Composition for acoustic lens, acoustic lens, acoustic wave probe, ultrasonic probe, acoustic wave measuring device, ultrasonic diagnostic device, photoacoustic wave measuring device, ultrasonic endoscope, and method for manufacturing acoustic wave probe

Abstract

The composition for acoustic lens of the present invention is not easy to wear and has excellent durability against high-level disinfectants, and the sound velocity is suppressed to achieve high-resolution observation at a short focal length. A composition for acoustic lens, which contains the following components (A) to (C): (A) polysiloxane having a vinyl group; (B) polysiloxane having two or more Si-H groups in the molecular chain; and (C) alumina particles surface-treated with at least one surface treatment agent selected from aminosilane compounds, mercaptosilane compounds, isocyanatosilane compounds, thiocyanatosilane compounds, aluminum alkoxide compounds, zirconium alkoxide compounds, and titanium alkoxide compounds.

Description

Technical Field

[0001] The present invention relates to a composition for an acoustic lens, an acoustic lens, an acoustic wave probe, an ultrasonic probe, an acoustic wave measuring device, an ultrasonic diagnostic device, a photoacoustic wave measuring device, an ultrasonic endoscope, and a method for manufacturing the acoustic wave probe. Background Art

[0002] The ultrasonic measuring device uses an ultrasonic probe, which irradiates the object or part to be examined (hereinafter referred to as "the object to be examined, etc.") with ultrasonic waves, receives the reflected waves (echoes) and outputs signals. The reflected waves received by the ultrasonic probe are converted into electrical signals and displayed as images. Thus, the inside of the object to be examined is visualized and observed.

[0003] As the acoustic wave, an acoustic wave having an appropriate frequency, such as an ultrasonic wave or a photoacoustic wave, is selected according to the object to be examined or the measurement conditions.

[0004] For example, an ultrasonic diagnostic device transmits ultrasonic waves into the interior of an object to be examined, receives ultrasonic waves reflected by tissues inside the object to be examined, and displays them as an image. A photoacoustic wave measuring device receives sound waves radiated from the interior of an object to be examined according to the photoacoustic effect, and displays them as an image. The photoacoustic effect refers to the phenomenon that when an electromagnetic wave pulse such as visible light, near-infrared light, or microwaves is irradiated onto an object to be examined, the object to be examined absorbs the electromagnetic wave, generates heat, and undergoes thermal expansion, thereby generating sound waves (typically ultrasonic waves).

[0005] Since the acoustic wave measuring device transmits and receives acoustic waves with the living body as the object to be examined, for example, the acoustic impedance between the living body (typically the human body) is required to match, and the acoustic wave attenuation is required to be suppressed. In addition, since it is used by friction on the living body, it is also required to have a certain mechanical strength. In order to meet these requirements, the acoustic lens uses silicone resin as the resin material (parent material), and inorganic fillers such as alumina particles are mixed to adjust the acoustic impedance, mechanical strength, etc.

[0006] For example, Patent Document 1 describes a composition for an acoustic lens and a silicone resin for an acoustic lens formed by curing the composition. The composition for an acoustic lens is composed of 100 parts by mass of a diorganopolysiloxane or a silicone rubber compound with the diorganopolysiloxane as the main material, 50 to 150 parts by mass of an aluminum oxide or titanium oxide powder having an average particle size of 0.1 to 1.0 μm, and 10 to 100 parts by mass of a thermoplastic resin powder having an average particle size of 0.1 to 50 μm and a melting point of 80° C. or above.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 62-11897 Summary of the invention

[0010] Technical issues to be solved by the invention

[0011] The ultrasonic measuring device equipped with an ultrasonic probe is used not only for internal body inspections such as the abdomen and heart, but also for inspections of tissues near the body surface such as the breast, thyroid gland, peripheral blood vessels, musculoskeletal muscles, nerves, and skin. These tissues near the body surface have fine structures, so high-resolution inspection images are required.

[0012] Generally, the higher the frequency of the sound wave, the higher the resolution of the sound wave image. Moreover, by reducing the sound velocity of the sound lens constituting the sound wave probe, the focal length can be shortened, and a higher resolution image of the tissue near the body surface can be obtained. That is, by reducing the sound velocity of the sound lens, more accurate information about the living tissue near the body surface can be obtained. However, the composition for the sound lens recorded in the above-mentioned patent document 1 is composed of a combination of aluminum oxide or titanium oxide powder of a specific particle size and a specific thermoplastic resin powder, which are respectively formulated in a silicone rubber compound in specific amounts, and the sound velocity is increased to 900 to 1100 m / sec while achieving the required acoustic impedance. However, the sound wave probe with an acoustic lens having a sound velocity within the above range cannot obtain the sufficiently accurate information required in recent years about the living tissue near the body surface.

[0013] Since the acoustic wave probe transmits and receives acoustic waves by rubbing against a living body, the acoustic lens is worn out by repeated use, and the change in shape of the acoustic lens caused by the wear causes the focus shift of the acoustic wave image. Therefore, the acoustic lens needs to have the property of not being easily worn out even when repeatedly rubbed against a living body.

[0014] In addition, the ultrasonic probe is required to be highly clean and must be disinfected with a strong bactericidal drug each time it is used. Therefore, the ultrasonic probe is required to be durable against the drug.

[0015] The present invention aims to provide a composition for an acoustic lens which is not easily abraded, has excellent durability against high-level disinfectants, and suppresses the speed of sound to enable high-resolution observation at a short focal length, and an acoustic lens obtained by curing the composition.

[0016] Furthermore, the present invention also aims to provide an acoustic wave probe, an ultrasonic probe, an acoustic wave measuring device, an ultrasonic diagnostic device, a photoacoustic wave measuring device, an ultrasonic endoscope and a method for manufacturing the acoustic wave probe having the above-mentioned acoustic lens.

[0017] Means for solving technical problems

[0018] The present inventors have conducted intensive studies in view of the above-mentioned problems, and have found that a cured product obtained by curing a polysiloxane having a vinyl group and a polysiloxane having two or more Si-H groups in the presence of alumina particles treated with a specific surface treatment agent has excellent wear durability and chemical durability, and also has excellent characteristics as an acoustic lens capable of sufficiently reducing and controlling the speed of sound and enabling high-resolution observation at a short focal length. The present invention has been completed based on these findings.

[0019] That is, the above-mentioned problems of the present invention are solved by the following means.

[0020] <1>

[0021] A composition for an acoustic lens, comprising the following components (A) to (C):

[0022] (A) polysiloxane having a vinyl group;

[0023] (B) polysiloxane having two or more Si-H groups in the molecular chain; and

[0024] (C) Alumina particles surface-treated with at least one surface treatment agent selected from the group consisting of aminosilane compounds, mercaptosilane compounds, isocyanatosilane compounds, thiocyanatosilane compounds, aluminum alkoxide compounds, zirconium alkoxide compounds, and titanium alkoxide compounds.

[0025] <2>

[0026] according to <1> The composition for acoustic lens, wherein:

[0027] The surface treatment agent is at least one of an aminosilane compound, a mercaptosilane compound, an isocyanatosilane compound, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound.

[0028] <3>

[0029] according to <1> or <2> The composition for acoustic lens, wherein:

[0030] The surface treatment agent is at least one of a mercaptosilane compound, an isocyanatosilane compound, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound.

[0031] <4>

[0032] according to <1> to <3> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0033] The surface treatment agent is at least one of an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound.

[0034] <5>

[0035] according to <1> to <4> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0036] The aluminum alkoxide compound includes an aluminum alkoxide compound having at least one structure of an acetonate structure and an acetate structure.

[0037] <6>

[0038] according to <1> to <5> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0039] The aluminum alkoxide compound contains at least one compound represented by the following general formula (1).

[0040] General formula (1): R 1a m1 -Al-(OR 2a ) 3-m1

[0041] R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group,

[0042] R 2a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S1 , R S1 represents a substituent,

[0043] m1 is an integer from 0 to 2.

[0044] <7>

[0045] according to <1> to <6> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0046] The zirconium alkoxide compound includes a zirconium alkoxide compound having at least one of an acetonate structure and an acetate structure.

[0047] <8>

[0048] according to <1> to <7> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0049] The zirconium alkoxide compound contains at least one compound represented by the following general formula (2).

[0050] General formula (2): R 1b m2 -Zr-(OR 2b ) 4-m2

[0051] R 1brepresents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0052] R 2b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S2 , R S2 represents a substituent,

[0053] m2 is an integer from 0 to 3.

[0054] <9>

[0055] according to <1> to <8> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0056] The titanium alkoxide compound includes a titanium alkoxide compound containing at least one atom of N, P, and S.

[0057] <10>

[0058] according to <1> to <9> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0059] The titanium alkoxide compound contains at least one compound represented by the following general formula (3).

[0060] General formula (3): R 1c m3 -Ti-(OR 2c ) 4-m3

[0061] R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group,

[0062] R 2c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S3 , R S3 represents a substituent,

[0063] m3 is an integer from 0 to 3.

[0064] <11>

[0065] according to <1> to <10> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0066] In the component (C), the content of the surface treatment agent is 1 to 100 parts by mass based on 100 parts by mass of the aluminum oxide particles.

[0067] <12>

[0068] according to <1> to <11> The composition for an acoustic lens according to any one of the preceding claims, wherein

[0069] The average primary particle size of the aluminum oxide particles constituting the component (C) is 10 to 400 nm.

[0070] <13>

[0071] An acoustic lens, which is composed of <1> to <12> The composition for an acoustic lens described in any one of the above is cured.

[0072] <14>

[0073] An acoustic wave probe having <13> The acoustic lens.

[0074] <15>

[0075] An ultrasonic probe having <13> The acoustic lens.

[0076] <16>

[0077] An acoustic wave measuring device comprising <14> The sonic probe.

[0078] <17>

[0079] An ultrasonic diagnostic device having <14> The sonic probe.

[0080] <18>

[0081] A photoacoustic wave measuring device comprising <13> The acoustic lens.

[0082] <19>

[0083] An ultrasonic endoscope having <13> The acoustic lens.

[0084] <20>

[0085] A method for manufacturing an acoustic wave probe, comprising using <1> to <12> The step of forming an acoustic lens with the composition for an acoustic lens described in any one of the preceding claims.

[0086] In the description of this specification, "metal alkoxide compound (specifically, for example, titanium alkoxide compound, aluminum alkoxide compound and zirconium alkoxide compound described later)" refers to a compound having a structure in which at least one alkoxy group is bonded to a metal atom. The alkoxy group may have a substituent. The substituent may be monovalent or divalent (for example, an alkylene group). Furthermore, two alkoxy groups bonded to one metal atom may be bonded to each other to form a ring.

[0087] In the description of this specification, unless otherwise specified, when there are multiple groups with the same symbol in the general formula representing the compound, they may be the same or different from each other, and the group determined by each group (for example, an alkyl group) may further have a substituent. In addition, the "Si-H group" represents a group having three connecting bonds on the silicon atom, but the description of the connecting bonds is omitted to simplify the description. Similarly, in the "Si-N-Si structure", each silicon atom has three connecting bonds and the nitrogen atom has one connecting bond.

[0088] Furthermore, in this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0089] Effects of the Invention

[0090] The composition for an acoustic lens of the present invention is not easily abraded and has excellent durability (chemical durability) against high-level disinfectants. In addition, an acoustic lens capable of short-focal-length and high-resolution observation can be realized by suppressing the speed of sound.

[0091] Furthermore, the acoustic lens of the present invention is not easily abraded, has excellent durability against high-level disinfectants, and can achieve high-resolution observation at a short focal length.

[0092] Furthermore, the acoustic wave probe, ultrasonic wave probe, acoustic wave measuring device, ultrasonic diagnostic device, photoacoustic wave measuring device, and ultrasonic endoscope of the present invention have an acoustic lens having the above-mentioned excellent characteristics.

[0093] Furthermore, according to the method for manufacturing an acoustic wave probe of the present invention, an acoustic wave probe including the above-mentioned acoustic lens can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0094] Figure 1 This is a perspective view of an example of a convex ultrasonic probe which is one form of an ultrasonic probe. DETAILED DESCRIPTION

[0095] <<Composition for acoustic lens>>

[0096] The composition for an acoustic lens of the present invention (hereinafter, also simply referred to as “composition”) contains the following components (A) to (C).

[0097] (A) Polysiloxane having a vinyl group (component (A))

[0098] (B) Polysiloxane having two or more Si-H groups in the molecular chain (component (B))

[0099] (C) Alumina particles surface-treated with at least one surface treatment agent selected from the group consisting of aminosilane compounds, mercaptosilane compounds, isocyanatosilane compounds, thiocyanatosilane compounds, aluminum alkoxide compounds, zirconium alkoxide compounds, and titanium alkoxide compounds (component (C))

[0100] As described above, the composition of the present invention contains (A) a polysiloxane having a vinyl group (polyorganosiloxane) and (B) a polysiloxane having two or more Si-H groups in its molecular chain. Among them, (B) a polysiloxane having two or more Si-H groups in its molecular chain is preferably (B) a polyorganosiloxane having two or more Si-H groups in its molecular chain.

[0101] Therefore, the composition of the present invention preferably contains at least the components (A), (B) a polyorganosiloxane having two or more Si-H groups in its molecular chain (component (B)), and the component (C).

[0102] The acoustic lens of the present invention obtained by curing the composition of the present invention having the above structure can achieve a low sound velocity, is not easily abraded, and has excellent durability against chemicals. The reasons for these are not clear, but can be presumed as follows.

[0103] That is, the component (C) contained in the acoustic lens of the present invention can improve the uniform dispersion in the lens with silicone resin as the matrix by surface-treating the aluminum oxide particles with a specific surface treatment agent. As a result, it is believed that the speed of sound is effectively reduced by increasing the phase delay generated at the interface of the aluminum oxide particles. In addition, it is believed that by further surface-treating the aluminum oxide particles with a high Mohs hardness and originally not easy to wear with a specific surface treatment agent, the adhesion between the aluminum oxide particles treated with the surface and the matrix is ​​also improved, and the acoustic lens is not easy to wear even if rubbed on a living body. In addition, it is also believed that the durability of the above-mentioned acoustic lens to body fluids is excellent because the above-mentioned surface treatment agent itself has excellent durability to body fluids.

[0104] In the following detailed description, (A) polyorganosiloxane having a vinyl group (component (A)) and (B) polyorganosiloxane having two or more Si-H groups in the molecular chain (component (B)) are described as preferred embodiments. However, the present invention is not limited to the embodiments described below.

[0105] <(A) Polyorganosiloxane Having a Vinyl Group (Component (A))>

[0106] The component (A) used in the present invention preferably has two or more vinyl groups in the molecular chain.

[0107] As component (A), for example, polysiloxane (a1) having vinyl groups at least at both ends of the molecular chain (hereinafter, also referred to as component (a1)) or polysiloxane (a2) having at least two -O-Si(CH3)2 (CH=CH2) groups in the molecular chain other than the ends (hereinafter, also referred to as polysiloxane (a2)) can be cited. Among them, polysiloxane (a1) having vinyl groups at least at both ends of the molecular chain is preferred.

[0108] The polysiloxane (a2) is preferably a polysiloxane (a2) in which -O-Si(CH3)2 (CH=CH2) is bonded to a Si atom constituting the main chain.

[0109] Component (A) is hydrosilylated by reaction with component (B) in the presence of a platinum catalyst, for example. A crosslinked structure (cured body) can be formed by this hydrosilylation reaction (addition reaction).

[0110] The vinyl content of component (A) is not particularly limited, but is preferably 0.01 to 5 mol %, more preferably 0.05 to 2 mol %, for example, from the viewpoint of forming a sufficient network with each component contained in the acoustic lens composition.

[0111] Here, the content of vinyl groups refers to the mole % of the vinyl-containing siloxane unit when all units constituting component (A) are set to 100 mol %. One vinyl-containing siloxane unit has 1 to 3 vinyl groups. Among them, one vinyl group is preferably used for one vinyl-containing siloxane unit. For example, when all Si atoms constituting the Si-O unit of the main chain and the terminal Si each have at least one vinyl group, it becomes 100 mol %.

[0112] In addition, the "unit" of polysiloxane refers to the Si-O unit constituting the main chain and the terminal Si.

[0113] Furthermore, component (A) preferably has a phenyl group, and the content of the phenyl group in the polyorganosiloxane (A) is not particularly limited. From the viewpoint of mechanical strength when used as an acoustic lens, for example, it is preferably 1 to 80 mol %, and more preferably 2 to 40 mol %.

[0114] Here, the content of phenyl groups refers to the mole % of the phenyl-containing siloxane unit when all units constituting component (A) are set to 100 mol %. One phenyl-containing siloxane unit has 1 to 3 phenyl groups. Among them, two phenyl groups are preferably used for one phenyl-containing siloxane unit. For example, when all Si atoms constituting the Si-O unit of the main chain and the terminal Si each have at least one phenyl group, it becomes 100 mol %.

[0115] Component (A) preferably does not have two or more Si—H groups in the molecular chain.

[0116] The degree of polymerization and specific gravity are not particularly limited. From the viewpoint of improving the mechanical strength (tear strength) and chemical stability of the obtained acoustic lens and the viscosity of the composition before curing, the degree of polymerization is preferably 200 to 3,000, more preferably 400 to 2,000, and the specific gravity is preferably 0.9 to 1.1.

[0117] The weight average molecular weight of the component (A) is preferably 20,000 to 200,000, more preferably 40,000 to 150,000, and even more preferably 45,000 to 120,000, from the viewpoint of the mechanical strength of the acoustic lens and the viscosity of the composition before curing.

[0118] The weight average molecular weight can be measured, for example, as follows: prepare a GPC (Gel Permeation Chromatography) apparatus HLC-8220 (trade name, manufactured by TOSOH CORPORATION), use toluene (manufactured by Shonan Wako Pure Chemical Industries, Ltd.) as an eluent, use TSKgel G3000HXL + TSKgel G2000HXL (both trade names, manufactured by TOSOH CORPORATION) as a column, and measure using an RI (Refractive Index) detector under the conditions of a temperature of 23°C and a flow rate of 1 mL / min.

[0119] The kinematic viscosity of component (A) at 25°C is preferably 1×10 -5 ~10m 2 / s, more preferably 1×10 -4 ~1m 2 / s, more preferably 1×10 -3 ~0.5m 2 / s.

[0120] The kinematic viscosity can be determined by measuring at a temperature of 25° C. using an Ubbelohde viscometer (for example, manufactured by SIBATA SCIENTIFICTECHNOLOGY LTD., trade name SU) in accordance with JIS Z8803.

[0121] The polyorganosiloxane (a1) having vinyl groups at least at both ends of the molecular chain is preferably a polyorganosiloxane represented by the following general formula (I).

[0122] [Chemical formula 1]

[0123]

[0124] In the general formula (I), R a1 Represents vinyl, Ra2 and R a3 Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. x1 and x2 each independently represent an integer greater than 1.

[0125] R a2 and R a3 The carbon number of the alkyl group in is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl and decyl.

[0126] R a2 and R a3 The number of carbon atoms of the cycloalkyl in is preferably 3 to 10, more preferably 5 to 10, and further preferably 5 or 6. The cycloalkyl is preferably a 3-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 5-membered ring or a 6-membered ring. Examples of the cycloalkyl include cyclopropyl, cyclopentyl, and cyclohexyl.

[0127] R a2 and R a3 The number of carbon atoms of the alkenyl group in is preferably 2 to 10, more preferably 2 to 4, and further preferably 2. Examples of the alkenyl group include vinyl, allyl, and butenyl.

[0128] R 2a and R a3 The carbon number of the aryl group in is preferably 6 to 12, more preferably 6 to 10, and further preferably 6 to 8. Examples of the aryl group include phenyl, tolyl, and naphthyl.

[0129] These alkyl groups, cycloalkyl groups, alkenyl groups and aryl groups may have a substituent, and examples of such substituents include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a silyl group and a cyano group.

[0130] Examples of the group having a substituent include a halogenated alkyl group.

[0131] R a2 and R a3 An alkyl group, an alkenyl group or an aryl group is preferred, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a phenyl group is more preferred, a methyl group, a vinyl group or a phenyl group is further preferred, and a methyl group or a phenyl group is particularly preferred.

[0132] Where R a2 Preferably methyl. a3 It is preferably a methyl group, a vinyl group or a phenyl group, more preferably a methyl group or a phenyl group, and particularly preferably a phenyl group.

[0133] x1 is preferably an integer of 200 to 3,000, more preferably an integer of 400 to 2,000.

[0134] x2 is preferably an integer of 1 to 3,000, more preferably an integer of 1 to 1,000, further preferably an integer of 40 to 1,000, and particularly preferably an integer of 40 to 700.

[0135] Furthermore, as another aspect, x1 is preferably an integer of 1 to 3,000, and more preferably an integer of 5 to 1,000.

[0136] In the present invention, the repeating unit "-Si(R a3 )2-O-” and “-Si(R a2 )3-O-" can exist in the form of block polymerization or in a random form.

[0137] Examples of polyorganosiloxanes having vinyl groups at at least both ends of the molecular chain include the DMS series (e.g., DMS-V31, DMS-V31S15, DMS-V33, DMS-V35, DMS-V35R, DMS-V41, DMS-V42, DMS-V46, DMS-V51, and DMS-V52), the PDV series (e.g., PDV-0341, PDV-0346, PDV-0535, PDV-0541, PDV-1631, PDV-1635, PDV-1641, and PDV-2335), PMV-9925, PVV-3522, FMV-4031, and EDV-2022, all of which are trade names manufactured by Gelest.

[0138] In addition, DMS-V31S15 has been formulated with fumed silica, so no special equipment is required for mixing.

[0139] In the present invention, the component (A) may be used alone or in combination of two or more.

[0140] <(B) Polyorganosiloxane Having Two or More Si—H Groups in the Molecular Chain (Component (B))>

[0141] The component (B) used in the present invention has two or more Si-H groups in the molecular chain. Here, when the component (B) has a "-SiH2-" structure, the Si-H groups in the "-SiH2-" structure are counted as two. And, when the component (B) has a "-SiH3" structure, the Si-H groups in the "-SiH3" structure are counted as three.

[0142] By having two or more Si—H groups in the molecular chain, the polyorganosiloxane having at least two polymerizable unsaturated groups can be cross-linked.

[0143] Component (B) preferably does not have a vinyl group.

[0144] Component (B) includes polyorganosiloxanes having a linear structure and polyorganosiloxanes having a branched structure, and polyorganosiloxanes having a linear structure are preferred.

[0145] From the viewpoint of the mechanical strength of the silicone resin and the viscosity of the composition before curing, the weight average molecular weight of component (B) is preferably 500 to 100,000, more preferably 1,500 to 50,000. The weight average molecular weight of component (B) can be measured in the same manner as the weight average molecular weight of component (A).

[0146] The component (B) having a linear structure is preferably a polyorganosiloxane represented by the following general formula (II).

[0147] [Chemical formula 2]

[0148]

[0149] In the general formula (II), R b1 ~R b3 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. y1 and y2 each independently represent an integer greater than 1. There are two or more Si-H groups in the molecular chain.

[0150] As R b1 ~R b3 The alkyl, cycloalkyl, alkenyl and aryl groups in the a2 and R a3 The alkyl, cycloalkyl, alkenyl and aryl groups in the

[0151] R b1 ~R b3 A hydrogen atom, an alkyl group, an alkenyl group or an aryl group is preferred, and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a phenyl group is more preferred.

[0152] Among them, R b1 and R b2 A hydrogen atom, an alkyl group, an alkenyl group or an aryl group is preferred, a hydrogen atom or an alkyl group is more preferred, a hydrogen atom or a methyl group is further preferred, and a methyl group is particularly preferred.

[0153] R b3 A hydrogen atom, an alkyl group, an alkenyl group or an aryl group is preferred, a hydrogen atom or an aryl group is more preferred, a hydrogen atom or a phenyl group is further preferred, and a hydrogen atom is particularly preferred.

[0154] y1 is preferably an integer of 0 to 2,000, more preferably an integer of 0 to 1,000, and still more preferably an integer of 0 to 30.

[0155] y2 is preferably an integer of 1 to 2,000, more preferably an integer of 1 to 1,000, and still more preferably an integer of 1 to 30.

[0156] y1+y2 is preferably an integer of 5 to 2,000, more preferably an integer of 7 to 1,000, further preferably an integer of 10 to 50, and particularly preferably an integer of 15 to 30.

[0157] In the present invention, the "-Si(R b2 )2-O-” and “-Si(R b2 )(R b3 )2-O-" can exist in the polysiloxane in the form of block polymerization or in the form of random polymerization.

[0158] As R b1 ~R b3 Combination of R b1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R b2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R b3 A combination of a hydrogen atom or an aromatic group.

[0159] In this preferred combination, the content of the hydrosilyl group represented by y2 / (y1+y2) is preferably greater than 0.1 and less than 1.0, and more preferably greater than 0.2 and less than 1.0.

[0160] Examples of the linear component (B) include methyl hydrogen siloxane-dimethyl siloxane copolymers (trimethylsiloxane ends) HMS-064 (MeHSiO: 5-7 mol%), HMS-082 (MeHSiO: 7-8 mol%), HMS-301 (MeHSiO: 25-30 mol%), HMS-501 (MeHSiO: 50-55 mol%), methyl hydrogen siloxane-phenyl methyl siloxane copolymers HPM-502 (MeHSiO: 45-50 mol%), and methyl hydrogen siloxane polymers HMS-991 (MeHSiO: 100 mol%), all manufactured by Gelest.

[0161] Here, the mol% of MeHSiO is related to the above R b1 ~R b3 The meaning of y2 / (y1+y2) multiplied by 100 in the preferred combination is the same.

[0162] The component (B) having a branched structure has a branched structure and two or more hydrosilyl groups (Si—H groups).

[0163] The specific gravity is preferably 0.9 to 0.95.

[0164] The branched component (B) is preferably a component represented by the following average composition formula (b).

[0165] Average composition formula (b): [Ha (R b6 ) 3-a SiO 1 / 2 ] y3 [SiO 4 / 2 ] y4

[0166] Here, R b6 represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, a represents 0.1 to 3, and y3 and y4 each independently represent an integer greater than 1.

[0167] As R b6 The alkyl, cycloalkyl, alkenyl and aryl groups in the a2 and R a3 The alkyl, cycloalkyl, alkenyl and aryl groups in the

[0168] a is preferably 1.

[0169] The content of the hydrosilyl group represented by a / 3 is preferably greater than 0.1 and less than 0.6, and more preferably greater than 0.1 and less than 0.4.

[0170] On the other hand, when the branched component (B) is represented by a chemical structural formula, a polyorganosiloxane in which -O-Si(CH3)2(H) is bonded to the Si atom constituting the main chain is preferred, and a structure represented by the following general formula (IIb) is more preferred.

[0171] [Chemical formula 3]

[0172]

[0173] In the general formula (IIb), * represents bonding to at least the Si atom of siloxane.

[0174] Examples of the branched structure component (B) include HQM-107 (trade name, manufactured by Gelest, hydrogenated Q resin) and HDP-111 (trade name, manufactured by Gelest, polyphenyl-(dimethylhydroxy)siloxane (hydrogen terminal), [(HMe2SiO)(C6H3Si)O]: 99-100 mol%).

[0175] The component (B) may be used alone or in combination of two or more. Furthermore, a component (B) having a linear structure and a component (B) having a branched structure may be used in combination.

[0176] <Surface-treated alumina particles (component (C))>

[0177] Component (C) is aluminum oxide particles surface-treated with at least one surface treatment agent selected from aminosilane compounds, mercaptosilane compounds, isocyanatosilane compounds, thiocyanatosilane compounds, aluminum alkoxide compounds, zirconium alkoxide compounds, and titanium alkoxide compounds.

[0178] The average primary particle size (average particle size) of the alumina particles constituting component (C) used in the present invention (alumina particles before surface treatment, hereinafter referred to as "alumina particles") is not particularly limited, but is preferably 5 to 500 nm, more preferably 10 to 400 nm, more preferably 10 to 250 nm, more preferably 10 to 200 nm, more preferably 10 to 160 nm, more preferably 20 to 150 nm, further preferably 20 to 100 nm, and particularly preferably 20 to 80 nm, from the viewpoint of the sound velocity, adhesion and chemical durability of the acoustic lens.

[0179] The average primary particle size of the component (C) is preferably 5 to 1000 nm, more preferably 10 to 600 nm, more preferably 10 to 300 nm, further preferably 20 to 200 nm, further preferably 30 to 150 nm, particularly preferably 30 to 100 nm.

[0180] The average primary particle size is recorded in the catalog of the alumina particle manufacturer. When the average primary particle size is not recorded in the catalog or the alumina particles are newly manufactured, the average primary particle size can be obtained by averaging the particle sizes measured by a transmission electron microscope (TEM). That is, the shortest diameter and the longest diameter of one alumina particle in the electron microscope photograph taken by TEM are measured, and the arithmetic mean thereof is used as the particle size of one alumina particle to obtain. In the present invention, the particle sizes of 300 randomly selected alumina particles are averaged to obtain the average primary particle size.

[0181] Commercially available alumina particles can be used, and examples thereof include NO series manufactured by Iolitec Ionic Liquids Technologies GmbH and NP-ALO-5-1K manufactured by EM Japan Co., Ltd. (both are trade names).

[0182] From the viewpoint of the sound velocity, wear durability and chemical durability of the acoustic lens, the surface treatment agent used in the present invention is preferably an aminosilane compound, a mercaptosilane compound, an isocyanatosilane compound, an aluminum alkoxide compound, a zirconium alkoxide compound and a titanium alkoxide compound, more preferably a mercaptosilane compound, an isocyanatosilane compound, an aluminum alkoxide compound, a zirconium alkoxide compound and a titanium alkoxide compound, further preferably an aluminum alkoxide compound, a zirconium alkoxide compound and a titanium alkoxide compound.

[0183] Hereinafter, the surface treatment agent used in the present invention will be specifically described.

[0184] (Aminosilane compound)

[0185] The aminosilane compound (silane compound having an amino group) is preferably a silane coupling agent having an amino group. Among them, the aminosilane compound preferably does not have a Si-N-Si structure.

[0186] The aminosilane compound preferably contains at least one compound represented by the following general formula (A).

[0187] [Chemical formula 4]

[0188] General formula (A)

[0189] In the formula, R 1 and R 2 represents a hydrogen atom or a substituent. 1a represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, or -NR a -, ester bond, thioester bond, amide bond, sulfamide bond or sulfonyl group or a divalent group formed by combining two or more of these groups or bonds. a represents a hydrogen atom or a substituent. 1a Y represents a hydroxyl group or an alkoxy group. 2a and Y 3a represents a hydroxyl group, an alkoxy group, an alkyl group or a ketoximate group.

[0190] As R 1 and R 2 Examples of substituents that can be used include alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms), and aryl groups (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms). These substituents may further have substituents, and examples of these substituents that can be used as R include 1 and R 2 The substituents listed above and the amino group are substituents.

[0191] And, R 1 and R 2 They may be combined to represent an alkylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms).

[0192] L 1a Preferably, it represents an alkylene group, an alkenylene group, an arylene group, -O- or -NR a -, more preferably represents an alkylene group, an arylene group or -NRa -, more preferably represents an alkylene group.

[0193] Y 1a Preferably it represents an alkoxy group.

[0194] Y 2a and Y 3a Preferably, it represents a hydroxyl group, an alkoxy group or an alkyl group, and more preferably, it represents an alkoxy group or an alkyl group.

[0195] As L 1a The alkylene group that can be used may be any of linear, branched and cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 25, further preferably 1 to 20, further preferably 1 to 15. Specific examples of the alkylene group include methylene, ethylene, propylene, tert-butylene, pentylene, cyclohexylene, heptylene, octylene, nonyl, decyl and undecene.

[0196] As L 1a The alkenylene group may be straight chain or branched. The number of carbon atoms in the alkenylene group is preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10, and further preferably 2 to 6. Specific examples of the alkenylene group include vinylene and propenylene.

[0197] As L 1a The alkynylene group that can be used may be either a straight chain or a branched chain. The number of carbon atoms in the alkynylene group is preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10, and further preferably 2 to 6. Specific examples of the alkynylene group include ethynylene and propynylene.

[0198] As L 1a The number of carbon atoms of the arylene group that can be adopted is preferably 6 to 20, more preferably 6 to 15, more preferably 6 to 12, and further preferably 6 to 10. Specific examples of the arylene group include a phenylene group and a naphthylene group.

[0199] AS-NR a -R a Examples of substituents that can be used include alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms), aryl groups (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), and heterocyclic groups. aThe heterocyclic ring of the heterocyclic group that can be adopted may be a saturated or unsaturated aliphatic heterocyclic ring, or an aromatic heterocyclic ring, and may be a monocyclic ring or a condensed ring. In addition, it may be a bridged ring. Examples of heteroatoms possessed by the heterocyclic ring include oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms contained in one heterocyclic ring is not particularly limited, and is preferably 1 to 3, more preferably 1 or 2. The number of carbon atoms in the heterocyclic ring is preferably 2 to 10, more preferably 4 or 5. The heterocyclic ring is preferably a 3-7-membered ring, more preferably a 3-6-membered ring, and further preferably a 3-5-membered ring. Specific examples of the heterocyclic ring include an epoxy ring, a 3,4-epoxycyclohexane ring, a furan ring, and a thiophene ring.

[0200] AS-NR a -, for example -NH-.

[0201] As L 1a The divalent group (hereinafter also referred to as "L") formed by combining two or more of the above groups or bonds can be used. 1a The number of the combined groups or bonds that can be adopted is preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.

[0202] And, as L 1a The molecular weight of the combining group that can be used is preferably 20 to 1,000, more preferably 30 to 500, and even more preferably 40 to 200.

[0203] As can be adopted as L 1a The combination group includes, for example, a urea bond, a thiourea bond, a carbamate group, a sulfonamide bond, an arylene-alkylene group, -O-alkylene group, an amide bond-alkylene group, -S-alkylene group, an alkylene-O-amide bond-alkylene group, an alkylene-amide bond-alkylene group, an alkenylene-amide bond-alkylene group, an alkylene-ester bond-alkylene group, an arylene-ester bond-alkylene group, -(alkylene-O)-, an alkylene-O-(alkylene-O-)alkylene group ("(alkylene-O)" are all repeating units), an arylene-sulfonyl-O-alkylene group and an ester bond-alkylene group.

[0204] Composition as Y 1a ~Y 3a The alkyl group of the alkoxy group that can be used may be any of a straight chain, a branched chain, and a cyclic group, or may have a combination of these forms. In the present invention, the alkyl group is preferably a straight chain alkyl group. The number of carbon atoms of the alkyl group constituting the alkoxy group is preferably 1 to 15, more preferably 1 to 10, more preferably 1 to 5, and further preferably 1 or 2. Specific examples of the alkyl group constituting the alkoxy group include a methyl group, an ethyl group, a propyl group, a tert-butyl group, a pentyl group, and a cyclohexyl group.

[0205] As can be adopted as Y 2a and Y 3aThe alkyl group of Y can be exemplified by 1a ~Y 3a The alkyl group of the alkoxy group that can be used has the same preferred form as Y. 1a ~Y 3a Preferred embodiments of the alkyl group of the alkoxy group that can be adopted are the same.

[0206] As Y 2a and Y 3a The ketoximo group that can be employed is a substituent having the following structure.

[0207] [Chemical formula 5]

[0208]

[0209] In the above structure, R 11 and R 12 represents a substituent, and * represents a portion bonding to a silicon atom.

[0210] As R 11 and R 12 The substituents that can be used include the above R a The preferred form of the substituent in R is also the same as a Preferred aspects of the substituents that can be adopted are the same.

[0211] Examples of the ketoxime group include a dimethylketoxime group, a methylethylketoxime group, and a diethylketoxime group.

[0212] Specific examples of the aminosilane compound used in the present invention are given below, but the present invention is not limited thereto.

[0213] 3-Aminopropyltrimethoxysilane

[0214] 3-Aminopropyldimethylmethoxysilane

[0215] 3-Aminopropylmethyldimethoxysilane

[0216] 3-Aminopropylmethyldiethoxysilane

[0217] 3-Aminopropyltrimethoxysilane

[0218] 3-Aminopropyltriethoxysilane

[0219] N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane

[0220] N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane

[0221] N-(2-aminoethyl)-3-aminopropyltrimethoxysilane

[0222] N-(2-aminoethyl)-3-aminopropyltriethoxysilane

[0223] 3-Methyldimethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine

[0224] 3-Methyldiethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine

[0225] 3-Trimethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine

[0226] 3-Triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine

[0227] N-phenyl-3-aminopropylmethyldimethoxysilane

[0228] N-phenyl-3-aminopropylmethyldiethoxysilane

[0229] N-phenyl-3-aminopropyltrimethoxysilane

[0230] N-phenyl-3-aminopropyltriethoxysilane

[0231] N-(Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane

[0232] (Mercaptosilane compound)

[0233] The mercaptosilane compound (a silane compound having a mercapto (sulfanyl) group) is preferably a silane coupling agent having a mercapto group. The aluminum oxide particles surface-treated with the mercaptosilane compound preferably have a mercapto group derived from the mercaptosilane compound.

[0234] The mercaptosilane compound preferably contains at least one compound represented by the following general formula (B).

[0235] [Chemical formula 6]

[0236] General formula (B)

[0237] L 1b , Y 1b , Y 2b and Y 3b The meanings are the same as those of L in the above general formula (A). 1a , Y 1a , Y 2a and Y 3a The meanings are the same, and the preferred ranges are also the same.

[0238] Specific examples of the mercaptosilane compound used in the present invention are given below, but the present invention is not limited thereto.

[0239] 3-Mercaptopropyltrimethoxysilane

[0240] 3-Mercaptopropyltriethoxysilane

[0241] 3-Mercaptopropylmethyldimethoxysilane

[0242] Mercaptomethylmethyldiethoxysilane

[0243] (Mercaptomethyl)methyldimethoxysilane

[0244] (Mercaptomethyl)dimethylethoxysilane

[0245] 11-Mercaptoundecyltrimethoxysilane

[0246] (isocyanatosilane compound)

[0247] The isocyanatosilane compound (preferably a silane compound having an isocyanate group) is preferably a silane coupling agent having an isocyanate group. The aluminum oxide particles surface-treated with the isocyanatosilane compound preferably have an isocyanate group derived from the isocyanatosilane compound.

[0248] The isocyanatosilane compound preferably contains at least one compound represented by the following general formula (C).

[0249] [Chemical formula 7]

[0250] Tongwu(C)

[0251] L 1c , Y 1c , Y 2c and Y 3c The meaning of L in the above general formula (A) is 1a , Y 1a , Y 2a and Y 3a The meanings of are the same, and the preferred ranges are also the same.

[0252] Furthermore, in the present invention, as the isocyanatosilane compound, it is preferred to use a condensate of a compound represented by the above general formula (C) and a compound in which the isocyanate group of the above general formula (C) is protected by a substituent. The above substituent can be introduced, for example, by an alcohol compound, a phenol compound, an aromatic amine, a lactam, and an oxime. Examples of these alcohol compounds include alkyl alcohols (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms). Examples of phenol compounds include phenol and cresol. Examples of lactams include ε-caprolactam.

[0253] The "compound in which the isocyanate group of the general formula (C) is protected by a substituent" means that -NCO of the general formula (C) is replaced by -NHC(=0)OR4 Substituted compounds. 4 It represents a substituent, and examples thereof include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms).

[0254] Specific examples of the isocyanate silane compound used in the present invention are given below, but the present invention is not limited thereto.

[0255] 3-Isocyanatopropyltrimethoxysilane

[0256] 3-Isocyanatopropyltriethoxysilane

[0257] Isocyanatomethyltrimethoxysilane

[0258] (The following are isocyanato silane compounds protected by condensation or substituents)

[0259] Tris(3-trimethoxysilylpropyl)isocyanurate

[0260] (3-Triethoxysilylpropyl)-tert-butylcarbamate

[0261] Triethoxysilylpropylethylcarbamate

[0262] (Thiocyanatosilane compounds)

[0263] The thiocyanatosilane compound (silane compound having a thiocyanate group) is preferably a silane coupling agent having a thiocyanate group. The aluminum oxide particles surface-treated with the thiocyanatosilane compound preferably have a thiocyanate group derived from the thiocyanatosilane compound.

[0264] The thiocyanatosilane compound preferably contains at least one compound represented by the following general formula (D).

[0265] [Chemical formula 8]

[0266] Tongwu(D)

[0267] L 1d , Y 1d , Y 2d and Y 3d The meaning of L in the above general formula (A) is 1a , Y 1a , Y 2a and Y 3a The meanings of are the same, and the preferred ranges are also the same.

[0268] Specific examples of the thiocyanate silane compound used in the present invention are given below, but the present invention is not limited thereto.

[0269] 3-Thiocyanatepropyltrimethoxysilane

[0270] 3-Thiocyanatepropyltriethoxysilane

[0271] Thioaminomethyltrimethoxysilane

[0272] (Aluminum alkoxide compound)

[0273] The aluminum alkoxide compound preferably includes an aluminum alkoxide compound having at least one structure of an acetonate structure and an acetate structure.

[0274] The aluminum alkoxide compound preferably contains at least one compound represented by the following general formula (1).

[0275] General formula (1): R 1a m1 -Al-(OR 2a ) 3-m1

[0276] R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group,

[0277] As R 1a The alkyl group that can be used includes a straight chain alkyl group, a branched chain alkyl group, and an aralkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 8, but in the case of an aralkyl group, it is preferably 7 to 30. Preferred specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a tridecyl group, an octadecyl group, a benzyl group, and a phenethyl group.

[0278] As R 1a The alkyl group which can be used preferably has an oxirane ring. 1a The number of rings of the cycloalkyl group (cycloalkyl group having a structure in which ethylene oxide rings are condensed) in the cyclooxyalkyl group that can be adopted is preferably 4 to 8, more preferably 5 or 6, and further preferably 6 (ie, cyclohexyl oxide).

[0279] And, as R 1a The alkyl group which can be adopted also preferably has a group selected from an amino group, an isocyanate group, a mercapto group, an ethylenically unsaturated group and an acid anhydride group.

[0280] As R 1a The number of carbon atoms in the cycloalkyl group that can be adopted is preferably 3 to 20, more preferably 3 to 15, further preferably 3 to 10, and particularly preferably 3 to 8. Preferred specific examples of the cycloalkyl group include cyclopropyl, cyclopentyl and cyclohexyl.

[0281] As R 1aThe number of carbon atoms of the acyl group that can be used is preferably 2 to 40, more preferably 2 to 30, further preferably 2 to 20, and particularly preferably 2 to 18.

[0282] As R 1a The number of carbon atoms of the aryl group that can be used is preferably 6 to 20, more preferably 6 to 15, further preferably 6 to 12, and particularly preferably 6 to 10. Preferred specific examples of the aryl group include phenyl and naphthyl, and phenyl is more preferred.

[0283] As R 1a The number of carbon-carbon unsaturated bonds of the unsaturated aliphatic group that can be used is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. The unsaturated aliphatic group may contain a heteroatom, and is also preferably a hydrocarbon group. When the unsaturated aliphatic group is a hydrocarbon group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 10, further preferably 2 to 8, and further preferably 2 to 5. The unsaturated aliphatic group is more preferably an alkenyl group or an alkynyl group.

[0284] R 1a A hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group is preferred, and an alkyl group or a cycloalkyl group is more preferred.

[0285] In the compound of general formula (1) having two or more R 1a In the case of two R 1a They can be connected to each other to form a ring.

[0286] R 2a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group (phosphonic acid group) or -SO2R S1 . R S1 represents a substituent,

[0287] As R 2a The meanings of the alkyl, cycloalkyl, acyl and aryl groups that can be used are the same as those for R. 1a The alkyl group, cycloalkyl group, acyl group and aryl group that can be adopted have the same meanings, and the preferred forms of each group are also the same. 2a The alkyl group which can be adopted also preferably has an amino group as a substituent.

[0288] As R 2a The alkenyl group that can be used includes a straight-chain alkenyl group and a branched alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 18, more preferably 2 to 7, and further preferably 2 to 5. Preferred specific examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, and hexenyl. The alkenyl group is preferably a substituted alkenyl group.

[0289] As R 2a The phosphonate groups that can be used are -P(=O)(-OR P1)OR P2 Represents a group. P1 and R P2 represents a hydrogen atom or a substituent, and the substituent is preferably an alkyl group or a phosphonate group. P1 and R P2 The meanings of the alkyl groups that can be used are the same as those mentioned above as R 1a The meanings of the alkyl groups that can be adopted are the same, and the preferred forms of the alkyl groups are also the same. P1 and R P2 The meanings of the phosphonate groups that can be used are the same as those for R 2a The phosphonate groups that can be used have the same meanings and the same preferred forms. P1 or R P2 In the case of a phosphonate group, R constituting the phosphonate group P1 and R P2 An alkyl group is preferred.

[0290] As R 2a The phosphonate group that can be used is preferably R P1 and R P2 All are alkyl or R P1 is a hydrogen atom, R P2 It is a phosphonate group.

[0291] In addition, since a phosphonate group and a phosphite group (phosphite group) are tautomers, the phosphonate group in the present invention means including a phosphite group.

[0292] As R 2a Available-SO2R S1 In the case of S1 Alkyl or aryl is preferred. S1 Preferred forms of the alkyl group and the aryl group include the above-mentioned R 1a Preferred forms of alkyl and aryl groups that can be used. S1 A phenyl group having an alkyl group as a substituent is preferred. The preferred form of the alkyl group is the same as that of the above-mentioned R 1a Preferred embodiments of the alkyl group that can be adopted are the same.

[0293] The compound represented by the general formula (1) has two or more R 2a In the case of two R 2a They can be connected to each other to form a ring.

[0294] m1 is an integer from 0 to 2.

[0295] In the above general formula (1), preferably OR 2aAt least one of them has an acetonato structure. The acetonato structure refers to a structure in which a hydrogen ion is removed from acetone or a compound having a structure in which acetone has a substituent and coordinated with Al. The coordinating atom coordinated with the Al is usually an oxygen atom. The acetonato structure preferably has an acetylacetone structure ("CH3-C(=O)-CH2-C(=O)-CH3") as a basic structure, and a structure in which a hydrogen ion is removed from the basic structure and an oxygen atom is coordinated with Al as a coordinating atom (i.e., an acetylacetone structure). The above-mentioned "having an acetylacetone structure as a basic structure" means that, in addition to the above-mentioned acetylacetone structure, it also includes a structure in which a hydrogen atom of the above-mentioned acetylacetone structure is replaced by a substituent. As OR 2a Examples of the morphology having an acetonide structure include compounds SL-2 and SL-3 described below.

[0296] In the above general formula (1), preferably OR 2a At least one of them has an acetate structure. In the present invention, the acetate structure refers to a structure in which a hydrogen ion is removed from a compound of acetic acid or an acetate ester or a structure having a substituent (including a form in which the methyl group of acetic acid has an alkyl group as a substituent) and coordinated with Al. The coordinating atom coordinated with the Al is usually an oxygen atom. The acetate structure is preferably the following structure (i.e., alkyl acetoacetate structure): with an alkyl acetoacetate structure ("CH3-C(=O)-CH2-C(=O)-OR alk ”(R alk represents an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms). )) as a basic structure, a structure in which one hydrogen ion is removed from the basic structure and an oxygen atom is coordinated with Al as a coordinating atom. The above-mentioned "using an alkyl acetoacetate structure as a basic structure" means that, in addition to the above-mentioned alkyl acetoacetate structure, a structure in which a hydrogen atom of the above-mentioned alkyl acetoacetate structure is substituted by a substituent. As OR 2a Examples of the form having an acetate structure include compounds SL-3, SL-4, and SL-5 described below.

[0297] As the above R 1a or R 2aEach group that can be adopted may contain an anionic group (salt-type substituent) having a counter cation as a substituent. Anionic groups refer to groups that can form anions. As the above-mentioned anionic groups having counter cations, for example, groups of carboxylic acid ions using ammonium ions as counter cations can be cited. In this case, the above-mentioned counter cations exist in the compound represented by the general formula (1) so that the charge of the entire compound is 0. This is also the same for the compounds represented by the general formula (2) and the compounds represented by the general formula (3) described later.

[0298] Specific examples of the aluminum alkoxide compound used in the present invention are given below, but the present invention is not limited thereto.

[0299] Aluminium triethylate

[0300] Aluminum triisopropoxide

[0301] Aluminum tri-sec-butyrate

[0302] Aluminum tris(ethyl acetoacetate)

[0303] Aluminum diisopropyl acetoacetate

[0304] Aluminum monoacetylacetonate bis(acetoacetate)

[0305] Aluminum tris(acetylacetonate)

[0306] Diisopropoxyaluminum-9-octadecene acetate

[0307] Aluminum diisopropoxy monoethyl acetate

[0308] Aluminum triacetoacetate

[0309] Aluminum triacetylacetonate

[0310] Aluminum mono-sec-butoxydiisopropylate

[0311] Aluminum diisopropyl acetoacetate

[0312] Diethyl acetate Aluminum acetate isopropylate

[0313] Ethyl bisacetoacetate Aluminum monoacetylacetonate

[0314] Aluminum triacetoacetate

[0315] Octadecylaluminum acetate diisopropyl acetate

[0316] (Zirconium alkoxide compound)

[0317] The zirconium alkoxide compound preferably includes a zirconium alkoxide compound having at least one structure selected from the group consisting of an acetonate structure, an acetate structure, and a lactate structure, and more preferably includes a zirconium alkoxide compound having at least one structure selected from the group consisting of an acetonate structure and an acetate structure.

[0318] The zirconium alkoxide compound preferably contains a compound represented by the following general formula (2).

[0319] General formula (2): R 1b m2 -Zr-(OR 2b ) 4-m2

[0320] R 1b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0321] As the alkyl group, cycloalkyl group, acyl group, aryl group and unsaturated aliphatic group, for example, R in the above general formula (1) can be used: 1a An alkyl group, a cycloalkyl group, an acyl group, an aryl group and an unsaturated aliphatic group can be used.

[0322] R 2b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S2 , R S2 represents a substituent,

[0323] As the alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group and phosphonate group, for example, R in the above general formula (1) can be used. 2a The alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group, and phosphonate group that can be used are also included. S2 The substituents may be, for example, R S1 Substituents that can be used.

[0324] m2 is an integer from 0 to 3.

[0325] In the above general formula (2), preferably OR 2b At least one of them has an acetonato structure. The meaning of the acetonato structure is the same as the meaning of the acetonato structure described in the general formula (1). 2b Examples of the morphology having an acetonide structure include compounds SZ-3 and SZ-6 described below.

[0326] Furthermore, in the above general formula (2), it is preferred that OR 2b At least one of them has an acetate structure. The acetate structure has the same meaning as the acetate structure described in the general formula (1). 2bThe morphology having an acetate structure includes, for example, the compound SZ-7 described below. In addition, the compound SZ-5 corresponds to R in the general formula (1). 2b In the form of acyl group.

[0327] Furthermore, in the above general formula (2), it is preferred that OR 2b At least one of them has a lactate structure. The lactate structure refers to a structure in which a lactate ion is used as a basic structure and a hydrogen ion is removed from the basic structure to coordinate with Zr. The above-mentioned "using a lactate ion as a basic structure" refers to a structure in which, in addition to the lactate ion, a hydrogen atom of the lactate ion is replaced by a substituent. The coordinating atom coordinated with the Zr is usually an oxygen atom. As OR 2b An example of a form having a lactate structure is the compound SZ-4 described below.

[0328] Specific examples of the zirconium alkoxide compound used in the present invention are given below, but the present invention is not limited thereto.

[0329] Tetrapropoxyzirconium (also known as tetra-n-propoxide zirconium)

[0330] Zirconium Tetrabutoxide (also known as Zirconium Tetra-n-Butoxide)

[0331] Zirconium Tetraacetylacetonate

[0332] Zirconium tributoxyacetylacetonate

[0333] Zirconium dibutoxybis(acetylacetonate)

[0334] Dibutoxybis(ethyl acetoacetate)zirconium

[0335] Zirconium ethyl tributoxyacetoacetate

[0336] Zirconium monobutoxyacetylacetonate bis(ethyl acetoacetate)

[0337] Zirconium tri-butoxy monostearate (also known as zirconium tri-n-butoxide stearate)

[0338] Zirconium stearate

[0339] Ammonium zirconium lactate

[0340] Zirconium monoacetylacetonate

[0341] (Titanium alkoxide compound)

[0342] The titanium alkoxide compound preferably includes a titanium alkoxide compound containing at least one atom of N, P, and S. Furthermore, the titanium alkoxide compound preferably includes a titanium alkoxide compound having an acetate structure.

[0343] The titanium alkoxide compound preferably contains at least one compound represented by the following general formula (3).

[0344] General formula (3): R 1c m3 -Ti-(OR 2c ) 4-m3

[0345] R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group,

[0346] As the alkyl group, cycloalkyl group, acyl group, aryl group and unsaturated aliphatic group, for example, R in the above general formula (1) can be used: 1a An alkyl group, a cycloalkyl group, an acyl group, an aryl group and an unsaturated aliphatic group can be used.

[0347] R 2c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S3 , R S3 represents a substituent,

[0348] As the alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group and phosphonate group, for example, R in the above general formula (1) can be used. 2a The alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group, and phosphonate group that can be used are also included. S3 The substituents may be, for example, R S1 Substituents that can be used.

[0349] m3 is an integer from 0 to 3.

[0350] The compound represented by the general formula (3) described above preferably contains at least one atom of N, P and S. When the compound represented by the general formula (3) has N, it preferably has the N as an amino group.

[0351] When the compound represented by the general formula (3) has P, it preferably has the P as a phosphate group (phosphate) or a phosphonate group (phosphonic acid group).

[0352] When the compound represented by the general formula (3) has S, it preferably has the S as a sulfonyl group (-SO2-).

[0353] Furthermore, the compound represented by the general formula (3) above preferably has an acyl group as R 2c , that is, having the above-mentioned acetate structure as OR 2c .

[0354] Specific examples of the titanium alkoxide compound used in the present invention are given below, but the present invention is not limited thereto.

[0355] Isopropyl triisostearyl titanate

[0356] Isopropyl tridodecylbenzenesulfonyl titanate

[0357] Isopropyl trioctanoyl titanate

[0358] Isopropyl tri(dioctyl phosphite) titanate

[0359] Isopropyl tri(dioctyl pyrophosphate) titanate

[0360] Isopropyl tri(dioctyl sulfate) titanate

[0361] Isopropyl tricumylphenyl titanate

[0362] Isopropyl tri(N-aminoethyl-aminoethyl) titanate

[0363] Isopropyl Dimethacryl Isostearyl Titanate

[0364] Isopropyl isostearyl titanate diacrylate

[0365] Isobutyl trimethyl titanate

[0366] Ethylene diisostearyl titanate

[0367] Diisopropyl bis(dioctyl pyrophosphate) titanate

[0368] Dioctyl bis(ditridecyl phosphate) titanate

[0369] Dicumylphenyloxyacetate titanate

[0370] Bis(dioctyl pyrophosphate)oxyacetate titanate

[0371] Bis(dioctyl pyrophosphate)ethylene titanate

[0372] Bis(dioctyl pyrophosphate)oxyacetate titanate

[0373] Tetraisopropyl titanate

[0374] Tetrabutyl titanate

[0375] Tetraoctyl titanate

[0376] Tetrastearyl titanate

[0377] Tetraisopropyl bis(dioctylphosphite) titanate

[0378] Tetraoctylbis(di-tridecylphosphite) titanate

[0379] Tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate

[0380] Butyl Titanate Dimer

[0381] Titanium Tetraacetylacetonate

[0382] Titanium acetoacetate

[0383] Titanium Octanoate

[0384] Bis(2-ethyl-3-hydroxyhexyloxy)titanium

[0385] In component (C), the mass ratio of aluminum oxide particles to the surface treatment agent is not particularly limited. For example, relative to 100 parts by mass of aluminum oxide particles, the surface treatment agent is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and more preferably 10 to 50 parts by mass. From the viewpoint of the sound velocity and durability of the acoustic lens, it is more preferably 20 to 50 parts by mass, and even more preferably 20 to 45 parts by mass.

[0386] The mass ratio of the alumina particles to the surface treatment agent in the component (C) has the same meaning as the mass ratio of the alumina particles to the amount of the surface treatment agent used when performing the surface treatment. The mass ratio of the alumina particles to the surface treatment agent in the component (C) can be calculated from the mass of the alumina particles and the mass of the component (C) after heating the component (C) to 500°C or higher to remove the organic component by thermogravimetric analysis (TGA) or the like to obtain an inorganic component (alumina particles).

[0387] Furthermore, a surface treatment agent other than the above-mentioned surface treatment agent may be used within a range not impairing the effects of the present invention.

[0388] The above-mentioned surface treatment method itself can be carried out by a conventional method.

[0389] Regarding component (C), the entire surface of the aluminum oxide particles does not need to be treated with a surface treatment agent. For example, out of 100% of the surface area of ​​the aluminum oxide particles, preferably 50% or more is surface treated, more preferably 70% or more is surface treated, and further preferably 90% or more is surface treated.

[0390] The component (C) may be used alone or in combination of two or more.

[0391] From the viewpoint of the acoustic velocity, wear durability and chemical durability of the acoustic lens, the lower limit of the content of component (C) is preferably 1 part by mass or more, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 40 parts by mass or more, in the total of 100 parts by mass of the contents of components (A) to (C). The upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 60 parts by mass or less.

[0392] Furthermore, the content of the components (A) and (B) in 100 parts by mass of the total of the contents of the components (A) to (C) is preferably within the following ranges.

[0393] The lower limit of the content of component (A) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 35 parts by mass or more, and the upper limit is preferably 80 parts by mass or less, more preferably 65 parts by mass or less, and further preferably 55 parts by mass or less.

[0394] The lower limit of the content of component (B) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and further preferably 0.3 parts by mass or more, and the upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less.

[0395] <Other ingredients>

[0396] In addition to components (A) to (C), the composition for an acoustic lens of the present invention can be appropriately formulated with at least one of a catalyst for addition polymerization, a curing retarder, a solvent, a dispersant, a pigment, a dye, an antistatic agent, an antioxidant, a flame retardant, and a thermal conductivity improver.

[0397] -catalyst-

[0398] Examples of the catalyst include platinum and a platinum-containing compound (hereinafter, also referred to simply as a platinum compound). As the platinum or the platinum compound, a common substance can be used.

[0399] Specifically, platinum black or platinum supported on inorganic compounds or carbon black, chloroplatinic acid or an alcohol solution of chloroplatinic acid, a complex salt of chloroplatinic acid and an olefin, a complex salt of chloroplatinic acid and vinylsiloxane, etc. The catalyst may be used alone or in combination of two or more.

[0400] The catalyst is preferably used for a hydrosilylation reaction (addition curing reaction) of adding Si—H groups of the component (B) to the vinyl groups of the component (A).

[0401] Here, the catalyst may be contained in the composition for an acoustic lens of the present invention, or may be in contact with the composition for an acoustic lens without being contained in the composition for an acoustic lens.

[0402] Examples of commercially available platinum catalysts include platinum compounds (trade name: PLATINUM CYCLOVINYLMETHYLSILOXANE COMPLEX IN CYCLIC METHYLVINYLSILOXANES (SIP6832.2), Pt concentration 2 mass % and trade name: PLATINUM DIVINYLTETRAMETHYLDISILOXANE COMPLEX IN VINYL-TERMINATED POLYDIMETHYLSILOXANE (SIP6830.3), Pt concentration 3 mass %, both manufactured by Gelest).

[0403] When the composition for an acoustic lens of the present invention contains a catalyst, the content of the catalyst is not particularly limited. However, from the viewpoint of reactivity, the content is preferably 0.00001 to 0.05 parts by mass, more preferably 0.00001 to 0.01 parts by mass, further preferably 0.00002 to 0.01 parts by mass, and particularly preferably 0.00005 to 0.005 parts by mass, relative to 100 parts by mass of the total of components (A) to (C).

[0404] Furthermore, the curing temperature can be adjusted by selecting a suitable platinum catalyst, for example, platinum-vinyl disiloxane is used for room temperature curing (RTV) below 50°C, and platinum-cyclic vinyl siloxane is used for high temperature curing (HTV) above 130°C.

[0405] -Curing Retardant-

[0406] In the present invention, a curing retarder for the curing reaction can be used appropriately. The curing retarder is used to delay the above-mentioned addition curing reaction, and examples thereof include low molecular weight vinylmethylsiloxane homopolymer (trade name: VMS-005, manufactured by Gelest).

[0407] The curing speed, ie the working time, can be adjusted according to the content of the curing retarder.

[0408] [Viscosity of Acoustic Lens Composition Before Curing]

[0409] From the viewpoint of uniformly dispersing components (A) to (C), the viscosity of the acoustic lens composition before the curing reaction is preferably low. From the viewpoint of measuring the viscosity before curing, the viscosity of the acoustic lens composition before adding a catalyst for initiating the curing reaction is measured. Specifically, it can be measured using the method described in International Publication No. 2017 / 130890.

[0410] The viscosity (23° C.) is preferably 5,000 Pa·s or less, more preferably 1,000 Pa·s or less, and particularly preferably 200 Pa·s or less. The practical lower limit is 10 Pa·s or more.

[0411] <Composition for acoustic lens, acoustic lens, and method for producing an acoustic wave probe>

[0412] The composition for an acoustic lens of the present invention can be prepared by a conventional method.

[0413] For example, the composition for an acoustic lens can be obtained by kneading the components constituting the composition using a kneader, a pressure kneader, a Banbury mixer (continuous kneader), or a two-roll kneading device. The order of mixing the components is not particularly limited.

[0414] In order to obtain a uniform composition, it is preferred to first disperse the component (C) in a polysiloxane mixture of the components (A) and (B). Then, a catalyst is added to the polysiloxane mixture in which the component (C) is dispersed, and the mixture is defoamed under reduced pressure to prepare a composition for an acoustic lens.

[0415] The kneading conditions of the polyorganosiloxane mixture in which the component (C) is dispersed are not particularly limited as long as the component (C) can be dispersed. For example, kneading is preferably performed at 10 to 50° C. for 1 to 72 hours.

[0416] By curing the thus obtained composition for acoustic lens of the present invention, a silicone resin can be obtained. Specifically, for example, by curing by heating at 20 to 200° C. for 5 to 500 minutes, a silicone resin can be obtained. The shape of the silicone resin is not particularly limited. For example, the silicone resin can be formed into a preferred shape for an acoustic lens by using a mold during the curing, or a sheet of silicone resin can be obtained and then cut to form a desired acoustic lens.

[0417] The composition for an acoustic lens of the present invention can be used for medical components, for example, it can be preferably used for an acoustic wave probe and an acoustic wave measuring device. In addition, the acoustic wave measuring device of the present invention is not limited to an ultrasonic diagnostic device or a photoacoustic wave measuring device, but refers to a device that receives acoustic waves reflected or generated by an object and displays them as an image or signal intensity.

[0418] In particular, the composition for an acoustic lens of the present invention can be preferably used as a material for an acoustic lens of a probe for an ultrasonic diagnostic device, an acoustic lens in a photoacoustic wave measuring device or an ultrasonic endoscope, and an acoustic lens in an ultrasonic probe having a capacitive micromachined ultrasonic transducer (cMUT: Capacitive Micromachined Ultrasonic Transducers) as an ultrasonic transducer array.

[0419] Specifically, the acoustic lens of the present invention can be preferably applied to acoustic wave measuring devices such as ultrasonic diagnostic devices described in Japanese Patent Application Laid-Open No. 2003-169802 and photoacoustic wave measuring devices described in Japanese Patent Application Laid-Open No. 2013-202050 and Japanese Patent Application Laid-Open No. 2013-188465.

[0420] The acoustic wave probe of the present invention can be produced by a conventional method except that the acoustic lens is formed using the composition for an acoustic lens of the present invention.

[0421] <<Sonic wave probe (probe)>>

[0422] according to Figure 1 The structure of the ultrasonic probe in the ultrasonic diagnostic device shown in the figure is described in more detail below. In addition, the ultrasonic probe is a probe that uses ultrasonic waves as sound waves in the ultrasonic probe. Therefore, the basic structure of the ultrasonic probe can be directly applied to the acoustic probe.

[0423] -Ultrasonic probe-

[0424] The ultrasonic probe 10 is a main component of the ultrasonic diagnostic device, which has the function of generating ultrasonic waves and receiving ultrasonic beams. Figure 1 As shown, an acoustic lens 1, an acoustic matching layer 2, a piezoelectric element layer 3, and a backing material 4 are provided in order from the front end (the surface in contact with the living body as the subject). In recent years, in order to receive high-order harmonics, it has also been proposed that the ultrasonic transducer (piezoelectric element) for transmission and the ultrasonic transducer (piezoelectric element) for reception are made of different materials and formed into a stacked structure.

[0425] <Piezoelectric Element Layer>

[0426] The piezoelectric element layer 3 is a portion that generates ultrasonic waves. Electrodes are attached to both sides of the piezoelectric element. When a voltage is applied, the piezoelectric element repeats contraction and expansion and vibrates, thereby generating ultrasonic waves.

[0427] As materials for piezoelectric elements, so-called ceramic inorganic piezoelectrics are widely used, which are obtained by polarizing crystal, single crystals such as LiNbO3, LiTaO3 and KNbO3, thin films such as ZnO and AlN, and sintered bodies such as Pb(Zr, Ti)O3. Generally, piezoelectric ceramics such as PZT: lead zirconate titanate with good conversion efficiency are used.

[0428] Furthermore, a piezoelectric element that detects a received wave on the high frequency side requires a wider bandwidth sensitivity. Therefore, an organic piezoelectric body using an organic polymer substance such as polyvinylidene fluoride (PVDF) is used as a piezoelectric element suitable for high frequencies and wide bands.

[0429] Japanese Patent Application Laid-Open No. 2011-071842 and the like describe a cMUT using MEMS (Micro Electro Mechanical Systems) technology, which exhibits excellent short pulse characteristics and broadband characteristics, has excellent mass productivity, and can obtain a layer structure with little characteristic variation.

[0430] In the present invention, any piezoelectric element material can be preferably used.

[0431] <Backing Material>

[0432] The backing material 4 is disposed on the back side of the piezoelectric element layer 3 and helps improve the distance resolution in ultrasonic diagnostic images by suppressing unnecessary vibrations and shortening the pulse width of ultrasonic waves.

[0433] <Acoustic Matching Layer>

[0434] The acoustic matching layer 2 is provided to reduce the difference in acoustic impedance between the piezoelectric element layer 3 and the object to be examined and to effectively transmit and receive ultrasonic waves.

[0435] <Acoustic Lens>

[0436] The acoustic lens 1 is provided to focus ultrasound in the slice direction by refraction and improve resolution. It is also required to be in close contact with a living body to be examined so that the ultrasound and the acoustic impedance of the living body (1.4 to 1.7 Mrayl in the human body) are matched.

[0437] That is, by using a material having a sound velocity sufficiently lower than that of the human body and an acoustic impedance close to the value of human skin as the material of the acoustic lens 1 , the ultrasonic transmission and reception sensitivity can be improved.

[0438] The composition for an acoustic lens of the present invention can be preferably used as an acoustic lens material.

[0439] The operation of the ultrasonic probe 10 having such a structure is described. Voltage is applied to the electrodes provided on both sides of the piezoelectric element layer 3 to cause the piezoelectric element layer 3 to resonate, and an ultrasonic signal is transmitted to the object under examination from the acoustic lens 1. When receiving, the piezoelectric element layer 3 is vibrated by the reflected signal (echo signal) from the object under examination, and the vibration is electrically converted into a signal to obtain an image.

[0440] In particular, the acoustic lens obtained from the acoustic lens composition of the present invention can be used as a common medical ultrasonic transducer, and a significant sensitivity improvement effect can be confirmed at an ultrasonic transmission frequency of about 10 MHz or more. In particular, a particularly significant sensitivity improvement effect can be expected at an ultrasonic transmission frequency of 15 MHz or more.

[0441] The acoustic lens obtained from the acoustic lens composition of the present invention can, for example, reduce the speed of sound to 800 m / s or more and less than 870 m / s, and can obtain sufficiently accurate information about living tissue located at a depth of 0.1 to 20 mm from the body surface at an ultrasonic frequency of 10 MHz or more and 30 MHz or less.

[0442] Hereinafter, a device in which an acoustic lens obtained from the composition for an acoustic lens of the present invention particularly functions to solve conventional problems will be described in detail.

[0443] Furthermore, the composition for an acoustic lens of the present invention also exhibits excellent effects on devices other than the devices described below.

[0444] -Ultrasonic probe with cMUT (capacitive microcomputer ultrasonic transducer)-

[0445] When the cMUT device described in Japanese Patent Application Laid-Open No. 2006-157320, Japanese Patent Application Laid-Open No. 2011-71842, etc. is used for an ultrasonic transducer array, the sensitivity is generally lower than that of a transducer using a general piezoelectric ceramic (PZT).

[0446] However, by using the acoustic lens obtained from the acoustic lens composition of the present invention, the lack of sensitivity of the cMUT can be compensated, thereby making the sensitivity of the cMUT close to the performance of the conventional transducer.

[0447] In addition, since the cMUT device is manufactured using MEMS technology, it is possible to provide the market with ultrasonic probes with high mass production rate and low cost compared to piezoelectric ceramic probes.

[0448] -Photoacoustic wave measurement device using photoacoustic wave imaging-

[0449] Photoacoustic imaging (PAI) described in Japanese Patent Application Laid-Open No. 2013-158435 and the like displays an image of ultrasound waves or the signal intensity of ultrasound waves generated when light (electromagnetic waves) is irradiated into the human body and human tissues adiabatically expand due to the irradiated light.

[0450] -Ultrasound endoscope-

[0451] The ultrasonic endoscope described in Japanese Patent Application Laid-Open No. 2008-311700 etc. has a signal cable that is longer than the transducer for the body surface due to its structure, so there is a problem that the sensitivity of the transducer increases with the loss of the cable. In addition, it is said that there is no effective method to improve the sensitivity for the following reasons.

[0452] First, if it is a body surface ultrasonic diagnostic device, it is possible to set an amplifier circuit, AD conversion IC, etc. at the front end of the transducer. In contrast, an ultrasonic endoscope is inserted into the body for use, so the installation space of the transducer is narrow and it is difficult to set an amplifier circuit, AD conversion IC, etc. at the front end of the transducer.

[0453] Second, the piezoelectric single crystal used in the transducer of the ultrasonic diagnostic device for body surface is difficult to be applied to the transducer with the ultrasonic transmission frequency of 10 to 15 MHz or more in terms of its physical properties and process suitability. However, the ultrasonic wave used in the endoscope is usually a probe with the ultrasonic transmission frequency of 10 to 15 MHz or more, so it is difficult to improve the sensitivity by using piezoelectric single crystal materials.

[0454] However, by using the acoustic lens obtained from the composition for an acoustic lens of the present invention, the sensitivity of the ultrasonic transducer for an endoscope can be improved.

[0455] Furthermore, even when the same ultrasonic transmission frequency (for example, 15 MHz) is used, it is particularly effective when the acoustic lens obtained from the acoustic lens composition of the present invention is used in an endoscopic ultrasonic transducer.

[0456] Example

[0457] The present invention is described in further detail below based on an embodiment using ultrasound as the sound wave. In addition, the present invention is not limited to ultrasound, and sound waves of audible frequencies may also be used as long as an appropriate frequency is selected according to the object to be examined and the measurement conditions.

[0458] [Preparation Example] Preparation Example of Surface-treated Alumina Particles (C-1)

[0459] 30 parts by mass of 3-aminopropyltrimethoxysilane, 100 parts by mass of methanol, and 3.3 parts by mass of distilled water were mixed and allowed to stand at 23°C for 1 hour to hydrolyze the methoxy groups. 100 parts by mass of alumina particles (manufactured by Iolitec Ionic Liquids Technologies GmbH, γ type, trade name "NO-0036-HP", average particle size 20 nm) were added to the solution. The mixture was cooled to a liquid temperature of not more than 50°C using a homogenizer ("Excel auto homogenizer ED-7" (trade name) manufactured by Nippon Seiki Co., Ltd.), stirred at a rotation speed of 10,000 rpm for 60 minutes, and the mixture was pulverized and surface treated.

[0460] The mixture stirred and pulverized in the above was filtered, and the obtained solid matter was dried by heating at 100° C. for 30 minutes to obtain powdery surface-treated alumina particles (C-1) (component (C)).

[0461] In the preparation of the surface-treated alumina particles (C-1), surface-treated alumina particles (C-2) to (C-30), (C-32) to (C-34) and surface-treated silica particles (C-31) were prepared in the same manner as the surface-treated alumina particles (C-1), except that the raw materials were used in the composition of Table 1 below.

[0462]

[0463]

[0464] [Alumina (Q)]

[0465] Q-1: Untreated alumina (manufactured by Iolitec Ionic Liquids Technologies GmbH, γ type, trade name "NO-0036-HP", average particle size 20 nm)

[0466] (“Untreated alumina” refers to alumina that has not been treated with a surface treatment agent.)

[0467] Q-2: Untreated alumina (manufactured by Iolitec Ionic Liquids Technologies GmbH, γ type, trade name "NO-0057-UP", average particle size 5 nm)

[0468] Q-3: Untreated alumina (manufactured by Iolitec Ionic Liquids Technologies GmbH, α type, trade name "NO-0003-UP", average particle size 80 nm)

[0469] Q-4: Untreated alumina (manufactured by Iolitec Ionic Liquids Technologies GmbH, α type, trade name "NO-0008-UP", average particle size 150 nm)

[0470] Q-5: Untreated alumina (manufactured by Iolitec Ionic Liquids Technologies GmbH, α type, trade name "NO-0050-UP", average particle size 200 nm)

[0471] Q-6: Untreated alumina (manufactured by EM Japan Co., Ltd., α type, trade name "NP-ALO-5-1K", average particle size 500 nm)

[0472] [Surface treatment agent (S)]

[0473] <Aminosilane Compound>

[0474] (SA-1):

[0475] 3-Aminopropyltrimethoxysilane (manufactured by Gelest, trade name "SIA0611.0")

[0476] <Mercaptosilane compound>

[0477] (SM-1):

[0478] 3-Mercaptopropyltrimethoxysilane (manufactured by Gelest, trade name "SIM6476.0")

[0479] (SM-2):

[0480] 11-Mercaptoundecyltrimethoxysilane (manufactured by Gelest, trade name "SIM6480.0")

[0481] <Isocyanatosilane compound>

[0482] (SI-1):

[0483] 3-Isocyanatopropyltrimethoxysilane (manufactured by Gelest, trade name "SII6456.0")

[0484] (SI-2):

[0485] Isocyanatomethyltrimethoxysilane (manufactured by Gelest, trade name "SII6453.8")

[0486] <Titanium alkoxide compound>

[0487] (ST-1):

[0488] Isopropyl triisostearyl titanate (manufactured by Ajinomoto Fine-Techno Co., Inc., trade name "PLENACT TTS")

[0489] [Chemical formula 9]

[0490]

[0491] (ST-2):

[0492] Dioctyl bis(ditridecyl phosphate) titanate ("PLENACT 46B" manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0493] [Chemical formula 10]

[0494]

[0495] (ST-3):

[0496] Isopropyl tri(N-aminoethyl-aminoethyl) titanate (manufactured by Ajinomoto Fine-Techno Co., Inc., trade name "PLENACT 44")

[0497] [Chemical formula 11]

[0498]

[0499] <Aluminum alkoxide compound>

[0500] (SL-1):

[0501] Aluminum tri-sec-butyrate (manufactured by Kawaken Fine Chemicals Co., Ltd., trade name "ASBD")

[0502] [Chemical formula 12]

[0503]

[0504] (SL-2):

[0505] Aluminum triacetylacetonate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIX AL-3100")

[0506] [Chemical formula 13]

[0507]

[0508] (SL-3):

[0509] Diethylaluminum acetate monoacetylacetonate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIX AL-3200")

[0510] [Chemical formula 14]

[0511]

[0512] (SL-4):

[0513] Aluminum triacetoacetate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIXAL-3215")

[0514] [Chemical formula 15]

[0515]

[0516] (SL-5): Octadecyl aluminum acetate diisopropyl acetate (manufactured by Ajinomoto Fine-Techno Co., Inc., trade name "PLENACT AL-M")

[0517] [Chemical formula 16]

[0518]

[0519] <Zirconium alkoxide compound>

[0520] (SZ-1):

[0521] Zirconium tetra-n-propoxide (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIX ZA-45")

[0522] [Chemical formula 17]

[0523]

[0524] (SZ-2):

[0525] Zirconium tetra-n-butoxide (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIXZA-65")

[0526] [Chemical formula 18]

[0527]

[0528] (SZ-3):

[0529] Zirconium tetraacetylacetonate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIXZC-150")

[0530] [Chemical formula 19]

[0531]

[0532] (SZ-4):

[0533] Ammonium zirconium lactate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIX ZC-300")

[0534] [Chemical formula 20]

[0535]

[0536] (SZ-5):

[0537] Zirconium stearate tri-n-butyl alcohol (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIX ZC-320")

[0538] [Chemical formula 21]

[0539]

[0540] (SZ-6):

[0541] Zirconium tris-butoxymonoacetylacetonate (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIX ZC-540")

[0542] [Chemical formula 22]

[0543]

[0544] (SZ-7):

[0545] Dibutoxybis(ethyl acetoacetate)zirconium (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name "ORGATIX ZC-580")

[0546] [Chemical formula 23]

[0547]

[0548] <Surface-treated Inorganic Particles Used in Comparative Examples>

[0549] q-7: untreated silica particles (manufactured by Evonik, trade name "AEROSIL90G", average particle size 20 nm), which are described in the same row as alumina (Q) in Table 1 for convenience.

[0550] <Surface Treatment Agent Used in Comparative Examples>

[0551] sa-2: N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (manufactured by Gelest, trade name "SIT8415.0", 50% methanol aqueous solution)

[0552] sc-1: methyltrichlorosilane (reagent manufactured by Tokyo Chemical Industry Co., Ltd.)

[0553] (sc-2): Vinyltrichlorosilane (reagent manufactured by Tokyo Chemical Industry Co., Ltd.)

[0554] st-4: titanium tetrachloride (reagent manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0555] s1-6: Aluminum chloride (reagent manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0556] sz-7: Zirconium oxychloride octahydrate (reagent manufactured by YONEYAMA YAKUHIN KOGYO CO., LTD.)

[0557] [Example 1]

[0558] 49.4 parts by mass of a vinyl-terminated dimethylsiloxane copolymer (component (A) in the following Table 2, "DMS-V41" (trade name) manufactured by Gelest, with a weight-average molecular weight of 62,7000), 0.6 parts by mass of a methylhydrogensiloxane polymer (component (B) in the following Table 2, "HMS-991" (trade name) manufactured by Gelest, with a weight-average molecular weight of 1,600 and a Si-H equivalent of 67 g / mol), and 50.0 parts by mass of the surface-treated alumina particles (C-1) (component (C) in the following Table 2) prepared in the above-mentioned preparation example were kneaded in a kneader at a temperature of 23°C for 2 hours to prepare a uniform paste. After adding 500 ppm (platinum is 10 ppm) of platinum catalyst solution (SIP6832.2 manufactured by Gelest, platinum concentration 2%) to the paste and mixing, it was decompressed and defoamed, placed in a 150mm×150mm metal mold, and heat treated at 60°C for 3 hours to obtain a silicone resin sheet with a thickness of 2.0 mm.

[0559] In the preparation of the silicone resin sheet of Example 1, the silicone resin sheets of Examples 2 to 31 and Comparative Examples 1 to 9 were prepared in the same manner as the silicone resin sheet of Example 1, except that the composition described in the following Table 2 was used. In addition, for each of the Examples and Comparative Examples, one silicone resin sheet for the sound velocity measurement test and two silicone resin sheets for the chemical durability test were prepared.

[0560] In the same manner, regarding each of the Examples and Comparative Examples, a disk-shaped silicone resin sheet (diameter 16 mm×thickness 6 mm) was prepared for the wear durability test.

[0561] [Sound velocity measurement test]

[0562] The silicone resin sheet was measured for sonic velocity at 25° C. using a sonic velocity measuring device (manufactured by Ultrasonic Engineering Co., Ltd., trade name “UVM-2”) in accordance with JIS Z2353 (2003), and evaluated using the following criteria. “A” and “B” were considered pass in this test.

[0563] <Evaluation Criteria>

[0564] A: less than 840m / s

[0565] B: 840m / s or more and less than 870m / s

[0566] C: 870m / s or more and less than 900m / s

[0567] D: 900m / s or more

[0568] [Chemical durability (sodium hypochlorite durability) test]

[0569] One of the two silicone resin sheets (I) was immersed in a 1% sodium hypochlorite aqueous solution at 23°C for 1 week (168 hours) and then rinsed with water. Then, it was dried at 23°C for 24 hours. Dumbbell specimens No. 3 (I) and (II) were punched out from the dried silicone resin sheet (I) and a different silicone resin sheet (II) (not immersed in sodium hypochlorite), and a tensile test was performed in accordance with JIS K 7161-1 (2014).

[0570] A tensile test was performed at 23°C using "TENSILON RTF-2410" manufactured by A&D Company, Limited.

[0571] The ratio (%) of the tensile strength (MPa) of sample (I) to the tensile strength (MPa) of sample (II) (100×tensile strength (MPa) of sample (I) / tensile strength (MPa) of sample (II)) was used as the retention rate of tensile strength (MPa), and the chemical durability was evaluated by applying the following evaluation criteria. "A" to "C" are pass in this test.

[0572] <Evaluation Criteria>

[0573] A: The retention rate of tensile strength is more than 95%

[0574] B: The retention rate of tensile strength is 85% or more and less than 95%

[0575] C: The retention rate of tensile strength is 70% or more and less than 85%

[0576] D: The retention rate of tensile strength is less than 70%

[0577] [Wear durability test]

[0578] The silicone resin sheet was subjected to an Akron wear tester ("AB-1511" (trade name) manufactured by Ueshima Seisakusho Co., Ltd.), and the wear volume (mL) of the test piece (disc-shaped silicone resin sheet) per 1000 revolutions was determined according to the A method of JIS K6264-2 (2005). The test conditions were set as follows: at 23°C, the load force was 27.0N, the inclination angle was 15°, and the test piece rotation speed was 75rpm. The wear volume (mL) was applied to the following evaluation criteria to evaluate the wear durability. "A" to "C" are qualified for this test.

[0579] <Evaluation Criteria>

[0580] A: Wear volume is less than 0.05mL

[0581] B: Wear volume is 0.05 mL or more and less than 0.10 mL

[0582] C: Wear volume is 0.10 mL or more and less than 0.15 mL

[0583] D: Wear volume is 0.15mL or more

[0584]

[0585]

[0586]

[0587] "EX": Example

[0588] "CEX": Comparative example

[0589] “Average primary particle size [nm]”: Average primary particle size of alumina particles before surface treatment [nm]

[0590] "php": 100 × mass parts of surface treatment agent / 100 mass parts of alumina particles

[0591] In Comparative Examples 2 to 5 and 7 to 9, alumina particles that do not satisfy the requirements of the present invention are described in the row of component (C) for comparison. Similarly, in Comparative Example 6, surface-treated silica particles are described in the row of component (C) for comparison.

[0592] [Polysiloxane having a vinyl group (A)]

[0593] A-1: Polydimethylsiloxane having vinyl groups at both ends (manufactured by Gelest, trade name "DMS-V41", weight average molecular weight 62,700)

[0594] A-2: Polydimethylsiloxane having vinyl groups at both ends (manufactured by Gelest, trade name "DMS-V46", weight average molecular weight 117,000)

[0595] A-3: Polysiloxane containing vinyl groups and phenyl groups at both ends (manufactured by Gelest, trade name "PDV-0541", weight average molecular weight 60,000, diphenylsiloxy units 5 mol%)

[0596] [Polysiloxane having Si—H group (B)]

[0597] B-1: polymethylhydrogensiloxane (manufactured by Gelest, trade name "HMS-991", weight average molecular weight 1,600, methylhydroxysiloxy unit 100 mol%, Si-H equivalent 67 g / mol)

[0598] B-2: methyl hydrogen siloxane-phenyl methyl siloxane copolymer (manufactured by Gelest, trade name "HPM-502", weight average molecular weight 4,500, methyl hydroxy siloxy unit 45-50 mol%, Si-H equivalent 165 g / mol)

[0599] As can be seen from Table 2, Comparative Example 1 which did not use the component (C) and Comparative Example 2 which used alumina particles whose surfaces were not treated failed in all the tests.

[0600] In addition, the sound velocity of Comparative Example 3 using N-trimethoxysilylpropyl-N,N,N-trimethoxyammonium chloride as the surface treatment agent was within the acceptable level. However, the chemical durability and abrasion durability were poor. This is believed to be because the surface treatment agent is hydrophilic and has a high affinity for chemicals, and the surface-treated alumina particles cannot be uniformly dispersed in the hydrophobic silicone resin sheet.

[0601] Comparative Examples 4, 5, and 7 to 9 using alumina particles treated with a surface treatment agent outside the scope of the present invention failed in all tests.

[0602] Comparative Example 6 using silica particles treated with the surface treatment agent specified in the present invention failed in all tests. This is believed to be because silica particles have high hydrophilicity and high affinity with chemicals even after surface treatment, making it difficult to evenly disperse in the hydrophobic silicone resin sheet, and the specific gravity of the silica particles themselves is low.

[0603] In contrast, Examples 1 to 31 of the present invention were at the pass level in all tests. Furthermore, the acoustic impedance of the silicone resin sheets of Examples 1 to 31 was within the range of 1.3 to 1.7 Mrayl, and thus they were practically usable.

[0604] Explanation of symbols

[0605] 1-acoustic lens, 2-acoustic matching layer, 3-piezoelectric element layer, 4-back material, 7-shell, 9-cord, 10-ultrasonic probe (probe).

Claims

1. A composition for an acoustic lens, comprising the following components (A) to (C): (A) polysiloxane having a vinyl group; (B) polysiloxane having two or more Si-H groups in the molecular chain; and (C) aluminum oxide particles surface-treated with at least one surface treatment agent selected from the group consisting of aminosilane compounds, mercaptosilane compounds, isocyanatosilane compounds, thiocyanatosilane compounds, aluminum alkoxide compounds, zirconium alkoxide compounds, and titanium alkoxide compounds, The aluminum alkoxide compound contains at least one compound represented by the following general formula (1): General formula (1): R 1 am1-Al-(OR 2 a)3-m1 R 1 a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group, R 2 a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S1 , R S1 represents a substituent, m1 is an integer from 0 to 2; The zirconium alkoxide compound comprises: a zirconium alkoxide compound having at least one of an acetonate structure and an acetate structure; The titanium alkoxide compound includes a titanium alkoxide compound containing at least one atom of N, P and S.

2. The composition for an acoustic lens according to claim 1, wherein The surface treatment agent is at least one of an aminosilane compound, a mercaptosilane compound, an isocyanatosilane compound, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound.

3. The composition for an acoustic lens according to claim 1 or 2, wherein The surface treatment agent is at least one of a mercaptosilane compound, an isocyanatosilane compound, an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound.

4. The composition for an acoustic lens according to claim 1 or 2, wherein The surface treatment agent is at least one of an aluminum alkoxide compound, a zirconium alkoxide compound, and a titanium alkoxide compound.

5. The composition for an acoustic lens according to claim 1 or 2, wherein The aluminum alkoxide compound includes an aluminum alkoxide compound, and the aluminum alkoxide compound contains at least one structure of an acetonate structure and an acetate structure.

6. The composition for an acoustic lens according to claim 1 or 2, wherein The zirconium alkoxide compound contains at least one compound represented by the following general formula (2): General formula (2): R 1 bm2-Zr-(OR 2 b)4-m2 R 1 b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group, R 2 b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S2 , R S2 represents a substituent, m2 is an integer from 0 to 3.

7. The composition for an acoustic lens according to claim 1 or 2, wherein The titanium alkoxide compound contains at least one compound represented by the following general formula (3): General formula (3): R 1 cm3-Ti-(OR 2 c)4-m3 R 1 c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group, R 2 c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group or -SO2R S3 , R S3 represents a substituent, m3 is an integer from 0 to 3.

8. The composition for an acoustic lens according to claim 1 or 2, wherein In the component (C), the content of the surface treatment agent is 1 to 100 parts by mass based on 100 parts by mass of the aluminum oxide particles.

9. The composition for an acoustic lens according to claim 1 or 2, wherein The average primary particle size of the aluminum oxide particles constituting the component (C) is 10 to 400 nm. 10 . An acoustic lens obtained by curing the composition for an acoustic lens according to claim 1 . An acoustic wave probe comprising the acoustic lens according to claim 10. 12 . An ultrasonic probe comprising the acoustic lens according to claim 10 . 13 . An acoustic wave measuring device comprising the acoustic wave probe according to claim 11 .

14. An ultrasonic diagnostic apparatus comprising the acoustic wave probe according to claim 11. 15 . A photoacoustic wave measuring device comprising the acoustic lens according to claim 10 . 16 . An ultrasonic endoscope comprising the acoustic lens according to claim 10 .

17. A method for manufacturing an acoustic wave probe, comprising: A step of forming an acoustic lens using the composition for an acoustic lens according to any one of claims 1 to 9.

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