JP2020074838A - Ultrasonic propagation component, and manufacturing method thereof - Google Patents
Ultrasonic propagation component, and manufacturing method thereof Download PDFInfo
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- JP2020074838A JP2020074838A JP2018208761A JP2018208761A JP2020074838A JP 2020074838 A JP2020074838 A JP 2020074838A JP 2018208761 A JP2018208761 A JP 2018208761A JP 2018208761 A JP2018208761 A JP 2018208761A JP 2020074838 A JP2020074838 A JP 2020074838A
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- Prior art keywords
- ultrasonic wave
- wave propagation
- propagation member
- ultrasonic
- forming
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Abstract
Description
本発明は、超音波伝搬部材及び超音波伝搬部材の製造方法に関する。 The present invention relates to an ultrasonic wave propagation member and a method for manufacturing an ultrasonic wave propagation member.
超音波診断は、超音波受信機を人体表面に当接させて、人体内部からでてくる超音波を受信して行うものである。この際、超音波受信機をそのまま人体表面に当てると、超音波受信機と人体表面の間に空気が介在するので、超音波伝搬の障害となり、診断ができなくなる場合がある。 Ultrasonic diagnosis is performed by bringing an ultrasonic receiver into contact with the surface of a human body and receiving ultrasonic waves coming from inside the human body. At this time, if the ultrasonic receiver is directly applied to the surface of the human body, air may be present between the ultrasonic receiver and the surface of the human body, which may hinder the propagation of ultrasonic waves and make diagnosis impossible.
この点を防止するために、超音波受信機と人体表面の間に、人体と音響インピーダンスが近いゲル状物質（ゼリー）を介在させて診断を行っている。しかし、ゲル状物質は取り扱いが不便であり、一般的にはチューブなどに収納され、使用時に人体表面に直接付与する。このゲル状物質は非常に粘着質であり、被験者に不快感を与える。また、使用後の拭き取りも困難であり、非常に煩わしいという問題がある。
前記問題点を解決するため、例えば、高分子含水ゲルからなる超音波ゲルシートが提案されている（例えば、特許文献１参照）。
In order to prevent this point, a gel substance (jelly) having an acoustic impedance close to that of the human body is interposed between the ultrasonic receiver and the surface of the human body for diagnosis. However, the gel-like substance is inconvenient to handle, and is generally stored in a tube or the like and applied directly to the human body surface during use. This gel-like substance is very sticky and makes the subject uncomfortable. Further, there is a problem that it is difficult to wipe off after use and it is very troublesome.
In order to solve the above problems, for example, an ultrasonic gel sheet made of a polymer hydrogel has been proposed (see, for example, Patent Document 1).
本発明は、被検査対象の表面に隙間なく密着できると共に、検査後の後処理を不要もしくは簡便にできる超音波伝搬部材を提供することを目的とする。 It is an object of the present invention to provide an ultrasonic wave propagation member that can be adhered to the surface of an object to be inspected without any gaps and that requires no or simple post-treatment after inspection.
前記課題を解決するための手段としての本発明の超音波伝搬部材は、少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なる。 An ultrasonic wave propagating member of the present invention as a means for solving the above problems is an ultrasonic wave propagating member having at least two surfaces, and the hardness of one surface is different from the hardness of the other surface.
本発明によると、被検査対象の表面に隙間なく密着できると共に、検査後の後処理を不要もしくは簡便にできる超音波伝搬部材を提供することができる。 According to the present invention, it is possible to provide an ultrasonic wave propagation member that can be closely attached to the surface of an object to be inspected without a gap and that can be post-processed after the inspection is unnecessary or simple.
（超音波伝搬部材）
本発明の超音波伝搬部材は、少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なる。
(Ultrasonic wave propagation member)
The ultrasonic wave propagating member of the present invention is an ultrasonic wave propagating member having at least two surfaces, and the hardness of one surface is different from the hardness of the other surface.
従来の超音波診断に用いられる超音波伝搬部材では、流動性ゲル（ゼリー）を被験者の皮膚表面に出し、これを超音波受信機で引き延ばし、皮膚表面に塗布して使用する。図１に示すように、流動性ゲル２を塗布した被験者の皮膚１の表面に超音波受信機３を当接させ、流動性ゲル２により両者の間に空気（空隙）が存在しないようにしながら診断を行う。このような流動性ゲルを用いる場合、被験者が変わるごとに、あるいは診断部位を変えるごとに流動性ゲルを塗布しなければならない。また、この流動性ゲルはベタベタした触感があり、被験者にとっては気持ち悪く感じる場合が多く、また、人体から拭き取る作業が必要になり、非常に煩雑であるという欠点がある。 In the conventional ultrasonic wave propagation member used for ultrasonic diagnosis, a fluid gel (jelly) is exposed on the skin surface of a subject, stretched by an ultrasonic wave receiver, and applied to the skin surface for use. As shown in FIG. 1, while the ultrasonic receiver 3 is brought into contact with the surface of the subject's skin 1 to which the fluid gel 2 has been applied, the fluid gel 2 prevents air (void) between the two. Make a diagnosis. When such a fluid gel is used, the fluid gel must be applied every time the subject changes or the diagnostic site changes. In addition, this fluid gel has a sticky feel and is often uncomfortable for the subject, and it has a drawback that it requires a work of wiping it from the human body and is very complicated.
また、従来技術では、図１に示すような流動性ゲル２を、図２に示すようなゲルシート５に変更した形態が知られている。この場合、ゲルシート５を被験者の皮膚１の表面に置いて、超音波受信機で押し付け、ゲルシート５を密着させるようにして診断を行う。
このゲルシート５は、型を用い作製した平板状の形状を有するものであるため、被験者の皮膚１の表面に隙間なく完全に密着させることは難しく、図２に示すように、皮膚表面に凸部４を有する場合には空隙６が生じ気泡が入りやすいという欠点がある。気泡が入りにくくするためには、超音波受信機を人体に強く押し付けることになるため、部位によっては被験者に苦痛を与えることもある。
In addition, in the prior art, a form is known in which the fluid gel 2 as shown in FIG. 1 is replaced with a gel sheet 5 as shown in FIG. In this case, the gel sheet 5 is placed on the surface of the subject's skin 1 and pressed by an ultrasonic receiver to bring the gel sheet 5 into close contact for diagnosis.
Since this gel sheet 5 has a flat plate shape produced by using a mold, it is difficult to completely adhere it to the surface of the skin 1 of the subject without any gap, and as shown in FIG. In the case of having 4, there is a drawback that voids 6 are generated and bubbles easily enter. In order to make it difficult for air bubbles to enter, the ultrasonic receiver is strongly pressed against the human body, which may cause pain to the subject depending on the site.
したがって、本発明の超音波伝搬部材は、以上のような知見に基づき発明されたものであり、少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なることにより、被検査対象である被験者の不快感を解消し、検査後の後処理も不要とする。また、操作性においても、密着性に優れ、スムーズに超音波診断を行えるものである。 Therefore, the ultrasonic wave propagating member of the present invention was invented based on the above knowledge, and is an ultrasonic wave propagating member having at least two surfaces, and the hardness of one surface and the hardness of the other surface. The difference in hardness eliminates the discomfort of the subject to be inspected and eliminates the need for post-treatment after inspection. Also, in terms of operability, the adhesiveness is excellent, and ultrasonic diagnosis can be performed smoothly.
被検査対象としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、超音波診断における被験者などが挙げられる。 The subject to be inspected is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a subject in ultrasonic diagnosis.
本発明の超音波伝搬部材は、少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なること特徴とし、前記他方の面が、前記一方の面に対向する面であることが好ましい。前記一方の面が超音波受信機に接する面であり、前記他方の面が被検査対象に接する面であることが好ましく、超音波受信機に接する面の硬度が、被検査対象に接する面の硬度よりも大きいことが好ましい。
超音波伝搬部材を被検査対象である被験者の人体表面に接触させる場合には、図３に示すように、超音波伝搬部材７の硬度が小さいほうが皮膚表面に凸部４を有する場合にも変形を伴って密着しやすい。しかしながら、超音波伝搬部材全体をその硬度に設定すると柔らかすぎてハンドリングが難しくなるだけでなく、超音波受信機の動き（表面を滑らせる）を妨げることになる。このため、超音波受信機側はある程度高い硬度が必要である。
このような構造を作るためには、２つの方式がある。１つは、超音波伝搬部材を積層構造として、硬度の異なる層５１、５２を複数積層することである（図４参照）。もう１つは、片方の面から反対側の面にかけて、漸次硬度が変化する傾斜構造を有する超音波伝搬部材５３を形成することである（図５参照）。
An ultrasonic wave propagating member of the present invention is an ultrasonic wave propagating member having at least two surfaces, characterized in that the hardness of one surface is different from the hardness of the other surface, and the other surface is one of the above. It is preferable that the surface is opposite to the surface. The one surface is a surface in contact with the ultrasonic receiver, preferably the other surface is a surface in contact with the object to be inspected, the hardness of the surface in contact with the ultrasonic receiver, the surface of the surface in contact with the object to be inspected It is preferably larger than the hardness.
When the ultrasonic wave propagating member is brought into contact with the human body surface of the subject to be inspected, as shown in FIG. 3, the ultrasonic wave propagating member 7 having a lower hardness is deformed even when the convex portion 4 is provided on the skin surface. It is easy to adhere with. However, if the hardness of the entire ultrasonic wave propagation member is set, it will be too soft and difficult to handle, and it will also hinder the movement (sliding of the surface) of the ultrasonic wave receiver. Therefore, the ultrasonic receiver side needs to have a certain degree of hardness.
There are two methods to make such a structure. One is that the ultrasonic wave propagation member has a laminated structure and a plurality of layers 51 and 52 having different hardnesses are laminated (see FIG. 4). The other is to form the ultrasonic wave propagation member 53 having an inclined structure in which the hardness gradually changes from one surface to the opposite surface (see FIG. 5).
本発明の超音波伝搬部材は、ハンドリング性、人体への密着性などを考慮すると、適度な硬さを有する必要がある。本発明の超音波伝搬部材のようにかなり柔かく、靭性を有するような材料（部材）の場合、硬度を定量化することが難しいが、ヤング率で規定することが可能である。
ヤング率は、例えば、機械的試験法、共振法、超音波パルス法などの方法により求めることができるが、本発明のようにかなり柔かい材料の場合には、簡便的に測定できる機械的試験法が有用である。
The ultrasonic wave propagation member of the present invention is required to have an appropriate hardness in consideration of handling property, adhesion to a human body, and the like. In the case of a material (member) that is considerably soft and has toughness like the ultrasonic wave propagating member of the present invention, it is difficult to quantify the hardness, but it is possible to specify it by Young's modulus.
The Young's modulus can be determined by, for example, a mechanical test method, a resonance method, an ultrasonic pulse method, or the like. However, in the case of a considerably soft material like the present invention, a mechanical test method that can be simply measured. Is useful.
本発明の超音波伝搬部材は、少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なることが一つの特徴である。前記一方の面が超音波受信機に接する面であり、前記他方の面が被検査対象に接する面であることが好ましい。
被検査対象に接する面においては、次のことが言える。ヤング率が小さすぎる場合、自重により形状を維持できなくなり、超音波伝搬部材としての機能を果たせず、逆にヤング率が大きすぎる場合には、被検査対象である人体への密着性が悪化することが起こり得る。このため、被検査対象に接する面の硬度は、ヤング率で０．５ｋＰａ以上３０ｋＰａ以下が好ましく、１ｋＰａ以上２０ｋＰａ以下がより好ましい。
一方、超音波受信機に接する面においては、ヤング率が小さすぎる場合には、超音波受信機が超音波伝搬部材表面を滑らかに動かすことができなくなり、診断そのものに影響を与える。逆に硬すぎる場合には超音波受信機との密着性が悪くなり、超音波伝搬部材としての機能を果たしにくくなる。このため、超音波受信機に接する面の硬度は、ヤング率で１０ｋＰａ以上２００ｋＰａ以下が好ましく、２０ｋＰａ以上１００ｋＰａ以下がより好ましい。
The ultrasonic wave propagating member of the present invention is an ultrasonic wave propagating member having at least two surfaces, and one of the characteristics is that the hardness of one surface is different from the hardness of the other surface. It is preferable that the one surface is a surface in contact with the ultrasonic receiver and the other surface is a surface in contact with an object to be inspected.
The following can be said with respect to the surface in contact with the object to be inspected. If the Young's modulus is too small, the shape cannot be maintained due to its own weight, and it cannot function as an ultrasonic wave propagating member. Conversely, if the Young's modulus is too large, the adhesion to the human body to be inspected deteriorates. Can happen. Therefore, the hardness of the surface in contact with the object to be inspected is preferably 0.5 kPa or more and 30 kPa or less in Young's modulus, and more preferably 1 kPa or more and 20 kPa or less.
On the other hand, when the Young's modulus is too small on the surface in contact with the ultrasonic receiver, the ultrasonic receiver cannot move the surface of the ultrasonic wave propagating member smoothly, which affects the diagnosis itself. On the other hand, if it is too hard, the adhesion with the ultrasonic receiver becomes poor and it becomes difficult to perform the function of the ultrasonic wave propagation member. Therefore, the hardness of the surface in contact with the ultrasonic receiver is preferably 10 kPa or more and 200 kPa or less in Young's modulus, and more preferably 20 kPa or more and 100 kPa or less.
本発明の超音波伝搬部材は、該超音波伝搬部材の被検査対象に接する面が、前記被検査対象表面に沿った形状を有することが好ましい。これにより、被検査対象である被験者の皮膚に隙間なくフィットした超音波伝搬部材が形成できる。
ここで、超音波伝搬部材の被検査対象に接する面が、被検査対象表面に沿った形状を有するとは、被検査対象表面の凹部又は凸部のそれぞれに対して凸部又は凹部となるような一定の形状を保持していることを意味し、被検査対象の凹凸に強く押付けて密着させる（凹凸に沿わせるように形状変化させる）ようなことは必要がない。例えば、超音波診断用途であれば、被験者となる人体の検査対象部位の凹凸に対応する形状を当初から有する超音波伝搬部材を用い、これを当該検査対象部位に位置合わせして配置するだけでよく、また診断時の多少の動きには追従するため、正確かつ迅速な超音波診断に寄与しうる。
In the ultrasonic wave propagating member of the present invention, it is preferable that the surface of the ultrasonic wave propagating member that is in contact with the object to be inspected has a shape along the surface of the object to be inspected. This makes it possible to form an ultrasonic wave propagation member that fits closely to the skin of the subject to be inspected.
Here, the surface of the ultrasonic wave propagating member in contact with the object to be inspected has a shape along the surface to be inspected means that it is a convex portion or a concave portion with respect to the concave portion or the convex portion of the surface to be inspected, respectively. It means that a certain constant shape is held, and it is not necessary to strongly press the unevenness of the object to be inspected to bring it into close contact (change the shape so as to follow the unevenness). For example, in the case of ultrasonic diagnostic use, an ultrasonic wave propagation member having a shape corresponding to the unevenness of the examination target portion of the human body to be tested from the beginning is used, and it is simply arranged by aligning it with the examination target portion. Good, and because it follows some movements during diagnosis, it can contribute to accurate and rapid ultrasonic diagnosis.
本発明の超音波伝搬部材は、水と、ポリマーと、鉱物とを含み、有機溶媒を含むことが好ましく、更に必要に応じてその他の成分を含む。
超音波伝搬部材は、有機溶媒に分散された鉱物と、重合性モノマーが重合したポリマーとが架橋して、複合化して形成された三次元網目構造の中に、溶媒が包含されているハイドロゲルからなることが好ましい。
The ultrasonic wave propagation member of the present invention contains water, a polymer, and a mineral, preferably contains an organic solvent, and further contains other components as necessary.
The ultrasonic wave propagation member is a hydrogel in which a solvent is contained in a three-dimensional network structure formed by crosslinking a mineral dispersed in an organic solvent and a polymer obtained by polymerizing a polymerizable monomer to form a composite. It is preferable that
−ポリマー−
前記ポリマーとしては、例えば、アミド基、アミノ基、水酸基、テトラメチルアンモニウム基、シラノール基、エポキシ基などを有するポリマーが挙げられ、水溶性であることが好ましい。
前記ポリマーは、ホモポリマー（単独重合体）であってもよいし、ヘテロポリマー（共重合体）であってもよく、また、変性されていてもよいし、公知の官能基が導入されていてもよく、また塩の形態であってもよいが、ホモポリマーが好ましい。
本発明において、前記ポリマーの水溶性とは、例えば、３０℃の水１００ｇに該ポリマーを１ｇ混合して撹拌したとき、その９０質量％以上が溶解するものを意味する。
前記ポリマーは、重合性モノマーを重合させることにより得られる。なお、前記重合性モノマーについては、後述する超音波伝搬部材の製造方法において説明する。
-Polymer-
Examples of the polymer include polymers having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group, and the like, and are preferably water-soluble.
The polymer may be a homopolymer (homopolymer) or a heteropolymer (copolymer), may be modified, and has a known functional group introduced. Although it may be in the form of a salt or a salt, a homopolymer is preferable.
In the present invention, the water solubility of the polymer means, for example, when 1 g of the polymer is mixed with 100 g of water at 30 ° C. and stirred, 90% by mass or more thereof is dissolved.
The polymer is obtained by polymerizing a polymerizable monomer. The polymerizable monomer will be described in the method of manufacturing an ultrasonic wave propagation member described later.
−水−
前記水としては、例えば、イオン交換水、限外濾過水、逆浸透水、蒸留水等の純水、又は超純水を用いることができる。
前記水の含有量は、超音波伝搬性の点から、超音波伝搬部材の全量に対して、７０質量％以上９５質量％以下が好ましく、７５質量％以上９０質量％以下がより好ましい。
なお、水には、保湿性付与、抗菌性付与、導電性付与、硬度調整等の目的に応じて有機溶媒などのその他の成分を溶解乃至分散させてもよい。
-Water-
As the water, for example, deionized water, ultrafiltered water, reverse osmosis water, distilled water, or other pure water, or ultrapure water can be used.
From the viewpoint of ultrasonic wave propagation, the water content is preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 90% by mass or less with respect to the total amount of the ultrasonic wave propagation member.
In addition, other components such as an organic solvent may be dissolved or dispersed in water depending on the purpose of imparting moisturizing property, imparting antibacterial property, imparting conductivity, adjusting hardness, and the like.
−鉱物−
前記鉱物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水膨潤性層状粘土鉱物などが挙げられる。
前記水膨潤性層状粘土鉱物は、単一層の状態で水に分散した図６の上図に示すように、単位格子を結晶内に持つ二次元円盤状の結晶が積み重なった状態を呈しており、前記水膨潤性層状粘土鉱物を水中で分散させると、図６の下図に示すように、各単一層状態で分離して円盤状の結晶となる。
− Minerals −
The mineral is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a water-swellable layered clay mineral.
The water-swellable layered clay mineral has a state in which two-dimensional disc-shaped crystals having a unit cell in the crystal are stacked as shown in the upper diagram of FIG. 6 dispersed in water in a single layer state, When the water-swellable layered clay mineral is dispersed in water, as shown in the lower diagram of FIG. 6, it separates into a single layer state to form a disk-shaped crystal.
前記水膨潤性層状粘土鉱物としては、例えば、水膨潤性スメクタイト、水膨潤性雲母などが挙げられる。より具体的には、ナトリウムを層間イオンとして含む水膨潤性ヘクトライト、水膨潤性モンモリナイト、水膨潤性サポナイト、水膨潤性合成雲母などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、高弾性の超音波伝搬部材が得られる点から、水膨潤性ヘクトライトが好ましい。
前記水膨潤性ヘクトライトは、適宜合成したものであってもよいし、市販品であってもよい。前記市販品としては、例えば、合成ヘクトライト（ラポナイトＸＬＧ、ＲｏｃｋＷｏｏｄ社製）、ＳＷＮ（Ｃｏｏｐ Ｃｈｅｍｉｃａｌ Ｌｔｄ．製）、フッ素化ヘクトライトＳＷＦ（Ｃｏｏｐ Ｃｈｅｍｉｃａｌ Ｌｔｄ．製）などが挙げられる。これらの中でも、超音波伝搬部材の弾性率の点から、合成ヘクトライトが好ましい。
前記水膨潤性とは、図６に示すように層状粘土鉱物の層間に水分子が挿入され、水中に分散されることを意味する。
Examples of the water-swellable layered clay mineral include water-swellable smectite and water-swellable mica. More specifically, water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable saponite, water-swellable synthetic mica, etc. may be mentioned. These may be used alone or in combination of two or more. Among these, water-swellable hectorite is preferable because a highly elastic ultrasonic wave propagation member can be obtained.
The water-swellable hectorite may be appropriately synthesized or may be a commercially available product. Examples of the commercially available product include synthetic hectorite (Laponite XLG, manufactured by Rockwood), SWN (manufactured by Coop Chemical Ltd.), and fluorinated hectorite SWF (manufactured by Coop Chemical Ltd.). Among these, synthetic hectorite is preferable from the viewpoint of the elastic modulus of the ultrasonic wave propagation member.
The water swelling property means that water molecules are inserted between layers of the layered clay mineral and dispersed in water as shown in FIG.
前記鉱物の含有量は、超音波伝搬部材の弾性率及び硬度の点から、超音波伝搬部材の全量に対して、１質量％以上４０質量％以下が好ましく、１質量％以上２５質量％以下がより好ましい。 The content of the mineral is preferably 1% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 25% by mass or less, with respect to the total amount of the ultrasonic wave propagation member, from the viewpoint of elastic modulus and hardness of the ultrasonic wave propagation member. More preferable.
−有機溶媒−
前記有機溶媒は、超音波伝搬部材の保湿性を高めるために含有される。
前記有機溶媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール等の炭素数１〜４のアルキルアルコール類；ジメチルホルムアミド、ジメチルアセトアミド等のアミド類；アセトン、メチルエチルケトン、ジアセトンアルコール等のケトン又はケトンアルコール類；テトラヒドロフラン、ジオキサン等のエーテル類；エチレングリコール、プロピレングリコール、１，２−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ジエチレングリコール、トリエチレングリコール、１，２，６−ヘキサントリオール、チオグリコール、ヘキシレングリコール、グリセリン等の多価アルコール類；ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール類；エチレングリコールモノメチル（又はエチル）エーテル、ジエチレングリコールメチル（又はエチル）エーテル、トリエチレングリコールモノメチル（又はエチル）エーテル等の多価アルコールの低級アルコールエーテル類；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類；Ｎ−メチル−２−ピロリドン、２−ピロリドン、１，３−ジメチル−２−イミダゾリジノンなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、保湿性の点から、多価アルコールが好ましく、グリセリン、プロピレングリコールがより好ましい。
-Organic solvent-
The organic solvent is contained in order to enhance the moisture retention property of the ultrasonic wave propagation member.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. Alkyl alcohols having 1 to 4 carbon atoms such as butyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone, methyl ethyl ketone, diacetone alcohol; ethers such as tetrahydrofuran and dioxane; ethylene glycol, Propylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2,6-hexanetriol, thioglycol, Polyhydric alcohols such as xylene glycol and glycerin; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, etc. Lower alcohol ethers of polyhydric alcohols; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Can be mentioned. These may be used alone or in combination of two or more. Among these, polyhydric alcohols are preferable, and glycerin and propylene glycol are more preferable, from the viewpoint of moisture retention.
前記有機溶媒の含有量は、超音波伝搬部材の全量に対して、１０質量％以上５０質量％以下が好ましい。前記含有量が、１０質量％以上であると、乾燥防止の効果が十分に得られる。また、５０質量％以下であると、層状粘土鉱物が均一に分散される。
前記有機溶媒の含有量が、１０質量％以上５０質量％以下であると、人体の組成からのずれが小さく、超音波伝搬部材としての良好な機能が得られる。
The content of the organic solvent is preferably 10% by mass or more and 50% by mass or less with respect to the total amount of the ultrasonic wave propagation member. When the content is 10% by mass or more, the effect of preventing drying can be sufficiently obtained. Moreover, when it is 50 mass% or less, the layered clay mineral is uniformly dispersed.
When the content of the organic solvent is 10% by mass or more and 50% by mass or less, the deviation from the composition of the human body is small, and a good function as an ultrasonic wave propagation member can be obtained.
−その他の成分−
前記その他の成分としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、１−ヒドロキシエタン−１，１−ジホスホン酸等のホスホン酸化合物、安定化剤、表面処理剤、重合開始剤、着色剤、粘度調整剤、接着性付与剤、酸化防止剤、老化防止剤、架橋促進剤、紫外線吸収剤、可塑剤、防腐剤、分散剤などが挙げられる。
-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phosphonic acid compounds such as 1-hydroxyethane-1,1-diphosphonic acid, stabilizers, surface treatment agents, Examples thereof include a polymerization initiator, a colorant, a viscosity modifier, an adhesiveness-imparting agent, an antioxidant, an antioxidant, a crosslinking accelerator, an ultraviolet absorber, a plasticizer, a preservative, and a dispersant.
＜皮膜＞
前記超音波伝搬部材の表面には、下記３つの目的から皮膜を設けることが有効である。
（１）超音波伝搬部材の形状を維持する。
（２）超音波伝搬部材の保存性（耐乾燥性、防腐性）を向上する。
（３）超音波伝搬部材の外観性を改善する。
<Film>
It is effective to provide a film on the surface of the ultrasonic wave propagation member for the following three purposes.
(1) Maintain the shape of the ultrasonic wave propagation member.
(2) The preservability (drying resistance and antiseptic property) of the ultrasonic wave propagation member is improved.
(3) To improve the appearance of the ultrasonic wave propagation member.
前記超音波伝搬部材の形状を維持するためには、前記超音波伝搬部材の自重による崩壊を防ぐため、皮膜に弾性力をもたせることが好ましい。前記皮膜の有無における超音波伝搬部材の硬度（ヤング率）の差が０．０１ＭＰａ以上であることが好ましい。
前記皮膜形成材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリエステル、ポリオレフィン、ポリエチレンテレフタレート、ＰＰＳ、ポリプロピレン、ポリビニルアルコール（ＰＶＡ）、ポリエチレン、ポリ塩化ビニル、セロハン、アセテート、ポリスチレン、ポリカーボネート、ナイロン、ポリイミド、フッ素樹脂、パラフィンワックスなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
前記皮膜形成材料としては、市販品を用いることができ、前記市販品として、例えば、プラスティコート＃１００（大京化学株式会社製）、ポバール２０５（株式会社クラレ製）などが挙げられる。
前記皮膜の膜厚としては、特に制限はなく、目的に応じて適宜選択することができるが、１００μｍ以下が好ましく、１０μｍ以上５０μｍ以下がより好ましい。前記膜厚が１００μｍ以下であると、超音波伝搬部材を構成するハイドロゲルの質感を保つことができる点で有利である。
In order to maintain the shape of the ultrasonic wave propagating member, it is preferable to impart elastic force to the film in order to prevent the ultrasonic wave propagating member from collapsing due to its own weight. The difference in hardness (Young's modulus) of the ultrasonic wave propagating member with or without the film is preferably 0.01 MPa or more.
The film forming material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyester, polyolefin, polyethylene terephthalate, PPS, polypropylene, polyvinyl alcohol (PVA), polyethylene, polyvinyl chloride and cellophane. Examples thereof include acetate, polystyrene, polycarbonate, nylon, polyimide, fluororesin, and paraffin wax. These may be used alone or in combination of two or more.
As the film-forming material, a commercially available product can be used, and examples of the commercially available product include Plasticoat # 100 (manufactured by Daikyo Chemical Co., Ltd.) and Poval 205 (manufactured by Kuraray Co., Ltd.).
The film thickness of the film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 μm or less, more preferably 10 μm or more and 50 μm or less. When the film thickness is 100 μm or less, it is advantageous in that the texture of the hydrogel forming the ultrasonic wave propagation member can be maintained.
前記超音波伝搬部材の表面に皮膜を形成することで、超音波伝搬部材の外観性を改善することができる。例えば、超音波伝搬部材の表面に傷や表面荒れが存在する場合には皮膜により外観性を補うことができる。また、表面の皮膜が犠牲層となることで、内部の超音波伝搬部材を保護することができる。
前記超音波伝搬部材の表面はマーキングなどの記入を行うことができないので、超音波伝搬部材の表面に皮膜を形成することにより、超音波診断時の手順や測定部位、被験者名などを書き込むことができるため、超音波伝搬部材に機能を付与することができる。
By forming a film on the surface of the ultrasonic wave propagation member, the appearance of the ultrasonic wave propagation member can be improved. For example, when there are scratches or surface roughness on the surface of the ultrasonic wave propagation member, the appearance can be supplemented by a film. In addition, since the film on the surface serves as a sacrificial layer, the ultrasonic wave propagating member inside can be protected.
Since the surface of the ultrasonic wave propagating member cannot be filled with markings or the like, by forming a film on the surface of the ultrasonic wave propagating member, it is possible to write the procedure, measurement site, subject name, etc. at the time of ultrasonic diagnosis. Therefore, it is possible to impart a function to the ultrasonic wave propagation member.
前記皮膜の形成方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、前記皮膜形成材料を溶媒に溶解して、超音波伝搬部材の表面に塗布する方法などが挙げられる。前記塗布方法としては、例えば、刷毛、スプレー、浸漬塗工などが挙げられる。
また、前記皮膜形成材料として熱収縮フィルムを用い、超音波伝搬部材の表面にラミネートする方法が挙げられる。
また、前記皮膜形成材料を溶剤に溶解して、超音波伝搬部材形成用液体材料を用いて三次元プリンターで超音波伝搬部材を造形する際に同時に皮膜を形成してもよい。
いずれの場合も、皮膚への密着性が重要であるため、被験者個人の放射線照射対象となる体表面の三次元データに基づき作製した超音波伝搬部材表面形状を損ねることの無い皮膜を形成することが肝要である。
The method for forming the film is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a method in which the film forming material is dissolved in a solvent and applied to the surface of the ultrasonic wave propagation member. Be done. Examples of the coating method include brush, spray, and dip coating.
Further, a method of using a heat shrinkable film as the film forming material and laminating it on the surface of the ultrasonic wave propagation member can be mentioned.
Further, the coating film-forming material may be dissolved in a solvent, and the coating film may be formed at the same time when the ultrasonic wave propagation member is formed by a three-dimensional printer using the liquid material for forming the ultrasonic wave propagation member.
In any case, since adhesion to the skin is important, form a film that does not damage the surface shape of the ultrasonic wave propagation member created based on the three-dimensional data of the body surface to be irradiated by the individual subject. Is essential.
超音波伝搬部材の保存性を向上させるには、耐乾燥性及び防腐性を向上させる必要がある。
前記耐乾燥性を向上させるには皮膜の水蒸気透過度や酸素透過度を低減することが効果的である。具体的には、超音波伝搬部材の水蒸気透過度（ＪＩＳ Ｋ７１２９）は５００ｇ／ｍ２・ｄａｙ以下であることが好ましい。また、超音波伝搬部材の酸素透過度（ＪＩＳ Ｚ１７０２）は１００，０００ｃｃ／ｍ２／ｈｒ／ａｔｍ以下であることが好ましい。
In order to improve the storage stability of the ultrasonic wave propagation member, it is necessary to improve the drying resistance and antiseptic property.
In order to improve the drying resistance, it is effective to reduce the water vapor permeability and oxygen permeability of the film. Specifically, the water vapor permeability (JIS K7129) of the ultrasonic wave propagation member is preferably 500 g / m 2 · day or less. Further, the oxygen transmission rate (JIS Z1702) of the ultrasonic wave propagation member is preferably 100,000 cc / m 2 / hr / atm or less.
前記防腐性を向上させるためには、前記皮膜に防腐剤を含有することが好ましい。前記防腐剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、デヒドロ酢酸塩、ソルビン酸塩、安息香酸塩、ぺンタクロロフェノールナトリウム、２−ピリジンチオール−１−オキサイドナトリウム、２，４−ジメチル−６−アセトキシ−ｍ−ジオキサン、１，２−ベンズチアゾリン−３−オンなどが挙げられる。 In order to improve the antiseptic property, the film preferably contains an antiseptic agent. The preservative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dehydroacetate, sorbate, benzoate, pentachlorophenol sodium, 2-pyridinethiol-1-oxide. Sodium, 2,4-dimethyl-6-acetoxy-m-dioxane, 1,2-benzthiazolin-3-one and the like can be mentioned.
前記超音波伝搬部材は、その形状、大きさ、構造、物性などについては、特に制限はなく、目的に応じて適宜選択することができる。 The shape, size, structure, and physical properties of the ultrasonic wave propagation member are not particularly limited and can be appropriately selected according to the purpose.
本発明の超音波伝搬部材に含まれるハイドロゲルは、ポリマーと水と鉱物から構成されることから、そもそも人体の組成に近いため、音響インピーダンスは人体の値に近い。このため、人体表面にハイドロゲルを配置した場合、両者の密着性が良ければ、体内から発せられる超音波を反射（減衰）させることなく、超音波受信機に伝えることができる。
また、密着度合いは、上述したように、人体表面側においては密着させるために十分な柔らかさを備える構造にすることにより十分に確保される。このように、ハイドロゲルを含む超音波伝搬部材は、超音波伝搬部材に必要な物性や特性を兼ね備えたものであり、超音波伝搬部材を構成する材料としてハイドロゲルは最も優れた材料の一つとして挙げられる。
Since the hydrogel contained in the ultrasonic wave propagation member of the present invention is composed of a polymer, water, and a mineral, it is close to the composition of the human body in the first place, and thus the acoustic impedance is close to the value of the human body. For this reason, when the hydrogel is placed on the surface of the human body, the ultrasonic waves emitted from the body can be transmitted to the ultrasonic receiver without being reflected (attenuated) if the adhesion between the two is good.
Further, as described above, the degree of close contact is sufficiently ensured by having a structure having sufficient softness on the front surface side of the human body for close contact. As described above, the ultrasonic wave propagation member including the hydrogel has physical properties and characteristics necessary for the ultrasonic wave propagation member, and the hydrogel is one of the most excellent materials as a material forming the ultrasonic wave propagation member. As.
−透過率−
超音波伝搬部材は人体への密着が重要であり、気泡の有無など、その接触度合いを目視で確認できることが好ましい。このため、可視領域（４００ｎｍ以上７００ｎｍ以下）の範囲で、透過率は７０％以上が好ましく、９０％以上がより好ましい。
透過率は、例えば、市販の分光光度計を用いて測定することができる。
-Transmissivity-
It is important for the ultrasonic wave propagation member to be in close contact with the human body, and it is preferable that the degree of contact such as the presence or absence of air bubbles can be visually confirmed. Therefore, the transmittance is preferably 70% or more, and more preferably 90% or more in the visible region (400 nm or more and 700 nm or less).
The transmittance can be measured using, for example, a commercially available spectrophotometer.
−超音波伝搬速度−
超音波伝搬部材は人体と密着して、受信した信号をセンサーまで伝搬する必要がある。人体の組成（ほぼ水と考えてよい）から超音波信号を効率よく受け取るためには、超音波伝搬部材の超音波伝搬速度が水に近いことが好ましい。
超音波伝搬速度は温度依存性を有するが、室温（２２℃）の水中ではおよそ１,５００ｍ／秒である。超音波伝搬部材は水を主成分とするハイドロゲルであるが、その組成によっては超音波伝搬速度が大きくなることがある。
人体（水）との差異が大きくなりすぎると、検出器におけるフォーカスのずれを生じ、結果として画像の解像度が劣るという不具合が生じるので好ましくない。このため、超音波伝搬部材の超音波伝搬速度は、同一条件で測定した水中の超音波伝搬速度に対して±５％以内であることが好ましい。
超音波伝搬速度は、例えば、ＪＩＳ Ｚ ２３５３に記載の方法に準拠して測定することができる。
-Ultrasonic wave propagation velocity-
The ultrasonic wave propagation member needs to be in close contact with the human body and propagate the received signal to the sensor. In order to efficiently receive an ultrasonic wave signal from the composition of the human body (which may be considered to be almost water), it is preferable that the ultrasonic wave propagation velocity of the ultrasonic wave propagation member be close to that of water.
The ultrasonic wave propagation velocity has a temperature dependency, but is approximately 1,500 m / sec in water at room temperature (22 ° C.). The ultrasonic wave propagating member is a hydrogel containing water as a main component, but the ultrasonic wave propagating velocity may increase depending on its composition.
If the difference from the human body (water) becomes too large, the detector will be out of focus, resulting in a problem that the resolution of the image will be poor, which is not preferable. Therefore, the ultrasonic wave propagation speed of the ultrasonic wave propagation member is preferably within ± 5% of the ultrasonic wave propagation speed in water measured under the same conditions.
The ultrasonic wave propagation velocity can be measured, for example, according to the method described in JIS Z 2353.
（超音波伝搬部材の製造方法）
本発明の超音波伝搬部材の製造方法は、水、鉱物、及び重合性モノマーを含有する超音波伝搬部材形成用液体材料を用いて超音波伝搬部材を製造するものである。
(Method of manufacturing ultrasonic wave propagation member)
The method for manufacturing an ultrasonic wave propagating member of the present invention is to manufacture an ultrasonic wave propagating member using a liquid material for forming an ultrasonic wave propagating member containing water, a mineral, and a polymerizable monomer.
＜超音波伝搬部材形成用液体材料＞
前記超音波伝搬部材形成用液体材料は、水、鉱物、及び重合性モノマーを含有し、有機溶媒を含有することが好ましく、更に必要に応じてその他の成分を含有する。
前記水、前記鉱物、前記有機溶媒、前記その他の成分としては、前記超音波伝搬部材と同様のものを用いることができる。
<Liquid material for forming ultrasonic wave propagation member>
The liquid material for forming the ultrasonic wave propagation member contains water, minerals, and a polymerizable monomer, preferably an organic solvent, and further contains other components as necessary.
As the water, the mineral, the organic solvent, and the other components, the same components as those of the ultrasonic wave propagation member can be used.
−重合性モノマー−
前記重合性モノマーは、不飽和炭素−炭素結合を１つ以上有する化合物であり、例えば、単官能モノマー、多官能モノマーなどが挙げられる。
前記多官能モノマーとしては、例えば、２官能モノマー、３官能モノマー、３官能以上のモノマーなどが挙げられる。
-Polymerizable monomer-
The polymerizable monomer is a compound having one or more unsaturated carbon-carbon bonds, and examples thereof include monofunctional monomers and polyfunctional monomers.
Examples of the polyfunctional monomer include a bifunctional monomer, a trifunctional monomer, and a trifunctional or higher functional monomer.
前記単官能モノマーは、不飽和炭素−炭素結合を１つ有する化合物であり、例えば、アクリルアミド、Ｎ−置換アクリルアミド誘導体、Ｎ，Ｎ−ジ置換アクリルアミド誘導体、Ｎ−置換メタクリルアミド誘導体、Ｎ，Ｎ−ジ置換メタクリルアミド誘導体、又はその他の単官能モノマーなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
前記Ｎ−置換アクリルアミド誘導体、Ｎ，Ｎ−ジ置換アクリルアミド誘導体、Ｎ−置換メタクリルアミド誘導体、又はＮ，Ｎ−ジ置換メタクリルアミド誘導体としては、例えば、Ｎ，Ｎ−ジメチルアクリルアミド（ＤＭＡＡ）、Ｎ−イソプロピルアクリルアミドなどが挙げられる。
前記その他の単官能モノマーとしては、例えば、２−エチルヘキシル（メタ）アクリレート（ＥＨＡ）、２−ヒドロキシエチル（メタ）アクリレート（ＨＥＡ）、２−ヒドロキシプロピル（メタ）アクリレート（ＨＰＡ）、アクリロイルモルホリン（ＡＣＭＯ）、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、イソボニル（メタ）アクリレート、３−メトキシブチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−フェノキシエチル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、トリデシル（メタ）アクリレート、カプロラクトン（メタ）アクリレート、エトキシ化ノニルフェノール（メタ）アクリレート、ウレタン（メタ）アクリレートなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
前記単官能モノマーを重合させることにより、アミド基、アミノ基、水酸基、テトラメチルアンモニウム基、シラノール基、エポキシ基などを有する水溶性有機ポリマーが得られる。
前記アミド基、アミノ基、水酸基、テトラメチルアンモニウム基、シラノール基、エポキシ基などを有する水溶性有機ポリマーは、超音波伝搬部材の強度を保つために有利な構成成分である。
The monofunctional monomer is a compound having one unsaturated carbon-carbon bond, and includes, for example, acrylamide, N-substituted acrylamide derivatives, N, N-disubstituted acrylamide derivatives, N-substituted methacrylamide derivatives, N, N-. Examples thereof include di-substituted methacrylamide derivatives, and other monofunctional monomers. These may be used alone or in combination of two or more.
Examples of the N-substituted acrylamide derivative, N, N-disubstituted acrylamide derivative, N-substituted methacrylamide derivative, or N, N-disubstituted methacrylamide derivative include, for example, N, N-dimethylacrylamide (DMAA) and N-. Isopropyl acrylamide etc. are mentioned.
Examples of the other monofunctional monomers include 2-ethylhexyl (meth) acrylate (EHA), 2-hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), acryloylmorpholine (ACMO). ), Caprolactone-modified tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, Examples thereof include isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, and urethane (meth) acrylate. These may be used alone or in combination of two or more.
By polymerizing the monofunctional monomer, a water-soluble organic polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group or the like can be obtained.
The water-soluble organic polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, an epoxy group, etc. is an advantageous constituent component for maintaining the strength of the ultrasonic wave propagation member.
前記単官能モノマーの含有量は、特に制限はなく、目的に応じて適宜選択することができるが、超音波伝搬部材形成用液体材料の全量に対して、１質量％以上１０質量％以下が好ましく、１質量％以上５質量％以下がより好ましい。前記含有量が、１質量％以上１０質量％以下であると、超音波伝搬部材形成用液体材料中の層状粘土鉱物の分散安定性が保たれ、かつ超音波伝搬部材の延伸性を向上させるという利点がある。前記延伸性とは、超音波伝搬部材を引っ張った際に伸び、破断しない特性のことを言う。 The content of the monofunctional monomer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1% by mass or more and 10% by mass or less with respect to the total amount of the liquid material for forming an ultrasonic wave propagation member. It is more preferably 1% by mass or more and 5% by mass or less. When the content is 1% by mass or more and 10% by mass or less, the dispersion stability of the layered clay mineral in the liquid material for forming an ultrasonic wave propagating member is maintained and the extensibility of the ultrasonic wave propagating member is improved. There are advantages. The stretchability refers to a property that the ultrasonic wave propagation member is stretched and is not broken when pulled.
前記２官能モノマーとしては、例えば、トリプロピレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート，テトラエチレングリコールジ（メタ）アクリレート，ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールヒドロキシピバリン酸エステルジ（メタ）アクリレート（ＭＡＮＤＡ）、ヒドロキシピバリン酸ネオペンチルグリコールエステルジ（メタ）アクリレート（ＨＰＮＤＡ）、１，３−ブタンジオールジ（メタ）アクリレート（ＢＧＤＡ）、１，４−ブタンジオールジ（メタ）アクリレート（ＢＵＤＡ）、１，６−ヘキサンジオールジ（メタ）アクリレート（ＨＤＤＡ）、１，９−ノナンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート（ＤＥＧＤＡ）、ネオペンチルグリコールジ（メタ）アクリレート（ＮＰＧＤＡ）、トリプロピレングリコールジ（メタ）アクリレート（ＴＰＧＤＡ）、カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールエステルジ（メタ）アクリレート、プロポキシ化ネオペンチルグリコールジ（メタ）アクリレート、エトキシ変性ビスフェノールＡジ（メタ）アクリレート、ポリエチレングリコール２００ジ（メタ）アクリレート、ポリエチレングリコール４００ジ（メタ）アクリレート、メチレンビス（メタ）アクリルアミドなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。 Examples of the bifunctional monomer include tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalic acid. Ester di (meth) acrylate (MANDA), hydroxypivalic acid neopentyl glycol ester di (meth) acrylate (HPNDA), 1,3-butanediol di (meth) acrylate (BGDA), 1,4-butanediol di (meth) Acrylate (BUDA), 1,6-hexanediol di (meth) acrylate (HDDA), 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate (DEGDA), neopentyl glycol di (meth) acrylate (NPGDA), tripropylene glycol di (meth) acrylate (TPGDA), caprolactone modified hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxy modified bisphenol A di (meth) Examples thereof include acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, and methylenebis (meth) acrylamide. These may be used alone or in combination of two or more.
前記３官能モノマーとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート（ＴＭＰＴＡ）、ペンタエリスリトールトリ（メタ）アクリレート（ＰＥＴＡ）、トリアリルイソシアネート、トリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート，プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化グリセリルトリ（メタ）アクリレートなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。 Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), triallyl isocyanate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. , Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate and the like. These may be used alone or in combination of two or more.
前記３官能以上のモノマーとしては、例えば、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヒドロキシペンタ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、ペンタ（メタ）アクリレートエステル、ジペンタエリスリトールヘキサ（メタ）アクリレート（ＤＰＨＡ）などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。 Examples of the trifunctional or higher functional monomers include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, penta ( Examples thereof include (meth) acrylate ester and dipentaerythritol hexa (meth) acrylate (DPHA). These may be used alone or in combination of two or more.
前記多官能モノマーの含有量は、超音波伝搬部材形成用液体材料の全量に対して、０．００１質量％以上１質量％以下が好ましく、０．０１質量％以上０．５質量％以下がより好ましい。前記含有量が、０．００１質量％以上１質量％以下の範囲であると、得られる超音波伝搬部材の弾性率や硬度を適正な範囲に調整することができる。 The content of the polyfunctional monomer is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, based on the total amount of the liquid material for forming an ultrasonic wave propagation member. preferable. When the content is in the range of 0.001% by mass or more and 1% by mass or less, the elastic modulus and hardness of the obtained ultrasonic wave propagation member can be adjusted to an appropriate range.
前記超音波伝搬部材形成用液体材料は、重合開始剤を用いて硬化させることが好ましい。前記重合開始剤は、超音波伝搬部材形成用液体材料中に添加して使用される。 The ultrasonic propagation member forming liquid material is preferably cured using a polymerization initiator. The polymerization initiator is used by adding it to the liquid material for forming the ultrasonic wave propagation member.
−重合開始剤−
前記重合開始剤としては、例えば、熱重合開始剤、光重合開始剤などが挙げられる。
前記熱重合開始剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、アゾ系開始剤、過酸化物開始剤、過硫酸塩開始剤、レドックス（酸化還元）開始剤などが挙げられる。
前記アゾ系開始剤としては、例えば、ＶＡ−０４４、ＶＡ−４６Ｂ、Ｖ−５０、ＶＡ−０５７、ＶＡ−０６１、ＶＡ−０６７、ＶＡ−０８６、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）（ＶＡＺＯ ３３）、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩（ＶＡＺＯ ５０）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）（ＶＡＺＯ ５２）、２，２’−アゾビス（イソブチロニトリル）（ＶＡＺＯ ６４）、２，２’−アゾビス−２−メチルブチロニトリル（ＶＡＺＯ ６７）、１，１−アゾビス（１−シクロヘキサンカルボニトリル）（ＶＡＺＯ ８８）（いずれもＤｕＰｏｎｔ Ｃｈｅｍｉｃａｌ社から入手可能）、２，２’−アゾビス（２−シクロプロピルプロピオニトリル）、２，２’−アゾビス（メチルイソブチレ−ト）（Ｖ−６０１）（和光純薬工業株式会社より入手可能）などが挙げられる。
-Polymerization initiator-
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include azo initiators, peroxide initiators, persulfate initiators, redox (redox) initiators. And so on.
Examples of the azo initiators include VA-044, VA-46B, V-50, VA-057, VA-061, VA-067, VA-086, 2,2'-azobis (4-methoxy-2). , 4-Dimethylvaleronitrile) (VAZO 33), 2,2′-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2′-azobis (2,4-dimethylvaleronitrile) (VAZO 52 ), 2,2′-azobis (isobutyronitrile) (VAZO 64), 2,2′-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) ( VAZO 88) (both available from DuPont Chemical), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (methylisobutyrate) (V-601) (Wako Pure Chemical Industries, Ltd. (Available from Kogyo Co., Ltd.) and the like.
前記過酸化物開始剤としては、例えば、過酸化ベンゾイル、過酸化アセチル、過酸化ラウロイル、過酸化デカノイル、ジセチルパーオキシジカーボネート、ジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート（Ｐｅｒｋａｄｏｘ １６Ｓ）（Ａｋｚｏ Ｎｏｂｅｌ社から入手可能）、ジ（２−エチルヘキシル）パーオキシジカーボネート、ｔ−ブチルパーオキシピバレート（Ｌｕｐｅｒｓｏｌ １１）（Ｅｌｆ Ａｔｏｃｈｅｍ社から入手可能）、ｔ−ブチルパーオキシ−２−エチルヘキサノエート（Ｔｒｉｇｏｎｏｘ ２１−Ｃ５０）（Ａｋｚｏ Ｎｏｂｅｌ社から入手可能）、過酸化ジクミルなどが挙げられる。 Examples of the peroxide initiator include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S). ) (Available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl peroxy-2-ethyl. Hexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide and the like.
前記過硫酸塩開始剤としては、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、ペルオキソ二硫酸ナトリウムなどが挙げられる。
前記レドックス（酸化還元）開始剤としては、例えば、前記過硫酸塩開始剤とメタ亜硫酸水素ナトリウム及び亜硫酸水素ナトリウムのような還元剤との組み合わせ、前記有機過酸化物と第３級アミンに基づく系（例えば、過酸化ベンゾイルとジメチルアニリンに基づく系）、有機ヒドロパーオキシドと遷移金属に基づく系（例えば、クメンヒドロパーオキシドとコバルトナフテートに基づく系）などが挙げられる。
Examples of the persulfate initiator include potassium persulfate, sodium persulfate, ammonium persulfate, sodium peroxodisulfate and the like.
Examples of the redox (oxidation-reduction) initiator include a combination of the persulfate initiator and a reducing agent such as sodium metabisulfite and sodium bisulfite, a system based on the organic peroxide and a tertiary amine. (For example, a system based on benzoyl peroxide and dimethylaniline), a system based on an organic hydroperoxide and a transition metal (for example, a system based on cumene hydroperoxide and cobalt naphthate), and the like.
前記光重合開始剤としては、光（波長２２０ｎｍ以上４００ｎｍ以下の紫外線）の照射によりラジカルを生成する任意の物質を用いることができる。
前記光重合開始剤としては、例えば、アセトフェノン、２，２−ジエトキシアセトフェノン、ｐ−ジメチルアミノアセトフェノン、ベンゾフェノン、２−クロロベンゾフェノン、ｐ，ｐ’−ジクロロベンゾフェノン、ｐ，ｐ−ビスジエチルアミノベンゾフェノン、ミヒラーケトン、ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−プロピルエーテル、ベンゾインイソブチルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンジルメチルケタール、チオキサントン、２−クロロチオキサントン、２−ヒドロキシ−２−メチル−１−フェニル−１−オン、１−（４−イソプロピルフェニル）２−ヒドロキシ−２−メチルプロパン−１−オン、メチルベンゾイルフォーメート、１−ヒドロキシシクロヘキシルフェニルケトン、アゾビスイソブチロニトリル、ベンゾイルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシドなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
なお、テトラメチルエチレンジアミンは、アクリルアミドをポリアクリルアミドゲルとする重合・ゲル化反応の開始剤として用いられる。
As the photopolymerization initiator, any substance that generates radicals by irradiation with light (ultraviolet rays having a wavelength of 220 nm to 400 nm) can be used.
Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p-bisdiethylaminobenzophenone, Michler's ketone. , Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl methyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2. -Methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 1-hydroxycyclohexylphenylketone, azobisisobutyronitrile , Benzoyl peroxide, di-tert-butyl peroxide and the like. These may be used alone or in combination of two or more.
In addition, tetramethylethylenediamine is used as an initiator of a polymerization / gelation reaction using acrylamide as a polyacrylamide gel.
本発明の超音波伝搬部材の製造方法としては、型を用いて形成する方法と、三次元プリンターを用いて直接形成する方法との２つの方法がある。 There are two methods of manufacturing the ultrasonic wave propagating member of the present invention, a method of forming using an mold and a method of forming directly using a three-dimensional printer.
＜型を用いて形成する方法＞
前記型を用いて形成する方法は、水、鉱物、及び重合性モノマーを含有する超音波伝搬部材形成用液体材料を型に流し込み、硬化させる方法である。
本発明の超音波伝搬部材の特徴は、少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なることである。所望の形状を有する型を用いて、少なくとも２層の構造の積層構造を有する超音波伝搬部材を形成することが好ましい。
このため、硬度の異なるハイドロゲルを形成できる超音波伝搬部材形成用液体材料を２種類以上用意して、これらを順次、型に流し込み硬化させる工程を複数回行って、超音波伝搬部材を形成する。
例えば、図７Ａに示すように、所望の型５０を用意し、硬化時の硬度の硬い超音波伝搬部材形成用液体材料５１（超音波受信機に接する面を形成）流し込み硬化させる。次いで、図７Ｂに示すように、硬度の低い超音波伝搬部材形成用液体材料５２（人体に接する面を形成）をその上に流し込み硬化させる、これを型から取り出すことにより、本発明の超音波伝搬部材が形成される。
<Method of forming using a mold>
The method of forming using the mold is a method of pouring a liquid material for forming an ultrasonic wave propagation member containing water, a mineral, and a polymerizable monomer into the mold and curing the material.
A feature of the ultrasonic wave propagating member of the present invention is that the ultrasonic wave propagating member has at least two surfaces, and the hardness of one surface and the hardness of the other surface are different. It is preferable to form the ultrasonic wave propagation member having a laminated structure of at least two layers by using a mold having a desired shape.
Therefore, two or more kinds of liquid materials for forming an ultrasonic wave propagation member capable of forming hydrogels having different hardness are prepared, and a step of sequentially pouring these liquid materials into a mold and curing the same is performed a plurality of times to form the ultrasonic wave propagation member. ..
For example, as shown in FIG. 7A, a desired mold 50 is prepared, and a liquid material 51 for forming an ultrasonic wave propagation member having a high hardness at the time of hardening (forming a surface in contact with an ultrasonic wave receiver) is poured and hardened. Next, as shown in FIG. 7B, a liquid material 52 for forming an ultrasonic wave propagation member having a low hardness (forming a surface in contact with the human body) is poured thereon to be cured, and the ultrasonic wave of the present invention is removed by removing it from the mold. A propagation member is formed.
本発明においては、更に使用する型として、被験者の皮膚表面の形状データに基づき、三次元プリンターにて作製した型に流し込み、硬化させて形成することも有用である。
ここで、前記体表面に沿った形状を有するとは、被験者個人の超音波診断対象となる体表面における、身体の凹部又は凸部のそれぞれに対して凸部又は凹部となるような一定の形状を保持していることを意味する。これにより、被験者の皮膚に隙間なくフィットした超音波伝搬部材が形成される。
In the present invention, as a mold to be further used, it is also useful to pour it into a mold prepared by a three-dimensional printer and cure it based on the shape data of the skin surface of the subject to form it.
Here, having a shape along the body surface means that a constant shape such that a convex or concave portion is formed for each concave or convex portion of the body on the body surface that is the subject of ultrasonic diagnosis. Means holding. As a result, an ultrasonic wave propagation member that fits the subject's skin without any gap is formed.
前記三次元プリンターとしては、特に方式を限定するものではないが、超音波伝搬部材形成用液体材料を注入して硬化させるものであるから、超音波伝搬部材形成用液体材料の漏れの無いような材質や方式で形成することが好ましく、インクジェット（マテリアルジェット）方式、光造形方式、レーザー焼結方式などが有効に用いられる。
熱重合開始剤を用いて硬化する場合には、開始剤の種類に応じて反応温度を制御する。超音波伝搬部材形成用液体材料を注入し、密閉して空気（酸素）を遮断した後、室温もしくは所定温度に加温して重合反応を進行させる。重合が完了した後、型から取り出すことにより、超音波伝搬部材が形成される。
光重合開始剤を用いて硬化する場合には、硬化手段として、紫外線等のエネルギー線を超音波伝搬部材形成用液体材料に照射する必要がある。このため、使用する型はエネルギー線に対して透明な材質で構成される。このような型に注入し、密閉して空気（酸素）を遮断した後、型の外側からエネルギー線を照射する。このようにして重合が完了した後、型から取り出すことにより、超音波伝搬部材が形成される。
The three-dimensional printer is not particularly limited in method, but since it is to inject and cure an ultrasonic wave propagation member forming liquid material, there is no leakage of the ultrasonic wave propagation member forming liquid material. It is preferably formed by a material or method, and an inkjet (material jet) method, a stereolithography method, a laser sintering method, or the like is effectively used.
When curing using a thermal polymerization initiator, the reaction temperature is controlled according to the type of the initiator. After injecting the liquid material for forming the ultrasonic wave propagation member and sealing it to block air (oxygen), it is heated to room temperature or a predetermined temperature to proceed the polymerization reaction. After the polymerization is completed, the ultrasonic wave propagation member is formed by removing from the mold.
When curing using a photopolymerization initiator, it is necessary to irradiate the liquid material for forming the ultrasonic wave propagation member with energy rays such as ultraviolet rays as a curing means. Therefore, the mold used is made of a material transparent to the energy rays. After being injected into such a mold and hermetically sealed to block air (oxygen), energy rays are irradiated from the outside of the mold. After the polymerization is completed in this manner, the ultrasonic wave propagating member is formed by taking out from the mold.
例えば、乳房形状に合わせた型を作製する場合、被験者の乳房のＣＴデータを取得し、これを元にオスメスの型を作製できるように三次元（３Ｄ）データに変換する。この三次元データを基に、三次元プリンターにより、図８に示す被験者の乳房用三次元超音波伝搬部材を形成するためのオス型１２１を作製する。被験者個人データを用い三次元プリンターにより、図９に示す乳房用三次元超音波伝搬部材を形成するためのメス型１２２を作製する。図１０に示すように、作製したオス型１２１とメス型１２２とを組み合わせることにより、両者の間に隙間１２３が形成される。この隙間１２３に超音波伝搬部材形成用液体材料を注入し、硬化すると、図１１に示す乳房用三次元超音波伝搬部材１２４を形成することができる。 For example, in the case of creating a mold that matches the shape of the breast, CT data of the breast of the subject is acquired and converted into three-dimensional (3D) data so that a male and female mold can be created based on the CT data. Based on this three-dimensional data, a male mold 121 for forming the three-dimensional ultrasonic wave propagation member for the breast of the subject shown in FIG. 8 is produced by a three-dimensional printer. A female die 122 for forming the three-dimensional breast ultrasonic wave propagation member shown in FIG. 9 is produced by a three-dimensional printer using the individual data of the subject. As shown in FIG. 10, by combining the produced male die 121 and female die 122, a gap 123 is formed between them. When the ultrasonic propagation member forming liquid material is injected into the gap 123 and cured, the three-dimensional breast ultrasonic propagation member 124 shown in FIG. 11 can be formed.
＜三次元プリンターを用いて直接形成する方法＞
前記三次元プリンターを用いた造形は、前記超音波伝搬部材形成用液体材料を用い、三次元プリンターにて直接造形するものである。
前記三次元プリンターとしては、インクジェット方式の三次元プリンター、又は光造形方式の三次元プリンターであることが好ましい。これらの方法を用いると、被験者個人の診断部位の状態に合わせて、組成分布及び形状制御を行うことができる。
このため、図４に示すような硬度の異なる層を複数積層した超音波伝搬部材や、図５に示すような硬度傾斜を有する超音波伝搬部材を造形することができる。
<Direct forming method using a three-dimensional printer>
The modeling using the three-dimensional printer is a modeling using the liquid material for forming the ultrasonic wave propagation member directly by the three-dimensional printer.
The three-dimensional printer is preferably an inkjet type three-dimensional printer or a stereolithography type three-dimensional printer. By using these methods, composition distribution and shape control can be performed according to the condition of the diagnostic site of the individual subject.
Therefore, an ultrasonic wave propagation member having a plurality of layers having different hardnesses as shown in FIG. 4 and an ultrasonic wave propagation member having a hardness gradient as shown in FIG. 5 can be formed.
また、被験者の個人データに基づき、超音波診断対象となる人体表面に沿った形状を有することができる。この場合も被験者個人のデータを基に作製する。
例えば、乳房形状に合わせた型を作製する場合、乳房のＣＴデータを取得し、これを元にオスメスの型を作製できるように三次元（３Ｄ）データに変換する。この３Ｄデータを基に、三次元プリンターにて直接超音波伝搬部材を作製する。
前記三次元プリンターは、超音波伝搬部材形成用液体材料を印字できる方式が好ましく、インクジェット（マテリアルジェット）方式、あるいはディスペンサー方式にてインクを吐出し、ＵＶ光により硬化する方式が有効に用いられる。
Further, it can have a shape along the surface of the human body to be ultrasonically diagnosed, based on the personal data of the subject. Also in this case, it is created based on the individual data of the subject.
For example, in the case of making a mold that matches the shape of the breast, CT data of the breast is acquired, and based on this, it is converted into three-dimensional (3D) data so that a male / female mold can be made. Based on this 3D data, an ultrasonic wave propagation member is directly produced by a three-dimensional printer.
The three-dimensional printer is preferably a system capable of printing a liquid material for forming an ultrasonic wave propagation member, and an ink jet (material jet) system or a dispenser system for ejecting ink and curing by UV light is effectively used.
ここで、図１２に示すようなインクジェット（ＩＪ）方式の三次元プリンター１０は、インクジェットヘッドを配列したヘッドユニットを用いて、超音波伝搬部材形成用液体材料噴射ヘッドユニット１１から超音波伝搬部材形成用液体材料を、支持体形成用液体材料噴射ヘッドユニット１２、１２から支持体形成用液体材料を噴射し、隣接した紫外線照射機１３、１３で超音波伝搬部材用液体材料及び支持体形成用液体材料を硬化しながら積層する。
超音波伝搬部材形成用液体材料噴射ヘッドユニット１１、支持体形成用液体材料噴射ヘッドユニット１２、及び紫外線照射機１３と、超音波伝搬部材１７及び支持体１８とのギャップを一定に保つため、積層回数に合わせて、ステージ１５を下げながら積層する。
前記三次元プリンター１０では、紫外線照射機１３、１３は矢印Ａ、Ｂいずれの方向に移動する際も使用し、その紫外線照射に伴って発生する熱により、積層された支持体形成用液体材料表面が平滑化され、結果として超音波伝搬部材の寸法安定性が向上できる。
造形終了後、図１３に示すように超音波伝搬部材１７と支持体１８を水平方向に引っ張り剥離したところ、支持体１８は一体として剥離され、超音波伝搬部材１７を容易に取り出すことができる。
Here, the inkjet (IJ) type three-dimensional printer 10 as shown in FIG. 12 uses a head unit in which inkjet heads are arranged to form an ultrasonic wave propagation member forming liquid material ejecting head unit 11 into an ultrasonic wave propagation member. The liquid material for forming ultrasonic waves is ejected from the liquid material ejecting head units 12, 12 for forming a support, and the liquid material for ultrasonic wave propagating member and the liquid for forming a support by the adjacent ultraviolet irradiators 13, 13. Laminate the materials while curing.
In order to keep a constant gap between the ultrasonic wave propagation member forming liquid material ejecting head unit 11, the support forming liquid material ejecting head unit 12, the ultraviolet irradiator 13, and the ultrasonic wave transmitting member 17 and the support 18, Depending on the number of times, the stages 15 are stacked while being lowered.
In the three-dimensional printer 10, the ultraviolet irradiators 13 and 13 are used when moving in either direction of arrows A and B, and the heat generated by the irradiation of the ultraviolet rays causes the stacked support-forming liquid material surfaces. Is smoothed, and as a result, the dimensional stability of the ultrasonic wave propagation member can be improved.
When the ultrasonic wave propagating member 17 and the supporting body 18 are pulled in the horizontal direction and peeled off after completion of the shaping as shown in FIG. 13, the supporting body 18 is exfoliated as a unit, and the ultrasonic wave propagating member 17 can be easily taken out.
＜超音波伝搬部材の用途＞
本発明の超音波伝搬部材は、少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なることにより、被検査対象に密着させ非破壊・非侵襲で検査する用途に好適である。例えば、被検査対象である被験者の皮膚表面に隙間なく密着できると共に、超音波診断を行う際に被験者が感じる不快感を解消し、診断後の後処理を不要もしくは簡便にできるので、人間ドック等で行われる腹部エコー検査のような超音波診断などに好適に用いられる。
通常の超音波診断装置のように、超音波発振器と超音波受信機が一体となっているようなプローブを用いる方法に有用である。
この他に、超音波発振器と超音波受信機が別の装置になっている形態、あるいは人体から超音波を発信させるために何らかのエネルギーを入力する装置との併用であっても構わない。
<Application of ultrasonic wave propagation member>
The ultrasonic wave propagating member of the present invention is an ultrasonic wave propagating member having at least two surfaces, and the hardness of one surface is different from the hardness of the other surface, so that the ultrasonic wave propagating member is brought into close contact with an object to be inspected and nondestructive. It is suitable for non-invasive inspection. For example, it can be adhered to the skin surface of the subject to be inspected without gaps, eliminates the discomfort felt by the subject when performing ultrasonic diagnosis, and post-processing after diagnosis can be unnecessary or simple, so it is possible to use it in a physical dock, etc. It is preferably used for ultrasonic diagnosis such as abdominal echography performed.
This is useful for a method using a probe in which an ultrasonic oscillator and an ultrasonic receiver are integrated, as in a normal ultrasonic diagnostic apparatus.
In addition, the ultrasonic oscillator and the ultrasonic receiver may be separate devices, or may be used in combination with a device for inputting some energy in order to transmit ultrasonic waves from the human body.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（調製例１）
−超音波伝搬部材形成用液体材料Ａの調製−
まず、純水２００質量部を撹拌させながら、水膨潤性層状粘土鉱物として［Ｍｇ５．３４Ｌｉ０．６６Ｓｉ８Ｏ２０（ＯＨ）４］Ｎａ− ０．６６の組成を有する合成ヘクトライト（ラポナイトＸＬＧ、ＲｏｃｋＷｏｏｄ社製）１５質量部を少しずつ添加し、更に１−ヒドロキシエタン−１，１−ジホスホン酸０．８質量部を添加し、撹拌して分散液を作製した。
次に、得られた分散液に、重合性モノマーとして、活性アルミナのカラムを通過させ重合禁止剤を除去したアクリロイルモルホリン（ＫＪケミカルズ株式会社製）を２０質量部、及びライトアクリレート９ＥＧ−Ａ（共栄社化学株式会社製）１質量部を添加した。
次に、氷浴で冷却しながら、ペルオキソ二硫酸ナトリウム（和光純薬工業株式会社製）の純水２質量％水溶液を１５質量部添加し、更にテトラメチルエチレンジアミン（和光純薬工業株式会社製）を１質量部添加して、撹拌混合した後、減圧脱気を１０分間実施した。続いて、ろ過を行い、不純物等を除去し、均質な超音波伝搬部材用液体材料Ａを調製した。
(Preparation example 1)
-Preparation of Liquid Material A for Forming Ultrasonic Wave Propagation Member-
First, while stirring the pure water 200 parts by mass, as a water-swellable layered clay mineral [Mg 5.34 Li 0.66 Si 8 O 20 (OH) 4] Na - 0.66 synthetic hectorite having a composition of ( 15 parts by mass of Laponite XLG (manufactured by Rockwood) was added little by little, 0.8 parts by mass of 1-hydroxyethane-1,1-diphosphonic acid was further added, and the mixture was stirred to prepare a dispersion liquid.
Next, 20 parts by mass of acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd.) obtained by passing a column of activated alumina to remove a polymerization inhibitor, and light acrylate 9EG-A (Kyoeisha Co., Ltd.) were added to the obtained dispersion liquid as a polymerizable monomer. (Chemical Co., Ltd.) 1 part by mass was added.
Next, while cooling with an ice bath, 15 parts by mass of a 2% by mass pure water solution of sodium peroxodisulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and further tetramethylethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.). 1 part by mass was added and mixed by stirring, and then degassing under reduced pressure was performed for 10 minutes. Subsequently, filtration was performed to remove impurities and the like, and a homogeneous liquid material A for ultrasonic wave propagation member was prepared.
（調製例２）
−超音波伝搬部材形成用液体材料Ｂの調製−
調製例１において、純水２００質量部を４００質量部に変更した以外は、調製例１と同様にして、超音波伝搬部材形成用液体材料Ｂを調製した。
(Preparation example 2)
-Preparation of Liquid Material B for Forming Ultrasonic Wave Propagation Member-
A liquid material B for forming an ultrasonic wave propagation member was prepared in the same manner as in Preparation Example 1 except that 200 parts by mass of pure water was changed to 400 parts by mass in Preparation Example 1.
（調製例３）
−超音波伝搬部材形成用液体材料Ｃの調製−
調製例１において、純水２００質量部を６６０質量部に変更した以外は、調製例１と同様にして、超音波伝搬部材形成用液体材料Ｃを調製した。
(Preparation example 3)
-Preparation of Liquid Material C for Forming Ultrasonic Wave Propagation Member-
A liquid material C for forming an ultrasonic wave propagation member was prepared in the same manner as in Preparation Example 1 except that 200 parts by mass of pure water was changed to 660 parts by mass in Preparation Example 1.
（調製例４）
−超音波伝搬部材形成用液体材料Ｄの調製−
調製例１において、純水２００質量部を３３０質量部に変更した以外は、調製例１と同様にして、超音波伝搬部材形成用液体材料Ｄを調製した。
(Preparation example 4)
—Preparation of Liquid Material D for Forming Ultrasonic Wave Propagation Member—
A liquid material D for forming an ultrasonic wave propagation member was prepared in the same manner as in Preparation Example 1 except that 200 parts by mass of pure water was changed to 330 parts by mass in Preparation Example 1.
（調製例５）
−超音波伝搬部材形成用液体材料Ｅの調製−
調製例１において、純水２００質量部のうち、５０質量部をグリセリンに置き換えた以外は、調製例１と同様にして、超音波伝搬部材形成用液体材料Ｅを調製した。
(Preparation example 5)
—Preparation of Liquid Material E for Forming Ultrasonic Wave Propagation Member—
A liquid material E for forming an ultrasonic wave propagation member was prepared in the same manner as in Preparation Example 1 except that 50 parts by mass of 200 parts by mass of pure water was replaced with glycerin.
（調製例６）
−超音波伝搬部材形成用液体材料Ｆの調製−
調製例１において、重合性モノマーとしてのアクリロイルモルホリン２０質量部のうち、１０質量部をＮ,Ｎ−ジメチルアクリルアミド（和光純薬工業株式会社製）に置き換えた以外は、調製例１と同様にして、超音波伝搬部材形成用液体材料Ｆを調製した。
(Preparation example 6)
—Preparation of Liquid Material F for Forming Ultrasonic Wave Propagation Member—
In Preparation Example 1, except that 10 parts by mass of 20 parts by mass of acryloylmorpholine as a polymerizable monomer was replaced with N, N-dimethylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 1 was performed. A liquid material F for forming an ultrasonic wave propagation member was prepared.
（調製例７）
−超音波伝搬部材形成用液体材料Ｇの調製−
調製例１において、純水２００質量部を２,０００質量部に変更した以外は、調製例１と同様にして、超音波伝搬部材形成用液体材料Ｇを調製した。
(Preparation Example 7)
—Preparation of Liquid Material G for Forming Ultrasonic Wave Propagation Member—
A liquid material G for forming an ultrasonic wave propagation member was prepared in the same manner as in Preparation Example 1 except that 200 parts by mass of pure water was changed to 2,000 parts by mass in Preparation Example 1.
（調製例８）
−超音波伝搬部材形成用液体材料Ｈの調製−
調製例１において、純水２００質量部を１７０質量部に変更した以外は、調製例１と同様にして、超音波伝搬部材形成用液体材料Ｈを調製した。
(Preparation Example 8)
—Preparation of Liquid Material H for Forming Ultrasonic Wave Propagation Member—
A liquid material H for forming an ultrasonic wave propagation member was prepared in the same manner as in Preparation Example 1 except that 200 parts by mass of pure water was changed to 170 parts by mass in Preparation Example 1.
（実施例１）
まず、１０ｃｍ四方の容器（深さ３ｃｍ）を用意し、これを型として用い、容器の底（下）側を被検査対象に接する面として、平板形状の超音波伝搬部材を作製した。
次に、超音波伝搬部材形成用液体材料Ｃを１ｃｍの深さになるように注ぎ、これを窒素パージ状態で２時間硬化させた。次いで、超音波伝搬部材形成用液体材料Ａを１ｃｍの深さになるように注ぎ、同様に窒素パージ状態で２時間硬化させた。型から取り出すことにより、超音波伝搬部材を作製した。
(Example 1)
First, a 10 cm square container (3 cm deep) was prepared, and this was used as a mold to prepare a flat plate-shaped ultrasonic wave propagation member with the bottom (lower) side of the container in contact with the object to be inspected.
Next, the liquid material C for forming an ultrasonic wave propagation member was poured to a depth of 1 cm, and this was cured for 2 hours in a nitrogen purged state. Next, the ultrasonic wave propagation member forming liquid material A was poured to a depth of 1 cm, and similarly cured in a nitrogen purged state for 2 hours. An ultrasonic wave propagation member was produced by taking it out of the mold.
（実施例２）
実施例１において、超音波伝搬部材形成用液体材料Ｃの代わりに、超音波伝搬部材形成用液体材料Ｂを用いた以外は、実施例１と同様にして、超音波伝搬部材を作製した。
(Example 2)
An ultrasonic wave propagating member was produced in the same manner as in Example 1 except that the ultrasonic wave propagating member forming liquid material B was used in place of the ultrasonic wave propagating member forming liquid material C.
（実施例３）
実施例１において、超音波伝搬部材形成用液体材料Ａの代わりに、超音波伝搬部材形成用液体材料Ｄを用いた以外は、実施例１と同様にして、超音波伝搬部材を作製した。
(Example 3)
An ultrasonic wave propagation member was manufactured in the same manner as in Example 1 except that the ultrasonic wave propagation member forming liquid material D was used in place of the ultrasonic wave propagation member forming liquid material A.
（実施例４）
実施例３において、超音波伝搬部材形成用液体材料Ｄの代わりに、超音波伝搬部材形成用液体材料Ｇを用いた以外は、実施例１と同様にして、超音波伝搬部材を作製した。
(Example 4)
An ultrasonic wave propagating member was produced in the same manner as in Example 1 except that the ultrasonic wave propagating member forming liquid material G was used in place of the ultrasonic wave propagating member forming liquid material D in Example 3.
（実施例５）
実施例３において、超音波伝搬部材形成用液体材料Ｄの代わりに、超音波伝搬部材形成用液体材料Ｈを用いた以外は、実施例１と同様にして、超音波伝搬部材を作製した。
(Example 5)
An ultrasonic wave propagating member was produced in the same manner as in Example 3 except that the ultrasonic wave propagating member forming liquid material H was used in place of the ultrasonic wave propagating member forming liquid material D.
（実施例６）
実施例１において、超音波伝搬部材形成用液体材料Ａの代わりに、超音波伝搬部材形成用液体材料Ｅを用いた以外は、実施例１と同様にして、超音波伝搬部材を作製した。
(Example 6)
An ultrasonic wave propagating member was produced in the same manner as in Example 1 except that the ultrasonic wave propagating member forming liquid material E was used in place of the ultrasonic wave propagating member forming liquid material A.
（実施例７）
実施例１において、超音波伝搬部材形成用液体材料Ａの代わりに、超音波伝搬部材形成用液体材料Ｆを用いた以外は、実施例１と同様にして、超音波伝搬部材を作製した。
(Example 7)
An ultrasonic wave propagating member was produced in the same manner as in Example 1 except that the ultrasonic wave propagating member forming liquid material F was used in place of the ultrasonic wave propagating member forming liquid material A.
（実施例８）
実施例１で作製した超音波伝搬部材表面に、プラスティコート＃１００（大京化学株式会社製）を浸漬塗工法により塗布し、厚み３０μｍの皮膜を形成した以外は、実施例１と同様にして、超音波伝搬部材を作製した。
(Example 8)
Plasticoat # 100 (manufactured by Daikyo Kagaku Co., Ltd.) was applied to the surface of the ultrasonic wave propagating member produced in Example 1 by a dip coating method to form a film having a thickness of 30 μm. Then, an ultrasonic wave propagation member was produced.
（比較例１）
−ゲルシートの作製−
特開平３−２７２７５０号公報の実施例の記載に準じて超音波伝搬部材を作製した。即ち、イオン交換水にポリビニルアルコール（ＰＶＡ）粉末（重合度１,７００、ケン化度９９．５％）を加えて６０℃に加熱して、ＰＶＡ濃度１０質量％のＰＶＡ水溶液を作製した。この水溶液を一辺の長さが６ｃｍで、厚さ４ｍｍの型に注入し、−２０℃で凍結した後に室温（２５℃）で解凍することにより、含水率９０％の柔軟性を有するゲルシートを作製した。
(Comparative Example 1)
-Preparation of gel sheet-
An ultrasonic wave propagating member was produced according to the description in the example of JP-A-3-272750. That is, polyvinyl alcohol (PVA) powder (polymerization degree 1,700, saponification degree 99.5%) was added to ion-exchanged water and heated to 60 ° C. to prepare a PVA aqueous solution having a PVA concentration of 10 mass%. This aqueous solution was poured into a mold having a side length of 6 cm and a thickness of 4 mm, frozen at -20 ° C and then thawed at room temperature (25 ° C) to prepare a flexible gel sheet having a water content of 90%. did.
（比較例２）
比較例２として一般的に用いられる超音波診断用ゲル（ジェクス社製、プロゼリー）を用いて、以下の（６）及び（７）の項目についてのみ評価を行った。
(Comparative example 2)
An ultrasonic diagnostic gel (Proxel, manufactured by Jex Co.) generally used as Comparative Example 2 was used to evaluate only the following items (6) and (7).
次に、実施例１〜８及び比較例１で作製した超音波伝搬部材の硬度（ヤング率）、透過率、及び超音波伝搬速度を以下のようにして測定した。結果を表１に示した。 Next, the hardness (Young's modulus), the transmittance, and the ultrasonic wave propagation velocity of the ultrasonic wave propagation members produced in Examples 1 to 8 and Comparative Example 1 were measured as follows. The results are shown in Table 1.
＜硬度（ヤング率）＞
柔さ測定システム（株式会社堀内電機製作所製、ＳＯＦＴＭＥＡＳＵＲＥ ハンディタイプ ＨＧ１００３）を用いて、２５℃、５０％ＲＨの条件で硬度（ヤング率）を測定した。人体に接する面、及び超音波受信機に接する面を、それぞれ３回の測定を行って、それぞれの平均値を求めた。
<Hardness (Young's modulus)>
The hardness (Young's modulus) was measured under the conditions of 25 ° C. and 50% RH using a softness measurement system (SOFTMEASURE Handy Type HG1003 manufactured by Horiuchi Electric Co., Ltd.). The surface in contact with the human body and the surface in contact with the ultrasonic receiver were measured three times, and the respective average values were obtained.
＜透過率＞
分光光度計（株式会社日立製作所製、ＵＶ−３１００）を用いて、２５℃、５０％ＲＨの条件で透過率を測定した。波長４００ｎｍ以上７００ｎｍ以下の範囲における透過率の平均値を求め、各超音波伝搬部材の透過率とした。
<Transmittance>
The transmittance was measured under the conditions of 25 ° C. and 50% RH using a spectrophotometer (UV-3100 manufactured by Hitachi, Ltd.). The average value of the transmittances in the wavelength range of 400 nm or more and 700 nm or less was obtained and used as the transmittance of each ultrasonic wave propagation member.
＜超音波伝搬速度＞
ＪＩＳ Ｚ ２３５３に記載の方法に準拠して超音波伝搬速度を測定した。なお、測定温度は２２℃に固定した。
<Ultrasonic propagation velocity>
The ultrasonic wave propagation velocity was measured according to the method described in JIS Z 2353. The measurement temperature was fixed at 22 ° C.
＜他の諸特性評価＞
実施例１〜８及び比較例１で作製した超音波伝搬部材、並びに比較例２の超音波診断用ゲルについて、以下の試験項目を評価した。結果を表２に示した。
<Other characteristics evaluation>
The following test items were evaluated for the ultrasonic wave propagating members produced in Examples 1 to 8 and Comparative Example 1 and the ultrasonic diagnostic gel of Comparative Example 2. The results are shown in Table 2.
（１）外観性
各超音波伝搬部材の外観性について、下記の基準で評価した。
［評価基準］
○：透明性が高く、気泡の混入もない
△：透明性がやや低い
×：透明性が低い
(1) Appearance The appearance of each ultrasonic wave propagation member was evaluated according to the following criteria.
[Evaluation criteria]
◯: High transparency, no inclusion of bubbles Δ: Slightly low transparency ×: Low transparency
（２）寸法性
各超音波伝搬部材の寸法性について、下記の基準で評価した。
［評価基準］
○：厚み及び長さが均一である
×：厚み及び長さが不均一である
(2) Dimensionality The dimensionality of each ultrasonic wave propagation member was evaluated according to the following criteria.
[Evaluation criteria]
◯: Thickness and length are uniform x: Thickness and length are uneven
（３）弾性
各超音波伝搬部材の弾性について、下記の基準で評価した。
［評価基準］
◎：適度な弾性を有し、１８０度まで折り曲げても裂けるなどの変化はない
○：適度な弾性を有する
×：弾性が低く、１８０度まで折り曲げると裂ける
(3) Elasticity The elasticity of each ultrasonic wave propagation member was evaluated according to the following criteria.
[Evaluation criteria]
⊚: Moderate elasticity, no change such as tearing even when bent up to 180 ° ◯: Moderate elasticity ×: Low elasticity, tearing when bent up to 180 °
（４）耐熱性
各超音波伝搬部材を６０℃の熱水中で３０分間加熱した後、形状及び物性を測定し、下記基準で評価した。
［評価基準］
○：形状及び物性に変化なし
×：形状及び物性が劣化する
(4) Heat resistance After heating each ultrasonic wave propagation member for 30 minutes in 60 degreeC hot water, the shape and physical property were measured and evaluated by the following criteria.
[Evaluation criteria]
○: No change in shape and physical properties ×: Deterioration of shape and physical properties
（５）耐溶剤性
各超音波伝搬部材を、エタノールを用いて洗浄した後、形状及び物性を測定し、下記基準で評価した。
［評価基準］
○：形状及び物性に変化なし
△：やや膨潤する
×：形状及び物性が劣化する
(5) Solvent resistance After cleaning each ultrasonic wave propagation member using ethanol, the shape and physical properties were measured and evaluated according to the following criteria.
[Evaluation criteria]
◯: No change in shape and physical properties Δ: Swelling somewhat ×: Deterioration in shape and physical properties
（６）人体表面への密着性
各超音波伝搬部材を、被験者の皮膚表面に接触させ、その密着度合いについて、下記基準で評価した。
［評価基準］
○：人体における凹凸部の皮膚に、気泡の存在なく密着している。
×：人体における凹凸部の皮膚に、完全には密着せず、空隙を生じる。
(6) Adhesion to human body surface Each ultrasonic wave propagation member was brought into contact with the skin surface of a subject, and the degree of adhesion was evaluated according to the following criteria.
[Evaluation criteria]
◯: It adheres to the skin of the uneven portion of the human body without the presence of bubbles.
X: The skin is not completely adhered to the skin of the uneven portion of the human body and a void is generated.
（７）密着時の状態、及び評価後の後処理
各超音波伝搬部材の密着時の状態、評価後の後処理について、下記の基準で評価した。
［評価基準］
〇：ぴったりとフィットするため、押し付ける必要なく、被験者の苦痛なし、残存物が無いため、拭き取りは不要である
△：凹凸部のフィットが弱く、超音波検出器を強く押し付ける必要あり、被験者に違和感あり、残存物が無いため、拭き取りは不要である
×：評価後、皮膚に残存物があり、拭き取りが必要であり、被験者に違和感あり
(7) State during adhesion and post-treatment after evaluation The state during adhesion of each ultrasonic wave propagation member and the post-treatment after evaluation were evaluated according to the following criteria.
[Evaluation criteria]
◯: It fits snugly, there is no need to press it, there is no pain on the subject, and there is no residue, so wiping is unnecessary. Yes, there is no residue, so wiping is not necessary. ×: After evaluation, there is residue on the skin and it needs to be wiped off, and the subject feels uncomfortable.
（８）保存性
各超音波伝搬部材を密閉した状態（２５℃、５０％ＲＨ）で７日間保存した後、形状及び物性を測定し、下記基準で保存性を評価した。
［評価基準］
◎：形状及び物性の変化なし
○：形状変化はなし、ごくわずかに乾燥（重量変化率３％以内）
×：形状及び物性が劣化する
(8) Storability After storing each ultrasonic wave propagating member in a sealed state (25 ° C, 50% RH) for 7 days, the shape and physical properties were measured, and the storability was evaluated according to the following criteria.
[Evaluation criteria]
◎: No change in shape and physical properties ○: No change in shape, very slightly dried (weight change rate within 3%)
X: Shape and physical properties deteriorate
（９）画像評価
実施例１〜８で作製した超音波伝搬部材を用い、超音波診断装置により画像診断を行った。いずれの超音波伝搬部材を用いた場合にも、鮮明な画像が得られた。
実施例５の場合、超音波検出器を強く押し付けないと画像が撮りにくい部分があった。更に画像細部まで比較すると、ごく僅か解像度が劣る部分があった。
(9) Image evaluation Using the ultrasonic wave propagation members produced in Examples 1 to 8, image diagnosis was performed with an ultrasonic wave diagnostic apparatus. A clear image was obtained using any of the ultrasonic wave propagation members.
In the case of Example 5, there was a portion where it was difficult to take an image unless the ultrasonic detector was strongly pressed. Further, when the image details were compared, there was a portion where the resolution was slightly inferior.
（実施例９）
−型の作製−
患者（被治療者）の乳房表面のＣＴデータを用い、これを元に三次元（３Ｄ）プリント用のデータに変換した。このデータを基に、インクジェット光造形装置としてのキーエンス社製アジリスタを用い、図８及び図９に示すような乳房用三次元超音波伝搬部材用のオス型１２１及びメス型１２２を作製した。
(Example 9)
-Mold production-
CT data on the breast surface of a patient (treatment subject) was used, and based on this, it was converted into data for three-dimensional (3D) printing. Based on this data, a male type 121 and a female type 122 for a breast three-dimensional ultrasonic wave propagation member as shown in FIGS. 8 and 9 were manufactured using an azilister manufactured by Keyence Corporation as an inkjet stereolithography device.
−乳房用三次元超音波伝搬部材の作製−
メス型側に超音波伝搬部材形成用液体材料Ａを１ｃｍの深さになるように注ぎ、窒素パージ状態で２時間硬化させた。更に、超音波伝搬部材形成用液体材料Ｃを１ｃｍの深さになるように注ぎ、オス型を押し当てて、窒素パージ状態で２時間硬化させた。その後、型から取り出すことにより、超音波伝搬部材を得た。
-Preparation of three-dimensional ultrasonic wave propagation member for breast-
The liquid material A for forming an ultrasonic wave propagating member was poured to the female side so as to have a depth of 1 cm, and was cured in a nitrogen purged state for 2 hours. Further, the liquid material C for forming an ultrasonic wave propagating member was poured to a depth of 1 cm, a male mold was pressed, and the material was cured for 2 hours in a nitrogen purged state. Then, by taking out from the mold, an ultrasonic wave propagation member was obtained.
（実施例１０）
−超音波伝搬部材形成用液体材料Ｉの調製−
まず、純水３３０質量部を撹拌させながら、水膨潤性層状粘土鉱物として［Ｍｇ５．３４Ｌｉ０．６６Ｓｉ８Ｏ２０（ＯＨ）４］Ｎａ− ０．６６の組成を有する合成ヘクトライト（ラポナイトＸＬＧ、ＲｏｃｋＷｏｏｄ社製）１６質量部を少しずつ添加し、３時間撹拌した。次いで、１−ヒドロキシエタン−１，１−ジホスホン酸（東京化成株式会社製）を０．６質量部添加し、更に１時間撹拌を行った。その後、グリセリン（坂本薬品工業株式会社製）６０質量部を添加し、撹拌を１０分間行い、分散液を調製した。
次に、得られた分散液に、重合性モノマーとして、活性アルミナのカラムを通過させ重合禁止剤を除去したアクロイルモルフォリン（ＫＪケミカルズ株式会社製）１６質量部、Ｎ，Ｎ−ジメチルアクリルアミド（和光純薬工業株式会社製）４質量部、ライトアクリレート９ＥＧ−Ａ（共栄社化学株式会社製）１質量部添加した。更に、界面活性剤としてエマルゲンＳＬＳ−１０６（花王株式会社製）１質量部添加して混合した。
次に、氷浴で冷却しながら、光重合開始剤（イルガキュア１８４、ＢＡＳＦ社製）のメタノール４質量％溶液を２．２質量部添加し、撹拌混合の後、減圧脱気を２０分間実施した。続いて、ろ過を行い、不純物等を除去し、超音波伝搬部材形成用液体材料Ｉを得た。
(Example 10)
—Preparation of Liquid Material I for Forming Ultrasonic Wave Propagation Member—
First, while stirring the pure water 330 parts by mass, as a water-swellable layered clay mineral [Mg 5.34 Li 0.66 Si 8 O 20 (OH) 4] Na - 0.66 synthetic hectorite having a composition of ( 16 parts by mass of Laponite XLG (manufactured by Rockwood) was added little by little and stirred for 3 hours. Next, 0.6 part by mass of 1-hydroxyethane-1,1-diphosphonic acid (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was further stirred for 1 hour. Then, 60 parts by mass of glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added and stirred for 10 minutes to prepare a dispersion liquid.
Next, 16 parts by mass of acroylmorpholine (manufactured by KJ Chemicals Co., Ltd.) obtained by passing a column of activated alumina as a polymerizable monomer to remove the polymerization inhibitor into the obtained dispersion liquid, N, N-dimethylacrylamide ( 4 parts by mass of Wako Pure Chemical Industries, Ltd. and 1 part by mass of light acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) were added. Furthermore, 1 part by mass of Emulgen SLS-106 (manufactured by Kao Corporation) as a surfactant was added and mixed.
Next, while cooling in an ice bath, 2.2 parts by mass of a 4% by mass solution of a photopolymerization initiator (IRGACURE 184, manufactured by BASF) in methanol was added, and after stirring and mixing, deaeration under reduced pressure was carried out for 20 minutes. .. Then, filtration was performed to remove impurities and the like, and an ultrasonic wave propagation member forming liquid material I was obtained.
−超音波伝搬部材形成用液体材料Ｊの調製−
超音波伝搬部材形成用液体材料Ｉの調製において、純水３３０質量部を１,０００質量部に変更した以外は、超音波伝搬部材形成用液体材料Ｉの調製と同様にして、超音波伝搬部材形成用液体材料Ｊを調製した。
—Preparation of Liquid Material J for Forming Ultrasonic Wave Propagation Member—
In the preparation of the liquid material I for forming an ultrasonic wave propagating member, the ultrasonic wave propagating member was prepared in the same manner as the liquid material I for forming an ultrasonic wave propagating member except that 330 parts by mass of pure water was changed to 1,000 parts by mass. A forming liquid material J was prepared.
−支持体形成用液体材料の調製−
ウレタンアクリレート（三菱レイヨン株式会社製、商品名：ダイヤビームＵＫ６０３８）１０質量部、重合性モノマーとしてネオペンチルグリコールヒドロキシピバリン酸エステルジ（メタ）アクリレート（日本化薬株式会社製、商品名：ＫＡＹＡＲＡＤ ＭＡＮＤＡ）９０質量部、及び重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製、商品名：イルガキュア１８４）３質量部を、ホモジナイザー（日立工機株式会社製、ＨＧ３０）を用いて、回転数２，０００ｒｐｍで均質な混合物が得られるまで分散した。続いてろ過を行い、不純物等を除去し、最後に真空脱気を１０分間実施し、均質な支持体形成用液体材料を得た。
-Preparation of liquid material for forming a support-
10 parts by mass of urethane acrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Diabeam UK6038), neopentyl glycol hydroxypivalate ester di (meth) acrylate as a polymerizable monomer (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD MANDA) 90 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184) as a polymerization initiator and a homogenizer (HG30 manufactured by Hitachi Koki Co., Ltd.) were used to rotate at 2,000 rpm. And dispersed until a homogeneous mixture was obtained. Subsequently, filtration was performed to remove impurities and the like, and finally vacuum deaeration was carried out for 10 minutes to obtain a homogeneous support-forming liquid material.
−３Ｄ超音波伝搬部材の形成−
図１２に示すようなインクジェット方式の三次元プリンターに、前記超音波伝搬部材形成用液体材料Ｉ及びＪ、及び前記支持体形成用液体材料を充填し、インクジェットヘッド（リコーインダストリー株式会社製、ＧＥＮ４）２個に充填し、噴射させ、製膜を行った。
造形は、患者（被治療者）の乳房表面のＣＴデータを用い、これを元に３Ｄプリント用のデータに変換した。このデータを基に、超音波伝搬部材を造形した。先に超音波伝搬部材形成用液体材料Ｉを用い、超音波伝搬部材に接する面を造形し（超音波伝搬部材全体の半分の厚み相当）、次いで、超音波伝搬部材形成用液体材料Ｊを用い、人体に接する面を造形した。
紫外線照射機（ウシオ電機株式会社製、ＳＰＯＴ ＣＵＲＥ ＳＰ５−２５０ＤＢ）で３５０ｍＪ／ｃｍ２の光量を照射して前記超音波伝搬部材形成用液体材料Ｉ及びＪ、及び前記支持体形成用液体材料を硬化させながら、超音波伝搬部材及び支持体の形成を行った。
造形後、図１３に示すように超音波伝搬部材１７と支持体１８を水平方向に引っ張り剥離したところ、支持体１８は一体として剥離され、超音波伝搬部材１７を容易に取り出すことができた。以上により、乳房用三次元超音波伝搬部材を形成した。
-Formation of 3D ultrasonic wave propagation member-
An inkjet type three-dimensional printer as shown in FIG. 12 is filled with the ultrasonic propagation member forming liquid materials I and J and the support forming liquid material, and an inkjet head (Ricoh Industry Co., Ltd., GEN4) is used. Two pieces were filled and sprayed to form a film.
For modeling, CT data on the breast surface of a patient (patient) was used, and based on this CT data was converted into data for 3D printing. Based on this data, an ultrasonic wave propagation member was formed. First, the liquid material I for forming an ultrasonic wave propagating member is used to form a surface in contact with the ultrasonic wave propagating member (corresponding to half the thickness of the entire ultrasonic wave propagating member), and then the liquid material J for forming an ultrasonic wave propagating member J is used. , I created the surface that touches the human body.
The ultrasonic wave propagation member forming liquid materials I and J and the support forming liquid material are cured by irradiating a light amount of 350 mJ / cm 2 with an ultraviolet irradiation device (SPOT CURE SP5-250DB manufactured by USHIO INC.). While doing so, the ultrasonic wave propagation member and the support were formed.
After shaping, as shown in FIG. 13, when the ultrasonic wave propagating member 17 and the supporting body 18 were pulled and peeled in the horizontal direction, the supporting body 18 was separated as a unit, and the ultrasonic wave propagating member 17 could be easily taken out. By the above, the three-dimensional ultrasonic wave propagation member for breasts was formed.
（実施例１１）
−超音波伝搬部材形成用液体材料Ｋの調製−
超音波伝搬部材形成用液体材料Ｉの調製において、ライトアクリレート９ＥＧ−Ａ（共栄社化学株式会社製）１質量部のうち、０．５質量部をＮ，Ｎ−メチレンビスアクリルアミド（和光純薬工業株式会社製）に置き換えた以外は、超音波伝搬部材形成用液体材料Ｉの調製と同様にして、超音波伝搬部材形成用液体材料Ｋを調製した。
(Example 11)
-Preparation of Liquid Material K for Forming Ultrasonic Wave Propagation Member-
In the preparation of the liquid material I for forming the ultrasonic wave propagation member, 0.5 part by mass of N, N-methylenebisacrylamide (Wako Pure Chemical Industries, Ltd.) out of 1 part by mass of Light Acrylate 9EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) A liquid material K for forming an ultrasonic wave propagating member was prepared in the same manner as the liquid material I for forming an ultrasonic wave propagating member, except that the liquid material I was changed to a product manufactured by a company.
−３Ｄ超音波伝搬部材の形成−
実施例１０において、超音波伝搬部材形成用液体材料Ｉを超音波伝搬部材形成用液体材料Ｋに代えた以外は、実施例１０と同様にして、乳房用三次元超音波伝搬部材を作製した。
-Formation of 3D ultrasonic wave propagation member-
A breast three-dimensional ultrasonic wave propagating member was produced in the same manner as in Example 10 except that the ultrasonic wave propagating member forming liquid material I was replaced with the ultrasonic wave propagating member forming liquid material K.
（実施例１２）
実施例１０で作製した乳房用三次元超音波伝搬部材の表面に、ポバール２０５（株式会社クラレ製）を浸漬塗工法により塗布し、厚み３０μｍの皮膜を形成した。
(Example 12)
Poval 205 (manufactured by Kuraray Co., Ltd.) was applied onto the surface of the breast three-dimensional ultrasonic wave propagation member produced in Example 10 by a dip coating method to form a film having a thickness of 30 μm.
次に、実施例９〜１２で作製した各乳房用三次元超音波伝搬部材について、実施例１と同様にして、硬度（ヤング率）、透過率、超音波伝搬速度、及び他の諸特性を評価した。結果を表３及び４に示した。 Next, the hardness (Young's modulus), the transmittance, the ultrasonic wave propagation velocity, and other various characteristics of each three-dimensional ultrasonic wave propagation member for breasts produced in Examples 9 to 12 were measured in the same manner as in Example 1. evaluated. The results are shown in Tables 3 and 4.
（９）画像評価
実施例９〜１２で作製した乳房用三次元超音波伝搬部材を用い、超音波診断装置により画像診断を行った。いずれの乳房用三次元超音波伝搬部材を用いた場合にも、細部まで鮮明な画像が得られた。
(9) Image evaluation Using the breast three-dimensional ultrasonic wave propagation members produced in Examples 9 to 12, image diagnosis was performed using an ultrasonic diagnostic apparatus. No matter which breast three-dimensional ultrasonic wave propagation member was used, a clear image was obtained in every detail.
本発明の態様としては、例えば、以下のとおりである。
＜１＞ 少なくとも２つの面を有する超音波伝搬部材であって、一方の面の硬度と、他方の面の硬度とが異なることを特徴とする超音波伝搬部材である。
＜２＞ 前記他方の面が、前記一方の面に対向する面である前記＜１＞に記載の超音波伝搬部材である。
＜３＞ 前記一方の面が超音波受信機に接する面であり、前記他方の面が被検査対象に接する面である前記＜１＞から＜２＞のいずれかに記載の超音波伝搬部材である。
＜４＞ 前記超音波伝搬部材の超音波伝搬速度が、同じ温度で測定した水中の超音波伝搬速度と±５％の範囲である前記＜１＞から＜３＞のいずれかに記載の超音波伝搬部材である。
＜５＞ 前記超音波受信機に接する面の硬度が、前記被検査対象に接する面の硬度よりも大きい前記＜３＞から＜４＞のいずれかに記載の超音波伝搬部材である。
＜６＞ 水とポリマーと鉱物から構成されるハイドロゲルを含む前記＜１＞から＜５＞のいずれかに記載の超音波伝搬部材である。
＜７＞ 前記被検査対象に接する面の硬度が、ヤング率で１ｋＰａ以上２０ｋＰａ以下である前記＜３＞から＜６＞のいずれかに記載の超音波伝搬部材である。
＜８＞ 前記超音波受信機に接する面の硬度が、ヤング率で２０ｋＰａ以上１００ｋＰａ以下である前記＜３＞から＜７＞のいずれかに記載の超音波伝搬部材である。
＜９＞ 前記超音波伝搬部材の透過率が、７０％以上である前記＜１＞から＜８＞のいずれかに記載の超音波伝搬部材である。
＜１０＞ 前記超音波伝搬部材の被検査対象に接する面が、前記被検査対象表面に沿った形状を有する前記＜１＞から＜９＞のいずれかに記載の超音波伝搬部材である。
＜１１＞ 表面に皮膜を有する前記＜１＞から＜１０＞のいずれかに記載の超音波伝搬部材である。
＜１２＞ 前記＜１＞から＜１１＞のいずれかに記載の超音波伝搬部材の製造方法であって、
水、鉱物、及び重合性モノマーを含有する超音波伝搬部材形成用液体材料を、被検査対象表面の形状データに基づき、三次元プリンターにて作製した型に流し込み、硬化させて形成することを特徴とする超音波伝搬部材の製造方法である。
＜１３＞ 前記＜１＞から＜１１＞のいずれかに記載の超音波伝搬部材の製造方法であって、
水、鉱物、及び重合性モノマーを含有する超音波伝搬部材形成用液体材料を、被検査対象表面の形状データに基づき、インクジェットヘッドにて吐出し、紫外線光を照射して硬化させるインクジェット方式の三次元プリンターにて形成することを特徴とする超音波伝搬部材の製造方法である。
＜１４＞ 前記＜１＞から＜１１＞のいずれかに記載の超音波伝搬部材の製造装置であって、
水、鉱物、及び重合性モノマーを含有する超音波伝搬部材形成用液体材料を、被検査対象表面の形状データに基づき、インクジェットヘッドにて吐出する吐出手段と、
吐出した超音波伝搬部材形成用液体材料に紫外線光を照射して硬化させる硬化手段と、
を有することを特徴とする超音波伝搬部材の製造装置である。
＜１５＞ インクジェット方式の三次元プリンターを用いる前記＜１４＞に記載の超音波伝搬部材の製造装置である。
Aspects of the present invention are as follows, for example.
<1> An ultrasonic wave propagation member having at least two surfaces, wherein the hardness of one surface is different from the hardness of the other surface.
<2> The ultrasonic wave propagating member according to <1>, wherein the other surface is a surface facing the one surface.
<3> The ultrasonic wave propagating member according to any one of <1> to <2>, wherein the one surface is a surface in contact with an ultrasonic receiver and the other surface is a surface in contact with an object to be inspected. is there.
<4> The ultrasonic wave according to any one of <1> to <3>, wherein the ultrasonic wave propagation speed of the ultrasonic wave propagation member is within ± 5% of the ultrasonic wave propagation speed in water measured at the same temperature. It is a propagation member.
<5> The ultrasonic wave propagation member according to any one of <3> to <4>, wherein the hardness of the surface in contact with the ultrasonic receiver is higher than the hardness of the surface in contact with the inspection target.
<6> The ultrasonic wave propagation member according to any one of <1> to <5>, which includes a hydrogel composed of water, a polymer, and a mineral.
<7> The ultrasonic wave propagation member according to any one of <3> to <6>, wherein the hardness of the surface in contact with the inspection target is 1 kPa or more and 20 kPa or less in Young's modulus.
<8> The ultrasonic wave propagation member according to any one of <3> to <7>, wherein the hardness of the surface in contact with the ultrasonic wave receiver is 20 kPa or more and 100 kPa or less in Young's modulus.
<9> The ultrasonic wave propagating member according to any one of <1> to <8>, wherein the ultrasonic wave propagating member has a transmittance of 70% or more.
<10> The ultrasonic wave propagating member according to any one of <1> to <9>, wherein a surface of the ultrasonic wave propagating member which is in contact with the object to be inspected has a shape along the surface of the object to be inspected.
<11> The ultrasonic wave propagation member according to any one of <1> to <10>, which has a film on the surface.
<12> The method for manufacturing an ultrasonic wave propagation member according to any one of <1> to <11>,
A liquid material for forming an ultrasonic wave propagation member that contains water, minerals, and polymerizable monomers is poured into a mold made by a three-dimensional printer based on the shape data of the surface to be inspected, and is formed by curing. And a method for manufacturing an ultrasonic wave propagation member.
<13> A method for manufacturing an ultrasonic wave propagation member according to any one of <1> to <11>,
An inkjet-type tertiary that ejects a liquid material for forming an ultrasonic wave propagation member containing water, minerals, and polymerizable monomers with an inkjet head based on the shape data of the surface to be inspected, and irradiates and cures with ultraviolet light. It is a method for manufacturing an ultrasonic wave propagation member, which is characterized by being formed by an original printer.
<14> The ultrasonic wave propagation member manufacturing apparatus according to any one of <1> to <11>,
Water, a mineral, and an ultrasonic wave propagation member forming liquid material containing a polymerizable monomer, based on the shape data of the surface to be inspected, a discharge means for discharging with an inkjet head,
A curing unit that irradiates the ejected ultrasonic wave propagation member forming liquid material with ultraviolet light to cure it.
An apparatus for manufacturing an ultrasonic wave propagation member, comprising:
<15> The ultrasonic wave propagation member manufacturing apparatus according to <14>, which uses an inkjet type three-dimensional printer.
前記＜１＞から＜１１＞のいずれかに記載の超音波伝搬部材、前記＜１２＞から＜１３＞のいずれかに記載の超音波伝搬部材の製造方法、及び前記＜１４＞から＜１５＞のいずれかに記載の超音波伝搬部材の製造装置によると、従来における諸問題を解決し、本発明の目的を達成することができる。 The ultrasonic wave propagation member according to any one of <1> to <11>, the method for manufacturing an ultrasonic wave propagation member according to any of <12> to <13>, and <14> to <15>. According to the apparatus for manufacturing an ultrasonic wave propagation member described in any one of the above, various problems in the related art can be solved and the object of the present invention can be achieved.
１０ 三次元プリンター
１１ 超音波伝搬部材形成用液体材料噴射ヘッドユニット
１２ 支持体形成用液体材料噴射ヘッドユニット
１３ 紫外線照射機
１４ 造形体支持基板
１５ ステージ
１６ 平滑化部材
１７ 超音波伝搬部材
１８ 支持体
５１ 超音波伝搬部材形成用液体材料（人体に接する面）
５２ 超音波伝搬部材形成用液体材料（超音波受信機に接する面）
５３ 超音波伝搬部材
１２１ オス型
１２２ メス型
１２３ 隙間
１２４ 乳房用三次元超音波伝搬部材
DESCRIPTION OF SYMBOLS 10 Three-dimensional printer 11 Liquid material jetting head unit for ultrasonic wave propagation member formation 12 Liquid material jetting head unit for support body formation 13 Ultraviolet irradiation machine 14 Model support substrate 15 Stage 16 Smoothing member 17 Ultrasonic wave propagation member 18 Support body 51 Liquid material for ultrasonic wave propagation member formation (surface in contact with human body)
52 Liquid Material for Forming Ultrasonic Wave Propagation Member (Surface in Contact with Ultrasonic Receiver)
53 ultrasonic wave propagation member 121 male type 122 female type 123 gap 124 three-dimensional ultrasonic wave propagation member for breast
Claims (13)
水、鉱物、及び重合性モノマーを含有する超音波伝搬部材形成用液体材料を、被検査対象表面の形状データに基づき、三次元プリンターにて作製した型に流し込み、硬化させて形成することを特徴とする超音波伝搬部材の製造方法。 It is a manufacturing method of the ultrasonic wave propagation member in any one of Claim 1 to 11, Comprising:
A liquid material for forming an ultrasonic wave propagation member containing water, minerals, and polymerizable monomers is poured into a mold made by a three-dimensional printer based on the shape data of the surface to be inspected, and cured to form. And a method for manufacturing an ultrasonic wave propagating member.
水、鉱物、及び重合性モノマーを含有する超音波伝搬部材形成用液体材料を、被検査対象表面の形状データに基づき、インクジェットヘッドにて吐出し、紫外線光を照射して硬化させるインクジェット方式の三次元プリンターにて形成することを特徴とする超音波伝搬部材の製造方法。
It is a manufacturing method of the ultrasonic wave propagation member in any one of Claim 1 to 11, Comprising:
An inkjet-type tertiary that ejects a liquid material for forming an ultrasonic wave propagation member containing water, minerals, and polymerizable monomers with an inkjet head based on the shape data of the surface to be inspected, and irradiates it with ultraviolet light to cure it. A method for manufacturing an ultrasonic wave propagating member, which is characterized by being formed by a former printer.
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