Acoustic wave probe, acoustic wave measurement device, and ultrasonic diagnostic device

Abstract

Provided are an acoustic wave probe, an acoustic wave measurement device, and an ultrasonic diagnostic device, the acoustic wave probe having a base material, an intermediate layer on the base material, and an acoustic lens layer on the intermediate layer, the intermediate layer being a layer containing a siloxane compound having a constituent component derived from a hydrolyzed silicate compound, the acoustic lens layer is a layer obtained by curing a room-temperature-curable silicone, and the room-temperature-curable silicone contains a structural unit having a phenyl group.

Description

Technical Field

[0001] The invention relates to an acoustic wave probe, an acoustic wave measuring device and an ultrasonic diagnostic device. Background Art

[0002] In the acoustic wave measuring device, an acoustic wave probe is used, which irradiates the object or part to be inspected (hereinafter referred to as the object), receives the reflected wave (echo) and outputs a signal. The electrical signal converted from the reflected wave received by the acoustic wave probe is displayed as an image. Thus, the inside of the object to be inspected 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 toward the inside 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 inside 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 to an object to be examined, the object to be examined absorbs the electromagnetic wave and generates heat and thermal expansion, thereby generating sound waves (typically ultrasonic waves).

[0005] Since the acoustic wave measuring device transmits and receives acoustic waves to and from a living body as a test object, for example, it is necessary to match the acoustic impedance of the living body (typically a human body) and to suppress the attenuation of acoustic waves.

[0006] For example, a probe for an ultrasonic diagnostic device (also called an ultrasonic probe) as a type of acoustic wave probe includes a piezoelectric element for transmitting and receiving ultrasonic waves and an acoustic lens as a portion in contact with a living body. The ultrasonic waves emitted from the piezoelectric element are incident on the living body through the acoustic lens. If the acoustic impedance (density × sound velocity) of the acoustic lens differs greatly from the acoustic impedance of the living body, the ultrasonic waves will be reflected by the surface of the living body, and the ultrasonic waves cannot be effectively incident on the living body. As a result, it is difficult to obtain good resolution. In addition, in order to transmit and receive ultrasonic waves with high sensitivity, it is desirable to suppress the ultrasonic wave attenuation of the acoustic lens to a small amount.

[0007] Therefore, as one of the materials of the acoustic lens, a material with an acoustic impedance close to that of a living body (1.4 to 1.7×10 6 kg / m 2 In order to reduce the difference in acoustic impedance between the piezoelectric element and the acoustic lens and effectively transmit and receive ultrasonic waves, an acoustic matching layer is usually provided between the piezoelectric element and the acoustic lens.

[0008] Furthermore, when using an acoustic wave measuring device, the acoustic wave probe is rubbed against a living body to transmit and receive acoustic waves. Therefore, the acoustic lens, which is a part that is rubbed against or sometimes pressed against a living body, requires high mechanical strength. Since silicone resin is generally soft and has poor mechanical strength, inorganic fillers are mixed into silicone resin or a cross-linked structure is introduced to improve the mechanical strength.

[0009] For example, Patent Document 1 describes a composition for an acoustic wave probe, which contains a polysiloxane mixture comprising a polysiloxane having a vinyl group, a polysiloxane having two or more Si-H groups in the molecular chain, and surface-treated silica particles having an average primary particle size of more than 16 nm and less than 100 nm.

[0010] In addition, patent document 2 describes a probe, which is an elevation-focusing ultrasonic probe having an array of ultra-fine machined ultrasonic transducer (MUT) units, wherein a fixing material layer is included between the above-mentioned array and a lens made of room-temperature curing silicone rubber, and the fixing material layer contains a fixing agent composed of silicate, organometallic compound or reactive organosilane.

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: International Publication No. 2017 / 130890

[0014] Patent Document 2: Japanese Patent Application Publication No. 2005-103294 Summary of the invention

[0015] Technical issues to be solved by the invention

[0016] The sonic probe used to examine or treat the human body is usually used in direct contact with the human body. For example, the intracavitary probe used for intracavitary treatment such as vaginal, rectal or esophageal treatment is likely to come into contact with the mucous membrane and may come into contact with sterile tissue or blood. In addition, the surface probe used to scan the abdomen or pelvis may also come into contact with sterile tissue, traumatic skin, mucous membrane, or skin without wounds during treatment.

[0017] Therefore, in order to prevent bacterial infection, the acoustic wave probe requires high cleanliness exceeding the sterilization level of disinfection. As such sterilization treatment, sterilization treatment using EOG (ethylene oxide gas) capable of low temperature treatment is widely performed, and application of hydrogen peroxide plasma treatment is also expected.

[0018] As a result of research conducted by the present inventors, it was found that in an acoustic wave probe in which an acoustic lens is directly arranged on an acoustic matching layer as described in the above-mentioned Patent Document 1, the close adhesion between the acoustic matching layer and the acoustic lens is low, and even in an ultrasonic probe in which a fixing material layer containing a fixing agent composed of silicate, an organic metal compound or a reactive organic silane as described in the above-mentioned Patent Document 2 is sandwiched between the acoustic matching layer and the acoustic lens, the close adhesion between the acoustic matching layer and the acoustic lens is reduced if the hydrogen peroxide plasma sterilization treatment is repeatedly performed. This reduction in close adhesion causes the performance of the acoustic wave probe to be reduced. Therefore, the acoustic wave probe needs to have a high degree of sterilization durability.

[0019] An object of the present invention is to provide an acoustic wave probe having excellent adhesion and excellent sterilization durability, and an acoustic wave measuring device or an ultrasonic diagnostic device including the acoustic wave probe.

[0020] Means for solving technical problems

[0021] The present inventors have conducted intensive research in view of the above-mentioned problems and have found that the above-mentioned problems can be solved by providing an intermediate layer between a base material such as an acoustic matching layer and an acoustic lens layer, wherein the acoustic lens layer is a layer formed by curing a room temperature curing silicone containing a structural unit having a phenyl group, and wherein the intermediate layer is a layer containing a siloxane compound and the siloxane compound has a structure containing a constituent component derived from a hydrolyzed silicate compound. The present invention has been completed through further research based on these findings.

[0022] The above-mentioned problems were solved by the following means.

[0023] <1>

[0024] An acoustic wave probe comprises a substrate, an intermediate layer on the substrate, and an acoustic lens layer on the intermediate layer.

[0025] The intermediate layer is a layer containing a siloxane compound, and the siloxane compound has a constituent component derived from a hydrolyzed silicate compound.

[0026] The acoustic lens layer is a layer formed by curing room temperature curing silicone, and the room temperature curing silicone includes a structural unit having a phenyl group.

[0027] <2>

[0028] The acoustic wave probe according to <1>, wherein:

[0029] The substrate includes at least one of iron, non-ferrous metal, inorganic material other than metal, and organic material.

[0030] <3>

[0031] The acoustic wave probe according to <2>, wherein:

[0032] The non-ferrous metal includes at least one of aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten or cobalt, or an alloy of at least two of these metals.

[0033] <4>

[0034] The acoustic wave probe according to <2> or <3>, wherein:

[0035] The inorganic material other than the above-mentioned metals includes at least one of glass, ceramics and graphite.

[0036] <5>

[0037] The acoustic wave probe according to any one of <2> to <4>, wherein

[0038] The organic material includes at least one of a thermoplastic resin and a thermosetting resin.

[0039] <6>

[0040] The acoustic wave probe according to <5>, wherein:

[0041] The thermoplastic resin includes at least one of an acrylic resin, a polycarbonate resin, a styrene resin, and a polyphenylene sulfide resin.

[0042] <7>

[0043] The acoustic wave probe according to <5> or <6>, wherein:

[0044] The above-mentioned thermoplastic resin is a cross-linked thermoplastic resin.

[0045] <8>

[0046] The acoustic wave probe according to any one of <1> to <7>, wherein

[0047] The substrate is a substrate having a surface on the intermediate layer side subjected to a hydrophilic treatment.

[0048] <9>

[0049] The acoustic wave probe according to <8>, wherein:

[0050] The substrate is a substrate having a surface on the intermediate layer side subjected to at least one of ultraviolet treatment, ozone treatment, plasma treatment, and corona treatment.

[0051] <10>

[0052] The acoustic wave probe according to any one of <1> to <9>, wherein

[0053] The intermediate layer includes a constituent component derived from at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound.

[0054] <11>

[0055] The acoustic wave probe according to any one of <1> to <10>, wherein

[0056] The room temperature curing silicone is a silicone composition comprising vinyl silicone and hydrogen silicone.

[0057] <12>

[0058] The acoustic wave probe according to <11>, wherein:

[0059] The silicone composition comprises surface-treated oxide particles.

[0060] <13>

[0061] The acoustic wave probe according to <12>, wherein:

[0062] The silicone composition comprises surface-treated spherical silica particles.

[0063] <14>

[0064] The acoustic wave probe according to any one of <1> to <13>, wherein

[0065] The above-mentioned acoustic wave probe is an ultrasonic wave probe.

[0066] <15>

[0067] An acoustic wave measuring device comprising the acoustic wave probe according to any one of <1> to <13>.

[0068] <16>

[0069] An ultrasonic diagnostic device comprises the acoustic wave probe described in <14>.

[0070] In the present invention, "metal alkoxide compound (for example, aluminum alkoxide compound, zirconium alkoxide compound and titanium 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 bond to each other to form a ring.

[0071] In the present invention, when there are multiple substituents or linking groups (hereinafter referred to as substituents) represented by specific symbols, or when multiple substituents are specified simultaneously or selectively, it means that each substituent may be the same or different. Furthermore, even if there is no special description, it means that when multiple substituents are adjacent, they may be connected or fused to form a ring.

[0072] In the present invention, a substituent not indicating whether it is substituted or unsubstituted (the same also applies to a linking group) means that the group may have any substituent within the scope of exerting the desired effect. The meaning is also the same for a compound not indicating whether it is substituted or unsubstituted.

[0073] In the present invention, when the number of carbon atoms in a group is specified, the number of carbon atoms refers to the number of carbon atoms in the entire group. That is, when the group further has a substituent, it refers to the total number of carbon atoms including the substituent.

[0074] In the present invention, "Si-H group" and "Si-OH group" refer to groups having three additional bonds (not shown) on the silicon atom. Also, [-Si-O] refers to a group having two additional bonds (not shown) on the silicon atom.

[0075] In the present invention, "reactive functional group" is used in a broader sense than usual. That is, it refers to a group that generates an interaction (ionic interaction, hydrogen bond, etc.) with other groups in addition to a group that reacts with other groups to form a covalent bond, etc. In addition, in the present invention, an unsubstituted alkoxy group is not a structure having a reactive functional group.

[0076] Furthermore, in the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after the numerical range as a lower limit and an upper limit.

[0077] Effects of the Invention

[0078] The acoustic wave probe of the present invention has excellent initial adhesion and excellent sterilization durability. In addition, the acoustic wave measuring device and ultrasonic diagnostic device of the present invention include the acoustic wave probe having the above-mentioned excellent performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0079] Figure 1 This is a perspective view of an example of a convex ultrasonic probe which is one form of an acoustic wave probe. DETAILED DESCRIPTION

[0080] <<Acoustic probe (acoustic probe)>>

[0081] The acoustic wave probe of the present invention comprises a substrate, an intermediate layer on the substrate, and an acoustic lens layer on the intermediate layer, wherein the intermediate layer is a layer containing a siloxane compound, and the siloxane compound has a constituent component derived from a hydrolyzed silicate compound, and the acoustic lens layer is a layer formed by curing room temperature curing silicone, and the room temperature curing silicone contains a structural unit having a phenyl group.

[0082] The acoustic wave probe of the present invention has excellent initial adhesion and excellent sterilization durability. The reason is not clear, but one of the reasons is believed to be that the siloxane compound contained in the intermediate layer has a constituent component derived from a hydrolyzed silicate compound, and the acoustic lens layer is a layer formed by curing room temperature curing silicone. Therefore, the hydrophilic group (silanol group [Si-OH]) of the hydrolyzed silicate compound reacts with the hydrosilyl group [Si-H] in the room temperature curing silicone to form a chemical bond at the interface between the intermediate layer and the acoustic lens layer. In addition, one of the reasons is believed to be that the acoustic lens layer in the present invention is a layer formed by curing a room temperature curing silicone containing a structural unit having a phenyl group. Therefore, due to the large molecular size of the phenyl group present in the acoustic lens layer, even when subjected to hydrogen peroxide plasma sterilization treatment having a strong chemical force, the decomposition of hydrogen peroxide gas and hydrogen peroxide gas generated by plasma irradiation, the permeation of active substances, etc. (hereinafter referred to as "hydrogen peroxide gas, etc.") can be suppressed, thereby reducing the amount of hydrogen peroxide gas, etc. reaching the interface between the acoustic lens layer and the intermediate layer, and further reaching the interface between the intermediate layer and the base material such as the acoustic matching layer. Hydrogen peroxide gas, etc. may break the chemical bonds that contribute to the adhesion of organic components, especially materials near the interface, and thus, the structure of the present invention is believed to be able to show excellent hydrogen peroxide plasma sterilization resistance.

[0083] <Base material>

[0084] The base material in the acoustic wave probe of the present invention is not particularly limited, and a wide range of base materials of components used for the periphery of the acoustic lens layer, such as an acoustic matching layer in the acoustic wave probe, can be used.

[0085] That is, the acoustic wave probe of the present invention is a structure in which the components located around the acoustic lens layer in a conventional acoustic wave probe are bonded to the acoustic lens layer via the intermediate layer. Among the components located around the acoustic lens layer, the components bonded to the acoustic lens layer via the intermediate layer become the base material in the acoustic wave probe of the present invention.

[0086] An acoustic matching layer is suitable as the substrate, and the acoustic matching layer is preferably formed by bonding the acoustic lens layer to the intermediate layer.

[0087] The substrate preferably includes at least one of iron, non-ferrous metal, inorganic material other than metal, and organic material.

[0088] In the present invention, a material containing an iron element among metal materials is classified as iron, and a material not containing an iron element among metal materials is classified as non-ferrous metal.

[0089] That is, the above-mentioned iron includes not only pure iron consisting of iron element, but also alloys of iron element and non-ferrous metal element and / or non-metal element. As an example of such alloy containing iron element, stainless steel can be cited.

[0090] Examples of the non-ferrous metal include aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, cobalt, vanadium, gold, and alloys of at least two of these metals.

[0091] As the metal material, non-ferrous metal is preferred from the viewpoint of being more excellent in hydrogen peroxide plasma sterilization resistance.

[0092] From the viewpoint of low catalytic effect on hydrogen peroxide, the non-ferrous metal preferably includes at least one of aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten or cobalt, or an alloy of at least two of these metals, more preferably includes at least one of aluminum, titanium, nickel, copper, chromium, tungsten or cobalt, or an alloy of at least two of these metals, further preferably includes copper, aluminum or tungsten, or at least one of an alloy of at least two of these metals, and particularly preferably includes copper, aluminum, or at least one of an alloy of these metals.

[0093] Examples of the inorganic material other than the above-mentioned metals include glass, ceramics, and graphite. It is preferred that at least one of glass, ceramics, and graphite is contained.

[0094] Examples of the glass include soda carbonate glass, Pyrex (registered trademark) glass, quartz glass, and alkali-free glass.

[0095] The ceramics mentioned above refer to inorganic compounds such as oxides, carbides, nitrides or borides of at least one element among metal elements and non-metal elements, and examples thereof include aluminum oxide, zirconium oxide, silicon carbide and silicon nitride.

[0096] Examples of the graphite include natural graphite and artificial graphite.

[0097] The organic material is usually a solid material, and preferably contains at least one of a thermoplastic resin and a thermosetting resin.

[0098] Examples of the thermoplastic resin include polyolefin resins such as polyethylene resins, polypropylene resins, and polymethylpentene resins, styrene resins such as polystyrene resins, ABS resins (acrylonitrile-butadiene-styrene copolymer resins), and acrylonitrile-styrene copolymer resins, acrylic resins, thermoplastic polyimide resins, thermoplastic polyamide resins, polyetherimide resins, polyphenylene ether resins, polycarbonate resins, polyester resins such as polyethylene terephthalate resins, polybutylene terephthalate resins, and polyethylene naphthalate resins, polyphenylene sulfide resins, polyetheretherketone resins, polyethersulfone resins, and thermoplastic polycycloolefin resins such as thermoplastic polynorbornene resins.

[0099] From the viewpoint of excellent secondary processability such as cutting and machining for making ultrasonic probes, the above-mentioned thermoplastic resin preferably comprises at least one of acrylic resin, polycarbonate resin, styrene resin and polyphenylene sulfide resin. Among them, from the viewpoint of better resistance to hydrogen peroxide plasma sterilization and thermal cycle resistance, a cross-linked thermoplastic resin is more preferred, and a cross-linked polystyrene resin is further preferred.

[0100] The cross-linked thermoplastic resin may be a thermoplastic resin in which a cross-linked structure is introduced. The cross-linked structure is not particularly limited and can be introduced by a conventional method.

[0101] Examples of the thermosetting resin include thermosetting polycycloolefin resins such as epoxy resins, phenolic resins, melamine resins, polyurethane resins, thermosetting polyimide resins, thermosetting polyamide resins, polyamideimide resins, unsaturated polyester resins, and thermosetting polynorbornene resins.

[0102] The unsaturated polyester resin is a resin obtained by dissolving an unsaturated polyester produced by polycondensation of an unsaturated dicarboxylic acid such as fumaric acid and maleic anhydride with a diol such as ethylene glycol in a polymerizable monomer such as styrene and methyl methacrylate.

[0103] From the viewpoint of further improving the resistance to hydrogen peroxide plasma sterilization, the above-mentioned thermosetting resin preferably includes at least one of a phenolic resin, an unsaturated polyester resin, a thermosetting polyimide resin, a thermosetting polyamide resin, a polyamideimide resin and a thermosetting polycycloolefin resin, and more preferably includes at least one of an unsaturated polyester resin, a thermosetting polyimide resin and a thermosetting polyamideimide resin.

[0104] As the above-mentioned organic material, from the viewpoint of further improving the hydrogen peroxide plasma sterilization resistance and thermal cycle resistance, it is preferred to include at least one of a thermosetting resin and a cross-linked thermoplastic resin, and more preferably to include at least one of a thermosetting polyimide resin, an unsaturated polyester resin and a cross-linked polystyrene resin.

[0105] As the above-mentioned substrate, from the viewpoint of further improving the resistance to hydrogen peroxide plasma sterilization, it is preferred that it contains at least one of non-ferrous metal, inorganic material other than metal, and organic material. From the viewpoint of further improving the thermal cycle resistance in addition to the hydrogen peroxide plasma sterilization resistance, it is more preferred that it contains at least one of inorganic material other than metal and organic material. From the viewpoint of further improving the hydrogen peroxide plasma sterilization resistance and thermal cycle resistance, it is further preferred that it contains at least one of a thermosetting resin and a cross-linked thermoplastic resin.

[0106] The total content of iron, non-ferrous metals, inorganic materials other than metals, and organic materials contained in the substrate is not particularly limited, and can be, for example, 80% by mass or more, preferably 90% by mass or more, and may be 100% by mass.

[0107] In addition, when the iron, non-ferrous metal, inorganic material other than metal and organic material contained in the above-mentioned substrate are limited to specific materials (materials), the total content of the limited materials can be set to, for example, 80% by mass or more, preferably 90% by mass or more, or 100% by mass. Therefore, when the above-mentioned substrate contains iron and organic materials, but does not contain non-ferrous metals or inorganic materials other than metals, the total content of iron and organic materials in the substrate can be set to the above-mentioned preferred content.

[0108] From the viewpoint of improving the adhesion between the substrate and the intermediate layer, the substrate is preferably a substrate subjected to a hydrophilic treatment on the surface of the intermediate layer side. There are many reaction points (hydrophilic groups) with the siloxane compound having a constituent component derived from the hydrolyzed silicate compound contained in the intermediate layer on the surface of the hydrophilic treated substrate, so that the peel strength can be further improved, and the peel strength can be maintained at an excellent level even after thermal cycling and hydrogen peroxide plasma sterilization.

[0109] The hydrophilization treatment is not particularly limited as long as it can impart (introduce) reaction sites with the siloxane compound having a constituent component derived from the hydrolyzed silicate compound contained in the intermediate layer to the substrate surface, and for example, at least one of ultraviolet (UV) treatment, ozone treatment, plasma treatment, and corona treatment can be cited. In addition, when two or more of these treatments are performed, the two or more treatments may be performed simultaneously or separately.

[0110] The UV treatment, ozone treatment, plasma treatment, and corona treatment can be performed by a common method unless the effects of the present invention are impaired.

[0111] From the viewpoint of further improving thermal cycle resistance and hydrogen peroxide plasma sterilization resistance, the hydrophilization treatment is preferably at least one of UV treatment, plasma treatment and corona treatment, and more preferably at least one of UV treatment and plasma treatment.

[0112] <Middle layer>

[0113] The intermediate layer in the acoustic wave probe of the present invention is a layer containing a siloxane compound, and the siloxane compound has a constituent component derived from a hydrolyzed silicate compound.

[0114] The siloxane compound is a compound having a repeating structure of siloxane bonds ([—Si—O]), and is an oligomer or polymer obtained by polycondensation of silanol groups (Si—OH groups) possessed by a hydrolyzed silicate compound.

[0115] The hydrolyzed silicate compound is a compound obtained by hydrolyzing a hydrolyzable group in a silicate compound having a hydrolyzable group and converting the hydrolyzable group into a silanol group.

[0116] In addition, a silicate compound refers to a compound having a structure in which four O atoms are coordinated around one Si atom, and a plurality of Si atoms coordinated with four O atoms may exist in the compound. A compound in which one Si atom is coordinated with four O atoms is called a silicate monomer (also called a silane compound), and a compound in which two or more Si atoms are coordinated with four O atoms is called a silicate oligomer.

[0117] In the present invention, the hydrolyzed silicate compound is preferably a hydrolyzed silicate oligomer.

[0118] The hydrolysis rate of the hydrolyzed silicate compound is not particularly limited as long as the effect of the present invention can be obtained, and may be, for example, 50% or more, preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. As described later, when a silicate compound having a hydrolyzable group is hydrolyzed in the presence of an acid or an alkali, a hydrolyzed silicate compound having a hydrolysis rate corresponding to the amount of water used can usually be obtained. The hydrolysis rate of the commercially available product or the hydrolyzed silicate compound obtained by hydrolysis used in the examples described later is 80% or more.

[0119] The hydrolysis rate in the hydrolyzed silicate compound refers to the number of hydrolyzable groups in the hydrolyzed silicate compound. H and the number of hydroxyl groups in the silanol group X OH , and the value calculated by the following calculation formula. In addition, the number of hydroxyl groups in -Si(OH)3 is X OH Counted as 3.

[0120] Hydrolysis rate in hydrolyzed silicate compound = 100% x x OH / (X H +X OH )

[0121] The hydrolyzed silicate compound can be purchased from the market and used. For example, silicate hydrolyzates manufactured by Colcoat Co., Ltd., namely Colcoat PX, Colcoat N-103X, HAS-1, HAS-6, HAS-10 (all trade names), etc. can be used.

[0122] Furthermore, a compound obtained by hydrolyzing a silicate compound having a hydrolyzable group can also be used as the hydrolyzed silicate compound.

[0123] The hydrolysis reaction can be carried out by reacting the silicate compound having a hydrolyzable group in the presence of an acid or a base as a catalyst. In contrast, the hydrolysis reaction hardly proceeds under a neutral condition in the absence of an acid or a base.

[0124] As the acid or base used as a catalyst, an acid or base generally used in the hydrolysis reaction of a silicate compound can be used without particular limitation.

[0125] Among these, when a base is used as a catalyst, it is preferred to use an acid catalyst, and it is more preferred to use hydrochloric acid, from the viewpoint of facilitating gelation.

[0126] The amount of water used in the hydrolysis reaction can be appropriately adjusted according to the desired hydrolysis rate.

[0127] As the solvent used for the hydrolysis reaction, a silicate compound having a hydrolyzable group and a water-soluble solvent can be used, and preferably, one or a mixture of two or more alcohol solvents such as methanol, ethanol, isopropanol, and ethyl cellosolve are used.

[0128] The reaction time of the hydrolysis reaction can be adjusted appropriately, and can be set to, for example, 1 to 24 hours.

[0129] Examples of the hydrolyzable group include an alkoxy group (alkyloxy group), an alkenyloxy group, an acyloxy group, an aminooxy group, an oxime group, and an amide group, and an alkoxy group is preferred.

[0130] The alkyl group in the alkoxy group may be any of a linear, branched, and cyclic group. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, and particularly preferably 1 or 2. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a butyl group, and a cyclopentyl group.

[0131] When the acyloxy group, aminooxy group, oxime group and amide group are substituted with an alkyl group, the description of the alkyl group in the alkoxy group described above can be applied as the alkyl group in the acyloxy group, aminooxy group, oxime group and amide group.

[0132] The alkenyl group in the alkenyloxy group may be linear, branched or cyclic. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms.

[0133] Examples of the silicate compound as a silicate monomer among the silicate compounds having a hydrolyzable group include tetraalkoxysilane compounds.

[0134] The tetraalkoxysilane compound is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane.

[0135] Furthermore, a hydrolyzed silicate compound can also be obtained by hydrolyzing a mixture of the above-mentioned tetraalkoxysilane compound and a trialkoxysilane compound and / or a dialkoxysilane compound. The above-mentioned trialkoxysilane compound and dialkoxysilane compound are compounds having a structure in which three or two O atoms are coordinated around one Si atom, and are not silicate compounds.

[0136] As for the conditions for the hydrolysis reaction of the mixture, the conditions for the hydrolysis reaction of the silicate compound having a hydrolyzable group described above can be applied.

[0137] The trialkoxysilane compound is not particularly limited, and examples thereof include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

[0138] The dialkoxysilane compound is not particularly limited, and examples thereof include dimethyldimethoxysilane and dimethyldiethoxysilane.

[0139] Among silicate compounds having hydrolyzable groups, silicate oligomers can be obtained by hydrolysis-condensation reaction of silicate monomers. Among silicate compounds having hydrolyzable groups, examples of silicate oligomers include hydrolysis-condensation products of the above-mentioned tetraalkoxysilane compounds, and hydrolysis-condensation products of mixtures of the above-mentioned tetraalkoxysilane compounds and trialkoxysilane compounds and / or dialkoxysilane compounds.

[0140] The number of Si atoms coordinated with four O atoms in the silicate oligomer is preferably 2-200, more preferably 2-120.

[0141] Among them, a hydrolysis condensate of tetraalkoxysilane is preferred, a hydrolysis condensate of tetramethoxysilane and / or tetraethoxysilane is more preferred, and a hydrolysis condensate of tetramethoxysilane or tetraethoxysilane is further preferred.

[0142] Silicate compounds having a hydrolyzable group can be purchased from the market and used. For example, as silicate monomers, ethyl silicate 28, N-propyl silicate, N-butyl silicate (all trade names) manufactured by Colcoat Co., Ltd. can be cited. As silicate oligomers, ethyl silicate 40, ethyl silicate 48, methyl silicate 51, methyl silicate 53A, EMS-485 (all trade names) manufactured by Colcoat Co., Ltd. and MKC silicate MS51, MS56, MS57, MS56S (all trade names) manufactured by Mitsubishi Chemical Corporation can be used.

[0143] It is preferred that the hydrolyzed silicate compound has no organic group other than the methyl group and the ethyl group.

[0144] The weight average molecular weight of the hydrolyzed silicate compound is not particularly limited, and is, for example, preferably 100 to 10,000, more preferably 150 to 4,000, and particularly preferably 200 to 2,500.

[0145] The weight average molecular weight or number average molecular weight of the compound described in the present specification is determined as follows.

[0146] The weight average molecular weight or number average molecular weight can be measured as a molecular weight in terms of polystyrene by gel permeation chromatography (GPC).

[0147] Specifically, a GPC apparatus HLC-8220 (trade name, manufactured by TOSOH CORPORATION) was used, tetrahydrofuran was used as an eluent, a column using G3000HXL+G2000HXL (both trade names, manufactured by TOSOH CORPORATION), at 23°C and a flow rate of 1 mL / min, and detection was possible using RI (differential refractive index).

[0148] The acoustic wave probe of the present invention includes a layer containing a siloxane compound as an intermediate layer that reacts with at least one of a substrate and an acoustic lens layer. For example, the intermediate layer is a layer that allows the hydroxyl groups of the siloxane compound to react with the groups on the surface of the acoustic lens layer or the substrate.

[0149] The content of the siloxane compound in the intermediate layer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit is not particularly limited, for example, 100% by mass or less, preferably 99% by mass or less, and more preferably 98% by mass or less. That is, the content of the siloxane compound in the intermediate layer is preferably 50 to 100% by mass, more preferably 70 to 99% by mass, and further preferably 80 to 98% by mass.

[0150] The content of the hydrolyzed silicate compound in the solution (which may contain a solvent) used to form the intermediate layer is, for example, preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 4% by mass or more. The upper limit is not particularly limited, and is, for example, 100% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 25% by mass or less. That is, the content of the hydrolyzed silicate compound in the solution (containing a solvent) used to form the above-mentioned intermediate layer is preferably 1 to 100% by mass, more preferably 2 to 70% by mass, further preferably 3 to 50% by mass, and particularly preferably 4 to 25% by mass.

[0151] In the present invention, from the viewpoint of obtaining better peel strength, the intermediate layer further preferably contains a constituent component derived from at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound and a zirconium alkoxide compound, and from the viewpoint of better thermal cycle resistance and hydrogen peroxide plasma sterilization resistance, it is more preferably contained a constituent component derived from an aluminum alkoxide compound.

[0152] (Silane coupling agent)

[0153] As the silane coupling agent used in the present invention, a wide range of common silane coupling agents that can be used as a primer layer of a component of an acoustic wave probe can be adopted.

[0154] The silane coupling agent preferably has no siloxane bond and preferably has a group other than a methyl group, an ethyl group, a methoxy group, and an ethoxy group (for example, an amino group, a vinyl group, a propyl group, an acid anhydride group, an epoxy group, and a mercapto group).

[0155] (Titanium alkoxide compound)

[0156] As the titanium alkoxide compound (preferably a titanium coupling agent) used in the present invention, a wide range of common titanium alkoxide compounds that can be used as a primer layer of a component of an acoustic wave probe can be adopted.

[0157] The titanium alkoxide compound preferably contains at least one of the compounds represented by the following general formula (a) or (b), and more preferably contains at least one of the compounds represented by the following general formula (a). The total content ratio of the compounds represented by the following general formula (a) or (b) in the titanium alkoxide compound is not particularly limited, and can be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and can also be 100% by mass.

[0158] General formula (a): R 1a m1 -Ti-(OR 2a ) 4-m1

[0159] General formula (b): O-[Ti-(OR 2a )3]2

[0160] R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0161] As able to act as R 1a The alkyl group, cycloalkyl group, acyl group, aryl group and unsaturated aliphatic group used may be, for example, the following general formula (c) which can be used as R 1b The alkyl, cycloalkyl, acyl, aryl and unsaturated aliphatic groups are used.

[0162] 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.

[0163] As able to act as R 2a The alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group and phosphonate group used may be, for example, those of the general formula (c) described below. 2b The alkyl, cycloalkyl, acyl, alkenyl, aryl and phosphonate groups used are also included. S1 The substituents used may be, for example, those of the general formula (c) described below that can be used as R S2 And the substituents used.

[0164] m1 is an integer from 0 to 3.

[0165] The compound represented by the above-mentioned general formula (a) or (b) preferably contains at least one atom of N, P and S.

[0166] When the compound represented by the general formula (a) or (b) has N, it preferably has the N as an amino group.

[0167] When the compound represented by the general formula (a) or (b) has P, it is preferred that the P be a phosphate group (phosphoric acid group) or a phosphonate group (phosphonic acid group).

[0168] When the compound represented by the general formula (a) or (b) has S, it is preferred to have the S as a sulfonyl group (—SO 2 —).

[0169] Furthermore, the compound represented by the above general formula (a) or (b) also preferably has an acyl group as R 2a , that is, having an acetyl structure described later as OR 2a .

[0170] Specific examples of the titanium alkoxide compound used in the present invention are given below, but the present invention is not limited thereto.

[0171] Isopropyl triisostearyl titanate

[0172] Isopropyl tridodecylbenzenesulfonyl titanate

[0173] Isopropyl trioctanoyl titanate

[0174] Isopropyl tri(dioctyl phosphite) titanate

[0175] Isopropyl tri(dioctyl pyrophosphate) titanate

[0176] Isopropyl tri(dioctyl sulfate) titanate

[0177] Isopropyl tricumylphenyl titanate

[0178] Isopropyl tri(N-aminoethyl-aminoethyl) titanate

[0179] Isopropyl dimethacrylate isostearyl titanate

[0180] Isopropyl isostearyl titanate diacrylate

[0181] Isobutyl trimethyl titanate

[0182] Diisostearyl Ethylene Titanate

[0183] Diisopropyl bis(dioctyl pyrophosphate) titanate

[0184] Dioctyl bis(di-tridecyl phosphate) titanate

[0185] Dicumylphenyloxyacetate titanate

[0186] Bis(dioctyl pyrophosphate)oxyacetate titanate

[0187] Bis(dioctyl pyrophosphate)ethylene titanate

[0188] Tetraisopropyl titanate

[0189] Tetrabutyl titanate

[0190] Tetraoctyl titanate

[0191] Tetrastearyl Titanate

[0192] Tetraisopropyl bis(dioctylphosphite) titanate

[0193] Tetraoctylbis(di-tridecylphosphite) titanate

[0194] Tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate

[0195] Butyl Titanate Dimer

[0196] Titanium Tetraacetylacetonate

[0197] Titanium acetoacetate

[0198] Titanium octylene glycolate

[0199] Bis(2-ethyl-3-hydroxyhexyloxy)titanium

[0200] (Aluminum alkoxide compound)

[0201] As the aluminum alkoxide compound (preferably an aluminum coupling agent) used in the present invention, a wide range of common aluminum alkoxide compounds that can be used as a primer layer of a component of an acoustic wave probe can be adopted.

[0202] The aluminum alkoxide compound preferably comprises at least one of the compounds represented by the following general formula (c) or (d), and more preferably comprises at least one of the compounds represented by the following general formula (c). The ratio of the total content of the compounds represented by the following general formula (c) or (d) in the above-mentioned aluminum alkoxide compound is not particularly limited, and for example, can be set to 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and can also be 100% by mass.

[0203] General formula (c): R 1b m2 -Al-(OR 2b ) 3-m2

[0204] General formula (d): O-[Al-(OR 2b )2]2

[0205] R 1brepresents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0206] Can be used as R 1b The alkyl group used includes a straight chain alkyl group, a branched chain alkyl group and an aralkyl group. The number of carbon atoms of 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.

[0207] Can be used as R 1b The alkyl group used is preferably an oxirane ring, for example, 1b , cycloalkylene oxide can be mentioned. 1b The number of ring members of the cycloalkyl group (cycloalkyl group formed by condensing an oxirane ring, i.e., an oxirane ring) in the cyclooxyalkyl group is preferably 4 to 8, more preferably 5 or 6, and further preferably 6 (i.e., the cyclooxyalkyl group is an cyclohexyl group).

[0208] And, can be used as R 1b The alkyl group used 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.

[0209] Can be used as R 1b The carbon number of the cycloalkyl group 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.

[0210] Can be used as R 1b The number of carbon atoms of the acyl group to be used is preferably 2 to 40, more preferably 2 to 30, further preferably 2 to 20, and particularly preferably 2 to 18.

[0211] Can be used as R 1b The carbon number of the aryl group 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.

[0212] Can be used as R 1bThe number of carbon-carbon unsaturated bonds of the unsaturated aliphatic group 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 heteroatoms, 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 also preferably 2 to 5. The unsaturated aliphatic group is more preferably an alkenyl group or an alkynyl group.

[0213] R 1b It is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and more preferably an alkyl group or a cycloalkyl group.

[0214] In the compound of general formula (c), there are two or more R 1b In the case of 2 R 1b They can be connected to each other to form a ring.

[0215] R 2b 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 S2 . R S2 represents a substituent.

[0216] Can be used as R 2b The meanings of alkyl, cycloalkyl, acyl and aryl used are respectively the same as those of 1b The meanings of alkyl, cycloalkyl, acyl and aryl used are the same, and the preferred forms of each group are also the same. 2b The alkyl group to be used also preferably has an amino group as a substituent.

[0217] Can be used as R 2b The alkenyl group 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.

[0218] Can be used as R 2b The phosphonate group used is -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 meaning of the alkyl group used is the same as that of the above-mentioned group that can be used as R 1b The meaning of the alkyl group used is the same, and the preferred form of the alkyl group is also the same. P1 and RP2 The meaning of the phosphonate group used is the same as that of the group that can be used as R 2b The phosphonate group used has the same meaning and the preferred form is also the same. 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.

[0219] Can be used as R 2b The phosphonate group used is preferably R P1 and R P2 are all alkyl, or R P1 is a hydrogen atom, and R P2 It is a phosphonate group.

[0220] In addition, a phosphonate group and a phosphite group (phosphite group) are tautomers, and therefore, in the present invention, a phosphonate group includes a phosphite group.

[0221] In being able to act as R 2b The -SO2R S2 In the case of S2 , preferably an alkyl group or an aryl group. S2 The preferred forms of the alkyl and aryl groups used include the above-mentioned 1b The preferred forms of alkyl and aryl groups are used. S2 Preferably, it is a phenyl group having an alkyl group as a substituent. The preferred form of the alkyl group is the same as the above-mentioned group that can be used as R 1b The preferred forms of the alkyl groups used are the same.

[0222] In the compound represented by the general formula (c), there are two or more R 2b In the case of 2 R 2b In the compound represented by the general formula (d), two R 2b They can be connected to each other to form a ring.

[0223] m2 is an integer from 0 to 2.

[0224] In the above general formulae (c) and (d), preferably OR 2bAt least one of them has an acetonate structure. The pyruvate structure refers to a structure in which one 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 pyruvate structure is preferably a structure in which one hydrogen ion is removed from the acetylacetone structure ("CH3-C(=O)-CH2-C(=O)-CH3") as a basic structure, and an oxygen atom is coordinated with Al as a coordinating atom (i.e., an acetylacetonate structure). The above-mentioned "having an acetylacetone structure as a basic structure" refers to a structure in which, in addition to the above-mentioned acetylacetone structure, a hydrogen atom of the above-mentioned acetylacetone structure is substituted with a substituent. As OR 2b Examples of the form having a pyruvate structure include compounds AL-1 and AL-2 described below.

[0225] In the above general formulae (c) and (d), preferably OR 2b At least one of them has an acetyl structure. In the present invention, the acetyl structure refers to a structure in which one hydrogen ion is removed from acetic acid or acetate or a compound having 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 generally an oxygen atom. The acetyl 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, but may also be an alkyl group having 1 to 10 carbon atoms, and may more preferably be an alkyl group having 1 to 4 carbon atoms). )) as a basic structure, from which one hydrogen ion is removed, and an oxygen atom is coordinated with Al as a coordinating atom. The above-mentioned "having an acetoacetate alkyl ester structure as a basic structure" means, in addition to the above-mentioned acetoacetate alkyl ester structure, a structure in which a hydrogen atom of the above-mentioned acetoacetate alkyl ester structure is substituted with a substituent. As OR 2b Examples of the compound having an acetyl structure include compounds AL-2, AL-3, and AL-4 described below.

[0226] Can be used as the above R 1b or R 2bEach group used may contain an anionic group (salt-type substituent) having a counter cation as a substituent. Anionic group refers to a group that can form anions. As anionic groups having the above-mentioned counter cations, for example, groups of carboxylate ions using ammonium ions as counter cations can be cited. In this case, the above-mentioned counter cations only need to exist in the compound represented by the above-mentioned general formula (c) or (d) in such a way that the charge of the entire compound becomes 0. This is also the same for the compounds represented by the aforementioned general formula (a) or (b) and the compounds represented by the general formula (e) or (f) described later.

[0227] Specific examples of the aluminum alkoxide compound used in the present invention are given below, but the present invention is not limited thereto.

[0228] Aluminium triethylate

[0229] Aluminum triisopropoxide

[0230] Aluminum tri-sec-butylate

[0231] Aluminum tris(acetoacetate)

[0232] Aluminum diisopropyl acetoacetate

[0233] Aluminum monoacetylacetonate bis(ethyl acetoacetate)

[0234] Aluminum tris(acetylacetonate)

[0235] Diisopropoxy-9-octadecenyl aluminum acetoacetate

[0236] Diisopropoxy monoethyl acetoacetate aluminum

[0237] Aluminum mono-sec-butoxydiisopropylate

[0238] Aluminum diethyl acetoacetate isopropoxide

[0239] Aluminum bis(ethyl acetoacetate) monoacetylacetonate

[0240] Octadecyl Acetoacetate Aluminum Diisopropylate

[0241] (Zirconium alkoxide compound)

[0242] As the zirconium alkoxide compound (preferably a zirconium coupling agent) used in the present invention, a wide range of common zirconium alkoxide compounds that can be used as a primer layer of a component of an acoustic wave probe can be adopted.

[0243] The zirconium alkoxide compound preferably contains at least one of the compounds represented by the following general formula (e) or (f), and more preferably contains at least one of the compounds represented by the following general formula (e). The ratio of the total content of the compounds represented by the following general formula (e) or (f) in the above-mentioned zirconium alkoxide compound is not particularly limited, and for example, can be set to 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and can also be 100% by mass.

[0244] General formula (e): R 1c m3 -Zr-(OR 2c ) 4-m3

[0245] General formula (f): O-[Zr-(OR 2c )3]2

[0246] R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group or an unsaturated aliphatic group.

[0247] As able to act as R 1c The alkyl, cycloalkyl, acyl, aryl and unsaturated aliphatic groups used may be, for example, those of the general formula (c) as R 1b The alkyl, cycloalkyl, acyl, aryl and unsaturated aliphatic groups are used.

[0248] 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.

[0249] As able to act as R 2c The alkyl, cycloalkyl, acyl, alkenyl, aryl and phosphonate groups used may be, for example, those of the general formula (c) as R 2b The alkyl, cycloalkyl, acyl, alkenyl, aryl and phosphonate groups used are also included. S3 The substituents used may be, for example, those of the general formula (c) above that can be used as R S2 And the substituents used.

[0250] m3 is an integer from 0 to 3.

[0251] In the above general formulae (e) and (f), preferably OR 2c At least one of them has a pyruvate structure. The meaning of the pyruvate structure is the same as the meaning of the pyruvate structure described in general formula (c). 2cExamples of the form having a pyruvate structure include compounds ZR-1 and ZR-3 described below.

[0252] Furthermore, in the above general formula (e), preferably OR 2c At least one of them has an acetyl structure. The meaning of the acetyl structure is the same as the meaning of the acetyl structure described in the general formula (c). 2c Examples of the compound having an acetyl structure include ZR-4 described below.

[0253] Furthermore, in the above general formulae (e) and (f), preferably OR 2c At least one of them has a lactate structure. The lactate structure refers to a structure in which a lactate ion (lactate) is used as a basic structure, one hydrogen ion is removed from the basic structure, and the structure is coordinated with Zr. The above-mentioned "lactate ion as a basic structure" refers to a structure in which, in addition to the above-mentioned lactate ion, the hydrogen atom of the above-mentioned lactate ion is replaced by a substituent. The coordinating atom coordinated with the Zr is usually an oxygen atom. As OR 2c Examples of the form having a lactate structure include the compound ZR-2 described below.

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

[0255] Tetrapropoxyzirconium (also known as tetra-n-propoxide zirconium)

[0256] Zirconium Tetrabutoxide (also known as Zirconium Tetra-n-Butoxide)

[0257] Zirconium Tetraacetylacetonate

[0258] Zirconium tributoxyacetylacetonate

[0259] Zirconium dibutoxybis(acetylacetonate)

[0260] Dibutoxybis(ethyl acetoacetate)zirconium

[0261] Zirconium ethyl tributoxyacetoacetate

[0262] Zirconium monobutoxyacetylacetonate bis(ethyl acetoacetate)

[0263] Zirconium tri-butoxy monostearate (also known as zirconium tri-n-butyl stearate)

[0264] Zirconium stearate

[0265] Ammonium zirconium lactate

[0266] Zirconium monoacetylacetonate

[0267] The molecular weight of the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound and zirconium alkoxide compound used in the present invention is not particularly limited, and is, for example, preferably 100 to 2,000, and more preferably 200 to 500.

[0268] In addition, a polymer silane coupling agent can also be used.

[0269] The silane coupling agent, the aluminum alkoxide compound, the zirconium alkoxide compound, and the titanium alkoxide compound that can be contained in the intermediate layer may be one kind each, or two or more kinds thereof.

[0270] In the case where the intermediate layer contains at least one constituent component derived from a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound, the total content of the constituent components derived from the silane coupling agent, the titanium alkoxide compound, the aluminum alkoxide compound, and the zirconium alkoxide compound contained in the intermediate layer is not particularly limited, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more. The upper limit is not particularly limited, for example, preferably 99% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less. That is, the total content of the constituent components derived from the silane coupling agent, the titanium alkoxide compound, the aluminum alkoxide compound, and the zirconium alkoxide compound contained in the intermediate layer is preferably 1 to 99% by mass, more preferably 5 to 99% by mass, further preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.

[0271] The total content of the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound and zirconium alkoxide compound in the solution (including solvent) for forming the intermediate layer is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. The upper limit is not particularly limited, for example, 99% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 25% by mass or less. That is, the total content of the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound and zirconium alkoxide compound in the solution (including solvent) for forming the above-mentioned intermediate layer is preferably 0.02 to 99% by mass, more preferably 0.1 to 70% by mass, further preferably 0.3 to 50% by mass, and particularly preferably 0.5 to 25% by mass.

[0272] In the present invention, "the intermediate layer contains a constituent component derived from at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound" means a mode including containing at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound in a state of reacting with the acoustic lens layer and / or the substrate. For example, at least a part of the silane coupling agent, the titanium alkoxide compound, the aluminum alkoxide compound, and the zirconium alkoxide compound is hydrolyzed to expose hydroxyl groups, and these can react with the groups on the surface of the acoustic lens layer and / or the substrate to exist.

[0273] As long as the effects of the present invention are not impaired, the intermediate layer may contain a siloxane compound having constituent components derived from a hydrolyzed silicate compound, and components other than constituent components derived from at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound. Examples of such components include additives such as surfactants, antioxidants, thickeners, leveling agents, stabilizers, and defoaming agents.

[0274] In addition, the intermediate layer may be a single layer or a multi-layer, but is preferably a single layer.

[0275] The average thickness of the intermediate layer is not particularly limited, and is, for example, preferably 5 nm to 100 μm, more preferably 10 nm to 20 μm, further preferably 25 nm to 10 μm, and particularly preferably 40 nm to 5 μm. The average thickness of the intermediate layer is a value measured by the method described in the examples below.

[0276] <Acoustic lens layer>

[0277] The acoustic lens layer in the acoustic wave probe of the present invention is a layer formed by curing room temperature curing silicone, and the room temperature curing silicone contains a structural unit having a phenyl group.

[0278] As described above, by setting the acoustic lens layer in the acoustic wave probe of the present invention as a layer formed by curing room temperature curing silicone containing a structural unit having a phenyl group, the permeability of the acoustic lens layer to hydrogen peroxide gas, etc. is suppressed, thereby reducing the amount of hydrogen peroxide gas, etc. reaching the interface between the acoustic lens layer and the intermediate layer, and further reaching the interface between the intermediate layer and the substrate. As a result, it is believed that excellent hydrogen peroxide plasma sterilization resistance can be exhibited.

[0279] The content of phenyl groups in the cured product of room temperature curing silicone is preferably 1 to 50 mol%, more preferably 2 to 30 mol%, further preferably 3 to 20 mol%, and particularly preferably 4 to 10 mol% from the viewpoint of better thermal cycle resistance and hydrogen peroxide plasma sterilization resistance.

[0280] In addition, the phenyl group in the cured product of the room temperature curing silicone may be unsubstituted or may have a substituent. Examples of the phenyl group having a substituent include an alkyl substituted phenyl group (a group in which the hydrogen atoms in the phenyl group are replaced by a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms), and a group in which the hydrogen atoms in the phenyl group are replaced by at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, a carboxyl group, a cyano group and a nitro group.

[0281] The content of phenyl groups in the cured product of room temperature curing silicone refers to the mol% of the phenyl-containing siloxane unit when all units constituting the cured product of room temperature curing silicone are set to 100 mol%. One phenyl-containing siloxane unit has 1 to 3 phenyl groups. Preferably, two phenyl groups are present per one phenyl-containing siloxane unit. For example, it becomes 100 mol% when all Si atoms of the Si-O unit and the terminal Si each have at least one phenyl group.

[0282] In addition, the unit refers to a Si-O unit and a terminal Si.

[0283] Room temperature curing silicone, also called RTV silicone, refers to silicone that can be cured at a temperature of 50° C. or less. For example, a silicone composition containing vinyl silicone and hydrogen silicone can be used as RTV silicone, and can be cured in the presence of a platinum catalyst at a temperature of 50° C. or less, and can therefore be preferably used.

[0284] (Silicone composition)

[0285] A silicone composition comprising vinyl silicone and hydrogen silicone as room temperature curing silicone (also referred to simply as "silicone composition" in the present invention) contains vinyl silicone as polysiloxane having a vinyl group and hydrogen silicone as polysiloxane having two or more Si-H groups in the molecular chain.

[0286] The structural unit having a phenyl group may be included as a structural unit of at least one of vinyl silicone and hydrogen silicone, and is preferably included as at least a structural unit of vinyl silicone.

[0287] The content of vinyl silicone in a total of 100 parts by mass of the silicone composition is preferably 80 to 99.9 parts by mass, and the content of hydrogen silicone is preferably 0.1 to 20 parts by mass. When the silicone composition contains components other than vinyl silicone and hydrogen silicone, the content of vinyl silicone is more preferably 40 to 70 parts by mass, and further preferably 45 to 65 parts by mass. The content of hydrogen silicone is more preferably 0.3 to 15 parts by mass, further preferably 0.3 to 10 parts by mass, particularly preferably 0.4 to 5 parts by mass, and particularly preferably 0.4 to 3 parts by mass.

[0288] From the viewpoint of further suppressing the permeability of hydrogen peroxide gas or the like through the acoustic lens layer and further improving the hydrogen peroxide plasma sterilization resistance, the silicone composition preferably contains surface-treated oxide particles described below, and more preferably contains surface-treated spherical silica particles described below.

[0289] When the silicone composition contains surface-treated oxide particles, the preferred contents of the respective components are as follows.

[0290] The content of vinyl silicone in a total of 100 parts by mass of the silicone composition is preferably 29.9 to 74.9 parts by mass, and the content of hydrogen silicone is preferably 0.1 to 20 parts by mass. The content of vinyl silicone is more preferably 40 to 70 parts by mass, and further preferably 45 to 65 parts by mass. The content of hydrogen silicone is more preferably 0.3 to 15 parts by mass, further preferably 0.3 to 10 parts by mass, particularly preferably 0.4 to 5 parts by mass, and particularly preferably 0.4 to 3 parts by mass.

[0291] The content of the surface-treated oxide particles (preferably the surface-treated spherical silica particles) in a total of 100 parts by mass of the silicone composition is preferably 25 to 70 parts by mass, more preferably 30 to 60 parts by mass, and further preferably 35 to 50 parts by mass. When the content of the surface-treated oxide particles (preferably the surface-treated spherical silica particles) is within the above range, the tear strength, bending durability, and acoustic wave sensitivity are increased.

[0292] When the content of the polysiloxane (vinyl silicone and hydrogen silicone) is within the above range, the obtained cured product (silicone resin) has an excellent balance among hardness, tear strength, and acoustic impedance.

[0293] The silicone composition refers to a composition that does not contain a catalyst for cross-linking polymerization (curing) of vinyl silicone and hydrogen silicone. Therefore, the silicone composition contains silica particles but does not contain a catalyst.

[0294] Furthermore, 100 parts by mass of the total amount of the silicone composition means that the total amount of each component contained in the silicone composition is 100 parts by mass.

[0295] The above-mentioned silicones contained in the silicone composition may be any silicones as long as they are silicones having a vinyl group and silicones having two or more Si-H groups in the molecular chain. However, in the present invention, the vinyl silicone is preferably a polyorganosiloxane (A) having a vinyl group as described below, and the hydrogen silicone is preferably a polyorganosiloxane (B) having two or more Si-H groups in the molecular chain as described below.

[0296] The structural unit having a phenyl group may be included as a structural unit of at least one of the polyorganosiloxane (A) having a vinyl group and the polyorganosiloxane (B) having two or more Si—H groups in the molecular chain, and is preferably included as a structural unit of at least the polyorganosiloxane (A) having a vinyl group.

[0297] Therefore, in the present invention, a silicone composition preferably contains at least a polyorganosiloxane having a vinyl group (A) and a polyorganosiloxane having two or more Si-H groups in its molecular chain (B) as components, and more preferably a composition containing at least a polyorganosiloxane having a vinyl group (A), a polyorganosiloxane having two or more Si-H groups in its molecular chain (B) and silica particles (C) as components.

[0298] In the following detailed description, a silicone composition containing a polyorganosiloxane (A) having a vinyl group and a polyorganosiloxane (B) having two or more Si-H groups in the molecular chain is described as a preferred embodiment. However, the silicones contained in the silicone composition are not limited to the polyorganosiloxanes (A) and (B).

[0299] (Polyorganosiloxane having a vinyl group (A))

[0300] The polyorganosiloxane (A) having a vinyl group (hereinafter, also simply referred to as polyorganosiloxane (A)) used in the present invention preferably has two or more vinyl groups in the molecular chain.

[0301] Examples of the polyorganosiloxane (A) include polyorganosiloxane (a) having vinyl groups at least at both ends of the molecular chain (hereinafter, also referred to as polyorganosiloxane (a)), and polyorganosiloxane (b) having at least two -O-Si(CH3)2(CH=CH2) groups in the molecular chain (hereinafter, also referred to as polyorganosiloxane (b)). Among them, polyorganosiloxane (a) having vinyl groups at least at both ends of the molecular chain is preferred.

[0302] The polyorganosiloxane (a) is preferably linear, and the polyorganosiloxane (b) is preferably -O-Si(CH3)2 (CH=CH2) bonded to Si atoms constituting the main chain.

[0303] The polyorganosiloxane (A) is hydrosilylated by reacting with the polyorganosiloxane (B) having two or more Si-H groups, for example, in the presence of a platinum catalyst. A crosslinked structure (cured product) is formed by the hydrosilylation reaction (addition reaction).

[0304] The vinyl content of the polyorganosiloxane (A) is not particularly limited, but is preferably 0.01 to 5 mol %, more preferably 0.05 to 2 mol %, from the viewpoint of forming a sufficient network with the components included in the acoustic lens layer.

[0305] The content of vinyl groups refers to the mol% of the vinyl-containing siloxane units when all units constituting the polyorganosiloxane (A) are set to 100 mol%. One vinyl-containing siloxane unit has 1 to 3 vinyl groups. Preferably, one vinyl group is used for one vinyl-containing siloxane unit. For example, when all Si atoms constituting the Si-O units of the main chain and the terminal Si each have at least one vinyl group, the content is 100 mol%.

[0306] Furthermore, the polyorganosiloxane (A) preferably has a phenyl group. From the viewpoint of mechanical strength when used as an acoustic lens layer and hydrogen peroxide plasma sterilization resistance, the phenyl group content is preferably, for example, 1 to 50 mol%, more preferably 2 to 30 mol%, further preferably 3 to 20 mol%, and particularly preferably 4 to 10 mol% from the viewpoint of better thermal cycle resistance and hydrogen peroxide plasma sterilization resistance.

[0307] The phenyl content refers to the mol% of the phenyl-containing siloxane unit when all units constituting the polyorganosiloxane (A) are set to 100 mol%. One phenyl-containing siloxane unit has 1 to 3 phenyl groups. Preferably, two phenyl groups are used for one phenyl-containing siloxane unit. For example, it becomes 100 mol% when all Si atoms constituting the Si-O unit of the main chain and the terminal Si each have at least one phenyl group.

[0308] In addition, the unit refers to the Si-O unit constituting the main chain and the terminal Si.

[0309] The degree of polymerization and specific gravity are not particularly limited. In addition, from the viewpoint of improving the mechanical strength, hardness and chemical stability of the silicone resin (hereinafter also referred to as silicone resin) constituting the obtained acoustic lens layer, 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.

[0310] The mass average molecular weight of the polyorganosiloxane (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 mechanical strength, hardness, and / or ease of processing.

[0311] In the present invention, regarding the mass average molecular weight, for example, a GPC apparatus HLC-8220 (trade name, manufactured by TOSOH CORPORATION) is prepared, toluene (manufactured by FUJIFILM Wako Pure Chemical Corporation) is used as an eluent, and TSKgel (registered trademark) G3000HXL + TSKgel (registered trademark) G2000HXL are used as columns, and measurement can be performed using an RI (differential refractive index) detector at a temperature of 23° C. and a flow rate of 1 mL / min.

[0312] The kinematic viscosity of the polyorganosiloxane (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.

[0313] The kinematic viscosity can be determined by measuring at a temperature of 25° C. using an Ubbelohde viscometer (for example, manufactured by SIBATA SCIENTIFIC TECHNOLOGY LTD., trade name: SU) in accordance with JIS Z8803.

[0314] As the polyorganosiloxane (a) having vinyl groups at least at both ends of the molecular chain, a polyorganosiloxane represented by the following general formula (A) is preferred.

[0315] [Chemical formula 1]

[0316]

[0317] In the general formula (A), R a1 Represents vinyl, R a2 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.

[0318] 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, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl and n-decyl.

[0319] R a2 and R a3The 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.

[0320] 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.

[0321] R a2 and R a3 The number of carbon atoms 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.

[0322] 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.

[0323] Examples of the group having a substituent include a halogenated alkyl group.

[0324] R a2 and R a3 It is preferably an alkyl group, an alkenyl group or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms, a vinyl group or a phenyl group, further preferably a methyl group, a vinyl group or a phenyl group, and particularly preferably a methyl group or a phenyl group.

[0325] In the case where the polyorganosiloxane (a) having vinyl groups at least at both ends of the molecular chain contains a structural unit having a phenyl group, ( x2 R in the repeating unit a2 and R a3 All are phenyl, and R a2 It is a methyl group, that is, preferably a vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer.

[0326] x1 is preferably an integer of 200 to 3,000, more preferably an integer of 400 to 2,000.

[0327] 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.

[0328] Furthermore, as another aspect, x1 is preferably an integer of 1 to 3,000, and more preferably an integer of 5 to 1,000.

[0329] Examples of polyorganosiloxanes having vinyl groups at least at both ends of the molecular chain include 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), 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 manufactured by Gelest.

[0330] In addition, since fumed silica is pre-blended in DMS-V31S15, no special equipment is required for kneading.

[0331] The polyorganosiloxane (A) having a vinyl group in the present invention may be used alone or in combination of two or more.

[0332] (Polyorganosiloxane (B) having two or more Si-H groups in the molecular chain)

[0333] The polyorganosiloxane (B) having two or more Si-H groups in the molecular chain (hereinafter, also referred to as polyorganosiloxane (B)) used in the present invention has two or more Si-H groups in the molecular chain. Wherein, 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.

[0334] By having two or more Si-H groups in the molecular chain, it can react with a polyorganosiloxane having a polymerizable unsaturated group (vinyl group, etc.) (preferably a polyorganosiloxane having at least two polymerizable unsaturated groups (vinyl group, etc.)) to form a crosslinked structure.

[0335] The polyorganosiloxane (B) has a linear structure and a branched structure, and the linear structure is preferred.

[0336] From the viewpoint of the mechanical strength and hardness of the acoustic lens layer, the mass average molecular weight of the linear structure is preferably 500 to 100,000, and more preferably 1,500 to 50,000.

[0337] The polyorganosiloxane (B) having a linear structure having two or more Si—H groups in the molecular chain is preferably a polyorganosiloxane represented by the following general formula (B).

[0338] [Chemical formula 2]

[0339]

[0340] In the general formula (B), R b1 ~R b3 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or -O-Si(R b5 )2(R b4 ). b4 and R b5 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. y1 represents an integer greater than 0, and y2 represents an integer greater than 1. b1 , multiple R b2 , multiple R b3 , multiple R b4 and multiple R b5 can be the same as or different from each other, and R b1 ~R b5 Each of the groups in may be substituted by a substituent. There are two or more Si-H groups in the molecular chain.

[0341] R b1 ~R b3 The meanings of alkyl, cycloalkyl, alkenyl and aryl in R a2 and R a3 The alkyl, cycloalkyl, alkenyl and aryl groups in are the same in meaning and preferred ranges are also the same.

[0342] -O-Si(R b5 )2(R b4 ) b4 and R b5 The meanings of alkyl, cycloalkyl, alkenyl and aryl in R b1 ~R b3 The alkyl, cycloalkyl, alkenyl and aryl groups in are the same in meaning and preferred ranges are also the same.

[0343] R b1 ~R b3 Preferably, it is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an -O-Si(R b5 )2(R b4 ), more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group or -O-Si(CH3)2H.

[0344] Among them, R b1 and R b2 More preferably, it is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, further preferably, it is a hydrogen atom or an alkyl group, and particularly preferably, it is a hydrogen atom or a methyl group.

[0345] R b3 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.

[0346] In addition, in the present invention, in R b3 In the case of phenyl, R b1 Preferably, it is a hydrogen atom, and more preferably, R b1 is a hydrogen atom and satisfies the following conditions.

[0347] 1) One R in the repetition of y1 b2 is a hydrogen atom and the remaining R b2 is an alkyl group, and R in the repetition of y2 b2 is an alkyl group, R b3 Phenyl

[0348] 2) y1 is 0, R in the repetition of y2 b2 is an alkyl group, R b3 Phenyl

[0349] 3) y1 is 0, R in the repetition of y2 b2 -O-Si(R b5 )2(R b4 ), R b3 Phenyl

[0350] In addition, in the above 3), R b4 is a hydrogen atom and R b5 An alkyl group is particularly preferred.

[0351] y1 is preferably an integer of 0 to 2,000, more preferably an integer of 0 to 1,000, and even more preferably an integer of 0 to 30.

[0352] y2 is preferably an integer of 1 to 2,000, more preferably an integer of 1 to 1,000, and even more preferably an integer of 1 to 30.

[0353] 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.

[0354] In the present invention, the "-Si(R b2 )2-O-" and "-Si(R b2 )(R b3 )2-O-" may exist in the polysiloxane in the form of block polymerization or in the form of random existence.

[0355] As R b1 ~R b3 A combination of Rb1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R b2 is an alkyl group having 1 to 4 carbon atoms, R b3 is a combination of hydrogen atoms, more preferably R b1 is an alkyl group having 1 to 4 carbon atoms, R b2 is an alkyl group having 1 to 4 carbon atoms, R b3 A combination of hydrogen atoms.

[0356] In this preferred combination, the content of the hydrosilyl group represented by y2 / (y1+y2) is preferably more than 0.1 and less than 1.0, and more preferably more than 0.2 and less than 1.0. That is, a form in which y1 is 0 is included.

[0357] Examples of the polyorganosiloxane (B) having a linear structure include methyl hydrogen siloxane-dimethyl siloxane copolymer (trimethylsiloxane terminal), i.e., 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 copolymer, i.e., HPM-502 (MeHSiO: 45-50 mol%), and methyl hydrogen siloxane polymer, i.e., HMS-991 (MeHSiO: 100 mol%), all of which are manufactured by Gelest.

[0358] The mol% of MeHSiO has the same meaning as that of R b1 ~R b3 The meaning of y2 / (y1+y2) multiplied by 100 in the preferred combination is the same.

[0359] Furthermore, from the viewpoint of preventing a crosslinking reaction from proceeding in the molecule, it is preferred that both the linear structure and the branched structure have no vinyl group, and it is preferred that the branched structure have no vinyl group.

[0360] As the branched polyorganosiloxane (B) having two or more Si—H groups in the molecular chain, the branched polyorganosiloxane described in

[0051] to

[0058] of International Publication No. 2017 / 130890 can be directly applied.

[0361] The polyorganosiloxane (B) having two or more Si-H groups in the molecular chain used in the present invention may be used alone or in combination of two or more. Furthermore, a polyorganosiloxane (B) having a linear structure and a polyorganosiloxane (B) having a branched structure may be used in combination.

[0362] The vinyl group of the polyorganosiloxane (A) and the Si—H group of the polyorganosiloxane (B) usually react in a stoichiometric ratio of 1:1.

[0363] However, from the viewpoint of reacting all vinyl groups with Si—H groups, the equivalent of Si—H groups in the polyorganosiloxane (B) to vinyl groups in the polyorganosiloxane (A) is preferably vinyl groups:Si—H groups=1:1.1 to 1:8, more preferably 1:1.2 to 1:5.

[0364] (Surface treated oxide particles)

[0365] As described above, the silicone composition preferably includes surface-treated oxide particles.

[0366] The surface-treated oxide particles are particles in which the surfaces of inorganic oxide particles are subjected to surface treatment.

[0367] From the viewpoint of improving the acoustic impedance, hardness and mechanical strength of the acoustic lens layer, the average primary particle size of the surface-treated oxide particles is preferably greater than 3 nm and less than 500 nm, more preferably greater than 16 nm and less than 250 nm, further preferably 18 to 100 nm, particularly preferably 20 to 80 nm, and most preferably 25 to 70 nm.

[0368] By adding the surface-treated oxide particles to the silicone composition, the acoustic impedance, hardness, and mechanical strength of the obtained acoustic lens layer can be improved.

[0369] In particular, when surface-treated oxide particles having an average primary particle size of more than 16 nm and less than 250 nm are used, the acoustic wave attenuation can be reduced, and the viscosity before curing can be reduced.

[0370] Wherein, average primary particle diameter refers to volume average particle diameter. This volume average particle diameter can be calculated, for example, by measuring particle size distribution using a laser diffraction scattering particle size distribution measuring device (e.g., manufactured by HORIBA, Ltd., trade name "LA910"). In this specification, particles whose average primary particle diameter is not recorded in the catalog or particles manufactured anew are the average primary particle diameters obtained by the above-mentioned determination method.

[0371] Here, the average primary particle size of the surface-treated oxide particles refers to the average primary particle size in a state where the surface has been treated.

[0372] Furthermore, the inorganic oxide particles constituting the surface-treated oxide particles are preferably particles of inorganic oxides selected from silica, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, magnesium oxide and calcium oxide, more preferably particles of inorganic oxides selected from silica, titanium oxide and zinc oxide, and even more preferably silica particles.

[0373] The surface-treated oxide particles may be used alone or in combination of two or more.

[0374] From the viewpoint of improving the hardness and / or mechanical strength of the silicone resin obtained, the specific surface area of ​​the surface-treated oxide particles used in the present invention is preferably 1 to 400 m 2 / g, more preferably 5 to 200 m 2 / g, particularly preferably 10 to 100 m 2 / g.

[0375] Examples of the surface treatment method for the surface-treated oxide particles used in the present invention include surface treatment using an inorganic compound and / or an organic compound, and surface treatment using a silane compound is preferred.

[0376] For example, the inorganic surface treatment can be performed using aluminum hydroxide, aluminum oxide, zirconium oxide, silicon dioxide, and / or cerium oxide.

[0377] And, as the specific example of the organic surface treatment agent that can be used for surface treatment, can enumerate dimethylpolysiloxane, methyl hydrogen polysiloxane, (polydimethylsiloxane / polymethylsiloxane) copolymer, methylphenyl silicone, amino modified silicone, triethoxysilylethyl polydimethylsiloxyethyl polydimethylsiloxane, triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethylsiloxane and other silicone oils, alkyl silanes such as octylsilane, decylsilane, perfluorooctylsilane, alkyl titanate, alkyl aluminate, polyolefin, polyester, amino acid such as lauroyl lysine, polyamide and their salts, aluminum stearate, aluminum isostearate, metal soaps such as zinc stearate and nylon, polyester, hydrophobic resins such as polyacrylic acid, etc. And, can also use coupling agents such as silane coupling agent, titanium coupling agent.Can carry out surface treatment with at least one compound selected from these organic compounds.

[0378] Furthermore, inorganic surface treatment and organic surface treatment can be combined by additionally performing surface treatment. In particular, organic surface treatment is very effective in improving dispersibility in the composition.

[0379] Examples of the method of surface treatment with a silane compound include a method of surface treatment with a silane coupling agent and a method of coating with a silicone compound.

[0380] (i) Silane coupling agent

[0381] From the viewpoint of improving the hardness and / or mechanical strength of the acoustic lens layer, the silane coupling agent is preferably a silane coupling agent having a hydrolyzable group. The hydrolyzable group in the silane coupling agent is hydrolyzed by water to become a hydroxyl group, which undergoes a dehydration condensation reaction with the hydroxyl group on the surface of the silica particles, thereby modifying the surface of the silica particles, and improving the hardness and / or mechanical strength of the obtained silicone resin. Examples of the hydrolyzable group include alkoxy groups, acyloxy groups, and halogen atoms.

[0382] Furthermore, it is preferred that the surface of the surface-treated oxide particles is modified to be hydrophobic because the affinity of the surface-treated oxide particles with the polyorganosiloxanes (A) and (B) becomes good and the resistance to hydrogen peroxide plasma sterilization is improved.

[0383] Examples of the silane coupling agent having a hydrophobic group such as an alkyl group or an aryl group as a reactive functional group include alkoxysilanes such as methyltrimethoxysilane (MTMS), dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and decyltrimethoxysilane; chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and phenyltrichlorosilane; and hexamethyldisilazane (HMDS).

[0384] Furthermore, examples of the silane coupling agent having a vinyl group as a reactive functional group include alkoxysilanes such as methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinylmethyldimethoxysilane; chlorosilanes such as vinyltrichlorosilane and vinylmethyldichlorosilane; and divinyltetramethyldisilazane.

[0385] The surface-treated oxide particles surface-treated with a silane coupling agent are preferably surface-treated oxide particles treated with a trialkylsilylating agent, and more preferably surface-treated oxide particles treated with a trimethylsilylating agent.

[0386] Examples of the silane compound include the above-mentioned silane coupling agents and silane coupling agents in which a part of the alkoxy groups in the above-mentioned silane coupling agents are substituted with an alkyl group.

[0387] Examples of the trimethylsilylating agent include trimethylchlorosilane, hexamethyldisilazane (HMDS), methyltrimethoxysilane (MTMS) and the like described above as the silane coupling agent, and trimethylmethoxysilane, which is a silane coupling agent in which a part of the alkoxy groups in the above silane coupling agent is substituted with an alkyl group.

[0388] Examples of commercially available silane coupling agents include hexamethyldisilazane (HMDS) (for example, trade name: HEXAMETHYLDISILAZANE (SIH6110.1), available from Gelest Corporation).

[0389] The hydroxyl groups on the surface of the oxide particles react with hexamethyldisilazane (HMDS), methyltrimethoxysilane (MTMS), trimethylmethoxysilane, etc. to be covered with trimethylsilyl groups, thereby modifying the surface of the silica particles to be hydrophobic.

[0390] In the present invention, a silane coupling agent may be used alone or in combination of two or more.

[0391] (ii) Silicone compounds

[0392] The silicone compound covering the surface-treated oxide particles may be a polymer composed of siloxane bonds.

[0393] Examples of the silicone compound include silicone compounds in which all or part of the side chains and / or terminals of polysiloxane are methyl groups, silicone compounds in which part of the side chains are hydrogen atoms, modified silicone compounds in which organic groups such as amino groups and / or epoxy groups are introduced into all or part of the side chains and / or terminals, and silicone resins having a branched structure. In addition, the silicone compound may have a linear or cyclic structure.

[0394] Examples of silicone compounds in which all or part of the side chains and / or terminals of the polysiloxane are methyl groups include monomethyl polysiloxanes such as polymethyl hydrogen siloxane (hydrogen terminal), polymethyl hydrogen siloxane (trimethylsiloxy terminal), polymethyl phenyl siloxane (hydrogen terminal) and polymethyl phenyl siloxane (trimethylsiloxy terminal), and dimethyl polysiloxanes such as dimethyl polysiloxane (hydrogen terminal), dimethyl polysiloxane (trimethylsiloxy terminal) and cyclic dimethyl polysiloxane.

[0395] Examples of silicone compounds in which a part of the side chain is a hydrogen atom include methylhydrogensiloxane-dimethylsiloxane copolymer (trimethylsiloxy terminal), methylhydrogensiloxane-dimethylsiloxane copolymer (hydrogen terminal), polymethylhydrogensiloxane (hydrogen terminal), polymethylhydrogensiloxane (trimethylsiloxy terminal), polyethylhydrogensiloxane (triethylsiloxy terminal), polyphenyl-(dimethylhydrogensiloxy)siloxane (hydrogen terminal), methylhydrogensiloxane-phenylmethylsiloxane copolymer (hydrogen terminal), methylhydrogensiloxane-octylmethylsiloxane copolymer, and methylhydrogensiloxane-octylmethylsiloxane-dimethylsiloxane ternary polymer.

[0396] Furthermore, examples of modified silicones into which organic groups have been introduced include reactive silicones into which organic groups such as amino groups, epoxy groups, methoxy groups, (meth)acryloyl groups, phenoxy groups, carboxylic anhydride groups, hydroxyl groups, mercapto groups, carboxyl groups and / or hydrogen atoms have been introduced, and non-reactive silicones modified with, for example, polyether, aralkyl groups, fluoroalkyl groups, long-chain alkyl groups, long-chain aralkyl groups, higher fatty acid esters, higher fatty acid amides and / or polyether methoxy groups.

[0397] Silica particles coated with a silicone compound can be obtained by a conventional method, for example, by mixing and stirring silica particles in dimethylpolysiloxane for a certain period of time and filtering the mixture.

[0398] Furthermore, when reactive modified silicone is used as the silicone compound, the organic group reacts with the hydroxyl group on the surface of the oxide particles, thereby modifying the surface of the oxide particles and improving the hardness and / or mechanical strength of the obtained acoustic lens layer.

[0399] Examples of commercially available silicone compounds include polymethylhydrogensiloxane (trimethylsilyl group-terminated), namely, methylhydrogen silicone oil (MHS) (trade name: KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0400] The surface-treated oxide particles preferably have a methanol hydrophobization degree of 40 to 80% by mass, more preferably 50 to 80% by mass, and even more preferably 60 to 80% by mass, as calculated by the following methanol titration test. A larger methanol hydrophobization degree indicates a higher hydrophobicity, and a smaller methanol hydrophobization degree indicates a higher hydrophilicity.

[0401] 50 ml of ion exchange water and 0.2 g of surface-treated oxide particles as a sample were placed in a beaker and heated to 25°C. While stirring with a magnetic stirrer, methanol was added dropwise from a burette, and the amount of methanol added (X g) was measured until the entire sample sank. The methanol hydrophobization degree was calculated using the following formula.

[0402] Methanol hydrophobization degree (mass %) = 100% × X / (50 + X)

[0403] When the degree of methanol hydrophobization is within the above preferred range, the viscosity of the silicone composition before curing does not increase, and a decrease in acoustic wave sensitivity when used as an acoustic lens layer can be suppressed.

[0404] The Wadell sphericity of the primary particles of the surface-treated oxide particles is preferably 0.7-1, more preferably 0.8-1, and further preferably 0.9-1.

[0405] Among them, "Wardell's sphericity" (reference Chemical Engineering Handbook, published by Maruzen Co., Ltd.) is an index that measures the sphericity of a particle by (the diameter of a circle equal to the projected area of ​​the particle) / (the diameter of the smallest circle circumscribing the projected image of the particle), and the closer the index is to 1.0, the closer the particle is to a true sphere.

[0406] In the measurement of Wardle sphericity (hereinafter, also referred to as sphericity), for example, a SEM (Scanning Electron Microscope) photograph can be used. Specifically, for example, about 100 primary particles are observed using the SEM photograph, and their sphericity is calculated. The total of the calculated sphericity is divided by the number of observed primary particles to obtain an average value as the sphericity.

[0407] If the Wardle sphericity is within the preferred range, the hydrogen peroxide plasma sterilization resistance is further improved, which is preferred. In addition, when the acoustic lens layer is irradiated with acoustic waves, the area of ​​the acoustic waves irradiated to the surface-treated oxide particles is reduced, thereby improving the acoustic wave sensitivity.

[0408] In the present specification, “spherical” includes slightly deformed spheres having a Wardell sphericity within a range of 0.9 to 1, and the surface-treated spherical silica particles are spherical particles among the surface-treated silica particles.

[0409] The silica particles among the oxide particles are generally classified into combustion silica (i.e., fumed silica) obtained by burning a silane compound, deflagration silica obtained by exploding and burning metallic silicon powder, wet silica obtained by a neutralization reaction of sodium silicate and an inorganic acid (wherein, silica synthesized under alkaline conditions is called precipitated silica, and silica synthesized under acidic conditions is called gel silica), and sol-gel silica obtained by hydrolysis of hydrocarbyloxy silane (so-called Stoeber process), according to their production methods.

[0410] As a method for producing spherical silica particles, preferably, an explosion method and a sol-gel method are mentioned.

[0411] The sol-gel method is a method of obtaining hydrophilic spherical silica particles essentially composed of SiO2 units by hydrolyzing and condensing hydrocarbyloxysilane (preferably tetrahydrocarbyloxysilane) or a partial hydrolysis-condensation product thereof, or a combination thereof.

[0412] Furthermore, the hydrophobic treatment of the silica particle surface can be achieved by introducing R 3 3SiO 1 / 2 Unit (R 3 are the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0413] Specifically, for example, it can be performed by the method described in Japanese Patent Application Laid-Open No. 2007-99582 and Japanese Patent Application Laid-Open No. 2014-114175. The surface treatment of other oxide particles is also not particularly limited and can be performed by a common method.

[0414] (Other ingredients)

[0415] The silicone composition may be appropriately mixed with at least one of a curing retarder, a solvent, a dispersant, a pigment, a dye, an antistatic agent, an antioxidant, a flame retardant, and a thermal conductivity improver, in addition to the polyorganosiloxane (A) having a vinyl group, the polyorganosiloxane (B) having two or more Si-H groups in the molecular chain, and the surface-treated oxide particles.

[0416] -Curing Retardant-

[0417] In the present invention, a curing retarder can be used appropriately in the curing reaction. The curing retarder is used to delay the addition curing reaction, and examples thereof include low molecular weight vinylmethylsiloxane homopolymer (trade name: VMS-005, manufactured by Gelest).

[0418] The curing speed, that is, the working time, can be adjusted according to the content of the curing retarder.

[0419] -catalyst-

[0420] In the present invention, a catalyst is used to obtain a layer formed by curing the silicone composition. As the catalyst, for example, platinum or a compound containing platinum (hereinafter, also referred to as a platinum compound) can be cited. As the platinum or the platinum compound, platinum or a platinum compound used in room temperature curing (RTV) can be used without particular limitation, for example, platinum-vinyl disiloxane can be used.

[0421] Specifically, platinum black or platinum supported on an inorganic compound 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.

[0422] A catalyst is required in the hydrosilylation reaction of adding Si-H groups of polyorganosiloxane (B) to vinyl groups of polyorganosiloxane (A). By carrying out the hydrosilylation reaction (addition curing reaction), polyorganosiloxane (A) and polyorganosiloxane (B) are crosslinked to form a silicone resin.

[0423] The catalyst may be mixed in the silicone composition to act, or may be in contact with the silicone composition without being contained in the silicone composition. The latter is preferred.

[0424] 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).

[0425] The content of the catalyst acting on the silicone composition is not particularly limited, but from the viewpoint of reactivity, it 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 silicone composition.

[0426] [Viscosity of silicone composition before curing]

[0427] From the viewpoint of uniformly dispersing the components contained in the silicone composition, the viscosity of the silicone composition before the curing reaction is preferably low. The viscosity before curing refers to the viscosity of the silicone composition before adding a catalyst to start the curing reaction. Specifically, it can be measured by the method described in International Publication No. 2017 / 130890.

[0428] The viscosity (23° C.) is preferably 5000 Pa·s or less, more preferably 1000 Pa·s or less, and even more preferably 200 Pa·s or less. The practical lower limit is 10 Pa·s or more.

[0429] In the acoustic wave probe of the present invention, another layer may be provided between the substrate and the intermediate layer.

[0430] As other layers, any layer used in the acoustic wave probe can be used without particular limitation as long as it has a reactive group that has excellent adhesion to the substrate and reacts (preferably forms a chemical bond) with the -OH group of the hydrolyzed silicate compound in the intermediate layer. For example, a polyimide layer can be cited, which is known as a layer provided between the acoustic matching layer and the acoustic lens in the acoustic wave probe to impart resistance to agents such as sterilization and disinfection, and can be preferably used.

[0431] Furthermore, the reactive group possessed by the hydrolyzed silicate compound in the intermediate layer possessed by the other layers, which reacts with the -OH group (preferably forms a chemical bond), can also be introduced by chemically and / or physically treating the surface of the layer after forming a layer having excellent adhesion to the substrate.

[0432] <Method for manufacturing sonic wave probe>

[0433] The acoustic wave probe of the present invention can be prepared by conventional methods.

[0434] For example, the substrate, the solution for forming the intermediate layer, and the room temperature curing silicone for forming the acoustic lens layer are prepared respectively by conventional methods.

[0435] When the surface of the substrate on the side where the intermediate layer is provided is subjected to a hydrophilic treatment, the hydrophilic treatment is applied to the side where the intermediate layer is provided by a conventional method.

[0436] Regarding the solution for forming the intermediate layer, a solution containing a hydrolyzed silicate compound is prepared by hydrolyzing a silicate compound having a hydrolyzable group, or a solution formed by adding and mixing a commercially available hydrolyzed silicate compound is prepared. In the case of preparing a solution containing a hydrolyzed silicate compound by hydrolyzing a silicate compound having a hydrolyzable group, it is preferably neutralized. Other components such as a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound that may be contained in the solution for forming the intermediate layer may be added and mixed while preparing these solutions, or may be added and mixed separately. In addition, in the case of preparing by hydrolyzing a silicate compound having a hydrolyzable group, it is preferably mixed while adding other components after neutralization.

[0437] The room temperature curing silicone used to form the acoustic lens layer can be obtained by kneading the components constituting the room temperature curing silicone using a kneading machine, a pressure kneading machine, a Banbury mixer (continuous kneading machine), or a twin-roll kneading device. The mixing order of the components is not particularly limited. The kneading conditions are not particularly limited, for example, preferably kneading at 10 to 50° C. for 1 to 72 hours. After the kneading, it is preferably brought into contact with a catalyst before use.

[0438] The acoustic wave probe of the present invention can form an intermediate layer by coating a solution for forming an intermediate layer on a substrate and drying the solution, and further, by laminating a room temperature curing silicone for forming an acoustic lens layer on the intermediate layer and curing the solution, thereby manufacturing an acoustic wave probe in which the substrate and the acoustic lens layer are bonded. In addition, the intermediate layer may react separately from the acoustic lens layer, but preferably, the intermediate layer reacts simultaneously and completely in the process of curing the room temperature curing silicone to form the acoustic lens layer.

[0439] In addition, when the above-mentioned other layer is provided between the base material and the intermediate layer, the other layer may be formed before the step of forming the intermediate layer on the base material.

[0440] By curing the room temperature curing silicone thus obtained, a silicone resin constituting the acoustic lens layer can be obtained. Specifically, for example, by heat curing at 20 to 50° C. for 5 to 500 minutes, a silicone resin can be obtained. The shape of the silicone resin is not particularly limited. For example, a shape preferred for an acoustic lens can be formed using the mold during the curing, or a desired acoustic lens can be formed by obtaining a sheet of silicone resin and cutting the resin.

[0441] The acoustic wave probe of the present invention can be preferably used in 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.

[0442] In particular, the acoustic wave probe of the present invention can be suitably used as an ultrasonic probe including capacitive micromachined ultrasonic transducers (cMUT: Capacitive Micromachined Ultrasonic Transducers) as an ultrasonic transducer array, and is also preferably used in an ultrasonic diagnostic apparatus including the ultrasonic probe.

[0443] Specifically, the acoustic wave probe 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.

[0444] according to Figure 1 The structure of the ultrasonic probe in the ultrasonic diagnostic device described in the specification and the structure of the acoustic wave probe of the present invention is described in more detail below. In addition, the ultrasonic probe refers to a probe that uses ultrasonic waves as acoustic waves in particular among acoustic wave probes. Therefore, the basic structure of the ultrasonic probe can be directly applied to the acoustic wave probe.

[0445] -Ultrasonic probe-

[0446] The ultrasonic probe 10 is a main component of the ultrasonic diagnostic device, and has the function of generating ultrasonic waves and receiving ultrasonic beams at the same time. 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, for the purpose of receiving high-order harmonics, a technology has been proposed in which a transmitting ultrasonic transducer (piezoelectric element) and a receiving ultrasonic transducer (piezoelectric element) are made of different materials and formed into a stacked structure.

[0447] <Piezoelectric element layer>

[0448] The piezoelectric element layer 3 is a portion that generates ultrasonic waves. Electrodes are attached to both sides of the piezoelectric element. When voltage is applied, the piezoelectric element repeats expansion and contraction and vibrates, thereby generating ultrasonic waves.

[0449] As materials for piezoelectric elements, inorganic piezoelectric materials called ceramics are widely used, which are made by polarizing single crystals such as crystal, 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.

[0450] Furthermore, the piezoelectric element for detecting the received wave on the high frequency side needs to have sensitivity in a wider bandwidth. Therefore, as a piezoelectric element suitable for high frequency and wide bandwidth, an organic piezoelectric body using an organic polymer substance such as polyvinylidene fluoride (PVDF) is used.

[0451] Japanese Patent Application Laid-Open No. 2011-071842 and the like describe a cMUT using MEMS (Micro Electro Mechanical Systems) technology, which can obtain an array structure that exhibits excellent short pulse characteristics and broadband characteristics, is highly producible, and has little variation in characteristics.

[0452] In the present invention, any piezoelectric element material can be preferably used.

[0453] <Backing material>

[0454] The backing material 4 is provided on the back surface of the piezoelectric element layer 3 and reduces the pulse width of ultrasonic waves by suppressing unnecessary vibrations, thereby contributing to improving the distance resolution in ultrasonic diagnostic images.

[0455] <Acoustic matching layer>

[0456] 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 efficiently transmit and receive ultrasonic waves.

[0457] <Acoustic lens>

[0458] The acoustic lens 1 is provided to focus ultrasound in the slice direction by refraction to improve resolution, and needs to be in close contact with the living body to be examined, and to match the ultrasound with the acoustic impedance of the living body (1.4 to 1.7 Mrayl for the human body).

[0459] That is, by using a material whose sound velocity is sufficiently lower than that of the human body and whose acoustic impedance is close to the value of human skin as the material of the acoustic lens 1 , the ultrasonic transmission and reception sensitivity becomes good.

[0460] <Middle layer>

[0461] As one embodiment of the acoustic wave probe of the present invention, the base material in the acoustic wave probe of the present invention corresponds to the acoustic matching layer 2, the acoustic lens layer in the acoustic wave probe of the present invention corresponds to the acoustic lens 1, and the intermediate layer (in Figure 1 ) The acoustic matching layer 2 and the acoustic lens 1 are bonded together.

[0462] In addition, the base material in the acoustic wave probe of the present invention is preferably a component other than the acoustic matching layer 2 around the acoustic lens 1. In this case, the acoustic matching layer 2 and the components other than the acoustic matching layer 2 around the acoustic lens 1 have a structure in which they are bonded to the acoustic lens 1 via an intermediate layer containing the above-mentioned specific siloxane compound.

[0463] The operation of the ultrasonic probe 10 of such a structure is described. Voltage is applied to the electrodes provided on both sides of the piezoelectric element layer 3 to resonate the piezoelectric element layer 3, and an ultrasonic signal is transmitted to the object under examination from the acoustic lens 1. When receiving, the reflected signal (echo signal) from the object under examination causes the piezoelectric element layer 3 to vibrate, and the vibration is electrically converted into a signal, thereby obtaining an image.

[0464] In particular, the acoustic lens layer in the acoustic wave probe of the present invention can be used as a general medical ultrasonic transducer to confirm a significant sensitivity improvement effect at an ultrasonic transmission frequency of approximately 10 MHz or more, and can be expected to have a particularly significant sensitivity improvement effect at an ultrasonic transmission frequency of 15 MHz or more.

[0465] The acoustic lens layer in the acoustic wave probe of the present invention can reduce the speed of sound to less than 900 m / s, for example, 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 less than 50 MHz.

[0466] Hereinafter, a device in which the acoustic lens layer in the acoustic wave probe of the present invention performs a special function to solve the conventional problems will be described in detail.

[0467] In addition, the acoustic wave probe of the present invention also exhibits excellent effects on devices other than the devices described below.

[0468] -Ultrasonic probe with cMUT (capacitive micromachined ultrasonic transducer)-

[0469] 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 thereof is generally lower than that of a transducer using a general piezoelectric ceramic (PZT).

[0470] However, as described in International Publication No. 2017 / 130890, as an acoustic lens layer for the acoustic wave probe of the present invention, the lack of sensitivity of the cMUT can be compensated by using an acoustic lens obtained from a specific acoustic wave probe composition. Thus, the sensitivity of the cMUT can be made close to the performance of conventional transducers.

[0471] In addition, since the cMUT device is manufactured using MEMS technology, it is possible to provide the market with an ultrasonic probe that is highly mass-producible and low-cost compared to a piezoelectric ceramic probe.

[0472] -Photoacoustic wave measurement device using photoacoustic wave imaging-

[0473] Photoacoustic imaging (PAI) described in Japanese Patent Application Laid-Open No. 2013-158435 and the like displays an image obtained by imaging 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.

[0474] -Ultrasound endoscope-

[0475] Regarding the ultrasonic wave in the ultrasonic endoscope described in Japanese Patent Application Laid-Open No. 2008-311700, etc., in terms of its structure, the signal line cable is longer than that of the transducer for body surface, so there is a problem that the sensitivity of the transducer is improved with the loss of the cable. In addition, for this problem, it can be said that there is no solution to effectively improve the sensitivity for the following reasons.

[0476] First, as long as it is an ultrasonic diagnostic device for body surface, an amplifier circuit, an AD conversion IC (analog-digital conversion integrated circuit), etc. can be set at the front end of the transducer. In contrast, since the ultrasonic endoscope is inserted into the body for use, the installation space of the transducer is narrow, and it is difficult to set an amplifier circuit, an AD conversion IC, etc. at the front end of the transducer.

[0477] Secondly, 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 10-15MHz or more in terms of its physical properties and process adaptability. However, the ultrasonic probe in the ultrasonic endoscope is usually a probe with the ultrasonic transmission frequency of 10-15MHz or more, so it is difficult to improve the sensitivity by using piezoelectric single crystal materials.

[0478] However, as described in International Publication No. 2017 / 130890, as an acoustic lens layer used for the acoustic wave probe of the present invention, the sensitivity of the endoscopic ultrasonic transducer can be improved by using an acoustic lens obtained from a specific acoustic wave probe composition.

[0479] Furthermore, even when the same ultrasonic transmission frequency (e.g., 15 MHz) is used, the acoustic lens layer of the acoustic wave probe of the present invention used in an endoscopic ultrasonic transducer is particularly effective when an acoustic lens obtained from a specific acoustic wave probe composition is used, as described in International Publication No. 2017 / 130890.

[0480] Example

[0481] Hereinafter, the present invention will be described in further detail based on Examples. The present invention should not be construed as being limited to the Examples shown below except as specified in the present invention.

[0482] <1. Base material (B)>

[0483] Test pieces of 80 mm in length × 20 mm in width × 1 mm in thickness were cut out from various substrates (B-1) to (B-14) described in the table below. One side of the test pieces of these substrates was treated with "UVO-Cleaner Model 42" (trade name, manufactured by Jelight Company, Inc., center wavelength 254 nm) for 2 minutes, thereby preparing substrates (B-1) to (B-14) pretreated with UV1, respectively.

[0484] One side of the test piece of the substrate (B-4) was treated with a Xe excimer UV irradiation device "ASM86 Excimer" (trade name, manufactured by Asumi Giken Co., Ltd., center wavelength 172 nm) to prepare a substrate (B-4) subjected to UV2 pretreatment.

[0485] One surface of the test piece of the substrate (B-4) was treated with a plasma processing apparatus "PM100" (trade name, manufactured by Yamato Scientific Co., Ltd.) to prepare a plasma pretreated substrate (B-4).

[0486] One surface of the test piece of the substrate (B-4) was treated with a corona discharge surface modification device "Corona Master PS-1M" (trade name, manufactured by Shinko Electric & Instrumentation Co., Ltd.) to prepare a corona pretreated substrate (B-4).

[0487] <2. Preparation of solution for intermediate layer>

[0488] (1) Preparation of intermediate layer solution (m-1)

[0489] 2.4 g of hydrolyzed silicate "HAS-1" (trade name, manufactured by Colcoat Co., Ltd., silica content 21%) and 7.6 g of methanol were mixed to obtain an intermediate layer solution (m-1).

[0490] (2) Formation of intermediate layer solution (m-2)

[0491] 2.4 g of hydrolyzed silicate "HAS-1" (trade name, manufactured by Colcoat Co., Ltd., silica content 21%), 0.3 g of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) and 7.3 g of methanol were mixed to obtain a solution for the intermediate layer (m-2).

[0492] (3) Formation of Intermediate Layer Solutions (m-3) to (m-25)

[0493] In the same manner as in the above (m-1) and (m-2), the components described in Table A were mixed to obtain intermediate layer solutions (m-3) to (m-25).

[0494] In addition, the intermediate layer solutions (m-18) to (m-20) are prepared as follows: the components listed in Table A are mixed and stirred until the hydrolysis of the hydrolyzable groups of the silicate compound is carried out and the aforementioned hydrolysis rate becomes 80% or more. After the hydrolysis reaction, the solutions are neutralized with 0.02N ammonia water to adjust the pH to 5 to 7.

[0495]

[0496] (Table Notes)

[0497] [Compound for preparing solution for intermediate layer]

[0498] In the following description, the silicon dioxide content refers to the ratio based on the mass standard of the hydrolyzed silicate compound or the silicate compound having a hydrolyzable group in the product.

[0499] In addition, the content of each component described in the table is based on mass.

[0500] (Hydrolyzed silicate compounds)

[0501] HAS-1: Trade name, manufactured by Colcoat Co., Ltd., silica content 21%, weight average molecular weight 650

[0502] (Silicate compound having a hydrolyzable group)

[0503] Methyl silicate 51: Trade name, manufactured by Colcoat Co., Ltd., Si4O3(OCH3) 10 (Average tetramer), silica content 51%, weight average molecular weight 470

[0504] MKC Silicate MS56: Trade name, manufactured by Mitsubishi Chemical Corporation, Si m O m-1 (OCH3) 2m+2 (m=2-100), silica content 56%, weight average molecular weight 1,150

[0505] TEOS: Tetraethoxysilane

[0506] (Silane coupling agent)

[0507] (SI-1): N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0508] (SI-2): 3-aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0509] (SI-3): 3-Trimethoxysilylpropylsuccinic anhydride (trade name: X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0510] (SI-4): 3-glycidyloxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0511] (Titanium alkoxide compound)

[0512] (TI-1): Isopropyl tris(N-aminoethyl-aminoethyl) titanate (trade name "PLENACT44", manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0513] (TI-2): Diisopropyl bis(dioctyl pyrophosphate) titanate (trade name: PLENACT 38S, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0514] (TI-3): Isopropyl tridodecylbenzenesulfonyl titanate (trade name: PLENACT9SA, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0515] (TI-4): Tetra-n-butyl titanate (trade name: ORGATIX TA-21, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0516] (Aluminum alkoxide compound)

[0517] (AL-1): Aluminum triacetylacetonate (trade name: ORGATIX AL-3100, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0518] (AL-2): Ethyl bisacetoacetate aluminum monoacetylacetonate (trade name: ORGATIX AL-3200, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0519] (AL-3): Aluminum triacetoacetate (trade name: ORGATIX AL-3215, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0520] (AL-4): Aluminum sec-butoxide (trade name: ASBD, manufactured by Kawaken Fine Chemicals Co., Ltd.)

[0521] (Zirconium alkoxide compound)

[0522] (ZR-1): Zirconium tetraacetylacetonate (trade name: ORGATIX ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0523] (ZR-2): ammonium zirconium lactate (trade name: ORGATIX ZC-300, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0524] (ZR-3): tri-n-butoxy zirconium monoacetylacetonate (trade name: ORGATIX ZC-540, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0525] (ZR-4): Zirconium tetra-n-butoxide (trade name: ORGATIX ZA-65, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0526] <3. Preparation of resin for acoustic lens>

[0527] (1) Preparation of Resin for Acoustic Lens (L-1)

[0528] 54.0 parts by mass of a vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer ("PDV-0535" manufactured by Gelest, mass average molecular weight 47,500, diphenylsiloxane amount 5 mol%), 1.0 parts by mass of polymethylhydrogensiloxane ("HMS-991" manufactured by Gelest, mass average molecular weight 1,600), and 45.0 parts by mass of spherical surface-treated silica ("QSG-30" manufactured by Shin-Etsu Chemical Co., Ltd., average primary particle size 30 nm, surface treated with methyltrimethoxysilane and hexamethyldisilazane (HMDS), methanol hydrophobization degree 67 mass%) were kneaded in a kneader at a set temperature of 23°C for 2 hours to prepare a uniform paste.

[0529] 0.05 parts by mass of a platinum catalyst solution (manufactured by Gelest, trade name “SIP6830.3”, Pt concentration 3 mass%) was added thereto, mixed, and then degassed under reduced pressure to prepare an uncured acoustic lens resin (L-1).

[0530] (2) Preparation of Resin for Acoustic Lens (L-2)

[0531] In the preparation of the resin for acoustic lens (L-1), the uncured resin for acoustic lens (L-2) was prepared in the same manner except that the vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer was set to 54.0 parts by mass of "PDV-0341" (manufactured by Gelest, with a mass average molecular weight of 62,000 and a diphenylsiloxane amount of 3 mol%).

[0532] (3) Preparation of Resin for Acoustic Lens (L-3)

[0533] In the preparation of the resin for acoustic lens (L-1), the uncured resin for acoustic lens (L-3) was prepared in the same manner except that the silica was replaced with 45.0 parts by mass of surface-treated titanium oxide "TITONE R-24" (trade name, manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size 0.20 μm, surface treatment agent: silica-alumina-organic).

[0534] (4) Preparation of Resin for Acoustic Lens (L-4)

[0535] In the preparation of the resin (L-1) for acoustic lens, the uncured resin (L-4) for acoustic lens was prepared in the same manner except that the silica was set to 45.0 parts by mass of non-spherical surface-treated fumed silica ("AEROSIL (registered trademark) NAX50" manufactured by NIPPON AEROSIL CO., LTD., average primary particle size 30 nm, hexamethyldisilazane (HMDS) surface-treated product, methanol hydrophobization degree 28% by mass).

[0536] (5) Preparation of Resin for Acoustic Lens (L-5)

[0537] In the preparation of the resin for acoustic lens (L-1), the uncured resin for acoustic lens (L-5) was prepared in the same manner except that the vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer was set to 54.0 parts by mass of the vinyl-terminated dimethylsiloxane copolymer "DMS-V41" (manufactured by Gelest, mass average molecular weight 62,700, diphenylsiloxane amount 0 mol%).

[0538] <4. Preparation of laminated body>

[0539] The intermediate layer solution (m-1) was applied to the entire surface of the UV1 pre-treated substrate (B-1) using a cotton swab and dried at 50° C. for 15 minutes to form an intermediate layer (M-1).

[0540] The substrate provided with the intermediate layer was set in a mold, and the pre-degassed and mixed acoustic lens resin (L-1) was poured onto the treated surface so that the thickness of the lens resin became 1 mm (the total thickness of the laminate was about 2 mm), and then cured at 100° C. for 10 minutes, thereby obtaining laminate No. 101 in which the acoustic lens layer (L) was imparted to the substrate (B) via the intermediate layer (M).

[0541] In the preparation of the above-mentioned laminate No. 101, laminates Nos. 102 to 140 and c01 to c07 were prepared in the same manner except that the substrate (B), the intermediate layer (M) and the acoustic lens layer (L) were changed to the structures described in the following Tables 1-1 and 1-2.

[0542] Laminated bodies Nos. 101 to 140 are the acoustic wave probes of the present invention, and laminated bodies Nos. c01 to c07 are acoustic wave probes for comparison.

[0543] The average thickness of the middle layer (M) is calculated as follows.

[0544] Five random cuts were made on the laminate produced above, and the cross section of each intermediate layer (M) was observed at 50,000 times using a scanning electron microscope (S-5500 (trade name), manufactured by Hitachi High-Technologies Corporation), and the thickness of the intermediate layer (M) was obtained point by point for each cross section. The average value calculated from the values ​​of the five obtained thicknesses was taken as the average layer thickness. In the table described below, it is recorded in the column of film thickness.

[0545] <5. Evaluation of laminated body>

[0546] The laminates prepared above were evaluated for peel strength, thermal cycle durability, and hydrogen peroxide plasma sterilization resistance as follows. The obtained results are summarized in the following Tables 1-1 and 1-2. In addition, hydrogen peroxide plasma sterilization resistance is indicated as H2O2 gas sterilization durability in the table.

[0547] [Test Example 1] Evaluation of peel strength

[0548] A test piece of 80 mm in length and 10 mm in width (about 2 mm in thickness) was cut out from the laminate produced above to obtain a laminate test piece. A 1 cm wide incision was cut into the middle layer of the 10 mm wide edge of the laminate test piece. For the laminate test piece with the incision, the 90° peel strength between the substrate (B) and the acoustic lens layer (L) was measured as follows: at 25°C, the end of the acoustic lens layer side of the 1 cm wide incision made was grasped, while the angle between the substrate and the acoustic lens layer was kept at 90°, and 20 mm was peeled off along the length direction at a peeling speed of 2 mm / min. The peel strength is a value obtained by measuring with a dynamometer, and the unit is N / cm. The average value of the entire area of ​​the measured peel strength was evaluated using the following criteria.

[0549] <Peel Strength Evaluation Criteria>

[0550] AA: The peel strength is 12 N / cm or more, or cohesive failure of the resin constituting the acoustic lens layer occurs.

[0551] A: 10N / cm or more and less than 12N / cm

[0552] B: 6N / cm or more and less than 10N / cm

[0553] C: 2N / cm or more and less than 6N / cm

[0554] D: less than 2N / cm

[0555] If the peel strength is less than 12 N / cm, cohesive failure of the resin constituting the acoustic lens layer does not occur.

[0556] [Test Example 2] Evaluation of thermal cycle durability

[0557] The laminate test piece prepared in the above-mentioned Test Example 1 was subjected to a heat cycle test 500 times using a constant temperature and humidity machine (manufactured by Satake Chemical Equipment MFG., Ltd., KHWV-40HP (trade name)), wherein 2 hours at -20°C and 2 hours at 60°C were regarded as one cycle. For the laminate test piece after 500 cycles of the heat cycle test, the 90° peel strength was measured by the method described in the above-mentioned Test Example 1.

[0558] The 90° peel strength before the heat cycle treatment measured in the above-mentioned Test Example 1 is set as "PSB(1)", and the 90° peel strength after the above-mentioned heat cycle treatment is set as "PSA(1)". The ratio of "PSA(1)" to "PSB(1)" {(PSA(1) / PSB(1))×100(%)} is calculated and evaluated using the following standards.

[0559] <Evaluation criteria for thermal cycle resistance>

[0560] AA: above 80%

[0561] A: 60% or more and less than 80%

[0562] B: 40% or more and less than 60%

[0563] C: 20% or more and less than 40%

[0564] D: less than 20%

[0565] [Test Example 3] Evaluation of hydrogen peroxide plasma sterilization resistance

[0566] The laminate test piece prepared in the above-mentioned Test Example 1 was subjected to 50 times of low-temperature plasma sterilization treatment in an advanced course of a hydrogen peroxide gas sterilizer ("STERRAD (registered trademark) NX" manufactured by Advanced Sterilization Products). The 90° peel strength of the laminate test piece after the 50-time hydrogen peroxide plasma sterilization test was measured by the method described in the above-mentioned Test Example 1. In addition, the laminate test piece was placed on a stainless steel plate for decomposition of hydrogen peroxide gas and a stronger hydrogen peroxide gas generated by plasma irradiation thereto and through which active substances hardly penetrate, so that the acoustic lens layer (L) was on the upper side and the substrate (B) was on the lower side, and the above-mentioned hydrogen peroxide plasma sterilization treatment was performed.

[0567] The 90° peel strength before the hydrogen peroxide plasma sterilization treatment measured in the above-mentioned Test Example 1 is set as "PSB(2)", and the 90° peel strength after the above-mentioned hydrogen peroxide plasma sterilization test is set as "PSA(2)". The ratio of "PSA(2)" to "PSB(2)" {(PSA(2) / PSB(2))×100(%)} was calculated and evaluated using the following standards.

[0568] <Evaluation criteria for hydrogen peroxide plasma sterilization resistance>

[0569] AA: above 80%

[0570] A: 60% or more and less than 80%

[0571] B: 40% or more and less than 60%

[0572] C: 20% or more and less than 40%

[0573] D: less than 20%

[0574]

[0575]

[0576]

[0577] [Base material (B)]

[0578] (Material)

[0579] (B-1): Acrylic resin (trade name: ACRYLITE L, manufactured by Mitsubishi Chemical Corporation)

[0580] (B-2): PC (polycarbonate) resin (trade name: Panlite L-1225Y, manufactured by TEIJIN LIMITED.)

[0581] (B-3): GPPS (general purpose polystyrene) resin (trade name: PSJ-polystyrene HF77, manufactured by PS Japan Corporation)

[0582] (B-4): Cross-linked PS (cross-linked polystyrene) resin (trade name: Rexolite, manufactured by Ensinger)

[0583] (B-5): A resin obtained by curing an epoxy resin (trade name: two-component epoxy resin adhesive 6100, manufactured by ARTECOCO., LTD.) at 25° C. for 24 hours.

[0584] (B-6): A resin obtained by curing a phenol resin (trade name: SUMIKON PM-760, manufactured by Sumitomo Bakelite Co., Ltd.) by heating at 180° C. for 30 minutes.

[0585] (B-7): A resin obtained by heat-curing an unsaturated polyester (PEs) resin (trade name: U-Pica 4072, manufactured by Japan U-Pica Company Ltd.) at 100°C for 24 hours.

[0586] (B-8): PI (polyimide) resin (thermosetting polyimide resin, trade name: Kapton, manufactured by DuPont-Toray Co., Ltd.)

[0587] (B-9): A resin obtained by heat-curing a melamine resin (trade name: MEWLUS MBF-C, manufactured by Panasonic Corporation) at 150° C. for 10 minutes.

[0588] (B-10): Glass

[0589] (B-11): Ceramics

[0590] (B-12): Graphite

[0591] (B-13): Al (aluminum)

[0592] (B-14): Cu (copper)

[0593] (Preprocessing)

[0594] UV1, UV2, plasma, corona: refer to the aforementioned UV1 pretreatment, UV2 pretreatment, plasma pretreatment, and corona pretreatment, respectively.

[0595] “-” means no preprocessing is performed.

[0596] [Middle layer (M)]

[0597] Intermediate layers (M-1) to (M-25): These were prepared using the above-mentioned intermediate layer solutions (m-1) to (m-25), respectively.

[0598] [Acoustic lens layer (L)]

[0599] Acoustic lens layers (L-1) to (L-5): These layers are produced using the above-mentioned acoustic lens resins (L-1) to (L-5), respectively.

[0600] The following can be seen from Tables 1-1 and 1-2.

[0601] Comparative laminate No. c01 does not meet the requirements of the present invention in that the substrate and the acoustic lens layer specified in the present invention are directly bonded without an intermediate layer. Comparative laminate No. c01 has low initial peel strength and poor initial adhesion, and poor hydrogen peroxide plasma sterilization resistance.

[0602] Although an intermediate layer is interposed between the substrate and the acoustic lens layer specified in the present invention, the comparative laminates No. c02 to c06 do not meet the requirements of the present invention in that the intermediate layer does not contain a siloxane compound derived from a hydrolyzed silicate compound. These comparative laminates No. c02 to c06 all have poor hydrogen peroxide plasma sterilization resistance.

[0603] Although the intermediate layer specified in the present invention is interposed between the substrate and the acoustic lens layer, the comparative laminate No. c07 does not meet the requirements of the present invention in that the acoustic lens layer is a layer formed by curing a room temperature curing silicone that does not contain a structural unit having a phenyl group. The comparative laminate No. c07 has poor hydrogen peroxide plasma sterilization resistance.

[0604] In contrast, it can be seen that the initial peel strength of laminated bodies No. 101 to 140, which are formed by laminating the substrate, the intermediate layer and the acoustic lens layer in this order as specified in the present invention, is high, and the peel strength after hydrogen peroxide plasma sterilization is maintained at more than 20% of the initial value, and the initial adhesion and hydrogen peroxide plasma sterilization resistance are excellent.

[0605] The present invention has been described together with its embodiments, but unless otherwise specified, it is considered that the present invention should not be limited to any details in the description and should be broadly interpreted without departing from the spirit and scope of the invention shown in the attached technical solutions.

[0606] This application claims priority based on Japanese Patent Application No. 2022-104704 filed in Japan on June 29, 2022, the contents of which are incorporated herein by reference as a part of the description of this specification.

[0607] Explanation of symbols

[0608] 1-acoustic lens, 2-acoustic matching layer, 3-piezoelectric element layer, 4-backing material, 7-shell, 9-cord, 10-ultrasonic probe (ultrasonic probe).

Claims

1. An acoustic wave probe comprising a substrate, an intermediate layer on the substrate, and an acoustic lens layer on the intermediate layer, The intermediate layer is a layer containing a siloxane compound, and the siloxane compound has a constituent component derived from a hydrolyzed silicate compound, The acoustic lens layer is a layer formed by curing room temperature curing silicone, and the room temperature curing silicone includes a structural unit having a phenyl group.

2. The acoustic wave probe according to claim 1, wherein: The substrate includes at least one of iron, non-ferrous metal, inorganic material other than metal, and organic material.

3. The acoustic wave probe according to claim 2, wherein: The non-ferrous metal includes at least one of aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten or cobalt, or an alloy of at least two of these metals.

4. The acoustic wave probe according to claim 2 or 3, wherein: The inorganic material other than metal includes at least one of glass, ceramics, and graphite.

5. The acoustic wave probe according to any one of claims 2 to 4, wherein: The organic material includes at least one of a thermoplastic resin and a thermosetting resin.

6. The acoustic wave probe according to claim 5, wherein: The thermoplastic resin includes at least one of an acrylic resin, a polycarbonate resin, a styrene resin, and a polyphenylene sulfide resin.

7. The acoustic wave probe according to claim 5 or 6, wherein: The thermoplastic resin is a cross-linked thermoplastic resin.

8. The acoustic wave probe according to any one of claims 1 to 7, wherein: The substrate is a substrate having a surface on the intermediate layer side subjected to a hydrophilic treatment.

9. The acoustic wave probe according to claim 8, wherein: The substrate is a substrate having a surface on the intermediate layer side subjected to at least one of ultraviolet treatment, ozone treatment, plasma treatment, and corona treatment.

10. The acoustic wave probe according to any one of claims 1 to 9, wherein: The intermediate layer includes a constituent component derived from at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound.

11. The acoustic wave probe according to any one of claims 1 to 10, wherein: The room temperature curing silicone is a silicone composition comprising vinyl silicone and hydrogen silicone.

12. The acoustic wave probe according to claim 11, wherein: The silicone composition comprises surface-treated oxide particles.

13. The acoustic wave probe according to claim 12, wherein: The silicone composition comprises surface-treated spherical silica particles.

14. The acoustic wave probe according to any one of claims 1 to 13, wherein: The acoustic wave probe is an ultrasonic wave probe. 15 . An acoustic wave measuring device comprising the acoustic wave probe according to claim 1 . 16 . An ultrasonic diagnostic apparatus comprising the acoustic wave probe according to claim 14 .

Images