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WO2010026871A1 - Materiau piezo-electrique organique, oscillateur ultrasonore et sonde ultrasonore - Google Patents

Materiau piezo-electrique organique, oscillateur ultrasonore et sonde ultrasonore Download PDF

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Publication number
WO2010026871A1
WO2010026871A1 PCT/JP2009/064433 JP2009064433W WO2010026871A1 WO 2010026871 A1 WO2010026871 A1 WO 2010026871A1 JP 2009064433 W JP2009064433 W JP 2009064433W WO 2010026871 A1 WO2010026871 A1 WO 2010026871A1
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group
ultrasonic
organic piezoelectric
general formula
piezoelectric material
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English (en)
Japanese (ja)
Inventor
理枝 藤澤
福坂　潔
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Konica Minolta Medical and Graphic Inc
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Konica Minolta Medical and Graphic Inc
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Priority to JP2010527749A priority Critical patent/JP5459216B2/ja
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B8/00—Diagnosis using ultrasonic, sonic or infrasonic waves
    • A61B8/42—Details of probe positioning or probe attachment to the patient
    • A61B8/4272—Details of probe positioning or probe attachment to the patient involving the acoustic interface between the transducer and the tissue
    • A61B8/4281—Details of probe positioning or probe attachment to the patient involving the acoustic interface between the transducer and the tissue characterised by sound-transmitting media or devices for coupling the transducer to the tissue
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R17/00—Piezoelectric transducers; Electrostrictive transducers
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret

Definitions

  • the present invention relates to an organic piezoelectric material and an ultrasonic probe, and more particularly to an organic piezoelectric material containing a compound having a mesogenic group, an ultrasonic transducer using the organic piezoelectric material, and an ultrasonic probe.
  • acoustic devices such as microphones and speaker diaphragms, various thermal sensors, pressure sensors, measuring devices such as infrared detectors, ultrasonic probe, vibration sensors that detect mutations such as genes and proteins with high sensitivity, etc.
  • Organic piezoelectric materials having piezoelectricity and pyroelectricity that can be used to convert heat and mechanical stimulation into electrical energy are known.
  • the pyroelectric material a so-called inorganic material in which 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 is subjected to polarization treatment.
  • Piezoelectric materials are widely used. However, these inorganic piezoelectric materials have characteristics such as high elastic stiffness, high mechanical loss coefficient, high density and high dielectric constant.
  • organic piezoelectric materials such as polyvinylidene fluoride (hereinafter abbreviated as “PVDF”) and polycyanovinylidene (hereinafter abbreviated as “PVDCN”) have also been developed (see, for example, Patent Document 1).
  • PVDF polyvinylidene fluoride
  • PVDCN polycyanovinylidene
  • This organic piezoelectric material is excellent in workability such as thin film and large area, can be made in any shape and shape, and has features such as low elastic modulus and low dielectric constant, so it can be used as a sensor. When considering the use of, it has a feature that enables highly sensitive detection.
  • organic piezoelectric materials have low heat resistance and lose their pyroelectric properties at high temperatures, and the physical properties such as elastic stiffness are greatly reduced.
  • polyurea resin compositions composed of urea bonds have a large dipole moment of urea bonds and excellent temperature characteristics as resins, and thus various studies have been made as organic piezoelectric materials.
  • vapor deposition polymerization method in which a polyurea film is formed by simultaneously evaporating a diisocyanate compound such as 4,4′-diphenylmethane diisocyanate (MDI) and a diamine compound such as 4,4′-diaminodiphenylmethane (MDA). It is disclosed (for example, see Patent Documents 2 and 3).
  • the polyurea resin composition prepared by the vapor deposition polymerization method described in these documents has a non-uniform molecular weight of the oligomer or high molecular weight product. In this state, the polyurea resin composition is formed. For this reason, the dipole moment of the urea bond cannot be fully utilized, and further improvement has been demanded as an organic piezoelectric material.
  • the present invention has been made in view of the above-mentioned problems and circumstances, and the object thereof is an organic piezoelectric material having piezoelectricity and pyroelectricity that has excellent piezoelectric characteristics and can convert heat and mechanical stimulation into electrical energy.
  • it is to provide an organic piezoelectric material ultrasonic transducer which is excellent in piezoelectric characteristics due to high orientation and is thermally stable, and an ultrasonic probe using the same.
  • An organic piezoelectric material comprising a compound represented by the following general formula (1):
  • R 1 -Q-A 1 -Y-Z [Wherein, R 1 represents a group selected from an aliphatic group, an aromatic group, and a heterocyclic group. Q represents a single bond or an oxygen atom. A 1 represents a mesogenic group. Y represents a urea group (—NHCONH—), a thiourea group (—NHCSNH—), a urethane group (—NHCOO—), a sulfamoyl group (—SO 2 NH—), or a carbonate group (—OCOO—). Z represents a group selected from an aliphatic group having 1 to 25 carbon atoms, an aromatic group, and a heterocyclic group. ] 2. 2. The organic piezoelectric material as described in 1 above, wherein R 1 in the general formula (1) represents an alkyl group having 1 to 20 carbon atoms.
  • organic piezoelectric material according to any one of 1 to 4, further comprising a compound represented by the following general formula (2).
  • R 21 represents a hydrogen atom or a methyl group.
  • p represents an integer of 5 or more.
  • B 1 represents an alkylene group or an oxyalkylene group
  • B 2 represents a mesogenic group
  • Z 2 represents a group selected from an aliphatic group having 1 to 25 carbon atoms, an aromatic group, and a heterocyclic group.
  • An ultrasonic transducer comprising an organic piezoelectric film containing the organic piezoelectric material according to any one of 1 to 5 above.
  • An ultrasonic probe comprising: an ultrasonic transmission transducer; and the ultrasonic transducer described in 7 above.
  • an organic piezoelectric material having piezoelectricity and pyroelectricity that is excellent in piezoelectric characteristics and capable of converting heat and mechanical stimulation into electrical energy.
  • the piezoelectric properties are excellent due to high orientation
  • a thermally stable organic piezoelectric material, an ultrasonic transducer using the same, and an ultrasonic probe could be provided.
  • the orientation is high, and not only the piezoelectricity and pyroelectricity are excellent, but also thermally stable. It can be effectively used as a highly versatile organic piezoelectric material.
  • R 1 represents a group selected from an aliphatic group, an aromatic group, and a heterocyclic group.
  • the “aliphatic group” in the present specification means an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an alkynyl group, which are substituted or unsubstituted, respectively.
  • aliphatic group represented by R 1 examples include an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, Dodecyl group, octadecyl group, etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group etc.), alkenyl group, cycloalkenyl group, alkynyl group (propargyl group etc.) can be mentioned.
  • alkyl group methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, Dodecyl group, octadecyl group, etc
  • aromatic group examples include phenyl group, naphthyl group, anthracenyl group and the like.
  • heterocyclic group examples include lysyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl.
  • R 1 is preferably an aliphatic group having 1 to 20 carbon atoms, more preferably an alkyl group having 3 to 20 carbon atoms, and still more preferably an alkyl group having 6 to 18 carbon atoms.
  • Q represents a single bond or an oxygen atom.
  • the single bond means that R 1 and A 1 are directly bonded.
  • a 1 represents a mesogenic group.
  • the mesogenic group in the present invention is a rigid unit essential for a compound exhibiting liquid crystallinity, and refers to a group in which two or more ring structures are connected directly or with a bonding group.
  • the mesogenic group represented by A 1 is, for example, a group represented by the following formulas (A-1) to (A-10).
  • Preferred mesogenic groups are groups between Q and Y represented by the following formulas (a-1) to (a-20).
  • Y represents a urea group (—NHCONH—), a thiourea group (—NHCSNH—), a urethane group (—NHCOO—), a sulfamoyl group (—SO 2 NH—), or a carbonate group (—OCOO—).
  • Y is preferably a urea group, a thiourea group, or a urethane group.
  • Examples of the substituent represented by Z include an alkyl group having 1 to 25 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, etc.), halogen Alkyl group (trifluoromethyl group, perfluorooctyl group etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group etc.), alkynyl group (propargyl group etc.), aromatic group (phenyl group, naphthyl group etc.), heterocyclic ring Groups (pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, triphoranyl group,
  • Z is preferably a substituent containing an asymmetric carbon, and is not particularly limited as long as it is a substituent containing at least one asymmetric carbon, but is represented by the following general formula (4) or general formula (5). Are preferred.
  • * represents an asymmetric carbon atom.
  • R 41 , R 42 and R 43 each represent a hydrogen atom or a substituent, but each does not become the same group.
  • substituents represented by R 41 , R 42 and R 43 include alkyl groups having 1 to 25 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group).
  • R 41 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a trifluoromethyl group, or a halogen atom, and still more preferably a methyl group, a trifluoromethyl group, a fluorine atom. Is an atom.
  • R 42 is preferably a methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, hexyl group, octyl group, dodecyl group or the like.
  • R 43 is preferably a hydrogen atom.
  • R 51 , R 52 , R 53 , R 54 , and R 55 each represent a hydrogen atom or a substituent, but R 51 and R 53 , and R 52 , R 54, and R 55 are not the same group.
  • Examples of the substituent represented by R 51 , R 52 , R 53 , R 54 , R 55 are specific examples of the substituent represented by R 41 , R 42 , R 43 in the general formula (4). The substituents mentioned are mentioned.
  • R 51 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a trifluoromethyl group, or a halogen atom, still more preferably a methyl group, a trifluoromethyl group, or fluorine.
  • R 53 is preferably a hydrogen atom.
  • R 52 is preferably an alkyl group having 1 to 12 carbon atoms.
  • R 54 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a trifluoromethyl group, or a halogen atom, and still more preferably a methyl group, an ethyl group, or a trifluoro group.
  • R 55 is preferably a hydrogen atom or a fluorine atom.
  • the compound represented by the general formula (1) can be synthesized by a known method. For example, it can be synthesized with reference to the methods described in JP-A-61-47427 and JP-A-5-119304.
  • R 21 represents a hydrogen atom or a methyl group.
  • B 1 represents an alkylene group or an oxyalkylene group, and B 2 represents a mesogenic group.
  • the mesogenic group represented by B 2 has the same meaning as the mesogenic group represented by A 1 in the general formula (1).
  • p represents an integer of 5 or more.
  • P is preferably 5 to 5000, more preferably 5 to 2000, and particularly preferably 5 to 1000.
  • substituent represented by Z 2 include the examples given as specific examples of the substituent represented by Z in the general formula (1).
  • Z 2 preferably represents a group containing an asymmetric carbon.
  • the group containing an asymmetric carbon represented by Z 2 is not particularly limited as long as it is a group containing at least one asymmetric carbon, but is preferably represented by the following general formula (6) or general formula (7). It is a substituent represented.
  • R 61 , R 62 and R 63 each represent a hydrogen atom or a substituent, but each does not become the same group.
  • Examples of the substituent represented by R 61 , R 62 and R 63 include the examples given as examples of the substituent represented by R 41 , R 42 and R 43 in the general formula (4).
  • R 61 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a trifluoromethyl group, or a halogen atom, and still more preferably a methyl group, a trifluoromethyl group, a fluorine atom. Is an atom.
  • R 62 is preferably a methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group or the like.
  • R 63 is preferably a hydrogen atom.
  • R 71 , R 72 , R 73 , R 74 and R 75 each represent a hydrogen atom or a substituent, but R 71 and R 73 , and R 72 , R 74 and R 75 are not the same group.
  • Specific examples of the substituent represented by R 71 , R 72 , R 73 , R 74 and R 75 include the substituents represented by R 41 , R 42 and R 43 in the general formula (4). The substituents mentioned are mentioned.
  • R 71 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a trifluoromethyl group, or a halogen atom, still more preferably a methyl group, a trifluoromethyl group, or fluorine. Is an atom.
  • R 72 is preferably a methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group or the like.
  • R 73 is preferably a hydrogen atom.
  • R 74 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a trifluoromethyl group, or a halogen atom, and still more preferably a methyl group, an ethyl group, or a trifluoro group.
  • R 75 is preferably a hydrogen atom or a fluorine atom.
  • the compound represented by the general formula (2) can be synthesized by a known method. Specific examples of the synthesis can be synthesized by referring to the methods described in JP-A-2-124995, JP-A-2-232208, JP-A-5-132558, and the like. Although the specific example of a compound represented by General formula (2) below is given, this invention is not limited to these.
  • the mixing ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) is preferably a general formula for the compound represented by the general formula (1).
  • the proportion of the compound represented by (2) is 0 to 50%, more preferably 0 to 30% from the viewpoint of film forming properties and heat resistance.
  • Organic piezoelectric material of the present invention is represented by forming a film containing the compound represented by the general formula (1), or represented by the compound represented by the general formula (1) and the general formula (2).
  • An organic piezoelectric film is formed by forming a film containing a compound or by subjecting the film to further polarization treatment, and is used for an ultrasonic transducer.
  • the organic piezoelectric film when a stress is applied to the piezoelectric film, charges of opposite signs appear in proportion to both ends of the piezoelectric film, that is, an electric polarization phenomenon occurs, and conversely, the piezoelectric material is transmitted. It has the property (piezoelectric performance) that a distortion proportional to the occurrence of the electric field (applying an electric field) is generated.
  • a large piezoelectric effect is generated by polarization due to orientation freezing of the dipole moment of the polymer main chain or side chain.
  • the organic piezoelectric film is preferably formed by coating.
  • the coating method include spin coating, solvent casting, melt casting, melt press, roll coating, flow coating, printing, dip coating, and bar coating.
  • the compound represented by the general formula (1) is applied or formed in a temperature range in which the liquid crystal phase is exhibited or the compound represented by the general formula (2) is in a temperature range in which the liquid crystal phase is exhibited. It is preferable that the formed film may be further subjected to a polarization treatment described later.
  • any non-liquid crystal polymer compound may be mixed to improve the film formability.
  • a thermoplastic resin, a thermosetting resin, or a photocurable resin having a number average molecular weight of 1500 or more is used as the non-liquid crystal polymer compound.
  • thermoplastic resin any resin having a number average molecular weight of 1500 or more, preferably 1500 to 100,000 can be used without particular limitation. If the number average molecular weight of the thermoplastic resin is less than 1500, the glass transition temperature is too low, and the mechanical stability of the organic piezoelectric film may be lowered.
  • thermoplastic resin examples include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride- Vinylidene chloride copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-vinylidene chloride- Vinyl acetate copolymer, vinylidene chloride, polytetrafluoroethylene, polytetrafluorochloroethylene, polyvinylidene fluoride and other halogenated vinyl polymers or copolymers; polyvinyl alcohol, polyallyl alcohol, polyvinyl ether, polyallyl ether, etc.
  • Polymers or copolymers having an unsaturated bond in them Unsaturated nitrile polymers or copolymers such as acrylonitrile or methacrylonitrile polymers or copolymers, polycyanide vinylidene, malononitrile or fumaronitrile polymers or copolymers
  • thermosetting resin it is possible to use various types including those that are commercially available, such as epoxy adhesives and acrylic adhesives.
  • the photo-curable resin various kinds of resins including those that are commercially available such as an adhesive that is cured by visible light, UV light, electron beam, or the like can be used. These non-liquid crystalline polymer substances may be appropriately selected from the manufacturing method of the organic piezoelectric film and the required durability.
  • heat or photo-curable resin examples include, for example, epoxy adhesives, acrylic adhesives, unsaturated polyester adhesives, polyurethane adhesives, hot melt adhesives, and elastomer adhesives. .
  • a bisphenol A type is preferable as the main agent.
  • a main agent in which the bisphenol A portion is a bisphenol compound as shown below can also be used.
  • polyurethane adhesives examples include methylene bis (p-phenylene diisocyanate), tolylene diisocyanate, hexamethylene diisocyanate, 1-chlorophenyl diisocyanate, 1,5-naphthylene diisocyanate, thiodipropyl diisocyanate, ethylbenzene- ⁇ - as isocyanate components.
  • Examples include 2-di-isocyanate, 4,4,4-triphenylmethane triisocyanate, and the components that react with them include ethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, glycerol, hexanetriol, and xylylene diene. All, lauric acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, polyethylene glycol, polyp Propylene glycol, polyesters, polyamides, and the like.
  • the amount of the non-liquid crystalline polymer substance is 2 to 40% by mass, preferably 2 to 20% by mass with respect to the compound represented by the general formula (1).
  • the amount of the non-liquid crystalline polymer substance is less than 2% by mass, the film forming property of the liquid crystal layer may be deteriorated and the mechanical strength may be insufficient.
  • it exceeds 40% by mass unnecessary light scattering may occur, and the performance of the organic piezoelectric film may be deteriorated.
  • 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 supply is -1 to -20 kV
  • the current is 1 to 80 mA
  • the distance between the electrodes is 1 to 10 cm.
  • 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 corona discharge treatment when the corona discharge treatment is performed as the polarization treatment in the state where the solvent of the coating solution remains, it is sufficient to remove the volatile components of the solvent in order to avoid the danger of flammable explosion. It is necessary for safety to carry out with ventilation.
  • the organic piezoelectric film is used together with a substrate to constitute an ultrasonic transducer and an ultrasonic probe.
  • the selection of the substrate differs depending on the application and use method of the organic piezoelectric film of the present invention. It may be a plastic plate or film such as polyimide, polyamide, polyimide amide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate resin, cycloolefin polymer.
  • the surface 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.
  • PZT is preferably within the range of the formula of Pb (Zr 1-X Ti X ) O 3 (0.47 ⁇ X ⁇ 1).
  • Pb Zr 1-X Ti X
  • K potassium niobium tantalate
  • BaTiO 3 barium titanate
  • LiTaO 3 lithium tantalate
  • strontium titanate SrTiO 3
  • the composition of various ceramic materials can be selected as appropriate in terms of performance.
  • the ultrasonic transducer of the present invention has an organic piezoelectric film formed using the organic piezoelectric material of the present invention.
  • the ultrasonic transducer of the present invention is preferably an ultrasonic reception transducer for reception, together with an ultrasonic transmission transducer, For example, it is preferably used for a probe for an ultrasonic medical image diagnostic apparatus.
  • an ultrasonic vibrator has a pair of electrodes sandwiched between layers (or films) made of a film-like piezoelectric material (also referred to as “piezoelectric film”, “piezoelectric film”, or “piezoelectric layer”).
  • An ultrasonic probe is configured by arranging a plurality of transducers, for example, 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.
  • the transducer for ultrasonic reception according to the present invention is a transducer that is preferably used for a probe for an ultrasonic medical diagnostic imaging apparatus, and uses the organic piezoelectric material of the present invention as a piezoelectric film constituting the transducer.
  • the formed organic piezoelectric film is used.
  • the organic piezoelectric material or the organic piezoelectric film used for the ultrasonic receiving vibrator preferably has a relative dielectric constant of 10 to 50 at the thickness resonance frequency.
  • the relative dielectric constant is adjusted by adjusting the number, composition, degree of polymerization, etc. of polar functional groups such as the substituent R, CF 2 group, and CN group of the compound constituting the organic piezoelectric film, and the polarization described above. It can be done by processing.
  • the ultrasonic transmission vibrator according to the present invention is preferably made of a piezoelectric material having an appropriate relative dielectric constant in relation to the reception vibrator. Moreover, it is preferable to use a piezoelectric material excellent in heat resistance and voltage resistance.
  • ultrasonic transmission vibrator constituting material
  • various known organic piezoelectric materials and inorganic piezoelectric materials can be used.
  • organic piezoelectric material a polymer material similar to the above-described organic piezoelectric material for an ultrasonic receiving vibrator can be used.
  • Inorganic materials include quartz, lithium niobate (LiNbO 3 ), potassium tantalate niobate [K (Ta, Nb) O 3 ], barium titanate (BaTiO 3 ), lithium tantalate (LiTaO 3 ), or titanate Lead zirconate (PZT), strontium titanate (SrTiO 3 ), barium strontium titanate (BST), or the like can be used.
  • PZT is preferably Pb (Zr 1-n Ti n ) O 3 (0.47 ⁇ n ⁇ 1).
  • the ultrasonic transducer of the present invention is preferably produced by forming electrodes on both sides or one side of a piezoelectric film (layer) and subjecting the piezoelectric film to polarization treatment.
  • 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, and then the metal mainly composed of the above metal element and the above A metal material made of the above alloy, and further, if necessary, a part of insulating material is formed to a thickness of 1 to 10 ⁇ m by sputtering or other suitable methods.
  • 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.
  • 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.
  • An ultrasonic probe of the present invention is a probe for an ultrasonic diagnostic imaging apparatus that includes an ultrasonic transmission transducer and an ultrasonic reception transducer.
  • the ultrasonic receiving transducer according to the invention is used.
  • 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 ultrasonic receiving transducer of the present invention can be disposed on or in parallel with the ultrasonic 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 combined film thickness of the ultrasonic wave receiving transducer and the other polymer material is matched with a preferable reception frequency band in terms of 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. 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.
  • it can be suitably used in an ultrasonic medical image diagnostic apparatus having a configuration as shown in FIG.
  • FIG. 1 is a conceptual diagram showing a configuration of a main part of an ultrasonic medical image diagnostic apparatus including the ultrasonic probe of the present invention.
  • This ultrasonic medical diagnostic imaging apparatus transmits an ultrasonic wave to a subject such as a patient, and an ultrasonic probe in which piezoelectric vibrators that receive ultrasonic waves reflected by the subject as echo signals are arranged. (Probe).
  • 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
  • a transmission / reception control circuit is provided.
  • an image data conversion circuit for converting the echo signal received by the transmission / reception circuit into ultrasonic image data of the subject is provided. Further, a display control circuit for controlling and displaying the monitor with the ultrasonic image data converted by the image data conversion circuit and a control circuit for controlling the entire ultrasonic medical image diagnostic apparatus are provided.
  • the transmission / reception control circuit, the image data conversion circuit, and the display control circuit are connected to the control circuit, and the control circuit controls the operations of these units. Then, an electric signal is applied to each ultrasonic transducer of the ultrasonic probe to transmit an ultrasonic wave to the subject, and the reflected wave generated by the mismatch of acoustic impedance 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 taking advantage of the characteristics of the ultrasonic 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 Production of Organic Piezoelectric Film
  • a compound represented by the general formula (1) shown in Table 1 or a polymer compound and a general formula (2) is formed on a 25 ⁇ m polyimide film whose surface has been subjected to aluminum vapor deposition in advance. The compound was applied so that the dry film pressure was 7 ⁇ m and dried to obtain organic piezoelectric film-1 to organic piezoelectric film-18.
  • Comparative Piezoelectric Films A to C were produced using Comparative-A, Comparative-B and Comparative-C shown in Table 2 instead of the compound represented by the general formula (1).
  • the obtained organic piezoelectric film was evaluated for piezoelectric characteristics while being heated to room temperature and 100 ° C. by a resonance method. The results are shown in Table 1. The piezoelectric characteristics are shown as relative values with respect to the PVDF film measured at room temperature as 100%.
  • Example 2 Fabrication and evaluation of ultrasonic probe ⁇ Manufacture 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 0.03 ) Weighed to be Bi 4.01 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
  • the above-mentioned laminated laminated vibrator was laminated on the above-mentioned piezoelectric material for transmission, and a backing layer and an acoustic matching layer were installed to produce an ultrasonic probe.
  • a probe similar to the above-described ultrasonic probe was manufactured using the comparative piezoelectric film-A instead of the above-described laminated resonator for reception.
  • 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 ultrasonic probe including the receiving piezoelectric (body) laminated vibrator according to the present invention has a relative receiving sensitivity about 1.3 times that of the comparative example, and has a dielectric breakdown. It was confirmed that the strength was good and the piezoelectric properties were excellent. That is, it was confirmed that the ultrasonic wave receiving transducer of the present invention can be suitably used for a probe used in an ultrasonic medical image diagnostic apparatus as shown in FIG.

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Abstract

L'invention concerne un matériau piézo-électrique organique caractérisé en ce qu'il comprend un composé de formule générale (1). Le matériau selon l'invention présente d'excellentes propriétés piézo-électriques et il est stable sur le plan thermique. L'invention concerne également un oscillateur ultrasonore ainsi qu'une sonde ultrasonore. Formule générale (1) : R1-Q-A1-Y-Z
PCT/JP2009/064433 2008-09-02 2009-08-18 Materiau piezo-electrique organique, oscillateur ultrasonore et sonde ultrasonore Ceased WO2010026871A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1192761A (ja) * 1997-09-17 1999-04-06 Toshiba Corp 液晶素子
JP2003324222A (ja) * 2002-04-30 2003-11-14 Fuji Photo Film Co Ltd 圧電変換複合材料及びその製造方法
JP2005247815A (ja) * 2004-03-08 2005-09-15 Mitsubishi Gas Chem Co Inc 分岐型ポリフェノール化合物とその製造方法
JP2006016352A (ja) * 2004-07-02 2006-01-19 Chiba Univ 強誘電性を示す柱状液晶化合物
JP2007163894A (ja) * 2005-12-14 2007-06-28 Fujifilm Corp 液晶表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1192761A (ja) * 1997-09-17 1999-04-06 Toshiba Corp 液晶素子
JP2003324222A (ja) * 2002-04-30 2003-11-14 Fuji Photo Film Co Ltd 圧電変換複合材料及びその製造方法
JP2005247815A (ja) * 2004-03-08 2005-09-15 Mitsubishi Gas Chem Co Inc 分岐型ポリフェノール化合物とその製造方法
JP2006016352A (ja) * 2004-07-02 2006-01-19 Chiba Univ 強誘電性を示す柱状液晶化合物
JP2007163894A (ja) * 2005-12-14 2007-06-28 Fujifilm Corp 液晶表示装置

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