JPWO2009081681A1 - Polyurea resin composition, organic piezoelectric material, manufacturing method thereof, ultrasonic transducer and ultrasonic probe using the same - Google Patents

Abstract

An object of the present invention is to provide a resin composition and an organic piezoelectric material for forming an organic piezoelectric film having excellent piezoelectricity, and a method for producing the same. Moreover, it is providing the ultrasonic transducer | vibrator and ultrasonic probe using the organic piezoelectric material film | membrane formed using the said resin composition or organic piezoelectric material. The polyurea resin composition or the organic piezoelectric material of the present invention is a resin formed by a polymerization reaction between a macromonomer having at least two bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea. It is characterized by containing.

Description

  The present invention relates to a resin composition formed using polyurea and a macromonomer, an organic piezoelectric material, a method for producing the same, an ultrasonic transducer using the same, and an ultrasonic probe.

  Specifically, for example, acoustic devices such as microphones and diaphragms for speakers, various thermal sensors, pressure sensors, infrared detectors and other measuring devices, ultrasonic probe, mutations such as genes and proteins are highly sensitive The present invention relates to an organic piezoelectric material having piezoelectricity or pyroelectricity that can be used to convert heat or mechanical stimulus into electrical energy, such as a vibration sensor to detect.

As 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.

  Meanwhile, organic piezoelectric materials such as polyvinylidene fluoride (hereinafter abbreviated as “PVDF”) and polycyanovinylidene (hereinafter abbreviated as “PVDCN”) have also been developed (see Patent Document 1). 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. On the other hand, 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.

  In contrast to these limitations, 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. . For example, there is a so-called 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). (See Patent Document 2 and Patent Document 3). However, 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.

On the other hand, when a polyurea resin composition having a high degree of polymerization is synthesized by a solution polymerization method, since the resulting resin composition has a low elastic modulus and becomes a strong resin, improvements in film properties and handling properties are required. It was.
JP-A-6-216422 JP-A-2-284485 Japanese Patent Laid-Open No. 5-31399

  The present invention has been made in view of the above-described problems and circumstances, and its solution is to provide a resin composition, an organic piezoelectric material, and a method for producing the same for forming an organic piezoelectric film having excellent piezoelectricity. It is to be. Moreover, it is providing the ultrasonic transducer | vibrator and ultrasonic probe using the organic piezoelectric material film | membrane formed using the said resin composition or organic piezoelectric material.

  The above-mentioned problem according to the present invention is solved by the following means.

  1. A polyurea resin composition comprising a resin formed by a polymerization reaction between a macromonomer having at least two bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea.

  2. An organic piezoelectric material formed by a polymerization reaction of a macromonomer having at least two types of bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea.

  3. 3. The organic piezoelectric material as described in 2 above, wherein the polyurea has an aromatic condensed ring structure.

  4). 4. The organic piezoelectric material as described in 2 or 3 above, wherein the macromonomer has an aromatic condensed ring structure.

  5). 5. The organic piezoelectric material according to any one of 2 to 4, wherein a terminal of the chemical structure of the macromonomer is an isocyanate group.

  6). 5. The organic piezoelectric material according to any one of 2 to 4, wherein in the chemical structure of the macromonomer, a terminal is a group having active hydrogen.

  7). The method for producing an organic piezoelectric material according to any one of 2 to 6, wherein a macromonomer having at least two bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond, or an amide bond and a polyurea are produced. A method for producing an organic piezoelectric material comprising polymerizing.

  8). The method for producing an organic piezoelectric material according to any one of 2 to 6, wherein the macromonomer and polyurea are applied on a substrate and then polymerized by heating. .

  9. 7. The method for producing an organic piezoelectric material according to any one of 2 to 6, wherein a polyurea resin composition containing a resin formed by a polymerization reaction of the macromonomer and polyurea is applied on a substrate. A manufacturing method of an organic piezoelectric material characterized.

  10. An ultrasonic vibrator using the organic piezoelectric material according to any one of 2 to 6 above.

  11. An ultrasonic probe including an ultrasonic transmission transducer and an ultrasonic reception transducer, wherein the ultrasonic transducer using the organic piezoelectric material according to any one of 2 to 6 is ultrasonicated. An ultrasonic probe comprising a receiving transducer.

  An object of the present invention is to provide a resin composition, an organic piezoelectric material, and a method for producing the same for forming an organic piezoelectric film having excellent piezoelectricity. Moreover, it is providing the ultrasonic transducer | vibrator and ultrasonic probe using the organic piezoelectric material film | membrane formed using the said resin composition or organic piezoelectric material.

Conceptual diagram showing the configuration of the main part of an ultrasonic medical diagnostic imaging apparatus

Explanation of symbols

1 Receiving piezoelectric material (film)
2 Support 3 Piezoelectric material for transmission (film)
4 Backing layer 5 Electrode 6 Acoustic lens

  The polyurea resin composition and the organic piezoelectric material of the present invention comprise a resin formed by a polymerization reaction between a macromonomer having at least two bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea. It is a resin composition or an organic piezoelectric material contained. This feature is a technical feature common to the inventions according to claims 1 to 11.

  In the present application, the “macromonomer” has a polymerizable functional group such as an isocyanate group or a group having active hydrogen at least at one end of the molecular chain, and includes a urea bond, a urethane bond, an ester bond, A compound having two or more types of bonds selected from an ether bond and an amide bond.

  As an embodiment of the present invention, it is preferable that the polyurea has an aromatic condensed ring structure. Moreover, it is preferable that the said macromonomer is an aspect which has an aromatic condensed ring structure. Furthermore, in the chemical structure of the macromonomer, the terminal is preferably an isocyanate group or the terminal is a group having active hydrogen.

  The production method of the organic piezoelectric material of the present invention is preferably a production method of polymerizing a macromonomer having at least two bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and polyurea. Moreover, in the said manufacturing method, after apply | coating the said macromonomer and polyurea on a board | substrate, it is the method of superposing | polymerizing by heating, or the resin composition containing the resin formed by the polymerization reaction of the said macromonomer and polyurea. A method of coating on a substrate is preferred.

  The organic piezoelectric material of the present invention can be suitably used for an ultrasonic vibrator as an organic piezoelectric film. Furthermore, in an ultrasonic probe including an ultrasonic transmission transducer and an ultrasonic reception transducer, the ultrasonic transducer can be suitably used as an ultrasonic reception transducer.

  Hereinafter, the present invention, its components, and the best mode and mode for carrying out the present invention will be described in detail.

(Polyurea)
The polyurea used for the organic piezoelectric material of the present invention can be obtained by polycondensation of polyisocyanate and polyamine.

  Alternatively, polyurea may be synthesized by the method described in JP-A-61-203129 and JP-A-61-203130 using polyamine as a raw material.

  The polyisocyanate used as a raw material is, for example, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 9H. -Fluorene-2,7-diisocyanate, 9H-fluoren-9-one-2,7-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, tolylene-2,4-diisocyanate Narate, tolylene-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 1,5-diisocyanate Door naphthalene, and the like.

  Examples of the polyamine used as a raw material include 2,7-diamino-9H-fluorene, 3,6-diaminoacridine, acriflavine, acridine yellow, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-Diaminobenzophenone, bis (4-aminophenyl) sulfone, 4,4'-diaminodiphenyl ether, bis (4-aminophenyl) sulfide, 1,1-bis (4-aminophenyl) cyclohexane, 4,4'-diamino Diphenylmethane, 3,3′-diaminodiphenylmethane, 3,3′-diaminobenzophenone, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4- (phenyldiazenyl) benzene-1,3-diamine, 1,5 -Diaminonaphthalene, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,8-diaminonaphthalene, 1,3-diaminopropane, 1,3-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1, 5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, N, N-bis (3-aminopropyl) methylamine, 1,3-diamino-2-propanol, diethylene glycol bis (3-aminopropyl) ether, m-xylylenediamine, tetraethylenepentamine, 1,3-bis (aminomethyl) cyclohexane, benzoguanamine, 2,4-diamino-1,3,5-triazine, 2,4- Diamino-6-methyl-1,3,5-triazine, 6-chloro-2,4-diaminopyrimidine, 2-chloro 4,6-diamino-1,3,5-triazine. These polyamines may be reacted with phosgene or triphosgene to synthesize polyisocyanates and used as raw materials.

  The reaction between polyisocyanate and polyamine may be performed by solution polymerization, vapor deposition polymerization, or polymerization without solvent, but solution polymerization or polymerization without solvent is preferred.

  In the polymerization of polyisocyanate and polyamine, when the molar ratio at the time of polymerization is equimolar, the degree of polymerization becomes high and the solubility in a solvent is remarkably lowered, so the reaction with the macromonomer may not proceed sufficiently. . For this reason, it is preferable to carry out the reaction in a system in which either one of polyamine or polyisocyanate is excessive, and one is preferably 1.5 times by mole to 10 times by mole, more preferably 2.0 times the other raw material. It is a double mole to a 5-fold mole. At this time, when an excess of polyisocyanate is used as a raw material, polyurea having a main terminal group of an isocyanate group can be obtained. On the other hand, when an excess of polyamine is used as a raw material, a polyurea in which the main terminal group is an amino group can be obtained.

  As the solvent used for the reaction, it is necessary to use a highly polar solvent in order that the target polyurea has a high polarity and the polymerization proceeds efficiently. For example, it is preferable to select a highly polar aprotic solvent such as DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide), DMSO (dimethylsulfoxide), NMP (N-methylpyrrolidone), As long as the reaction substrate and target compound dissolve well, aliphatic hydrocarbons such as cyclohexane, pentane and hexane, aromatic hydrocarbons such as benzene, toluene and chlorobenzene, THF (tetrahydrofuran), diethyl ether, ethylene glycol diethyl It may be a solvent such as ethers such as ether, ketones such as acetone, methyl ethyl ketone, 4-methyl-2-pentanone, esters such as methyl propionate, ethyl acetate, butyl acetate, etc. May be.

  The polymerization temperature may be any temperature as long as the reaction proceeds, but is preferably -50 ° C to 50 ° C, more preferably -20 ° C to 30 ° C, and particularly preferably -20 ° C to 15 ° C.

  Polyurea may be isolated and purified, or the reaction solution may be reacted with the macromonomer as it is. Preferably, it is a method of performing isolation and purification by reprecipitation.

  For reprecipitation purification of polyurea, any means may be used, but a method in which a reaction solution is dropped into a poor solvent to precipitate or a method in which a poor solvent is added to the reaction solution to precipitate is preferable. The poor solvent may be any solvent as long as it does not dissolve polyurea, but is an aliphatic hydrocarbon such as cyclohexane, pentane or hexane, an aromatic hydrocarbon such as benzene, toluene or chlorobenzene, diethyl ether, Mention may be made of ethers such as ethylene glycol diethyl ether, esters such as methyl propionate, ethyl acetate and butyl acetate, and alcohols such as methanol, ethanol and propanol.

  The molecular weight of the polyurea is preferably 500 or more and 200,000 or less, more preferably 1,000 or more and 100,000 or less in consideration of solubility in a solvent in order to react with the macromonomer. The polyurea may have a molecular weight distribution, and the molecular weight distribution is preferably from 1.0 to 7.0, and more preferably from 1.0 to 6.0. The molecular weight is a weight average molecular weight obtained by measurement of gel permeation chromatography (hereinafter referred to as GPC).

  Specific examples of polyurea are given below, but the present invention is not limited thereto.

(Macromonomer)
The macromonomer according to the present invention is characterized by having at least two types of bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond.

  Preferably, it has at least two types of bonds selected from a urea bond, a urethane bond, an ester bond or an ether bond. More preferably, it has at least two types of bonds selected from a urea bond, a urethane bond or an ether bond.

  Since the macromonomer according to the present invention can introduce a plurality of bonds and linking groups having a dipole moment by sequentially condensing a monomer having a reactive group, it has been difficult to dissolve a resin composition. It is possible to adjust the property and rigidity by selecting the raw material. Moreover, since the influence of the residual monomer can be eliminated by using the macromonomer as a raw material, the heat resistance and piezoelectric characteristics as the piezoelectric material can be remarkably improved.

  Each combination will be described in detail below.

<Urea bond>
In general, the “urea bond” is represented by the general formula: —NR ₁ CONR ₂ —. In the present application, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group). Group, etc., preferably a hydrogen atom or an alkyl group having 5 or less carbon atoms.

  The urea bond may be formed by any means, but can be obtained by a reaction between an isocyanate and an amine. In addition, a hydroxyl group at the end or a group such as 1,3-bis (2-aminoethyl) urea, 1,3-bis (2-hydroxyethyl) urea, 1,3-bis (2-hydroxypropyl) urea, etc. The macromonomer may be synthesized using a urea compound substituted with an alkyl group having an amino group as a raw material.

  The isocyanate used as the raw material is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in the molecule, but diisocyanate is preferable.

  Examples of the polyisocyanate include 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 9H-fluorene- 2,7-diisocyanate, 9H-fluoren-9-one-2,7-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene -2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 1,5-diisocyanatona The array type, and the like.

  The amine used as a raw material is preferably a polyamine having two or more amino groups in the molecule, and most preferably a diamine. Examples of polyamines include 2,7-diamino-9H-fluorene, 3,6-diaminoacridine, acriflavine, acridine yellow, 2,2-bis (4-aminophenyl) hexafluoropropane, and 4,4′-diaminobenzophenone. Bis (4-aminophenyl) sulfone, 4,4′-diaminodiphenyl ether, bis (4-aminophenyl) sulfide, 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4- (phenyldiazenyl) benzene-1,3-diamine, 1,5-diaminonaphthalene, 1,3-phenylenediamine, 2,4-dia Minotoluene, 2,6-diaminotoluene, 1,8-diaminonaphthalene, 1,3-diaminopropane, 1,3-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, N, N-bis (3-aminopropyl) methylamine, 1,3-diamino-2-propanol, diethylene glycol bis (3-aminopropyl) ) Ether, m-xylylenediamine, tetraethylenepentamine, 1,3-bis (aminomethyl) cyclohexane, benzoguanamine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-methyl -1,3,5-triazine, 6-chloro-2,4-diaminopyrimidine, 2-chloro-4,6- Amino-1,3,5-triazine. These polyamines may be reacted with phosgene or triphosgene to synthesize polyisocyanates and used as macromonomer raw materials.

<Urethane bond>
In the present application, the “urethane bond” is represented by a general formula: —OCONR ₁ —. Here, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, etc.), preferably Is a hydrogen atom or an alkyl group having 5 or less carbon atoms, more preferably a hydrogen atom or a methyl group.

  The urethane bond may be formed by any means, but can be obtained by a reaction between an isocyanate and a hydroxyl group.

  The isocyanate used as a raw material is preferably a polyisocyanate having two or more isocyanate groups in the molecule, and more preferably a diisocyanate. As polyisocyanate, the polyisocyanate mentioned by the said urea bond can be mentioned.

  Examples of the compound having a hydroxyl group used as a raw material include polyols, amino alcohols, aminophenols, alkylaminophenols, and the like, preferably polyols or amino alcohols.

  The polyol is a compound having at least two hydroxyl groups in the molecule, and preferably a diol. Moreover, you may have an ester bond or an ether bond in a molecule | numerator. Examples of the polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, 1,4-cyclohexanedi Methanol, pentaerythritol, 3-methyl-1,5-pentanediol, poly (ethylene adipate), poly (diethylene adipate), poly (propylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), poly ( Neopentylene adipate) and the like.

  An amino alcohol is a compound having an amino group and a hydroxyl group in the molecule, and may further have an ether bond in the molecule. Examples of amino alcohol include aminoethanol, 3-amino-1-propanol, 2- (2-aminoethoxy) ethanol, 2-amino-1,3-propanediol, and 2-amino-2-methyl-1,3- Examples thereof include propanediol and 1,3-diamino-2-propanol.

<Amide bond>
In general, the “amide bond” is represented by the general formula: —CONR ₁ —. In the present application, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, etc.) A hydrogen atom or an alkyl group having 5 or less carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.

  The amide bond may be formed by any means, but can be obtained by reacting an acid chloride with an amine.

  The acid chloride used as a raw material is preferably a compound having two or more acid chlorides, and may be synthesized by reacting polycarboxylic acid as a raw material with thionyl chloride, phosphorus oxychloride, phosphorus trichloride or the like. Examples of the compound having two or more acid chlorides include isophthaloyl chloride, terephthaloyl chloride, trimelliyl chloride, succinyl chloride, malonyl chloride, glutaric acid chloride, suberoyl chloride, azela oil chloride, adipoyl chloride, and sebacoyl chloride. .

  The amine used as a raw material is preferably a polyamine having two or more amino groups in the molecule, and most preferably a diamine. Examples of the polyamine include the polyamines mentioned for the urea bond.

<Ester bond>
In the present application, the “ester bond” is represented by a general formula: —CO ₂ —.

  The ester bond may be formed by any means, but can be obtained by a reaction between an acid chloride and a polyol.

  The acid chloride used as a raw material is preferably a compound having two or more acid chlorides, and examples of the acid chloride include the acid chlorides mentioned above for the amide bond.

  The polyol used as a raw material is preferably a polyol having two or more hydroxyl groups in the molecule, and most preferably a diol. As a polyol, the polyol quoted by the said urethane bond can be mentioned.

  The macromonomer has a molecular weight of 350 to 10,000, but may have a molecular weight distribution because a dimer or trimer is generated at the stage of sequential synthesis. The molecular weight is a weight average molecular weight obtained by measurement of gel permeation chromatography (hereinafter referred to as GPC), preferably 400 to 5000, and more preferably 400 to 3000. The molecular weight distribution is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

  In addition, the measurement of molecular weight and molecular weight distribution can be performed based on the following method and conditions.

Solvent: 30 mM LiBr in N-methylpyrrolidone Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperAWM-H x 2 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample concentration: 1.0 g / L
Injection volume: 40 μl
Flow rate: 0.5 ml / min
Calibration curve: Standard polystyrene: PS-1 (manufactured by Polymer Laboratories) Mw = 580 to 2,560,000 calibration curves with 9 samples were used.

  In the present invention, since the macromonomer can be reacted with polyurea to obtain a resin composition having piezoelectric properties, at least one of the macromonomer terminals is preferably an isocyanate group or a group having active hydrogen. Examples of the group having active hydrogen include an amino group, a hydroxyl group, a carboxyl group, an imino group, and a thiol group, preferably an amino group, a hydroxyl group, or a carboxyl group, and more preferably an amino group or a hydroxyl group. It is.

(Synthesis of macromonomer)
A macromonomer is a method in which a compound having active hydrogen is used as a starting material, and a polyisocyanate and a compound having active hydrogen are alternately condensed. A compound having active hydrogen and a polyisocyanate are condensed alternately using polyisocyanate as a starting material. It is possible to synthesize by the method of letting.

  Examples of the compound having active hydrogen include the urea compounds substituted with an alkyl group having a hydroxyl group or an amino group at the terminal, polyamine, polyol, aminoalcohol, aminophenol, alkylaminophenol, and the like. As a starting material, a urea compound or polyamine substituted with an alkyl group having a hydroxyl group or an amino group at a terminal is preferable, and a polyamine having an aromatic condensed ring structure is more preferable. When used in the step of alternately condensing, amino alcohol or polyol is preferable.

  When polyisocyanate is used as a starting material, the starting material is preferably a polyisocyanate having an aromatic fused ring structure. A compound having active hydrogen at the terminal may be synthesized by condensing with a compound having active hydrogen, or a diamine may be formed by the method described in JP-A No. 5-115842.

  In the reaction of the polyisocyanate and the compound having active hydrogen, when at least one of the terminals is an isocyanate group, the polyisocyanate is preferably used in an amount of 1 to 10 moles, more preferably 1 with respect to the compound having active hydrogen. The molar ratio is from 5 to 5 moles, more preferably from 1 to 3 moles.

  In the reaction between the polyisocyanate and the compound having active hydrogen, when at least one of the terminals is active hydrogen, the compound having active hydrogen is preferably used in an amount of 1 to 10 moles, more preferably 1 with respect to the polyisocyanate. The molar ratio is from 5 to 5 moles, more preferably from 1 to 3 moles.

  The reaction temperature to be condensed is preferably as low as possible, and is −40 to 60 ° C., preferably −20 to 30 ° C., and more preferably −10 to 10 ° C. The reaction temperature may be a constant temperature from the start to the end of the reaction, or may be initially low and then increased.

  As the solvent used for the reaction, it is necessary to use a highly polar solvent in order that the target resin composition is highly polar and the polymerization proceeds efficiently. For example, it is preferable to select a highly polar aprotic solvent such as DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide), DMSO (dimethylsulfoxide), NMP (N-methylpyrrolidone), As long as the reaction substrate and target compound dissolve well, aliphatic hydrocarbons such as cyclohexane, pentane and hexane, aromatic hydrocarbons such as benzene, toluene and chlorobenzene, THF (tetrahydrofuran), diethyl ether, ethylene glycol diethyl It may be a solvent such as ethers such as ether, ketones such as acetone, methyl ethyl ketone, 4-methyl-2-pentanone, esters such as methyl propionate, ethyl acetate, butyl acetate, etc. May be.

  In order to advance the urethane bond formation efficiently, tertiary alkylamines such as N, N, N ′, N′-tetramethyl-1,3-butanediamine, triethylamine, tributylamine, 1,4-diazabicyclo [2. 2.2] Known urethane bond formation catalysts such as condensed amines such as octane and 1,8-diazabicyclo [5.4.0] unde-7-ene, and alkyltins such as DBTL, tetrabutyltin and tributyltin acetate Can be used.

  The amount of the catalyst used is preferably 0.1 to 30 mol% based on the monomer substrate in consideration of efficient reaction and reaction operation.

  The macromonomer may be isolated and purified, or the reaction solution may be reacted with polyurea as it is. Preferably, it is a method of performing isolation and purification by recrystallization or reprecipitation.

  The method for reprecipitation of the macromonomer is not particularly limited, but a method in which the macromonomer is dissolved in a good solvent and then dropped into a poor solvent for precipitation is preferable.

  The “good solvent” as used herein may be any solvent as long as it dissolves the macromonomer, but is preferably a polar solvent, specifically, DMF (N, N-dimethylformamide), DMAc. Examples thereof include highly polar aprotic solvents such as (N, N-dimethylacetamide), DMSO (dimethyl sulfoxide), and NMP (N-methylpyrrolidone).

  The “poor solvent” may be any solvent as long as it does not dissolve the macromonomer, but is an aliphatic hydrocarbon such as cyclohexane, pentane or hexane, or an aromatic hydrocarbon such as benzene, toluene or chlorobenzene. And ethers such as diethyl ether and ethylene glycol diethyl ether, esters such as methyl propionate, ethyl acetate and butyl acetate, and alcohols such as methanol, ethanol and propanol.

  Specific examples of the macromonomer are listed below, but the present invention is not limited thereto.

(Macromonomer synthesis example)
<Synthesis Example 1: Synthesis of Macromonomer (M-17)>
Under nitrogen atmosphere, 5.0 g of 9H-fluorene-2,7-diisocyanate was dissolved in 50 ml of THF, and 3.2 g of 3-aminopropanol dissolved in 30 ml of THF was slowly added dropwise at 0 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 1 hour to obtain a solution (A).

  13.0 g of 1,3-phenylene diisocyanate was dissolved in 65 ml of THF, and the solution (A) was added dropwise while heating the reaction solution to 70 ° C. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 5 hours, and then the solvent amount of the reaction solution was concentrated to 3/2 under reduced pressure. 12.5g of macromonomers (M-17) were obtained by adding the liquid mixture of ethyl acetate-heptane to the residue, stirring, removing the supernatant with decant and drying under reduced pressure. The weight average molecular weight by GPC measurement was 750, and molecular weight distribution was 2.0.

<Synthesis Example 2: Synthesis of Macromonomer (M-20)>
Under nitrogen atmosphere, 5.0 g of 9H-fluorene-2,7-diisocyanate was dissolved in 50 ml of THF, and 10.0 g of 2- (2-aminoethoxy) ethanol dissolved in 30 ml of THF at room temperature was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours. The residue was concentrated and then recrystallized to obtain 9.2 g of a macromonomer (M-35). 1H-NMR confirmed the target product.

<Synthesis Example 3: Synthesis of Macromonomer (M-27: n = 2)>
Under a nitrogen atmosphere, 20.0 g of diethylene glycol was dissolved in 100 ml of dimethyl sulfoxide, and the reaction solution was heated to 70 ° C. While maintaining 70 ° C., a solution obtained by dissolving 5.0 g of the macromonomer (M-17) obtained in Synthesis Example 1 in 50 ml of dimethyl sulfoxide was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for 2 hours and at 80 ° C. for 2 hours, and then the solvent amount of the reaction solution was concentrated to 3/2 under reduced pressure. To the residue, a mixed solution of ethyl acetate-heptane was added and stirred. The supernatant was removed by decantation and dried under reduced pressure to obtain 5.5 g of a macromonomer (M-27). The weight average molecular weight measured by GPC was 950, and the molecular weight distribution was 2.6.

(Aromatic condensed ring structure)
In order to improve the orientation of the resin composition, it is preferable that the polyurea or the macromonomer has at least one aromatic condensed ring structure as a partial structure. Examples of the aromatic condensed ring structure include naphthalene structure, quinoline structure, anthracene structure, phenanthrene structure, pyrene structure, triphenylene structure, perylene structure, fluoranthene structure, indacene structure, acenaphthylene structure, fluorene structure, fluoren-9-one structure, Examples thereof include a carbazole structure, a tetraphenylene structure, and a structure further condensed with these structures (for example, an acridine structure, a benzoanthracene structure, a benzopyrene structure, a pentacene structure, a coronene structure, a chrysene structure, etc.).

  Preferable aromatic condensed ring structures include structures of the following general formulas (1) to (4).

In the general formula (1), R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a substituent, and examples of the substituent 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., cycloalkyl group (cyclohexyl group, cyclopentyl group etc.), aryl group (phenyl group etc.), heterocyclic group (pyridyl group, thiazolyl group, oxazolyl) Group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sriphoranyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), alkoxy group (methoxy group, ethoxy group, propyloxy group, Pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclo Xyloxy group etc.), aryloxy group (phenoxy group etc.), acyloxy group (acetyloxy group, propionyloxy group etc.), alkoxycarbonyl group (methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group etc.), aryloxy Carbonyl group (such as phenyloxycarbonyl group), sulfonamide group (such as methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, hexanesulfonamide group, cyclohexanesulfonamide group, benzenesulfonamide group), carbamoyl group (amino) Carbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl , 2-pyridylaminocarbonyl group), a carboxyl group, and a hydroxyl group. A hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, an acyloxy group or an alkyl group is preferred, a hydrogen atom, an alkyl group, a hydroxyl group or an acyloxy group is more preferred, and a hydrogen atom or an alkyl group is particularly preferred. is there.

  An asterisk (*) represents a coupling point.

In the general formula (2), X ₂ represents an oxygen atom, N—R ₂₃ , or C—R ₂₄ , and R ₂₃ represents a hydrogen atom, a hydroxyl group, an alkoxy group, an alkyl group, or an amino group, preferably A hydroxyl group or an alkoxy group; R ₂₄ represents an alkyl group, an aryl group, or a heterocyclic group, preferably an alkyl group or an aryl group, and particularly preferably an alkyl group.

  An asterisk (*) represents a coupling point.

In the general formula (3), X ₃ represents a nitrogen atom or N ⁺ —R ₃₃ , and R ₃₃ represents an alkyl group or an aryl group. When X ₃ is N ⁺ , it may have a counter ion for neutralizing the charge, and examples of the counter ion include Cl ⁻ , Br ⁻ , I ⁻ and BF ₄ ⁻ .

  An asterisk (*) represents a coupling point.

  In the general formula (4), an asterisk (*) represents a bonding point.

  These aromatic condensed ring structures may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 25 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group). Group, pentyl group, hexyl group, cyclohexyl group, etc.), halogenated alkyl group (trifluoromethyl group, perfluorooctyl group, etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group, etc.), alkynyl group (propargyl group, etc.), Glycidyl group, acrylate group, methacrylate group, aryl group (phenyl group, etc.), heterocyclic group (pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group , Sriphoranyl group, Piperidinyl group, Pyrazolyl group, Tetrazo Group), halogen atom (chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group) ), Aryloxy groups (phenoxy group, etc.), alkoxycarbonyl groups (methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, etc.), aryloxycarbonyl groups (phenyloxycarbonyl group, etc.), sulfonamide groups (methane) Sulfonamide group, ethanesulfonamide group, butanesulfonamide group, hexanesulfonamide group, cyclohexanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (aminosulfonyl group, methylaminosulfonyl group, dimethyl group) Ruaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc., urethane group (methylureido group, ethylureido group, pentylureido group, cyclohexylureido) Group, phenylureido group, 2-pyridylureido group, etc.), acyl group (acetyl group, propionyl group, butanoyl group, hexanoyl group, cyclohexanoyl group, benzoyl group, pyridinoyl group etc.), carbamoyl group (aminocarbonyl group, methyl group) Aminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylamino Carbonyl group etc.), amide group (acetamide group, propionamide group, butanamide group, hexaneamide group, benzamide group etc.), sulfonyl group (methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, anilino group, 2-pyridylamino group, etc.), cyano group, carboxyl group, hydroxyl group, etc. Can be mentioned. These groups may be further substituted with these groups. When there are a plurality of substituents, they may be the same or different, and may be bonded to each other to form a condensed ring structure. Preferred is a hydrogen atom, halogen atom, amide group, alkyl group or aryl group, more preferred is a hydrogen atom, halogen atom, amide group or alkyl group, and particularly preferred is a hydrogen atom, halogen atom or alkyl group. is there.

  Specific examples of preferred aromatic condensed ring structures are listed below, but the present invention is not limited thereto.

(Organic piezoelectric material)
The organic piezoelectric material of the present invention comprises a polyurea resin composition containing a resin formed by a polymerization reaction of a macromonomer having at least two types of bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea An organic piezoelectric film can be formed by forming a film using an object or by further subjecting the film of the resin composition to polarization treatment.

  In 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. In particular, in the organic piezoelectric film made of the organic piezoelectric material of the present invention, a large piezoelectric effect is generated by polarization due to orientation freezing of the dipole moment of the polymer main chain or side chain.

  On the other hand, when energy (heat) is applied to the piezoelectric film, the magnitude of spontaneous polarization in the piezoelectric film changes accordingly. At this time, the surface charge existing on the surface of the piezoelectric film so as to neutralize the spontaneous polarization cannot respond to the energy change as quickly as the spontaneous polarization. There is a charge corresponding to the change in spontaneous polarization. The generation of electricity associated with this energy change is called pyroelectricity. In particular, in the organic piezoelectric film made of the organic piezoelectric material of the present invention, polarization by freezing orientation of the dipole moment of the main chain or side chain of the polymer Results in greater pyroelectric performance.

(Formation method of resin composition)
The polyurea resin composition according to the present invention is a resin containing a resin formed by a polymerization reaction of a macromonomer having at least two types of bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea. It can be prepared as a composition. In addition, you may make this resin composition contain additives other than the said resin according to the objective.

  When the end of the polyurea is an isocyanate group, it can be polymerized using a macromonomer having an active hydrogen at the end, and when the end of the polyurea has an active hydrogen, it is polymerized using a macromonomer having an isocyanate group at the end Can be made.

  The temperature for the polymerization may be any temperature as long as the polyurea and the macromonomer react with each other, but is preferably −50 to 250 ° C., more preferably −50 to 200 ° C.

  Polymerization of polyurea and macromonomer may be performed in the presence of a solvent or in the absence of a solvent.

  The solvent used for the polymerization can be selected from the solvents described in the above macromonomer, but DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide), DMSO (dimethylsulfoxide), NMP ( It is preferred to select a highly polar aprotic solvent such as N-methylpyrrolidone).

  The resin composition may be isolated and purified, or may be applied using the reaction solution as it is to form a film. Preferably, it is a method of performing isolation and purification by reprecipitation.

  Any means may be used for reprecipitation purification of the resin composition, but a method in which a reaction solution is dropped into a poor solvent to precipitate or a method in which a poor solvent is added to the reaction solution to precipitate is preferable.

  The “poor solvent” may be any solvent as long as it does not dissolve the macromonomer, but is an aliphatic hydrocarbon such as cyclohexane, pentane or hexane, an aromatic hydrocarbon such as benzene, toluene or chlorobenzene, Mention may be made of ethers such as diethyl ether and ethylene glycol diethyl ether, esters such as methyl propionate, ethyl acetate and butyl acetate, and alcohols such as methanol, ethanol and propanol.

(Method of forming organic piezoelectric film)
The organic piezoelectric film is preferably formed by coating. Examples of the coating method include spin coating, solvent casting, melt casting, roll coating, flow coating, printing, dip coating, and bar coating.

  In the method of forming a film by coating, a polymerized resin composition may be used, or after applying polyurea and a macromonomer, polymerization by heating may be performed.

  In the film formed on the substrate by coating, the solvent may be completely distilled off under heating or reduced pressure conditions. When polyurea and macromonomer are applied, the temperature is further increased after removing a predetermined amount of the solvent. The solvent may be distilled off and polymerization may be performed simultaneously.

  In the present invention, a method of performing polarization treatment described later on the formed film is preferable. When polyurea and macromonomer are applied, the polarization treatment may be performed after polymerization, or the polarization treatment is performed simultaneously with polymerization. May be. Particularly preferred is a method in which polymerization by heating and polarization treatment are performed simultaneously.

  The temperature when the polymerization by heating and the polarization treatment are simultaneously performed is preferably -50 to 250 ° C, more preferably -50 to 200 ° C. A method of changing the temperature in the above temperature range is also preferable.

(Polarization treatment)
As a polarization processing method in the polarization processing according to the present invention, various conventionally known methods can be applied.

  For example, in the case of the corona discharge treatment method, the corona discharge treatment can be performed by using a commercially available device comprising a high voltage power source and electrodes.

  Since the discharge conditions vary depending on the equipment and processing environment, it is preferable to select the conditions as appropriate. However, the voltage of the high voltage power source is −1 to −20 kV, the current is 1 to 80 mA, and the distance between the electrodes is 1 to 10 cm. The applied voltage is preferably 0.5 to 2.0 MV / m.

  As the electrodes, needle-like electrodes, linear electrodes (wire electrodes), and mesh-like electrodes that have been conventionally used are preferable, but the invention is not limited thereto.

  In addition, since heating is performed during corona discharge, it is necessary to install a heater via an insulator under the electrode in contact with the substrate manufactured according to the present invention.

  In the present invention, when the corona discharge treatment is performed as the polarization treatment in the state where the solvent of the raw material solution remains, the volatile components of the solvent are removed in order to avoid the danger of flammable explosion. It is necessary for safety to carry out with sufficient ventilation.

(substrate)
As the substrate, the selection of the substrate varies depending on the use and usage of the organic piezoelectric film according to 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. Alternatively, a single crystal plate or film of aluminum, gold, copper, magnesium, silicon alone, or a rare earth halide may be used.

Further, it may be formed on a multilayer piezoelectric element. As a method of using a multilayer for stacking piezoelectric elements, there is a method in which the organic piezoelectric film of the present invention is superposed on a ceramic piezoelectric element via an electrode. PZT is used as the ceramic piezoelectric element, but in recent years, one containing no lead has been recommended. PZT is preferably within the range of the formula of Pb (Zr1-XTiX) O ₃ (0.47 ≦ n ≦ 1). As deleading, natural or artificial quartz, lithium niobate (LiNbO ₃ ), For example, potassium niobium tantalate [K (Ta, Nb) O ₃ ], barium titanate (BaTiO ₃ ), lithium tantalate (LiTaO ₃ ), or strontium titanate (SrTiO ₃ ). The composition of various ceramic materials can be selected as appropriate in terms of performance.

(Ultrasonic transducer)
The ultrasonic transducer according to the present invention is characterized by using an organic piezoelectric film formed using the polyurea resin composition or organic piezoelectric material of the present invention. The ultrasonic transducer is preferably an ultrasonic receiving transducer used in an ultrasonic medical diagnostic imaging device probe including an ultrasonic transmitting transducer and an ultrasonic transmitting transducer. .

  In general, 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.

  Then, 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.

  Hereinafter, each of the ultrasonic wave receiving transducer and the ultrasonic wave transmitting transducer according to the present invention will be described in detail.

<Ultrasound receiving transducer>
An ultrasonic receiving transducer according to the present invention is a transducer used in a probe for an ultrasonic medical image diagnostic apparatus, and is formed using the organic piezoelectric material of the present invention as a piezoelectric material constituting the transducer. An 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 can be adjusted by adjusting the number, composition, degree of polymerization, etc. of polar functional groups such as CF ₂ groups and CN groups contained in the compound constituting the organic piezoelectric material, and the above-described polarization treatment. .

<Transmitter for ultrasonic transmission>
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.

  Various known organic piezoelectric materials and inorganic piezoelectric materials can be used as the ultrasonic transmitting vibrator constituent material.

  As the organic piezoelectric material, a polymer material similar to the above-described organic piezoelectric material for constituting an ultrasonic receiving vibrator can be used.

Examples of the inorganic material include quartz, lithium niobate (LiNbO ₃ ), potassium niobate tantalate [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.
Incidentally, PZT is _{Pb (Zr 1 - n Ti n} ) O 3 (0.47 ≦ n ≦ 1) is preferred.

<electrode>
The piezoelectric (body) vibrator 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. .

  In forming the electrodes, first, a base metal such as titanium (Ti) or chromium (Cr) is formed to a thickness of 0.02 to 1.0 μm by sputtering, and then the metal mainly composed of the above metal elements and those 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 μm by sputtering or other suitable methods. In addition to 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.

  Furthermore, a piezoelectric element is obtained by supplying a predetermined voltage between the electrodes formed on both surfaces of the piezoelectric film to polarize the piezoelectric film.

(Ultrasonic probe)
The ultrasonic probe according to the present invention is a probe for an ultrasonic diagnostic imaging apparatus including an ultrasonic transmission transducer and an ultrasonic reception transducer. The ultrasonic receiving vibrator according to the above is used.

  In the present invention, both transmission and reception of ultrasonic waves may be performed by a single transducer, but more preferably, the transducers are 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.

  In the ultrasonic probe according to the present invention, the ultrasonic receiving transducer of the present invention can be arranged on or in parallel with the transmitting transducer.

  As a more preferred embodiment, 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. You may laminate | stack on the vibrator | oscillator for transmission in the form joined together on the molecular material (The polymer (resin) film, for example, polyester film) whose relative dielectric constant is comparatively low as a support body. In this case, it is preferable that 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. Considering a practical ultrasonic medical diagnostic imaging apparatus and biological information collection from a practical frequency band, the film thickness is preferably 40 to 150 μm.

  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.

(Ultrasonic medical diagnostic imaging equipment)
The ultrasonic probe according to the present invention can be used for various types of ultrasonic diagnostic apparatuses. For example, it can be suitably used in an ultrasonic medical image diagnostic apparatus as shown in FIG.

  FIG. 1 is a conceptual diagram showing a configuration of a main part of an ultrasonic medical image diagnostic apparatus according to an embodiment 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). In addition, 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.

  Furthermore, an image data conversion circuit that converts echo signals 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.

  A transmission / reception control circuit, an image data conversion circuit, and a display control circuit are connected to the 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.

  According to the ultrasonic diagnostic apparatus as described above, 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.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these.

(Example 1): Synthesis of polyurea having an amino group at the terminal (1)
0.085 mol of diamine, 0.085 mol of ammonium carbonate and 0.175 mol of triphenylphosphine were added to 500 ml of pyridine and stirred. The reaction solution was heated to 70 ° C., 0.175 mol of hexachloroethane was added, and the mixture was stirred at 70 ° C. for 24 hours. The reaction solution was added to a mixed solvent of methanol-acetone 1: 1, and the precipitate was collected by filtration. The precipitate was washed successively with water and methanol and dried under reduced pressure to obtain polyurea having an amino group at the terminal.

  The polyurea obtained and the diamine used are shown below.

<PU-12>
Weight average molecular weight 12,000, molecular weight distribution 4.2
Diamine (2,7-diamino-9H-fluorene)
<PU-19>
Weight average molecular weight 6,700, molecular weight distribution 2.4
Diamine (2-chloro-4,6-diamino-1,3,5-triazine)
In this example, the weight average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were calculated by gel permeation chromatography (GPC) in the following manner. The measurement conditions are as follows.

Solvent: 30 mM LiBr in N-methylpyrrolidone Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperAWM-H x 2 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample concentration: 1.0 g / L
Injection volume: 40 μl
Flow rate: 0.5 ml / min
Calibration curve: Standard polystyrene: PS-1 (manufactured by Polymer Laboratories) Mw = 580 to 2,560,000 calibration curves with 9 samples were used.

(Example 2): Synthesis of polyurea having an amino group at the terminal (2)
Under a nitrogen atmosphere, diisocyanate was dissolved in 10 times the amount of NMP and cooled to 0 ° C. A diamine twice the mole of diisocyanate was dissolved in 10 times the amount of NMP and added to the reaction solution. After stirring at 0 ° C. for 1 hour, the reaction solution was returned to room temperature and further stirred for 3 hours. The reaction solution was added dropwise to ethyl acetate-heptane, and the supernatant was removed by decantation. The residue was washed with ethyl acetate to obtain a polyurea having an amino group at the terminal. The obtained polyurea and the raw materials used are shown below.

<PU-18>
Weight average molecular weight 22,000, molecular weight distribution 3.4
Diisocyanate (9H-fluorene-2,7-diisocyanate)
Diamine (2,2-dimethyl-1,3-propanediamine)
<PU-54>
Weight average molecular weight 15,000, molecular weight distribution 2.9
Diisocyanate (1,3-bis (isocyanatomethyl) cyclohexane)
Diamine (N-methyl-1,3-propanediamine)
(Example 3): Synthesis of polyurea having an isocyanate group at the terminal In a nitrogen atmosphere, diamine was dissolved in 10 times the amount of NMP and cooled to 0 ° C. 2 times mole diisocyanate of diamine was dissolved in 10 times amount of NMP and added to the reaction solution. After stirring at 0 ° C. for 1 hour, the reaction solution was returned to room temperature and further stirred for 3 hours. The reaction solution was added dropwise to ethyl acetate-heptane, and the supernatant was removed by decantation. The residue was washed with ethyl acetate to obtain polyurea having an isocyanate group at the terminal. The obtained polyurea and the raw materials used are shown below.

<PU-1>
Weight average molecular weight 27,000, molecular weight distribution 3.7
Diisocyanate (1,3-phenylene diisocyanate)
Diamine (N, N'-dimethyl-1,3-propanediamine)
<PU-26>
Weight average molecular weight 10,000, molecular weight distribution 3.1
Diisocyanate (1,3-diisocyanate cyclohexane)
Diamine (2-chloro-4,6-diamino-1,3,5-triazine)
<PU-57>
Weight average molecular weight 18,000, molecular weight distribution 3.3
Diisocyanate (1,3-bis (isocyanatomethyl) cyclohexane)
Diamine (2,2-dimethyl-1,3-propanediamine)
Example 4 Production of Resin Composition Film (1)
Under a nitrogen atmosphere, polyurea was dissolved in NMP, and the reaction solution was cooled to 0 ° C. An equimolar amount of macromonomer relative to the weight average molecular weight of polyurea was dissolved in NMP and added to the reaction solution. After the addition, the mixture was stirred at 0 ° C. for 1 hour, and then the internal temperature was gradually raised to 70 ° C. and further stirred for 3 hours. The obtained reaction liquid was dripped at methanol, the supernatant was removed with decane, and the resin compositions -1-7 were obtained by making it vacuum-dry. The weight average molecular weight and molecular weight distribution were determined in terms of polystyrene by measuring GPC as described above.

  These obtained resin compositions were applied and dried on a 25 μm polyimide film which had been pre-deposited on the surface with a 1% methanol solution of polyvinyl alcohol having a polymerization degree of 500 so that the dry film pressure would be 0.1 μm. The applied substrate was applied and dried so that the dry film pressure was 7 μm. Next, after an aluminum electrode is attached by vapor deposition to the surface of the substrate on which the film of the resin composition is thus formed, 100MV is used by using a high voltage power supply device HARB-20R60 (manufactured by Matsusada Precision Co., Ltd.). In a state where an electric field of / m is applied, the temperature is increased to 150 ° C. at a rate of 5 ° C./min. After holding at 150 ° C. for 15 minutes, the voltage is applied and then gradually cooled to room temperature, and subjected to poling treatment to obtain a resin composition Material films-1 to 7 were prepared. In addition, since the said resin composition film | membrane is equipped with the electrode, it can be used with an ultrasonic transducer | vibrator. The same applies below.

Example 5: Production of resin composition film (2)
Under a nitrogen atmosphere, polyurea was dissolved in NMP at room temperature. After adding the macromonomer dissolved in NMP, the reaction solution was heated to 80 ° C. and stirred for 3 hours.

  The substrate obtained by applying and drying the obtained reaction solution to a 25 μm polyimide film on which aluminum has been vapor-deposited on a surface in advance, with a methanol solution of polyvinyl alcohol having a polymerization degree of 1% of 500% and a dry film pressure of 0.1 μm. On top, coating was performed so that the dry film pressure was 7 μm. The solvent of the coated material was removed under reduced pressure, and a high voltage power supply HARB-20R60 (manufactured by Matsusada Precision Co., Ltd.) was used, and an electric field of 100 MV / m was applied to 150 ° C. at 5 ° C./min. After increasing at a rate and holding at 150 ° C. for 15 minutes, it was gradually cooled to room temperature while applying a voltage, and then subjected to poling treatment. Aluminum electrodes were attached by vapor deposition to the surface of the substrate on which the resin composition film was formed, to prepare resin composition films -8 and 9.

(Comparative Example 1): Preparation of Comparative Resin Composition Film-1 9H-fluorene-2,7-diisocyanate and 2- (2), which are the same raw materials as the macromonomer used in Resin Composition Film-5 of Example 4 -Aminoethoxy) ethanol was used at a molar ratio of 1: 2 and the following operation was performed.

  Under a nitrogen atmosphere, polyurea (PU-1) was dissolved in NMP, and the reaction solution was cooled to 0 ° C. An equimolar amount of 9H-fluorene-2,7-diisocyanate and 2-fold moles of 2- (2-aminoethoxy) ethanol with respect to the weight average molecular weight of PU-1 were each dissolved in NMP and simultaneously added to the reaction solution. After the addition, the mixture was stirred at 0 ° C. for 1 hour, and then the internal temperature was gradually raised to 70 ° C. and further stirred for 3 hours. After removing components insoluble in NMP by filtration, the reaction solution was added dropwise to methanol, and the supernatant was removed with decane. The residue was vacuum dried to obtain Comparative Resin Composition-1. The weight average molecular weight and molecular weight distribution were determined in terms of polystyrene by measuring GPC as described above.

  The obtained resin composition was applied and dried on a 25 μm polyimide film that had been pre-deposited on the surface with a methanol solution of polyvinyl alcohol having a polymerization degree of 1% of 500% so that the dry film pressure was 0.1 μm. Coating and drying were performed on the substrate so that the dry film pressure was 7 μm. Next, after an aluminum electrode is attached by vapor deposition to the surface of the substrate on which the film of the resin composition is thus formed, 100MV is used by using a high voltage power supply device HARB-20R60 (manufactured by Matsusada Precision Co., Ltd.). In a state where an electric field of / m is applied, the temperature is increased to 150 ° C. at a rate of 5 ° C./min. After holding at 150 ° C. for 15 minutes, the voltage is applied and then slowly cooled to room temperature, and subjected to a poling treatment for comparison resin Composition film-1 was produced.

(Comparative Example 2): Preparation of Comparative Resin Composition Film-2 Comparative Polymer Composition Film-2 was prepared in the same manner as in Example 4 using polyethylene glycol (PEG 2,000) having a molecular weight of 2,000 as a macromonomer. Produced.

(Comparative Example 3): Preparation of Comparative Resin Composition Film-3 Under a nitrogen atmosphere, terephthaloyl dichloride was dissolved in NMP, and the reaction solution was cooled to 0 ° C. NMP in which terephthaloyl dichloride and an equimolar amount of 3,5-diaminobenzoic acid were dissolved was added, and the reaction solution was returned to room temperature and stirred for 1 hour. Furthermore, the same amount of terephthaloyl dichloride dissolved in NMP was added and stirred for 15 minutes to obtain an NMP solution of polyamide (A) having an acid halide at the end group.

  The NMP solution of polyamide (A) was cooled to 0 ° C., and the macromonomer (M-38) dissolved in NMP was added. After the addition, the mixture was stirred at 0 ° C. for 1 hour, and then the internal temperature was gradually raised to 70 ° C. and further stirred for 3 hours. The obtained reaction liquid was dropped into methanol, the supernatant was removed with decane, and vacuum-dried to obtain comparative resin composition-3.

  The obtained resin composition was applied and dried on a 25 μm polyimide film that had been pre-deposited on the surface with a methanol solution of polyvinyl alcohol having a polymerization degree of 1% of 500% so that the dry film pressure was 0.1 μm. Coating and drying were performed on the substrate so that the dry film pressure was 7 μm. Next, after an aluminum electrode is attached by vapor deposition to the surface of the substrate on which the film of the resin composition is thus formed, 100MV is used by using a high voltage power supply device HARB-20R60 (manufactured by Matsusada Precision Co., Ltd.). In a state where an electric field of / m is applied, the temperature is increased to 150 ° C. at a rate of 5 ° C./min. After holding at 150 ° C. for 15 minutes, the voltage is applied and then slowly cooled to room temperature, and subjected to a poling treatment for comparison resin Composition film-3 was produced.

(Comparative Example 4): Preparation of Comparative Resin Composition Film-4 2,2-dimethyl-1 in place of 2,2-dimethyl-1,3-propanediamine used in Polyurea (PU-57) of Example 3 Except for using 1,3-propanediol, the same operation was performed to obtain a polyurethane (A) having an isocyanate group at the terminal.

  The obtained polyurethane (A) was used in place of polyurea, and a comparative resin composition film-4 was obtained in the same manner as in Example 4.

(Example 6): Evaluation of Resin Composition Film Using the obtained resin composition films as an ultrasonic vibrator, the piezoelectricity was evaluated by a resonance method in a state heated to room temperature and 100 ° C. The results are shown in Table 1. In addition, a piezoelectric characteristic is shown as a relative value with the value when measured at room temperature of the PVDF film as 100%.

(Example 7)
Of the obtained resin composition films, a part of the resin composition film is cut into 2 cm squares, and the pyroelectric property is set in a temperature bath whose temperature is variable from −100 degrees Celsius to 150 degrees Celsius, and the rate of temperature rise The pyroelectric rate was measured by observing the generated electric charge with a microammeter. The pyroelectric rate is shown as a relative value with the PVDF film value being 100%.

  The measurement results and the like are summarized in Table 1 and Table 2.

  As is apparent from the results shown in Table 2, the piezoelectric properties and pyroelectric properties of the organic piezoelectric film formed from the resin composition formed using polyurea and the macromonomer of the present invention are superior to those of the comparative example. I understand that

(Example 8)
(Preparation and evaluation of ultrasonic 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 .03} . ) Bi ₄ . Weighed to make 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. Next, pure water was added to the obtained calcined material, finely pulverized in a ball mill containing zirconia media in pure water, and dried to prepare a piezoelectric ceramic raw material powder. In the fine pulverization, 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 μm, and this plate-shaped temporary molded body is vacuum-packed and then 235 MPa. It shape | molded by the press with the pressure of. Next, the molded body was fired. The final sintered body had a thickness of 20 μm. 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.

<Production of laminated resonator for reception>
A laminated vibrator was produced in which the organic piezoelectric film produced in Example 1 and a polyester film having a thickness of 50 μm were bonded together with an epoxy adhesive. Thereafter, polarization treatment was performed in the same manner as described above.

  Next, according to a conventional method, an ultrasonic probe was prototyped by laminating a laminated receiver for reception on the above-described piezoelectric material for transmission and installing a backing layer and an acoustic matching layer.

  As a comparative example, in place of the above laminated resonator for reception, 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.

  Next, the above two types of ultrasonic probes were evaluated by measuring the reception sensitivity and the dielectric breakdown strength.

As for the reception sensitivity, a fundamental frequency f _{1 of} 5 MHz was transmitted, and a reception relative sensitivity of 10 MHz as the reception second harmonic f ₂ , 15 MHz as the third harmonic, and 20 MHz as the fourth harmonic was obtained. For the relative sensitivity of reception, a sound intensity measurement system Model 805 (1 to 50 MHz) manufactured by 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 reference 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.

  In the above evaluation, the ultrasonic probe provided with 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 has a dielectric breakdown. It was confirmed that the strength was good. 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.

Claims (11)

A polyurea resin composition comprising a resin formed by a polymerization reaction between a macromonomer having at least two bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea. An organic piezoelectric material formed by a polymerization reaction of a macromonomer having at least two types of bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond or an amide bond and a polyurea. The organic piezoelectric material according to claim 2, wherein the polyurea has an aromatic condensed ring structure. The organic piezoelectric material according to claim 2 or 3, wherein the macromonomer has an aromatic condensed ring structure. The organic piezoelectric material according to any one of claims 2 to 4, wherein a terminal of the chemical structure of the macromonomer is an isocyanate group. 5. The organic piezoelectric material according to claim 2, wherein the chemical structure of the macromonomer is a group having an active hydrogen at a terminal. 6. The method for producing an organic piezoelectric material according to any one of claims 2 to 6, wherein at least two bonds selected from a urea bond, a urethane bond, an ester bond, an ether bond, or an amide bond are provided. A method for producing an organic piezoelectric material, comprising polymerizing a macromonomer having polyurea. The method for producing an organic piezoelectric material according to any one of claims 2 to 6, wherein the macromonomer and polyurea are applied on a substrate and then polymerized by heating. Manufacturing method of organic piezoelectric material. A method for producing an organic piezoelectric material according to any one of claims 2 to 6, wherein a polyurea resin composition containing a resin formed by a polymerization reaction of the macromonomer and polyurea is used as a substrate. A method for producing an organic piezoelectric material, characterized by being applied on top. An ultrasonic transducer using the organic piezoelectric material according to any one of claims 2 to 6. An ultrasonic probe comprising an ultrasonic transmission transducer and an ultrasonic reception transducer, wherein the ultrasonic probe using the organic piezoelectric material according to any one of claims 2 to 6 is used. An ultrasonic probe comprising an ultrasonic transducer as an ultrasonic receiving transducer.