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DESCRIPTION JP2009179649

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DESCRIPTION JP2009179649
An organic polymer material and an organic piezoelectric material are provided. An organic
piezoelectric material in which some or all of monomers forming an organic polymer material are
made of a compound represented by the following general formula (1). (Wherein, X represents
an amino group, an isocyanate group, or an isothiocyanate group, R represents a carbon atom, a
hetero atom, or an oxidized form of these atoms, or -CR (R)-, R and R represent Each
independently represents a hydrogen atom, an alkyl group, a 3- to 10-membered non-aromatic
ring group, an aryl group or a heteroaryl group, and R and R are not simultaneously a hydrogen
atom. L to L each independently represent a hydrogen atom, an alkyl group or a halogen atom. )
【Selected figure】 None
Organic polymer material, organic composite material, organic piezoelectric material, method for
forming the same, and ultrasonic probe
[0001]
The present invention relates to an organic polymer material, an organic composite material, an
organic piezoelectric material, a method of forming the same, and an ultrasonic probe.
[0002]
Ultrasonic probes are rapidly increasing in use as medical ultrasonic diagnostic devices as well as
nondestructive inspection devices.
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For example, a probe such as an ultrasonic endoscope emits high-frequency acoustic vibration
from an ultrasonic transducer into a subject, reflects the reflected ultrasonic wave back by the
ultrasonic transducer, and By processing different information depending on the difference, a
cross-sectional image of the inside of the living body is obtained.
[0003]
In recent years, harmonic imaging (Harmonic Imaging) in which an image of the internal state in
the subject is formed not by the frequency (fundamental frequency) component of the ultrasound
transmitted from the ultrasound probe into the subject but by its harmonic frequency component
) Technology is researched and developed. This harmonic imaging technology has (1) smaller
side lobe levels compared to the level of the fundamental frequency component, better S / N ratio
(signal to noise ratio) and improved contrast resolution, and (2) frequency The beam width is
narrowed by increasing the beam width to improve the lateral resolution, (3) the sound pressure
is small and the variation of the sound pressure is small at a short distance, and multiple
reflection is suppressed, and (4) Attenuation beyond the focal point is similar to the fundamental
wave, and has various advantages such as a large depth velocity as compared to the case where
the high frequency wave is used as the fundamental wave.
[0004]
A piezoelectric body that generates an ultrasonic wave is used in such an ultrasonic probe.
Conventionally, so-called inorganic piezoelectric ceramics in which a piezoelectric, single crystal
of quartz, LiNbO 3, LiTaO 3, KNbO 3 etc., thin film of ZnO, AlN etc., sintered body of Pb (Zr, Ti) O
3 etc. Is widely used.
[0005]
On the other hand, an organic piezoelectric material (also referred to as "piezoelectric polymer
material" or "polymer piezoelectric material") using an organic polymer material such as
polyvinylidene fluoride (PVDF) or polyurea. ) Has also been developed (see, for example, Patent
Document 1). This organic piezoelectric material is more flexible than a ceramic piezoelectric
material, and can be easily made into a thin film, a large area, and a long film, and it can be made
into any shape and form. The dielectric constant ε is Since the hydrostatic pressure output
coefficient (gh constant) is small and extremely large, the sensitivity characteristics are excellent,
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and the low density and low elasticity enable efficient energy propagation.
[0006]
As a method of forming an organic piezoelectric (piezoelectric resin) film, for example, a
diisocyanate compound such as 4,4'-diphenylmethane diisocyanate (MDI) and 4,4'diaminodiphenylmethane (MDA) can be used. A so-called vapor deposition polymerization
method is known in which such a diamine compound is simultaneously evaporated to form a
polyurea film (see, for example, Patent Documents 2 and 3).
[0007]
In the case of the method disclosed in Patent Document 2, two kinds of monomers, the
diisocyanate compound and the diamine compound, are simultaneously evaporated to form
polyurea, so that the evaporation temperature of each monomer is different. There is a problem
that the composition ratio of the monomers in the formed polyurea film will be different from the
stoichiometry composition ratio, and it is necessary to set each monomer separately and to
deposit while controlling the temperature. there were.
Further, depending on the combination of the diisocyanate compound and the diamine
compound, the reactivity may not be good, and the polymerization does not proceed unless the
temperature of the substrate to be deposited is properly adjusted, and a desired organic
piezoelectric film can not be obtained. . Furthermore, in vapor deposition polymerization, it takes
a long time to form a thick film, requires a large vacuum facility, requires an apparatus for
adjusting the substrate temperature, and requires a large facility investment and manufacturing
time. It becomes a big problem.
[0008]
In order to solve the above problems, as disclosed in Patent Document 4, a method of obtaining
an organic piezoelectric film not by vapor deposition polymerization but by thermal
polymerization has been found. In this method, a polymer containing a cross-linking agent having
a large dipole is applied to a substrate, and thermal polymerization is carried out while
performing polarization treatment, so a large capital investment such as vapor deposition
polymerization is not necessary, and an organic piezoelectric material is easily obtained.
Membranes can be made.
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[0009]
However, in the above method, only the cross-linking agent having a structure having a large
dipole in the cross-linking agent contained in the organic piezoelectric film is oriented to induce
the piezoelectricity, so the piezoelectricity of the whole organic piezoelectric film is low. In
addition, it is necessary to prepare a crosslinker having a large dipole instead of a usual
crosslinker, which requires a large cost. JP-A-6-216422 JP-A-7-258370 JP-A-5-311399 JP-A2006-49418
[0010]
The present invention has been made in view of the above problems and circumstances, and the
problem to be solved is an organic polymer material, an organic composite material, which is
excellent in heat resistance and solubility, and can be easily formed (manufactured) at low cost.
An organic piezoelectric material and an ultrasonic probe are provided.
[0011]
The above object of the present invention can be achieved by the following constitution.
[0012]
1.
An organic polymeric material characterized in that a part or all of the monomers forming the
organic polymeric material is a compound represented by the following general formula (1).
[0013]
<img class = "EMIRef" id = "203557746-00002" />
[0014]
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(Wherein, X represents any of an amino group, an isocyanate group, and an isothiocyanate
group, R represents a carbon atom, a hetero atom, or an oxidized form of those atoms, or -CR1
(R2)-; R1 and R2 represent They are each independently a hydrogen atom, an alkyl group, a 3- to
10-membered non-aromatic ring group, an aryl group or a heteroaryl group, and R1 and R2 are
not simultaneously a hydrogen atom.
L1 to L4 each independently represent a hydrogen atom, an alkyl group or a halogen atom.
) 2. A compound in which X in the general formula (1) is an amino group together with part
or all of the monomers forming the organic polymer material and both X in the general formula
(1) is an isocyanate group or both isothiocyanate groups The organic polymer material as
described in 1 above, which is a compound of
[0015]
3. A compound in which a part or all of the monomers forming the organic polymer material is
both an isocyanate group or an isothiocyanate group in the above general formula (1), and the
following general formula (2), a general formula (3) Or the compound represented by the general
formula (4) or a derivative of these compounds.
[0016]
<img class = "EMIRef" id = "203557746-00003" />
[0017]
(Wherein, R 11 and R 12 each independently represent a hydrogen atom, an alkyl group, a 3- to
10-membered non-aromatic ring group, an aryl group or a heteroaryl group, and these groups
further have a substituent) Also good.
Each of R21 to R26 independently represents a hydrogen atom, an alkyl group, or an electron
withdrawing group. )
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[0018]
<img class = "EMIRef" id = "203557746-00004" />
[0019]
(Wherein R 13 represents a carboxyl group, a hydroxy group, a mercapto group or an amino
group, and these active hydrogens are further substituted with an alkyl group, a 3- to 10membered non-aromatic ring group, an aryl group or a heteroaryl group And R13 represents a
carbonyl group, a sulfonyl group, a thiocarbonyl group or a sulfone group, and these groups bind
a hydrogen atom, an aryl group or a heteroaryl group.
R21 to R26 each represent a group having the same meaning as R21 to R26 in the general
formula (2). )
[0020]
<img class = "EMIRef" id = "203557746-000005" />
[0021]
(Wherein Y represents a keto group, an oxime group, or a substituted vinylidene group, and R21
to R26 each represent a group having the same meaning as R21 to R26 in the general formula
(2)).
) 4. An organic composite material, which is formed by mixing the organic polymer material
according to 1, 2 or 3 with one or more other materials.
[0022]
5. An organic piezoelectric material comprising the organic polymer material according to 1, 2
or 3.
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[0023]
6. A method of forming an organic piezoelectric material comprising forming an organic
piezoelectric material using a liquid obtained by dissolving the organic polymer material
according to 1, 2 or 3 in a solvent.
[0024]
7. 6. The method for forming an organic piezoelectric material according to the above 6,
wherein the organic polymer material is dissolved in a solvent at a mass ratio of 0.01 to 80%.
[0025]
8. 5. The organic piezoelectric material as described in 5 above, wherein the organic polymer
material as described in 1, 2 or 3 further contains a plasticizer.
[0026]
9. An aliphatic urea structure is contained in the structure of the organic polymeric material as
described in said 1, 2 or 3, The organic piezoelectric material as described in said 5 or 8
characterized by the above-mentioned.
[0027]
10. Composed using at least one material selected from the organic polymer material
according to 1, 2 or 3 or the organic composite material according to 4 or the organic
piezoelectric material according to 5 or 8. An ultrasound probe characterized by
[0028]
The present invention has been able to be provided.
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[0029]
The above means of the present invention can provide an organic polymer material, an organic
composite material, an organic piezoelectric material and an ultrasonic probe which are excellent
in heat resistance and solubility and can be easily formed (manufactured) at low cost. .
[0030]
BEST MODE FOR CARRYING OUT THE INVENTION The present invention, its components, and
the best mode and mode for carrying out the invention will be described in detail below.
[0031]
(Compound Represented by General Formula (1)) Specific examples of the compound
represented by General Formula (1) may include the following compounds, but the present
invention is not limited thereto.
[0032]
As a compound in which X is an amino group, 1-1: 4,4'-diaminobenzophenone, 1-2: 4,4'dimethylamino-3,3'-dichlorobenzophenone, 1-3: 4,4 ' -Diamino-5,5'-diethyl-3,3'difluorobenzophenone, 1-4: 4,4'-diamino-3,3 ', 5,5'-tetrafluorobenzophenone, 1-5: 2,2 -Bis (4aminophenyl) propane, 1-6: 2, 2- bis (4- amino-3, 4- dichlorophenyl) propane, 1-7: 2, 2- bis (4aminophenyl) hexafluoropropane 1-8: 2, 2-bis (4-amino-3-fluorophenyl) hexafluoropropane, 1-9:
4, 4'-diaminodiphenyl ether (ODA), 1-10: 4, 4'-diamino- , 3 ', 5,5'-tetrachlorodiphenyl ether, 1-11:
4,4'-diaminodiphenyl sulfide, 1-12: 4,4'-diamino-3,3'-dibromodiphenyl sulfide, 1-13: 4,4'diaminodiphenyl disulfide, 1-14: 4,4'-diamino-3,3 ', 5,5'-tetrafluorodiphenyl disulfide, 1-15: bis
(4-aminophenyl) sulfone, 1- 16: bis (4-amino-3-chloro-5-methylphenyl) sulfone, 1-17: bis (4aminophenyl) sulfoxide, 1-18: bis (4-amino-3-bromophenyl) sulfoxide, 1 -19: 1, 1-bis (4aminophenyl) cyclopropane, 1-20: 1,1-bis (4-aminophenyl) cyclooctane, 1- 2: 1, 1-bis (4aminophenyl) cyclohexane, 1- 22: 1, 1-bis (4-amino-3,5-difluorophenyl) cyclohexane, 1-23: 4, 4'( Cyclohexylmethylene) dianiline, 1-24: 4,4 '-(cyclohexylmethylene) bis (2,6-dichloroaniline), 125: diethyl 2,2-bis (4-aminophenyl) malonate, 1-26 : Diethyl 2,2-bis (4-amino-3-chlorophenyl)
malonate, 1-27: 4- (di-p-aminophenylmethyl) pyridine, 1-28: 1- (di-p-aminophenylmethyl)- 1Hpyrrole, 1-29: 1- (di-p-aminophenylmethyl) -1H-imidazole, 1-30: 2- (di-p-aminophenylmethyl)
oxazole etc. It is possible.
[0033]
As a compound in which X is an isocyanate group, 1-40: benzophenone-4,4'-diisocyanate, 1-41:
3,3'-dichlorobenzophenone-4,4'-diisocyanate, 1-42: 5, 5'-diethyl-3,3'-difluorobenzophenone-4,4'-
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diisocyanate, 1-43: 2, 2-bis (4-isocyanatophenyl) propane, 1-44: 2, 2-bis (3, 5-dichloro-4isocyanatophenyl) propane, 1-45: 2, 2-bis (4-isocyanatophenyl) hexafluoropropane, 1-46: 2, 2-bis
(3-fluoro-4-isocyanatophenyl) hexa Fluoropropane, 1-47: bis (4-isocyanatophenyl) ether, 1-48:
bis (3,5-difluoro-4-i) Cyanate phenyl) ether, 1-49: bis (4-isocyanatophenyl) sulfide, 1-50: bis (3,5dibromo-4-isocyanatophenyl) sulfide, 1-51: bis (4-isocyanatophenyl) disulfide, 1-52: bis (4isocyanate phenyl) sulfone, 1-53: bis (4-isocyanate phenyl) sulfoxide, 1-54: bis (3,5-difluoro-4isocyanate phenyl) sulfoxide, 1-55: 1 1,1-bis (4-isocyanatophenyl) cyclopropane, 1-55: 1,1-bis (4isocyanatephenyl) cyclooctane, 1-56: 1,1-bis (4-isocyanatophenyl) cyclohexane, 1- 57: 1,1-bis
(3,5-dichloro-4-) 1-58: 4,4 '-(Cyclohexylmethylene) bis (isocyanatobenzene), 1-59: 4,4'(cyclohexylmethylene) bis (1-isocyanate-2-chlorobenzene), -60: diethyl 2,2-bis (4isocyanatophenyl) malonate, 1-61: 2, 2-bis (3-chloro-4-isocyanatophenyl) malonate, 1-62: 4- (dip
-Isocyanatophenylmethyl) pyridine, 1-63: 1- (di-p-isocyanatophenylmethyl) -1H-pyrrole, 1-64: 1(di-p-isocyanatophenylmethyl) -1H-imidazole, 1-65: And (di-p-isocyanatophenylmethyl) oxazole
and the like can be mentioned.
[0034]
As a compound in which X is an isothiocyanate group, 1-70: benzophenone-4,4'-diisothiocyanate,
1-71: 3,3'-difluorobenzophenone-4,4'-diisothiocyanate, 1-72. 2,2-bis (3,5-dichloro-4isothiocyanatophenyl) propane, 1-73: bis (4-isothiocyanatophenyl) ether, 1-74: bis (4isothiocyanatophenyl) sulfone, -75: bis (4-isothiocyanatophenyl) sulfoxide, 1-76: bis (3,5-difluoro4-isothiocyanatophenyl) sulfoxide, 1-77: 1,1-bis (4-isothiocyanatophenyl) cyclo Propane, 1-78:
1,1-bis (4-isothiocyanatophenyl) cyclook 1-79: 4,4 '-(cyclohexylmethylene) bis (isothiocyanate
benzene), 1-80: 2,2-bis (4-isothiocyanatophenyl) diethyl malonate, 1-81-1- (di- pisothiocyanatophenylmethyl) -1H-pyrrole, 1-82: 2- (di-p-isothiocyanatophenylmethyl) oxazole
and the like can be mentioned.
[0035]
(Copolymer) The organic composite material of the present invention is preferably a copolymer
containing the monomer represented by the general formula (1) of the present invention.
Even though these copolymers are copolymers consisting of two or more kinds of monomers
represented by the general formula (1) of the present invention, one is a monomer represented
by the general formula (1) but other monomers May be any monomer as long as it is a
copolymerizable monomer.
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[0036]
For example, if the monomer represented by the general formula (1) of the present invention is a
diamine type monomer, aliphatic diisocyanate, aromatic diisocyanate, aliphatic diisothiocyanate,
aromatic diisothiocyanate and the like can be mentioned.
And 1,5-pentamethylene diisocyanate (PMDI), 1,7-heptamethylene diisocyanate, 4,4'diphenylmethane diisocyanate (MDI), 4,4'-methylenebis (2,6-dichlorophenyl isocyanate), 4,4 'Methylenebis (2-bromophenylisocyanate) (2-BrMDI), 4,4'-methylenebis (2-chloro-6fluorophenylisocyanate), 4,4'-methylenebis (2,6-diethylphenylisocyanate), 4,4'-Methylenebis (2,6di-t-butylphenylisocyanate), 4,4 '-(phenylmethylene) bis (isocyanatobenzene), 1,5pentamethylenediisothiocyanate, 1,7-hepta Methylenediisothiocyanate, 4,4 -(Phenylmethylene)
bis (1-isocyanate-2-fluorobenzene), 4,4'-diphenylmethanediisothiocyanate, 4,4'-methylenebis
(2,6-dichlorophenylisothiocyanate), 4,4'-methylenebis ( Particularly preferred are 2,6diethylphenyl isothiocyanate), 4,4 '-(phenylmethylene) bis (1-isothiocyanate-2-fluorobenzene)
and the like.
[0037]
On the other hand, if the monomer represented by the general formula (1) of the present
invention is an isocyanate type or diisothiocyanate type monomer, aliphatic diamine, Nsubstituted aliphatic diamine, aromatic diamine, N-substituted aromatic diamine, aliphatic Diol,
aromatic diol and the like can be mentioned.
Preferably, 1,3-trimethylenediamine (TMDA), 1,9-diaminononane (DAN), 4,4′diaminodiphenylmethane (MDA), 4,4′-methylenebis (2,6-dichloroaniline), 4 4,4'-methylenebis
(2-bromoaniline), 4,4'-methylenebis (2-chloro-6-fluoroaniline), 4,4'-methylenebis (2,6diethylaniline), 4,4'-methylenebis (2,6-di-t-butylaniline), 4,4 '-(phenylmethylene) dianiline, 4,4'(phenylmethylene) bis (2-fluoroaniline), 4,4 '-(phenylmethylene) Bis (2-fluoroaniline), diamine
compounds having a fluorene skeleton, etc., ethylene glycol, glycerin, triethylene glycol, polyester
Alcohol compounds such as polyethylene glycol, polyvinyl alcohol, 4,4-methylene bisphenol, etc.,
and further ethanolanamine having both amino group and hydroxyl group, amino alcohols such
as aminobutylphenol, 4- (4-aminobenzyl) phenol (ABP), etc. Aminophenols can be mentioned.
In particular, a diamine compound having a fluorene skeleton is preferable, and a compound
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represented by the general formula (2), the general formula (3) or the general formula (4) or a
derivative of these compounds can be mentioned.
[0038]
In the present application, the “electron withdrawing group” refers to a substituent having a
Hammett substituent constant (σp) of 0.10 or more as an index indicating the degree of electron
withdrawing property.
As the value of the Hammett's substituent constant σp here, see Hansch, C., et al. Leo et al. (Eg, J.
Med.
Chem. 16, 1207 (1973); ibid. 20, 304 (1977)) is preferably used.
[0039]
For example, as a substituent or atom having a σp value of 0.10 or more, a halogen atom (a
fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, a cyano
group, a nitro group, a halogen-substituted alkyl group (eg, trichloro) Methyl, trifluoromethyl,
chloromethyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl),
aliphatic, aromatic or aromatic heterocyclic acyl group (eg formyl, acetyl, benzoyl), aliphatic /
aromatic Or aromatic heterocyclic sulfonyl group (eg trifluoromethanesulfonyl, methanesulfonyl,
benzenesulfonyl), carbamoyl group (eg carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chlorophenylcarbamoyl), alkoxycarbonyl (For example, methoxycarbonyl, ethoxycarbonyl,
diphenylmethylcarbonyl), substituted aryl group (for example, pentachlorophenyl,
pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), aromatic heterocyclic
group (for example, 2 -Benzoxazolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl),
azo group (eg phenylazo), ditrifluoromethylamino group, trifluoromethoxy group,
alkylsulfonyloxy group (eg methanesulfonyl) Oxy), acyloxy group (eg acetyloxy, benzoyloxy),
arylsulfonyloxy group (eg benzenesulfonyloxy), phosphoryl group (eg dimethoxyphosphonyl,
diphenylphosphoryl) ), Sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethyl) Sulfamoyl) and the like.
[0040]
In the present invention, preferred electron withdrawing groups, that is, preferred substituents R
are shown in the following specific examples.
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[0041]
Although the specific example of a compound represented by General formula (2), General
formula (3), or General formula (4) is shown below, this invention is not limited to these.
[0042]
<Compound Represented by General Formula (2)> Examples of the compound represented by
General Formula (2) include 2-1: 2,7-diaminofluorene; 2-2: 2,7-diamino-4,5-5- Dinitrofluorene, 23: 2,7-diamino-3,4,5,6-tetrachlorofluorene, 2-4: 2,7-diamino-3,6-difluorofluorene, 2-5: 2,7Diamino-9- (n-hexyl) fluorene, 2-6: 9, 9-dimethyl-2,7-diaminofluorene, 2-7: 2,7-diamino-9benzylfluorene, 2-8: 9, 9 -Bisphenyl-2,7-diaminofluorene, 2-9: 2,7-diamino-9-methylfluorene, 210: 9,9-bis (3,4-dichlorophenyl) -2,7-diaminofluorene, 2-11: 9, 9-bis (3- Ethyl 4-chlorophenyl) 2,7-diaminofluorene, 2-12: 9,9-bis (methyloxyethyl) -2,7-diaminofluorene, 2-13: 2,7-diamino-3,6Dimethyl-9-aminomethyl fluorene, and the like, but not limited thereto.
[0043]
<Compound Represented by General Formula (3)> As a compound represented by General
Formula (3), 3-1: 2, 7-diamino-9-fluorene carboxylic acid, 3-2: 2, 7-diamino -9-fluorene
carboxaldehyde, 3-3: 2, 7-diamino-9-hydroxyfluorene, 3-4: 2, 7-diamino-3, 6-difluoro-9hydroxyfluorene, 3-5: 2, 7 -Diamino-4,5-dibromo-9-mercaptofluorene, 3-6: 2, 7, 9triaminofluorene, 3-7: 2, 7-diamino-9-hydroxymethylfluorene, 3-8: 2, 7-diamino-9- (methyloxy)
fluorene, 3-9: 2,7-diamino-9-acetoxyfluorene, 3-10: 2,7-diamino-3,6-diethyl-9(perfluorophenyne) Oxy) fluorene, 3-11: 2,7-diamino-4,5-difluoro-9- (acetamido) fluorene, 3-12:
2,7-diamino-N-isopropylfluorene-9-carboxamide, 3-13 2,7-diamino-4,5-dibromo-9-methylsulfinyl
fluorene and the like, but not limited thereto.
[0044]
<Compound Represented by General Formula (4)> Examples of the compound represented by
General Formula (4) include 4-1: 9, 9-dimethyl-2,7-diaminofluorenone, 4-2: 2, 7- Diamino-9benzylfluorenone, 4-3: 9, 9-bisphenyl-2, 7-diaminofluorenone, 4-4: 2, 7-diamino-9methylfluorenone, 4-5: 9, 9-bis ( 3,4-Dichlorophenyl) -2,7-diaminofluorenone, 4-6: 9,9-bis (3methyl-4-chlorophenyl) -2,7-diaminofluorenone, 4-7: 9-hexylidene-2, 7-diamino-4,5dichlorofluorene, 4-8: 1- (2,7-diamino-9-fluorenylidene) -2-phenylhydrazine 4-9: 2-((2,7-diamino1, 8-dimethyl-9 -Fluorenylidene) methyl) pyridine, and the like, but not limited thereto.
[0045]
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(Composite Material) When forming the organic composite material used in the present
invention, other materials may be mixed in addition to the organic polymer material of the
present invention.
That is, in addition to the organic polymer material in which the material formed of the material
according to claim 1 is mixed, and the organic polymer material in which the copolymer formed
of the material described in the above (copolymer) is mixed, Inorganic materials, organic
materials, plasticizers, nucleating agents, mixtures of crystallization accelerators and the organic
polymer material of the present invention can be mentioned as examples.
[0046]
(Solvent) As a solvent which can be used in the present invention, for example, an aprotic solvent
such as dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone and
other amide solvents, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, chloride
Methylene, chloroform, toluene, hexane and the like can be mentioned.
The solvent is not particularly limited as long as it can dissolve both the diamine compound and
the compound having two or more carbonyl groups or thiocarbonyl groups.
[0047]
(Organic Piezoelectric Material) In the present invention, as a preferable organic piezoelectric
material, a material formed by the following combination of the raw materials, or a mixture of
materials polymerized by the following combination can be mentioned.
[0048]
4,4'-Methylenebis (2-chloro-6-fluoroaniline) / 4,4'-diphenylmethane diisocyanate (MDI), 4,4'diaminodiphenylmethane (MDA) / benzophenone-4,4'-diisocyanate, bis (4-Amino-3-chloro-5methylphenyl) sulfone / bis (4-isocyanatophenyl) sulfoxide, 2,2-bis (4-aminophenyl) propane / 2(di-p-isothiocyanatophenylmethyl) oxazole 4,4'-Diaminodiphenylether (ODA) / bis (4isocyanatephenyl) ether, 4,4 '-(phenylmethylene) bis (2-fluoroaniline) / 2,2-bis (4isocyanatephenyl) hexa Fluoropropane, 4,4'-diaminobenzophenone / 2,2-bis (4isothiocyanatophenyl) malonate diethyl, 2- (di-p-aminophenylmethyl) oxazole / benzophenone-
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4,4'-diisothiocyanic acid, 2,2-bis (4-aminophenyl) malon Acid diethyl / 2,2-bis (4isothiocyanatophenyl) malonate diethyl, 1,1-bis (4-aminophenyl) cyclohexane / 4,4'-methylenebis
(2-bromophenylisocyanate), 4- (di- p-aminophenylmethyl) pyridine / 2,2-bis (3,5-dichloro-4isothiocyanatophenyl) propane, 4,4'-diamino-3,3 ', 5,5'-tetrafluorodiphenyl disulfide / 1,1-bis (4isocyanatophenyl) cyclopropane and the like, but such No.
[0049]
(Substrate) The choice of the substrate differs depending on the use / method of use of the
organic polymer material, organic composite material and organic piezoelectric material
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, or these materials The surface may be covered with
aluminum, gold, copper, nickel, magnesium, silicon or the like.
Further, it may be a plate or a film of a single crystal of aluminum, gold, copper, nickel,
magnesium, silicon alone, or a rare earth halide.
[0050]
Furthermore, it may be formed on a multilayer piezoelectric element.
In the method of using a multilayer in which the piezoelectric element is laminated, there is a
method in which the organic polymer material, the organic composite material and the organic
piezoelectric material of the present invention are superimposed on the ceramic piezoelectric
element.
At this time, electrodes may be interposed between the layers.
As a ceramic piezoelectric element, PZT is used, but in recent years, one not containing lead is
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recommended.
The PZT is preferably within the range of the formula of Pb (Zr1-xTix) O3 (0.47 ≦ x ≦ 1), and as
lead removal, natural or artificial quartz, lithium niobate (LiNbO3), niobic acid Potassium
tantalate [K (Ta, Nb) O 3], barium titanate (BaTiO 3), lithium tantalate (LiTaO 3), strontium
titanate (SrTiO 3), or the like.
The composition of various ceramic materials can be appropriately selected in their use
performance.
[0051]
(Method of Forming Organic Polymer Material, Organic Composite Material, and Organic
Piezoelectric Material) The method of forming the organic polymer material, organic composite
material, and organic piezoelectric material according to the present invention comprises the
compound represented by the general formula (1), and The compound is formed by dissolving in
a suitable solvent a compound capable of successive reaction with the compound to form the
compound, and in some cases, the compound is formed by mixing with a suitable other material.
[0052]
(Polarization Treatment) As a polarization treatment method in the polarization treatment
according to the present invention, various methods known in the related art can be applied, but
a corona discharge treatment method is preferable.
[0053]
Corona discharge treatment can be treated using a device comprising a commercially available
high voltage power supply and electrodes.
[0054]
The discharge conditions vary depending on the equipment and processing environment, so it is
preferable to select appropriate conditions, but the voltage of the high voltage power supply is -1
to -20 kV, the current is 1 to 80 mA, and the distance between electrodes is 1 to 10 cm The
applied voltage is preferably 0.5 to 2.0 MV / m.
[0055]
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As an electrode for corona discharge, although a needle electrode, a linear electrode (wire
electrode), and a reticulated electrode which are conventionally used are preferable, the present
invention is not limited thereto.
[0056]
In addition, when the organic polymer material, the organic composite material and the organic
piezoelectric material are heated during the corona discharge, the polymerization further
proceeds, and it becomes possible to maintain the oriented structure by the polarization
treatment.
The heating temperature is preferably 30 to 250 ° C.
More preferably, it is preferable that it is 70-180 degreeC.
In the case of heating, it is necessary to install a heater via an insulator to an electrode of corona
discharge.
[0057]
In the present invention, when corona discharge treatment is performed as polarization
treatment in a state in which the solvent of the raw material solution remains, volatile
components of the solvent are removed in order to avoid the risk of explosion and explosion. It is
necessary for safety to do with sufficient ventilation.
[0058]
Hereinafter, the present invention will be described by way of examples, but the present
invention is not limited thereto.
[0059]
Example 1 << Preparation of Polarized Films 1 to 13 >> 50 ml of N-methylpyrrolidone was added
to two 200 ml flasks each having a temperature adjusted to 25 ° C., and 2,2-bis (4-
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16
aminophenyl) was added to one of them. 3.3 g of hexafluoropropane was added to the other, and
4.1 g of 4,4'-methylenebis (2-bromophenyl isocyanate) was added and dissolved.
Thereafter, while stirring the former solution, the latter solution was mixed dropwise over 20
minutes.
After 1 hour, the present polymerization solution is recovered, coated on a 20 μm thick
polyimide film on the aluminum electrode surface of a substrate provided with a 50 nm thick
aluminum electrode, and dried to a dry film thickness of 20 μm. The organic polymer film 1 was
produced.
Next, the temperature of the organic polymer film 1 was raised to 140 ° C. at a rate of 5 °
C./min, stagnated for 5 minutes, and then naturally cooled to 25 ° C.
During this time, corona discharge polarization treatment is carried out with a high voltage
power supply device HARb-20R60 (manufactured by Matsuda Precision Co., Ltd.) and a needlelike electrode at an electric field of 1.0 MV / m. An aluminum electrode was applied to the
surface on the molecular material side by vapor deposition to prepare a polarization treatment
film 1. The polarization treatment films 2 to 13 were also produced under the conditions
described in Table 1.
[0060]
<< Preparation of Polarized Films 14 to 17 >> The materials (monomers) listed in Table 1 are
polymerized with the respective materials in the same manner as in the above-mentioned <<
Preparation of polarized films 1 to 13>, and finally, two polymerization liquids are prepared. The
solution was mixed to obtain an organic polymer material solution. The subsequent film
formation and the polarization operation were also performed in the same manner as in the
above-mentioned << preparation of polarization treatment films 1 to 13 >> to fabricate
polarization treatment films 14 to 17.
[0061]
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<< Preparation of Comparative Membrane 1 >> 50 ml of N-methylpyrrolidone was added to two
200 ml flasks each having a temperature adjusted to 25 ° C., and 2.0 g of 4,4'diaminodiphenylmethane (MDA) was added to the other, to the other. 2.5 g of 4,4'diphenylmethane diisocyanate (MDI) was added and dissolved. Thereafter, while stirring the
former solution, the latter solution was mixed dropwise over 20 minutes. After 1 hour, the
present polymerization solution is recovered, and the solution is overcoated on the aluminum
electrode surface of a substrate obtained by applying a 50 nm thick aluminum electrode on a 20
μm thick polyimide film to a final dry film thickness of 20 μm. It dried and produced the
membrane. Next, the film was heated to a temperature of 140 ° C. at a rate of 5 ° C./min,
stagnated for 5 minutes, and then naturally cooled to 25 ° C. During this time, corona discharge
polarization treatment is carried out with a high voltage power supply device HARb-20R60
(manufactured by Matsuda Precision Co., Ltd.) and a needle-like electrode at an electric field of
1.0 MV / m. An aluminum electrode was applied to the surface on the molecular material side by
vapor deposition to prepare a comparative film 1.
[0062]
<< Evaluation of the produced film | membrane >> Evaluation of the polarization treatment film |
membrane 1-17 obtained and comparison film | membrane 1 is Nano-R2 / I2 closed loop linear
scanner mounted multifunctional AFM (made by PACIFIC NANOTECHNOLOGY) and FCE-1 type
strong Piezoelectricity is measured by a dielectric property evaluation system (manufactured by
Toyo Technica Co., Ltd.), and the relative film 1 is indicated as a relative value of 100.
[0063]
<< Solubility evaluation of organic polymer material >> Reproduction of the organic polymer
material solution polymerized by the above-mentioned << preparation of polarization treatment
films 1 to 13 >> and << preparation of polarization treatment films 14 to 17 >> using methanol It
refine | purified by the method, it was made to dry, and the corresponding organic polymeric
material 1-17 was produced, respectively.
The same operation was performed on the solution polymerized in << Preparation of
Comparative Film 1 >> to prepare Comparative Polymer Material 1. Thereafter, the solubility of
the organic polymer materials 1 to 17 and the comparative polymer material 1 in Nmethylpyrrolidone is evaluated, and the comparative polymer material 1 is shown as a relative
value of 100.
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[0064]
The evaluation results are shown in Table 1.
[0065]
[0066]
As apparent from the results shown in Table 1, it is understood that the solubility and the
piezoelectricity are superior to the comparative example in the example according to the present
invention.
[0067]
Example 2 <Preparation of Piezoelectric Vibrator for Transmission> CaCO 3, La 2 O 3, Bi 2 O 3
and TiO 2 which are component materials, and MnO which is a subcomponent material are
prepared, and for the component materials, the final composition of the component is
(Ca0.97La0. 03) Measured to be Bi4.01 Ti4O15.
Next, pure water was added, mixed in pure water in a ball mill containing zirconia media for 8
hours, and sufficiently dried to obtain a mixed powder.
The obtained mixed powder was preformed, and calcined in air at 800 ° C. for 2 hours to
prepare a calcined product.
Next, pure water was added to the obtained calcined product, finely pulverized in a pure water in
a ball mill containing a medium made of zirconia, and dried to prepare a piezoelectric ceramic
raw material powder. In the pulverization, piezoelectric ceramic raw material powder having a
particle diameter of 100 nm was obtained by changing the time for pulverization and the
pulverizing conditions. 6% by mass of pure water as a binder is added to each piezoelectric
ceramic raw material powder having different particle diameters, and press-formed to form a
plate-shaped temporary compact having a thickness of 100 μm, and the plate-shaped temporary
compact is vacuum-packed, It shape | molded by the press by the pressure of. Next, the above
molded body was fired. The final sintered body had a thickness of 20 μm. The firing
temperature was 1100 ° C., respectively. The polarization process was performed by applying
an electric field of 1.5 × Ec (MV / m) or more for 1 minute.
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[0068]
(Production of Piezoelectric Vibrator for Reception) A piezoelectric vibrator in which a polyester
film was bonded to the polarization treatment film 1 produced in Example 1 was produced.
[0069]
Next, in accordance with a conventional method, a piezoelectric transducer for reception was
laminated on the above-mentioned piezoelectric transducer for transmission, and a backing layer
and an acoustic matching layer were installed to fabricate an ultrasonic probe.
[0070]
As a comparative example, a piezoelectric transducer for reception using the comparative film 1
instead of the polarization treatment film 1 of the piezoelectric transducer for reception is used
as an ultrasonic probe in the same manner as the production of the piezoelectric transducer for
reception. Was produced.
[0071]
(Evaluation) The above two types of ultrasonic probes were evaluated by measuring the
reception sensitivity.
[0072]
As for the reception sensitivity, a fundamental frequency f1 of 5 MHz was transmitted, and a
reception relative sensitivity of 10 MHz as a reception second harmonic f2, 15 MHz as a third
harmonic, and 20 MHz as a fourth harmonic was determined.
The reception relative sensitivity used the sound intensity measurement system Model 805 (1 to
50 MHz) of Sonora Medical Systems, Inc. (Sonora Medical System, Inc: 2021 Miller Drive
Longmont, Colorado (0501 USA)).
[0073]
In the above evaluation, it was confirmed that the probe provided with the polarization treatment
film according to the present invention had a relative reception sensitivity of about 1.5 times that
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of the comparative example.
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