Modified silicone rubber and preparation method thereof, acoustic lens and ultrasonic probe

Abstract

The invention relates to modified silicone rubber and a preparation method thereof, an acoustic lens and an ultrasonic probe. The modified silicone rubber is prepared from the following raw materials: epoxy resin, silicone rubber and a curing agent, the silicone rubber comprises at least one of addition type silicone rubber and condensed type silicone rubber; the epoxy resin comprises at least one of addition polymerization type epoxy resin and ring opening polymerization type epoxy resin. According to the modified silicone rubber, the sound velocity and density of addition type and condensation type silicone rubber are improved through the epoxy resin, the acoustic impedance of the silicone rubber is effectively improved, the matching performance of the silicone rubber and the acoustic impedance of a human body is higher, meanwhile, due to the good compatibility of the two phases, sound attenuation of the material cannot be obviously increased, and the surface hardness of the material is also improved; and the modified silicon rubber can be used for preparing an acoustic transmission lens material matched with the acoustic impedance of human tissues.

Description

Technical Field

[0001] The invention relates to the technical field of acoustic materials, and in particular to a modified silicone rubber and a preparation method thereof, an acoustic lens and an ultrasonic probe. Background Art

[0002] In the medical field, ultrasonic imaging equipment is often used for ultrasonic medical imaging and treatment. Ultrasonic imaging equipment includes an ultrasonic probe, which is an ultrasonic transducer, and the acoustic transparent element is a part of the ultrasonic transducer. Among them, the ultrasonic transducer is a device that can convert electrical energy into ultrasonic energy. It generates ultrasonic waves by exciting the crystal through voltage. These ultrasonic waves can penetrate human tissue and be received by the receiver, thereby realizing the imaging and diagnosis of the internal structure of the human body. Medical ultrasonic probes are usually mainly composed of piezoelectric chips, backing layers, matching layers and acoustic lenses, among which the matching layers and acoustic lenses constitute ultrasonic elements. Ultrasonic detection is achieved by emitting the ultrasonic waves generated by the transducer, wherein the acoustic lens can converge the ultrasonic waves propagating in a straight line to achieve the effect of focusing gain. After passing through the acoustic lens, the ultrasonic energy is concentrated in a certain area and reflected by the organ part to obtain the echo signal. Therefore, the acoustic lens has the function of improving the ultrasonic intensity and optimizing the image quality.

[0003] As a sound-transmitting material, the acoustic lens is located at the outermost layer of the transducer and is in direct contact with the human body medium. As a contact interface, the acoustic lens not only needs to reduce its acoustic attenuation as much as possible, but also needs to have an acoustic impedance close to that of human tissue, so as to reduce reflected sound waves and enhance transmitted sound waves, and ultimately improve the sensitivity of the probe, thereby improving image quality. In addition, in addition to the above-mentioned acoustic characteristics, the acoustic lens is also required to have sufficient mechanical strength. Since the ultrasonic probe is used to rub or press the object being detected, the mechanical strength of the acoustic lens (such as hardness and tear strength) directly affects the service life of the ultrasonic probe. However, it is difficult for current sound-transmitting materials to simultaneously meet the multiple characteristics of low acoustic attenuation, suitable sound velocity, good acoustic impedance matching characteristics, and high hardness, so it is difficult to simultaneously meet the requirements of high service life and imaging quality. Summary of the invention

[0004] Based on this, the present application provides a modified silicone rubber and a preparation method thereof, an acoustic lens and an ultrasonic probe. The modified silicone rubber can be used as an acoustically transparent material for ultrasonic diagnostic equipment, and while improving the surface hardness and acoustic impedance value of the RTV silicone rubber lens, it has little effect on the acoustic attenuation of the lens, has good acoustic transparency, and has a long service life and imaging quality.

[0005] The present invention is achieved through the following technical solutions.

[0006] In one aspect of the present invention, a modified silicone rubber is provided, wherein the raw materials for preparing the modified silicone rubber include: epoxy resin, silicone rubber and curing agent;

[0007] The silicone rubber includes at least one of an addition type silicone rubber and a condensation type silicone rubber;

[0008] The epoxy resin includes at least one of an addition polymerization type epoxy resin and a ring-opening polymerization type epoxy resin.

[0009] In some embodiments, the silicone rubber is an addition-type silicone rubber, and the epoxy resin includes an addition-polymerization epoxy resin; or

[0010] The silicone rubber is a condensation type silicone rubber, and the epoxy resin includes a ring-opening polymerization type epoxy resin.

[0011] In some of these embodiments, at least one of the following features is met:

[0012] (1) The condensed silicone rubber contains silanol groups;

[0013] Optionally, the condensation type silicone rubber includes 107 silicone rubber;

[0014] (2) The addition silicone rubber contains carbon-carbon double bonds;

[0015] Optionally, the addition type silicone rubber includes RTV615 silicone rubber;

[0016] (3) The addition polymerization type epoxy resin contains carbon-carbon double bonds;

[0017] Optionally, the addition polymerization type epoxy resin includes epoxy vinyl ester resin;

[0018] (4) The ring-opening polymerization type epoxy resin contains siloxane;

[0019] Optionally, the ring-opening polymerization type epoxy resin includes at least one of an organosilicon-modified epoxy resin and a bisphenol A epoxy resin;

[0020] (5) The curing agent includes at least one of a silicone rubber curing agent and an epoxy resin curing agent;

[0021] Optionally, the silicone rubber curing agent includes at least one of RTV615 curing agent and KH560;

[0022] Optionally, the epoxy resin curing agent includes at least one of methyl ethyl ketone peroxide, cyclohexanone peroxide, an amine curing agent and an amino silicone resin;

[0023] (6) The sound velocity of the modified silicone rubber is 1202 m / s to 1551 m / s;

[0024] (7) The acoustic impedance of the modified silicone rubber is 1.22 MRayl~1.66 MRayl;

[0025] (8) The acoustic attenuation of the modified silicone rubber at a frequency of 5 MHz is 10.27 dB / cm to 52.72 dB / cm;

[0026] (9) The Shore hardness of the modified silicone rubber is 32 A~79 A.

[0027] In some embodiments, the silicone rubber is an addition silicone rubber, the epoxy resin includes epoxy vinyl ester resin, and the epoxy resin curing agent includes at least one of methyl ethyl ketone peroxide and cyclohexanone peroxide;

[0028] Optionally, the silicone rubber is RTV615, the epoxy resin is epoxy vinyl ester resin, and the curing agent is methyl ethyl ketone peroxide and RTV615 curing agent;

[0029] Or, the silicone rubber is a condensation silicone rubber, the epoxy resin includes at least one of bisphenol A epoxy resin and silicone epoxy resin, and the epoxy resin curing agent includes at least one of amino silicone resin and amine curing agent;

[0030] Optionally, the silicone rubber is 107 silicone rubber, the epoxy resin is bisphenol A epoxy resin, and the curing agent is an amine curing agent and KH560;

[0031] Optionally, the silicone rubber is 107 silicone rubber, the epoxy resin is silicone-modified epoxy resin, and the curing agent is amine curing agent T31 and KH560;

[0032] Optionally, the silicone rubber is 107 silicone rubber, the epoxy resin is silicone-modified epoxy resin, and the curing agent is amino silicone resin and KH560.

[0033] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components, measured by weight: 90 to 110 parts of the silicone rubber, 20 to 80 parts of the epoxy resin and 5 to 30 parts of the curing agent.

[0034] In some of the embodiments, the raw materials for preparing the modified silicone rubber further include at least one of a compatibilizer and an accelerator.

[0035] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components, measured by mass: 90 to 110 parts of the silicone rubber, 20 to 80 parts of the epoxy resin, 2 to 6 parts of the compatibilizer, 0.1 to 1 part of the accelerator and 5 to 30 parts of the curing agent.

[0036] In some embodiments, the accelerator includes a silicone rubber accelerator and / or an epoxy resin accelerator;

[0037] Optionally, the silicone rubber accelerator includes organotin;

[0038] Optionally, the epoxy resin accelerator includes at least one of cobalt isooctanoate and cobalt naphthenate;

[0039] and / or, the compatibilizer comprises a silane-modified epoxy resin;

[0040] Optionally, the compatibilizer includes silicone-modified epoxy resin.

[0041] One aspect of the present application also provides a modified silicone rubber, which includes a cured silicone rubber and a cured epoxy resin mixed with each other, wherein the cured silicone rubber includes at least one of an addition-cured silicone rubber and a condensation-cured silicone rubber, and the cured epoxy resin includes at least one of an addition-polymerization-cured epoxy resin and a ring-opening-polymerization-cured epoxy resin.

[0042] One aspect of the present application also provides a method for preparing a modified silicone rubber, comprising the following steps:

[0043] The modified silicone rubber is prepared by mixing the raw materials and curing and molding.

[0044] One aspect of the present application also provides an acoustic lens, the components of which include the above-mentioned modified silicone rubber.

[0045] One aspect of the present application further provides an ultrasonic probe, comprising a support frame and a sound absorbing block, a chip, a matching layer and the above-mentioned acoustic lens sequentially arranged on the support frame.

[0046] The above-mentioned modified silicone rubber and preparation method thereof are obtained by blending and modifying silicone rubber with epoxy resin. The epoxy resin increases the sound velocity and density of addition-type and condensation-type silicone rubbers, effectively increases the acoustic impedance of silicone rubber, and makes the silicone rubber more compatible with the acoustic impedance of the human body. At the same time, the good compatibility of the two phases prevents the acoustic attenuation of the material from increasing significantly, and the surface hardness of the material is also improved. The modified silicone rubber can be used as a sound-transmitting lens (i.e., acoustic lens) material that matches the acoustic impedance of human tissue, thereby making sound-transmitting elements such as acoustic lenses.

[0047] The modified silicone rubber can be used as a sound-transmitting material for ultrasonic diagnostic equipment. While improving the surface hardness and acoustic impedance value of the RTV silicone rubber lens, it has little effect on the acoustic attenuation of the acoustic lens, has a suitable sound velocity, has a high service life and imaging quality, and meets practical applications. DETAILED DESCRIPTION

[0048] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively below, and preferred embodiments of the present invention are given. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. It should be understood that the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0049] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0050] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0051] As described in the background technology, in the traditional technology, silicone rubber is currently a widely used low-acoustic attenuation lens material. Room temperature vulcanized silicone rubber (RTV) is widely used in various types of ultrasonic equipment acoustic lens materials due to its good processing and molding characteristics. Among them, one technology uses RTV615 silicone rubber as the molding material of the acoustic lens, but the acoustic impedance value of the silicone rubber is 1.05 MRayl, which is quite different from the 1.5 MRayl of the human body. There will be obvious acoustic reflection signals at the interface between the transducer and the human body, forming interference signals that are not conducive to ultrasonic imaging. Another technology proposes a polymer, wherein the specific polymer has a structural part having a polysiloxane bond and a structural part having at least one of an ester bond, an amide bond, an urethane bond, a urea bond and a structure from an aromatic ring vinyl. Its acoustic impedance value reaches 1.3 MRayl, which is relatively close to human tissue. The acoustic attenuation of a 2mm sheet at 10MHZ is as low as 66 dB or less, but the preparation method is complicated and requires multiple graft copolymerization of the silicone resin to obtain a resin polymer with improved impedance. Another technology modifies the material by adding fillers such as nano-sized white carbon black, metal oxides, and polymer resin powder to silicone rubber. After adding these fillers, the density of silicone rubber increases, the sound velocity slightly decreases, the acoustic impedance is improved, and the effect on acoustic attenuation is relatively low. Another technology prepares RTV615 / epoxy resin / dopamine hydrochloride composite materials. Epoxy resin increases the impedance of silicone rubber, but the compatibility between composite materials is poor, resulting in a greater impact of blending on the acoustic attenuation of the material.

[0052] Among them, the acoustic attenuation of the addition-type RTV615 silicone rubber at a frequency of 5MHz is only 16.3 dB / cm, and the acoustic attenuation of the condensation-type RTV silicone rubber 107 at a frequency of 5MHz after polymerization is only 4.27dB / cm, which has low attenuation characteristics, but the acoustic impedance is only about 1.0 MRayl, which is quite different from the 1.5 MRayl of the human body. The ultrasonic transmission coefficient is 94.48%, indicating that there will be a certain amount of reflection when the ultrasonic wave passes through the interface between the lens and the human body, resulting in a decrease in the transmittance of the sound wave, which is not conducive to ultrasonic imaging. In addition, the excessively strong reflected sound waves form artifacts during imaging, reducing the imaging quality. At the same time, the surface Shore hardness of RTV615 silicone rubber is 33A, and the surface Shore hardness of 107 silicone rubber is 15A. The surface hardness is low, and it is easy to deform during use, thereby affecting the focusing of the sound waves, resulting in poor ultrasonic imaging quality.

[0053] Based on this, an embodiment of the present application provides a modified silicone rubber, wherein the raw materials for preparing the modified silicone rubber include: epoxy resin, silicone rubber and curing agent;

[0054] The silicone rubber includes at least one of addition silicone rubber and condensation silicone rubber;

[0055] The epoxy resin includes at least one of an addition polymerization type epoxy resin and a ring-opening polymerization type epoxy resin.

[0056] Accordingly, the modified silicone rubber prepared by using the above-mentioned raw materials includes silicone rubber and epoxy resin mixed with each other. Among them, the epoxy resin is mixed and improved with the silicone rubber; the modified silicone rubber includes at least one of addition-cured silicone rubber and condensation-cured silicone rubber, and the modified silicone rubber includes at least one of addition-polymerization-cured epoxy resin and ring-opening-polymerization-cured epoxy resin.

[0057] In some of the embodiments, the mass ratio of the silicone rubber to the epoxy resin is (1.25-5:1).

[0058] The above-mentioned modified silicone rubber is modified by blending silicone rubber with epoxy resin. The epoxy resin increases the sound velocity and density of addition-type and condensation-type silicone rubbers, effectively increases the acoustic impedance of silicone rubber, and makes the silicone rubber more compatible with the acoustic impedance of the human body. At the same time, the good compatibility of the two phases prevents the acoustic attenuation of the material from increasing significantly, and the surface hardness of the material is also improved. The modified silicone rubber can be used as a sound-transmitting lens (i.e., acoustic lens) material that matches the acoustic impedance of human tissue, and further produces sound-transmitting elements such as acoustic lenses.

[0059] The modified silicone rubber can be used as a sound-transmitting material for ultrasonic diagnostic equipment. While improving the surface hardness and acoustic impedance value of the RTV silicone rubber lens, it has little effect on the acoustic attenuation of the acoustic lens, has a suitable sound velocity, has a high service life and imaging quality, and meets practical applications.

[0060] In some embodiments, the silicone rubber is an addition-type silicone rubber, and the epoxy resin includes an addition-polymerization epoxy resin.

[0061] In some embodiments, the silicone rubber is a condensation-type silicone rubber, and the epoxy resin includes a ring-opening polymerization-type epoxy resin.

[0062] In some embodiments, the condensation type silicone rubber contains silanol groups.

[0063] Optionally, the condensation type silicone rubber includes 107 silicone rubber.

[0064] In some embodiments, the addition silicone rubber contains carbon-carbon double bonds.

[0065] Optionally, the addition type silicone rubber includes RTV615.

[0066] In some embodiments, the addition polymerization type epoxy resin contains carbon-carbon double bonds.

[0067] Optionally, the addition polymerization type epoxy resin includes epoxy vinyl ester resin.

[0068] Further optionally, the epoxy vinyl ester resin includes at least one of bisphenol A epoxy vinyl ester resin and novolac epoxy vinyl ester resin.

[0069] In some embodiments, the ring-opening polymerization type epoxy resin contains siloxane.

[0070] Optionally, the ring-opening polymerization type epoxy resin includes at least one of an organosilicon-modified epoxy resin and a bisphenol A epoxy resin.

[0071] In some embodiments, the average molecular weight of the vinyl ester epoxy resin is 300-600.

[0072] In some embodiments, the average molecular weight of the bisphenol A epoxy resin is 300-600.

[0073] In some embodiments, the average molecular weight of the silicone-modified epoxy resin is 100-200.

[0074] In some embodiments, the viscosity of the vinyl ester epoxy resin at 25° C. is 10,000 cps-18,000 cps.

[0075] Preferably, the viscosity of the vinyl ester epoxy resin at 25° C. is 12000 cps to 15000 cps.

[0076] In some embodiments, the viscosity of the bisphenol A epoxy resin at 25° C. is 10,000 cps-18,000 cps.

[0077] Preferably, the viscosity of the bisphenol A epoxy resin at 25° C. is 12000 cps to 15000 cps.

[0078] In some embodiments, the viscosity of the silicone-modified epoxy resin at 25° C. is 1000 cps-3000 cps.

[0079] In some embodiments, the impedance of the vinyl ester epoxy resin is 2.2 MRayl~2.9 MRayl.

[0080] In some embodiments, the impedance of the bisphenol A epoxy resin is 2.2 MRayl-2.9 MRayl.

[0081] In some embodiments, the impedance of the silicone-modified epoxy resin is 2.2 Mrayl-2.6 Mrayl.

[0082] In some embodiments, the Shore hardness of the vinyl ester epoxy resin is 80D-90D.

[0083] In some embodiments, the Shore hardness of the bisphenol A epoxy resin is 80D-90D.

[0084] In some embodiments, the Shore hardness of the silicone-modified epoxy resin is 75D-85D.

[0085] In some embodiments, the bisphenol A epoxy resin has an epoxy equivalent of 170 g / eq to 244 g / eq.

[0086] Preferably, the epoxy equivalent of the bisphenol A epoxy resin is 180 g / eq to 200 g / eq.

[0087] In some of the embodiments, the epoxy equivalent of the silicone-modified epoxy resin is 350 g / eq to 600 g / eq.

[0088] Preferably, the epoxy equivalent of the above-mentioned silicone-modified epoxy resin is 350 g / eq to 400 g / eq.

[0089] In some embodiments, the curing agent includes at least one of a silicone rubber curing agent and an epoxy resin curing agent.

[0090] In some embodiments, the silicone rubber is an addition silicone rubber, the epoxy resin includes epoxy vinyl ester resin, and the epoxy resin curing agent includes at least one of methyl ethyl ketone peroxide and cyclohexanone peroxide.

[0091] It can be understood that the addition-type RTV silicone rubber is used as the base material, and the addition-type RTV silicone rubber is modified by adding epoxy vinyl ester resin. The reaction mechanism of both is to cure and crosslink through the addition reaction of unsaturated C=C. Epoxy resin and silicone rubber have the probability to form chemical bond grafting through the addition reaction of the unsaturated bond between the two. The prepared modified RTV silicone rubber will not have obvious phase separation due to agglomeration and has good compatibility. That is, epoxy vinyl ester resin modified addition-type RTV silicone rubber, because the polymerization mechanism of the two is consistent, it is conducive to the grafting reaction of the two materials during the polymerization process, so that the compatibility of the composite material is improved, thereby reducing the effect of the interface of the blended phase on the sound attenuation, and at the same time has higher surface hardness and higher matching degree with the human body acoustic impedance.

[0092] In some embodiments, the silicone rubber is a condensation silicone rubber, the epoxy resin includes at least one of bisphenol A epoxy resin and silicone epoxy resin, and the epoxy resin curing agent includes at least one of amino silicone resin and amine curing agent.

[0093] It can be understood that condensation-type RTV is modified by epoxy resin cured by ammonia curing agent, among which silicone-modified epoxy resin and epoxy resin cured by amino silicone resin have good compatibility with condensation-type RTV silicone rubber because their molecular chains are grafted with a large number of siloxane molecular chains, and the alkaline environment brought by the amine curing agent is more conducive to the dehydration condensation and curing of condensation-type RTV. Specifically, condensation-type silicone rubber mainly forms new siloxane bonds through the dehydration condensation of the silanol groups at the end or side groups between siloxane molecular chains, thereby achieving cross-linking and curing. The epoxy resin molecular chain cured by amino silicone resin carries a certain proportion of silanol methoxy and silanol ethoxy groups from amino silicone resin. The silanol groups formed after hydrolysis can be dehydrated and condensed with the silanol groups on the condensation-type silica gel, which can achieve the combination of epoxy resin molecular chains and silica gel molecular chains, thereby improving the compatibility of the two. That is, the condensation type RTV silicone rubber is modified by using the epoxy resin cured by amino silicone resin. The epoxy resin modified by silicone resin grafting has good compatibility with RTV, which improves the acoustic impedance and hardness while reducing the effect on the acoustic attenuation of the condensation type RTV silicone rubber.

[0094] In addition, amino groups and silanol groups can also undergo dehydration condensation to form Si-N bonds, but their reaction activity is relatively weak. In addition, the active hydrogen atoms on the amino groups preferentially react with the epoxy groups of the epoxy resin and are consumed. Therefore, the degree of reaction between the amino groups and silanol groups is limited, and the reaction has limited impact on the overall system.

[0095] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components, calculated by weight: 90 to 110 parts of silicone rubber, 20 to 80 parts of epoxy resin and 5 to 30 parts of curing agent.

[0096] It should be noted that the value range of silicone rubber is "90 parts to 110 parts", that is, the minimum and maximum values ​​of the range of 90 parts to 110 parts, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiment and the following point values: 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105 parts, 106 parts, 107 parts, 108 parts, 109 parts, 110 parts; or a range composed of any two of these values, as an example, including: 95 parts to 105 parts.

[0097] The value range of epoxy resin is "20 parts to 80 parts", that is, the minimum and maximum values ​​of the range of 20 parts to 80 parts, and every value between the minimum and maximum values ​​can be taken. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 ​​parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105 parts, 1 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80 parts; or a range composed of any two of these values, as an example, including: 20 parts to 65 parts.

[0098] The value range of the curing agent is "5 parts to 30 parts", that is, the minimum and maximum values ​​of the range of 5 parts to 30 parts, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts; or a range composed of any two of these values, as an example, including: 10 parts to 20 parts.

[0099] In some embodiments, the mass ratio of the silicone rubber to the epoxy resin is 1:0.2-0.8.

[0100] In some of the embodiments, the raw materials for preparing the modified silicone rubber further include at least one of a compatibilizer and an accelerator.

[0101] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components, measured by weight: 90 to 110 parts of silicone rubber, 20 to 80 parts of epoxy resin, 2 to 6 parts of compatibilizer, 0.1 to 1 part of accelerator and 5 to 30 parts of curing agent.

[0102] The range of the compatibilizer is "2 parts to 6 parts", that is, the minimum and maximum values ​​of the range of 2 parts to 6 parts, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiment and the following point values: 2 parts, 3 parts, 4 parts, 5 parts, 6 parts; or a range consisting of any two of these values, as an example, including: 2 parts to 5 parts.

[0103] The value range of the accelerator is "0.1 part to 1 part", that is, the minimum and maximum values ​​of the range of 0.1 part to 1 part, and each value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiment and the following point values: 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part; or a range composed of any two of these values, as an example, including: 0.1 part to 0.5 part.

[0104] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components, measured by weight: 90 to 110 parts of addition-type silicone rubber, 20 to 80 parts of addition-polymerized epoxy resin, 2 to 6 parts of a compatibilizer, 0.1 to 1 part of an accelerator, and 10 to 20 parts of a curing agent.

[0105] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components, measured by weight: 90 to 110 parts of condensation silicone rubber, 20 to 80 parts of ring-opening polymerization epoxy resin, 0.1 to 1 part of accelerator and 5 to 30 parts of curing agent.

[0106] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components, measured by weight: 90 to 110 parts of silicone rubber, 40 to 60 parts of epoxy resin, 2 to 6 parts of compatibilizer, 0.1 to 1 part of accelerator and 5 to 30 parts of curing agent.

[0107] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components: 90 to 110 parts of addition silicone rubber, 40 to 60 parts of addition polymerization epoxy resin, 2 to 6 parts of compatibilizer, 0.1 to 1 part of accelerator and 10 to 20 parts of curing agent.

[0108] In a specific example, the raw materials for preparing the modified silicone rubber include the following components, calculated by weight: 100 parts of addition silicone rubber, 40 parts of addition polymerization epoxy resin, 5 parts of compatibilizer, 0.5 parts of accelerator and 12 parts of curing agent.

[0109] In some of the embodiments, the raw materials for preparing the modified silicone rubber include the following components: 90 to 110 parts of condensation silicone rubber, 40 to 60 parts of ring-opening polymerization epoxy resin, 0.1 to 1 part of accelerator and 5 to 30 parts of curing agent.

[0110] In a specific example, the raw materials for preparing the modified silicone rubber include the following components, calculated by weight: 100 parts of condensation silicone rubber, 40 parts of ring-opening polymerization epoxy resin, 0.5 parts of accelerator and 21 parts of curing agent.

[0111] In some embodiments, the accelerator includes a silicone rubber accelerator and / or an epoxy resin accelerator.

[0112] In some embodiments, the compatibilizer includes a silane-modified epoxy resin.

[0113] Optionally, the compatibilizer includes silicone-modified epoxy resin.

[0114] In some embodiments, the viscosity of the compatibilizer at 25° C. is 1000 cps-3000 cps.

[0115] It can be understood that adding silane-modified epoxy resin as a compatibilizer to RTV silicone rubber can make the epoxy resin more evenly dispersed in the RTV silicone rubber and prevent the epoxy resin from agglomerating in the silicone rubber, thereby avoiding the problem of strong reflection of sound waves due to agglomeration in the blending system and the problem of large local differences in substrate performance.

[0116] In some embodiments, the silicone rubber curing agent includes at least one of RTV615 curing agent and KH560.

[0117] Alkaline environment is conducive to the curing of condensation-type silicone rubber. The silanol methoxy or silanol ethoxy groups in the above silicone rubber curing agent are hydrolyzed to form more silanol groups. The dehydration condensation reaction between a large number of silanol groups accelerates the dehydration condensation curing and cross-linking speed of silicone rubber.

[0118] In some embodiments, the epoxy resin curing agent includes at least one of methyl ethyl ketone peroxide, cyclohexanone peroxide, amine curing agent and amino silicone resin.

[0119] In some embodiments, the silicone rubber accelerator includes organotin.

[0120] In some embodiments, the epoxy resin accelerator includes at least one of cobalt isooctanoate and cobalt naphthenate.

[0121] In some embodiments, the silicone rubber is RTV615, the epoxy resin is epoxy vinyl ester resin, and the curing agent is methyl ethyl ketone peroxide and RTV615 curing agent.

[0122] In some embodiments, the silicone rubber is 107 silicone rubber, the epoxy resin is bisphenol A epoxy resin, and the curing agent is amine curing agent and KH560.

[0123] In some of the embodiments, the silicone rubber is 107 silicone rubber, the epoxy resin is silicone-modified epoxy resin, and the curing agent is amine curing agent T31 and KH560.

[0124] In some of the embodiments, the silicone rubber is 107 silicone rubber, the epoxy resin is silicone-modified epoxy resin, and the curing agent is amino silicone resin and KH560.

[0125] In a specific example, the silicone rubber is RTV615, the epoxy resin is epoxy vinyl ester resin, the curing agent is methyl ethyl ketone peroxide and RTV615 curing agent, the compatibilizer is silicone-modified epoxy resin, and the accelerator is cobalt isooctanoate.

[0126] In a specific example, the silicone rubber is RTV615, the epoxy resin is silicone-modified epoxy resin, the curing agent is amino silicone resin and KH560, and the accelerator is organotin.

[0127] In some of the embodiments, the sound velocity of the modified silicone rubber is 1202 m / s to 1551 m / s.

[0128] In some embodiments, the acoustic impedance of the modified silicone rubber is 1.22 MRayl~1.66 MRayl.

[0129] In some embodiments, the acoustic attenuation of the modified silicone rubber at a frequency of 5 MHz is 10.27 dB / cm to 52.72 dB / cm.

[0130] In some embodiments, the Shore hardness of the modified silicone rubber is 32A-79A.

[0131] Another embodiment of the present application provides a method for preparing a modified silicone rubber, comprising the following steps: mixing the raw materials for preparing the modified silicone rubber and curing and molding the mixture.

[0132] The above-mentioned modified silicone rubber preparation method is easy to operate and has a simple process. The silicone rubber is blended and modified by epoxy resin. The epoxy resin increases the sound velocity and density of addition-type and condensation-type silicone rubbers, effectively increases the acoustic impedance of the silicone rubber, and makes the silicone rubber more compatible with the acoustic impedance of the human body. At the same time, the good compatibility of the two phases prevents the material's acoustic attenuation from increasing significantly, and the surface hardness of the material is also improved. The modified silicone rubber can be used to prepare a sound-transmitting lens material that matches the acoustic impedance of human tissue.

[0133] Another embodiment of the present application also provides the use of the above-mentioned modified silicone rubber in the preparation of a sound-transmitting element.

[0134] Another embodiment of the present application further provides an acoustic lens, the components of which include the above-mentioned modified silicone rubber.

[0135] It can be understood that the acoustic lens can be made directly from the modified silicone rubber, or can contain other components in addition to the modified silicone rubber.

[0136] It can be understood that the above-mentioned acoustic lens is more compatible with the acoustic impedance of the human body, the acoustic attenuation will not increase significantly, and the surface hardness of the material is also improved, thereby effectively improving the service life and imaging quality.

[0137] Another embodiment of the present application further provides an ultrasonic probe, comprising a support frame and a sound absorbing block, a chip, a matching layer and the above-mentioned acoustic lens sequentially arranged on the support frame. The acoustic lens is arranged on the matching layer of the ultrasonic probe.

[0138] Furthermore, the matching layer and the acoustic lens constitute the acoustically transparent element.

[0139] The ultrasonic probe realizes ultrasonic detection by emitting ultrasonic waves generated by an ultrasonic transducer, wherein the sound-transmitting element can converge the ultrasonic waves propagating in a straight line to achieve the effect of focusing gain. After passing through the sound-transmitting element, the ultrasonic energy is concentrated in a certain area and reflected by the organ to obtain an echo signal. The ultrasonic probe is applied with the above-mentioned acoustic lens, has a long service life and imaging quality, and meets practical applications.

[0140] Another embodiment of the present application further provides an ultrasonic imaging device, comprising at least one of the above-mentioned acoustic lens and the above-mentioned ultrasonic probe.

[0141] The probe of the ultrasonic imaging device first emits ultrasonic waves, which are then transmitted and reflected by the object being detected, and then the reflected waves are received by the probe. The probe can convert the received ultrasonic signals into electrical signals, which are then processed by a computer to construct an image based on the time, intensity and other information of the reflected waves.

[0142] It can be understood that the ultrasonic imaging device can be an ultrasonic diagnostic apparatus.

[0143] In some embodiments, the ultrasonic imaging device further includes a data processing module and a display device, wherein the data processing module is used to process data obtained by the ultrasonic probe, and the display device is used to present the data obtained by the data processing module in the form of images or the like.

[0144] In order to make the purpose, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the following specific embodiments, but the present invention is by no means limited to these embodiments. The embodiments described below are only preferred embodiments of the present invention, which can be used to describe the present invention and cannot be understood as limiting the scope of the present invention. It should be pointed out that any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

[0145] In order to better illustrate the present invention, the present invention is further described below in conjunction with the embodiments. The following are specific embodiments.

[0146] Example 1

[0147] 100 g of room temperature vulcanized (RTV) 615 silicone rubber was added to a 250 ml flask, and then 0.5 g of cobalt isooctanoate and 20 g of epoxy vinyl ester resin (impedance 2.6 Mrayl, Shore hardness 88D, model 901, purchased from Xinxin Heavy Anticorrosion Materials Co., Ltd.) were added in sequence and stirred for 10 min. The mechanical stirring rod was kept at a speed of more than 300 r / min. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 1 g of methyl ethyl ketone peroxide and 10 g of 615 silicone curing agent (specifically Maitu RTV615 curing agent) were added to the system in sequence and stirred for 10 min. Then, the system was poured into a molding mold and placed at room temperature for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product was 38A, the sound velocity was 1202 m / s, the acoustic impedance was 1.23 MRayl, and the acoustic attenuation at a frequency of 5 MHz was 37.82 dB / cm.

[0148] Example 2

[0149] 100 g of room temperature vulcanized (RTV) 615 silicone rubber was added to a 250 ml flask, and 5 g of silicone modified epoxy resin (specific model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) was added as a compatibilizer. The mechanical stirring rod was kept at a speed of more than 300 r / min and stirred for 10 minutes to fully disperse the compatibilizer in the RTV615 silicone rubber. Then, 0.5 g of cobalt isooctanoate and 20 g of epoxy vinyl ester resin (impedance 2.6 Mrayl, hardness 88D, model 901, purchased from Xinxin Heavy Anticorrosion Materials Co., Ltd.) were added in sequence and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 1 g of methyl ethyl ketone peroxide and 10 g of RTV615 curing agent (specifically Maitu RTV615 curing agent) were added to the system in sequence and stirred for 10 minutes. Then, the system was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 39A, the sound velocity is 1231m / s, the acoustic impedance is 1.26MRayl, and the acoustic attenuation is 23.68dB / cm at a frequency of 5 MHz.

[0150] Example 3

[0151] 100 g of room temperature vulcanized (RTV) 615 silicone rubber was added to a 250 ml flask, and 5 g of silicone modified epoxy resin (specific model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) was added as a compatibilizer. The mechanical stirring rod was kept at a speed of more than 300 r / min and stirred for 10 minutes to fully disperse the compatibilizer in the RTV615 silicone rubber. Then, 0.5 g of cobalt isooctanoate and 40 g of epoxy vinyl ester resin (impedance 2.6 Mrayl, hardness 88D, model 901, purchased from Xinxin Heavy Anticorrosion Materials Co., Ltd.) were added in sequence and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 2 g of methyl ethyl ketone peroxide and 10 g of RTV615 curing agent (specifically Maitu RTV615 curing agent) were added to the system in sequence and stirred for 10 minutes. Then, the system was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 48A, the sound velocity is 1326m / s, the acoustic impedance is 1.37MRayl, and the acoustic attenuation is 28.37 dB / cm at a frequency of 5 MHz.

[0152] Example 4

[0153] 100 g of room temperature vulcanized (RTV) 615 silicone rubber was added to a 250 ml flask, and 5 g of silicone modified epoxy resin (specific model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) was added as a compatibilizer. The mechanical stirring rod was kept at a speed of more than 300 r / min and stirred for 10 minutes to fully disperse the compatibilizer in the RTV615 silicone rubber. Then, 0.5 g of cobalt isooctanoate and 60 g of epoxy vinyl ester resin (impedance 2.6 Mrayl, hardness 88D, model 901, purchased from Xinxin Heavy Anticorrosion Materials Co., Ltd.) were added in sequence and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 3 g of methyl ethyl ketone peroxide and 10 g of silicone curing agent (specifically Maitu RTV615 curing agent) were added to the system in sequence and stirred for 10 minutes. Then, the system was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 59A, the sound velocity is 1430m / s, the acoustic impedance is 1.51MRayl, and the acoustic attenuation is 35.62dB / cm at a frequency of 5 MHz.

[0154] Example 5

[0155] 100 g of room temperature vulcanized (RTV) 615 silicone rubber was added to a 250 ml flask, and 5 g of silicone modified epoxy resin (specific model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) was added as a compatibilizer. The mechanical stirring rod was kept at a speed of more than 300 r / min and stirred for 10 minutes to fully disperse the compatibilizer in the RTV615 silicone rubber. Then, 0.5 g of cobalt isooctanoate and 80 g of epoxy vinyl ester resin (impedance 2.6 Mrayl, hardness 88D, model 901, purchased from Xinxin Heavy Anticorrosion Materials Co., Ltd.) were added in sequence and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 4 g of methyl ethyl ketone peroxide and 10 g of silicone curing agent (specifically Maitu RTV615 curing agent) were added to the system in sequence and stirred for 10 minutes. Then, the system was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 72A, the sound velocity is 1551m / s, the acoustic impedance is 1.66MRayl, and the acoustic attenuation is 45.33dB / cm at a frequency of 5 MHz.

[0156] Example 6

[0157] 100 g of 107 silica gel and 0.5 g of organic tin (specifically dibutyltin dilaurate, model T-12, purchased from Shanghai Zhengui New Material Technology Co., Ltd.) accelerator were added to a 250 ml flask, and the mechanical stirring rod was kept at a speed of more than 300 r / min. The accelerator was stirred for 10 minutes to fully disperse the accelerator in the 107 silicone rubber. Then, 40 g of liquid bisphenol A epoxy resin (impedance 2.45 Mrayl, hardness 80D, model E51, purchased from Guangzhou Suixin Chemical Co., Ltd.) and 8 g of T31 curing agent were added in turn and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 5 g of KH560 silane coupling agent was added to the system and stirred for 2 minutes. Then, it was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 36A, the sound velocity is 1295m / s, the acoustic impedance is 1.36MRayl, and the acoustic attenuation is 32.62dB / cm at a frequency of 5 MHz.

[0158] Example 7

[0159] 100 g of 107 silica gel and 0.5 g of organotin (specifically dibutyltin dilaurate, model T-12, purchased from Shanghai Zhengui New Material Technology Co., Ltd.) accelerator were added to a 250 ml flask, and the mechanical stirring rod was kept at a speed of more than 300 r / min. The accelerator was stirred for 10 minutes to fully disperse the accelerator in the 107 silicone rubber. Then, 40 g of organosilicon-modified epoxy resin (impedance 2.33 Mrayl, hardness 82D, model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) and 4 g of T31 curing agent were added in turn and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 5 g of KH560 silane coupling agent was added to the system and stirred for 2 minutes. Then, it was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 38A, the sound velocity is 1263m / s, the acoustic impedance is 1.32MRayl, and the acoustic attenuation is 21.63dB / cm at a frequency of 5 MHz.

[0160] Example 8

[0161] 100 g of 107 silica gel and 0.5 g of organic tin (specifically dibutyltin dilaurate, model T-12, purchased from Shanghai Zhengui New Material Technology Co., Ltd.) accelerator were added to a 250 ml flask, and the mechanical stirring rod was kept at a speed of more than 300 r / min. The accelerator was stirred for 10 minutes to fully disperse the accelerator in the 107 silicone rubber. Then, 40 g of liquid bisphenol A epoxy resin (impedance 2.45 Mrayl, hardness 80D, model E51, purchased from Guangzhou Suixin Chemical Co., Ltd.) and 16 g of amino silicone resin were added in turn and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 5 g of KH560 silane coupling agent was added to the system and stirred for 2 minutes. Then, it was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 52A, the sound velocity is 1362m / s, the acoustic impedance is 1.43MRayl, and the acoustic attenuation is 27.31dB / cm at a frequency of 5 MHz.

[0162] Example 9

[0163] 100 g of 107 silica gel and 0.5 g of organotin (specifically dibutyltin dilaurate, model T-12, purchased from Shanghai Zhengui New Material Technology Co., Ltd.) accelerator were added to a 250 ml flask, and the mechanical stirring rod was kept at a speed of more than 300 r / min. The accelerator was stirred for 10 minutes to fully disperse the accelerator in the 107 silicone rubber. Then, 40 g of organosilicon-modified epoxy resin (impedance 2.33 Mrayl, hardness 82D, model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) and 8 g of amino silicone resin were added in turn and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 5 g of KH560 silane coupling agent was added to the system and stirred for 2 minutes. Then, it was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 47A, the sound velocity is 1314m / s, the acoustic impedance is 1.38MRayl, and the acoustic attenuation is 18.23dB / m at a frequency of 5 MHz.

[0164] Example 10

[0165] 100 g of 107 silica gel and 0.5 g of organotin (specifically dibutyltin dilaurate, model T-12, Shanghai Zhengui New Material Technology Co., Ltd.) accelerator were added to a 250 ml flask, and the mechanical stirring rod was kept at a speed of more than 300 r / min. The accelerator was stirred for 10 minutes to fully disperse the accelerator in the 107 silicone rubber. Then, 20 g of organosilicon-modified epoxy resin (impedance 2.33 Mrayl, hardness 82D, model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) and 4 g of amino silicone resin were added in turn and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 5 g of KH560 silane coupling agent was added to the system and stirred for 2 minutes. Then, the system was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 33A, the sound velocity is 1190m / s, the acoustic impedance is 1.22MRayl, and the acoustic attenuation is 10.27dB / m at a frequency of 5 MHz.

[0166] Embodiment 11

[0167] 100 g of 107 silica gel and 0.5 g of organotin (specifically dibutyltin dilaurate, model T-12, purchased from Shanghai Zhengui New Material Technology Co., Ltd.) accelerator were added to a 250 ml flask, and the mechanical stirring rod was kept at a speed of more than 300 r / min. The accelerator was stirred for 10 minutes to fully disperse the accelerator in the 107 silicone rubber. Then, 60 g of organosilicon-modified epoxy resin (impedance 2.33 Mrayl, hardness 82D, model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) and 12 g of amino silicone resin were added in turn and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 5 g of KH560 silane coupling agent was added to the system and stirred for 2 minutes. Then, it was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 63A, the sound velocity is 1446m / s, the acoustic impedance is 1.53MRayl, and the acoustic attenuation is 28.44dB / m at a frequency of 5 MHz.

[0168] Example 12

[0169] 100 g of 107 silica gel and 0.5 g of organotin (specifically dibutyltin dilaurate, model T-12, purchased from Shanghai Zhengui New Material Technology Co., Ltd.) accelerator were added to a 250 ml flask, and the mechanical stirring rod was kept at a speed of more than 300 r / min. The accelerator was stirred for 10 minutes to fully disperse the accelerator in the 107 silicone rubber. Then, 80 g of organosilicon-modified epoxy resin (impedance 2.33 Mrayl, hardness 82D, model TY-H26, purchased from Jining Tangyi Chemical Co., Ltd.) and 16 g of amino silicone resin were added in turn and stirred for 10 minutes. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 5 g of KH560 silane coupling agent was added to the system and stirred for 2 minutes. Then, it was poured into a molding mold and placed at room temperature for curing for 24 hours to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 79A, the sound velocity is 1587m / s, the acoustic impedance is 1.72MRayl, and the acoustic attenuation is 41.31dB / m at a frequency of 5 MHz.

[0170] Example 13

[0171] 100 g of 107 silica gel and 0.5 g of organotin (specifically dibutyltin dilaurate, model T-12, purchased from Shanghai Zhengui New Material Technology Co., Ltd.) were added to a 250 ml flask, and then 5 g of organosilicon-modified epoxy resin was added as a compatibilizer. The mechanical stirring rod was kept at a speed of more than 300 r / min and stirred for 10 min to fully disperse the compatibilizer and the organotin catalyst in the 107 silicone rubber. Then 0.5 g of cobalt isooctanoate and 40 g of epoxy vinyl ester resin (impedance 2.6 Mrayl, hardness 88D, model 901, purchased from Xinxin Heavy Anticorrosion Materials Co., Ltd.) were added in sequence and stirred for 10 min. After mixing evenly, a homogeneous reaction system was obtained. Subsequently, 2 g of methyl ethyl ketone peroxide and 5 g of KH560 were added to the system in sequence and stirred for 10 min. Then, the system was poured into a molding mold and placed at room temperature for curing for 24 h to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product is 32A, the sound velocity is 1276m / s, the acoustic impedance is 1.34MRayl, and the acoustic attenuation is 52.72dB / cm at a frequency of 5 MHz.

[0172] Comparative Example 1

[0173] 100 g of RTV615 was added to a 250 ml flask, and 10 g of curing agent was added. The speed was kept above 300 r / min and stirred for 10 min. After mixing evenly, the mixture was poured into a molding mold and cured at room temperature for 24 h to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product was 33A, the sound velocity was 1029 m / s, the acoustic impedance was 1.05 MRayl, and the acoustic attenuation at a frequency of 5 MHz was 16.3 dB / cm.

[0174] Comparative Example 2

[0175] 100 g of 107 silica gel and 0.5 g of organotin were added to a 250 ml flask, stirred at a speed of 300 r / min or above for 10 min, and then 5 g of KH560 was added. After mixing evenly, the mixture was poured into a molding mold and cured at room temperature for 24 h to obtain an RTV cured product, i.e., an acoustic lens material. The surface Shore hardness of the obtained RTV cured product was 15A, the sound velocity was 1011 m / s, the acoustic impedance was 1.0 MRayl, and the acoustic attenuation was 4.72 dB / cm at a frequency of 5 MHz.

[0176] Some parameters of each embodiment and comparative example and the sound velocity, acoustic impedance, acoustic attenuation and surface Shore hardness data of the prepared modified silicone rubber are shown in Table 1 below:

[0177] Table 1

[0178]

[0179] Among them, the sound velocity, acoustic impedance and acoustic attenuation are measured by water immersion insertion method, and the test standard refers to YY / T 1668-2019. The hardness test refers to the national standard GB / T 2411-2008.

[0180] Comparative Example 1 is an addition silicone rubber RTV615, without epoxy resin added, and the surface Shore hardness of the obtained RTV cured product is 33A, the sound velocity is 1029m / s, the acoustic impedance is 1.05 MRayl, and the acoustic attenuation at 5 MHz is 16.3 dB / cm. It can be seen that the acoustic impedance of the RTV cured product without epoxy resin modification in Comparative Example 1 is low, only 1.05dB / cm.

[0181] Comparative Example 2 is a condensed 107 silica gel without epoxy resin. The surface Shore hardness of the obtained RTV cured product is 15A, the sound velocity is 1011m / s, the acoustic impedance is 1.0 MRayl, and the acoustic attenuation at 5 MHz is 4.72 dB / cm. It can be seen that the acoustic impedance of the RTV cured product without epoxy resin modification in Comparative Example 1 is low, only 1.0 MRayl, and the hardness is only 15A.

[0182] The modified silicone rubber prepared in each embodiment has an acoustic impedance of more than 1.22 MRayl, a surface Shore hardness of more than 32, a sound velocity of 1202 m / s to 1551 m / s, and an acoustic attenuation of less than 52.72 dB / cm at a frequency of 5 MHz.

[0183] By comparing Comparative Example 1 with Example 1, it can be seen that the blending of epoxy vinyl ester resin and silicone can effectively improve the acoustic impedance and hardness of silicone rubber. By comparing Example 1 with Example 2, it can be seen that the silicone-modified epoxy resin can effectively improve the compatibility of liquid silicone and epoxy vinyl ester resin, refine the dispersion interface of the two phases, reduce the reflection and scattering of sound waves at the phase interface, thereby reducing the attenuation of sound wave energy, but at this time the material acoustic impedance is still low, and there is a certain difference with the 1.5 MRayl impedance of the human body. The impedance of the component sample in Example 3 is close to that of the human body, and the attenuation is also maintained at a low level. It has good strength and suitable sound velocity, and is more suitable as an acoustic convex lens material.

[0184] By comparing Example 1, Example 2, Example 3 and Example 4, it can be seen that as the amount of epoxy vinyl ester resin added increases to 60 parts, the acoustic impedance and Shore hardness of RTV silicone rubber can be gradually improved, but the acoustic attenuation of the material will increase, especially when the amount of epoxy vinyl ester resin added increases from 40 parts to 60 parts, the compatibility of the composite material decreases, and the increase in acoustic attenuation is too large. On the whole, it is more appropriate to add 40 parts of epoxy vinyl ester resin. In Example 5, when the epoxy vinyl ester resin is continuously increased to 80 parts or more, the hardness, impedance, sound velocity and attenuation of the composite material are further improved, among which the gap between the material impedance and the human body impedance will continue to increase, which is not conducive to the transmission of sound waves into the human body. The poor impedance matching will lead to an increase in the energy consumption of sound waves, and when the sound velocity of the material is greater than the sound velocity of the human body of about 1500m / s, the material is no longer suitable for preparing a sound-permeable material for convex lens focusing sound waves.

[0185] From the comparison between Comparative Example 1 and Example 6, it can be seen that the blending of liquid bisphenol A epoxy resin and condensation type silica gel can effectively improve the acoustic impedance and hardness of silicone rubber. From the comparison between Example 6 and Example 7, it can be seen that the silicone-modified epoxy resin has a large number of siloxane molecular chains grafted, so that the epoxy resin molecules and the condensation type silica gel have better compatibility when blended, and the acoustic impedance and hardness are improved while the impact on acoustic attenuation is smaller.

[0186] From the comparison between Example 6 and Example 8, it can be seen that the amino silicone resin can not only be used as a curing agent for liquid bisphenol A epoxy resin, but also because of the ring-opening reaction between the amino group and the epoxy group in the amino silicone resin, a large amount of siloxane is grafted on the epoxy resin molecular chain, so that the epoxy resin and the condensation type silica gel have better compatibility when blended, and the blending has less effect on sound attenuation. In addition, the amino silicone resin carries a large amount of methoxy and ethoxy siloxanes. The silanol groups formed after hydrolysis provide a large number of dehydration condensation cross-linking points for 107 silica gel, thereby improving the cross-linking degree of the condensation type silica gel and making the hardness of the composite material more significantly improved.

[0187] From the comparison between Example 7 and Example 9, it can be seen that amino silicone resin, as a curing agent for silicone-modified epoxy resin, can further improve the siloxane grafting rate of silicone-modified epoxy resin, and the compatibility of condensation silica gel and silicone-modified epoxy resin is also further improved. The size of the dispersed phase is finer, and the transmission rate of sound waves between the two phases is increased, thereby further reducing the sound attenuation of the composite material, and it also has higher acoustic impedance and surface hardness.

[0188] From the comparison of Examples 9, 10, 11 and 12, it can be seen that as the content of the organosilicon-modified epoxy resin increases from 20 parts to 80 parts, the sound velocity, impedance, attenuation and hardness of the composite material system gradually increase. When the content is not more than 20 parts, the material has low sound attenuation characteristics, but the impedance and strength are both low, and it is not suitable as an acoustic lens material; when the content is greater than or equal to 80 parts, the material has good mechanical strength characteristics, but the impedance, sound velocity and attenuation are all high, which is also not conducive to its application as an acoustic lens material.

[0189] In summary, the present application improves the acoustic impedance and hardness of the modified silicone rubber by blending and modifying silicone rubber with epoxy resin, and further reduces the effect of blending on acoustic attenuation by improving the blending compatibility, wherein the silicone-modified epoxy resin only acts as a compatibilizer in the addition-type silicone system to improve the compatibility between vinyl ester epoxy resin and silicone rubber, and does not participate in chemical reactions; the silicone-modified epoxy resin acts as a modified and reinforced substrate in the condensation-type silicone system, and it not only has good compatibility with silicone itself, but also can undergo a ring-opening reaction, thereby reinforcing the silicone. Compared with the acoustic attenuation of traditional silicone and epoxy blends at 5MHZ (greater than 40 dB / cm), the acoustic attenuation of the sample prepared by the blending modification method of the present application is relatively low, and the compatibility is improved to reduce the effect of blending on the acoustic attenuation of the material, which can enable ultrasonic imaging equipment to have better imaging quality and longer service life.

[0190] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0191] The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A modified silicone rubber, characterized in that: The raw materials for preparing the modified silicone rubber include: epoxy resin, silicone rubber and curing agent; The silicone rubber includes at least one of an addition type silicone rubber and a condensation type silicone rubber; The epoxy resin includes at least one of an addition polymerization type epoxy resin and a ring-opening polymerization type epoxy resin.

2. The modified silicone rubber according to claim 1, characterized in that The silicone rubber is an addition-type silicone rubber, and the epoxy resin includes an addition-polymerization-type epoxy resin; or The silicone rubber is a condensation type silicone rubber, and the epoxy resin includes a ring-opening polymerization type epoxy resin.

3. The modified silicone rubber according to claim 1, characterized in that Satisfy at least one of the following characteristics: (1) The condensed silicone rubber contains silanol groups; Optionally, the condensation type silicone rubber includes 107 silicone rubber; (2) The addition silicone rubber contains carbon-carbon double bonds; Optionally, the addition type silicone rubber includes RTV615 silicone rubber; (3) The addition polymerization type epoxy resin contains carbon-carbon double bonds; Optionally, the addition polymerization type epoxy resin includes epoxy vinyl ester resin; (4) The ring-opening polymerization type epoxy resin contains siloxane; Optionally, the ring-opening polymerization type epoxy resin includes at least one of an organosilicon-modified epoxy resin and a bisphenol A epoxy resin; (5) The curing agent includes at least one of a silicone rubber curing agent and an epoxy resin curing agent; Optionally, the silicone rubber curing agent includes at least one of RTV615 curing agent and KH560; Optionally, the epoxy resin curing agent includes at least one of methyl ethyl ketone peroxide, cyclohexanone peroxide, an amine curing agent and an amino silicone resin; (6) The sound velocity of the modified silicone rubber is 1202 m / s to 1551 m / s; (7) The acoustic impedance of the modified silicone rubber is 1.22 MRayl~1.66 MRayl; (8) The acoustic attenuation of the modified silicone rubber at a frequency of 5 MHz is 10.27 dB / cm to 52.72 dB / cm; (9) The Shore hardness of the modified silicone rubber is 32 A~79 A.

4. The modified silicone rubber according to claim 3, characterized in that The silicone rubber is an addition silicone rubber, the epoxy resin includes epoxy vinyl ester resin, and the epoxy resin curing agent includes at least one of methyl ethyl ketone peroxide and cyclohexanone peroxide; Optionally, the silicone rubber is RTV615, the epoxy resin is epoxy vinyl ester resin, and the curing agent is methyl ethyl ketone peroxide and RTV615 curing agent; Or, the silicone rubber is a condensation silicone rubber, the epoxy resin includes at least one of bisphenol A epoxy resin and silicone epoxy resin, and the epoxy resin curing agent includes at least one of amino silicone resin and amine curing agent; Optionally, the silicone rubber is 107 silicone rubber, the epoxy resin is bisphenol A epoxy resin, and the curing agent is an amine curing agent and KH560; Optionally, the silicone rubber is 107 silicone rubber, the epoxy resin is silicone-modified epoxy resin, and the curing agent is amine curing agent T31 and KH560; Optionally, the silicone rubber is 107 silicone rubber, the epoxy resin is silicone-modified epoxy resin, and the curing agent is amino silicone resin and KH560.

5. The modified silicone rubber according to any one of claims 1 to 4, characterized in that: The raw materials for preparing the modified silicone rubber include the following components by weight: 90 to 110 parts of the silicone rubber, 20 to 80 parts of the epoxy resin and 5 to 30 parts of the curing agent.

6. The modified silicone rubber according to claim 5, characterized in that The raw materials for preparing the modified silicone rubber also include at least one of a compatibilizer and an accelerator.

7. The modified silicone rubber according to claim 6, characterized in that The raw materials for preparing the modified silicone rubber include the following components in parts by mass: 90 to 110 parts of the silicone rubber, 20 to 80 parts of the epoxy resin, 2 to 6 parts of the compatibilizer, 0.1 to 1 part of the accelerator and 5 to 30 parts of the curing agent.

8. The modified silicone rubber according to any one of claims 6 to 7, characterized in that: The accelerator includes a silicone rubber accelerator and / or an epoxy resin accelerator; Optionally, the silicone rubber accelerator includes organotin; Optionally, the epoxy resin accelerator includes at least one of cobalt isooctanoate and cobalt naphthenate; and / or, the compatibilizer comprises a silane-modified epoxy resin; Optionally, the compatibilizer includes silicone-modified epoxy resin.

9. A modified silicone rubber, characterized in that: The modified silicone rubber includes a cured silicone rubber and a cured epoxy resin mixed with each other, the cured silicone rubber includes at least one of an addition-cured silicone rubber and a condensation-cured silicone rubber, and the cured epoxy resin includes at least one of an addition-polymerization-cured epoxy resin and a ring-opening-polymerization-cured epoxy resin.

10. A method for preparing modified silicone rubber, characterized in that: The steps include: The modified silicone rubber is prepared by mixing the raw materials for preparing the modified silicone rubber as claimed in any one of claims 1 to 8 and curing and molding the mixture.

11. An acoustic lens, characterized in that: Its components include the modified silicone rubber as described in any one of claims 1 to 9.

12. An ultrasonic probe, characterized in that: The invention comprises a supporting frame, and a sound absorbing block, a chip, a matching layer and the acoustic lens as claimed in claim 11 which are sequentially arranged on the supporting frame.

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