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JP2016108396

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DESCRIPTION JP2016108396
Abstract: A composition for an acoustic wave probe capable of obtaining a silicone resin having
high resin hardness, tear strength and resistance to flexing fatigue and maintaining sensitivity
while maintaining high acoustic wave sensitivity, A silicone resin for an acoustic wave probe, an
acoustic wave probe, an acoustic wave measurement device, an ultrasonic diagnostic device, a
photoacoustic wave measurement device, an ultrasonic endoscope, and a method for producing a
silicone resin for an acoustic wave probe using the same are provided. SOLUTION: The
polysiloxane mixture contains at least a polysiloxane, an organic peroxide, a polysiloxane resin
and a siloxane compound, and the content of the siloxane compound in the total 100 parts by
mass of the polysiloxane mixture is 0. Composition for acoustic wave probe having .001 to 5
parts by mass, silicone resin for acoustic wave probe, acoustic wave probe, acoustic wave
measurement device, ultrasonic diagnostic device, ultrasonic probe, photoacoustic wave
measurement device, and ultrasonic endoscopy Mirror and method of manufacturing silicone
resin for acoustic wave probe. 【Selection chart】 None
Composition for acoustic wave probe, silicone resin for acoustic wave probe using the same,
acoustic wave probe and ultrasonic probe, acoustic wave measurement device, ultrasonic
diagnostic device, photoacoustic wave measurement device, ultrasonic endoscope and acoustic
wave Method for producing silicone resin for probe
[0001]
The present invention relates to a composition for an acoustic wave probe and a silicone resin for
an acoustic wave probe using the same, an acoustic wave probe and an ultrasonic probe.
Furthermore, the present invention relates to an acoustic wave measurement device, an
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ultrasonic diagnostic device, a photoacoustic wave measurement device, and an ultrasonic
endoscope. The present invention also relates to a method of producing a silicone resin for an
acoustic wave probe.
[0002]
In an acoustic wave measurement apparatus, an acoustic wave probe is used which irradiates an
acoustic wave to an object, receives a reflected wave (echo), and outputs a signal. The inside of
the object is visualized and observed by displaying as an image based on the electric signal
converted from the reflected wave received by the acoustic wave probe.
[0003]
As the acoustic wave, an appropriate frequency is selected according to an object to be examined,
measurement conditions, and the like, such as an ultrasonic wave and a photoacoustic wave. For
example, the ultrasound diagnostic apparatus transmits ultrasound toward the inside of the
subject, receives ultrasound reflected by the tissue inside the subject, and displays the ultrasound
as an image. The photoacoustic wave measuring apparatus receives an acoustic wave emitted
from the inside of the subject by the photoacoustic effect and displays it as an image. The
photoacoustic effect is an acoustic wave (typical) when the subject absorbs the electromagnetic
wave, generates heat, and thermally expands when the subject is irradiated with an
electromagnetic wave pulse such as visible light, near infrared light, or microwave. ) Is a
phenomenon that occurs. In order to transmit and receive an acoustic wave to and from a living
body, the acoustic wave measuring device is required to satisfy requirements such as matching of
acoustic impedance with the living body and low acoustic wave attenuation.
[0004]
For example, a probe for an ultrasonic diagnostic apparatus (also referred to as an ultrasonic
probe), which is a type of acoustic wave probe, includes a piezoelectric element that transmits
and receives an ultrasonic wave and an acoustic lens that is a portion in contact with a living
body. The ultrasonic wave emitted from the piezoelectric element passes through the acoustic
lens and is incident on the living body. If the difference between the acoustic impedance (density
x speed of sound) of the acoustic lens and the acoustic impedance of the living body is large, the
ultrasonic wave is reflected on the living body surface, and hence it does not efficiently enter the
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living body, making it difficult to obtain high resolution is there. In addition, in order to transmit
and receive ultrasonic waves with high sensitivity, it is desirable that the amount of ultrasonic
attenuation of the acoustic lens be small. For this reason, as a material of the acoustic lens, a
silicone resin which is close to the acoustic impedance of a living body (1.4 to 1.7 × 10 6 kg / m
2 / sec) and which has a small amount of ultrasonic attenuation is mainly used. It is done.
[0005]
In addition, since silicone resins are soft alone and have low mechanical strength, inorganic fillers
such as silica (also referred to as inorganic fillers) are used to increase the molecular weight of
vinyl silicone resin at both ends for the purpose of improving hardness and mechanical strength.
And vinyl group-containing resins (also referred to as reinforcing agents). Under the present
circumstances, if it is going to achieve the required mechanical strength, the addition amount of
the inorganic filler and vinyl group containing resin with respect to a silicone resin will inevitably
increase, conversely, it will become a silicone resin with large acoustic wave attenuation. There
was a problem.
[0006]
To address this problem, for example, in Patent Document 1, as a composition for an acoustic
lens that forms an acoustic lens close to the acoustic impedance of a living body and has a small
amount of ultrasonic attenuation, a silicone rubber pound with a higher alkyl group or polyether
group There have been proposed compositions containing organopolysiloxanes into which
specific substituents such as those mentioned above have been introduced. Further, in Patent
Document 2, as a composition for an acoustic lens forming an acoustic matching layer with high
acoustic impedance and resin hardness, a silicone-modified organic resin or a silicone-modified
organic resin terminated with epoxy is blended with an organopolysiloxane. Compositions have
been proposed.
[0007]
JP, 08-305375, A JP, 2008-011494, A
[0008]
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However, it is difficult for conventional silicone resins to satisfy both low acoustic wave
attenuation (ie high acoustic wave sensitivity) and high mechanical strength (especially resin
hardness, tear strength and resistance to bending fatigue) at high levels. Met.
Therefore, in the present invention, in view of the above circumstances, a composition for an
acoustic wave probe capable of significantly improving resin hardness, tear strength and bending
fatigue resistance of a silicone resin while maintaining high acoustic wave sensitivity, An object
of the present invention is to provide a silicone resin for an acoustic wave probe, an acoustic
wave probe, an acoustic wave measurement apparatus, an ultrasonic diagnostic apparatus, and a
method for producing a silicone resin for an acoustic wave probe using the same.
[0009]
Also, an ultrasonic probe using capacitive micromachined ultrasonic transducers (cMUT:
Capacitive Micromachined Ultrasonic Transducers) with insufficient sensitivity as a transducer
array for ultrasonic diagnosis, because the amount of ultrasonic waves generated by
photoacoustic waves is small The sensitivity is low because the photoacoustic wave measurement
device with low sensitivity and deep observation of the human body is difficult and the signal line
cable is longer than for body surface, and it is difficult to improve sensitivity in terms of
structure, physical characteristics, and process suitability. Another object of the present invention
is to provide a composition for an acoustic wave probe and a silicone resin for an acoustic wave
probe, which can improve sensitivity in an ultrasonic endoscope.
[0010]
As a result of conducting studies on silicone resins, the present inventors have found that the
above problems can be solved by using a siloxane compound having a specific structure.
[0011]
The above problems are solved by the following means.
The <1> polysiloxane mixture contains at least a polysiloxane, an organic peroxide, a
polysiloxane resin and a siloxane compound, and the content of the siloxane compound in the
total 100 parts by mass of the polysiloxane mixture is 0. The composition for acoustic wave
probes which is 001-5 mass parts, and a siloxane compound has a structure represented by the
following general formula (D).
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[0012]
<img class = "EMIRef" id = "391047503-000002" />
[0013]
In formula (D), R <d> represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl
group, and nd represents an integer of 1 or more.
However, when nd is an integer of 2 or more, it may be cyclic.
The composition for acoustic wave probes as described in <1> whose <2> polysiloxane is vinyl
group containing polysiloxane. The composition for acoustic wave probes as described in <1> or
<2> whose <3> polysiloxane resin is a vinyl group containing polysiloxane resin. The composition
for acoustic wave probes as described in any one of <1>-<3> in which a <4> siloxane compound
is represented with the following general formula (D2).
[0014]
<img class = "EMIRef" id = "391047503-000003" />
[0015]
In formula (D2), R <d21> and R <d22> each independently represent an alkyl group, a cycloalkyl
group, an alkenyl group or an aryl group, and nd2 represents an integer of 1 or more.
The plurality of R <d22> may be the same as or different from one another. The composition for
acoustic wave probes as described in any one of <1>-<3> whose <5> siloxane compound is a
compound which has cyclic structure. For the acoustic wave probe according to any one of <1>
to <5>, wherein 0.1 to 30 parts by mass of silica having an average primary particle diameter of
less than 12 nm is contained in 100 parts by mass of the <6> polysiloxane mixture Composition.
The composition for acoustic wave probes as described in <2> whose mass mean molecular
weights of a <7> vinyl group containing polysiloxane are 20,000-1,000,000. The composition for
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acoustic wave probes as described in <2> whose mass mean molecular weights of a <8> vinyl
group containing polysiloxane are 40,000-300,000. <9> A silicone resin for an acoustic wave
probe formed by curing the composition for an acoustic wave probe according to any one of <1>
to <8>. The acoustic wave probe which has an acoustic lens and / or an acoustic matching layer
which consist of silicone resin for acoustic wave probes as described in <10> <9>. <11> An
ultrasonic probe comprising: a capacitive micromachined ultrasonic transducer as an ultrasonic
transducer array; and an acoustic lens made of a silicone resin for an acoustic wave probe
according to <9>. The acoustic wave measuring apparatus provided with the acoustic wave probe
as described in <12> <10>. <13> An ultrasound diagnostic apparatus comprising the acoustic
wave probe according to <10>. The photoacoustic wave measuring apparatus provided with the
acoustic lens which consists of silicone resin for acoustic wave probes as described in <14> <9>.
<15> An ultrasound endoscope comprising an acoustic lens made of the silicone resin for an
acoustic wave probe according to <9>. An acoustic wave probe for curing an acoustic wave probe
composition after adding an organic peroxide to a polysiloxane mixture containing at least a
polysiloxane, a polysiloxane resin, and a siloxane compound to form a composition for an
acoustic wave probe Method for silicone resin.
[0016]
In each general formula of the present specification, unless otherwise specified, when there are a
plurality of groups having the same code, they may be the same or different from each other, and
a group specified by each group (for example, The alkyl group etc. may be further substituted by
a substituent. Moreover, in this specification, "-" is used in the meaning included including the
numerical value described before and after that as a lower limit and an upper limit. In addition,
the mass mean molecular weight in this specification is a measured value (polystyrene
conversion) by gel permeation chromatography (Gel Permeation Chromatography: GPC) unless
there is particular notice.
[0017]
According to the present invention, a composition for an acoustic wave probe capable of
obtaining a silicone resin having high resin hardness, tear strength and resistance to bending
fatigue while maintaining high acoustic wave (particularly preferably ultrasonic) sensitivity. It is
possible to provide a silicone resin for an acoustic wave probe, an acoustic wave probe, an
acoustic wave measurement apparatus, an ultrasonic diagnostic apparatus, and a method for
producing a silicone resin for an acoustic wave probe. In addition, it is possible to provide an
ultrasonic probe using cMUT as a transducer array for ultrasonic diagnosis, a photoacoustic wave
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measuring apparatus, and a silicone resin for an acoustic wave probe capable of improving the
sensitivity in an ultrasonic endoscope.
[0018]
Such an effect is considered to be enhanced by formation of a suitable crosslinked structure by
the polysiloxane resin and the polyfunctional siloxane compound having a vinyl group in the side
chain, as long as good acoustic properties can be maintained.
[0019]
It is a perspective transmission figure about the convex type | mold ultrasonic probe which is one
aspect | mode of an acoustic wave probe.
[0020]
<< Composition for Acoustic Wave Probe >> The composition for acoustic wave probe of the
present invention (hereinafter, also simply referred to as a composition).
Is at least containing a polysiloxane, an organic peroxide, a polysiloxane resin and a siloxane
compound in a polysiloxane mixture, and the content of the siloxane compound in the total 100
parts by mass of the polysiloxane mixture is 0. It is a composition for acoustic wave probes which
is 001-5 mass parts, and has a structure where a siloxane compound is denoted by a belowmentioned general formula (D).
In addition, when the composition for acoustic wave probes of this invention contains the belowmentioned silica particle (E), a silica particle (E) is also contained in a total of 100 mass parts of a
polysiloxane mixture.
[0021]
In the present invention, the above-described polysiloxane, polysiloxane resin and siloxane
compound contained in the polysiloxane mixture have structures represented by
polyorganosiloxane (A), polyorganosiloxane resin (C) and general formula (D). In the present
invention, the organosiloxane compound (D) is preferred. Therefore, in the present invention, the
polyorganosiloxane mixture has a structure represented by the polyorganosiloxane (A), the
polyorganosiloxane resin (C) and the general formula (D) It is preferable to contain at least the
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organosiloxane compound (D).
[0022]
In the following detailed description, polyorganosiloxane (A), polyorganosiloxane resin (C) and
organosiloxane compound (D) having a structure represented by formula (D), which are preferred
embodiments, will be described.
However, the polysiloxane, the polysiloxane resin and the siloxane compound contained in the
polysiloxane mixture are not limited to the polyorganosiloxane, the polyorganosiloxane resin and
the organosiloxane compound.
[0023]
<Polyorganosiloxane (A)> The polyorganosiloxane (A) in the present invention may be any
polyorganosiloxane as long as it is a millable silicone which is crosslinked by a radical curing
reaction with the organic peroxide (B). Here, the state before curing is similar to natural rubber
or an unvulcanized compounded rubber of a general synthetic rubber, and mirable type silicone
can be plasticized and mixed by a kneading roll machine, a closed mixer, etc. It is a generic term
of things, and the state before hardening is distinguished from paste or liquid silicone that is
liquid.
[0024]
Hereinafter, specific millable silicones will be described by taking linear and branched
polyorganosiloxanes as an example. In addition, polyorganosiloxane (A) is not limited to the
polyorganosiloxane described below, For example, the linear polyorganosiloxane which has a
branched structure in part may be sufficient.
[0025]
[Linear Polyorganosiloxane] As the linear polyorganosiloxane, those represented by the following
general formula (A1) can be mentioned.
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[0026]
<img class = "EMIRef" id = "391047503-00004" />
[0027]
In the general formula (A1), R <a1> each independently represents a hydrogen atom, an alkyl
group, a cycloalkyl group, an alkenyl group or an aryl group, and R <a2> and R <a3> each
independently represent a hydrogen atom And an alkyl group, a cycloalkyl group, an alkenyl
group having 3 or more carbon atoms or an aryl group.
Each of x1 and x2 independently represents an integer of 1 or more.
Here, the plurality of R <a1>, the plurality of R <a2>, and the plurality of R <a3> may be the same
or different from one another. Moreover, each group of R <a1> to R <a3> may be further
substituted by a substituent.
[0028]
1-10 are preferable, as for carbon number of the alkyl group in R <a1> -R <a3>, 1-4 are more
preferable, 1 or 2 is more preferable, and 1 is especially preferable. Examples of the alkyl group
include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl and ndecyl.
[0029]
3-10 are preferable, as for carbon number of the cycloalkyl group in R <a1> -R <a3>, 5-10 are
more preferable, and 5 or 6 are more preferable. The cycloalkyl group is preferably a 3-, 5- or 6membered ring, more preferably a 5- or 6-membered ring. Examples of the cycloalkyl group
include cyclopropyl, cyclopentyl and cyclohexyl.
[0030]
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2-10 are preferable, as for carbon number of the alkenyl group in R <a1>, 2-4 are more
preferable, and 2 is more preferable. Examples of the alkenyl group include vinyl, allyl and
butenyl. 3-10 are preferable and, as for carbon number of the alkenyl group in R <a2> and R
<a3>, 3 or 4 is more preferable. Examples of the alkenyl group include allyl and butenyl.
[0031]
6-12 are preferable, as for carbon number of the aryl group in R <a1> -R <a3>, 6-10 are more
preferable, and 6-8 are more preferable. Examples of the aryl group include phenyl, tolyl and
naphthyl.
[0032]
These alkyl group, cycloalkyl group, alkenyl group and aryl group may have a substituent. Such
substituents include, for example, halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups,
aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, silyl groups and
cyano groups. As a group which has a substituent, a halogenated alkyl group is mentioned, for
example.
[0033]
R <a1> is preferably an alkyl group or an alkenyl group, more preferably an alkyl group having 1
to 4 carbon atoms or a vinyl group, still more preferably a methyl group or a vinyl group, and
particularly preferably a vinyl group, Most preferably, both are vinyl groups. Each of R <a2> and
R <a3> is preferably an alkyl group, an alkenyl group having 3 or more carbon atoms or an aryl
group, more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and still
more preferably a methyl group.
[0034]
The integer of 200-3000 is preferable and, as for x1, the integer of 400-2000 is more preferable.
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The integer of 1-1000 is preferable and, as for x2, the integer of 40-700 is more preferable.
[0035]
The linear polyorganosiloxane preferably has at least one vinyl group in the molecular chain, and
more preferably at least two vinyl groups in the molecular chain. Among them, a
polyorganosiloxane having a vinyl group at least at the molecular chain terminal is preferable,
and a polyorganosiloxane having a vinyl group at least at both molecular chain terminals is more
preferable.
[0036]
The degree of polymerization and specific gravity are not particularly limited. In addition, silicone
resin for acoustic wave probes obtained (hereinafter, also simply referred to as silicone resin).
200-3000 are preferable, 400-2000 are more preferable, and, as for a specific gravity, 0.9-1.1
are preferable from the point of an improvement of the mechanical characteristics of the above,
hardness, chemical stability, etc.
[0037]
The mass average molecular weight of the polyorganosiloxane (A) is preferably 20,000 to
1,000,000, and 40,000 to 300, from the viewpoint of mechanical strength, hardness, bending
fatigue resistance and ease of processing. 000 is more preferable, and 45,000 to 250,000 is
more preferable.
[0038]
For example, GPC apparatus HLC-8220 (manufactured by Tosoh Corp.) is used as mass average
molecular weight, and toluene (manufactured by Shonan Wako Pure Chemical Industries, Ltd.) is
used as an eluent, and TSKgel (registered trademark) G3000HXL + TSKgel (registered trademark)
as a column. It can measure using RI detector using G2000HXL, the temperature of 23 degreeC,
and the conditions of flow volume 1mL / min.
[0039]
The kinematic viscosity at 25 ° C. is preferably 1 × 10 <−5> to 10 m <2> / s, more preferably
1 × 10 <−4> to 1 m <2> / s, 1 × 10 <−3> It is further preferable that ∼0.5 m <2> / s.
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[0040]
Polyorganosiloxanes having vinyl groups at least at both molecular chain ends are, for example,
trade names manufactured by Gelest, DMS series (eg, DMS-V31, DMS-V31S15, DMS-V33, DMSV35, DMS-V35R, DMS -V41, DMS-V42, DMS-V46, DMS-V51, DMS-V52), trade names made by
Gelest, PDV series (for example, PDV-0341, PDV-0346, PDV-0535, PDV-0541, PDV- [0196] PDV01635, PDV-01641, PDV-2335, PMV-9925, PVV-3522, FMV-4031, EDV-2022).
In addition, since fumed silica is mix | blended beforehand, DMS-V31 S15 does not need
kneading | mixing in a special apparatus.
In particular, by using a polysiloxane having a vinyl group at the end of a high molecular weight
molecular chain, the tear strength of the silicone resin is further greatly improved.
[0041]
[Branched polyorganosiloxane] As the branched polyorganosiloxane, those represented by the
following general formula (A2) can be mentioned.
[0042]
<img class = "EMIRef" id = "391047503-000005" />
[0043]
In general formula (A2), R <1> and R <4> each independently represent a hydrogen atom, an
alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
R <2> and R <3> each independently represent a hydrogen atom, an alkyl group, a cycloalkyl
group, an alkenyl group having 3 or more carbon atoms, or an aryl group.
m represents an integer of 1 or more, and n represents an integer of 0 or 1 to 5.
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Here, the plurality of R <1>, the plurality of R <2>, the plurality of R <3>, the plurality of R <4>,
and the plurality of m may be identical to or different from each other, and R <4>. Each group of
1> to R <4> may be further substituted by a substituent.
[0044]
In the general formula (A2), a polyorganosiloxane in which n is 0 can be represented by the
following general formula (a2).
[0045]
<img class = "EMIRef" id = "391047503-000006" />
[0046]
In formula (a2), R <1> and R <4> each independently represent a hydrogen atom, an alkyl group,
a cycloalkyl group, an alkenyl group or an aryl group.
R <2> and R <3> each independently represent a hydrogen atom, an alkyl group, a cycloalkyl
group, an alkenyl group having 3 or more carbon atoms, or an aryl group.
m represents an integer of 1 or more. Here, the plurality of R <2>, the plurality of R <3>, the
plurality of R <4> and the plurality of m may be identical to or different from one another, and R
<1> to R <4>. Each group of may be further substituted by a substituent.
[0047]
In the general formulas (A2) and (a2), each of the above-mentioned groups in R <1> and R <4>
has the same meaning as the corresponding group in R <a1> of the general formula (A1). The
same as the corresponding group. Each of the above groups in R <2> and R <3> has the same
meaning as the corresponding group in R <a 2> and R <a 3> of general formula (A1), and the
preferred range is also the corresponding group It is the same. At least two or more of the
plurality of R <1> and R <4> are preferably vinyl groups, and more preferably, at least two or
04-05-2019
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more of the plurality of R <4> are vinyl groups.
[0048]
The n, m and mass average molecular weights in the general formulas (A2) and (a2) are not
particularly limited as long as they are millable silicones having a gum-like dynamic viscosity at
25 ° C. Specific kinematic viscosity values are the same as the preferred range of kinematic
viscosity described for linear polyorganosiloxanes.
[0049]
The polyorganosiloxane (A) in the present invention is preferably a vinyl group-containing
polysiloxane having one or more vinyl groups in the molecular chain. The content of the vinyl
group when the polyorganosiloxane (A) has a vinyl group is not particularly limited. In addition,
it is 0.01-5 mol% from a viewpoint of forming the sufficient network by organic peroxide (B), for
example, Preferably it is 0.05-2 mol%. Here, the content of the vinyl group is the mol% of the
vinyl group-containing siloxane unit when the total unit constituting the polyorganosiloxane (A)
is 100 mol%, and it is relative to one vinyl group-containing siloxane unit. And one vinyl group.
In addition, a unit means Si-O unit which comprises a principal chain, and Si of the terminal.
[0050]
As the polyorganosiloxane (A) in the present invention, only one type may be used alone, or two
or more types may be used in combination. In addition, 2 or less types are preferable and 1 type
individual is more preferable.
[0051]
<Organic Peroxide (B)> The organic peroxide (B) in the present invention is a hydroperoxide, a
dialkyl peroxide, a peroxy ester, a diacyl peroxide, a peroxy compound having an ̶O̶O̶ bond
in the molecule. Commonly used organic peroxides such as oxydicarbonates, peroxyketals and
ketone peroxides can be mentioned.
[0052]
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Specifically, the following organic peroxides may be mentioned.
Hydroperoxide: p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, etc.
[0053]
Dialkyl peroxide: bis (2,4-dichlorobenzoyl) peroxide, bis (4-chlorobenzoyl) peroxide, bis (2methylbenzoyl) peroxide, bis (2-t-butylperoxyisopropyl) benzene, Dicumyl peroxide, 2,5dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl
peroxide and 2, 5-Bis (t-butylperoxy) -2,5-dimethyl-3-hexyne etc.
[0054]
Peroxy esters: t-butyl peroxybenzoate, cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl
peroxy neodecanoate, t-hexyl peroxy neodecanoate, t- Butyl peroxy neodecanoate, t-butyl peroxy
neoheptanoate, t-hexyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, 2,5Bis (2-ethylhexylperoxy) -2,5-dimethylhexane, t-hexylperoxy-2-ethylhexanoate, tbutylperoxymaleate, t-butylperoxy-3,5,5-trimethyl Hexanoate, t-butyl peroxy laurate, t-butyl
peroxy isopropyl monocarbone , T-Butylperoxy-2-ethylhexyl monocarbonate, thexylperoxybenzoate, 2,5-bis (benzoylperoxy) -2,5-dimethylhexane, t-butylperoxyacetate and tbutyl Peroxy-3-methyl benzoate etc
[0055]
Diacyl peroxide: diisobutyryl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide,
bis (3-carboxypropionyl) peroxide, bis (3-methylbenzoyl) peroxide, Benzoyl (3-methylbenzoyl)
peroxide, dibenzoyl peroxide, bis (4-methylbenzoyl) peroxide, 1,6-hexanediol-bis (t-butylperoxy
carbonate), etc.
[0056]
Peroxydicarbonate: di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-tbutylcyclohexyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate and di-sec -Butyl
peroxy dicarbonate etc
[0057]
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Peroxy ketal: 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy)
cyclohexane, 1,1-bis (t-butyl) Peroxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane,
2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylper) Oxy) valerate and 2,2-bis (4,4-bis (tbutylperoxy) cyclohexyl) propane etc.
[0058]
· Ketone peroxide: methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide,
etc.
[0059]
Among these organic peroxides, those having a 10-hour half-life decomposition temperature of
100 ° C. to 120 ° C. are preferable because the half-life decomposition temperature conforms
to the processing temperature, and specifically, dicumyl peroxide 2,5-Dimethyl-2,5-bis (tbutylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, bis (2-t-butylperoxyisopropyl)
benzene, t -Butylperoxybenzoate, 2,5-bis (benzoylperoxy) -2,5-dimethylhexane, tbutylperoxyacetate, 2,2-bis (t-butylperoxy) butane or n-butyl 4 Preferred is 4-bis (t-butylperoxy)
valerate.
The organic peroxide may be used alone or in combination of two or more.
[0060]
0.1-15 mass parts is preferable with respect to 100 mass parts of polysiloxane mixtures, and, as
for the addition amount of an organic peroxide (B), 0.2-10 mass parts is more preferable.
When the addition amount is in the above range, the crosslinking reaction sufficiently proceeds,
and deterioration in physical properties such as hardness reduction of the silicone resin,
insufficient rubber strength, and increase in compression set is suppressed.
Moreover, it is economically preferable, and the generation of the decomposition product of the
curing agent can be suppressed, thereby suppressing the deterioration of physical properties
such as increase in compression set and the discoloration of the obtained silicone resin sheet.
04-05-2019
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[0061]
<Polyorganosiloxane resin (C)> The polyorganosiloxane resin (C) in the present invention has at
least two or more aliphatic unsaturated hydrocarbon groups in one molecule, and is reticulated
in at least a part of the skeleton. Any polyorganosiloxane resin having a structure may be used.
In addition, as for content of the aliphatic unsaturated hydrocarbon group in 1 molecule, 1 * 10
<-5> -1 * 10 <-2> mol / g is preferable, and 1 * 10 <-4> -2 * 10. <-3> mol / g is more preferable.
[0062]
Examples of the polyorganosiloxane resin (C) include MQ resin, DT resin, and MDT resin.
Among them, preferred is an MQ resin containing at least SiO 4/2 units (Q units) and R <c 1> 2R
<c 2> SiO 1/2 units (M units).
[0063]
R <c1> in the M unit represents an alkyl group having no aliphatic unsaturated bond, a cycloalkyl
group, an aryl group or an aralkyl group.
R <c2> represents an aliphatic unsaturated hydrocarbon group, preferably an alkenyl group or
an alkynyl group. Here, a plurality of R <C1> may be the same or different. Moreover, each group
of R <C1> may be further substituted by the substituent.
[0064]
1-18 are preferable, as for carbon number of the alkyl group in R <c1>, 1-10 are more
preferable, 1-4 are more preferable, 1 or 2 is especially preferable, and 1 is most preferable.
04-05-2019
17
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl,
pentyl, 2,2-dimethylpropyl, hexyl, n-octyl, n-nonyl and n-decyl. Be Among them, methyl is
preferred.
[0065]
3-10 are preferable, as for carbon number of the cycloalkyl group in R <c1>, 5-10 are more
preferable, and 5 or 6 are more preferable. The cycloalkyl group is preferably a 3-, 5- or 6membered ring, more preferably a 5- or 6-membered ring. Examples of the cycloalkyl group
include cyclopropyl, cyclopentyl and cyclohexyl.
[0066]
6-18 are preferable, as for carbon number of the aryl group in R <c1>, 6-10 are more preferable,
and 6-8 are more preferable. Aryl groups include, for example, phenyl, tolyl, xylyl and naphthyl.
7-18 are preferable and, as for carbon number of the aralkyl group in R <c1>, 7-10 are more
preferable. Examples of the aralkyl group include benzyl, phenylethyl and phenylpropyl.
[0067]
These alkyl group, cycloalkyl group, aryl group and aralkyl group may have a substituent. Such
substituents include, for example, halogen atoms (such as fluorine, bromine and chlorine), alkyl
groups, cycloalkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio
groups, silyl groups and cyano groups. Be Examples of the group having a substituent include
chloromethyl, chloropropyl, bromoethyl, trifluoropropyl and cyanoethyl. Particularly preferred is
a methyl group.
[0068]
2-8 are preferable, as for carbon number of the alkenyl group in R <c2>, C2-C6 is more
preferable, and 2 or 3 is more preferable. Examples of the alkenyl group include vinyl, allyl,
propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl and octenyl. Among them, vinyl is
preferred.
04-05-2019
18
[0069]
M unit / Q unit, which is a molar ratio of R <c1> 2R <c2> SiO1 / 2 unit (M unit) to SiO 4/2 unit (Q
unit), is a point that the silicone resin has good resin strength Therefore, 0.1 to 3.0 is preferable,
0.3 to 2.5 is more preferable, and 0.5 to 2.0 is more preferable. Moreover, the
polyorganosiloxane resin (C) in the present invention is such that R <c1> 2SiO2 / 2 units (D
units) and / or R <c1 in the molecule within a range not to impair the properties of the silicone
resin of the present invention. > May contain SiO 3/2 units (T units). In addition, R <c1> is
synonymous with R <c1> in said M unit, and its preferable range is also the same.
[0070]
The polyorganosiloxane resin (C) in the present invention is a solid or viscous liquid at room
temperature, and the weight average molecular weight is not particularly limited. The kinematic
viscosity of the 50% by mass xylene solution of the polyorganosiloxane resin (C) in the present
invention is 0.5 to 10 mm <2> / s from the viewpoint of ease of processing of the composition
for acoustic wave probe of the present invention. Is preferable, and 1.0 to 5.0 mm <2> / s is more
preferable. The kinematic viscosity is a value measured at 25 ° C. using a Ubbelohde-type
Ostwald viscometer.
[0071]
The polyorganosiloxane resin (C) in the present invention more preferably has a SiO 4/2 unit, an
R <c1> 2R <c2> SiO1 / 2 unit, and an R <c2> 3SiO1 / 2 unit. In addition, R <c1> and R <c2> are
synonymous with R <c1> and R <c2> in said M unit, and their preferable range is also the same.
[0072]
The polyorganosiloxane resin (C) in the present invention is preferably one represented by the
following average composition formula (c).
[0073]
Average compositional formula (c): (SiO 4/2) b (R <c 1> 2 R <c 2> SiO 1/2) c (R <c 1> 3 SiO 1/2)
04-05-2019
19
d
[0074]
In formula (c), R <c1> and R <c2> have the same meanings as R <c1> and R <c2> described
above, and the preferred ranges are also the same.
Also, b, c and d each represent an independent positive number.
0.1-3.0 are preferable, as for (c + d) / b which is the sum of c and d with respect to b, 0.3-2.5 are
more preferable, and 0.5-2.0 are more preferable.
[0075]
2-50 mass parts is preferable, as for content of polyorganosiloxane resin (C) in a total of 100
mass parts of a polysiloxane mixture, 10-40 mass parts is more preferable, and 10-35 mass parts
is further more preferable. When the content of the polyorganosiloxane resin (C) is in the above
range, it is possible to obtain a silicone resin having good resin hardness, tear strength and
compression set.
[0076]
Among the polyorganosiloxane resins (C) in the present invention, vinyl group-containing
polyorganosiloxane resins in which the above R <c2> is vinyl are preferable. Commercially
available vinyl group-containing polyorganosiloxane resins are available. For example, a vinyl
group-containing vinyl Q resin dispersion liquid (trade name: “VQM-135” (base), in which a
vinyl group-containing polyorganosiloxane (Q resin) having Q units (SiO 4/2 units) is dispersed
in a dispersion liquid DMS-V41), "VQM-146" (the base is DMS-V46), "VQX-221" (the base is
xylene), all of which are manufactured by Gelest.
[0077]
The polyorganosiloxane resin (C) in the present invention may be used alone or in combination
04-05-2019
20
of two or more.
[0078]
<Organosiloxane Compound (D)> The organosiloxane compound (D) in the present invention has
a structure represented by the following general formula (D).
[0079]
<img class = "EMIRef" id = "391047503-00007" />
[0080]
In formula (D), R <d> represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl
group, and nd represents an integer of 1 or more.
However, when nd is an integer of 2 or more, it may be cyclic.
[0081]
The alkyl group, cycloalkyl group and aryl group in R <d> are the same as the alkyl group,
cycloalkyl group and aryl group in R <a2> and R <a3>, and the preferred range is also the same.
2-10 are preferable and, as for carbon number of the alkenyl group in R <d>, 2-4 are more
preferable.
Examples of the alkenyl group include vinyl, allyl and butenyl.
[0082]
Among them, a methyl group is preferable as R <d>.
[0083]
04-05-2019
21
The integer of 1-20 is preferable and, as for nd, the integer of 2-15 is more preferable.
[0084]
Here, "may be cyclic" means that a compound having a cyclic structure (hereinafter also referred
to as a cyclic siloxane compound) in which silicon atoms at both ends of nd structural units and
an oxygen atom are bonded may be used. .
That is, the organosiloxane compound (D) in the present invention may be a linear siloxane
compound in which the structure represented by the general formula (D) is linearly linked, or a
cyclic siloxane compound having a cyclic structure.
In addition, when a cyclic siloxane compound is used, excellent tear strength is obtained as
compared with the case where a linear siloxane compound is used. Moreover, when a linear
siloxane compound is used, superior resin hardness and flex fatigue resistance can be obtained
as compared with the case where a cyclic siloxane compound is used.
[0085]
The organosiloxane compound (D) in the present invention may contain other structures as long
as the properties of the silicone resin of the present invention are not impaired, in addition to the
structure represented by the general formula (D). As another structure, the structure represented
by the following general formula (D1) is mentioned, for example.
[0086]
<img class = "EMIRef" id = "391047503-000008" />
[0087]
In formula (D1), R <d1> represents an alkyl group, a cycloalkyl group or an aryl group, and nd1
represents an integer of 2 or more.
04-05-2019
22
Here, the plurality of R <d1> may be the same as or different from one another. Moreover, each
group of R <d1> may be further substituted by the substituent.
[0088]
The alkyl group, cycloalkyl group and aryl group in R <d1> are the same as the alkyl group,
cycloalkyl group and aryl group in R <d>, and the preferred range is also the same. Among them,
a methyl group is preferable as R <d1>.
[0089]
These alkyl group, cycloalkyl group and aryl group may have a substituent. Such substituents
include, for example, halogen atoms (such as fluorine, bromine and chlorine), alkyl groups,
cycloalkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups,
silyl groups and cyano groups. Be
[0090]
nd1 is preferably an integer of 1 to 500, and more preferably an integer of 1 to 200.
[0091]
The organosiloxane compound (D) in the present invention may contain two or more of the
structures represented by formula (D1).
[0092]
The specific gravity is not particularly limited.
The specific gravity is preferably 0.9 to 1.1 from the viewpoint of improvement in mechanical
properties, hardness, chemical stability and the like of the obtained silicone resin for acoustic
wave probe.
04-05-2019
23
[0093]
The mass average molecular weight of the organosiloxane compound (D) is preferably 200 to
15,000, and more preferably 200 to 10,000, from the viewpoint of mechanical strength,
hardness, and ease of processing.
[0094]
1 * 10 <-6> -10m <2> / s is preferable, and, as for the kinematic viscosity in 25 degreeC, 1 * 10
<-6> -1m <2> / s is more preferable, 1 * 10 <-6 >> It is further preferable that ∼0.5 m <2> / s.
The kinematic viscosity is a value measured at 25 ° C. using a Ubbelohde-type Ostwald
viscometer.
[0095]
Among the organosiloxane compounds (D) in the present invention, the linear siloxane
compound is preferably represented by the following general formula (D2).
[0096]
<img class = "EMIRef" id = "391047503-000009" />
[0097]
In formula (D2), R <d21> and R <d22> each independently represent an alkyl group, a cycloalkyl
group, an alkenyl group or an aryl group, and nd2 represents an integer of 1 or more.
The plurality of R <d22> may be the same as or different from one another.
[0098]
The alkyl group, cycloalkyl group, alkenyl group and aryl group in R <d21> and R <d22> have
the same meanings as the alkyl group, cycloalkyl group, alkenyl group and aryl group in R <d>,
and the preferred range is also the same. It is.
04-05-2019
24
[0099]
Among them, a methyl group is preferable as R <d21> and R <d22>.
[0100]
The integer of 1-20 is preferable and, as for nd2, the integer of 2-10 is more preferable.
[0101]
Among the organosiloxane compounds (D) in the present invention, the cyclic siloxane compound
is preferably represented by the following general formula (D3).
[0102]
<img class = "EMIRef" id = "391047503-000010" />
[0103]
In formula (D3), R <d31> represents an alkyl group, a cycloalkyl group, an alkenyl group or an
aryl group, and nd3 represents an integer of 2 or more.
[0104]
The alkyl group, cycloalkyl group, alkenyl group and aryl group in R <d31> have the same
meanings as the alkyl group, cycloalkyl group, alkenyl group and aryl group in R <d21> and R
<d22>, and the preferred range is also the same. It is.
[0105]
Among them, a methyl group is preferable as R <d31>.
[0106]
The integer of 3-20 is preferable and, as for nd3, the integer of 3-10 is more preferable.
[0107]
04-05-2019
25
The organosiloxane compound (D) can be obtained commercially.
For example, a low molecular weight vinylmethylsiloxane homopolymer (trade name: "VMS-005
(cyclic)", "VMS-T11 (linear)", all manufactured by Gelest, Inc.) can be mentioned.
[0108]
The content of the organosiloxane compound (D) in the total 100 parts by mass of the
polysiloxane mixture is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 4 parts by
mass, and 0.2 to 3 parts by mass. Is more preferred.
When the content of the organosiloxane compound (D) is in the above range, it is possible to
obtain a silicone resin having good resin hardness, tear strength and resistance to flexing fatigue.
[0109]
As the organosiloxane compound (D) in the present invention, only one type may be used alone,
or two or more types may be used in combination.
[0110]
<Silica (E) having an average primary particle size of less than 12 nm> The polysiloxane mixture
in the present invention is also referred to as silica (E) having an average primary particle size of
less than 12 nm (hereinafter simply referred to as silica particles (E)).
It is also preferable to further contain
The silica particles are components added for the purpose of improving the hardness and
mechanical strength of the obtained silicone resin, in particular, improving the tear strength.
[0111]
04-05-2019
26
By reducing the average primary particle diameter of the silica particles (E) to less than 12 nm, it
is considered that the increase in the amount of acoustic wave attenuation can be suppressed
and the tear strength of the silicone resin can be improved.
That is, it is thought that the crack of the silicone resin by mechanical stress is suppressed by the
fine silica particle (E) functioning as a stopper.
In particular, since the distance between particles is reduced due to the small average primary
particle diameter, it is presumed that the function as a stopper is more exhibited and the tear
strength of the silicone resin is significantly improved.
[0112]
Examples of the silica particles (E) include fumed silica, calcined silica, precipitated silica, and
vinyl group-containing silicone resin.
As the silica particles (E), only one type may be used alone, or two or more types may be used in
combination.
[0113]
The average primary particle diameter of the silica particles (E) is less than 12 nm from the
viewpoint of suppressing the increase in the acoustic wave attenuation of the silicone resin and
improving the tear strength, preferably more than 3 nm and less than 12 nm, more than 3 nm
and 10 nm Less than is more preferable.
The smaller the average primary particle diameter, the higher the tearing strength, and thus the
more preferable.
[0114]
04-05-2019
27
The average primary particle size is described in the catalog of the manufacturer of silica
particles.
However, those in which the average primary particle diameter is not described in the catalog or
those newly manufactured can be determined by averaging the particle diameters measured by
Transmission Electron Microscopy (TEM).
That is, for one particle of an electron micrograph taken by TEM, the minor axis and the major
axis are measured, and the average value is determined as the particle size of one particle.
In the present specification, the particle sizes of 300 or more particles are averaged to obtain an
average primary particle size.
[0115]
The silica particles (E) preferably have a specific surface area of 50 to 400 m <2> / g, and more
preferably 100 to 400 m <2> / g, from the viewpoint of improving the hardness and mechanical
strength of the obtained silicone resin.
[0116]
The silica particles (E) are preferably silica particles whose surface has been surface-treated.
As surface treatment, silica particles treated with saturated fatty acid or silane are preferable, and
among them, silica particles treated with silane are preferable.
[0117]
In the silane treatment, it is preferable to treat the surface of the silica particles with a silane
coupling agent.
04-05-2019
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From the viewpoint of improving the hardness and mechanical strength of the silicone resin,
silane coupling agents having a hydrolyzable group are preferred. The hydrolyzable group in the
silane coupling agent is hydrolyzed by water to become a hydroxyl group, and the hydroxyl
group reacts with the hydroxyl group on the surface of the silica particle by dehydration
condensation reaction, thereby surface modification of the silica particle is performed, and a
silicone resin is obtained. Hardness and mechanical strength are improved. Examples of the
hydrolyzable group include an alkoxy group, an acyloxy group, and a halogen atom. In addition,
when the surface of the silica particles is surface-modified to be hydrophobic, the affinity
between the silica particles (E) and the polyorganosiloxane (A), the polyorganosiloxane resin (C)
and the siloxane compound (D) is good. And the hardness and mechanical strength of the
resulting silicone resin are improved.
[0118]
As a silane coupling agent having a hydrophobic group as a functional group, for example,
methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane,
methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltriol Alkoxysilanes
such as methoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane,
decyltrimethoxysilane; methyltrichlorosilane, dimethyldichlorosilane (DDS),
trimethylchlorosilane, phenyltrichlorosilane, etc. Chlorosilane; hexamethyldisilazane (HMDS).
Also, as a silane coupling agent having a vinyl group as a functional group, for example,
methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane,
methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane,
vinyltriethoxy And silanes, vinyltrimethoxysilane, alkoxysilanes such as
vinylmethyldimethoxysilane; vinyltrichlorosilane, chlorosilanes such as
vinylmethyldichlorosilane; and divinyltetramethyldisilazane.
[0119]
The silica particles (E) are preferably silica particles treated with a silane compound, more
preferably silica particles treated with a trialkylsilylating agent, and still more preferably silica
particles treated with a trimethylsilylating agent. As a silane compound, the said silane coupling
agent and the silane coupling agent by which the functional group in the silane coupling agent
was substituted by the alkyl group are mentioned, for example. Further, as the trimethylsilylating
agent, for example, trimethylchlorosilane described in the above-mentioned silane coupling
agent, hexamethyldisilazane (HMDS), and trimethylmethoxysilane which is a silane coupling
04-05-2019
29
agent in which a functional group is substituted by an alkyl group are mentioned. Be
[0120]
Examples of commercially available silane coupling agents include hexamethyldisilazane (HMDS)
(trade name: HEXAMETHYLDISILAZANE (SIH 611 0.1), manufactured by Gelest). The silanol
group (Si-OH group) present on the surface of the silica particle is covered with a trimethylsilyl
group by the reaction with hexamethyldisilazane (HMDS), and the surface of the silica particle is
modified to be hydrophobic.
[0121]
As commercially available silica particles (E), for example, Aerosil (registered trademark) R 812
(average primary particle diameter 7 nm, HMDS surface treatment) and Aerosil (registered
trademark), all of which are hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd. )
R812S (average primary particle diameter 7 nm, HMDS surface treatment), Aerosil (registered
trademark) RX300 (average primary particle diameter 7 nm, HMDS surface treatment), Aerosil
(registered trademark) RX 380 S (average primary particle diameter 5 nm, HMDS surface
treatment), Aerosil (registered trademark) R976S (average primary particle diameter 7 nm, DDS
surface treatment) or hydrophilic fumed silica manufactured by Nippon Aerosil Co., Ltd., Aerosil
(registered trademark) 300 (average primary particle diameter 7 nm), Aerosil (Registered
trademark) 300 CF (average primary particle diameter 7 nm), Aero Le (R) 380 (average primary
particle diameter 7 nm) can be mentioned.
[0122]
In addition, when the composition for acoustic wave probes of this invention contains a silica
particle (E), polyorganosiloxane (A) polyorganosiloxane resin (C) and a siloxane compound (D)
have an average primary particle diameter in the clearance gap. Due to the close packing of the
small silica particles (E), the movement of the molecular chains is limited.
In addition, since the radical curing reaction proceeds due to the organic peroxide (B), the
polyorganosiloxane and / or vinyl group having vinyl group is more preferable than the
polyorganosiloxane and / or polyorganosiloxane resin having no vinyl group in the molecule. It is
preferable to use a polyorganosiloxane resin because a silicone resin having more excellent
mechanical strength can be obtained. Among them, polyorganosiloxanes having a vinyl group at
04-05-2019
30
the molecular chain end are more preferable from the viewpoint of reactivity in a state in which
molecular chain motion of the polyorganosiloxane (A) is restricted, and high molecular weight
vinyl group-containing polyorganosiloxanes Is more preferable in terms of mechanical strength
and reactivity.
[0123]
When the composition for an acoustic wave probe of the present invention contains silica
particles (E), the content of silica having an average primary particle diameter of less than 12 nm
in a total of 100 parts by mass of the polysiloxane mixture is 0.1 to 30. A mass part is preferable,
1-25 mass parts is more preferable, 5-20 mass parts is more preferable.
[0124]
<Other materials> The composition for an acoustic wave probe according to the present
invention comprises polyorganosiloxane (A), organic peroxide (B), polyorganosiloxane resin (C),
siloxane compound (D) and an average primary particle diameter. In addition to silica (E) of less
than 12 nm, a curing retarder, a solvent, a dispersant, a pigment, a dye, an antistatic agent, an
antioxidant, a flame retardant, a thermal conductivity improver and the like can be appropriately
blended.
However, it is preferable not to mix a platinum catalyst.
[0125]
<Composition for Acoustic Wave Probe and Method for Producing Silicone Resin for Acoustic
Wave Probe> The composition for acoustic wave probe of the present invention can be prepared
by a known method. For example, the components constituting the acoustic wave probe
composition can be obtained by kneading using a kneader, a pressure kneader, a Banbury mixer
(continuous kneader), a two-roll kneader, or the like.
[0126]
From the viewpoint of obtaining a uniform composition for acoustic wave probe, first,
04-05-2019
31
polyorganosiloxane (A), polyorganosiloxane resin (C) and organosiloxane compound (D) are
mixed, and then organic peroxide ( It is preferred to add B). When the composition for an
acoustic wave probe according to the present invention contains silica (E) having an average
primary particle size of less than 12 nm, or other materials, polyorganosiloxane (A),
polyorganosiloxane resin (C) and It is preferable to add the organic peroxide (B) after obtaining a
mixture in which the silica particles (C) and other materials are dispersed in the organosiloxane
compound (D).
[0127]
The silicone resin for an acoustic wave probe of the present invention comprises an organic
peroxide (B) added to a polysiloxane mixture containing at least a polyorganosiloxane (A), a
polyorganosiloxane resin (C) and an organosiloxane compound (D). The composition for acoustic
wave probe of the present invention can be produced by curing the composition for acoustic
wave probe. Each component can be kneaded by the method described above. Specifically, for
example, the composition for an acoustic wave probe of the present invention obtained by the
above-described method is heat cured at 50 to 180 ° C. for 5 minutes to 240 minutes, and
further, if necessary, 100 to 220 ° C. The silicone resin for an acoustic wave probe can be
obtained by secondary crosslinking for 1 to 5 hours. In particular, since the organic peroxide (B)
is used in the present invention, secondary crosslinking by reheating contributes to the heat
removal of the decomposition product of the organic peroxide (B) and the stabilization of the
silicone resin characteristics.
[0128]
<Mechanical Strength and Acoustic Wave Properties of Silicone Resin> The mechanical strength
and acoustic wave properties of the silicone resin are described in detail below. Here, the
acoustic wave characteristics will be described for ultrasonic characteristics. However, the
acoustic wave characteristic is not limited to the ultrasonic wave characteristic, and relates to an
acoustic wave characteristic of an appropriate frequency which is selected according to an object
to be examined, a measurement condition, and the like.
[0129]
[Hardness] With respect to a silicone resin sheet having a thickness of 2 mm, the type A
04-05-2019
32
durometer hardness is measured using a rubber hardness meter (for example, "RH-201A"
manufactured by Excell Co., Ltd.) according to JIS K6253-3 (2012). If it is too soft, it may be
deformed when incorporated and used as part of an acoustic wave probe, so the hardness is
preferably 19 or more, more preferably 30 or more, and still more preferably 35 or more. Note
that the practical upper limit is 80 or less.
[0130]
[Tear Strength Test] A 2 mm-thick silicone resin sheet was prepared in accordance with JIS
K6252 (2007) to prepare a trouser-type test piece, and the tear strength was measured. 17 N /
cm or more is preferable, 20 N / cm or more is more preferable, and 30 N / cm or more is
further more preferable. In addition, a realistic upper limit is 100 N / cm or less.
[0131]
[Bending Fatigue Test] For a silicone resin sheet having a thickness of 1 mm, the number of
bending at which a third-class crack occurs is measured in accordance with JIS K6260 (2010).
The number of bending is preferably 200,000 or more, and more preferably 250,000 or more.
The practical upper limit is 5 million times or less.
[0132]
[Acoustic impedance] With respect to a silicone resin sheet having a thickness of 2 mm, an
electronic hydrometer (for example, Alpha Mirage Co., Ltd.) according to the density
measurement method of Method A (substitution method in water) described in JIS K7112
(1999). Manufactured using "SD-200L"). The sound velocity of the acoustic wave is measured at
25 ° C. according to JIS Z 2353 (2003) using a single-around sound velocity measuring
apparatus (for example, “UVM-2 type” manufactured by Ultrasonic Industry Co., Ltd.), and the
measured density Determine the acoustic impedance from the product of the speed of sound.
[0133]
[Acoustic Wave (Ultrasonic Wave) Attenuation, Sensitivity] Ultrasonic wave of 5 MHz sine wave
04-05-2019
33
signal (one wave) output from ultrasonic oscillator (for example, function generator “FG-350”
manufactured by Iwatsu Measurement Co., Ltd.) A probe (for example, made by Japan Probe Co.,
Ltd.) is input, and an ultrasonic pulse wave having a center frequency of 5 MHz is generated in
water from the ultrasonic probe. The amplitude of the generated ultrasonic waves before and
after passing through a 2 mm thick silicone resin sheet was measured by an ultrasonic wave
receiver (for example, an oscilloscope "VP-5204A" manufactured by Matsushita Electric
Industrial Co., Ltd.). The acoustic wave (ultrasonic wave) attenuation of each material is
compared by measuring in an environment of ° C. and comparing the acoustic wave (ultrasonic
wave) sensitivity. Here, the acoustic wave (ultrasonic wave) sensitivity is a sheet of an acoustic
wave (ultrasonic wave) generated for the voltage peak value Vin of an input wave such as a
rectangular wave with a half width of 50 nsec or less or a spike wave by an ultrasonic oscillator.
The voltage value obtained when the ultrasonic wave generator receives an acoustic wave
(ultrasound) reflected from the opposite side of the sheet as Vs, and has a numerical value given
by the following equation.
[0134]
Acoustic wave (ultrasonic) sensitivity = 20 x Log (Vs / Vin)
[0135]
In the evaluation system of the present invention, the acoustic wave (ultrasound) sensitivity is
preferably -75 dB or more, more preferably -73 dB or more, and still more preferably -72 dB or
more.
[0136]
The composition for an acoustic wave probe of the present invention is useful for a medical
member, and can be preferably used, for example, in an acoustic wave probe or an acoustic wave
measurement device.
The acoustic wave measuring apparatus according to the present invention is not limited to an
ultrasonic diagnostic apparatus or a photoacoustic wave measuring apparatus, and refers to an
apparatus that receives an acoustic wave reflected or generated by an object and displays it as an
image or a signal intensity.
In particular, the composition for acoustic wave probe according to the present invention is
04-05-2019
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provided between the acoustic lens of the ultrasonic diagnostic apparatus or between the
piezoelectric element and the acoustic lens to have the role of matching the acoustic impedance
between the piezoelectric element and the acoustic lens. Acoustic matching layer material,
photoacoustic wave measuring device and acoustic lens material in ultrasound endoscope and
acoustic probe in ultrasound probe with Capacitive Micromachined Ultrasonic Transducers
(cMUT) as ultrasound transducer array It can be suitably used as a material of a lens or the like.
Specifically, the silicone resin for an acoustic wave probe of the present invention may be, for
example, an ultrasonic diagnostic apparatus described in JP-A-2005-253751, JP-A-2003169802, or the like, JP-A-2013-202050 Preferred for the acoustic wave measuring apparatus
such as the photoacoustic wave measuring apparatus described in Japanese Patent Application
Laid-Open Nos. 2013-188465, 2013-180330, 2013-158435, 2013-154139 etc. Applied.
[0137]
<< Acoustic Wave Probe (Probe) >> The structure of the acoustic wave probe of the present
invention will be described in more detail based on the structure of the ultrasonic probe in the
ultrasonic diagnostic apparatus described in FIG. 1 below. In addition, an ultrasonic probe is a
probe which uses an ultrasonic wave especially as an acoustic wave in an acoustic wave probe.
Therefore, the basic structure of the ultrasound probe is applied to the acoustic wave probe as it
is.
[0138]
-Ultrasonic probe-The ultrasonic probe 10 is a main component of an ultrasonic diagnostic
apparatus, and has a function of generating an ultrasonic wave and transmitting and receiving an
ultrasonic beam. The configuration of the ultrasonic probe 10 is, as shown in FIG. 1, provided in
the order of the acoustic lens 1, the acoustic matching layer 2, the piezoelectric element layer 3,
and the backing material 4 from the tip (surface in contact with a living body being a subject)
There is. In recent years, in order to receive high-order harmonics, a transmitting ultrasonic
transducer (piezoelectric element) and a receiving ultrasonic transducer (piezoelectric element)
are made of different materials and have a laminated structure. Is also proposed.
[0139]
<Piezoelectric Element Layer> The piezoelectric element layer 3 is a portion that generates
ultrasonic waves, and electrodes are attached to both sides of the piezoelectric element, and
when voltage is applied, the piezoelectric element repeatedly vibrates by expansion and
04-05-2019
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contraction. Ultrasonic waves are generated.
[0140]
As materials for constituting the piezoelectric element, quartz, single crystals such as LiNbO 3,
LiTaO 3, and KNbO 3, thin films such as ZnO and AlN, and sintered bodies such as Pb (Zr, Ti) O 3
series are subjected to polarization processing. So-called ceramic inorganic piezoelectric
materials are widely used.
In general, piezoelectric ceramics such as PZT: lead zirconate titanate having high conversion
efficiency are used. In addition, the piezoelectric element that detects the received wave on the
high frequency side needs sensitivity with a wider bandwidth. For this reason, an organic
piezoelectric material using an organic polymer substance such as polyvinylidene fluoride (PVDF)
is used as a piezoelectric element suitable for high frequency and wide band. Furthermore,
Japanese Patent Application Laid-Open No. 2011-071842 or the like uses MEMS (Micro Electro
Mechanical Systems) technology that exhibits excellent short pulse characteristics and wide band
characteristics, is excellent in mass productivity, and provides an array structure with less
characteristic variation. cMUT is described. In the present invention, any piezoelectric element
material can be preferably used.
[0141]
<Backing Material> The backing material 4 is provided on the back surface of the piezoelectric
element layer 3 and suppresses the extra vibration to shorten the pulse width of the ultrasonic
wave, thereby contributing to the improvement of the distance resolution in the ultrasonic
diagnostic image. .
[0142]
<Acoustic Matching Layer> The acoustic matching layer 2 is provided to reduce the difference in
acoustic impedance between the piezoelectric element layer 3 and the subject and efficiently
transmit and receive ultrasonic waves.
The composition for an ultrasonic probe according to the present invention has a small
difference from the acoustic impedance (1.4 to 1.7 × 10 6 <6> kg / m 2> / sec) of a living body,
04-05-2019
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and thus the material of the acoustic matching layer It can be preferably used as
[0143]
<Acoustic Lens> The acoustic lens 1 is provided for focusing ultrasonic waves in the slice
direction using refraction to improve resolution. In addition, it is in close contact with a living
body which is a subject, and the ultrasonic wave is matched with the acoustic impedance (1.4 to
1.7 × 10 6 <6> kg / m 2> / sec) of the living body, and the acoustic lens 1 It is required that the
ultrasonic attenuation amount of itself is small. That is, as the material of the acoustic lens 1, the
sound velocity is sufficiently smaller than the sound velocity of the human body, the attenuation
of the ultrasonic wave is small, and if the acoustic impedance is close to the value of the skin of
the human body, the transmission / reception sensitivity of the ultrasonic wave is improved. The
composition for ultrasonic probes of the present invention can also be preferably used as an
acoustic lens material.
[0144]
The operation of the ultrasonic probe 10 having such a configuration will be described. A voltage
is applied to electrodes provided on both sides of the piezoelectric element to cause the
piezoelectric element layer 3 to resonate, and an ultrasonic signal is transmitted from the
acoustic lens to the subject. At the time of reception, the piezoelectric element layer 3 is vibrated
by a reflection signal (echo signal) from the subject, and the vibration is electrically converted
into a signal to obtain an image.
[0145]
In particular, an acoustic lens obtained from the composition for an ultrasonic probe of the
present invention can confirm a remarkable sensitivity improvement effect at a transmission
frequency of ultrasonic waves of about 5 MHz or more as a general medical ultrasonic
transducer. In particular, at the transmission frequency of ultrasonic waves of 10 MHz or more, a
particularly remarkable sensitivity improvement effect can be expected. Hereinafter, an
apparatus in which an acoustic lens obtained from the composition for an ultrasonic probe of the
present invention exerts a function particularly against the conventional problems will be
described in detail. In addition, the composition for ultrasonic probes of this invention shows the
outstanding effect also to apparatuses other than describing below.
04-05-2019
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[0146]
-Ultrasonic probe provided with cMUT (capacitive micromachine ultrasonic transducer)-When
using the cMUT device described in JP 2006-157320 A, JP 2011-71842 A etc. for a transducer
array for ultrasonic diagnosis, in general In general, its sensitivity is lower than that of a
piezoelectric ceramic (PZT) based transducer. However, by using an acoustic lens obtained from
the composition for an acoustic wave probe of the present invention, it is possible to compensate
for the lack of sensitivity of the cMUT. This allows the sensitivity of the cMUT to be close to the
performance of a conventional transducer. In addition, since the cMUT device is manufactured by
the MEMS technology, it is possible to provide a low-cost ultrasonic probe with higher mass
productivity and lower cost than the piezoelectric ceramic probe.
[0147]
-Photoacoustic wave measuring device by optical ultrasonic imaging-Photoacoustic imaging (PAI:
Photo Acoustic Imaging) described in Japanese Patent Application Laid-Open No. 2013-158435
and the like irradiates light (electromagnetic wave) to the inside of a human body and the
irradiated light The ultrasound image generated when the human body tissue adiabatically
expands is displayed or the signal intensity of the ultrasound is displayed. Here, since the sound
pressure of the ultrasonic wave generated by light irradiation is very small, there is a problem
that it is difficult to observe the deep part of the human body. However, by using an acoustic lens
obtained from the composition for an acoustic wave probe of the present invention, it is possible
to exhibit an effective effect on this problem.
[0148]
-Ultrasonic endoscope-The ultrasonic wave in the ultrasonic endoscope described in Japanese
Patent Application Laid-Open No. 2008-311700, etc., has a long signal line cable compared to
the body surface transducer due to its structure, so cable loss The problem is to improve the
sensitivity of the transducer. Moreover, it is said that there is no effective sensitivity
improvement means to this subject by the following reasons.
[0149]
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First, in the case of an ultrasonic diagnostic apparatus for body surface, an amplifier circuit, an
AD conversion IC, etc. can be installed at the tip of the transducer. On the other hand, since the
ultrasonic endoscope is used by being inserted into the body, there is no installation space for
the transducer, and installation at the tip of the transducer is difficult. Second, the piezoelectric
single crystal employed in the transducer in the ultrasonic diagnostic apparatus for body surface
is difficult to apply to a transducer having a transmission frequency of 7 to 8 MHz or more in
terms of its physical characteristics and process suitability. . However, since ultrasound for
endoscopes is generally a probe with a transmission frequency of 7 to 8 MHz or more of
ultrasound, it is also difficult to improve sensitivity by a piezoelectric single crystal material.
[0150]
However, by using an acoustic lens obtained from the composition for an acoustic wave probe of
the present invention, it is possible to improve the sensitivity of an endoscopic ultrasonic
transducer. In addition, even when using the same ultrasonic transmission frequency (for
example, 10 MHz), the effectiveness is particularly effective when using an acoustic lens obtained
from the composition for an acoustic wave probe of the present invention in an ultrasonic
transducer for endoscopes. It is exhibited.
[0151]
Hereinafter, the present invention will be described in more detail based on an embodiment
using an ultrasonic wave as an acoustic wave. Note that the present invention is not limited to
ultrasonic waves, and audio waves of audible frequencies may be used as long as appropriate
frequencies are selected according to an object to be detected, measurement conditions, and the
like.
[0152]
[Example 1] 69.4 parts by mass of vinyl-terminated polydimethylsiloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000), vinyl group-containing silicone resin
(manufactured by Gelest, "VQX-221", 30 parts by mass of xylene solvent removed product, and
0.1 parts by mass of vinyl methyl siloxane polymer (manufactured by Gelest, “VMS-T11”, mass
04-05-2019
39
average molecular weight 1,200), are kneaded using a 6-inch double roll kneader , And then 0.5
parts by mass of 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane (Nippon Oil Co., Ltd., “Perhexa
25B”) is roll mixed to form a molding compound. Prepared. This was press-molded at 165 ° C.
for 10 minutes, and secondary crosslinking was further performed at 200 ° C. for 2 hours to
obtain silicone resin sheets of 1 mm and 2 mm in thickness, respectively.
[0153]
[Example 2] 69.2 parts by mass of vinyl-terminated polydimethylsiloxane (Gelest, "DMS-V42",
mass average molecular weight 72,000) as polyorganosiloxane, vinyl group-containing silicone
resin (Gelest, "VQX" -221 ", xylene solvent removed product) 30 parts by mass, and 0.3 parts by
mass of vinyl methyl siloxane polymer (manufactured by Gelest," VMS-T11 ", mass average
molecular weight 1,200) as a siloxane compound. It processed like 1 and obtained the
predetermined | prescribed silicone resin sheet.
[0154]
[Example 3] 69.0 parts by mass of vinyl-terminated polydimethylsiloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000), vinyl group-containing silicone resin
(manufactured by Gelest, "VQX-221") Treated in the same manner as in Example 1 except that 30
parts by mass of a xylene solvent-removed product and 0.5 parts by mass of a vinyl methyl
siloxane polymer (manufactured by Gelest, "VMS-T11", mass average molecular weight 1,200)
were used. Silicone resin sheet was obtained.
[0155]
[Example 4] 67.5 parts by mass of vinyl-terminated polydimethyl siloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000) as polyorganosiloxane, vinyl groupcontaining silicone resin (manufactured by Gelest, "VQX -221 ", xylene solvent removed product)
30 parts by mass, and 2 parts by mass of vinylmethyl siloxane polymer (manufactured by Gelest,"
VMS-T11 ", mass average molecular weight 1,200) as a siloxane compound are used. It processed
similarly and obtained the predetermined silicone resin sheet.
[0156]
[Example 5] 65.5 parts by mass of vinyl-terminated polydimethyl siloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000) as polyorganosiloxane, vinyl groupcontaining silicone resin (manufactured by Gelest, "VQX -221 ", xylene solvent removed product)
30 parts by mass, and 4 parts by mass of vinyl methyl siloxane polymer (manufactured by
Gelest," VMS-T11 ", mass average molecular weight 1,200) as a siloxane compound are used. It
processed similarly and obtained the predetermined silicone resin sheet.
04-05-2019
40
[0157]
[Example 6] 69.4 parts by mass of vinyl-terminated polydimethyl siloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000) as polyorganosiloxane, vinyl groupcontaining silicone resin (manufactured by Gelest, "VQX -221 ", xylene solvent removed product)
30 parts by mass, cyclic vinylmethylsiloxane (2,4,6,8-tetramethyl-2,4,6,8tetravinylcyclotetrasiloxane as a siloxane compound, manufactured by Gelest, It processed
similarly to Example 1 except having used 0.1 mass part of "VMS-005"), and obtained the
predetermined | prescribed silicone resin sheet.
[0158]
[Example 7] 69.2 parts by mass of vinyl-terminated polydimethylsiloxane (Gelest, "DMS-V42",
mass average molecular weight 72,000) as a polyorganosiloxane, vinyl group-containing silicone
resin (Gelest, "VQX" -221 ", xylene solvent removed product) 30 parts by mass, cyclic
vinylmethylsiloxane (2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane as a siloxane
compound, manufactured by Gelest, It processed similarly to Example 1 except having used 0.3
mass part of "VMS-005"), and obtained the predetermined | prescribed silicone resin sheet.
[0159]
[Example 8] 69.0 parts by mass of vinyl-terminated polydimethyl siloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000) as polyorganosiloxane, vinyl groupcontaining silicone resin (manufactured by Gelest, "VQX -221 ", xylene solvent removed product)
30 parts by mass, cyclic vinylmethylsiloxane (2,4,6,8-tetramethyl-2,4,6,8tetravinylcyclotetrasiloxane as a siloxane compound, manufactured by Gelest, It processed
similarly to Example 1 except having used 0.5 mass part of "VMS-005"), and obtained the
predetermined | prescribed silicone resin sheet.
[0160]
[Example 9] 67.5 parts by mass of vinyl-terminated polydimethyl siloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000) as polyorganosiloxane, vinyl groupcontaining silicone resin (manufactured by Gelest, "VQX -221 ", xylene solvent removed product)
30 parts by mass, cyclic vinylmethylsiloxane (2,4,6,8-tetramethyl-2,4,6,8tetravinylcyclotetrasiloxane as a siloxane compound, manufactured by Gelest, It processed
similarly to Example 1 except having used 2 mass parts of "VMS-005", and obtained the
predetermined | prescribed silicone resin sheet.
04-05-2019
41
[0161]
[Example 10] 65.5 parts by mass of vinyl-terminated polydimethylsiloxane (Gelest, "DMS-V42",
mass average molecular weight 72,000) as polyorganosiloxane, vinyl group-containing silicone
resin (Gelest, "VQX" -221 ", xylene solvent removed product) 30 parts by mass, cyclic
vinylmethylsiloxane (2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane as a siloxane
compound, manufactured by Gelest, It processed similarly to Example 1 except having used 4
mass parts of "VMS-005", and obtained the predetermined | prescribed silicone resin sheet.
[0162]
[Example 11] 84.0 parts by mass of vinyl-terminated polydimethylsiloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000), vinyl group-containing silicone resin
(manufactured by Gelest, "VQX-221", Treated as in Example 1 except that 15 parts by mass of a
xylene solvent-removed product and 0.5 parts by mass of a vinyl methyl siloxane polymer
(manufactured by Gelest, “VMS-T11”, mass average molecular weight 1,200) were used.
Silicone resin sheet was obtained.
[0163]
[Example 12] 59.0 parts by mass of vinyl-terminated polydimethylsiloxane (manufactured by
Gelest, "DMS-V42", mass average molecular weight 72,000), vinyl group-containing silicone resin
(manufactured by Gelest, "VQX-221", Treated in the same manner as in Example 1 except that 40
parts by mass of a xylene solvent-removed product and 0.5 parts by mass of a vinylmethyl
siloxane polymer (manufactured by Gelest, "VMS-T11", mass average molecular weight 1,200)
were used. Silicone resin sheet was obtained.
[0164]
[Example 13] The same as Example 3 except that 69.0 parts by mass of vinyl-free
polydimethylsiloxane ("DMS-T41" manufactured by Gelest, weight average molecular weight
60,000) was used as the polyorganosiloxane. To obtain a predetermined silicone resin sheet.
[0165]
[Example 14] The same as Example 3 except that 69.0 parts by mass of polydimethylsiloxane
containing no vinyl group (manufactured by Gelest, "DMS-T46", mass average molecular weight
115,000) was used as the polyorganosiloxane. To obtain a predetermined silicone resin sheet.
[0166]
[Example 15] The same as Example 3 except that 69.0 parts by mass of polydimethylsiloxane
04-05-2019
42
containing no vinyl group (manufactured by Gelest, "DMS-T61", mass average molecular weight
230,000) was used as the polyorganosiloxane. To obtain a predetermined silicone resin sheet.
[0167]
[Example 16] The same as Example 3 except that 69.0 parts by mass of polydimethylsiloxane
containing no vinyl group (manufactured by Gelest, "DMS-T63", mass average molecular weight
300,000) was used as the polyorganosiloxane. To obtain a predetermined silicone resin sheet.
[0168]
Example 17 The same as Example 3 except that 69.0 parts by mass of vinyl-free
polydimethylsiloxane (Gelest “DMS-T72”, mass average molecular weight 500,000) was used
as the polyorganosiloxane. To obtain a predetermined silicone resin sheet.
[0169]
Example 18 The procedure of Example 3 was repeated except that 69.0 parts by mass of vinylterminated polydimethylsiloxane ("DMS-V31" manufactured by Gelest, weight average molecular
weight 28,000) was used as the polyorganosiloxane. , A predetermined silicone resin sheet was
obtained.
[0170]
Example 19 The procedure of Example 3 was repeated except that 69.0 parts by mass of vinylterminated polydimethylsiloxane ("DMS-V35" manufactured by Gelest, weight average molecular
weight 49, 500) was used as the polyorganosiloxane. , A predetermined silicone resin sheet was
obtained.
[0171]
Example 20 The procedure of Example 3 was repeated except that 69.0 parts by mass of vinylterminated polydimethylsiloxane ("DMS-V46" manufactured by Gelest, weight average molecular
weight 117,000) was used as the polyorganosiloxane. , A predetermined silicone resin sheet was
obtained.
[0172]
Example 21 The procedure of Example 3 was repeated except that 69.0 parts by mass of vinylterminated polydimethylsiloxane ("DMS-V52" manufactured by Gelest, weight average molecular
weight 155,000) was used as the polyorganosiloxane. , A predetermined silicone resin sheet was
04-05-2019
43
obtained.
[0173]
Example 22 A silicone resin sheet was treated in the same manner as in Example 3 except that
0.5 parts by mass of dicumyl peroxide ("PARK MIL D" manufactured by NOF Corporation) was
used as the organic peroxide. I got
[0174]
Example 23 The procedure of Example 3 was repeated except that 0.5 parts by mass of tbutylperoxybenzoate ("Perbutyl Z", manufactured by NOF Corporation) was used as the organic
peroxide, and a predetermined silicone was obtained. A resin sheet was obtained.
[0175]
[Example 24] 25 parts by mass of vinyl group-containing silicone resin ("VQX-221"
manufactured by Gelest, product from xylene solvent removed) as polyorganosiloxane resin,
fumed silica (Aerosil RX300, average primary particle diameter: 7 nm) as silica particles It
processed similarly to Example 3 except having used 5 mass parts of hexamethyldisilazane
(HMDS) surface treatment, and obtained the predetermined | prescribed silicone resin sheet.
[0176]
[Example 25] 20 parts by mass of vinyl group-containing silicone resin ("VQX-221"
manufactured by Gelest Co., product removed from xylene solvent) as polyorganosiloxane resin,
fumed silica (Aerosil RX300, average primary particle diameter: 7 nm) as silica particles It
processed similarly to Example 3 except having used 10 mass parts of hexamethyldisilazane
(HMDS) surface treatment), and obtained the predetermined | prescribed silicone resin sheet.
[0177]
[Example 26] 15 parts by mass of vinyl group-containing silicone resin ("VQX-221"
manufactured by Gelest, product from xylene solvent removed) as polyorganosiloxane resin,
fumed silica (Aerosil RX300, average primary particle diameter: 7 nm) as silica particles It
processed similarly to Example 3 except having used 15 mass parts of hexamethyldisilazane
(HMDS) surface treatment, and obtained the predetermined | prescribed silicone resin sheet.
[0178]
[Example 27] 10 parts by mass of vinyl group-containing silicone resin ("VQX-221"
04-05-2019
44
manufactured by Gelest Co., product removed from xylene solvent) as polyorganosiloxane resin,
fumed silica (Aerosil RX300, average primary particle diameter: 7 nm) as silica particles It
processed similarly to Example 3 except having used 20 mass parts of hexamethyldisilazane
(HMDS) surface treatment, and obtained the predetermined | prescribed silicone resin sheet.
[0179]
[Example 28] 15 parts by mass of vinyl group-containing silicone resin (Gelest's "VQX-221",
xylene solvent-removed product) as polyorganosiloxane resin, fumed silica as silica particles
(Nippon Aerosil Co., Ltd., "Aerosil" It processed similarly to Example 3 except having used
(registered trademark) R976S ", an average primary particle diameter of 7 nm, and 15 mass parts
of dimethyldichlorosilane (DDS surface treatment), and obtained the predetermined silicone resin
sheet.
[0180]
[Example 29] 15 parts by mass of vinyl group-containing silicone resin (manufactured by Gelest,
"VQX-221", xylene solvent-removed product) as polyorganosiloxane resin, fumed silica as silica
particles (manufactured by Nippon Aerosil Co., Ltd., "Aerosil" A predetermined silicone resin
sheet was obtained in the same manner as in Example 3 except that 15 parts by mass of
(registered trademark) 300 "(average primary particle diameter 7 nm, no surface treatment) was
used.
[0181]
[Example 30] 15 parts by mass of vinyl group-containing silicone resin (Gelest's "VQX-221",
product removed from xylene solvent) as polyorganosiloxane resin, fumed silica (silica gel
particles, manufactured by Nippon Aerosil Co., Ltd., "Aerosil" It processed similarly to Example 3
except having used (registered trademark) RX380S ", an average primary particle diameter of 5
nm, and 15 mass parts of HMDS surface treatment, and obtained the predetermined silicone
resin sheet.
[0182]
[Comparative Example 1] 99 parts by mass of vinyl-terminated polydimethylsiloxane
(manufactured by Gelest, "DMS-V42", mass average molecular weight 72,000), vinylmethyl
siloxane polymer (manufactured by Gelest, "VMS-T11", mass average molecular weight The same
processing as in Example 1 was carried out except that 0.5 parts by mass of (1,200) was used, to
obtain a predetermined silicone resin sheet.
04-05-2019
45
[0183]
Comparative Example 2 69.5 parts by mass of vinyl-terminated polydimethylsiloxane
(manufactured by Gelest, “DMS-V42”, mass average molecular weight 72,000), vinyl groupcontaining silicone resin (manufactured by Gelest, “VQX-221”, It processed similarly to
Example 1 except having set it as 30 mass parts of xylene solvent removal goods, and obtained
the predetermined | prescribed silicone resin sheet.
[0184]
Comparative Example 3 The same processing as in Example 1 was repeated except that only 99.5
parts by mass of vinyl-terminated polydimethylsiloxane (manufactured by Gelest, “DMS-V42”,
mass average molecular weight 72,000) was used, and a predetermined silicone was obtained. A
resin sheet was obtained.
[0185]
Comparative Example 4 61.5 parts by mass of vinyl-terminated polydimethylsiloxane
(manufactured by Gelest, “DMS-V42”, mass average molecular weight 72,000), vinyl groupcontaining silicone resin (manufactured by Gelest, “VQX-221”, Treated in the same manner as
in Example 1 except that 30 parts by mass of a xylene solvent-removed product and 8.0 parts by
mass of a vinyl methyl siloxane polymer (manufactured by Gelest, “VMS-T11”, mass average
molecular weight 1,200) were used. Silicone resin sheet was obtained.
[0186]
<Evaluation of mechanical strength and ultrasonic characteristics> The following evaluations
were performed on the silicone resin sheets of Examples 1 to 30 and Comparative Examples 1 to
4.
[0187]
[Hardness] With respect to the obtained silicone resin sheet having a thickness of 2 mm, the type
A durometer hardness was measured using a rubber hardness meter ("RH-201A" manufactured
by Excell Co., Ltd.) according to JIS K6253-3 (2012).
[0188]
[Tear strength test] With respect to the obtained silicone resin sheet having a thickness of 2 mm,
a trousers type test piece was produced according to JIS K6252 (2007), and tear strength was
measured.
04-05-2019
46
[0189]
[Bending Fatigue Test] The number of bending at which a third-class crack is generated was
measured in accordance with JIS K6260 (2010) for the obtained 1 mm-thick silicone resin sheet.
[0190]
[Acoustic Impedance] The obtained silicone resin sheet having a thickness of 2 mm was
subjected to an electron densitometer (alpha mirage) according to the density measurement
method of Method A (substitution method in water) described in JIS K7112 (1999). It measured
using company make, "SD-200L").
Ultrasonic sound velocity is measured at 25 ° C. using a single-around sound velocity measuring
apparatus (“UVM-2 type” manufactured by Ultrasonic Industry Co., Ltd.) according to JIS Z
2353 (2003), and the product of the measured density and sound velocity The acoustic
impedance was obtained from
[0191]
[Acoustic wave (ultrasonic wave) sensitivity] Ultrasonic probe (Japan Probe Co., Ltd.) a 5 MHz
sine wave signal (one wave) output from an ultrasonic wave oscillator (function generator "FG350" manufactured by Iwatsuru Ltd.) An ultrasonic pulse wave with a center frequency of 5 MHz
was generated in water from an ultrasonic probe.
The amplitude of the generated ultrasonic waves before and after passing through the obtained 2
mm-thick silicone resin sheet was measured by using an ultrasonic wave receiver (oscilloscope
"VP-5204A" manufactured by Matsushita Electric Industrial Co., Ltd.). The acoustic wave
(ultrasonic wave) attenuation of each material was compared by measuring in an environment of
25 ° C. and comparing the acoustic wave (ultrasonic wave) sensitivity.
As for the acoustic wave (ultrasonic wave) sensitivity, the generated acoustic wave (ultrasonic
wave) passes through the sheet with respect to the voltage peak value Vin of the input wave
having a half width of 50 nsec or less by the ultrasonic oscillator, and The voltage value obtained
when the ultrasonic wave generator receives the reflected acoustic wave (ultrasound) is Vs, and
04-05-2019
47
the voltage is calculated according to the following equation.
[0192]
Acoustic wave (ultrasonic) sensitivity = 20 x Log (Vs / Vin)
[0193]
The obtained results are summarized and shown in Tables 1 to 3 below.
In Tables 1 to 3 below, polyorganosiloxane (A), organic peroxide (B), polyorganosiloxane resin
(C), organosiloxane compound (D), and silica (E having an average primary particle diameter of
less than 12 nm) ) Are abbreviated as components (A) to (E), respectively, and the mass average
molecular weight of polyorganosiloxane (A) is simply described as molecular weight.
Moreover, the kind of each material described the brand name.
In addition, the trade name of a silica particle (E) abbreviate | omitted and described Aerosil
(trademark).
[0194]
[0195]
[0196]
[0197]
As shown in Tables 1 to 3, the silicone resins for acoustic wave probes of Examples 1 to 30 all
have high resin hardness, tear strength and bending resistance while maintaining acoustic wave
(ultrasonic wave) sensitivity of -75 dB or more. I was able to get fatigue.
04-05-2019
48
On the other hand, the silicone resin for acoustic wave probe of Comparative Example 1
containing no polyorganosiloxane resin (C) and the acoustic wave probe of Comparative Example
3 containing neither a polyorganosiloxane resin (C) nor an organosiloxane compound (D) The
silicone resins for all had insufficient resin hardness and tear strength.
In addition, the silicone resin for an acoustic wave probe of Comparative Example 2 containing
no organosiloxane compound (D) and the silicone resin for an acoustic wave probe of
Comparative Example 4 having a high content of the organosiloxane compound (D) all have tear
strength and The bending fatigue resistance was not sufficient.
[0198]
From this result, the composition for acoustic wave probes of the present invention is useful for
medical members, and can be suitably used for the method for producing a silicone resin of the
present invention.
The silicone resin of the present invention can also be suitably used for an acoustic lens and / or
an acoustic matching layer of an acoustic wave probe, and an acoustic wave measurement device
and an ultrasonic diagnostic device.
In particular, the composition for an acoustic wave probe and the silicone resin for an acoustic
wave probe are used for the purpose of improving sensitivity in an ultrasonic probe, a
photoacoustic wave measuring apparatus and an ultrasonic endoscope using cMUT as a
transducer array for ultrasonic diagnosis. It can be used suitably.
[0199]
1 acoustic lens 2 acoustic matching layer 3 piezoelectric element layer 4 backing material 7
housing 9 code 10 ultrasonic probe (probe)
04-05-2019
49
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