TW201431967A - Production method of curable organopolysiloxane composition for transducers - Google Patents

Abstract

The present invention provides a production method of curable organopolysiloxane composition capable of producing a cured article that can be used as a transducer and provided with excellent mechanical characteristics and/or electrical characteristics. The present invention also relates to a production method of a curable organopolysiloxane composition for transducer use comprising a step of kneading a composition for kneading including: a curable organopolysiloxane, and at least one type of filler, wherein the kneading is performed using an extruder or kneading apparatus.

Description

Method for producing curable organopolyoxane composition for converter

The present invention relates to a method of making a curable organopolyoxane composition that can be advantageously used in a converter. The present invention provides a method for producing a curable organopolyoxane composition, which is used as an electroactive polyoxyxene elastomer material by curing an organic polyoxyalkylene cured article, which can be used as a converter Dielectric layer or electrode layer. In particular, the present invention relates to a method of making a curable organopolyoxane composition having electrical and mechanical properties suitable for use as a dielectric material and further particularly suitable for use as a dielectric layer of a converter. The invention further relates to a method of making an electroactive polymer material formed using a curable organopolyoxane composition and an assembly of a converter comprising the electroactive polymer material.

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, at B.Kussmaul et al., Actuator 2012, the 13th International Conference on New Actuators (13th International Conference on New Actuators), Bremen, Germany, June 18-20, 2012, pages 374 to 378, an actuator incorporating a dielectric elastomer material between electrodes, the dielectric elastomer The material has been used as an organic polydimethyl siloxane having a chemical modification of the group of the electric dipole, which modification is carried out by bonding the groups to polydimethyl methoxy alkane using a crosslinking agent.

However, the specific composition of the curable organopolyoxane composition is not disclosed in any of the references mentioned above, and the process and manufacturing apparatus suitable for industrial manufacture of the composition are not disclosed. Moreover, the physical properties of curable organopolyoxane compositions in practice are insufficient for materials for industrial applications of various types of converters. Accordingly, there is a need in the art for a method of manufacturing an electroactive polymer material that is industrially capable of meeting the mechanical and electrical properties of a practical application as a material for various types of converters. In particular, there is a great need in the art for a method of making a curable organopolyoxane composition that cures and provides an electroactive polymer material having excellent physical properties.

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 method of making a curable organopolyoxane composition capable of producing a cured article which can be used as a converter and which provides excellent mechanical and/or electrical properties.

Another object of the present invention is to provide a process for the manufacture of a curable organopolyoxane composition which is capable of providing excellent specific mechanical and/or electrical properties, and in particular provides a high specific dielectric constant, high dielectric Destructive strength and low Young's modulus High energy density; can achieve durability and practical displacement due to excellent mechanical strength (ie tensile strength, tear strength, elongation or the like) in the case of a dielectric layer used as a converter; Used as a cured object for materials for converters.

Further, it is an object of the present invention to provide a process for producing a curable organopolyoxane composition for a converter which can easily obtain an intermediate raw material for a curable organopolyoxane composition for a converter ( That is, an intermediate raw material of a polyoxyxene rubber compound containing a raw material polymer blended with various types of high-concentration fillers, hereinafter sometimes referred to as "masterbatch" or "polyoxyelastomer matrix", so that When the intermediate raw material is used, the manufacturing efficiency and performance of the obtained cured product are excellently improved. Furthermore, it is an object of the present invention to provide a process for the manufacture of a curable organopolyoxane composition for a converter which, from the point of view of the components used in the converter, the curable organopolyoxygen for the converter The alkane composition can be advantageously produced in that a uniform sheet-like cured product can be obtained, a film can be produced, the obtained sheet-like cured product is excellent in electrical characteristics or mechanical properties, and excellent in handling ability for lamination or the like. .

The present invention has been achieved by the present inventors that the present invention solves the above-mentioned problems by a method for producing a curable organopolyoxane composition for use in a converter, the method comprising kneading inclusion The following steps of the kneading composition: a curable organopolyoxane and at least one type of filler, wherein the kneading is carried out using an extruder or a kneading device.

Preferably, the kneading composition further comprises (D) a dielectric inorganic fine particle having a dielectric constant greater than or equal to 10 at 1 kHz at room temperature as at least one type of filler. More preferably, the composition further comprises at least one type of surface treatment agent. Further, the extruder or the kneading device is preferably at least one mechanical member selected from the group consisting of a twin screw extruder, a biaxial kneader, and a uniaxial blade extruder, and more preferably has the following Defining devices having a free volume of at least 5,000 (L/hr), at least 7,500 (L/hr), or at least 10,000 (L/hr) Double shaft extruder.

Free volume: gap cross-sectional area of the device (mm2) × wheelbase (mm) × rotation rate (rpm) × 60/1,000,000 (L / hr)

According to the method for producing a curable organopolyoxane composition for a converter according to the present invention, the filler is sufficiently dispersed in the curable organopolyoxane, and thus a converter having good electrical or mechanical properties can be produced. component. In addition, a method of producing a curable organopolyoxane composition for a converter can be provided which enables a higher loading of the filler in the curable organopolyoxane and can be used during the manufacture of the converter component A uniform film-like cured product is obtained to improve the electrical or mechanical properties of the obtained film-like cured product, and the handling ability for lamination or the like is excellent.

According to the manufacturing method of the converter member of the present invention, a converter member in which a filler is sufficiently dispersed in a polyoxyelastomer can be manufactured, and thus a converter member having good electrical characteristics or mechanical characteristics can be manufactured.

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

51‧‧‧Cylinder

51a‧‧‧First feed埠

51b‧‧‧Emissions

52‧‧‧Two-axis

52a‧‧‧First pinch plate

52b‧‧‧Second pinch plate

52c‧‧‧ third pinch plate

53‧‧‧ drive device

54‧‧‧ feeder

510‧‧‧Dual-axis extruder

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.

Figure 5 shows an example of a twin screw extruder.

The invention will be explained in detail below.

The method for producing a curable organopolyoxane composition for use in a converter of the present invention is characterized by comprising the step of kneading a kneading composition comprising: curable A polysiloxane and at least one type of filler, wherein the kneading is carried out using an extruder or a kneading device.

The electrical and mechanical properties of the converter component produced by the cured composition can be improved by the method for producing a curable organopolyoxane composition for use in a converter of the present invention. Further, by using this manufacturing method, a converter component having good quality when the film thickness is reduced can be manufactured. Further, by using the manufacturing method, various types of fillers can be easily obtained by blending the intermediate raw materials in the curable organopolysiloxane (i.e., raw materials) at a high concentration, and the final composition can be easily manufactured. Each configuration is explained below.

A curable organopolyoxane composition made by and in accordance with the present invention is used to cure a composition for making a converter component. The curable organopolyoxane composition produced in accordance with the present invention may especially have a filler dispersed in a curable organopolyoxane at a high concentration. This type of curable organopolyoxyalkylene composition can itself be used to make converter parts by curing, heating or the like, or alternatively, this type of curable organopolyoxyalkylene composition can be used for manufacturing. The intermediate material of the converter component (ie, masterbatch, polyoxyxene elastomer matrix or polyoxyxene rubber compound).

In particular, when a curable organopolyoxane composition is used as an intermediate raw material (masterbatch, polyoxyxide elastomer matrix or polyoxyxene rubber compound), a desired kneading device can be easily used to form a desired formulation with another The components (for example, curable organopolyoxane or the like) are blended, and thus the production efficiency is excellent. Further, during the kneading, the filler may be subjected to a surface treatment by adding at least one type of surface treating agent to the kneading composition.

[curable organic polyoxane]

The curable organic polyoxyalkylene is not particularly limited as long as the curable organopolyoxane can be subjected to a condensation curing reaction, an addition curing reaction, a peroxide compound curing reaction, a photocuring reaction or by removing a diluent solvent. Dry and solidify to cure. The curable organopolyoxane can be a combination of two or more types of different curable organopolyoxanes use.

The curable organopolyoxyalkylene cured by an addition curing mechanism is exemplified as an organic hydrogen polyoxyalkylene having at least 2 hydrazine-bonded hydrogen atoms in the molecule and/or an organic having at least 2 alkenyl groups in the molecule. Polyoxane. Further, for the addition curing mechanism of the curable organopolyoxane, the curable composition further includes a hydrazine hydrogenation reaction catalyst.

An organopolyoxyalkylene which can be cured by a condensation curing mechanism is exemplified as a diorganopolyoxyalkylene which is liquid at room temperature and whose molecular terminal is terminated by a hydrazide group or a hydrazine-bonded hydrolyzable group, or has A partially hydrolyzed condensate of an organic decane bonded to a hydrolyzable group. The partially hydrolyzed condensate of the diorganopolyoxyalkylene or organodecane further comprises an organodecane or an organodecane having a sufficient amount of a hydrazone-bonded hydrolyzable group for crosslinking the components during curing. Type crosslinker. Further, for the condensation curing mechanism of the curable organopolyoxane, the curable composition further includes a catalyst that promotes the condensation reaction.

The curable organopolyoxyalkylene of the present invention may be, for example, an organopolyoxyalkylene which can be cured by a peroxide compound curing mechanism, in addition to the organic polyoxyalkylene which can be cured by an addition curing mechanism and a condensation curing mechanism. . In the case of an organopolyoxane which can be cured by a peroxide compound curing mechanism, the organopolyoxyalkylene is generally exemplified as an organopolyoxane raw rubber. Further, an organic peroxide compound should be added during curing of the organopolyoxane raw rubber.

Preferably, the curable organopolyoxane system hydrogenation reaction cures the organopolyoxane. More specifically, the organopolyoxane may be at least one of the following: (A11) at least one type of organohydrogenpolyoxyalkylene having a hydrogen atom bonded to a ruthenium atom at the end of two molecules, a hydrogen atom The weight fraction is 0.1% by weight to 1.0% by weight; (A12) at least one type of organic hydrogen polyoxyalkylene having at least 3 hydrogen atoms bonded to a halogen atom in a single molecule, the weight fraction of hydrogen atoms 0.03 wt% to 2.0 wt%; and (A2) at least one type of organopolyoxane having at least 2 alkenyl groups in a single molecule, the alkenyl group having a weight fraction of 0.05% to 0.5% by weight. In addition, all of the use for converters can be solid Preferred composition formulations and structures of the organopolyoxane compositions are detailed in the following sections.

[filler]

The at least one type of filler may be at least one type of filler selected from the group consisting of high dielectric fillers, highly conductive fillers, electrically insulating fillers, and reinforcing fillers. This filler may be used singly or in combination of two or more types. In particular, when a filler is used in the dielectric layer or electrode layer of the converter, it is preferred to use one type or two or more types of fillings containing a high dielectric filler and/or a highly conductive filler. Agent.

However, from the viewpoint of the electrical properties of the converter member, the filler is preferably a dielectric fine particle or a conductive fine particle, and particularly preferably contains (D) a dielectric constant greater than or equal to 10 at 1 kHz at room temperature. Dielectric inorganic fine particles. Preferred dielectric inorganic fine particles are exemplified by one or more types of inorganic fine particles selected from the group consisting of titanium oxide, barium titanate, barium titanate, lead zirconate titanate, and barium titanate, and wherein barium titanate The composite metal oxide in which the titanium portion is partially replaced by an alkaline earth metal (for example, calcium or barium), zirconium or a rare earth metal (for example, lanthanum, cerium, lanthanum or cerium), and titanium oxide and barium titanate are most preferred. In addition, the filler components of all curable organopolyoxane compositions for use in converters are detailed in the following sections.

[surface treatment agent]

Although it is particularly preferable to partially or completely surface-treat the filler, it is particularly preferable to further knead at least one type of surface treatment agent in the kneading composition in the kneading step. The type of the treating agent is preferably a hydrophobized surface treating agent, and more preferably, the surface treating agent is exemplified by at least one hydrophobized surface treating agent selected from the group consisting of an organic titanium compound, an organic cerium compound, an organic zirconium compound, and an organic Aluminum compounds and organophosphorus compounds. The types of capabilities of all surface treatment agents for curable organopolyoxane compositions for converter applications are detailed in the following sections. By adding a surface treatment agent by means of an extruder or a kneading device at the time of kneading, the treatment agent treats the surface of the filler in an effective manner to improve the filler. The dispersibility can effectively improve the physical properties of the converter assembly manufactured using the curable organopolyoxane composition, and improve the higher filling content of the filler in the intermediate raw material obtained during the kneading step and can be treated Sex.

[Other components]

The curable organopolyoxane composition produced according to the present invention may further comprise at least one type of component selected from the group consisting of organopolysiloxanes having a high dielectric functional group and organic compounds having a high dielectric functional group. (except for organopolysiloxanes participating in the curing reaction), electrical insulation improvers and removers, vulcanizing agents, curing catalysts or the like. These components may be incorporated together with the components in the kneading composition, and the mixture may be kneaded using an extruder or a kneading device. Further, an extruder or a kneading device may be used to knead portions of the other components and the components of the kneading composition to produce an intermediate raw material of the curable organopolyoxane composition, and other components may be used. The remainder is blended with the intermediate material. Details of these components will be set forth in the following sections.

[Manufacture of intermediate raw materials (masterbatch, polyoxyxene elastomer matrix or polyoxyxene rubber compound)]

The production method of the present invention has the step of kneading a kneading composition containing the curable organopolysiloxane and a filler, and preferably further comprising a surface treatment agent, using an extruder or a kneading device. This step enables the filler content of the filler in the curable organopolyoxane composition to be uniform and high, and at the same time, the filler can be surface-treated by the curable organopolyoxane and the surface treatment agent. Therefore, this step is extremely useful as a manufacturing step for the intermediate raw material of the curable organopolyoxane composition for the converter. This intermediate material is referred to as "masterbatch", "polyoxyelastomer matrix" or "polyoxygen rubber compound" (hereinafter referred to as "masterbatch, etc."). This intermediate raw material is advantageously used in the manufacture of curable organopolyoxane compositions for converters, since it has advantages such as the ability to use the desired blending device at a desired concentration with other raw materials (eg, other curables) The organic polysiloxane raw material, filler or the like) is kneaded, the composition of the product is easy to design, and the manufacturing efficiency is excellent. In addition, due to the high filler content of the filler, the curable organic polyfluorene The viscosity of the oxyalkylene composition becomes high. Therefore, high shear force can be imparted in the step of kneading using the extruder or the kneading device of the present invention. Therefore, the mechanical and electrical properties of the converter component obtained using the curable organopolyoxane composition can be improved by producing a curable organopolyoxane composition having good filler dispersibility. In addition, due to the uniform dispersion of the filler, defects are prevented from occurring even after curing and molding to form a film. A film can therefore be used as the converter component.

In the total intermediate raw material, the filler content in the intermediate raw material obtained by kneading is greater than or equal to 30% by mass, greater than or equal to 50% by mass, greater than or equal to 60% by mass, greater than or equal to 70% by mass, and greater than or equal to 75. % by mass, or greater than or equal to 80% by mass. Specifically, it is relatively easy to obtain a filler content in the total intermediate raw material by kneading using at least one mechanical member selected from the group consisting of a twin screw extruder, a double rod kneading device, and a uniaxial blade extruder. 80% by mass of masterbatch, etc. The intermediate raw material loaded with the high-concentration filler has excellent handling and handleability due to lower viscosity than the use of only the filler, can improve manufacturing efficiency, and can be blended with other components for the desired composition. Therefore, it is easy to design a composition formulation of a curable organopolyoxane composition for a converter. In addition, since the filler is uniformly dispersed under high shear force, the dispersibility of the finally obtained filler in the curable organopolyoxane composition for the converter is improved, and even when the composition is molded and It still resists the appearance of defects when it is cured. Therefore, a thin-layer type component for a converter can be formed, and mechanical characteristics and electrical characteristics can be improved.

The intermediate raw material may be an intermediate raw material having a high content of a high dielectric filler or a highly conductive filler. The intermediate raw material is obtained by using at least one type of mechanical member selected from the group consisting of a twin screw extruder, a biaxial kneading device, and a uniaxial blade extruder to knead the curable organopolyoxane The filler content in the composition obtained by the high dielectric filler or the highly conductive filler and the at least one type of surface treatment agent is greater than or equal to 30% by mass, greater than or equal to 50% by mass, greater than or equal to the total composition. 60% by mass, 70% by mass or more, 75% by mass or more, or 80% by mass or more.

Specifically, the intermediate material and the curable organic polyfluorene oxide may be blended by the mechanical member to a filler content of 70% by mass or more, or greater than or equal to 75% by mass, or greater than or equal to 80% by mass of the total mass. Other raw materials used in the alkane composition, such as other curable organopolyoxyalkylenes, vulcanizing agents, curing catalysts, or other ingredients. Therefore, a curable organopolyoxane composition for a converter in which a filler and other components are uniformly dispersed can be easily obtained.

[Kneading by extruder or kneading device]

The production method of the present invention is characterized by comprising the step of kneading a kneading composition containing the respective components using an extruder or a kneading device.

Although the type of the extruder or the kneading device for producing the curable organopolyoxane composition for a converter of the present invention is not particularly limited, the extruder or the kneading device is exemplified as a single-axis extruder, Biaxial extruder, multi-axis extruder, single-axis blade extruder, twin-shaft kneading device, continuous kneading device, batch kneading device, Banbury mixer (hermetic sealed mixer), Henschel mixing , double roll mill, three roll mill, continuous double roll mill, continuous three roll mill, batch type roll mill, pressure kneader, change tank mixer, planetary mixer, continuous Ball mills, cone-shaft mixers, belt blenders, double-arm or sigma leaf mixers, impression powder mixers or the like or combinations of such devices.

In such apparatuses, in order to improve the dispersibility of the filler, an extruder or a kneading device capable of applying a high shear force to a curable organopolysiloxane containing a high-viscosity filler at the time of kneading can be used. An extruder or kneading device of this type is exemplified as at least one type of mechanical member selected from the group consisting of a twin screw extruder, a biaxial kneading device and a uniaxial blade extruder.

Further, in the case of using the kneading device or the extruder as described above in combination, it is possible to impart high shear force by using an extruder, a kneading device, a blending machine or the like which imparts relatively low shear force. The extruder or kneading device combines the premixed filler with the curable organopolyoxane to effect kneading.

An extruder, kneading device or blender for imparting relatively low shear force is exemplified as Henschel mixer, variable tank mixer, planetary mixer, cone-shaft mixer, belt blender, double or sigma leaf mixer, impression powder mixer or the like. Further, the above-mentioned extruder or kneading device can be exemplified as an extruder or a kneading device for imparting high shear force.

Further, the filler and the curable organopolyoxane may be carried out by further adding a filler and/or a curable organopolyoxane after the preparative blending as described above using a kneading device or an extruder. Kneading. Further, after kneading the filler and the curable organopolyoxane using a kneading device or an extruder, a filler and/or a curable organopolyoxyalkylene may be further added, and then a blending or kneading device or extrusion may be used. Get out of the machine to implement the kneading.

In kneading by means of an extruder or a kneading device, it is possible to design a concentration of a filler in a composition obtained by kneading a composition of a filler and a curable organopolyoxyalkylene by using an extruder or a kneading device as needed. To have (relative to the total composition) greater than or equal to 30% by mass, greater than or equal to 50% by mass, greater than or equal to 60% by mass, greater than or equal to 70% by mass, greater than or equal to 75% by mass, or greater than or equal to 80% by mass; and even by using a combination with a suitable surface treating agent, even a very high filler concentration of 98% by mass of the filler can be obtained. Specifically, the concentration of the filler relative to 100 parts by mass of the curable organopolyoxane may range from 1 part by mass to 5,000 parts by mass. The lower limit of the filler concentration may be 5 parts by mass, 10 parts by mass, 25 parts by mass, 50 parts by mass or 100 parts by mass. The upper limit of the filler concentration may be 5,000 parts by mass, 4,000 parts by mass, 3,000 parts by mass, 2,000 parts by mass or 1,500 parts by mass, 1,000 parts by mass or 750 parts by mass. The filler concentration can be appropriately selected depending on the desired filler concentration or according to the dielectric properties and mechanical strength. The concentration of the filler is usually selected in the range of 100 parts by mass to 2,000 parts by mass from the viewpoint of industrial equipment and manufacturing efficiency.

Although there is no particular limitation on the temperature setting during the formation of the intermediate raw material (masterbatch, etc.) not containing the vulcanizing agent (curing catalyst) in the kneading by means of the extruder or the kneading device, the temperature can be set at 40 ° C to 200 °C, 80 ° C to 190 ° C or 100 ° C to 180 ° C range. this In addition, the residence time for treatment in a continuous process using a twin screw extruder or the like can be set in the range of from about 30 seconds to about 5 minutes. The temperature conditions during the continuous processing or the like can be appropriately adjusted by setting the temperature of the extruder or the like.

From the viewpoint of producing an intermediate raw material (i.e., a master batch or the like) containing a high concentration of a filler in a curable organopolysiloxane, it is particularly preferable to use kneading by means of a twin screw extruder or a biaxial kneading device.

An example of a twin screw extruder is shown in Figure 5. In the cylinder 51, the twin-screw extruder 510 is equipped with a rotatable biaxial shaft 52 connected to a driving device 53, and the cylinder 51 has an opening for feeding material into the cylinder 51 (feeding crucible 51a) ). Due to the rotational driving of the double shaft 52, the material fed from the first feed port 51a into the cylinder 51 is sent in the left-to-right direction as seen in the drawing, and the material is self-disposed at the tip end of the cylinder 51. The discharge weir 51b is discharged to the outside of the cylinder 51, and the tip end of the feed weir 51a is disposed opposite thereto. In the direction in which the material is transported within the cylinder 51, the left side direction of Fig. 5 is sometimes hereinafter described as the upstream side, and the right side direction of Fig. 5 is sometimes hereinafter explained as the downstream side. In addition, a single feed crucible may be used as the cylinder 51 feed crucible as may be desired, or alternatively, other feed crucibles than the first feed crucible 51a may be provided. Further, heating and cooling can be controlled by providing the cylinder 51 with a heating/cooling jacket and a temperature sensor (omitted in the drawing) to obtain a desired temperature at a desired position. In addition, the shafts can be rotated in the same direction or in opposite directions.

According to the example shown in Fig. 5, the first kneading disk 52a, the second kneading disk 52b, and the third kneading disk 52c are disposed in this order from the feed port 51a to the discharge port 51b along the biaxial shaft 52. These kneading discs are used to sufficiently knead the material in the cylinder 51. The material transported from the upstream direction is held on the upstream side of each kneading disc, and due to the rotation of the kneading disc, the material can be subjected to kneading due to high compression and shearing force. There is no particular limitation on the cross-sectional shape of this type of kneading disc. The kneading discs used may have various types of shapes, such as an elliptical shape, an approximately elliptical shape, a triangular shape, an approximately triangular shape, a rectangular shape, an approximately rectangular shape, a cross shape, an approximate cross shape, or the like.

Each raw material component is fed using the example shown in Figure 5 in detail below. Further, during the pre-blending, components other than the curable organopolyoxane and the filler (for example, the surface treating agent) may each be fed together with the raw material to a twin-screw extruder or a biaxial kneading device. Alternatively, the components other than the curable organopolyoxane and the filler may be fed to a twin screw extruder or a biaxial kneading device without pre-doping.

According to the example shown in Fig. 5, the feeder 54 is disposed above the first feed crucible 51a, and the filler for the kneading and the curable organopolyoxane can be fed to the feed crucible 51a. Further, although not shown in the drawing, in the case where the second feed crucible is disposed between the feed crucible 51a and the discharge crucible 51b in the cylinder 51, for example, it can be fed only from the first feed crucible 51a. The organopolyoxane can be cured and the filler can only be fed from the second feed. Alternatively, a pre-blended mixture of filler and curable organopolyoxane may be fed from the first feed crucible 51a and the filler may only be fed from the second feed crucible. Alternatively, a pre-blended mixture of filler and curable organopolyoxane may be fed from the first feed crucible 51a, and the curable organopolyoxane may only be fed from the second feed crucible. In the case of kneading by using the second feed which only feeds the curable organopolyoxane, the overall viscosity of the kneaded mixture containing the filler can be lowered, and this method is sometimes referred to as a polymer dilution method.

If only the feed crucible 1a is used as the feed crucible, and if the curable organopolyoxane is cured by an addition curing mechanism, the intermediate raw material of the curable organopolyoxane composition for the converter can be borrowed It is prepared, for example, by (i) feeding an organic hydrogen polyoxyalkylene oxide (i.e., solidified organopolyoxane) and a filler into the cylinder 51 through a feed crucible 51a. Further, an intermediate raw material of the curable organopolyoxane composition for a converter can be prepared by (ii) an organic polyoxyalkylene having at least two alkenyl groups in the molecule (ie, curing) The organic polyoxane and the filler are fed into the cylinder 51 through the feed crucible 51a. Further, the intermediate raw material of the curable organopolyoxane composition for the converter can be prepared by (iii) organic hydrogen polyoxane, organic polymerization having at least two alkenyl groups in the molecule. The decane and the filler are fed into the cylinder 51 through the feed crucible 51a.

If only the feed crucible 51a is used as the feed crucible, and if the curable organopolyoxane is cured by a condensation solidification mechanism, the intermediate raw material of the curable organopolyoxane composition for the converter can be used For example, it is prepared by dissolving a diorganopolysiloxane or a hydrolyzable group having a hydrazone bond which is a liquid at room temperature and whose molecular terminal is terminated by a hydrazino group or a hydrazine-bonded hydrolyzable group. The partially hydrolyzed condensate of the organic decane and the filler are fed into the cylinder 51 through the feed crucible 51a.

If only the feed crucible 51a is used as the feed crucible, and if the organopolyoxyalkylene is curable by the peroxide compound curing mechanism, the intermediate raw material of the curable organopolyoxane composition for the converter can be It is prepared, for example, by feeding the component organopolyoxane raw rubber and a filler into the cylinder 51 through the feed crucible 51a.

If both the first feed crucible 51a and the second feed crucible are used (i.e., two feed crucibles are used), the intermediate raw material of the curable organopolyoxane composition for the converter can be obtained, for example, by Preparation: Each curable organopolyoxane is fed from the first feed crucible 51a into the cylinder 51, and the filler is fed into the cylinder 51 through the second feed crucible. Further, the intermediate raw material of the curable organopolyoxane composition for the converter can be prepared by feeding each curable organopolyoxane and filler through the first feed crucible 51a. To the cylinder 51, and each of the curable organopolyoxanes is further fed into the cylinder 51 through the second feed crucible (polymer dilution method).

If the extruder shown in FIG. 5 is used to manufacture the curable organopolyoxane composition for a converter of the present invention, the cylinder 51 can be first set to a certain temperature, and the driving device 53 is operated to The twin shaft 52 rotates. Further, the temperature of the cylinder 51 may vary depending on the position in the cylinder 51, or alternatively, the entire cylinder 51 may be set to a fixed temperature.

Thereafter, each desired and selected type of pre-mixed curable organopolyoxane and filler is placed in feeder 54 and the curable organopolyoxane and filler are passed through feed 埠51a. It is fed into the cylinder 51.

Due to the rotation and driving of the double shaft 52, the curable organic polyoxane and the filler are as shown in the figure It is seen from left to right, and the curable organopolyoxane and the filler are kneaded by the kneading effect of the internal meshing of the twin shaft 52 and the kneading disc.

Further, according to the example shown in FIG. 5, the kneading discs are disposed at three positions in the cylinder 51. However, additional kneading discs may be provided as needed.

The filler and the curable organopolyoxane which are kneaded in this manner are discharged from the discharge crucible 51b, and a curable organopolyoxane composition for the converter or an intermediate raw material thereof can be obtained. By kneading in this manner by means of a twin-screw extruder, an intermediate raw material of a curable organopolyoxane composition for a converter can be obtained, wherein a high concentration of the filler is sufficiently dispersed in the organopolysiloxane, or Such a composition as the curable organopolyoxane composition itself for the converter, depending on the composition.

Specifically, from the viewpoint of blending various types of high-concentration fillers in the raw material polymer to produce an intermediate raw material, the extruder or the kneading device is preferably a twin-screw extruder, wherein the extruder or kneading is as follows The free volume defined by the device is set to be greater than or equal to 5,000 (L/hr), greater than or equal to 7,500 (L/hr), or greater than or equal to 10,000 (L/hr). Specifically, in order to efficiently produce an intermediate raw material (ie, a master batch or the like) having a filler content of 80% by mass or more, a suitable apparatus is a device having a free volume of 10,000 (L/hr) to 30,000 (L/hr), such as It is exemplified as a biaxial kneading device such as a model 4BKRC or a TEM-100 kneading device.

Definition of the term "free volume":

Cross-sectional area of the device (mm ² ) × wheelbase (mm) × rotation rate (rpm) × 60/1,000,000 (L / hr)

In addition, the free volume of commercial devices is listed below for reference.

In the same manner, although the ratio of the total length/inner diameter (L/D) of the device is not specifically limited, the L/D ratio is preferably less than or equal to 50, or less than or equal to 20.

[Manufacturing Method of Curable Organic Polyoxane Composition for Converter Use]

The method of making a converter component of the present invention has the step of curing a curable organopolyoxane composition for use in a converter. According to this manufacturing method of the converter component, a converter component in which a filler is sufficiently dispersed in a polyoxyxene elastomer (that is, a cured product of a solidified organopolyoxane) can be produced, and thus can be manufactured with good electrical characteristics or mechanical properties. Characteristic converter component.

In the case of using the intermediate raw material obtained by the production method of the present invention, each curing agent (i.e., crosslinking agent, catalyst or polymerization) is used before heat curing the curable organopolyoxyalkylene composition for the converter. The initiator is added to the curable organopolyoxane composition, and if necessary, a solvent and/or an additive or the like is added and blended to prepare a curable organopolyoxane composition. The components and all formulations of the curable organopolyoxane composition are detailed in the following sections.

Solvent can be used from the standpoint of, for example, processability during the manufacture of converter components The agent is used to dilute the curable organopolyoxane composition. Solvents of this type are preferably exemplified by water and organic solvents, such as lower alcohols such as ethyl alcohol, butyl alcohol, isopropyl alcohol or the like; ketones such as methyl isobutyl ketone, methyl ethyl ketone , acetone or the like; an ether such as dioxane, diethylene glycol dimethyl ether, tetrahydrofuran, methyl-tert-butyl ether or the like; a cellosolve such as methyl cellosolve, ethyl cellosolve , butyl cellosolve, propylene glycol monomethyl ether acetate or the like. In addition, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, diethyl succinate, diethyl adipate, dibutyl phthalate, phthalic acid can be used. Octyl esters and similar esters (eg dibasic acid esters) and the like; chlorinated and fluorinated hydrocarbons, trichloroethane and similar halogenated hydrocarbons (eg chlorinated hydrocarbons, fluorinated hydrocarbons) and the like; toluene, xylene, hexyl Alkanes and similar hydrocarbons; and the like.

[curable organopolyoxane composition]

As far as the production method is obtained, the curing system is not particularly limited, and any curing reaction system can be used for the curable organopolyoxane composition of the present invention. Typically, the curable organopolyoxane composition of the present invention is 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.

Preferably, the curable organopolyoxane composition comprises a reactive organopolyoxane, and the composition satisfies the conditions of [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 Oxane component in the composition When the ratio of the total amount 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 25 ° C at a shear rate of 10 (s ^-1 ), 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. phase 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 polyoxylene 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.

(index of reaction rate between end groups)

(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 j-th component of the component (B); M _wi represents the number average molecular weight of the ith 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.

By molecular design to adjust the molecular weight per unit weight and the molecular weight between the cross-linking points after solidification of the organopolysiloxane to some extent based on the formulae set forth in this patent specification, it is possible to implement an adjustment to 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 of the hydrazine. can. 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-tetramethyldioxane, 1,3- Divinyl-1,3-dimethyl-1,3-diphenyldioxane, 1,3-divinyl-1,1,3,3-tetraphenyldioxane, 1, 3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane or the like alkenyloxyalkylene oligomer; or dimethyloxane oligomer; And so on. 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 in that it contains 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, Ma is ^a Group 2 metal of the periodic table; M ^{b '} is a Group 5 metal of the periodic table; na is a number in the range of 0.9 to 1.1; nb' is in the range of 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. There is no particular limitation on the particle diameter of the inorganic fine particles, and if the spherical fine particles are measured by a laser diffraction method, for example, the volume is flat. The average particle diameter may range, for example, from 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 the dielectric inorganic fine particles used in the present invention such as the particle size distribution described above, various methods such as a combination of two or more types having different average diameters or particle diameters may be employed. The fine particles of the distribution, 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 organohydrogen polyoxyalkylene having a hydrogen atom bonded to a ruthenium atom at two molecular ends and having a hydrogen atom weight content of 0.01% by weight to 1.0% by weight, (A2) at least one type of organic hydrogen polyoxygen An alkane having at least 3 helium atom bonded hydrogen atoms in a single molecule and having a hydrogen atom weight content of 0.03 wt% to 2.0 wt%, (B) at least one type of organopolyoxane in a single molecule Having at least 2 alkenyl groups and having an alkenyl weight content of 0.05% by weight to 0.5% by weight, (C1) hydrazine hydrogenation reaction catalyst, and (D) dielectric inorganic fine particles having a room temperature at 1 kHz A dielectric constant greater than or equal to 10.

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.

There is no particular limitation on the conductive inorganic particles to be used, as long as the conductive inorganic particles impart The conductivity is sufficient, 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.

Further, the conductive inorganic fine particles may be fibers such as glass fibers, cerium oxide alumina fibers, alumina fibers, carbon fibers or the like; or acicular reinforcing materials such as aluminum borate whiskers, potassium titanate whiskers or the like; Inorganic filler materials such as glass beads, talc, mica, graphite, apatite, dolomite or the like, the surfaces of which are coated with a conductive material 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.

Polyoxymethane cured articles can be added by blending reinforcing inorganic particles into the composition Mechanical strength and dielectric breakdown strength. 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, in particular, a portion or the total amount of the dielectric inorganic fine particles mentioned above for use in the curable organopolyoxane composition of the present invention can be obtained by using at least one type of surface treating agent ( D) and at least one type of inorganic particle (E) undergo a 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 oxane, trialkoxy fluorenyl mono-terminated organic functional group mono-terminated polydimethyl siloxane, three Alkoxyfluorenyl double-terminated polydimethyloxane, organic functional double-terminated polydimethyloxane 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 explained previously, the use of alkyl trioxane The oxydecane and trialkoxyindenyl monocapped polydimethyloxane are most 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 further improves these characteristics of the curable organopolyoxane composition of the present invention, and the additive may be used singly or in 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 ruthenium 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 gold of the aliphatic carboxylic acids a salt (such as sodium stearate, magnesium stearate, calcium stearate or the like); an ester of a fatty carboxylic acid with an alcohol (eg 2-ethylhexyl stearate, glyceryl tristearate, neopentyl) Tetrahydrin monostearate or the like), an aliphatic hydrocarbon (liquid paraffin, paraffin or the like), an ether (distiaryl ether or the like), a ketone (distearyl ketone or the like), a high carbon number alcohol ( 2-hexadecyl octadecyl alcohol 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 greater than or equal to 0.1% by weight and less than or equal to 30 weights relative to the total amount of the curable organopolyoxane. Within the range of %.

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 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 organopolyoxyalkylene contained in the curable composition further has a high dielectric functional reactive organic polyoxygen The specific dielectric constant of the alkane and the electroactive polysiloxane elastomer obtained by curing 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, the organic compound having the high dielectric group is incorporated into the matrix of the 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, chloroform Base, 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- Alcohol or the like; an enyne compound such as 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. A hybrid copolymer of this type can be used as an intermediate raw material for a curable organopolyoxane composition for converter use by the following steps: adding the curable organic polyoxane as a filler to the kneading The composition is kneaded using an extruder or a kneading device.

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. The curable system may further comprise a method of introducing the organopolyoxygen by adding the above-mentioned dielectric functional group to an acrylic group, a methacrylic group, an epoxy group or a thiol group. Alkane 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 the composition exhibits an excellent specific dielectric constant in the low frequency region in addition to obtaining the mechanical properties such as those set forth above by means of the compositions of the present invention.

(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 be based on the desired form of the dielectric layer and The type of the converter varies, but the preferred range of the dielectric constant is greater than or equal to 5.0 under the measurement conditions mentioned above.

[Production method]

The method for producing the curable organopolyoxane composition of the present invention is set forth above. Preferably, the curable organopolyoxane is produced by kneading a reactive organopolyoxane component, a dielectric inorganic fine particle and a surface treating agent using a twin-screw extruder having a free volume of at least 5,000 (L/h). In the composition, the present invention can form a masterbatch or the like including a high concentration (for example, at least 80% by weight) of a filler. 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. Further, a uniform film-like cured article can be obtained during the manufacture of the transducer member, the obtained film-like cured article is excellent in electrical characteristics and mechanical properties, and excellent in handling ability for lamination or the like.

In the kneading process mentioned above, the temperature during formation of the polyoxyxene rubber compound (masterbatch, etc.) 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. In particular, after the curable organopolyoxane composition is molded into a sheet or film, it can usually be cured by heating, by high energy beam irradiation or the like. component. 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.

[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 mentioned above 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 specifically limited, methods such as the following may be used: (1) Curable The organopolyoxyalkylene composition is coated on the substrate, a cured polyoxyxene elastomer layer is obtained during coating, and then the curable organopolyoxyalkylene composition is further applied on the same cured layer to repeat the coating and Curing to stack multiple 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 organopolyoxygen oxides that have been coated in a stacked manner An alkane composition; or a combination of the methods of (1) and (2).

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 applying the above-mentioned curable organopolyoxane composition to a substrate, and then borrowing at room temperature The assembly is cured by heating or by irradiation with a high energy beam such as 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, sometimes The "electrode layer" is 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 in that it has 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 can have a layer including, in particular, a highly stacked layer. The structure of the structure (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. Furthermore, displacements greater than the displacement obtained by using a single layer can be obtained by stacking multiple 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. Conductive elastomers and conductive trees having conductive fillers dispersed in the resin can be used fat.

The electrode may include only one of the above-mentioned conductive materials, or may include two or more of the 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 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.

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 via the respective wires 12. 13.

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, electrode layers 21a, 21b, 21c, and 21d, a wire 22, and a 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. In addition, the dielectric layer 30 can Two or more layers of the same dielectric layer containing an organopolyoxane are included.

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.

Further, 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 like of the electrodes may be appropriately selected depending on the application.

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 The state (below), so a potential is generated between the electrode layers 41a and 41b Poor, and the power generating 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.

Industrial applicability

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 may be composed of a single layer or a stacked layer of a film-like polyoxyelastomer.

Instance

In order to embody the invention, practical 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. The properties of each polyoxyelastomer composition were measured by the following method.

[Mechanical strength]

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.

[Electrical characteristics]

The polyoxyxene elastomer composition was press cured at 150 ° C for 15 minutes to make a 0.07 mm thick sheet, and the insulation was measured using an electrical insulation breakdown voltage oil tester (ie, PORTATEST 100A-2) manufactured by Soken Electric Co., Ltd. Destructive 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. Further, the volume resistivity of the same sample was evaluated using a Model 4339A high resistance meter (volume resistance measuring device, manufactured by HP).

Practical example 1

Using a two-axis kneading device (manufactured by Kurimoto Co., Ltd., model name = "S4KRC kneader", L/D ratio = 7.0, void cross-sectional area = 8,332 mm2, wheelbase = 80 mm, rotation rate = 500 rpm, calculated freedom Volume = 11,998 L / hr, and shaft diameter = 50 mm) 100 parts of 2,000 mPa. s (viscosity at 25 ° C) and two molecular ends terminated by dimethylvinyl methoxy group dimethyl polyoxy siloxane A (vinyl content = 0.23% by mass) and 3.3 parts of trimethyl methoxy A mixture of decane and 330 parts of spherical titanium oxide particles (CR-80, Ishihara Sangyo Kaisha Co., Ltd.) having an average particle diameter of 0.25 μm. The kneading conditions of the biaxial kneading apparatus were as follows: a jacket temperature of 150 ° C and a residence time of 1 minute. The feed rate of the mixture of dimethylpolysiloxane A and trimethylmethoxydecane was 4 kg/hr, and the feed rate of titanium oxide was 16 kg/hr. The concentration of titanium oxide in the obtained polyoxyxene elastomer matrix was about 76% by mass.

To the obtained polyoxyxene rubber matrix, 0.3 parts of a dimethyl methoxy alkane-methylhydroquinone copolymer having two molecular ends terminated by trimethyl methoxy group was added (degree of polymerization = 6, SiH content) = 0.73 mass%), 6.0 parts of a dimethyl methoxy alkane-methylhydroquinoxane copolymer terminated with a dimethylhydroquinone group at the end of the molecule (degree of polymerization = 14, SiH content = 0.13% by mass) ), 1.7% by mass of 1,3-divinyl-1,1,3,3-tetramethyldioxanane platinum complex Dimethylvinyl methoxy-di-terminated dimethyl polyoxymethane solution and 3.1 parts of phenylbutynol as a reaction control agent 0.5% dimethylvinyl decyloxy-double-capped dimethyl A polyoxyalkylene solution. The mixture was blended uniformly (about 10 minutes), and a polyoxymethylene rubber composition was obtained. The molar ratio of total SiH functional groups to total vinyl groups (SiH groups/vinyl groups) in this polyoxyxene elastomer composition is one.

The mechanical strength and electrical properties of the electroactive polyoxyxene elastomer sheet obtained by curing the polyoxyethylene rubber composition obtained in the single layer practical example 1 were measured by the method described below. The measurement results of mechanical strength and electrical properties are shown in Table 2.

Practical example 2

A practical example 2 was prepared in the same manner as in Practical Example 1 except that a twin-screw extruder (manufactured by Plastic Technology Co., Ltd., model name BT-30-SL) was used instead of the biaxial kneading device of Practical Example 1. A curable organopolyoxane composition and converter assembly for the converter.

Practical example 3

The practical example 3 was prepared in the same manner as in the practical example 1, except that the uniaxial blade type kneading device (manufactured by KCK Engineering Co., Ltd., model name KCK 130X2-65X) was used instead of the biaxial kneading device of Practical Example 1. Compressible organic polyoxane Composition and converter assembly.

Reference example:

The polyoxyxene elastomer composition can be prepared by the following examples of the composition and using the intermediate raw material of the polyoxyxene elastomer matrix obtained by the kneading procedure of the biaxial kneading device of Practical Example 1. This manufacturing method is excellent in the properties, mass yield, and the like of the polyoxyxene elastomer composition for a converter of the present invention.

Reference Example 1: "Using a polyoxyxene elastomer matrix comprising barium titanate and a surface treatment agent"

85.35% was added to 14.22% of dimethylpolyoxyalkylene (B ₂ ) (vinyl content of 0.23%) having a viscosity of 2,000 mPa at 25 ° C and two ends terminated by dimethylvinyl methoxy group (vinyl content: 0.23%) Spherical barium titanate (manufactured by Fuji Titanium Industry Co., Ltd., HPBT-1B) having an average particle diameter of 1.0 μm, 0.356% of trimethoxysulfonyl mono-terminated dimethylvinyl monocapped polyoxyalkylene ( Average degree of polymerization = 25) and 0.071% 1,1,3-trimethyl-3,3-diphenyl-1-carboxyindenyldioxane. The composition was uniformly kneaded by using the biaxial kneading device of Practical Example 1, to obtain a polyoxyxene elastomer matrix.

To the polyoxyxene elastomer matrix, dimethyl polyoxyalkylene (B ₂ ), dimethylhydroperoxy group dissolved in dimethylvinyl decyl double-terminated methyl polyoxyalkylene is added to the matrix. - a double molecular chain terminated polydimethyl methoxyalkane (A ₁₁ , SiH content = 0.155%), a trimethyl decyloxy group - a bimolecular chain terminated dimethyl methoxy oxane - methyl hydrazine Alkyl copolymer (A ₂₂ , SiH content of 0.83%), 0.67% (in terms of platinum) of platinum of 1,3-divinyl-1,1,3,3-tetramethyldioxane complex A complex compound and tetramethyltetravinylcyclotetraoxane as a reaction controlling 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.

Reference Example 2: "Using a polyoxyxene elastomer matrix comprising barium titanate and a surface treatment agent"

The viscosity to 2,000 mPa at 25 ° C to 100 parts by mass. s and two ends of dimethylpolyoxyalkylene terminated by dimethylvinyl methoxy group (vinyl content of 0.23%) added 293 The mass fraction of barium titanate (manufactured by Sakai Chemical Industry Co., Ltd., BT-04) having an average particle diameter of 0.4 μm and 4.1 parts by mass of methyltrimethoxydecane. The composition was uniformly kneaded by using the biaxial kneading device of Practical Example 1, to obtain a polyoxyxene elastomer matrix.

To the polyoxyxene elastomer matrix, 16.12 parts by mass of dimethylhydroquinoneoxy-bi-molecular chain-terminated polydimethyloxane (SiH content = 0.15%) and 0.13 parts by mass of trimethyl group were added. a methoxy-bi-molecular chain-terminated dimethyl methoxy oxane-methylhydroquinoxane copolymer (SiH content of 0.75%), 80 ppm (in terms of platinum, the platinum metal content is in parts by mass and relative to 1,3-divinyl-1,1,3,3-tetramethyldioxane as a curing agent for the mixture of dimethylpolysiloxane in a polyoxyxene elastomer matrix a platinum complex of the complex compound and 0.009 parts by mass of 2-phenyl-3-butyn-2-ol as a reaction controlling agent and 0.62 parts by mass of tetramethyltetravinylcyclotetraoxane ( The vinyl content was 31.4%). 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.

Reference Example 3: "Using a polyoxyxene elastomer matrix comprising barium titanate and two surface treatment agents"

The viscosity to 2,000 mPa at 25 ° C to 100 parts by mass. And 325 parts by mass of barium titanate having an average particle diameter of 0.4 μm by adding dimethyl methoxy-oxyl-terminated dimethyl polysiloxane (vinyl content of 0.23%) Manufactured by Sakai Chemical Industry Co., Ltd., BT-04), 0.12 parts by mass of 1,3-divinyl-1,1,3,3-tetramethyldiazepine and 1,46 parts by mass of 1,1, 1,3,3,3-hexamethyldioxane. The composition was uniformly kneaded by using the biaxial kneading device of Practical Example 1, to obtain a polyoxyxene elastomer matrix.

To the polyoxyxene elastomer matrix, 16.93 parts by mass of dimethylhydroquinoneoxy-bi-molecular chain-terminated polydimethyloxane (SiH content = 0.15%) and 0.14 parts by mass were added. a methyl methoxy-bi-molecular chain-terminated dimethyl methoxy oxane-methylhydroquinone copolymer (SiH content of 0.75%), 80 ppm (based on platinum, platinum metal content by mass fraction) And 1,3-divinyl-1,1,3,3-tetramethyldifluorene as a curing agent for the mixture of dimethyl polyoxyalkylene in a polyoxyxene elastomer matrix Platinum complex of oxane complex and 0.009 parts by mass of 2-phenyl-3-butyn-2-ol as reaction control agent and 0.67 parts by mass of tetramethyltetravinylcyclotetrasiloxane alkyl. 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.

Reference Example 4: "Using a polyoxyxene elastomer matrix comprising barium titanate and two surface treatment agents"

The viscosity to 2,000 mPa at 25 ° C to 100 parts by mass. And 296 parts by mass of barium titanate having an average particle diameter of 0.4 μm were added to both ends via dimethylvinyloxyl-terminated dimethyl polyoxyalkylene (vinyl content of 0.23%). Manufactured by Sakai Chemical Industry Co., Ltd., BT-04), 1.25 parts by mass of methyltrimethoxydecane and 0.42 parts by mass of 1,1,3-trimethyl-3,3-diphenyl-1-carboxyl Mercaptodioxane. The composition was uniformly kneaded by using the biaxial kneading device of Practical Example 1, to obtain a polyoxyxene elastomer matrix.

To the polyoxyxene elastomer matrix, 15.42 parts by mass of dimethylhydroquinoneoxy-bi-molecular chain-terminated polydimethyloxane (SiH content = 0.15%) and 0.28 parts by mass of the top three were added. a methoxy-bi-molecular chain-terminated dimethyl methoxy alkane-methylhydroquinone copolymer (SiH content of 0.75%), 80 ppm (in terms of platinum, the platinum metal content is by mass fraction and 1,3-divinyl-1,1,3,3-tetramethyldioxine as a curing agent for the mixture of dimethyl polyoxyalkylene in a polyoxyxene elastomer matrix a platinum complex of an alkane complex and 0.009 parts by mass of 2-phenyl-3-butyn-2-ol as a reaction controlling agent and 0.63 parts by mass of tetramethyltetravinylcyclotetraoxane . Mix the mixture until uniform (about 10 minutes) Clock) 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.

Reference Example 4: "Using a polyoxyxene elastomer matrix each containing barium titanate or carbon black and a surface treatment agent"

Adding 85.35% to 14.22% of dimethylpolyoxyalkylene (A ₂₂ ) (with a vinyl content of 0.23%) having a viscosity of 2,000 mPa at 25 ° C and terminated with dimethylvinyl methoxy group Spherical barium titanate (manufactured by Fuji Titanium Industry Co., Ltd., HPBT-1B) having an average particle diameter of 1.0 μm, 0.356% of trimethoxysulfonyl mono-terminated dimethylvinyl monocapped polyoxyalkylene ( Average degree of polymerization = 25) and 0.071% 1,1,3-trimethyl-3,3-diphenyl-1-carboxyindenyldioxane. The composition was uniformly kneaded by using the biaxial kneading device of Practical Example 1, to obtain a No. 1 polyoxyelastomer substrate.

In addition, the viscosity to 50.00% at 25 ° C is 2,000 mPa. s and both ends were added with dimethylvinyloxyl-terminated dimethyl polyoxane (A ₂₂ ) (with a vinyl content of 0.23%) with 50.00% carbon black (manufactured by Cancarb, Thermax Floform N990) ). The composition was uniformly kneaded by using the biaxial kneading device of Practical Example 1, to obtain a No. 2 polyoxyelastomer substrate.

Adding dimethylpolyoxane (A) dissolved in dimethylvinyl decyl double-terminated methyl polyoxyalkylene to the No. 1 polyoxyelastomer substrate and the No. 2 polyoxyxene elastomer matrix ₂₂ ), dimethylhydroquinone-bi-molecular chain-terminated polydimethyl decane (A ₁₁₂ , SiH content = 0.015%), trimethyl decyloxy-bi-molecular chain terminated dimethyl A quinone-methyl-hydroxane copolymer (A ₁₂₁ , SiH content of 0.75%) and 0.67% (in terms of platinum) of 1,3-divinyl-1,1,3,3-tetra A platinum complex of a bis oxane 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.

As shown in Table 2, the curable organopolyoxane composition is obtained by the manufacturing method of the present invention, and thus provides excellent mechanical properties (e.g., expressed by elongation at break) and dielectric properties (e.g., by dielectric constant) Shown) polyoxyelastomer. In addition, by optimizing the crosslinked structure and inorganic fine particles, materials can be designed according to the desired converter application.

Further, the polyoxyxene elastomer obtained from the curable organopolyoxane composition of the present invention achieves high dielectric properties even in a low voltage region.

1‧‧‧Actuator

10a‧‧‧ dielectric layer

10b‧‧‧ dielectric layer

11a‧‧‧electrode layer

11b‧‧‧electrode layer

12‧‧‧ wire

13‧‧‧Power supply

Claims (18)

A method for producing a curable organopolyoxane composition for use in a converter, comprising the steps of kneading a kneading composition comprising: a curable organopolyoxane and at least one type of filler, wherein The kneading is carried out using an extruder or a kneading device. A method of producing a curable organopolyoxane composition for use in a converter according to claim 1, wherein the at least one type of filler comprises at least one type of filler selected from the group consisting of: high dielectric Fillers, highly conductive fillers, electrically insulating fillers and reinforcing fillers. A method of producing a curable organopolyoxane composition for use in a converter of claim 1 or 2, wherein the at least one type of filler comprises (D) having greater than or equal to 10 at 1 kHz at room temperature Dielectric inorganic fine particles having a specific dielectric constant. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 3, wherein the kneading composition further comprises at least one type of surface treating agent. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 4, wherein the extruder or kneading device is at least one mechanical member selected from the group consisting of : Twin-screw extruder, twin-shaft kneader and single-axis blade extruder. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 5, wherein the extruder or kneading device is a twin screw extruder having at least 5,000 ( L/hr) is defined as the device free volume of the device's void cross-sectional area (mm ² ) × wheelbase (mm) × rotation rate (rpm) × 60/1,000,000 (L/hr). A curable organopolyoxygen for use in a converter as claimed in any one of claims 1 to 6. The method for producing an alkane composition, wherein the step of kneading the kneading composition is a step of kneading the filler content by using the extruder or the kneading device at a content of 50% by mass or more based on the total composition. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 7, wherein the step of kneading the kneading composition is in a temperature range of from 100 ° C to 180 ° C. Implemented within. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 8, wherein the step of kneading the kneading composition is performed using an extruder for 30 seconds. The residence time in the range of up to 5 minutes is implemented. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 9, wherein the composition obtained by kneading the kneading composition is used as the composition. An intermediate raw material for a curable organopolyoxane composition for use in converters. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 10, wherein the composition obtained by kneading the following is used as a converter for use. An intermediate material of the curable organopolyoxane composition: a curable organopolyoxyalkylene; (D) a dielectric inorganic fine particle having a specific dielectric constant of greater than or equal to 10 at 1 kHz at room temperature; At least one type of surface treatment agent is present in an amount such that the filler content is greater than or equal to 70% by mass of the total composition. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 11, wherein the curable organopolysiloxane is a hydrazine hydrogenation curable organopolyoxane . The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 12, wherein the curable organopolyoxane is at least one of the following: (A11) at least one type of organohydrogen polyoxyalkylene having a hydrogen atom bonded to a ruthenium atom at a terminal of two molecules, the hydrogen atom having a weight fraction of 0.1% by weight to 1.0% by weight; (A12) at least one type An organohydrogen polyoxyalkylene having at least 3 hydrogen atoms bonded to a halogen atom in a single molecule, the hydrogen atom having a weight fraction of 0.03% by weight to 2.0% by weight; and (A2) at least one type of organic poly A oxane having at least 2 alkenyl groups in a single molecule, the alkenyl groups having a weight fraction of from 0.05% by weight to 0.5% by weight. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 13, wherein the filler comprises one or more types of inorganic fine particles selected from the group consisting of : titanium oxide, barium titanate, barium titanate, lead zirconate titanate and barium titanate, and wherein the barium and titanium in the barium titanate is partially passed through an alkaline earth metal such as calcium or barium, zirconium or such as cerium, lanthanum, cerium or A composite metal oxide substituted with a rare earth metal such as ruthenium. The method for producing a curable organopolyoxane composition for use in a converter according to any one of claims 1 to 14, wherein another curable organopolyoxane is blended using an extruder or a kneading device, The vulcanizing agent, curing catalyst or other component and the intermediate raw material obtained by kneading the kneading composition, the kneading composition comprising: a curable organopolyoxane and at least one type of filler. A method of producing a converter component, comprising the step of at least partially curing a curable organopolyoxane composition for a converter obtained by the production method according to any one of claims 1 to 15. A method of manufacturing a converter, comprising the step of disposing a polyoxyxene elastomer intermediate layer between at least one pair of electrodes, wherein the polyoxyxene elastomer intermediate layer is cured or at least partially cured by a request The curable organopolyoxane composition for a converter obtained by the production method of any one of 1 to 15 is formed. The converter manufacturing method of claim 17, wherein at least two of the layers of the polyoxyelastomer layers are stacked as the intermediate layer of the polyoxyelastomer.