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WO2015098072A1 - Composition d'organopolysiloxane durcissable, élément pour transducteurs - Google Patents

Composition d'organopolysiloxane durcissable, élément pour transducteurs Download PDF

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WO2015098072A1
WO2015098072A1 PCT/JP2014/006358 JP2014006358W WO2015098072A1 WO 2015098072 A1 WO2015098072 A1 WO 2015098072A1 JP 2014006358 W JP2014006358 W JP 2014006358W WO 2015098072 A1 WO2015098072 A1 WO 2015098072A1
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organopolysiloxane composition
curable organopolysiloxane
groups
mass
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Takuya Ogawa
Sawako Inagaki
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DuPont Toray Specialty Materials KK
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Dow Corning Toray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/098—Forming organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
    • H10N30/206—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators using only longitudinal or thickness displacement, e.g. d33 or d31 type devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/857—Macromolecular compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Definitions

  • the present invention relates to a curable organopolysiloxane composition capable of use with advantage in electrical and/or electronics applications, especially in transducers.
  • the present invention provides a curable organopolysiloxane composition of which the organopolysiloxane cured product formed by curing can be advantageously used as an electrically active silicone elastomer material capable of use as a dielectric layer or electrode layer of a transducer.
  • the present invention particularly relates to a curable organopolysiloxane composition of which the organopolysiloxane cured product has electrical characteristics and mechanical characteristics suitable for a material used as a dielectric material, and more particularly for use as a dielectric layer of a transducer.
  • a curable organopolysiloxane composition comprising an organopolysiloxane represented by formula (I) below: R a a R b b SiO (4-a-b)/2 (I) (wherein R a is a monovalent aromatic hydrocarbon group having from 6 to 10 carbons, and R b is at least one type of monovalent functional group (however, R b is a group other than a monovalent aromatic hydrocarbon group having from 6 to 10 carbons), wherein at least part of R b is a group capable of a curing reaction, and 0 ⁇ a, 0 ⁇ b, 1.9 ⁇ a+b ⁇ 2.1), and one or more types of inorganic microparticles having an average primary particle diameter of not less than 50 nm, wherein, the mass fraction of the monovalent aromatic hydrocarbon groups having from 6 to 10 carbons (Z) in the total of organopolysiloxanes is not less than 0.2% by mass and not
  • the mass fraction of the monovalent aromatic hydrocarbon groups (Z) is preferably not less than 0.5% by mass and not greater than 30% by mass.
  • the mass fraction of the straight-chain organopolysiloxanes (W) is preferably not less than 75.0% by mass and not greater than 99.9% by mass.
  • the curable organopolysiloxane composition more preferably has these preferred aspects of "Z" and "W" simultaneously.
  • the monovalent aromatic hydrocarbon group having from 6 to 10 carbons is preferably a phenyl group.
  • the one or more types of inorganic microparticles having an average primary particle diameter of not less than 50 nm preferably include dielectric inorganic microparticles having a specific dielectric constant at 1 kHz at room temperature of not less than 10, and, more preferably, part or all of the inorganic microparticles are surface-treated by one or more types of surface treatment agent.
  • the curing mechanism of the curable organopolysiloxane composition of the present invention is not particularly limited, but the group capable of a curing reaction may be a group capable of a curing reaction in a condensation reaction, addition reaction, peroxide reaction, or photoreaction, and is preferably a group capable of an addition curing reaction typified by a hydrosilylation reaction (particularly a silicon-bonded unsaturated hydrocarbon group such as an alkenyl group, or a silicon atom-bonded hydrogen atom).
  • a hydrosilylation reaction particularly a silicon-bonded unsaturated hydrocarbon group such as an alkenyl group, or a silicon atom-bonded hydrogen atom.
  • the monovalent aromatic hydrocarbon R a is a mandatory substituent, a > 0, and more specifically, the value of a must be a number in a range that results in the mass fraction of the monovalent aromatic hydrocarbons having from 6 to 10 carbons (Z) being not less than 0.2% by mass and not greater than 50% by mass relative to the total of organopolysiloxanes.
  • the organopolysiloxane containing a monovalent aromatic hydrocarbon having from 6 to 10 carbons may be the same as or different from the straight-chain organopolysiloxane represented by formula (II) above, but the organopolysiloxane represented by formula (I) above preferably contains a plurality of curable organopolysiloxanes, in which case the mass fraction of the monovalent aromatic hydrocarbons (Z) satisfies the aforementioned range relative to the total of organopolysiloxanes, and the mass fraction of the straight-chain organopolysiloxanes represented by formula (II) above (W) is not less than 50% by mass relative to the total of organopolysiloxanes.
  • the content of the monovalent aromatic hydrocarbon groups is not less than 0.2% by mass and not greater than 50% by mass. If Z is less than 0.2% by mass, the dielectric breakdown strength improvement effect is not sufficiently exhibited in the obtained cured product, while on the other hand, if it exceeds 50% by mass, the elastic modulus of the obtained cured product is too high and the molded product is inadequate because it is too brittle.
  • a preferred range of Z is not less than 0.5% by mass and not greater than 30% by mass, and a more preferred range is not less than 0.5% by mass and not greater than 10% by mass.
  • These monovalent aromatic hydrocarbon groups are contained in a monovalent aromatic hydrocarbon group-containing organopolysiloxane constituting part or all of the organosiloxane components.
  • These monovalent aromatic hydrocarbon group-containing organopolysiloxanes are exemplified by dimethylsiloxane/methylphenylsiloxane copolymer capped at both molecular terminals with dimethylvinylsiloxy groups, dimethylsiloxane/methylvinylsiloxane/methylphenylsiloxane copolymer capped at both molecular terminals with dimethylvinylsiloxy groups, polymethylphenylsiloxane capped at both molecular terminals with dimethylvinylsiloxy groups, dimethylsiloxane/diphenylsiloxane copolymer capped at both molecular terminals with dimethylvinylsiloxy groups, dimethylsiloxane/methylphenylsiloxane copo
  • part of the substituent R b is particularly preferably a non-reactive functional group.
  • the reactive group capable of a curing reaction that is part of the substituent R b may be one type or two or more types of reactive group (for example, a combination of an addition reactive functional group and a photoreactive functional group).
  • the substituent R b that is a non-reactive group is specifically exemplified by alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and the like.
  • a methyl group is preferred from the standpoint of economics.
  • the preferred tensile breaking characteristics are elongation at tensile breaking of not less than 200% as measured according to JIS K 6249, and the preferred content of straight-chain organopolysiloxanes for realizing this is in the range of not less than 70% by mass and not greater than 99.9% by mass.
  • R 1 R 2 2 Si(OSiR 3 R 4 ) n (OSiR 3 R 1 ) m OSiR 1 R 2 2 (II)
  • R 1 is a group capable of a curing reaction
  • R 2 , R 3 , and R 4 represent each independently, the same or different, monovalent aliphatic hydrocarbon groups having from 1 to 10 carbons and monovalent aromatic hydrocarbon groups having from 6 to 10 carbons
  • R 2 , R 3 , and R 4 are each independently, the same or different, monovalent aliphatic hydrocarbon groups having from 1 to 10 carbons and monovalent aromatic hydrocarbon groups having from 6 to 10 carbons, and are exemplified by a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a phenyl group, a naphthyl group, a substituted phenyl group, a substituted naphthyl group, a benzyl group, a phenethyl group, and the like, but from the standpoint of economy, a methyl group and a phenyl group are preferred.
  • n is a number exceeding 200. If it is a number not greater than 200, the mechanical characteristics (particularly breaking elongation) of the obtained cured product are low, and therefore are inadequate in the present invention. In consideration of molding processability, a number not greater than 20,000 is preferred. On the other hand, there is no distinct upper limit on the value of m, but it must be a value not greater than (n/20) in consideration of breaking elongation of the obtained cured product, similar to above. Furthermore, this condition is closely associated with advantageous improvement upon the problem of the present invention due to the fact that the total of siloxane components in the curable organopolysiloxane composition to be described later satisfy the specified compositional features.
  • a silicon atom-bonded hydrogen atom-containing organopolysiloxane and a silicon atom-bonded unsaturated hydrocarbon group-containing organopolysiloxane in combination are used as the organopolysiloxane or the components constituting the organopolysiloxane of the invention of the present application.
  • the number average molecular weight (Mw) of the reactive organopolysiloxane is preferably in the range of 250 to 100,000.
  • viscosity of the reactive organopolysiloxane measured under conditions of shear rate 10 (1/s) at 25C using a rheometer equipped with a cone plate of 20 mm diameter although this viscosity is preferably in the range of 1 to 50,000 mPa s, and particularly preferably in the range of 5 to 10,000 mPa s.
  • the average primary particle diameter of the microparticles is not less than 50 nm.
  • the microparticles may be a mixture of microparticles of different particle diameters.
  • Average particle diameter may be measured by a measurement method commonly used in the field. For example, if the average particle diameter is not less than 50 nm and not greater than approximately 500 nm, average primary particle diameter can be measured by averaging the particle diameter measured by microscope observation using a transmission electron microscope (TEM), field emission-type transmission electron microscope (FE-TEM), scanning electron microscope (SEM), field emission-type scanning electron microscope (FE-SEM), or the like.
  • TEM transmission electron microscope
  • FE-TEM field emission-type transmission electron microscope
  • SEM scanning electron microscope
  • FE-SEM field emission-type scanning electron microscope
  • these inorganic microparticles are not particularly limited, but examples include electrically conductive inorganic microparticles, insulating inorganic microparticles, thermally conductive inorganic microparticles, and dielectric inorganic microparticles. It is preferable if one or more types selected from these microparticles is used in the composition of the present invention.
  • dielectric inorganic microparticles it is preferable to use dielectric inorganic microparticles, and it is particularly preferable if the dielectric inorganic microparticles are dielectric inorganic microparticles in which at least part of the one or more types of inorganic microparticles having an average primary particle diameter of not less than 50 nm has a specific dielectric constant at 1 kHz at room temperature of not less than 10.
  • the upper limit on the preferred size (average primary particle diameter) of the inorganic microparticles is 20,000 nm (20 maicrometers), but considering processability into a thin film for transducers to be described later, 10,000 nm (10 maicrometers) is more preferable.
  • the dielectric inorganic microparticles (C) are, advantageously, dielectric inorganic microparticles (C1) having a specific dielectric constant at 1 kHz at room temperature of not less than 10.
  • metal oxide (C2) examples include barium titanate, calcium titanate, and strontium titanate.
  • Preferred examples of the group 2 metal element M a of the periodic table in the metal oxide (C3) include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).
  • Preferred examples of the period 5 metal element M b' of the periodic table include tin (Sn), antimony (Sb), zirconium (Zr), and indium (In).
  • M a and M b' may each be a single type of element, or may be two or more elements.
  • dielectric inorganic microparticles (C) include one or more types of inorganic microparticles selected from the group consisting of titanium oxide, barium titanate, strontium titanate, lead titanate zirconate, and composite metal oxides in which the barium and titanium positions of barium titanate are partially substituted with an alkaline earth metal such as calcium or strontium; zirconium; or rare earth metals such as yttrium, neodymium, samarium, and dysprosium. Titanium oxide, barium titanate, barium calcium titanate zirconate, and strontium titanate are more preferred, and titanium oxide and barium titanate are most preferred.
  • the dielectric inorganic microparticles (C) may be mono-dispersed, or alternatively, it is possible to produce a distribution in the particle diameters so as to improve mechanical strength by filling at higher density by lowering the void fraction between microparticles.
  • the ratio (D 90 /D 10 ) of the particle diameter at 90% cumulative area (D 90 ) to the particle diameter at 10% cumulative area (D 10 ) of the cumulative particle size distribution curve measured by the laser light diffraction method is preferably not less than 2.
  • the particle size distribution shape (relationship between particle diameter and particle concentration). It is possible to have a so-called plateau shaped distribution, or a particle size distribution that is multi-modal, i.e., bimodal (i.e., having two hill-shaped distributions), tri-modal, or the like.
  • the blended amount (filling ratio) of the dielectric inorganic microparticles (C) in the curable organopolysiloxane composition of the present invention may be not less than 10%, preferably not less than 15%, and further preferably not less than 20%. Moreover, this blended amount relative to the total volume of the composition is preferably not greater than 70%, and further preferably not greater than 60%.
  • the one or more types of inorganic microparticles having an average primary particle diameter of not less than 50 nm are preferably the dielectric inorganic microparticles (C), but they may also include the following electrically conductive inorganic microparticles, insulating inorganic microparticles, and thermally conductive inorganic microparticles.
  • the electrically conductive inorganic microparticles in the composition By blending the electrically conductive inorganic microparticles in the composition, it is possible to increase the specific dielectric constant of the organopolysiloxane cured product.
  • the blended amount of such electrically conductive inorganic microparticles relative to the curable organopolysiloxane composition is, depending on the application thereof, preferably in the range of 0.01 to 10% by mass, and more preferably in the range of 0.05 to 5% by mass.
  • the blended amount of the electrically conductive inorganic microparticles departs from the aforementioned preferred range, the effect of blending is not obtained, or there may be a lowering of the dielectric breakdown strength of the cured product.
  • the curable organopolysiloxane composition contains an organopolysiloxane represented by the general formula: M a M R b D c D R d T e T R f Q g wherein the value of (a + c)/(b + d + e + f + g) is less than 3, in an amount not less than 0.1% by mass and not greater than 10% by mass relative to the total of organopolysiloxane components in the curable organopolysiloxane composition.
  • M is a triorganosiloxy unit
  • D is a diorganosiloxy unit
  • T is a monoorganosiloxy unit
  • Q is a siloxy unit represented by SiO 4/2
  • substituent R on each of the siloxy units is a group capable of a curing reaction in a condensation reaction, addition reaction, peroxide reaction, or photoreaction.
  • the curable organopolysiloxane composition contains a reactive organopolysiloxane having only at both molecular terminals a group capable of a curing reaction in a condensation reaction, addition reaction, peroxide reaction, or photoreaction, in an amount not less than 75% by mass and not greater than 99.9% by mass relative to the total of siloxane components in the curable organopolysiloxane composition.
  • the utilized amount of the component (B) may be any amount capable of promoting an addition reaction of the organopolysiloxane components of the present composition, without particular limitation.
  • the concentration of platinum group metal atoms contained in the component (B) is normally in the range of 0.01 to 500 ppm, preferably in the range of 0.1 to 100 ppm, and particularly preferably in the range of 0.1 to 50 ppm.
  • An example of a preferred embodiment of the curable organopolysiloxane composition of the present invention is a composition comprising, as mandatory ingredients, at least one type of reactive organohydrogenpolysiloxane (A1) having at least two silicon atom-bonded hydrogen atoms in a molecule, the weight fraction of hydrogen atoms being from 0.01 to 2.0% by weight, at least one type of reactive organopolysiloxane (A2) having a number of repeating units exceeding 200 and having alkenyl groups at both molecular terminals, the weight fraction of alkenyl groups being from 0.05 to 5.0% by weight, a hydrosilylation reaction catalyst (B), and dielectric inorganic microparticles (C1) having a specific dielectric constant at 1 kHz at room temperature of not less than 10.
  • the organic titanium compound is exemplified by coupling agents such as alkoxy titanium, titanium chelates, titanium acylate, or the like.
  • Preferred coupling agents among such compounds are exemplified by alkoxy titanium compounds such as tetraisopropyl titanate or the like, and titanium chelates such as tetraisopropyl bis(dioctylphosphate) titanate or the like.
  • the organosilicon compound is exemplified by low molecular weight organosilicon compounds such as silanes, silazanes, siloxanes, or the like; and organosilicon polymers or oligomers such as polysiloxanes, polycarbosiloxanes, or the like.
  • organosilicon compounds such as silanes, silazanes, siloxanes, or the like
  • organosilicon polymers or oligomers such as polysiloxanes, polycarbosiloxanes, or the like.
  • Preferred silanes are exemplified by so-called silane coupling agents.
  • the number n of siloxane bonds in this case is preferably from 2 to 150.
  • Preferred examples of silazanes include hexamethyldisilazane, 1,3-dihexyl-tetramethyldisilazane, and the like.
  • Preferred polycarbosiloxanes are exemplified by polymers that have Si-C-C-Si-O bonds in the polymer main chain.
  • the proportion of the surface treatment agent to the total amount of the inorganic microparticles is preferably not less than 0.1% by mass and not greater than 10% by mass, and more preferably not less than 0.3% by mass and not greater than 5% by mass. Furthermore, the treatment concentration is the ratio of the fed inorganic particles to the fed surface treatment agent, and the excess surface treatment agent is preferably removed after treatment.
  • the curable organopolysiloxane composition of the present invention has excellent mold releasability, and thus the curable organopolysiloxane composition is advantageous in that it is possible to improve speed of production of the film without damaging the film.
  • This additive further improves these features of the curable organopolysiloxane composition of the present invention, and this additive may be used as a single type or as a combination of two or more types.
  • an additive for improvement of dielectric breakdown characteristics is used for improvement of dielectric breakdown strength of the silicone elastomer sheet obtained by the curing.
  • Mold release improvement additives i.e., mold release agents
  • mold release agents are exemplified by carboxylic acid-based release agents, ester-based release agents, ether-based release agents, ketone-based release agents, alcohol-based release agents, fluorine-based release agents, and the like.
  • Such release agents may be used alone as a single type or may be used as a combination of two or more types.
  • the release agents do not contain silicon atoms, it is also possible to use a release agent that contains silicon atoms, or it is possible to use a mixture of such release agents.
  • the dielectric breakdown characteristic improvement agent is preferably an electrical insulation improvement agent.
  • the dielectric breakdown characteristic improvement agent is exemplified by aluminum or magnesium hydroxides or salts, clay minerals, and mixtures of such.
  • the dielectric breakdown characteristic improvement agent may be selected from the group consisting of aluminum silicate, aluminum sulfate, aluminum hydroxide, magnesium hydroxide, calcined clays, montmorillonite, hydrotalcite, talc, and mixtures of such agents.
  • this insulation improvement agent may be surface-treated by the surface treatment method.
  • this amount is preferably not less than 0.1% by mass and not greater than 30% by mass, relative to the total amount of the curable organopolysiloxane composition.
  • the curable organopolysiloxane composition of the present invention may further comprise a compound that has highly dielectric functional groups and at least one group capable of reacting by condensation curing reaction, addition curing reaction, peroxide curing reaction, or photo-curing reaction.
  • This highly dielectric functional group is introduced to the obtained cured product (i.e., electrically active silicone elastomer) by the curing reaction.
  • the specific dielectric constant of the dielectric layer is preferably high, and highly dielectric functional groups may be introduced in order to improve the specific dielectric constant of the elastomer.
  • dielectric properties may be increased for the curable organopolysiloxane composition and cured silicone elastomer obtained by curing the curable organopolysiloxane composition, by a method such as adding to the curable organopolysiloxane composition a component for imparting high dielectric properties, a method of introducing a group for imparting high dielectric properties to the organopolysiloxane component constituting the curable organopolysiloxane composition, or a combination of such methods.
  • a method such as adding to the curable organopolysiloxane composition a component for imparting high dielectric properties, a method of introducing a group for imparting high dielectric properties to the organopolysiloxane component constituting the curable organopolysiloxane composition, or a combination of such methods.
  • an organic compound having highly dielectric groups and functional groups reactive with the reactive organopolysiloxane contained in the curable composition is added to the curable organopolysiloxane composition, thereby increasing specific dielectric constant of the silicone elastomer obtained by curing.
  • highly dielectric groups are introduced into the silicone elastomer obtained by curing.
  • a fourth embodiment of the present invention by adding an organic compound miscible with the curable organopolysiloxane composition and having highly dielectric groups to the curable organopolysiloxane composition, the specific dielectric constant of the silicone elastomer obtained by curing is increased. Due to miscibility between the organic compound and the organopolysiloxane in this curable composition, an organic compound having these highly dielectric groups is incorporated in the matrix of the silicone elastomer obtained by curing.
  • the highly dielectric group in the present invention may be any group capable of increasing dielectric properties of the obtained cured product obtained by curing the curable organopolysiloxane composition of the present invention in comparison to the dielectric properties when the group is not contained.
  • examples of the highly dielectric group used in the present invention are listed below.
  • Nitrogen atom-containing groups are exemplified by the nitro groups, cyano groups (e.g., cyanopropyl group and cyanoethyl group), amido groups, imido groups, ureido groups, thioureido groups, and isocyanate groups.
  • Oxygen Atom-containing Groups The oxygen atom-containing group is exemplified by ether groups, carbonyl groups, and ester groups.
  • Heterocyclic Groups The heterocyclic group is exemplified by an imidazole group, pyridine group, furan group, pyran group, thiophene group, phthalocyanine group, and complexes of such.
  • the curable organopolysiloxane composition of the present invention may comprise additives normally blended in organopolysiloxane compositions. As long as the object of the curable organopolysiloxane composition of the present invention is not impaired, it is possible to blend any additives, such as a curing retardant (curing suppression agent), flame retardant, heat resistance improvement agent, colorant, solvent, or the like.
  • a curing retardant curing retardant
  • flame retardant flame retardant
  • heat resistance improvement agent colorant
  • solvent solvent
  • the curing retardant is exemplified by alkyne alcohols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, or the like; enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, or the like; and benzotriazole; without limitation.
  • the utilized concentration of the curing retardant (curing suppression agent), relative to the total composition by mass is preferably in the range of 1 to 50,000 ppm.
  • hybridization is possible by combining the curable organopolysiloxane composition for transducers of the present invention with a polymer other than the organopolysiloxane.
  • a polymer having a higher dielectric constant than that of the organopolysiloxane with the organopolysiloxane it may be possible to increase the dielectric constant of the composition of the present invention and of the cured product obtained from the composition.
  • the type of curing of the curable organopolysiloxane composition of the present invention may be condensation curable, addition-curable, peroxide curable, or photo-curable; however, an addition-curable organopolysiloxane composition is preferred.
  • an acrylic group, methacrylic group, epoxy group, or thiol group may be introduced to an organopolysiloxane molecule chain of the curable organopolysiloxane composition in accordance with the method of introducing the dielectric functional group described above.
  • a compound known as a monomer and/or oligomer capable of curing by light or electron beam may be further added to the curable composition.
  • a so-called photosensitizer may be added.
  • the dielectric silicone elastomer that is the member for transducers obtained by at least partially curing the curable organopolysiloxane composition of the present invention has the below listed mechanical properties as measured based on JIS K 6249.
  • Young's modulus (MPa) at room temperature may be set in the range of 0.1 to 10 MPa, and the particularly preferred range is 0.1 to 2.5 MPa.
  • Tear strength (N/mm) at room temperature may be set to not less than 1 N/mm, and particularly preferably not less than 2 N/mm.
  • Tear strength (MPa) at room temperature may be set to not less than 1 MPa, and particularly preferably not less than 2 MPa.
  • Breaking elongation (%) may be set to not less than 200%, and from the standpoint of displacement amount of the transducer, is particularly preferably in the range of 200 to 1,000%.
  • the specific dielectric constant measured at 1 MHz measurement frequency and 23C measurement temperature may be set to not less than 3.0.
  • the preferred specific dielectric constant will change according to the required form of the dielectric layer and the type of the transducer, a particularly preferred range of specific dielectric constant under the aforementioned measurement conditions is not less than 5.0.
  • the curable organopolysiloxane composition of the present invention can be produced by kneading the curable organopolysiloxane component, a curing catalyst, dielectric inorganic microparticles having a specific dielectric constant at 1 kHz at room temperature of not less than 10, and optionally at least one type of inorganic microparticles and other additive, in an extruder or kneader (more specifically, at least one type of mechanical means selected from the group consisting of twin screw extruders, twin screw kneaders, and single blade extruders).
  • the temperature during formation of the silicone rubber compound (master batch) that does not contain a curing catalyst is set in the range of 40C to 200C, and may be set in the range of 100C to 180C.
  • the residence time during treatment may be set to about 30 seconds to 5 minutes.
  • the method of molding the curable organopolysiloxane composition into a film-like shape is exemplified by a method of forming a coating film by coating of the curable organopolysiloxane composition on a substrate using conventionally known coating methods, a method of molding by passing the curable organopolysiloxane composition through an extruder equipped with a slot of the desired shape, or the like.
  • Thickness of this type of film-like curable organopolysiloxane composition may be set in the range of 0.1 to 5,000 maicrometers, for example. Depending on the coating method and the absence or presence of a volatile solvent, thickness of the obtained cured product may be made thinner than thickness at the time of application of the composition.
  • the thin film-like silicone elastomer is particularly useful as a dielectric layer for a transducer. It is possible to form a transducer by arranging electrode layers at both ends of the thin film-like silicone elastomer. Furthermore, by blending electrically conductive inorganic particles into the curable organopolysiloxane composition of the present invention, it is possible to impart functionality as an electrode layer. Furthermore, the "electrode layer" in the specification of the present invention is sometimes simply referred to as the "electrode.”
  • the transducer of the present invention is capable of use particularly as an artificial muscle, actuator, sensor, or electricity generating element due to the dielectric and mechanical characteristics of the transducer of the present invention.
  • An artificial muscle is anticipated 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 as an example of the present invention.
  • an actuator when mechanical energy (such as pressure or the like) is applied from outside to the transducer of the present invention, it is possible to generate an electrical potential difference as electrical energy between the mutually insulated electrode layers. That is to say, use is possible as a sensor for the conversion of mechanical energy into electrical energy. This embodiment of a sensor will be described below.
  • An electricity generating element is a transducer for conversion of mechanical energy into electrical energy.
  • This electricity generating element may be applied for devices that generate electricity, beginning with electricity generation by natural energy such as wave power, water power, water power, or the like, as well as generation of electricity due to vibration, impact, pressure change, or the like. An embodiment of this electricity generating element will be described below.
  • FIG. 4 shows a cross sectional view of the electricity generating element 4 of the present embodiment, in which dielectric layers are stacked.
  • the dielectric layer is composed of 2 dielectric layers, for example.
  • the electricity generating element 4 is composed of the dielectric layers 40a and 40b and the electrode layers 41a and 41b.
  • the electrode layers 41a and 41b are arranged covering one face of the respective contacted dielectric layer.
  • a curable organopolysiloxane composition having constituent components of a curable organopolysiloxane containing an organopolysiloxane having reactive groups at both molecular terminals and having more than 200 repeating units and containing a prescribed quantity of monovalent aromatic hydrocarbon groups, and inorganic microparticles having an average primary particle diameter of not less than 50 nm, provides a silicone elastomer having excellent mechanical characteristics represented by breaking elongation and electrical characteristics represented by dielectric breakdown strength.
  • Electrode layer (electrically conductive layer) 12, 22 Wire 13, 23 Electrical power source 3 Sensor 30 Dielectric layer 31a, 31b, 31c Upper electrode layer 32a, 32b, 32c Lower electrode layer 4 Electricity generating element 40a, 40b Dielectric layer 41a, 41b Electrode layer

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Abstract

Cette invention a pour objet de pourvoir à une composition d'organopolysiloxane durcissable ayant d'excellentes caractéristiques mécaniques et/ou caractéristiques électriques, et en particulier, à une composition capable de former un produit durci en élastomère de type silicone pouvant être utilisé à titre d'élément pour transducteurs. La composition d'organopolysiloxane durcissable ci-décrite comprend un organopolysiloxane et au moins un type de microparticules inorganiques ayant un diamètre de particule primaire moyen qui n'est pas inférieur à 50 nm, la fraction en poids des groupes hydrocarbures aromatiques monovalents ayant de 6 à 10 atomes de carbone (Z) par rapport au total des organopolysiloxanes n'étant pas inférieure à 0,2 % en poids et pas supérieure à 50 % en poids, et la fraction en poids des organopolysiloxanes à chaîne droite ayant une certaine plage de longueur de chaîne et un groupe capable d'une réaction de durcissement (W) par rapport au total des organopolysiloxanes n'étant pas inférieure à 50 % en poids.
PCT/JP2014/006358 2013-12-27 2014-12-20 Composition d'organopolysiloxane durcissable, élément pour transducteurs Ceased WO2015098072A1 (fr)

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WO2020116440A1 (fr) 2018-12-07 2020-06-11 ダウ・東レ株式会社 Composition d'organopolysiloxane durcissable, produit durci associé, transducteur et analogue équipés dudit produit durci
CN115103881A (zh) * 2020-02-17 2022-09-23 美国陶氏有机硅公司 弹性体硅酮材料和其应用
EP4079811A4 (fr) * 2019-12-20 2024-01-10 Dow Toray Co., Ltd. Composition d'élastomère durcissable, produit durci de celle-ci, film doté d'un produit durci, corps multicouche pourvu d'un film, procédé de production dudit corps multicouche, composant électronique et dispositif d'affichage comprenant chacun un produit durci, procédé de conception de composition d'élastomère durcissable et procédé de conception de dispositif transducteur
WO2024075661A1 (fr) 2022-10-05 2024-04-11 ダウ・東レ株式会社 Composition d'organopolysiloxane duricssable pour transducteur, objet durci associé, et transducteur, ou similaire, équipé de cet objet durci

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WO2018211981A1 (fr) 2017-05-18 2018-11-22 東レ・ダウコーニング株式会社 Composition d'organopolysiloxane durcissable contenant un groupe fluoroalkyle, produit durci associé, et transducteur ou analogue pourvu du produit durci
US11479670B2 (en) 2017-05-18 2022-10-25 Dow Toray Co., Ltd. Fluoroalkyl group-containing curable organopolysiloxane composition, cured product thereof, and transducer or the like provided with cured product
WO2020116440A1 (fr) 2018-12-07 2020-06-11 ダウ・東レ株式会社 Composition d'organopolysiloxane durcissable, produit durci associé, transducteur et analogue équipés dudit produit durci
CN113166543A (zh) * 2018-12-07 2021-07-23 陶氏东丽株式会社 固化性聚有机硅氧烷组合物、其固化物以及具备该固化物的换能器等
US12122880B2 (en) 2018-12-07 2024-10-22 Dow Toray Co., Ltd. Curable organopolysiloxane composition, cured product thereof, and transducer and the like equipped with said cured product
EP4079811A4 (fr) * 2019-12-20 2024-01-10 Dow Toray Co., Ltd. Composition d'élastomère durcissable, produit durci de celle-ci, film doté d'un produit durci, corps multicouche pourvu d'un film, procédé de production dudit corps multicouche, composant électronique et dispositif d'affichage comprenant chacun un produit durci, procédé de conception de composition d'élastomère durcissable et procédé de conception de dispositif transducteur
CN115103881A (zh) * 2020-02-17 2022-09-23 美国陶氏有机硅公司 弹性体硅酮材料和其应用
WO2024075661A1 (fr) 2022-10-05 2024-04-11 ダウ・東レ株式会社 Composition d'organopolysiloxane duricssable pour transducteur, objet durci associé, et transducteur, ou similaire, équipé de cet objet durci
KR20250081900A (ko) 2022-10-05 2025-06-05 다우 도레이 캄파니 리미티드 트랜스듀서용 경화성 오가노폴리실록산 조성물, 그의 경화물 및 당해 경화물을 구비한 트랜스듀서 등

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