TW201431966A - Transducers and production method thereof - Google Patents

Abstract

The present invention relates to a transducer with two or more layers containing organopolysiloxane. Specifically, said two or more layers containing organopolysiloxane is preferred to be silicone elastomer layers obtained by curing two or more curable organopolysiloxane compositions different in the electric characteristics or the mechanical strength of its cured body, and the two or more layers are especially preferred to having a concentration gradient of ingredient or function groups in the layers to the direction of its thickness as entire body.

Description

Converter and method of manufacturing same

The present invention relates to a converter having two or more layers containing an organopolysiloxane, in particular two or more polyoxyxide layers obtained by curing a curable organopolyoxane composition . Further, the present invention relates to a converter having a layer having a concentration gradient of a component or a functional group in the thickness direction thereof in the layers as a whole. Furthermore, the invention relates to a method of manufacturing such converters.

AGBenjanariu et al. indicate that dielectric polymers are potential materials for artificial muscles (AGBenjanariu et al., "New elastomeric silicone based networks applicable as electroactive systems", Proc. of SPIE No. 7976 volumes 79762V-1 to 79762V-8 (2011)). Here, it shows the physical properties of a material having a unimodal or bimodal network formed by addition of a curable polyoxyxene rubber. To form the polyoxyxene rubber, a short-chain organic hydroquinone having 4 hydrazine-bonded hydrogen atoms is used as a crosslinking agent to crosslink a linear poly(dimethyl oxane) having a vinyl group (PDMS). polymer. In addition, in B. Kussmaul et al., Actuator 2012, 13th International Conference on New Actuators, Bremen, Germany, June 18-20, 2012, pp. 374-378 And an actuator having a dielectric elastomer material interposed between the electrodes, the dielectric elastomer material being used as an organic polydimethyl siloxane having a chemical modification of the group of the electric dipole, the modification being This is carried out by bonding these groups to polydimethyloxane using a crosslinking agent.

However, the specific composition of the curable organopolyoxane composition is not disclosed in any of the references mentioned above, and further, in practice, the physical properties of the curable organopolyoxane composition are used. Insufficient materials for industrial applications of various types of converters. Accordingly, there is a need in the art to combine electroactive polymer materials that are capable of meeting the mechanical and electrical properties of practical applications of materials for various types of converters. In particular, there is a great need in the art for a curable organopolyoxane composition that cures and provides an electroactive polymer with excellent physical properties. Moreover, any such references have never taught or indicated a converter having two or more polyoxyxide elastomer layers obtained by curing a curable organopolyoxane composition.

Background file

Non-Patent Document 1: "New elastomeric silicone based networks applicable as electroactive systems", Proc. of SPIE No. 7976 Volume 79762V-1 to 79762V-8 (2011)

Non-Patent Document 2: Actuator 2012, 13th International Conference on New Actuators, Bremen, Germany, June 18-20, 2012, pp. 374-378

It is an object of the present invention to provide a converter having a multilayer structure with excellent mechanical and/or electrical properties.

Another object of the present invention is to provide a converter having two or more polyoxyxide elastomer layers formed by curing a curable organopolyoxane composition, which composition can provide excellent mechanical properties And / or electrical characteristics, and in particular to provide high specific dielectric constant, high dielectric breakdown strength and low Young's modulus to achieve high energy density; can be used in the case of the dielectric layer used as a converter Good mechanical strength (i.e., tensile strength, tear strength, elongation, or the like) achieves durability and practical displacement; and it is possible to manufacture a cured article that can be used as a material for a converter. In addition, various types of fillers (including fillers that have been surface treated) can be blended with the curable organopolyoxane compositions of the present invention. And obtaining the desired electrical characteristics, and the curable organopolyoxane composition of the present invention may include a release additive to prevent breakage upon molding into a sheet, and may also include an additive for improving insulation breakdown characteristics.

Other objects of the present invention are to provide a curable polyoxoelastomer material that can be used as an electroactive polymer material for a converter, to provide a method of making the curable polyoxoelastomer material, and to provide a curable polyoxyxide Various types of converters for elastomeric materials.

The present invention has been achieved by the inventors by the following findings: The present invention solves the above-mentioned problems by the means set forth below.

The problems mentioned above are solved by a converter having two or more layers containing organopolyoxane. In particular, the two or more organic polyoxane-containing layers are preferably a curable organopolyoxane combination which cures two or more of its cured bodies by electrical or mechanical strength. The polyoxyxene elastomer layer obtained is obtained, and the two or more layers preferably have a concentration gradient of a component or a functional group in the thickness direction thereof in the layers as a whole.

Furthermore, the above mentioned problems are solved extremely well by using a curable organopolyoxane composition of the converter associated with the present invention.

1‧‧‧Actuator

2‧‧‧Actuator

3‧‧‧Sensor

4‧‧‧Power generation components

10a‧‧‧ dielectric layer

10b‧‧‧ dielectric layer

11a‧‧‧electrode layer

11b‧‧‧electrode layer

12‧‧‧ wire

13‧‧‧Power supply

20a‧‧‧ dielectric layer

20b‧‧‧ dielectric layer

20c‧‧‧ dielectric layer

21a‧‧‧electrode layer

21b‧‧‧electrode layer

21c‧‧‧electrode layer

21d‧‧‧electrode layer

22‧‧‧Wire

23‧‧‧Power supply

30‧‧‧Dielectric layer

31a‧‧‧Upper electrode layer

31b‧‧‧Upper electrode layer

31c‧‧‧ upper electrode layer

32a‧‧‧lower electrode layer

32b‧‧‧lower electrode layer

32c‧‧‧lower electrode layer

40a‧‧‧ dielectric layer

40b‧‧‧ dielectric layer

41a‧‧‧electrode layer

41b‧‧‧electrode layer

1 shows a cross-sectional view of an actuator 1 of an embodiment of the present invention in which a dielectric layer is stacked.

2 shows a cross-sectional view of an actuator 2 of an embodiment of the present invention in which a dielectric layer and an electrode layer are stacked.

Figure 3 shows the structure of a sensor 3 in accordance with an embodiment of the present invention.

4 shows a cross-sectional view of a power generating element 4 of an embodiment of the present invention in which a dielectric layer is stacked.

Fig. 5 refers to the thickness strain (%) of the variation of the electric field (V/μm) with reference to the example number 23 and the comparative reference example number 4.

The converter of the present invention is characterized by having two or more layers containing an organopolyoxane. Although the function of two or more layers containing an organic polyoxyalkylene is not specifically limited, the layers are preferably a dielectric layer or a conductive layer. Furthermore, the term "converter" as used in the present invention means an element, machine or device for converting a certain type of energy into a different type of energy. The converter is exemplified as an artificial muscle and an actuator for converting electrical energy into mechanical energy; a sensor and a power generating element for converting mechanical energy into electrical energy; a speaker for converting electrical energy into sound energy, a microphone and a headphone; a fuel cell for converting chemical energy into electrical energy; and a light emitting diode for converting electrical energy into light energy.

Further, the two or more layers containing the organopolyoxyalkylene may be obtained by curing two or more curable organopolyoxane compositions having different electrical properties or mechanical strengths of the cured body. Polyoxyelastomer layer. The polyoxyxene elastomer used for the purpose of the converter can be cured by any curing reaction system as long as the initial uncured raw material containing the organopolyoxysiloxane, especially the flowable raw material, can form a cured body. Generally, the curable compositions of the present invention are cured by a condensation cure system or an addition cure system. However, a peroxidation curing (free radical induced curing) system or a high energy ray (e.g., ultraviolet) curing system can be employed and can be used in the curing system of the composition. Further, a method of forming a solidified body by forming a crosslinked structure in a solution state and removing the drying by a solvent may be employed.

Although the shape of the polyoxylene elastomer as the converter member is not particularly limited, a film form or a sheet form is preferred. The polyoxyelastomer film can generally be formed by: after molding the curable organopolyoxane composition into a sheet or film, the part can usually be cured by heating, by high energy beam irradiation or the like. . Although the method for molding the curable organopolyoxane composition into a film form is not particularly limited, the method is exemplified as a method of curing the organic polyoxyalkylene by using a previously known coating method. The composition is applied to a substrate to form a coating film by molding the curable organopolyoxane composition through an extruder equipped with a slit of a desired shape, or the like.

The converter of the present invention can be prepared by using a component for a converter having two or more stacked polyoxyelastomer films. For example, two or more polyoxyphthalide films having high dielectric properties may be stacked as the entire dielectric layer. Similarly, one or more polyoxyxene elastomer films having high dielectric properties may be stacked as electrodes between the polyoxoelastomer films having electrically conductive properties.

[Design of concentration gradient]

The converter of the present invention may be stacked with two or more layers having a concentration gradient of components or functional groups in the thickness direction thereof in the layers as a whole. The concentration gradient can be at least one concentration gradient selected from the group consisting of: the functional group content of one or more organopolyoxysiloxanes, the content of one or more fillers, the amount of one or more insulating additives, and one or more In addition to the content of the additive. Although there is no particular limitation on the method of designing the concentration gradient in the layer, the concentration gradient can be easily designed by stacking a polyoxyxene elastomer film formed by curing two or more curable organopolyoxane compositions. At least one of the curable organopolyoxane compositions is selected from the group consisting of a filler content, an insulating additive content, and a removal additive content contained in the solidified body.

[elastic film and lamination]

The thickness of this type of film-like curable organopolyoxane composition can be set, for example, in the range of from 0.1 μm to 5,000 μm. Depending on the coating method and the presence or absence of a volatile solvent, the thickness of the cured article obtained can be made thinner than when the composition is applied.

After the film-form curable organopolyoxane composition is produced by the method mentioned above, heat curing, room temperature curing or high energy beam irradiation curing may be performed, and the target of dielectric inorganic fine particles as the case may be. An electric field or a magnetic field is applied in the orientation direction, or curing is performed after the filler is oriented by applying a magnetic field or an electric field for a fixed period of time. Although the conditions during each curing operation or each curing operation are not specifically limited, if the curable organopolyoxane composition is a form-formable curable organopolyoxane composition, the curing is preferably at 90 ° C. The temperature range of up to 180 ° C is carried out by staying in this temperature range for 30 seconds to 30 minutes.

The polyoxylene elastomer used for the converter is not particularly limited, and the thickness may be, for example, 1 μm to 2,000 μm. The polyoxyxene elastomer for a converter of the present invention may be stacked in one or two or more layers. Further, an electrode layer may be provided at both tips of the dielectric elastic layer, and a configuration in which the converter itself is composed of a plurality of stacked electrode layers and a dielectric elastic layer may be used. The thickness of the polyoxyxene elastomer for the converter of each of the single layers can be from 0.1 μm to 1,000 μm. If the layers are stacked in at least 2 layers, each single layer may have a thickness of 0.2 μm to 2,000 μm.

Although the molding method of the two or more yttrium elastic cured layers stacked in the manner mentioned above is not particularly limited, methods such as the following may be used: (1) Combination of curable organic polyoxane Applying on the substrate, curing the coating, obtaining a cured polyoxyxene elastomer layer, and then further applying the curable organopolyoxyalkylene composition on the same cured layer to repeatedly coat and cure to stack the plurality of layers; 2) coating the curable organopolyoxane composition in an uncured or semi-cured state on a substrate in a stacked manner, and curing all of the curable organopolyoxane compositions that have been applied in a stacked manner; or a combination (1) Method and (2) Method of method.

For example, the curable organopolyoxyalkylene composition can be applied to the substrate by die coating, can be cured, and 2 or more of the polyoxyelastomer cured layers can be formed by stacking, and The ruthenium elastomer cured layer is attached to the electrode layer for use in the manufacture of the present invention. For this configuration, the two or more stacked tantalum elastomer cured layers are preferably dielectric layers, and the electrodes are preferably conductive layers.

High speed coating can be carried out by die coating, and this coating method has a high yield. After coating a monolayer comprising an organopolyoxane composition, the multi-layered configuration of the present invention can be fabricated by coating a layer comprising a different organopolyoxane composition. Further, it can be produced by simultaneously coating a plurality of layers containing each organopolyoxane composition.

The film-like polyoxyxene elastomer as a converter component can be obtained by coating the above-mentioned curable organopolyoxane composition on a substrate, and The assembly is then cured at room temperature and by heating or by using high energy beam irradiation (e.g., ultraviolet radiation or the like). Further, when the film-like dielectric polyoxyelastomer is stacked, the uncured curable organopolyoxane composition may be applied to the cured layer and then sequentially cured, or the uncured curable organic polymer may be polymerized. The oxoxane composition is stacked in layers and the layers can then be cured simultaneously.

The film-like polyoxynene elastomer mentioned above is especially useful as a dielectric layer for a converter. The converter can be formed by disposing an electrode layer on both ends of the film-like polyoxyelastomer. Further, the electrode layer function can be provided by blending conductive inorganic particles into the curable organopolyoxane composition of the present invention. Further, in the patent specification of the present invention, the "electrode layer" may be simply referred to as "electrode".

One embodiment of the converter component mentioned above is in the form of a sheet or a film. The film thickness is usually from 1 μm to 2,000 μm, and the film may have a single layer, two or more layers or other number of stacked layer structures. Further, the stacked electroactive polyoxoelastic layers may be used as a film thickness of 5 μm to 10,000 μm when used as a dielectric layer, or may be stacked to obtain a larger thickness, as may be required.

The film-like polyoxoelastic layer as the converter member can be formed by stacking the same film-like polyoxyelastomer, or can be formed into a film-like polyoxoelastic having two or more different physical properties. The pre-cured composition is stacked to form this converter component. Further, the film-like polyoxoelastic layer may function as a dielectric layer or an electrode layer. Specifically, in a preferred converter component, the thickness of the dielectric layer is from 1 to 1,000 μm, and the thickness of the electrode layer is from 0.05 μm to 100 μm.

The converter of the present invention is characterized by having such a converter component manufactured by curing the curable organopolyoxane composition for a converter of the present invention, and the converter of the present invention has a layer structure including, in particular, a highly stacked layer The structure of (ie, 2 or more dielectric layers). The converter of the present invention may further have a structure including three or more dielectric layers. A converter having this height stack type can generate more force by including multiple layers. In addition, A displacement greater than the displacement obtained by using a single layer can be obtained by stacking a plurality of layers.

The converter of the present invention preferably has (i) a stacked dielectric layer member containing an organopolyoxane, or (ii) a dielectric layer having an organopolyoxane and at least on one side of the dielectric layer. A stack structure of electrode layers. Stacking the dielectric layer component (i) or a stacked structure (ii) having a dielectric layer and an electrode layer on at least one side of the dielectric layer may cure each of the curable organopolyoxane compositions in a stepwise manner One layer is formed by a one-time curing of the stacked coating.

Preferably, in the step-wise curing method, the component (i) or the stacked structure (ii) is prepared by the following steps: curing organic polymerization of two or more cured bodies having different electrical properties or mechanical strengths A curable organopolyoxane composition in the oxoxane composition is applied to the substrate, and the coating is cured into a cured polyoxyxene elastomer layer, and then the other curable organopolyoxane composition is further Apply on the same cured layer and, if necessary, repeat the cured coating. On the other hand, in the one-time curing method, the component (i) or the stacked structure (ii) is preferably prepared by the following steps: curing the electrical properties or mechanical strength of two or more of the cured bodies thereof A curable organopolyoxane composition in the organopolyoxane composition is coated on the substrate, and then the other curable organopolyoxyalkylene composition is further coated on the same coating layer, and the stack is cured. Two or more different coating layers.

Electrodes may be included at both ends of the dielectric layer used in the converter of the present invention. The electrode materials used are exemplified by metals and metal alloys such as gold, platinum, silver, palladium, copper, nickel, aluminum, titanium, zinc, zirconium, iron, cobalt, tin, lead, indium, chromium, molybdenum, manganese or the like. a metal oxide such as an indium-tin compound oxide (ITO), a bismuth-tin compound oxide (ATO), cerium oxide, titanium oxide, zinc oxide, tin oxide, and the like; a carbon material such as a carbon nanotube, carbon A nanohorn, a carbon nanosheet, a carbon fiber, a carbon black or the like; and a conductive resin such as poly(extended ethyl-3,4-dioxythiophene) (PEDOT), polyaniline, polypyrrole or the like. A conductive elastic material and a conductive resin having a conductive filler dispersed in the resin can be used.

The electrode may include only one of the above-mentioned conductive materials, or may include two Or more of these conductive materials. If the electrode includes two or more types of conductive materials, one of the conductive materials functions as an active material, and the remaining conductive materials function as a conductive material that lowers electrode resistance.

The total thickness of the dielectric layer used in the converter of the present invention can be set in the range of 10 μm to 2,000 μm (2 mm), but the total thickness can be set to a value greater than or equal to 200 μm in particular. Specifically, the thickness of each of the single layers of the dielectric polyoxyelastomer layer forming the dielectric layer is preferably from 0.1 μm to 500 μm, and the thickness is particularly preferably from 0.1 μm to 200 μm. Characteristics such as dielectric breakdown voltage, dielectric constant, and displacement amount can be improved by stacking two or more layers of the thin layers of the polyoxyelastomers as compared with the use of a single layer.

The converter of the present invention is particularly useful as an artificial muscle, actuator, sensor or power generating component due to the dielectric and mechanical properties of the converter of the present invention. Artificial muscles are expected to be used for applications such as robots, nursing equipment, rehabilitation training equipment, or the like. An embodiment as an actuator will be explained below in the form of an example of the present invention.

[Fig. 1 to Fig. 4]

1 shows a cross-sectional view of an actuator 1 of an embodiment of the present invention in which a dielectric layer is stacked. In this embodiment, the dielectric layer is composed of, for example, two dielectric layers. The actuator 1 is provided with dielectric layers 10a and 10b, electrode layers 11a and 11b, wires 12, and a power source 13. The electrode layers 11a and 11b cover respective contact surfaces of the dielectric layer, and the electrode layers are connected to the power source 13 via respective wires 12.

The actuator 1 can be driven by applying a voltage between the electrode layer 11a and the electrode layer 11b. By applying a voltage, the dielectric layers 10a and 10b are thinned by dielectric properties, and are elongated parallel to the faces of the electrode layers 11a and 11b. That is, electrical energy can be converted into force or mechanical energy for movement or displacement.

2 shows a cross-sectional view of an actuator 2 of an embodiment of the present invention in which a dielectric layer and an electrode layer are stacked. For example, according to an embodiment of the present invention, the dielectric layer is composed of three layers, and the electrode layer is composed of four layers. The actuator 2 is provided with dielectric layers 20a, 20b and 20c, an electrode layer 21a, 21b, 21c and 21d; wire 22; and power source 23. The electrode layers 21a, 21b, 21c, and 21d each cover respective contact surfaces of the dielectric layer, and the electrode layers are connected to the power source 23 via respective wires 22. The electrode layers are alternately connected to different voltage sides, and the electrode layers 21a and 21c are connected to the side different from the electrode layers 21b and 21d.

The actuator 2 can be driven by applying a voltage between the electrode layer 21a and the electrode layer 21b, applying a voltage between the electrode layer 21b and the electrode layer 21c, and applying a voltage between the electrode layer 21c and the electrode layer 21d. By applying a voltage, the dielectric layers 20a, 20b, and 20c are thinned by dielectric properties, and are elongated parallel to the faces of the electrode layers 21a, 21b, 21c, and 21d. That is, electrical energy can be converted into force or mechanical energy for movement or displacement.

Although an embodiment of the actuator is illustrated as an example of a converter of the present invention, when mechanical energy (e.g., pressure or the like) is applied from the outside to the converter of the present invention, a potential difference form may be generated between mutually insulated electrode layers. Electrical energy. That is, it can be used as a sensor for converting mechanical energy into electrical energy. This embodiment of the sensor will be explained below.

Figure 3 shows the structure of a sensor 3 in accordance with an embodiment of the present invention. The sensor 3 has a structure in which the dielectric layer 30 is disposed between the upper electrode layers 31a, 31b, and 31c and the lower electrode layers 32a, 32b, and 32c in a matrix-like mode. According to an embodiment of the present invention, for example, the electrode layers are arranged in a matrix mode of three columns in the vertical direction and the horizontal direction, respectively. An insulating layer can be used to protect the surface of each electrode layer that does not contact the dielectric layer 30. Further, the dielectric layer 30 may include two or more layers of the same dielectric layer containing an organopolyoxane.

When an external force is applied to the surface of the sensor 3, the thickness of the dielectric layer 30 interposed between the upper electrode layer and the lower electrode layer changes at the pressing position, and the static capacitance between the electrode layers changes accordingly. And change. The external force can be detected by measuring the potential difference between the electrode layers caused by the change in the static capacitance between the electrode layers. That is, this embodiment can be used as a sensor for converting mechanical energy into electrical energy.

In addition, although three pairs of opposite electrode layers sandwiching the dielectric layer are formed in the sensor 3 of the embodiment of the present invention, the number, size, layout or the electrodes of the electrodes may be appropriately selected depending on the application. And so on.

A power generation component is a converter for converting mechanical energy into electrical energy. This power generating element can be used for a power generating device, starting with power generation by natural energy (such as wave, hydraulic, hydraulic, or the like) and power generation due to vibration, impact, pressure change, or the like. Embodiments of this power generating component will be described below.

4 shows a cross-sectional view of a power generating element 4 of an embodiment of the present invention in which a dielectric layer is stacked. In this embodiment, the dielectric layer is composed of, for example, two dielectric layers. The power generating element 4 is composed of dielectric layers 40a and 40b and electrode layers 41a and 41b. The electrode layers 41a and 41b are configured to cover one face of the respective dielectric layers that are in contact.

The electrode layers 41a and 41b are electrically connected to a load not illustrated. This power generating element 4 can change the static capacitance by changing the distance between the electrode layers 41a and 41b, thereby generating electric energy. That is, since the shape of the element between the electrode layers 41a and 41b in the electrostatic charge induction state is changed by the formation of the electrostatic field by the dielectric layers 40a and 40b, the charge distribution is shifted, and the static capacitance between the electrode layers is caused. This shift changes and a potential difference is generated between the electrode layers.

In the embodiment of the present invention, since the state in which the compressive force is applied in the direction parallel to the faces of the electrode layers 41a and 41b of the power generating element 4 shown in Fig. 4 (upper image) becomes uncompressed as shown in the same figure In the state (below), a potential difference is generated between the electrode layers 41a and 41b, and the power generation element can be realized by outputting this potential difference change in the form of electric power. That is, mechanical energy can be converted into electrical energy. Further, a plurality of components may be disposed on the substrate, and a power generating device that generates a larger amount of electricity may be constructed by connecting the plurality of components in series or in parallel.

The converter of the present invention can be operated in air, water, vacuum or an organic solvent. Further, the converter of the present invention can be suitably sealed in accordance with the environment in which the converter is used. The sealing method is not particularly limited, and this sealing method is exemplified by using a resin material or the like.

Preferably, the converter of the present invention has a solid state for use in a converter by curing A polyoxyxene elastomer component formed from an organopolyoxane composition.

First, each of the polyoxyn components of the curable organopolyoxane composition will be explained, [characteristic 1] to [characteristic 3] and optional [characteristic 4] and [characteristic 5].

[Reactive Organic Polyoxane]

The curable organopolyoxane composition of the present invention comprises _a reactive organopolyoxane represented by the general formula M _a M ^R _b D _c D ^R _d T _e T ^R _f Q _g . In the above-mentioned formula, M represents a triorganomethoxy group, D represents a diorganomethoxy group, T represents a _{monoorganomethoxy} group, and Q represents a methoxy group of SiO _4/2 . M ^R , D ^R and T ^R are decyloxy units, wherein one R substituent group of the methoxy unit represented by M, D and T, respectively, can be subjected to a condensation reaction, an addition reaction, a peroxidation reaction or a photoreaction reaction. The substituent group in which the curing reaction is carried out; however, the group is preferably a group capable of undergoing an addition reaction. Among these groups, in view of a high reaction rate and a low side reaction, a substituent group capable of undergoing a curing reaction is preferably a group active in a hydrogenation reaction, that is, a hydrogen atom or a fat containing a ruthenium atom-bonded bond. a group of a group of unsaturations (for example, an alkenyl group having 2 to 20 carbon atoms or the like). Further, the non-R substituent group of the reactive organopolyoxyalkylene mentioned above is preferably a group which does not participate in the addition reaction or is a high dielectric functional group, as exemplified as an alkyl group such as a methyl group, Ethyl, propyl, butyl, hexyl or the like; aryl, such as phenyl, o-tolyl, p-tolyl, naphthyl, halophenyl or the like; alkoxy; or the like. From an economic point of view, the methyl group is preferred in such groups. Specific examples of the reactive organopolyoxyalkylene include a trimethyl methoxy-bi-molecular chain-terminated dimethyl methoxy oxane-methylhydroquinone copolymer, a trimethyl decyloxy-bi-molecular chain a blocked dimethyl methoxy alkane-methylvinyl fluorene copolymer, a dimethylhydroquinone-bi-molecular chain-terminated dimethyl methoxy oxane-methyl hydrazine copolymer, Dimethylvinyl methoxy-bi-molecular chain-terminated dimethyl methoxy oxane-methyl vinyl fluorene copolymer, methyl oxa oxide - dimethyl methoxy hydride - methyl hydrazine An alkane copolymer, a methyl oxane-dimethyl methoxyalkane-methylvinyl fluorene copolymer, a dimethyl hydrogen functional MQ resin, a dimethyl vinyl functional MQ resin or the like.

The reactive organic polyoxyalkylene mentioned above has a number average molecular weight (Mw) in the range of from 300 to 10,000. Further, although there is no particular limitation on the viscosity of the rheological measurement equipped with a 20 mm diameter cone plate at a shear rate of 10 (s ^-1 ) at 25 ° C, the viscosity is preferably between 1 mPa. s to 10,000mPa. Within the s range, and especially between 5mPa. s to 5,000mPa. Within the scope of s.

[Characteristic 1]: Content of reactive organic polyoxane

When the reactive organopolysiloxane described above is formed such that the value of (a+c)/(b+d+e+f+g) is less than 3) relative to the curable organopolyoxane When the proportion of the total amount of the oxoxane component in the composition is less than 0.1% by weight, the number of crosslinking points in the polyoxyalkylene component is too low, and thus the mechanical strength and dielectric breakdown strength after the curing reaction are insufficient. On the contrary, a ratio of more than 25% by weight is not suitable because the number of crosslinking points is excessive, and thus the elasticity after curing is high, and the elongation at break is low. This ratio is preferably less than or equal to 10% by weight.

[Characteristic 2]: Reactive organopolyoxane having only a group capable of undergoing a curing reaction at both ends of the molecule

Reactive organopolyoxane having only a group capable of undergoing a curing reaction at the end of two molecular chains will be explained below. Here, the term "group capable of undergoing a curing reaction" means a group which can be used as a group in a condensation reaction, an addition reaction, a peroxidation reaction or a photoreaction. However, for reasons similar to those set forth above, this group is preferably capable of undergoing an addition reaction. In such groups capable of undergoing an addition reaction, the group is preferably active in a hydrogenation reaction, that is, the group contains a group of a hydrogen atom bonded to a halogen atom or a group containing an aliphatic unsaturated bond. a group (for example, an alkenyl group having 2 to 20 carbon atoms or the like). Specific examples of the reactive organopolyoxyalkylene include dimethylhydroquinoneoxy-bi-molecular chain-terminated polydimethyl methoxy oxane and dimethylvinyl fluorenyl-bi-molecular chain terminated poly Methyl decane. To further suit material properties such as mechanical properties, dielectric properties, heat resistance properties, or the like, a portion of the methyl groups of the polymers can be replaced with ethyl, propyl, butyl, hexyl or phenyl groups.

The number average molecular weight (Mw) of the reactive organopolyoxane having only a group capable of undergoing a curing reaction at the end of two molecular chains is in the range of 300 to 100,000. Further, although there is no particular limitation on the viscosity of the rheological measurement equipped with a 20 mm diameter cone plate at a shear rate of 10 (s ^-1 ) at 25 ° C, the viscosity is preferably between 1 mPa. s to 100,000mPa. Within the s range, and especially between 5mPa. s to 10,000mPa. Within the scope of s.

a proportion of the reactive organopolyoxane having only a group capable of undergoing a curing reaction at the end of two molecular chains with respect to less than 75% by weight of the total oxane component in the curable organopolyoxane composition Not suitable, because high elongation at break may not be achieved. On the contrary, when the value exceeds 99.9% by weight, the proportion of molecules participating in the crosslinking reaction becomes low, and the mechanical strength and dielectric breakdown strength after curing are insufficient. Therefore, a ratio of more than 99.9% by weight is not suitable.

[Characteristic 3]: Application of two types of reactive organopolyoxyalkylenes (S) and (L)

The reactive organic polyoxyalkylene (S) has an average molecular weight of less than 10,000 between the two groups capable of undergoing a curing reaction, and is a reactive organic having at least two groups capable of undergoing a curing reaction in a single molecule. Polyoxyalkylenes are used in the present invention. The reactive organic polyoxyalkylene (L) has an average molecular weight between the two groups capable of undergoing a curing reaction of greater than or equal to 10,000 and less than or equal to 150,000, which has at least two capable of curing in a single molecule. The reactive organopolyoxane of the group is used in the present invention. The reactive organopolyoxanes are contained in the molecule as a short chain non-reactive polymer portion and a long chain non-reactive polymer portion, respectively. Here, in the case of a chain type organopolyoxane having only a reactive functional group at both ends of a molecular chain, the molecular weight between the two groups capable of undergoing a crosslinking reaction is defined as non-reactivity The molecular weight of the polyoxyalkylene moiety (which does not contain the two terminal methoxy units). In the case of a molecular weight between a plurality of groups capable of undergoing a crosslinking reaction, this molecular weight is the molecular weight of the longest portion.

When the component (S) and the component (L) are used together as a reactive organopolyoxane raw material in the range of 1:99 to 40:60, portions of different chain lengths may be introduced into the polyoxyxene chain moiety. thereby A polyoxyxene elastomer obtained by a curing reaction is formed. In this way, the permanent strain of the obtained polyoxynitride polymer can be reduced, and the mechanical energy conversion loss can be reduced. Specifically, when the polyoxyxene elastomer of the present invention is used in a dielectric layer of a converter, the combined use of the component (S) and the component (L) has a practical advantage of improving energy conversion efficiency.

As mentioned previously, a group capable of undergoing a condensation reaction, an addition reaction, a peroxidation reaction or a photoreaction may be used as a group capable of undergoing a curing reaction of the components. However, this group is preferably a group capable of undergoing an addition reaction. In the group capable of undergoing an addition reaction, the group is preferably a group active in a hydrogenation reaction, that is, a group containing a hydrogen atom bonded to a halogen atom or an aliphatic unsaturated bond (for example, having 2 to Alkenyl of 20 carbon atoms or the like). Specific examples of reactive organopolyoxyalkylenes (S) and (L) are cited as reactive organic compounds represented by M _a M ^R _b D _c D ^R _d T _e T ^R _f Q _g as mentioned above. Examples of polyoxyalkylenes and examples cited as reactive organopolysiloxanes having the groups capable of undergoing a curing reaction at the ends of two molecular chains mentioned above. For the same reasons as explained above, a portion of the methyl group may be replaced by an ethyl group, a propyl group, a butyl group, a hexyl group or a phenyl group.

The ratio of the composition (S) deviating from the range of 1:99 to 40:60 to the composition (L) described below (weight ratio) S:L cannot satisfy the at least one type of the cured article obtained. The characteristics are unsuitable, and these characteristics include high elongation at break, high mechanical strength, high dielectric breakdown strength, and low modulus of elasticity.

The blend ratio (mol ratio) of the hydrogen atom bonded to the ruthenium atom in the polyoxyalkylene to the unsaturated hydrocarbon group (Vi) bonded to the ruthenium atom is preferably in the range of 0.5 to 3.0. When the blend ratio deviates from the range mentioned above, the residual functional groups remaining after the curing due to the hydrogenation reaction may adversely affect the physical properties of the material of the cured article.

[Characteristic 4] Number of crosslinking points per unit weight after curing reaction

Further, the curable organopolyoxane composition for a converter of the present invention includes (A) and (B) as explained below. The number of cross-linking points per unit weight of the reactive polyoxyalkylene after the curing reaction is defined by the following formulas based on the following formula: (A) component and (B) each component of the component The number average molecular weight, the values of a _i to g _i and a _j to g _{j in} the formulae described below, and the content of each component in the composition. The number of crosslinking points per unit weight of the reactive polyoxyalkylene after the curing reaction is preferably in the range of from 0.5 μmol/g to 20 μmol/g, and further preferably in the range of from 0.5 μmol/g to 10 μmol/g.

(A) an organohydrogen polyoxyalkylene comprising one or more components represented by the formula M _ai M ^H _bi D _ci D ^H _di T _ei T ^H _fi Q _gi having a range of from 300 to 15,000 a number average molecular weight (Mw) and an average of at least 2 矽 bonded hydrogen atoms in a single molecule

(B) an organopolyoxane comprising one or more components, represented by the formula M _aj M ^Vi _bi D _ci D ^Vi _dj T _ej T ^Vi _fj Q _gj , having a quantity ranging from 300 to 100,000 It has an average molecular weight (Mw) and has an average of at least 2 alkenyl groups in a single molecule.

In the above-mentioned formula, M represents R ₃ SiO _1/2 ; D represents R ₂ SiO _2/2 ; T represents RSiO _3/2 ; and Q is a siloxane unit represented by SiO _4/2 . R is a monovalent organic group having no aliphatic carbon-carbon double bond; M ^H , D ^H and T ^H is a oxoxane unit, wherein one R group of a oxoxane unit represented by M, D and T, respectively; Substitution of a hydrogen atom via a ruthenium atom; M ^Vi , D ^Vi and T ^Vi are oxoxane units, wherein one R group of the oxoxane unit represented by M, D and T, respectively, has 2 to 20 carbons Alkenyl substitution of atoms; a is the average of each single molecule; b is the average of each single molecule; c is the average of each single molecule; d is the average of each single molecule; e is the average of each single molecule f is the average number per single molecule; and g is the average number per single molecule; i is the ith component of component (A); and j is the jth component of component (B).

The number of cross-linking points per unit weight mentioned above is calculated using the index values listed below, which are defined by each of the formulas for: (i) end groups The index of the probability of reaction, (ii) the index of the number of crosslinking points of the reaction composition, (iii) the index of the molar count of the raw material in the reaction composition, and (iv) the index of the molecular weight of the reaction composition:

Here, the formula defining each of the above mentioned indices is listed below:

(i) The index of the probability of reaction between the end groups is represented by the following formula.

(ii) The index of the number of crosslinking points of the reaction composition is represented by the following formula based on the index of the reaction rate between the end groups mentioned above.

However, in the calculation of the index of the number of crosslinking points of the reaction composition, (a+c)/(b+d+e) which represents the average number of organic oxirane units between the reactive groups in the molecular chain The component having a value of less than 3 of +f+g) is regarded as a single crosslinking point, and for this component, calculation is performed in accordance with (b+d)=0 and (e+f+g)=1.

(iii) The index of the raw material molar count in the reaction composition is represented by the following formula.

(iv) The index of the molecular weight of the reaction composition is represented by the following formula.

Here, [alpha] _i-based parts component (A) of the i-th component of the blended amount of the α ^w _i (by weight of the amount) of the component divided by the number of bonds of silicon bound hydrogen atoms H (A) contained in the (Mohr) and the ratio of the alkenyl number Vi (mole) contained in the component (B) (γ = H (mole) / Vi (mole)), that is, α _i = α ^w _i / γ ; β _j represents the blending amount (by weight) of the jth component of the component (B); M _wi represents the number average molecular weight of the i-th component of the component (A); and M _wj represents The number average molecular weight of the jth component of component (B).

[Characteristic 5] Molecular weight between crosslinking points after curing reaction

Further, the molecular weight between the cross-linking points of the reactive polyoxyalkylene after the curing reaction is defined by the following formula: the number average molecular weight of each component of the component (A) and the component (B), The values of a _i to g _i and a _j to g _j of the following general formula and the concentration of each component in the composition, wherein the molecular weight between the crosslinking points of the reactive polyoxyalkylene after the curing reaction is preferably from 100,000 to Within 2,000,000, and further preferably in the range of 200,000 to 2,000,000:

(A) is an organohydrogen polyoxyalkylene comprising one or more components represented by the formula M _ai M ^H _bi D _ci D ^H _di T _ei T ^H _fi Q _gi having a range of from 300 to 15,000 The number average molecular weight (Mw) and has an average of at least 2 ruthenium-bonded hydrogen atoms in a single molecule.

(B) is an organopolyoxane comprising one or more components, represented by the formula M _aj M ^Vi _bi D _ci D ^Vi _dj T _ej T ^Vi _fj Q _gj , having a range of from 300 to 100,000 The number average molecular weight (Mw) and has an average of at least 2 alkenyl groups in a single molecule.

(C) is a catalyst for carrying out an addition reaction between the component (A) and the component (B) mentioned above.

In the above-mentioned formula, M represents R ₃ SiO _1/2 ; D represents R ₂ SiO _2/2 ; T represents RSiO _3/2 ; and Q is a siloxane unit represented by SiO _4/2 . R is a monovalent organic group having no aliphatic carbon-carbon double bond; M ^H , D ^H and T ^H is a oxoxane unit, wherein one R group of a oxoxane unit represented by M, D and T, respectively; Substitution of a hydrogen atom via a ruthenium atom; M ^Vi , D ^Vi and T ^Vi are oxoxane units, wherein one R group of the oxoxane unit represented by M, D and T, respectively, has 2 to 20 carbons Alkenyl substitution of atoms; a is the average of each single molecule; b is the average of each single molecule; c is the average of each single molecule; d is the average of each single molecule; e is the average of each single molecule f is the average number per single molecule; and g is the average number per single molecule; i is the ith component of component (A); and j is the jth component of component (B).

The cross-linking point molecular weight mentioned above is based on an index value calculated based on the calculation formula for the following items: (i) an index of the reaction rate between the end groups, and (ii') an organic hydrazine of the reaction composition. The index of the oxyalkylene chain count, (iii) the index of the raw material mole count in the reaction composition, and (iv) the index of the molecular weight of the reaction composition:

Here, the formula defining each of the above mentioned indices is listed below:

(i) The index of the probability of reaction between the end groups is represented by the following formula.

(ii') The index of the organooxyne chain count of the reaction composition is represented by the following formula.

However, in the calculation of the index of the number of crosslinking points of the reaction composition, (a+c)/(b+d+e) representing the average of the organooxane units between the reactive groups in the molecular chain. A component having a value of less than 3 of +f+g) is regarded as a single cross-linking point, and the calculation assumption (d+2e+2f+3g+1)=0 for the component.

(iii) The index of the raw material molar count in the reaction composition is represented by the following formula.

(iv) The index of the molecular weight of the reaction composition is represented by the following formula.

In the formula mentioned above, [alpha] _i-based parts component (A) of the i-th component of the blended amount of the α ^w _i (the amount by weight) divided by the silicon component (A) contained in the The ratio of the number of bonded hydrogen atoms H (mole) to the number of alkenyl groups Vi (mole) contained in the component (B) (γ = H (mole) / Vi (mole)), that is, α _i =α ^w _i /γ; β _j represents the blending amount of the jth component of component (B) (by weight); M _wi represents the average number of the ith component of component (A) Molecular weight; and M _wj represents the number average molecular weight of the jth component of component (B). The number average molecular weight (Mw) mentioned above is a value measured by nuclear magnetic resonance (NMR) measurement.

Molecular design to adjust the molecular weight per unit weight and the molecular weight between cross-linking points after solidification of the organopolysiloxane to some of the formulas based on the formulae described in this patent specification Within the enclosure, adjustments may be made such that the obtained polyoxyelastomer cured article has electrical and mechanical properties suitable for the components of the converter. The addition curable organopolyoxane composition for producing a polyoxyxene elastomer cured article and a polyoxyxene elastomer can be obtained by the molecular design, and the polyoxyxene elastomer cured article and the polyoxyxene elastomer Suitable as a material for use as a dielectric material with excellent properties, a dielectric material for converter components, in particular a dielectric elastomer, and further particularly a converter component.

[curing agent (C)]

The curable organopolyoxane composition for a converter of the present invention comprises a curing agent (C) as an essential component.

Component (C) is preferably a generally known hydrogenation reaction catalyst. The component (C) used in the present invention is not particularly limited as long as the component (C) is a substance capable of promoting the hydrogenation reaction. This component (C) is exemplified as a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst. Since the catalytic activity is high, a platinum family element catalyst and a platinum family element compound catalyst are particularly cited as the component (C). The platinum-based catalyst is exemplified by platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin-platinum complex, platinum-carbonyl complex, for example, without specific limitation. Bis-acetonitrile platinum, bis(acetic acid) platinum or the like; chloroplatinic acid-alkenyl alkoxylate complex, such as chloroplatinic acid-divinyltetramethyldioxane complex, Chloroplatinic acid-vinyltetramethylcyclotetraoxane complex or the like; platinum-alkenyl alkoxylate complex, such as platinum-divinyltetramethyldioxane complex, platinum- a tetravinyltetramethylcyclotetraoxane complex or the like; and a complex between chloroplatinic acid and acetylene alcohol. Since the catalytic activity for the hydrogenation reaction is high, a preferred example of the component (C) is a platinum-alkenyl alkane complex, and in particular platinum 1,3-divinyl-1,1,3 , 3-tetramethyldioxane complex.

Further, in order to further improve the stability of the platinum-alkenyl alkoxysilane complex, the platinum-alkenyl alkoxylate complex may be dissolved in an organic siloxane oxide oligomer such as: 1,3 -divinyl-1,1,3,3-tetramethyldioxane, 1,3-diallyl-1,1,3,3-tetramethyldioxine Alkane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldioxane, 1,3-divinyl-1,1,3,3-tetraphenyl a decane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane or the like alkenyl oxyalkylene oligomer; or dimethyloxane An alkane oligomer; or the like. Specifically, a platinum-alkenyl alkoxylate complex dissolved in an alkenyloxyalkane oligomer is preferably used.

The component (C) may be used in an amount which is capable of promoting the addition reaction of the polyoxyalkylene component of the composition of the present invention, without particular limitation. The concentration of the platinum group metal element (for example, platinum) contained in the component (C) is usually in the range of 0.01 ppm to 500 ppm, preferably in the range of 0.1 ppm to 100 ppm, based on the total weight of the polyoxyalkylene component. And further preferably in the range of 0.1 ppm to 50 ppm.

[Dielectric Inorganic Fine Particles (D)]

The curable organopolyoxane composition for a converter of the present invention is characterized by containing as an essential component: a curable organopolyoxane composition having the above-mentioned characteristics, a curing agent, and (D) A dielectric particle having a specific dielectric constant greater than or equal to 10 at 1 kHz at room temperature. By supporting the dielectric inorganic fine particles in the cured article comprising the curable organopolysiloxane described above, both the physical and electrical properties required for the converter are satisfied.

The dielectric inorganic fine particles may be selected, for example, from the metal oxide (D1) represented by the formula (D1) listed below (hereinafter sometimes abbreviated as "metal oxide (D1)"): M ^a _na M ^b _nb O _nc (D1)

(In the formula, M ^a train of periodic table Group 2 metal; a metal of Group 4 of the Periodic Table of the lines M ^b; Na-based number from the range from 0.9 to 1.1; Nb lines between the range of 0.9 to 1.1 Number; and nc is a number between 2.8 and 3.2).

Preferred examples of the Group 2 metal M ^a of the periodic table in the metal oxide (D1) include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba). A preferred example of the titanium (Ti) is cited as the Group 4 metal M ^b of the periodic table. In the particles of the metal oxide represented by the formula (X1), each of M ^a and M ^b may be a single element or may be two or more elements.

Specific examples of the metal oxide (D1) include barium titanate, calcium titanate, and barium titanate.

Further, the dielectric inorganic fine particles may be selected, for example, from a metal oxide represented by the following formula (hereinafter may be referred to as "metal oxide (D2)"): M ^a _na M ^b' _nb' O _nc (D2)

(In the formula, M ^a train of periodic table Group 2 metal; M ^{b 'train} of periodic table Group 5 metal; Na-based number from the range from 0.9 to 1.1; nb' line range between 0.9 to 1.1 The number within; and nc is a number between 2.8 and 3.2).

Preferred examples of the Group 2 metal M ^a of the periodic table in the metal oxide (D2) include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba). Preferred examples of the Group 5 metal element M ^{b '} of the periodic table include tin (Sn), bismuth (Sb), zirconium (Zr), and indium (In). In the particles of the metal oxide represented by the formula (X2), each of M ^a and M ^{b '} may be a single type of element or may be two or more elements.

Specific examples of the metal oxide (D2) include magnesium stannate, calcium stannate, barium stannate, barium stannate, magnesium citrate, calcium citrate, barium strontium citrate, barium strontium silicate, magnesium zirconate, calcium zirconate, Barium zirconate, barium zirconate, magnesium indium, calcium indium, barium indium, barium indium or the like.

Furthermore, in combination with such metal oxide particles, particles of other metal oxides may be permitted, such as lead zirconate titanate, zinc titanate, lead titanate, titanium oxide or the like (especially in addition to those previously listed) Titanium oxide composite oxides other than those). Further, a solid solution including a metal element different from the above examples may be used as the dielectric inorganic fine particles (D). In this case, other metal elements are exemplified as La (镧), Bi (铋), Nd (钕), Pr (鐠), or the like.

Among the inorganic fine particles, preferred examples of the dielectric inorganic fine particles (D) include one or more types of inorganic fine particles selected from the group consisting of titanium oxide, barium titanate, barium titanate, and zirconium titanium. Lead acid and barium titanate, and composite metal oxides in which the barium and barium titanate portions are replaced by an alkaline earth metal such as calcium or barium, zirconium or a rare earth metal such as lanthanum, cerium, lanthanum or cerium. Titanium oxide, barium titanate, barium titanate, and a composite metal oxide in which the barium strontium titanate and barium zirconate are partially replaced by calcium, and titanium oxide and barium titanate are preferred.

The form of the dielectric inorganic fine particles (D) is not particularly limited, and any form such as a spherical shape, a flat shape, a needle shape, a fibrous shape or the like can be used. The particle diameter of the inorganic fine particles is not particularly limited, and if the spherical fine particles are measured by a laser diffraction method, for example, the volume average particle diameter may be, for example, in the range of 0.01 μm to 1.0 μm. The average particle diameter is preferably in the range of from 0.1 μm to 5 μm from the viewpoint of molding processing ability and film forming ability. If the inorganic fine particles are anisotropic fine particles in which the form is flat, needle-like, fibrous or the like, the aspect ratio may be usually greater than or equal to 5 although the aspect ratio of the fine particles is not limited.

The particle size distribution of the dielectric inorganic fine particles is not particularly limited, and the dielectric inorganic fine particles may be monodisperse fine particles, or alternatively, may be filled at a higher density by reducing the void fraction between the fine particles. To produce a particle diameter distribution to improve mechanical strength. As a measure of the particle diameter distribution, the ratio of the particle diameter under the 90% cumulative area (D ₉₀ ) of the cumulative particle diameter distribution curve measured by the laser light diffraction method to the particle diameter under the 10% cumulative area (D ₁₀ ) ( D ₉₀ /D ₁₀ ) is preferably greater than or equal to 2. Further, there is no limitation on the particle diameter distribution shape (the relationship between the particle diameter and the particle concentration). There may be a so-called high prototype distribution or a particle diameter distribution that is multimodal (i.e., bimodal (i.e., having two mountain-shaped distributions), three peaks, or the like).

In order to produce a particle size distribution of a particle size distribution such as the above-described dielectric inorganic fine particles used in the present invention, various methods may be employed, for example, two or more types are used in combination. Fine particles having different average diameters or particle size distributions, doped with particles of various particle diameter fractions obtained by sieving or the like to produce a desired particle size distribution, or the like.

Furthermore, the dielectric inorganic fine particles can be treated using various types of surface treatment agents as set forth below.

Considering the mechanical properties and dielectric properties of the cured article obtained, the blending amount (load fraction) of the dielectric inorganic fine particles of the curable organopolyoxane composition for a converter of the present invention is relative to the composition. The total volume may be greater than or equal to 10%, preferably greater than or equal to 15%, and further preferably greater than or equal to 20%. Further, the blending amount is preferably less than or equal to 80%, and further preferably less than or equal to 70%, relative to the total volume of the composition.

As a preferred embodiment of the curable organopolyoxane composition for a converter of the present invention, a composition comprising the following as an essential component is cited: (A1) at least one type of organohydrogenpolyoxane, It has a hydrogen atom bonded to a ruthenium atom at two molecular ends and has a hydrogen atom weight content of 0.01% by weight to 1.0% by weight, (A2) at least one type of organohydrogen polyoxyalkylene having at least one molecule in a single molecule 3 helium atom-bonded hydrogen atoms and having a hydrogen atom weight content of 0.03 wt% to 2.0 wt%, (B) at least one type of organopolyoxane having at least 2 alkenyl groups in a single molecule and having 0.05% by weight to 0.5% by weight of alkenyl weight content, (C1) hydrazine hydrogenation reaction catalyst, and (D) dielectric inorganic fine particles having a specific dielectric constant of greater than or equal to 10 at 1 kHz at room temperature .

Here, (A1) is preferably a dimethylhydroquinone-bi-molecular chain-terminated polydimethyloxane. Preferred examples of (A2) include a trimethyl decyloxy-bi-molecular chain-terminated dimethyl methoxy oxane-methylhydroquinone copolymer and a dimethylhydroquinone-bi-molecular chain termination Dimethyloxane-methylhydroquinoxane copolymer. On the other hand, the component (B) is exemplified by a dimethylvinyl methoxy-bi-molecular chain-terminated polydimethyl siloxane. To further optimize converter material properties (eg, mechanical properties, dielectric properties, heat resistance, or the like), one or more of the methyl groups of the polymer may be replaced with ethyl, propyl, butyl, hexyl or phenyl groups.

The molecular weights of (A1), (A2) and (B) are not particularly limited as long as the weight content of the hydrogen atom and the weight content of the alkenyl group are within the ranges mentioned above. However, the number of units of the oxane is preferably from 5 to 1,500.

The curable organopolyoxane composition of the present invention is used in a curable organopolyoxane composition of a converter, and the curable organopolyoxane composition of the present invention can be further provided with the characteristics set forth below. .

[Other inorganic particles (E)]

The curable organopolyoxane composition of the present invention may further comprise one or more types of inorganic particles (E) selected from the group consisting of conductive inorganic particles, insulating inorganic particles, and reinforcing inorganic particles.

The conductive inorganic particles to be used are not particularly limited as long as the conductive inorganic particles impart conductivity, and any form such as a particle shape, a flake shape, and a fiber shape (including whiskers) can be used. Specific examples of conductive inorganic particles include: conductive carbon, such as conductive carbon black, graphite, single-layer carbon nanotubes, double-layer carbon nanotubes, multilayer carbon nanotubes, fullerene, fullerene encapsulation Metal, carbon nanofibers, vapor grown single length carbon (VGCF), carbon microcoils or the like; and metal powders such as platinum, gold, silver, copper, nickel, tin, zinc, iron, aluminum or the like Powder; and coated pigments such as antimony doped tin oxide, phosphorus doped tin oxide, tin/bismuth oxide, tin oxide, indium oxide, antimony oxide, zinc antimonate, carbon and graphite surface treated acicular oxidation Titanium or tin oxide or such surface treated carbon whisker; at least one type of conductive oxide (eg tin doped indium oxide (ITO), fluorine doped tin oxide (FTO), phosphorus doped tin oxide and phosphorus doped Nickel oxide coated pigment; a pigment having conductivity and containing tin oxide and phosphorus in the surface of the titanium oxide particles; the conductive inorganic particles are surface-treated as appropriate using various types of surface treatment agents as described below. The conductive inorganic particles may be used in one type or in a combination of two or more types.

In addition, the conductive inorganic fine particles may be fibers, such as glass fibers, cerium oxide. Aluminum fiber, alumina fiber, carbon fiber or the like; or needle-like reinforcing material such as aluminum borate whisker, potassium titanate whisker or the like; or inorganic filler material such as glass beads, talc, mica, graphite, ash stone The dolomite or the like, the surfaces of the fine particles have been coated with a conductive substance such as a metal or the like.

The specific dielectric constant of the polyoxyalkylene cured article can be increased by blending the conductive inorganic particles into the composition. The amount of the conductive inorganic particles blended is preferably in the range of 0.01% by weight to 10% by weight, and more preferably in the range of 0.05% by weight to 5% by weight, based on the curable organopolyoxane composition. When the blending amount deviates from the above-mentioned preferred range, the blending effect is not obtained, or the dielectric breakdown strength of the cured article may be weakened.

The insulating inorganic particles used in the present invention may be any insulating inorganic material generally known. That is, the volume resistance value can be 10 ¹⁰ ohms without limitation. Centimeters (Ohm.cm) to 10 ¹⁹ ohms. Any of the inorganic material particles may be used in any form, such as particulate, flake, and fibrous (including whiskers). Preferred specific examples include ceramic spherical particles, flat particles and fibers; metal silicates such as alumina, mica and talc or the like; and quartz, glass or the like. Further, the insulating inorganic particles may be subjected to surface treatment using various types of surface treating agents described below. The conductive inorganic particles may be used in one type or in a combination of two or more types.

The mechanical strength and dielectric breakdown strength of the cured material of the polyoxyalkylene oxide can be increased by blending the insulating inorganic particles into the composition, and sometimes the specific dielectric constant is observed to increase. The blending amount of the insulating inorganic particles is preferably in the range of 0.1% by weight to 20% by weight, and further preferably in the range of 0.1% by weight to 5% by weight based on the curable organopolyoxane composition. When the blending amount of the insulating inorganic particles deviates from the above-mentioned preferred range, the blending effect is not obtained, or the mechanical strength of the cured article may be weakened.

The reinforcing inorganic particles used in the present invention are exemplified by fuming cerium oxide, wet cerium oxide, cerium powder, calcium carbonate, diatomaceous earth, fine quartz powder, various types of non-alumina metal oxide powder, and glass fiber. , carbon fiber or the like. Further, the reinforced inorganic particles can be used after being treated with various types of surface treating agents set forth below. Here, although there is no limitation on the particle diameter of the reinforcing inorganic particles, the specific surface area is preferably greater than or equal to 50 m ² /g and less than or equal to 300 m ² /g from the viewpoint of improved mechanical strength, fuming cerium oxide Especially good. Further, from the viewpoint of improving the dispersibility, it is preferred to surface-treat the fumed cerium oxide using the cerium oxide coupling agent described below. However, when the (A) curable organopolyoxane composition is added to the curable organopolyoxane composition, the decazane surface treated fumed cerium oxide is not used as the reinforcing inorganic particles. The reinforcing inorganic particles may be used in a single type or may be used in combination of two or more types.

The mechanical strength and dielectric breakdown strength of the polyoxyalkylene cured article can be increased by blending the reinforcing inorganic particles into the composition. The blending amount of the reinforcing inorganic particles is preferably in the range of from 0.1% by weight to 30% by weight, and further preferably in the range of from 0.1% by weight to 10% by weight, based on the curable organopolyoxane composition. When the blending amount deviates from the above-mentioned preferred range, the blending effect of the inorganic particles is not obtained, or the mold processability of the curable organopolyoxane composition can be lowered.

The curable organopolyoxane composition of the present invention may further comprise thermally conductive inorganic particles. The thermally conductive inorganic particles are exemplified by metal oxide particles such as magnesium oxide, zinc oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, silver oxide or the like; and inorganic compound particles such as aluminum nitride, boron nitride, tantalum carbide , tantalum nitride, boron carbide, titanium carbide, diamond, diamond-like carbon or the like. Zinc oxide, boron nitride, tantalum carbide and tantalum nitride are preferred. The thermal conductivity of the polyoxyalkylene cured article can be increased by blending the thermally conductive inorganic particles into the composition. The blending amount of the reinforcing inorganic particles is preferably in the range of from 0.1% by weight to 30% by weight based on the curable organopolyoxane composition.

[Surface treatment of inorganic particles or the like]

However, partial or total can be achieved by using at least one type of surface treatment agent The above-mentioned dielectric inorganic fine particles (D) and at least one type of inorganic particles (E) used in the curable organopolyoxane composition of the present invention are subjected to surface treatment. The type of the surface treatment is not particularly limited, and the surface treatment is exemplified by a hydrophilization treatment and a hydrophobizing treatment. Hydrophobization treatment is preferred. When the inorganic particles which have been subjected to the hydrophobization treatment are used, the degree of loading of the inorganic particles in the organopolyoxane composition can be increased. In addition, the viscosity increase of the composition is suppressed, and the mold processability is improved.

The surface treatment mentioned above can be carried out by treating (or coating) the inorganic particles with a surface treating agent. The surface treatment agent for hydrophobization is exemplified by at least one type of surface treatment agent selected from the group consisting of an organotitanium compound, an organic cerium compound, an organozirconium compound, an organoaluminum compound, and an organophosphorus compound. The surface treatment agent may be used in a single type or may be used in a combination of two or more types.

The organotitanium compound is exemplified by a coupling agent such as titanium alkoxide, titanium chelate, titanium acrylate or the like. Preferred coupling agents in such compounds are exemplified by titanium alkoxide compounds such as tetraisopropyl titanate or the like; and titanium chelates such as tetraisopropylbis(dioctyl phosphate) titanate or And so on.

The organic ruthenium compound is exemplified as a low molecular weight organic ruthenium compound such as decane, decane, decane or the like; and an organic ruthenium polymer or oligomer such as polyoxyalkylene, polycarbazane or the like. Preferred decanes are exemplified by the so-called decane coupling agents. Representative examples of such decane coupling agents include alkyl trialkoxy decanes (e.g., methyl trimethoxy decane, vinyl trimethoxy decane, hexyl trimethoxy decane, octyl trimethoxy decane, or the like), containing An organofunctional trialkoxysilane (for example, glycidoxypropyltrimethoxydecane, epoxycyclohexylethyltrimethoxydecane, methacryloxypropyltrimethoxydecane, aminylpropyl) Trimethoxy decane or the like). Preferably, the decane and the polyoxyalkylene comprise hexamethyldioxane, 1,3-dihexyl-tetramethyldioxane, a trialkoxyfluorenyl mono-terminated polydimethyloxane , trialkoxyfluorenyl mono-terminated dimethylvinyl single-terminated polydimethyl methoxy olefin, trialkoxy fluorenyl mono-terminated organic functional group single-end poly 2 Methyl methoxy alkane, trialkoxy fluorenyl double-terminated polydimethyl siloxane, organic functional double-terminated polydimethyl methoxy alkane or the like. When a decane is used, the number of decane bonds n is preferably in the range of 2 to 150. Preferred decazins are exemplified by hexamethyldioxane, 1,3-dihexyl-tetramethyldiazepine or the like. Preferred polycarbomethoxyanes are exemplified as polymers having Si-C-C-Si linkages in the polymer backbone.

The organic zirconium compound is exemplified by an alkoxy zirconium compound (e.g., tetraisopropoxy zirconium or the like) and a zirconium chelate.

The organoaluminum compound is exemplified by aluminum alkoxide and aluminum chelate.

The organophosphorus compound is exemplified by a phosphite, a phosphate, and a phosphoric acid chelate.

Among these surface treatment agents, an organic ruthenium compound is preferred. Among these organic ruthenium compounds, decane, decane and polyoxane are preferred. As stated previously, the use of alkyltrialkoxydecane and trialkoxyfluorenyl monocapped polydimethyloxane is preferred.

The ratio of the surface treating agent to the total amount of the inorganic particles mentioned above is preferably in the range of 0.1% by weight or more and 10% by weight or less, and the range is further preferably greater than or equal to 0.3% by weight and less than or Equal to 5% by weight. Further, the treatment concentration is a ratio (weight ratio) of the fed inorganic particles to the fed treatment agent, and it is preferred to remove the excess treatment agent after the treatment.

[Additive (F)]

The curable organopolyoxane composition of the present invention may further comprise an additive (F) for improving mold release property or dielectric breakdown property. An electroactive polysiloxane elastomer sheet obtained by curing the polyoxyalkylene composition into a sheet can be advantageously used as an electroactive film (dielectric layer or electrode layer) constituting the converter. However, when the release sheet of the polyoxyelastomer sheet during film molding is inferior, and especially when the dielectric film is manufactured at a high speed, the dielectric film may be damaged by demolding. However, the curable organopolyoxane composition for a converter of the present invention has excellent release properties, and thus the curable organopolyoxane composition is advantageous in that it does not damage the film. In the case of the improvement of the manufacturing speed of the film. This additive is further improved These features of the curable organopolyoxane composition are invented, and the additives may be used in a single type or in a combination of two or more types. On the other hand, the dielectric breakdown strength of the polyoxyxene elastomer sheet is improved by using an additive which improves the dielectric breakdown characteristics according to the name of the additive.

The release improving additive (i.e., mold release agent) which can be used is exemplified as a carboxylic acid type release agent, an ester type release agent, an ether type release agent, a ketone type release agent, an alcohol type release agent or the like. These release agents may be used singly in a single type or in combination of two or more types. Further, although the above-mentioned release agent does not contain a halogen atom, a release agent containing a halogen atom may be used, or a mixture of the release agents may be used.

The release agent containing no halogen atoms may be selected, for example, from the group consisting of saturated or unsaturated aliphatic carboxylic acids such as palmitic acid, stearic acid or the like; alkali metal salts of such fatty carboxylic acids (for example, stearic acid) Sodium, magnesium stearate, calcium stearate or the like); esters of fatty carboxylic acids with alcohols (eg 2-ethylhexyl stearate, glyceryl tristearate, pentaerythritol monostearate) Or the like), an aliphatic hydrocarbon (liquid paraffin, paraffin or the like), an ether (distearyl ether or the like), a ketone (distearyl ketone or the like), a high carbon number alcohol (2-hexadecyl 10) Octaol or the like) and mixtures of such compounds.

The release agent containing a ruthenium atom is preferably a non-curable polyfluorene type release agent. Specific examples of such polyoxotype release agents include non-organic modified polyoxyxides such as polydimethylsiloxane, polymethylphenyloxane, poly(dimethyloxane-A) Phenyl phenyl oxyalkylene) copolymer, poly(dimethyl methoxy oxane-methyl (3,3,3-trifluoropropyl) decane copolymer or the like; and modified polyoxyl oil, for example Amine-modified polyfluorene oxide, amino polyether modified polyfluorene oxide, epoxy modified polyoxymethylene, carboxyl modified polyoxyl, polyoxyalkylene modified polyoxyl or the like. The release agent of the ruthenium atom may have any structure, such as a linear or partially branched linear or cyclic structure. Further, the viscosity of the eucalyptus oil at 25 ° C is not particularly limited. The viscosity is preferably between 10 mPa. s is in the range of 100,000 mPa.s, and further preferably in the range of 50 mPa.s to 10,000 mPa.s.

Although the blending amount of the demolding improving additive relative to the total amount of the curable organopolyoxane is not particularly limited, the amount is preferably in the range of 0.1% by weight or more and 30% by weight or less.

On the other hand, the dielectric breakdown property improver is preferably an electrical insulation improver. The dielectric breakdown property improver is exemplified by aluminum or magnesium hydroxide or a salt, a clay mineral, and a mixture of such materials. In particular, the dielectric breakdown property modifier may be selected from the group consisting of aluminum citrate, aluminum sulfate, aluminum hydroxide, magnesium hydroxide, calcined clay, montmorillonite, hydrotalcite, talc, and mixtures of such agents. Further, the insulation modifier may be surface-treated by the surface treatment method mentioned above as may be required.

The blending amount of the insulating improver is not specifically limited. The blending amount is preferably in the range of 0.1% by weight or more and 30% by weight or less based on the total amount of the curable organopolyoxane.

The curable organopolyoxane composition of the present invention may comprise another organopolyoxane having a dielectric functional group other than the reactive organopolyoxyalkylene mentioned above.

[Curing mechanism]

In the same manner, the curable organopolyoxane composition of the present invention may further comprise a high dielectric functional group in the molecule and at least one capable of undergoing a condensation curing reaction, an addition curing reaction, a peroxidation curing reaction or a photocuring reaction. a compound of the group. This high dielectric functional group is introduced into the obtained cured article (i.e., electroactive polyoxoelastomer) by the curing reaction mentioned above.

[Introduction of high dielectric functional groups]

For the curable organopolyoxane composition of the present invention, part or all of the reactive organopolyoxane mentioned above may be a reactive organopolyoxane further having a high dielectric functional group.

If the electroactive polyxene oxide obtained by curing the curable organopolyoxane composition for a converter of the present invention is used for a dielectric layer, the specific dielectric constant of the dielectric layer is higher. It is preferably higher and a high dielectric functional group can be introduced to improve the specific dielectric constant of the elastomer.

In particular, the dielectric properties of the curable organopolyoxane composition and the cured electroactive polyoxoelastomer obtained by curing the curable organopolyoxane composition can be increased by, for example, the following method: Adding a component imparting high dielectric properties to the cured organopolyoxane composition, introducing a high dielectric group into the organopolyoxane component constituting the curable organopolyoxane composition, or the methods The combination. These particular embodiments and the high dielectric functional groups that can be introduced are explained below.

In a first embodiment, the curable organopolyoxane composition for a converter is formed from a curable organopolyoxane composition comprising an organic cerium compound having a high dielectric group. In the curable composition, a part or all of the reactive organopolyoxane contained in the curable composition further has a reactive organic polyoxane having a high dielectric functional group, and the electricity obtained by curing The specific dielectric constant of the reactive polyoxyelastomer is increased.

In the second embodiment, an organic cerium compound having a high dielectric group is added to the curable organopolyoxane composition, and the mixture is cured to obtain an electroactive polyoxyxene elastomer having a higher specific dielectric constant. An organic cerium compound having a high dielectric group can be added separately from the component for curing in the curable composition.

In a third embodiment, an organic compound having a high dielectric group and a functional group reactive with a reactive organopolyoxyalkylene contained in the curable composition is added to the curable organopolyoxane composition. Thereby increasing the specific dielectric constant of the electroactive polysiloxane elastomer obtained by curing. Due to the functional group of the organic compound reacting with the reactive organopolyoxane in the curable composition, a bond is formed between the organic compound and the organopolyoxane, thereby introducing a high dielectric group An electroactive polyoxyelastomer obtained by curing.

In a fourth embodiment of the present invention, an organic compound miscible with a curable organopolyoxane composition and having a high dielectric group is added to the curable organopolyoxane composition, and thus increased The specific dielectric constant of the electroactive polysiloxane elastomer obtained by curing. Due to the miscibility between the organic compound and the organopolyoxane in the curable composition An organic compound having the same high dielectric group is incorporated into a matrix of an electroactive polyoxyelastomer obtained by curing.

The high dielectric group in the present invention is not particularly limited, and the high dielectric group can be added to cure the curable organopolyoxane of the present invention by comparison with the dielectric properties in the absence of the group. Any group from which the composition obtains the dielectric properties of the cured article obtained. Examples of high dielectric groups used in the present invention are listed below without limitation.

a) a halogen atom and a group containing a halogen atom

The halogen atom is not particularly limited, and the halogen atom is exemplified by a fluorine atom and a chlorine atom. A group containing a halogen atom may be selected as the organic group having one or more types of atoms selected from a fluorine atom and a chlorine atom, as exemplified as a halogenated alkyl group, a halogenated aryl group and a halogenated arylalkyl group. . Specific examples of halogen-containing organic groups include, but are not limited to, chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and perfluoroalkyl. By introducing such groups, it is also expected to improve the mold release ability of the cured article of the present invention and the cured article obtained from the composition.

b) a group containing a nitrogen atom

The group containing a nitrogen atom is exemplified by a nitro group, a cyano group (for example, a cyanopropyl group and a cyanoethyl group), a decylamino group, an imido group, a urea group, a thiourea group, and an isocyanate group.

c) a group containing an oxygen atom

The group containing an oxygen atom is exemplified by an ether group, a carbonyl group, and an ester group.

d) heterocyclic groups

The heterocyclic group is exemplified by an imidazole group, a pyridyl group, a furan group, a pyran group, a thiophene group, an anthraquinone group, and a complex of such groups.

e) boron-containing groups

Boron-containing groups are exemplified as borate groups and borate groups.

f) phosphorus-containing groups

Phosphorus-containing groups are exemplified by phosphine groups, phosphine oxide groups, phosphonate groups, phosphite groups, and phosphate groups.

g) sulfur-containing groups

Sulfur-containing groups are exemplified by thiol groups, thioether groups, anthracene groups, anthracene groups, thioketone groups, sulfonate groups, and sulfonamide groups.

[Other optional ingredients: curing retarders or the like]

The curable organopolyoxane composition for a converter of the present invention may comprise an additive typically incorporated into an organopolyoxane composition. Any additive such as a curing retarder (curing inhibitor), a flame retardant, a heat resistance improver, and coloring may be blended as long as the object of the curable organopolyoxane composition for a converter of the present invention is not impaired. Agent, solvent or the like. If the curable organopolyoxane composition is an addition reaction curable organopolyoxane composition, the curing retarder (curing inhibitor) is exemplified by, but not limited to, an alkyne alcohol, such as 2- Methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol or the like; an enyne compound, for example 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene-1-yne or the like; and benzotriazole. The concentration of the curing retarder (curing inhibitor) is preferably in the range of from 1 ppm to 50,000 ppm with respect to the total composition (by weight).

[Hybrid type]

Hybridization can be carried out by combining the curable organopolyoxane composition for a converter of the present invention with a polymer other than the organopolysiloxane, as long as the object of the present invention is not impaired. By mixing the organopolyoxane with a polymer having a higher dielectric constant than the organopolyoxane, the dielectric constant of the composition of the present invention and the cured article obtained from the composition can be increased. Hybrids encompass so-called polymer blending of organopolyoxyalkylenes with non-organic polyoxyalkylene polymers and by fusion of organic polyoxyalkylenes with other polymers (so-called copolymerization) polymer.

The curable organopolyoxane composition of the present invention may be a condensation curable, addition curable, peroxide curable or photocurable organopolyoxane composition, but an addition curable organopolyoxane combination The material is preferred. This curable system can be further included by The method of adding a dielectric functional group to an acrylic group, a methacrylic group, an epoxy group or a thiol group to introduce an organic polyoxyalkylene molecular chain. In addition to the addition curing reaction, a photocuring reaction or an electron beam curing reaction may also be used by using the photocurable portion or the electron beam curable portion. When such a combination reaction is used, a compound called a monomer and/or an oligomer (for example, a (meth) acrylate and a polyfunctional (meth) acrylate compound which can be cured by light or electron beam can be used. Further added to the curable composition mentioned above. Further, a so-called photosensitizer can be added.

[Mechanical properties]

When a dielectric polyoxyelastomer as a component of the converter obtained by curing the curable organopolyoxane composition of the present invention is thermoformed into a sheet having a thickness of 2.0 mm, it may have the following It is shown as a mechanical property based on the measurement of JIS K 6249. However, depending on the application of the dielectric polyoxyelastomer and other desired electrical properties, dielectric polyoxyelastomers having mechanical properties outside the range of such mechanical properties may be used.

(1) The Young's modulus (MPa) at room temperature can be set in the range of 0.1 MPa to 10 MPa, and particularly preferably in the range of 0.1 MPa to 2.5 MPa.

(2) The tear strength (N/mm) at room temperature may be set to be greater than or equal to 1 N/mm, and particularly preferably greater than or equal to 2 N/mm.

(3) The tear strength (MPa) at room temperature may be set to be greater than or equal to 1 MPa, and particularly preferably greater than or equal to 2 MPa.

(4) The elongation at break (%) may be set to be greater than or equal to 100%, and is particularly preferably in the range of 200% to 1,000% from the viewpoint of the displacement amount of the transducer.

[Dielectric characteristics]

The dielectric polyoxyelastomer as the converter component obtained by curing the curable organopolyoxane composition of the present invention has the dielectric properties listed below. In particular, an important feature of the present invention is that, in addition to obtaining the mechanical properties such as those set forth above by means of the compositions of the present invention, the composition exhibits excellent specific dielectric properties in the low frequency region. number.

(1) When the curable organopolyoxane composition is thermoformed into a sheet having a thickness of 0.07 mm, the dielectric breakdown strength (V/μm) can be set to be greater than or equal to 20 V/μm. Although the preferred dielectric breakdown strength will vary depending on the application of the converter, the dielectric breakdown strength is particularly preferably in the range of greater than or equal to 30 V/μm.

(2) When the curable organopolyoxane composition is hot molded into a sheet having a thickness of 1 mm, the specific dielectric constant measured at a measurement frequency of 1 MHz and a measurement temperature of 23 ° C may be set to be greater than or equal to 3.0. Although the preferred specific dielectric constant will vary depending on the desired form of the dielectric layer and the type of converter, a preferred range of specific dielectric constants under the above-described measurement conditions is greater than or equal to 5.0.

[Production method]

The curable organopolyoxane composition of the present invention can be produced by curing a curable organopolyoxane component, a curing catalyst, and having a specific dielectric constant greater than or equal to 10 at room temperature at 1 kHz. The dielectric inorganic fine particles and optionally at least one type of inorganic particles and other additives are added to an extruder or a kneader (for example, at least one type of mechanical member selected from the group consisting of: a twin screw extruder, a twin shaft In a kneader and a single blade extruder, and then kneading the mixture. Specifically, the present invention can be formed by kneading a reactive organopolyoxane component, a dielectric inorganic fine particle, and a surface treatment agent using a twin-screw extruder having a free volume of at least 5,000 (L/h). A high concentration (eg, at least 80% by weight) filler rubber composite (masterbatch). The other reactive organopolyoxane component, curing catalyst and other components are then preferably added and kneaded to produce a curable organopolyoxane composition.

The dielectric inorganic fine particles are sufficiently dispersed at a high density in the curable organopolyoxane composition of the curable organopolyoxane composition for a converter obtained by the above-mentioned production method, and Therefore, a converter component having good electrical characteristics and mechanical characteristics can be manufactured. In addition, a uniform film-like cured article can be obtained during the manufacture of the transducer member, and the obtained film-like cured article is excellent in electrical and mechanical properties, and is used for lamination or the like. Excellent ability to set.

In the kneading process mentioned above, the temperature during formation of the polyoxyxene rubber compound (masterbatch) containing no vulcanizing agent (curing catalyst) is not specifically limited. However, this temperature is set in the range of 40 ° C to 200 ° C and can be set in the range of 100 ° C to 180 ° C. In a continuous process using a twin screw extruder or the like, the residence time during the treatment can be set to about 30 seconds to 5 minutes.

[Application of Curable Organic Polyoxane Composition for Converters of the Invention]

Since the dielectric properties and mechanical properties of the electroactive polyoxoelastomer obtained by curing or semi-curing the curable organopolyoxane composition of the present invention, it can be particularly advantageously used as a group selected from the group consisting of Converter components: artificial muscles, actuators, sensors and power generation components.

The curable organopolyoxane composition for a converter of the present invention can be suitably used to manufacture a converter. The curable organopolyoxane composition for a converter of the present invention may comprise a so-called B-stage material rather than only an uncured curable composition which is partially reactive with a reactive organopolyoxane. And not fully cured. The material of the B-stage of the present invention is exemplified as a material which is in the form of a gel or a fluid. Accordingly, embodiments of the present invention also include components in which the curing reaction of the curable organopolyoxane composition for the converter has been carried out in part, and wherein the converter member is in a gel or fluid state . Further, the converter member of the semi-cured state type is preferably composed of a film-like polyoxylene of a stacked layer.

Instance

In order to embody the invention, practical examples and reference examples will now be given. However, it should be understood that such practical examples do not limit the scope of the invention. Further, "%" below indicates a weight percentage.

Practical example: preparation of the converter

As shown in the following reference examples, the physical properties of the cured body prepared are different. A curable polyoxyxene elastomer composition or a formulation thereof. The physical properties of the formulations and measurements in a single layer are shown in Table 1.

As shown in Table 1, a polyoxyxene elastomer having excellent mechanical properties (e.g., expressed by elongation at break) and dielectric properties (e.g., expressed by dielectric constant) is provided. In addition, by optimizing the crosslinked structure and inorganic fine particles, materials can be designed according to the desired converter application. Specifically, as shown in FIG. 5, the polyoxyxene elastomer obtained from the curable organopolyoxane composition of the present invention achieves high dielectric properties even in a low voltage region.

The converter of the present invention is prepared by stacking two or more polyoxyelastomers into a dielectric layer of the converter as a whole and forming an electrode layer. Further, by stacking two or more dielectric fine particles or polyelectron oxides having different contents of conductive fine particles, a concentration gradient of dielectric fine particles or conductive fine particles can be formed in the stacked layer as a whole. Similarly, by stacking two or more polyoxyelastomers having different electrical or mechanical strengths, multilayer components of the converter having a variety of physical properties can be designed and formed.

Further, regardless of the evaluation method in the reference example, the desired multilayer size of the converter can be formed using a desired thickness size or curing method.

Reference example 1

The viscosity to 14.22% at 25 ° C is 2,000 mPa. And spheroidal titanium having an average particle diameter of 1.0 μm added with 85.35% of dimethylpolyoxyalkylene (B ₂ ) (vinyl content of 0.23%) at both ends via dimethylvinyloxyl-terminated Acid bismuth (manufactured by Fuji Titanium Industry Co., Ltd., HPBT-1B), 0.356% trimethoxydecyl mono-terminated dimethylvinyl monocapped polyoxyalkylene (average degree of polymerization = 25) and 0.071% 1,3-Trimethyl-3,3-diphenyl-1-carboxyindenyldioxane. After uniformly mixing using a Ross mixer, the mixture was further heated and mixed at 150 ° C for 30 minutes to obtain a polyoxyxene elastomer matrix.

To the polyoxyxene elastomer, dimethylpolysiloxane (B _{2 )} dissolved in dimethylvinyl decyl double-terminated methyl polyoxyalkylene was added to the polyoxyether elastomer shown in Table 1. , dimethylhydroquinone-bi-molecular chain-terminated polydimethyloxane (A ₁₁ , SiH content = 0.155%), trimethyl decyloxy-bi-molecular chain terminated dimethyl a decane-methylhydroquinone copolymer (A ₂₂ , SiH content of 0.83%), 0.67% (in terms of platinum) of 1,3-divinyl-1,1,3,3-tetramethyl A platinum complex of a dioxane complex and a tetramethyltetravinylcyclotetraoxane as a reaction control agent. The mixture was mixed until homogeneous (about 10 minutes) to obtain a polyoxyxene elastomer composition. Here, the molar ratio of all SiH functional groups to all vinyl groups (SiH groups/vinyl groups) in the polyoxyxene elastomer composition was 1.3.

Here, when the reactive organopolyoxane is represented by M _a M ^R _b D _c D ^R _d T _e T ^R _f Q _g , it has (a+c)/(b+d+e+f+g The weight fraction (X) of the organopolyoxane relative to the total oxane component of the curable organopolyoxane composition is less than 3 (i.e., X = 0.7%). The weight fraction (Y) of the bimolecular chain-terminated reactive organopolyoxane relative to the total amount of the oxoxane component of the curable organopolyoxane composition was 99.3%. Reactive organopolyoxane (S) having at least 2 groups capable of undergoing a curing reaction in a single molecule and having an average molecular weight of less than 10,000 between two groups capable of undergoing a curing reaction An organopolysiloxane (L) having at least 2 groups capable of undergoing a curing reaction in a single molecule and having greater than or equal to 10,000 and less than or equal to 150,000 between two groups capable of undergoing a curing reaction The blending ratio (weight ratio S/L) of the average molecular weight) was 5.7/94.3.

On the other hand, based on the chemical structure of the polyorganosiloxane raw material mentioned above, the content of the hydrazine-bonded hydrogen atom, the content of the alkenyl group, and the number average molecular weight, the number of crosslinking points per unit weight (J value) is It was calculated to be 1.9 μmol/g, and the molecular weight (K value) between the crosslinking points was calculated to be about 898,000.

The polyoxyxene elastomer composition was press cured at 150 ° C for 15 minutes and then post cured in an oven at 150 ° C for 60 minutes. The Young's modulus, tensile strength, elongation at break, and tear strength of the obtained cured article were measured based on JIS K 6249. To measure the mechanical strength, a sheet having a thickness of 2 mm was produced. Hardness test A hard based on JIS K 6253 measuring 6mm thick sheet degree.

Further, the polyoxyxene elastomer composition was press-cured at 150 ° C for 15 minutes to manufacture a 0.07 mm thick sheet, and an electrical insulation breakdown voltage oil tester (ie, PORTATEST 100A-2) manufactured by Soken Electric Co., Ltd. was used. Measure the dielectric breakdown strength. In the same manner, the ruthenium elastomer composition was press-cured at 150 ° C for 15 minutes to produce a sheet having a thickness of 1 mm. The specific dielectric constant was measured using a TR-1100 dielectric constant-tangent measuring device manufactured by Ando Electric Co., Ltd. at a temperature of 23 ° C and a measurement frequency of 1 MHz. The results are shown in Table 1.

Reference Examples 2 to 33 and Comparative Reference Examples 1 to 3

The same procedure as in Reference Example 1 was carried out except that the addition amount and chemical structure of the crosslinking agent A and the polymer B were changed, or the fine particles listed in Table 1 were used as necessary to obtain a polyoxyethylene rubber composition. . The X, Y, S/L, J and K values mentioned above were calculated in the same manner. The obtained composition was heated and cured in the same manner, and mechanical strength and electrical properties were evaluated. These results are shown in Table 1. Further, in the table, the chemical structures of the crosslinking agent and the polymer not described above are as follows.

B ₁ : dimethyl vinyl double-terminated polydimethyl decane

B ₃ : dimethylvinyl double-terminated dimethylmethylperfluoroalkyl fluorene copolymer

B ₄ : MQ resin

B ₅ , B ₆ : vinyl functionalized MQ resin

A ₁₂ : Dimethyl hydrogen double-terminated polydimethyl decane

A ₂₁ -A ₂₄ : Trimethyl decyl double-terminated dimethyl methyl hydroquinone copolymer

A ₂₅ : Dimethyl hydrogen functionalized MQ resin

(F) Reaction Control Agent: Tetramethyltetravinylcyclotetraoxane

(C) Pt catalyst: platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane complex

"Electromechanical Testing of Cured Polyoxo Elastomer Films" (Refer to Example 23 for Comparative Example 4)

An electrode paste composed of carbon black and polyoxygenated oil ([Asbury conductive carbon grade 5303]/[Dow Corning FS1265 fluoropolyanhydride]=1/7 (w/w)) was used. A brush is applied based on the cured film of the present invention (Example No. 23). The electrode application (circle) defining the active EAP region has a diameter ranging from 10 mm to 20 mm. An electromechanical test was performed using a Dow Corning electromechanical tester constructed by SRI International to analyze the relationship between electric field and thickness strain. The measurement conditions are as follows.

1) Temperature and humidity: at 21 ° C - 23 ° C, and the relative humidity is 35% - 52%

2) Initial film thickness: 67 μm

3) Biaxial pre-stretching: 25%

4) Film thickness after biaxial stretching: 43 μm

5) The voltage mode is a 0.5 Hz square wave type. The change in the diameter of the electrode circle defines the actuating radial strain at "0" volt versus test voltage. The thickness strain is related to the radial strain due to the incompressibility of the polyxmethylene sample. The electric field is defined as the test voltage divided by the "final" film thickness (film thickness after re-stretching and actuation)

The thickness strain (%) which varies with the electric field (V/μm) is shown in Fig. 5 together with Sylgard 186 (Comparative Reference Example No. 4) as a control material.

Figure 5. Thickness strain (%) as a function of electric field (V/μm) with reference example number 23 and comparative reference example number 4.

1‧‧‧Actuator

10a‧‧‧ dielectric layer

10b‧‧‧ dielectric layer

11a‧‧‧electrode layer

11b‧‧‧electrode layer

12‧‧‧ wire

13‧‧‧Power supply

Claims (16)

A converter having two or more layers containing an organopolyoxane. The converter of claim 1, wherein the two or more layers containing the organopolyoxane are curable organic polycondensation by curing two or more of their cured bodies having different electrical or mechanical strengths The polyoxyxene elastomer layer obtained from the oxyalkylene composition. The converter of claim 1 or 2, wherein the two or more layers containing the organopolyoxane are as a unitary dielectric layer and are cured by curing two or more of them The isoelectric properties or the stacked polyoxyxene elastomer layer obtained by the curable organopolyoxane composition having different mechanical strengths. The converter of any one of claims 1 to 3, wherein the two or more layers have a concentration gradient of a component or a functional group in a thickness direction thereof in the layers as a whole. The converter of claim 3, wherein the concentration gradient of the component or functional group is at least one concentration gradient selected from the group consisting of: a functional group content of one or more organopolyoxanes, one or more fillers The content, the amount of one or more insulating additives, and the amount of one or more removal additives. The converter of any one of claims 1 to 5, wherein at least one of the two or more organic polyoxane-containing layers is cured by curing the organic polyfluorene used for the converter The polyoxyxene elastomer layer formed by the alkane composition, the curable organopolyoxane composition comprising: (A+B) curable organic poly group satisfying the following [characteristic 1], [characteristic 2], and [characteristic 3] A siloxane composition: [Characteristic 1] contains an organopolyoxane which is _a reactive organopolyoxane represented by the formula M _a M ^R _b D _c D ^R _d T _e T ^R _f Q _g , and Wherein the value of (a+c)/(b+d+e+f+g) is less than 3, and the concentration range is greater than or equal to the total organopolyoxane component of the curable organopolyoxane composition Equivalent to 0.1% by weight and less than or equal to 25% by weight, (in the formula, M represents a triorganomethoxy unit; D represents a diorganomethoxy unit; T represents a monoorganomethoxy unit, and Q represents SiO _a methoxy group represented by _4/2 ; each of M ^R , D ^R and T ^R is a methoxy group having a substituent group R capable of undergoing a curing reaction, and the curing reaction is, for example, a group selected from the group consisting of Type: condensation reaction, addition reaction, peroxidation reaction, and photoreaction); [characteristic 2] contains greater than or equal to 75% by weight relative to the total oxetane component of the curable organopolyoxane composition a reactive organic polyoxane having less than or equal to 99.9% by weight, the reactive organopolyoxyalkylene having a curing reaction in a condensation reaction, an addition reaction, a peroxidation reaction or a photoreaction at only two molecular terminals a group; [characteristic 3] includes: (S) a reactive organopolyoxane having at least two groups capable of undergoing a curing reaction such as a group selected from the group consisting of a condensation reaction in a single molecule: a condensation reaction, An addition reaction, a peroxidation reaction, and a photoreaction, the reactive organopolyoxane having an average molecular weight of less than 10,000 between the two groups capable of undergoing the curing reaction; (L) a reactive organopolyoxane a group having at least two curing reactions in a single molecule capable of performing, for example, a type selected from the group consisting of a condensation reaction, an addition reaction, a peroxidation reaction, and a photoreaction, the reactive organic polyoxygen alkyl Having an average molecular weight of greater than or equal to 10,000 and less than or equal to 150,000 between the two groups capable of performing the curing reaction; the blending ratio (weight ratio) of the component (S) to the component (L) In the range of 1:99 to 40:60; (C) a curing agent for the curable organopolyoxane composition; and (D) a dielectric inorganic fine particle having a larger than 1 kHz at room temperature Or equal to the dielectric constant of 10. The converter of any one of claims 1 to 6, wherein at least one of the two or more organic polyoxane-containing layers is cured by curing the organic polyfluorene used for the converter A polyoxyxene elastomer layer formed from an alkane composition, the curable organopolyoxane composition comprising as an essential component: (A1) at least one type of organohydrogen polyoxyalkylene at the end of two molecules a hydrogen atom having a ruthenium atom bonded, the hydrogen atom having a weight fraction of 0.1% by weight to 1.0% by weight; (A2) at least one type of organic hydrogen polyoxyalkylene having at least 3 ruthenium atom bonds in a single molecule The hydrogen atom of the junction, the hydrogen atom having a weight fraction of 0.03 wt% to 2.0 wt%; (B) at least one type of organopolyoxane having at least 2 alkenyl groups in a single molecule, the alkenyl group The weight fraction is 0.05% by weight to 0.5% by weight; (C1) a hydrogenation reaction catalyst; and (D) a dielectric inorganic fine particle having a dielectric constant of greater than or equal to 10 at 1 kHz at room temperature. The converter of any one of claims 1 to 7, wherein at least one of the two or more layers containing the organopolyoxane comprises (E) at least one type of inorganic fine particles of polyoxyl The elastomer layer, the at least one type of inorganic fine particles is selected from the group consisting of conductive inorganic particles, insulating inorganic particles, and reinforcing inorganic particles. The converter of any one of claims 1 to 8, wherein at least one of the two or more organic polyoxane-containing layers comprises one or more fine particles of a polyoxyxene elastomer layer, The surface of the one or more fine particles is treated with one or more types of surface treatment agents, and the particles are at least one of: (D) having a dielectric ratio greater than or equal to 10 at 1 kHz at room temperature The constant dielectric inorganic fine particles and (E) at least one type of inorganic particles selected from the group consisting of conductive inorganic particles, insulating inorganic particles, and reinforcing inorganic particles. The converter according to any one of claims 1 to 9, wherein at least one of the two or more layers containing the organopolyoxane comprises (F) for improving mold release property or dielectric breakdown property. A layer of polyoxyxene elastomer of the additive. The converter of any one of claims 1 to 10, wherein at least one of the two or more layers containing the organopolyoxane is a polyoxyxene elastomer layer having a high dielectric functional group. A method of manufacturing a transducer according to any one of claims 1 to 11, comprising the steps of: curing two or more curable organopolyoxane compositions having different electrical or mechanical strengths of the cured body One of the curable organopolyoxane compositions is coated on the substrate, and the coating is cured into a cured polyoxyxene elastomer layer, and then the other curable organopolyoxane composition is further coated thereon. The same cured layer is cured and the coating is cured. A method of manufacturing a transducer according to any one of claims 1 to 11, comprising the steps of: curing two or more curable organopolyoxane compositions having different electrical or mechanical strengths of the cured body One of the curable organopolyoxane compositions is applied to the substrate, and then the other curable organopolyoxyalkylene composition is further coated on the same coating layer, and two or more of the stack are cured. Multiple different coating layers. The converter manufacturing method of claim 12 or 13, wherein the curable organopolyoxane composition is applied by die coating. The converter manufacturing method according to any one of claims 12 to 14, wherein a dielectric layer containing an organopolysiloxane is formed as the two or more layers, and then an electrode layer is formed on at least one side thereof. The converter manufacturing method according to any one of claims 12 to 14, wherein a dielectric layer containing an organopolysiloxane and an electrode layer are formed at a time as the two or more layers.