WO2010001634A1 - 有機圧電材料、超音波振動子及び超音波医用画像診断装置 - Google Patents
有機圧電材料、超音波振動子及び超音波医用画像診断装置 Download PDFInfo
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- WO2010001634A1 WO2010001634A1 PCT/JP2009/053373 JP2009053373W WO2010001634A1 WO 2010001634 A1 WO2010001634 A1 WO 2010001634A1 JP 2009053373 W JP2009053373 W JP 2009053373W WO 2010001634 A1 WO2010001634 A1 WO 2010001634A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/04—Combined thermoforming and prestretching, e.g. biaxial stretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/22—Details, e.g. general constructional or apparatus details
- G01N29/24—Probes
- G01N29/2437—Piezoelectric probes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
- B29C2071/022—Annealing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/16—PVDF, i.e. polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
Definitions
- the present invention relates to an organic piezoelectric material for constituting an ultrasonic vibrator suitable for high frequency and wide band, an ultrasonic vibrator using the same, and an ultrasonic medical image diagnostic apparatus.
- Ultrasound is a general term for sound waves of 16 kHz or higher, and can be examined non-destructively and harmlessly, so 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).
- an additional treatment such as a heat treatment below the melting point or a polarization method combining them.
- Patent Documents 2 and 3 when a piezoelectric body mainly composed of PVDF is produced by these known methods, although the piezoelectric characteristics are improved, the degree of crystallinity is high, so that flexibility, which is an advantage as an organic piezoelectric body, is lost. Instead, it becomes vulnerable.
- PVDF has a glass transition temperature below room temperature, so even when cooled from the heat treatment temperature to room temperature, the molecular motion is not sufficiently frozen, the film deforms according to the residual stress lurking inside, and the flatness is remarkably lost. That is, the processing suitability for a probe for ultrasonic diagnostic equipment is not sufficient.
- a new problem unique to the ultrasonic probe has been found that the reception sensitivity of the ultrasonic probe is lowered and the dielectric breakdown strength is lowered.
- the present invention has been made in view of the above problems and circumstances, and a solution to the problem is an organic piezoelectric material for forming an ultrasonic vibrator having excellent piezoelectric characteristics and suitable for a high frequency and a wide band.
- the present invention provides an ultrasonic probe and an ultrasonic medical image diagnostic apparatus.
- a film-like organic piezoelectric material wherein the organic piezoelectric material is heat-treated while applying tension at a temperature not lower than room temperature and not higher than 10 ° C. from the melting point of the organic piezoelectric material, and subsequently cooled to room temperature.
- the organic piezoelectric material is biaxially stretched or uniaxially stretched, and the stress applied to the organic piezoelectric material does not become zero after the stretching process is completed.
- the heat treatment is performed at a temperature of 100 ° C. or higher and 140 ° C. or lower while applying tension under a condition of 30 minutes or longer and within 10 hours, and subsequently ⁇ 15% or higher and + 10% in the direction of applying tension while cooling to room temperature.
- the organic piezoelectric material according to 1 or 2 which is subjected to the following relaxation treatment.
- the organic piezoelectric material is made of a copolymer of vinylidene fluoride and trifluoroethylene, and the ratio of vinylidene fluoride is 95 to 60 mol% and trifluoroethylene is 5 to 40 mol%. 4. The organic piezoelectric material according to any one of 1 to 3.
- 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.
- the ultrasonic transducer for transmission and the ultrasonic transducer for reception and either one or both of the ultrasonic transducers are the ultrasonic transducers described in 6 above, Ultrasonic medical diagnostic imaging device.
- an organic piezoelectric material for forming an ultrasonic transducer excellent in piezoelectric characteristics and heat resistance and suitable for high frequency and wide band, an ultrasonic probe using the same, and an ultrasonic medical image A diagnostic device can be provided.
- An ultrasonic receiving vibrator is an ultrasonic vibrator having an ultrasonic piezoelectric material used for a probe for an ultrasonic medical diagnostic imaging apparatus, and the ultrasonic piezoelectric material is mainly composed of vinylidene fluoride.
- the organic piezoelectric material is subjected to a heat treatment while applying tension at a temperature not lower than room temperature and not higher than 10 ° C. from the melting point, and subsequently subjected to relaxation treatment while being cooled to room temperature.
- the ultrasonic piezoelectric material is biaxially or uniaxially stretched, and tension is applied at a temperature of room temperature or higher and a melting point of ⁇ 10 ° C.
- Heat treatment followed by relaxation treatment while cooling to room temperature. Further, the heat treatment is performed while applying tension at a temperature of 100 ° C. or higher and 140 ° C. or lower for 30 minutes or longer and within 10 hours, and subsequently ⁇ 15% or higher in the direction in which tension is applied while cooling to room temperature + 10% % Relaxation treatment is preferable.
- the ultrasonic transducer of the present invention can be combined with other ultrasonic transducers to constitute an ultrasonic probe.
- the ultrasonic probe may be an organic piezoelectric material of the same type as the ultrasonic transducer of the present invention, or another known piezoelectric material, and the piezoelectric material may be an inorganic material or a polymer material, and further combined.
- the material may be another polymeric material that is not a piezoelectric material.
- the ultrasonic probe is preferably a laminated vibrator having two or more layers formed by bonding the above materials, and the laminated vibrator has a thickness of 20 to 600 ⁇ m.
- the method for manufacturing the ultrasonic vibrator of the present invention is a manufacturing method of a mode in which polarization treatment is performed either before or after formation of electrodes on both sides of an organic piezoelectric material, after formation of electrodes on one side or after formation of electrodes on both sides.
- polarization treatment is performed either before or after formation of electrodes on both sides of an organic piezoelectric material, after formation of electrodes on one side or after formation of electrodes on both sides.
- the said polarization process is a voltage application process.
- the ultrasonic transducer of the present invention can be combined with other ultrasonic transducers to constitute an ultrasonic probe.
- the ultrasonic probe has the ultrasonic vibrator of the present invention, and is a laminated vibrator having two or more layers formed by being bonded to a polymer material different from the organic piezoelectric material constituting the ultrasonic vibrator. It is preferable that the thickness of the laminated vibrator is 40 to 150 ⁇ m.
- the ultrasonic transducer of the present invention or an ultrasonic probe using the ultrasonic transducer can be suitably used for an ultrasonic medical image diagnostic apparatus.
- the ultrasonic transducer of the present invention is used for a probe for an ultrasonic medical diagnostic imaging apparatus including an ultrasonic transmission transducer and an ultrasonic reception transducer.
- an ultrasonic transducer 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 piezoelectric layer or a “piezoelectric film” made of a film-like piezoelectric material interposed therebetween.
- an ultrasonic probe is configured by one-dimensionally arranging a plurality of transducers.
- 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.
- 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 can be made thinner than an inorganic piezoelectric material made of ceramics, the organic piezoelectric material is characterized in that it can be used as a vibrator corresponding to transmission and reception of higher frequencies.
- the organic piezoelectric material has a relative dielectric constant of 10 to 50 at a thickness resonance frequency. Adjustment of the relative dielectric constant is performed by CF 2 contained in a compound constituting the organic piezoelectric material. It can be carried out by adjusting the quantity, composition, degree of polymerization, etc. of polar functional groups such as groups and CN groups, and polarization treatment described later.
- the organic piezoelectric material constituting the 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 is relaxed while it is heat-treated while applying tension at a temperature not lower than room temperature and not higher than 10 ° C. from the melting point, with the polymer material as a main constituent, and subsequently cooled to room temperature. It can be made by processing.
- the organic piezoelectric material containing vinylidene fluoride according to the present invention is used as a vibrator, it is formed into a film shape, 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 crystalline form with spontaneous polarization only when it is made into a film, but in order to further improve the characteristics, a process for aligning the molecular arrangement should be added. Is useful. Examples of means include stretching film formation and polarization treatment.
- the stretching film forming method various known methods can be employed. For example, 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 end portion when heat-treating a film-like material, it is preferable to place the end portion near a predetermined temperature by supporting the end with a chuck, a clip or the like in order to efficiently and uniformly heat the film surface.
- the relaxation treatment is more effective for the flatness against the shrinkage during heating.
- the relaxation treatment here refers to changing 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.
- 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 amount of relaxation treatment in the present invention is about 10% in length when the stretched direction is determined to be positive, and about 15% in order to follow slack when the film stretches during cooling, and is subjected to negative relaxation treatment. Do. Further processing may cause stretching during cooling and may cause film breakage.
- the end is supported by a chuck, a clip, etc.
- the upper limit is a temperature 10 ° C. lower than the melting point of the film. It is preferable to place it near the temperature.
- the melting point is 150 ° C. to 180 ° C., and therefore, it is preferable to perform heat treatment at a temperature of 100 ° C. or more and 140 ° C. or less.
- the longer the time is, the longer the effect is expressed and the longer the effect is exhibited, the longer the crystal growth is promoted. However, since the saturation occurs with time, it is practically about 10 hours and at most about day and night.
- Polarization treatment As a polarization treatment method in the polarization treatment according to the present invention, a conventionally known method such as DC voltage application treatment, AC voltage application treatment, or corona discharge treatment 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. .
- 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.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PMMA polymethyl methacrylate
- 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 alone, or a rare earth halide may be used.
- the vibrator having the piezoelectric material according to the present invention is manufactured by forming electrodes on both surfaces or one surface of a piezoelectric film (layer) and polarizing the piezoelectric film.
- 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.
- these electrodes can be formed by screen printing, dipping, or thermal spraying using a conductive paste in which fine metal powder and low-melting glass are mixed.
- a piezoelectric element can be obtained by supplying a predetermined voltage between the electrodes formed on both surfaces of the piezoelectric film to polarize the piezoelectric film.
- the ultrasonic probe according to the present invention is used for a probe for an ultrasonic medical image diagnostic apparatus including an ultrasonic transmission transducer and an ultrasonic reception transducer.
- both the 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 receiving transducer of the present invention can be arranged on or in parallel with the transmitting transducer.
- the structure for laminating the ultrasonic receiving transducer of the present invention on the ultrasonic transmitting transducer is good, and in this case, the ultrasonic receiving transducer of the present invention is another high-frequency transducer.
- the film thickness of the receiving vibrator and the other polymer material be matched to a preferable receiving frequency band in terms of probe design. In view of a practical ultrasonic medical image diagnostic apparatus and biological information collection from a practical frequency band, 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. Also, 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.
- the ultrasonic probe according to the present invention can be used for various types of ultrasonic diagnostic apparatuses.
- an ultrasonic probe probe
- piezoelectric body transducers that transmit ultrasonic waves to a subject such as a patient and receive ultrasonic waves reflected from the subject as echo signals is arranged
- An ultrasonic medical diagnostic imaging 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. Then, an electrical signal is applied to each piezoelectric vibrator of the ultrasonic probe to transmit an ultrasonic wave to the subject, and the reflected wave caused by acoustic impedance mismatch inside the subject is detected by the ultrasonic probe. Receive at.
- the transmission / reception circuit corresponds to “means for generating an electric signal”
- the image data conversion circuit corresponds to “image processing means”.
- the ultrasonic diagnostic apparatus by utilizing the characteristics of the ultrasonic wave receiving vibrator excellent in piezoelectric characteristics and heat resistance of the present invention and suitable for high frequency and wide band, the image quality and its An ultrasonic image with improved reproduction and 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. Thereafter, the solvent was dried at 50 ° C. to obtain a film (organic piezoelectric material) having a thickness of about 140 ⁇ m and a melting point of 155 ° C.
- MEK Ethyl methyl ketone
- sample 2 As with sample 1, a film (organic piezoelectric material) having a thickness of about 140 ⁇ m was stretched 4 times at room temperature. The tension in the direction of the stretching axis at the end of the 4-times stretching was 2.2 N per unit width (mm). Next, the distance between chucks in the direction of the stretching axis was shortened while heating the stretching machine to 135 ° C. and controlling the tension to be 0.1 N / mm. Sample 2 was obtained by performing heat treatment under tension control for 1 hour after the temperature in the stretching machine reached 135 ° C. Thereafter, the amount of remanent polarization was determined in the same manner as Sample 1.
- Example 2 (Fabrication and evaluation of the probe) (Production of piezoelectric material for transmission) Component raw materials CaCO 3 , La 2 O 3 , Bi 2 O 3 and TiO 2 , and subcomponent raw materials MnO are prepared, and for the component raw materials, the final composition of the components is (Ca 0. 97 La 0.0 3 . ) Bi 4 . Weighed to be 01 Ti 4 O 15 . Next, pure water was added, mixed in a ball mill containing zirconia media in pure water for 8 hours, and sufficiently dried to obtain a mixed powder. The obtained mixed powder was temporarily molded and calcined in air at 800 ° C. for 2 hours to prepare a calcined product.
- the piezoelectric ceramic raw material powder having a particle diameter of 100 nm was obtained by changing the pulverization time and pulverization conditions. 6% by mass of pure water as a binder is added to each piezoelectric ceramic raw material powder having a different particle diameter, press-molded to form a plate-shaped temporary molded body having a thickness of 100 ⁇ m, and this plate-shaped temporary molded body is vacuum-packed and then 235 MPa. It shape
- 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.
- 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.
- a sound 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 sensitivity was evaluated as good when the decrease in sensitivity was within 1% before the load test, more than 1% and less than 10%, and 10% or more as bad.
- 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. That is, it was confirmed that the ultrasonic transducer of the present invention can be suitably used for a probe used in an ultrasonic medical image diagnostic apparatus.
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Abstract
Description
本発明の超音波振動子は、超音波送信用振動子と超音波受信用振動子と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。
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体材料は、上記高分子材料を主たる構成成分として室温以上、融点から10℃低い温度以下の温度において、張力をかけながら熱処理され、続いて室温まで冷却される間に弛緩処理をされて作製することができる。
本発明に係る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、交流電圧印加処理又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又はフィルムを用いることができる。また、これらの素材の表面をアルミニウム、金、銅、マグネシウム、珪素等で覆ったものでもよい。またアルミニウム、金、銅、マグネシウム、珪素単体、希土類のハロゲン化物の単結晶の板又はフィルムでもかまわない。
本発明に係る圧電材料を有する振動子は、圧電体膜(層)の両面上又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。当該電極は、金(Au)、白金(Pt)、銀(Ag)、パラジウム(Pd)、銅(Cu)、ニッケル(Ni)、スズ(Sn)などを主体とした電極材料を用いて形成する。
本発明に係る超音波探触子は、超音波送信用振動子と超音波受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。
本発明に係る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。また当該超音波探触子に電気信号を供給して超音波を発生させるとともに、当該超音波探触子の各圧電体振動子が受信したエコー信号を受信する送受信回路と、送受信回路の送受信制御を行う送受信制御回路を備えていることが好ましい。
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。その後、50℃にて溶媒を乾燥させ、厚さ約140μm、融点155℃のフィルム(有機圧電材料)を得た。
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。なお、試料8については、切り出す方向を直交させて評価を行った。
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。同様に、厚み共振周波数付近の抵抗値のピーク周波数P、コンダクタンスのピーク周波数Sをそれぞれ求めたとき、下記式にて電気機械結合定数kt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。
(探触子の作製と評価)
(送信用圧電材料の作製)
成分原料であるCaCO3、La2O3、Bi2O3とTiO2、及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。次に、純水を添加し、純水中でジルコニア製メディアを入れたボールミルにて8時間混合し、十分に乾燥を行い、混合粉体を得た。得られた混合粉体を、仮成形し、空気中、800℃で2時間仮焼を行い仮焼物を作製した。次に、得られた仮焼物に純水を添加し、純水中でジルコニア製メディアを入れたボールミルにて微粉砕を行い、乾燥することにより圧電セラミックス原料粉末を作製した。微粉砕においては、微粉砕を行う時間および粉砕条件を変えることにより、それぞれ粒子径100nmの圧電セラミックス原料粉末を得た。それぞれ粒子径の異なる各圧電セラミックス原料粉末にバインダーとして純水を6質量%添加し、プレス成形して、厚み100μmの板状仮成形体とし、この板状仮成形体を真空パックした後、235MPaの圧力でプレスにより成形した。次に、上記の成形体を焼成した。最終焼結体の厚さは20μmの焼結体を得た。なお、焼成温度は、それぞれ1100℃であった。抗電界の1.5倍以上の電界を1分間印加して分極処理を施した。
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(有機圧電材料)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。その後、上記と同様に分極処理をした。
Claims (7)
- フィルム状の有機圧電材料であって、該有機圧電材料が、室温以上、かつ該有機圧電材料の融点から10℃低い温度以下の温度で、張力をかけながら熱処理され、続いて室温まで冷却される間に弛緩処理されて作製されることを特徴とする有機圧電材料。
- 前記有機圧電材料が、二軸延伸処理ないしは一軸延伸処理され、該延伸処理終了後に該有機圧電材料にかかる応力が0になることなく、該有機圧電材料が、室温以上、かつ該有機圧電材料の融点から10℃低い温度以下の温度において張力をかけながら熱処理され、続いて室温まで冷却される間に弛緩処理されて作製されることを特徴とする請求の範囲第1項に記載の有機圧電材料。
- 前記熱処理が、100℃以上140℃以下の温度で30分以上10時間以内の条件で張力をかけながら行われ、続いて室温まで冷却される間に張力をかけた方向に-15%以上+10%以下の弛緩処理をされることを特徴とする請求の範囲第1項又は第2項に記載の有機圧電材料。
- 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の共重合体からなり、フッ化ビニリデンが95~60モル%、トリフルオロエチレン5~40モル%の比率の範囲であることを特徴とする請求の範囲第1項~第3項のいずれか1項に記載の有機圧電材料。
- 前記有機圧電材料の電気機械結合定数が0.3以上であることを特徴とする請求の範囲第1項~第4項のいずれか1項に記載の有機圧電材料。
- 請求の範囲第1項~第5項のいずれか1項に記載の有機圧電材料を用いる超音波振動子であって、該有機圧電材料が超音波振動子の長辺方向と弛緩処理をされた方向とが平行になるように作製されたことを特徴とする超音波振動子。
- 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の範囲第6項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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JP2010518942A JP5533651B2 (ja) | 2008-07-03 | 2009-02-25 | 有機圧電材料の製造方法、超音波振動子及び超音波医用画像診断装置 |
US13/000,358 US20110105903A1 (en) | 2008-07-03 | 2009-02-25 | Organic piezoelectric material, ultrasonic vibrator, and ultrasonic image diagnosis apparatus for medical application |
US13/890,573 US20130241101A1 (en) | 2008-07-03 | 2013-05-09 | Method for producing an organic piezoelectric material shaped in a film |
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US8449466B2 (en) * | 2009-05-28 | 2013-05-28 | Edwards Lifesciences Corporation | System and method for locating medical devices in vivo using ultrasound Doppler mode |
US10939905B2 (en) | 2016-08-26 | 2021-03-09 | Edwards Lifesciences Corporation | Suture clips, deployment devices therefor, and methods of use |
JP7112492B2 (ja) * | 2018-07-13 | 2022-08-03 | 古野電気株式会社 | 超音波撮像装置、超音波撮像システム、超音波撮像方法および超音波撮像プログラム |
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2009
- 2009-02-25 WO PCT/JP2009/053373 patent/WO2010001634A1/ja active Application Filing
- 2009-02-25 JP JP2010518942A patent/JP5533651B2/ja not_active Expired - Fee Related
- 2009-02-25 US US13/000,358 patent/US20110105903A1/en not_active Abandoned
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2013
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JPS5914911B2 (ja) * | 1979-03-20 | 1984-04-06 | ウエスタ−ン エレクトリツク カムパニ−,インコ−ポレ−テツド | 分極ポリビニリデン弗化物フイルムとその製法 |
JPS5780602A (en) * | 1980-11-05 | 1982-05-20 | Matsushita Electric Ind Co Ltd | Method of producing piezoelectric or pyroelectric film |
JPS58186984A (ja) * | 1982-04-26 | 1983-11-01 | Japan Synthetic Rubber Co Ltd | 高分子圧電フイルムの製造方法及び装置 |
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US20130241101A1 (en) | 2013-09-19 |
JPWO2010001634A1 (ja) | 2011-12-15 |
JP5533651B2 (ja) | 2014-06-25 |
US20110105903A1 (en) | 2011-05-05 |
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