では有機圧電材料に張力を掛け続けて張力を解除せず、該熱処理は張力が0.1~500kPaの範囲内になるように保ちながらの加熱処理であることを特徴とする有機圧電材料の延伸処理方法。
該1次延伸工程から冷却工程では有機圧電材料に張力を掛け続けて張力を解除せず、該熱処理は張力が0.1~500kPaの範囲内になるように保ちながらの加熱処理であることを特徴とする。この特徴は、請求項1から請求項8に係る発明に共通する技術的特徴である。
本発明の超音波振動子は、超音波送信用振動子と超音波送信用振動子を具備する超音波医用画像診断装置用探触子(プローブ)に用いられる超音波振動子である。
本発明の超音波振動子を構成する圧電材料の構成材料としての有機圧電材料としては低分子材料、高分子材料を問わず採用でき、低分子の有機圧電材料であれば、例えば、フタル酸エステル系化合物、スルフェンアミド系化合物、フェノール骨格を有する有機化合物などが挙げられる。高分子の有機圧電材料であれば、例えば、ポリフッ化ビニリデン、あるいはポリフッ化ビニリデン系共重合体、ポリシアン化ビニリデンあるいはシアン化ビニリデン系共重合体あるはナイロン9、ナイロン11などの奇数ナイロンや、芳香族ナイロン、脂環族ナイロン、あるいはポリ乳酸や、ポリヒドロキシブチレートなどのポリヒドロキシカルボン酸、セルロース系誘導体、ポリウレアなどが挙げられる。良好な圧電特性、加工性、入手容易性等の観点から、高分子の有機圧電材料、特にフッ化ビニリデンを主成分とする高分子材料であることを要する。
本発明に係る有機圧電材料は、上記高分子材料を主たる構成成分として有し、室温以上、融点から10℃低い温度以下の温度において、延伸可能なフィルム状であり、まず、二軸延伸処理又は一軸延伸処理(1次延伸)される。そして、張力を上記一定の範囲に保ちながら熱処理され、続いて熱処理された有機圧電材料が室温まで冷却される間に二段階目の延伸(2次延伸)をして作製することができる。
延伸製膜の方法については、種々の公知の方法を採用することができる。例えば、上記高分子材料をエチルメチルケトン(MEK)などの有機溶媒に溶解した液をガラス板などの基板上に流延し、常温にて溶媒を乾燥させ、所望の厚さのフィルムを得て、このフィルムを室温で所定の倍率の長さに延伸する。当該延伸は、所定形状の有機圧電材料が破壊されない程度に一軸・二軸方向に延伸することができる。延伸倍率は2~10倍、好ましくは2~6倍である。
熱処理工程では、1次延伸処理された有機圧電材料を、1次延伸工程の後、張力を解除せず(張力を0にすることはなく)、張力は掛けた状態にして引き続き、延伸長手方向に沿った張力が0.1~500kPaの範囲内になるように保ちながら加熱処理する。
冷却工程は、熱処理された有機圧電材料の温度を室温まで低下させ有機圧電材料を冷却する工程であり、有機圧電材料を室温まで冷却する間に2次延伸処理を行う。
本発明に係る有機圧電材料は、分極処理されて超音波振動子に用いられるが、分極処理における分極処理方法としては、従来公知の直流電圧印加処理、交流電圧印加処理またはコロナ放電処理等の方法が適用され得る。
基板としては、本発明に係る有機圧電材料の用途・使用方法等により基板の選択は異なる。本発明においては、ポリイミド、ポリアミド、ポリイミドアミド、ポリエチレンテレフタラート(PET)、ポリエチレンナフタレート(PEN)、ポリメタクリル酸メチル(PMMA)、ポリカーボネート樹脂、シクロオレフィンポリマーのようなプラスチック板またはフィルムを用いることができる。
本発明に係る有機圧電材料を有する超音波振動子は、有機圧電材料を有する圧電体膜(層)の両面上または片面上に電極を形成し、その圧電体膜を分極処理することによって作製されるものである。
本発明の超音波振動子は、超音波探触子に用いられる。
音響レンズは、屈折を利用して超音波ビームを集束し分解能を向上するために配置される。
超音波探触子は、超音波振動子の背面に配置し、後方への超音波の伝搬を抑制することを目的としてバッキング層を備えることも好ましい。これにより、パルス幅を短くすることができる。
音響整合層(「λ/4層」ともいう。)は、振動子と生体間の音響インピーダンス差を少なくし、超音波を効率よく送受信するために多層配置される。
本発明の上記超音波探触子は、種々の態様の超音波診断装置に用いることができる。例えば、患者などの被検体に対して超音波を送信し、被検体で反射した超音波をエコー信号として受信する圧電体振動子が配列されている超音波探触子(プローブ)を備えている超音波医用画像診断装置が好ましい。
実施例1
フッ化ビニリデン(以下VDF)とトリフルオロエチレン(以下3FE)のモル比率が75:25であるポリフッ化ビニリデン共重合体粉末(重量平均分子量29万)を50℃に加熱したエチルメチルケトン(以下MEK)、ジメチルホルムアミド(以下DMF)の9:1混合溶媒に溶解した液をガラス板上に流延した。
上記のようにして得られた、電極付きの有機圧電材料を延伸方向に100mm、延伸方向と直交する方向に20mmの長方形に切り出した。切り出した圧電膜を透明なアクリル板の上に置き、金属板片を介して上から10kg/cm2(980kPa)の荷重で押しつけ、アクリル板側からの目視によって平面性を評価した。
B:しわがないが、電極および圧電体膜にヒビが入っており、実用上耐えない
C:しわがあり、電極および圧電体膜にヒビが入っており、実用上耐えない
[有機圧電材料の評価方法]
上記のようにして得られた電極付の試料の両面の電極にリード線を付け、アジレントテクノロジー社製インピーダンスアナライザ4294Aを用いて、25℃雰囲気下において、40Hzから110MHzまで等間隔で600点周波数掃引した。厚み共振周波数における比誘電率の値を求めた。
インピーダンスアナライザを用いて厚み共振周波数から電気機械結合定数を求める方法としては、電子情報技術産業協会規格JEITA EM-4501(旧EMAS-6100)圧電セラミック振動子の電気的試験方法に記載の円盤状振動子の厚みたて振動に4.2.6項に準拠している。上記評価結果を表1に示す。
(超音波探触子の作製と評価)
成分原料であるCaCO3、La2O3、Bi2O3とTiO2、および副成分原料であるMnOを準備し、成分原料については、成分の最終組成が(Ca0.97La0.03)Bi4.01Ti4O15となるように秤量した。
前記実施例1において作製した電子線照射済みのポリフッ化ビニリデン共重合体のフィルム(有機圧電体膜)と厚さ50μmのポリエステルフィルムをエポキシ系接着剤にて貼り合わせた積層振動子を作製した。
2 支持体
3 送信用圧電材料
4 バッキング層
5 電極
6 音響レンズ
10 超音波探触子
Claims (8)
- 未延伸の有機圧電材料を1次延伸する1次延伸工程、1次延伸された有機圧電材料に加熱処理を行う熱処理工程、熱処理された有機圧電材料を室温まで冷却する間に2次延伸処理する冷却工程を、順次行う有機圧電材料の延伸処理方法であって、
該1次延伸工程から冷却工程では有機圧電材料に張力を掛け続けて張力を解除せず、該熱処理は張力が0.1~500kPaの範囲内になるように保ちながらの加熱処理であることを特徴とする有機圧電材料の延伸処理方法。 - 前記加熱処理が100~140℃の温度範囲内であり、前記熱処理の時間が30分~10時間の範囲であることを特徴とする請求項1に記載の有機圧電材料の延伸処理方法。
- 前記1次延伸が二軸延伸又は一軸延伸であり、延伸倍率は2~10倍であり、2次延伸処理が延伸長手方向に10%以下延伸させる延伸処理であることを特徴とする請求項2に記載の有機圧電材料の延伸処理方法。
- 前記有機圧電材料が、フッ化ビニリデンとトリフルオロエチレンとの共重合体からなり、当該フッ化ビニリデンが95~60モル%、当該トリフルオロエチレンが5~40モル%の含有比率の範囲であることを特徴とする請求項1から3のいずれか1項に記載の有機圧電材料の延伸処理方法。
- 請求項1から4のいずれか1項に記載の有機圧電材料の延伸処理方法により製造される有機圧電材料に分極処理することを特徴とする有機圧電材料の製造方法。
- 請求項5に記載の有機圧電材料の製造方法によって製造される有機圧電材料および電極を有することを特徴とする超音波振動子。
- 請求項6に記載の超音波振動子を有することを特徴とする超音波探触子。
- 電気信号を発生する手段と、前記電気信号を受けて超音波を被検体に向けて送信し、前記被検体から受けた反射波に応じた受信信号を生成する複数の振動子が配置された超音波探触子と、前記超音波探触子が生成した前記受信信号に応じて、前記被検体の画像を生成する画像処理手段とを有する超音波医用画像診断装置において、前記超音波探触子が、送信用超音波振動子と受信用超音波振動子の両方を具備し、かつ、該超音波振動子のどちらか一方もしくは両方が、請求項6に記載の超音波振動子であることを特徴とする超音波医用画像診断装置。
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JP2011504809A JP5582136B2 (ja) | 2009-03-18 | 2010-03-05 | 有機圧電材料の延伸処理方法、有機圧電材料の製造方法、超音波振動子、超音波探触子および超音波医用画像診断装置 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014149179A (ja) * | 2013-01-31 | 2014-08-21 | Sekisui Chem Co Ltd | 漏洩検出器、漏洩位置特定方法および配管装置 |
WO2016159354A1 (ja) * | 2015-04-02 | 2016-10-06 | 株式会社イデアルスター | 圧電膜、およびその製造方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012205726A (ja) * | 2011-03-29 | 2012-10-25 | Toshiba Corp | 超音波プローブ及び超音波プローブの製造方法 |
JP2015112326A (ja) * | 2013-12-12 | 2015-06-22 | キヤノン株式会社 | プローブ、被検体情報取得装置 |
JP6626959B2 (ja) * | 2016-03-25 | 2019-12-25 | 富士フイルム株式会社 | 音響波プローブ用組成物、これを用いた音響波プローブ用シリコーン樹脂、音響波プローブおよび超音波プローブ、ならびに、音響波測定装置、超音波診断装置、光音響波測定装置および超音波内視鏡 |
JP6995669B2 (ja) | 2018-03-05 | 2022-01-14 | 株式会社クレハ | 圧電体フィルム、圧電体フィルムの製造方法、および、圧電体デバイス |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5723286A (en) * | 1980-07-18 | 1982-02-06 | Matsushita Electric Ind Co Ltd | Manufacture of film for piezoelectricity or pyroelectricity |
JPS5780602A (en) * | 1980-11-05 | 1982-05-20 | Matsushita Electric Ind Co Ltd | Method of producing piezoelectric or pyroelectric film |
JP2005213376A (ja) * | 2004-01-29 | 2005-08-11 | Mitsui Chemicals Inc | ポリ乳酸系樹脂と無機化合物からなる高分子圧電材料 |
JP2008187079A (ja) * | 2007-01-31 | 2008-08-14 | Tokai Rubber Ind Ltd | 電歪型アクチュエータ用誘電体エラストマー膜およびその製造方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3197538A (en) * | 1960-10-31 | 1965-07-27 | Pennsalt Chemicals Corp | Stretch orientation of polyvinylidene fluoride |
JPS5130595B2 (ja) * | 1972-04-06 | 1976-09-01 | ||
JPS5569902A (en) * | 1978-11-21 | 1980-05-27 | Kureha Chemical Ind Co Ltd | Preparing piezoelectric* electrically scorchable film |
JPS606220B2 (ja) * | 1979-04-11 | 1985-02-16 | 三菱油化株式会社 | ポリ弗化ビニリデンもしくは弗化ビニリデン共重合体の延伸薄膜製造法 |
US4510300A (en) * | 1982-04-08 | 1985-04-09 | E. I. Du Pont De Nemours And Company | Perfluorocarbon copolymer films |
US4510301A (en) * | 1982-06-01 | 1985-04-09 | E. I. Du Pont De Nemours And Company | Fluorocarbon copolymer films |
JPS5962115A (ja) * | 1982-10-01 | 1984-04-09 | Kureha Chem Ind Co Ltd | 誘電体フイルム |
US4577132A (en) * | 1983-07-05 | 1986-03-18 | Toray Industries, Inc. | Ultrasonic transducer employing piezoelectric polymeric material |
US4778867A (en) * | 1987-07-21 | 1988-10-18 | Seymour Pries | Ferroelectric copolymers of vinylidene fluoride and trifluoroethylene with increased Curie temperature and their methods of production |
JPH0542592A (ja) * | 1991-08-09 | 1993-02-23 | Shin Etsu Chem Co Ltd | ポリフツ化ビニリデン樹脂延伸フイルムの製造方法 |
JP2681032B2 (ja) * | 1994-07-26 | 1997-11-19 | 山形大学長 | 強誘電性高分子単結晶、その製造方法、およびそれを用いた圧電素子、焦電素子並びに非線形光学素子 |
JP3742574B2 (ja) * | 2001-09-10 | 2006-02-08 | 弘二 大東 | 強誘電性高分子膜の製造方法 |
JP5392090B2 (ja) * | 2007-11-21 | 2014-01-22 | コニカミノルタ株式会社 | 超音波受信用振動子、その製造方法、超音波探触子及び超音波医用画像診断装置 |
-
2010
- 2010-03-05 JP JP2011504809A patent/JP5582136B2/ja not_active Expired - Fee Related
- 2010-03-05 US US13/256,781 patent/US20120004555A1/en not_active Abandoned
- 2010-03-05 WO PCT/JP2010/053633 patent/WO2010106924A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5723286A (en) * | 1980-07-18 | 1982-02-06 | Matsushita Electric Ind Co Ltd | Manufacture of film for piezoelectricity or pyroelectricity |
JPS5780602A (en) * | 1980-11-05 | 1982-05-20 | Matsushita Electric Ind Co Ltd | Method of producing piezoelectric or pyroelectric film |
JP2005213376A (ja) * | 2004-01-29 | 2005-08-11 | Mitsui Chemicals Inc | ポリ乳酸系樹脂と無機化合物からなる高分子圧電材料 |
JP2008187079A (ja) * | 2007-01-31 | 2008-08-14 | Tokai Rubber Ind Ltd | 電歪型アクチュエータ用誘電体エラストマー膜およびその製造方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014149179A (ja) * | 2013-01-31 | 2014-08-21 | Sekisui Chem Co Ltd | 漏洩検出器、漏洩位置特定方法および配管装置 |
WO2016159354A1 (ja) * | 2015-04-02 | 2016-10-06 | 株式会社イデアルスター | 圧電膜、およびその製造方法 |
JP2016197626A (ja) * | 2015-04-02 | 2016-11-24 | 株式会社イデアルスター | 圧電膜、およびその製造方法 |
US10535811B2 (en) | 2015-04-02 | 2020-01-14 | Ideal Star Inc. | Piezoelectric film and process for producing same |
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