Organopolysiloxane composition for transducer, laminate comprising cured film thereof, use therefor, and manucaturing method therefor

Abstract

The purpose of the present invention is to provide a laminate obtained by stacking an organopolysiloxane cured film that is a dielectric layer and an electrode layer / substrate layer, wherein the adhesion of an interface of the cured film is improved, and problems such as peeling and defects caused by insufficient adhesive strength and conformability of the film are unlikely to occur. The purpose of the present invention is also to provide a use and a manufacturing method therefor. A curable organopolysiloxane composition for a transducer according to the present invention contains (A) a polysiloxane having a C=C curing reactive group, (B1) an organohydrogen polysiloxane with a side-chain SiH, (B2) an organohydrogen polysiloxane with a terminal SiH, (C) a catalyst for a hydrosilylation reaction, (D) a reinforcing filler, and (E) an adhesiveness-imparting agent. Regarding the number of of Si-H atoms in components (B1) and (B2) and the total number (Vi) of the curing reactive group in component (A), the value of px1={HB1 / HB2} / {(HB1+HB2) / Vi} is in the range from 0.1-6.0.

Description

Organopolysiloxane composition for transducers, laminate comprising a cured film thereof, uses thereof, and method for producing same

[0001] The present invention relates to an organopolysiloxane composition for transducers, a laminate comprising a cured film of the composition, uses thereof, and a method for producing the same.

[0002] Cured organopolysiloxanes having a polysiloxane skeleton are excellent in transparency, electrical insulation, heat resistance, cold resistance, etc., and electrical activity can be improved by introducing highly dielectric functional groups such as fluoroalkyl groups if desired. Furthermore, they can be easily processed into film or sheet form, and are therefore used in a variety of applications, including adhesive films used in various electric and electronic devices and electroactive films used in transducer devices such as actuators. These cured organopolysiloxanes are classified into hydrosilylation reaction-curable types, condensation reaction-curable types, peroxide-curable types, etc., depending on their curing mechanism. In particular, cured organopolysiloxane films using curable organopolysiloxane compositions of the hydrosilylation reaction-curable type are widely used because they cure rapidly upon standing at room temperature or upon heating and do not produce by-products.

[0003] On the other hand, when an organopolysiloxane cured film is used as an electronic material for touch panels etc., an electronic component for display devices, and particularly as a transducer material for sensors, actuators etc., it is necessary to provide an electrode layer on the electroactive film as a dielectric layer. For example, Non-Patent Documents 1 and 2 propose forming an electrode layer having excellent conformity to the dielectric layer by adding a conductive filler to a silicone elastomer matrix having excellent flexibility.

[0004] The present inventors have also proposed that such cured organopolysiloxane films can be used for substrates or electrode layers with low conformability. For example, Patent Documents 1 and 2 propose that cured organopolysiloxane films can be sandwiched between film substrates and used as pressure-sensitive adhesive layers or dielectric layers. However, when producing and using laminates of cured organopolysiloxane films, imparting adhesiveness to each interface by pressure-sensitive adhesion or surface treatment of the substrate is insufficient or results in poor process efficiency, leaving room for improvement.

[0005] Kujawski, M.; Pearse, JD; Smela, E. Carbon 2010, 48, 2409-2417.Rosset, S.; Shea, HR Appl. Phys. A 2013, 110, 281-307.

[0006] International Publication (WO) No. 2016 / 098334 Brochure International Publication (WO) No. 2016 / 163069 Brochure

[0007] The present invention has been made to solve the above-mentioned problems, and aims to provide a laminate comprising an organopolysiloxane cured film with improved adhesion between a dielectric layer and an electrode layer or a substrate layer, which is less likely to suffer from peeling or defects at the interface of the cured film constituting the laminate due to insufficient adhesive strength and conformability, as well as uses and a production method for the laminate.

[0008] As a result of extensive research, the present inventors have found that the parameter p xl and more preferably the value of the weight percent (w f The present inventors have found that the above problems can be solved when the value of (a) is within a specific range, and have arrived at the present invention.

[0009] Specifically, the above-mentioned problem can be solved by providing an organopolysiloxane containing at least: (A) one or more types of organopolysiloxane having at least two alkenyl groups having 2 to 12 carbon atoms per molecule; (B1) an organohydrogenpolysiloxane having at least one silicon-bonded hydrogen atom in a side chain position of the molecular chain, no silicon-bonded hydrogen atom at at least one terminal of the molecular chain, and at least two silicon-bonded hydrogen atoms per molecule; (B2) an organohydrogenpolysiloxane having silicon-bonded hydrogen atoms at both terminals of the molecular chain and at least two silicon-bonded hydrogen atoms per molecule; (C) an effective amount of a hydrosilylation catalyst; (D) a reinforcing filler; and (E) an adhesion promoter; B1 ), the number of silicon-bonded hydrogen atoms in component (B2) (H B2 ), and the total number (Vi) of curing reactive groups containing carbon-carbon double bonds in component (A) are expressed by the following relationship: p ｘ１ ={H B1 / H B2} / {(H B1 +H B2 ) / Vi} defined by ｘ１ The aforementioned problems are solved by a curable organopolysiloxane composition for a transducer, characterized in that the value of

[0010] Here, when the total of components (A) to (E) is 100 mass%, the content (w ｆ ) is preferably in the range of 5 to 40 mass %, and at least a portion of component (A) is (A1) one or more types of alkenyl groups having at least two carbon atoms in the molecule, and 10 mol % or more of all substituents on silicon atoms are (C ｐ F ２ｐ＋１ )-R- (where R is an alkylene group having 1 to 10 carbon atoms, and p is an integer of 1 to 8) is particularly preferred.

[0011] Furthermore, the above-mentioned problems are preferably solved by a cured film for a transducer obtained by curing the above-mentioned composition, a laminate having a structure in which the cured film for a transducer, one or more layers selected from an electrode layer and a base material layer are laminated, and a transducer including the laminate.

[0012] The present invention provides a laminate comprising an organopolysiloxane cured film with improved adhesion between a dielectric layer and an electrode layer or a substrate layer, which is less susceptible to peeling or defects at the interface of the cured film constituting the laminate due to insufficient adhesive strength and conformability, as well as uses and a production method thereof.

[0013] In particular, the curable organopolysiloxane composition for transducers according to the present invention is prepared by applying the composition before curing to at least one surface of an electrode layer or a substrate layer and then curing the composition, thereby forming a laminate having an adhesive structure in which at least partial chemical bonds are formed at the interface between the two layers. This has the advantage that a laminate in which a cured film, an electrode layer, and / or a substrate layer are adhered with sufficient strength for practical use can be efficiently produced without the need for an additional bonding step or pretreatment, and that a laminate with excellent reliability for use as a transducer and a method for producing the same can be provided.

[0014] First, the curable organopolysiloxane composition for transducers according to the present invention will be described in detail. Hereinafter, in this specification, the term "transducer" refers to any electronic device having the function of converting mechanical energy and electrical energy into each other, and is a concept that includes sensors, speakers, actuators, and generators. The curable organopolysiloxane composition according to the present invention, when cured, and in particular a cured film, has properties before and after curing that are suitable for use as a component constituting the above-mentioned transducer.

[0015] The composition of the present invention contains at least: (A) one or more types of organopolysiloxanes having at least two alkenyl groups having 2 to 12 carbon atoms per molecule; (B1) an organohydrogenpolysiloxane having at least one silicon-bonded hydrogen atom in a side chain position of the molecular chain, no silicon-bonded hydrogen atom at at least one terminal of the molecular chain, and at least two silicon-bonded hydrogen atoms per molecule; (B2) an organohydrogenpolysiloxane having silicon-bonded hydrogen atoms at both terminals of the molecular chain and at least two silicon-bonded hydrogen atoms per molecule; (C) an effective amount of a hydrosilylation catalyst; (D) a reinforcing filler; and (E) an adhesion promoter; and may optionally contain a hydrosilylation inhibitor, other organic solvents, and other optional additives.

[0016] The composition of the present invention is a composition that cures via a hydrosilylation reaction between alkenyl groups and silicon-bonded hydrogen atoms, and has the advantages of relatively rapid overall cure and easy reaction control. The curing reaction can be accelerated by heating, high-energy radiation, or a combination of these.

[0017] The above-mentioned component (A) is an organopolysiloxane having a curing reactive group containing a carbon-carbon double bond, and examples thereof include linear, branched, cyclic, or resinous (network) organopolysiloxanes containing in the molecule a curing reactive group selected from an alkenyl group having 2 to 20 carbon atoms, such as a vinyl group, and a (meth)acrylic-containing group, such as a 3-acryloxypropyl group or a 3-methacryloxypropyl group.

[0018] The organopolysiloxane of component (A) may contain a group selected from a monovalent hydrocarbon group having no carbon-carbon double bond in the molecule, a hydroxyl group, and an alkoxy group having 1 to 3 carbon atoms. Furthermore, the monovalent hydrocarbon group may have some of its hydrogen atoms substituted with halogen atoms or hydroxyl groups. When used as a dielectric layer, a dielectric functional group, as described below, may be introduced. Industrially, methyl groups, phenyl groups, hydroxyl groups, alkoxy groups, and the dielectric functional groups, as described below, are preferred. When component (A) contains a hydroxyl group or the like, the component has condensation reactivity in addition to hydrosilylation reaction curability.

[0019] When used in a dielectric layer, component (A) preferably has the following average composition formula: １ ａ R ２ ｂ SiO （４－ａ―ｂ）／２ or a mixture thereof. １ is a curing reactive group containing a carbon-carbon double bond as described above, and R ２ is a group selected from the above-mentioned monovalent hydrocarbon groups having no carbon-carbon double bond, hydroxyl groups, and alkoxy groups, and a and b are numbers that satisfy the following conditions: 1≦a+b≦3 and 0.001≦a / (a+b)≦0.33, and preferably are numbers that satisfy the following conditions: 1.5≦a+b≦2.5 and 0.005≦a / (a+b)≦0.2. This is because when a+b is equal to or greater than the lower limit of the above range, the flexibility of the cured product is increased, whereas when it is equal to or less than the upper limit of the above range, the mechanical strength of the cured product is increased, and when a / (a+b) is equal to or greater than the lower limit of the above range, the mechanical strength of the cured product is increased, whereas when it is equal to or less than the upper limit of the above range, the flexibility of the cured product is increased.

[0020] When using component (A), the parameter p, which is related to the crosslink density and crosslink structure of the present composition, which will be described later, is used. ｘ１ It is necessary to select or design the amount (Vi) of curing reactive groups containing a carbon-carbon double bond, such as alkenyl groups, in component (A) so that the value of (Vi) is in the range of 0.1 to 6.0, preferably 0.5 to 6.0, more preferably 1.0 to 6.0, and particularly preferably 1.5 to 5.5.

[0021] The component (A) in the present invention preferably contains, as a dielectric functional group in the molecule, the following: (C ｐ F ２ｐ＋１ )-R- (where R is an alkylene group having 1 to 10 carbon atoms, and p is an integer of 1 or more and 8 or less), can be introduced, and is preferred. From the viewpoints of dielectric properties, economy, ease of production, and moldability of the resulting curable organopolysiloxane composition, the group where p=1, i.e., a trifluoropropyl group, is preferred.

[0022] Preferably, at least a part or all of component (A) comprises (A1) one or more types of alkenyl groups having at least two carbon atoms in the molecule, and 10 mol % or more of all substituents on silicon atoms are (C ｐ F ２ｐ＋１ )-R- (where R is an alkylene group having 1 to 10 carbon atoms, and p is an integer of 1 to 8). By using such component (A1) as the main component, it is possible to obtain a fluoroorganopolysiloxane cured product film with excellent dielectric properties.

[0023] Furthermore, when a cured film obtained by curing the present composition is used for the dielectric layer of a transducer, the component (A) according to the present invention is particularly preferably: (a1-1) a linear or branched fluoroorganopolysiloxane having alkenyl groups only at the molecular chain terminals, or (a1-2) a fluoroorganopolysiloxane having at least one branched siloxane unit in the molecule and containing vinyl (CH ２ The alkenyl group-containing fluoroorganopolysiloxane resin has a content of (=CH-) groups in the range of 1.0 to 5.0 mass %, or a fluoroorganopolysiloxane mixture containing the same.

[0024] The component (a1-1) has (Alk)R at the end of its molecular chain. ２ ２ SiO １／２ (wherein Alk is an alkenyl group having 2 or more carbon atoms), and other siloxane units are substantially represented by R ２２ SiO ２／２ It is a linear or branched fluoroorganopolysiloxane consisting only of siloxane units represented by the formula: ２ represents the same group as above. The degree of siloxane polymerization of component (a1-1), including the terminal siloxane units, is in the range of 7 to 1002, and may be in the range of 102 to 902. Such component (a1-1) is particularly preferably a compound in which both ends of the molecular chain are (Alk)R ２ ２ SiO １／２ It is a linear fluoroorganopolysiloxane terminated with a siloxane unit represented by the formula:

[0025] Component (a1-2) is an alkenyl group-containing fluoroorganopolysiloxane resin having the average unit formula: (RSiO ３／２ )o(R ２ SiO ２／２ )p(R ３ SiO １／２ )q(SiO ４／２ )r(XO １／２ In the above formula, R is a group selected from alkenyl groups and the above-mentioned monovalent hydrocarbon groups having no carbon-carbon double bond, and X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. However, among all the Rs, at least the vinyl (CH ２ In the range where the content of the (=CH-) group is in the range of 1.0 to 5.0 mass%, R is an alkenyl group, and particularly, R ３ SiO １／２ Preferably, at least a portion of the R on the siloxane unit represented by the formula: is an alkenyl group.

[0026] In the above formula, (o+r) is a positive number, p is 0 or a positive number, q is 0 or a positive number, s is 0 or a positive number, and p / (o+r) is a number within the range of 0 to 10, q / (o+r) is a number within the range of 0 to 5, (o+r) / (o+p+q+r) is a number within the range of 0.3 to 0.9, and s / (o+p+q+r) is a number within the range of 0 to 0.4.

[0027] Particularly preferred as component (a1-2) are {(Alk)R ２ ２ SiO １／２}q1(R ２ ３ SiO １／２ ) q2(SiO ４／２ )r (where Alk, R ２ is the same group as defined above, q1+q2+r is a number in the range of 50 to 500, (q1+q2) / r is a number in the range of 0.1 to 2.0, and q2 is the number of vinyl (CH ２ The content of (=CH-) groups is in the range of 1.0 to 5.0 mass %.

[0028] Component (a1-1) having alkenyl groups only at the molecular chain terminals and component (a1-2) which is a fluoroorganopolysiloxane resin having a certain amount of alkenyl groups may be used in combination, and the composition as a whole will have excellent curability, and a cured reaction product excellent in mechanical strength and flexibility will be obtained, making it possible to provide a fluoroorganopolysiloxane cured film that is particularly suitable for adhesive layers or dielectric layers in the above-mentioned electronic components, etc.

[0029] Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule, and functions as a (B1) crosslinking agent or a (B2) chain extender for component (A). Specifically, component (B1) is an organohydrogenpolysiloxane having at least one silicon-bonded hydrogen atom in a side chain portion of the molecular chain, no silicon-bonded hydrogen atom at at least one terminal of the molecular chain, and at least two silicon-bonded hydrogen atoms in the molecule, and is distinguished from component (B2) in that it does not have silicon-bonded hydrogen atoms at both terminals. Preferably, component (B1) has a structure in which both molecular chain terminals are blocked with functional groups that are non-reactive to hydrosilylation reactions (particularly the reaction with component (A)). Because such component (B1) has hydrogen atoms (= hydrogen atoms bonded to side chain moieties) bonded to silicon atoms constituting the main chain of the siloxane molecule, it forms an intermolecular crosslink between the hydrogen atoms on the side chain and the curing reactive groups in component (A), but the chain extension effect of the crosslinked product is limited. On the other hand, component (B2) is an organohydrogenpolysiloxane having silicon-bonded hydrogen atoms at both ends of the molecular chain and at least two silicon-bonded hydrogen atoms per molecule, preferably two silicon-bonded hydrogen atoms (= only at both ends of the molecular chain). Such component (B2) is a chain extender that reacts with the curing reactive groups in component (A) to introduce a long siloxane molecular structure into the crosslinked product, and can impart appropriate flexibility and elasticity to the crosslinked product.

[0030] Examples of such component (B1) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, methylhydrogenpolysiloxane terminally capped with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer terminally capped with trimethylsiloxy groups, methylhydrogensiloxane-diphenylsiloxane copolymer terminally capped with trimethylsiloxy groups, methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer terminally capped with trimethylsiloxy groups, methylhydrogensiloxane-dimethylsiloxane-trifluoropropylmethylsiloxane copolymer terminally capped with trimethylsiloxy groups, hydrolysis condensation products of trimethoxysilane, (CH ３ ) ２ HSiO １ / ２ Units and SiO ４ / ２ a copolymer consisting of (CH ３ ) ２ HSiO １ / ２ Units and SiO ４ / ２ Units and (C ６ H ５ )SiO ３ / ２ Examples include copolymers consisting of these units and mixtures of two or more of these units.

[0031] Examples of such component (B2) include dimethylsiloxanes terminally blocked with dimethylhydrogensiloxy groups, dimethylsiloxane-diphenylsiloxane copolymers terminally blocked with dimethylhydrogensiloxy groups, dimethylsiloxane-trifluoropropylmethylsiloxane copolymers terminally blocked with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers terminally blocked with dimethylhydrogensiloxy groups, and mixtures of two or more of these.

[0032] [parameter p xlThe curable organopolysiloxane composition for transducers according to the present invention has p defined by the following parameters in relation to components (A), (B1), and (B2): xl The value of p is within a predetermined range. xl is a parameter used to describe the crosslink density and intermolecular crosslink structure of the cured product obtained by curing the composition, and is the number of silicon-bonded hydrogen atoms (H B1 ), the number of silicon-bonded hydrogen atoms in component (B2) (H B2 ), and the total number (Vi) of curing reactive groups containing carbon-carbon double bonds in component (A) are expressed by the following relationship: p ｘ１ ={H B1 / H B2} / {(H B1 +H B2 ) / Vi}, and the types and amounts of component (A), component (B1) and component (B2) used are defined by p ｘ１ It is necessary that the amount is such that the value of p is in the range of 0.1 to 6.0. In view of the performance of the cured product obtained by curing the present composition, particularly the cured film, as a transducer member and the adhesiveness to the substrate layer and the electrode layer, p ｘ１ The value of p is preferably in the range of 0.5 to 6.0, more preferably in the range of 1.0 to 6.0, and particularly preferably in the range of 1.5 to 6.0. xl If the value of p is outside the upper limit, the adhesiveness of the cured product will decrease and the storage modulus will not be suitable for the purpose of the present invention. xl If the value is less than the lower limit, the crosslinking or curing reaction may be insufficient.

[0033] p xl The technical significance of {H} will be explained. This composition contains two types of organohydrogenpolysiloxanes, with component (B1) functioning as a crosslinking agent and component (B2) functioning as a chain extender. B1 / H B2} represents the Si-H ratio in the crosslinking agent and chain extender, and when these ratios are within a specific range, a crosslinked structure is formed with a moderately long intermolecular distance with respect to the curing reactive groups in component (A), making it easier to achieve moderate hardness and a rubber-like storage modulus. Furthermore, it means the "SiH / Vi ratio" of the entire composition (H B1 +[H B2 ) / Vi divided by the value of p xl When the value of is in the range of 0.1 to 6.0, the storage modulus of the crosslinked, cured film is improved, as is the conformability and adhesion to the thermoplastic resin and the electrode layer. Furthermore, in the present invention, the adhesion-imparting agent, which is component (E), allows the two layers to have a structure in which they are chemically bonded together.

[0034] The amounts of components (B1) and (B2) used must satisfy the above-mentioned ranges, and are preferably amounts such that the sum of the silicon-bonded hydrogen atoms of components (B1) and (B2) is in the range of 0.1 to 10 moles, more preferably 0.5 to 2.5 moles, and particularly preferably 0.5 to 2.0 moles, per mole of carbon-carbon double bonds in component (A).

[0035] Component (C) is a catalyst that promotes the hydrosilylation reaction of components (A) and (B). Examples include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, with platinum-based catalysts being preferred. Examples of platinum-based catalysts include platinum fine powder, chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum-alkenylsiloxane complexes, platinum-olefin complexes, platinum-carbonyl complexes, and catalysts in which these platinum-based catalysts are dispersed or encapsulated in thermoplastic resins such as silicone resins, polycarbonate resins, and acrylic resins. Platinum-alkenylsiloxane complexes are particularly preferred. Platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes are particularly preferred, with the complex preferably being added in the form of an alkenylsiloxane solution. In addition, from the viewpoint of improving handling and workability and the pot life of the composition, a platinum-containing hydrosilylation catalyst in the form of fine particles dispersed or encapsulated in a thermoplastic resin may be used. Note that non-platinum metal catalysts such as iron, ruthenium, and iron / cobalt may also be used as catalysts for promoting the hydrosilylation reaction.

[0036] The hydrosilylation catalyst of component (C) may also be a hydrosilylation catalyst that is inactive in the absence of high-energy radiation but becomes active in the composition upon high-energy radiation, i.e., a high-energy radiation-activated catalyst or a photoactivated catalyst. By using such component (C), the composition as a whole can be cured even at low temperatures using high-energy radiation as a trigger, and the composition has excellent storage stability and is easy to control the reaction, resulting in excellent handling and workability.

[0037] Examples of high-energy rays include ultraviolet rays, gamma rays, X-rays, α-rays, and electron beams. Particularly, ultraviolet rays, X-rays, and electron beams irradiated from commercially available electron beam irradiation devices are mentioned. Among these, ultraviolet rays are preferred from the viewpoint of catalyst activation efficiency, and ultraviolet rays with a wavelength in the range of 280 to 380 nm are preferred from the viewpoint of industrial use. The irradiation dose varies depending on the type of high-energy ray activated catalyst, but in the case of ultraviolet rays, the cumulative irradiation dose at a wavelength of 365 nm is 100 mJ / cm.２ ~100 J / cm ２ It is preferable that the range is within the range of

[0038] Specific examples of component (C) include (methylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)trimethylplatinum(IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)dimethylethylplatinum(IV), (cyclopentadienyl)dimethylacetylplatinum(IV), (trimethylsilylcyclopentadienyl)trimethylplatinum(IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum(IV), (dimethylphenylsilylcyclopentadienyl)trimethylcyclopentadienylplatinum(IV), trimethyl(acetylacetonato)platinum(IV), and trimethyl(3,5-heptamethylcyclopentadienyl). Examples of suitable bis(2,4-pentanedionato)platinum(II), bis(2,4-hexanedionato)platinum(II), bis(2,4-heptanedionato)platinum(II), bis(3,5-heptanedionato)platinum(II), bis(1-phenyl-1,3-butanedionato)platinum(II), bis(1,3-diphenyl-1,3-propanedionato)platinum(II), and bis(hexafluoroacetylacetonato)platinum(II). Of these, (methylcyclopentadienyl)trimethylplatinum(IV) and bis(2,4-pentanedionato)platinum(II) are preferred in terms of versatility and ease of availability.

[0039] The amount of component (C) used is an effective amount, and is not particularly limited, provided that it is an amount that promotes curing of the curable organopolysiloxane composition of the present invention. Specifically, the amount is such that the metal atoms in the catalyst are 0.01 to 1,000 ppm by mass, and preferably the platinum metal atoms in component (C) are 0.1 to 500 ppm, based on the sum of components (A) to (C) (the total being 100 mass%). If the content of component (C) is below the lower limit of the above range, curing may be insufficient, while if it exceeds the upper limit of the above range, it may be uneconomical and may have adverse effects on the transparency, such as coloration, of the resulting cured product.

[0040] The curable organopolysiloxane composition of the present invention contains a reinforcing filler (D). When the composition is cured to obtain a cured film for a transducer, which is a dielectric layer, the reinforcing filler (component (D)) is preferably at least partially composed of inorganic oxide fine particles, typically silica, and preferably contains a reinforcing filler (component (D)) or a composite thereof that has been surface-treated with one or more organosilicon compounds and has a different average BET specific surface area, within a certain range relative to the sum of the components in the composition that form non-volatile solids upon curing reaction (i.e., components (A) to (F)).

[0041] From the viewpoint of the mechanical strength of the cured product, the reinforcing fine particles are preferably one or more types of reinforcing inorganic fine particles having an average primary particle size of less than 50 nm, and examples thereof include fumed silica, wet silica, pulverized silica, calcium carbonate, diatomaceous earth, finely pulverized quartz, various metal oxide powders other than alumina and zinc oxide, glass fiber, carbon fiber, etc., and these may be treated with one or more types of organosilicon compounds described below. There are no particular limitations on the shape of the fine particles, and any shape such as particulate, plate-like, needle-like, fibrous, etc. may be used.

[0042] A preferred example, from the viewpoint of improving the mechanical strength of the dielectric layer, is fumed silica or its metal oxide composite, which has an average primary particle diameter of 10 nm or less, is partially aggregated, and has different BET specific surface areas, as described below, that are hydrophilic or hydrophobic. Furthermore, from the viewpoint of improving dispersibility, fumed silica or its metal oxide composite treated with disilazane or a silane coupling agent, as described below, is preferred. These reinforcing inorganic particles may be used in combination of two or more types.

[0043] In the present invention, the reinforcing filler used in the dielectric layer is: (D1) a silicon dioxide powder having an average BET specific surface area of ​​100 m2 and surface-treated with one or more organic silicon compounds; ２ / g or more, and (D2) a reinforcing fine particle or a composite thereof, which has been surface-treated with one or more organic silicon compounds and has an average BET specific surface area of ​​10 to 100 m ２ / g, and the mass ratio of component (D1) to component (D2) is in the range of 50:50 to 99:1, or alternatively, 70:30 to 97:3, preferably 70:30 to 95:5. If the mass ratio is outside the above range, the viscosity of the curable fluoroorganopolysiloxane composition before curing may increase, and the mechanical strength and dielectric breakdown strength after curing may decrease.

[0044] By incorporating the reinforcing fillers (components (D1) and (D2)) into the composition, it is possible to increase the mechanical strength and dielectric breakdown strength of the organopolysiloxane cured product obtained by curing the curable organopolysiloxane composition of the present invention.

[0045] [Content of component (D) (w ｆ The composition of the present invention is such that the content (w ｆ The content (w) of component (D) is preferably in the range of 5 to 40% by mass, and particularly preferably in the range of 10 to 30% by mass. ｆ If the mass % content exceeds the upper limit, the viscosity of the composition tends to increase, making it difficult to apply the composition uniformly and in a thin film. Furthermore, the storage modulus after curing tends to increase, resulting in an excessively hard composition, which may prevent the composition from achieving sufficient performance in transducer applications. On the other hand, if the mass % content is less than the lower limit of the above range, the physical properties of the curable organopolysiloxane composition after curing may be insufficient.

[0046] More preferably, the sum of components (D1) and (D2), when the total of components (A) to (E) is taken as 100% by mass, is in the range of 5 to 40% by mass, or alternatively 5.0 to 35% by mass, with a range of 6.5 to 30% by mass being particularly preferred. If the upper limit of the above-mentioned mass % range is exceeded, it may be difficult to apply a uniform, thin film, and the storage modulus after curing may be high. If the mass % range is below the lower limit, the physical properties of the curable organopolysiloxane composition after curing may be insufficient.

[0047] The reinforcing fillers (D1) and (D2) are preferably surface-treated with one or more organosilicon compounds. Surface treatment with an organosilicon compound is a hydrophobic treatment, and reinforcing fillers surface-treated with such organosilicon compounds can be dispersed uniformly and at a high filling rate in the fluoroorganopolysiloxane composition. Furthermore, an increase in the viscosity of the composition is suppressed, improving moldability.

[0048] Examples of organosilicon compounds include low molecular weight organosilicon compounds such as silanes, silazanes, siloxanes, and the like, and organosilicon polymers or oligomers such as polysiloxanes, polycarbosiloxanes, and the like. Preferably, the organosilicon compound used in the surface treatment contains at least one selected from hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane.

[0049] In the surface treatment, the ratio of the surface treatment agent to the total amount of filler is preferably in the range of 0.1% by mass or more and 50% by mass or less, and more preferably in the range of 0.3% by mass or more and 40% by mass or less. The treatment amount is the ratio of the filler to the surface treatment agent, and it is preferable to remove excess treatment agent after treatment. Furthermore, additives that promote or assist the reaction may be used during treatment as necessary.

[0050] In the surface treatment, whether the surface treatment agent components are chemically or physically fixed to the filler surface is an important parameter. For example, the amount of fixed surface treatment agent can be analyzed by reacting a composition containing excess tetraethoxysilane and a filler under alkaline conditions and detecting the reaction product by gas chromatography. The amount of the surface treatment agent components fixed to the filler surface is preferably 1.0 part by mass or more, and preferably 3.0 parts by mass or more, per 100 parts by mass of filler. In particular, when the organosilicon compounds used in the surface treatment of components (D1) and (D2) according to the present invention are hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane, the ratio of each to be fixed on the filler surface can be changed as needed. For example, in the present invention, as described above, the highly dielectric functional group (C) may be present in part or all of component (A) or components (B1) and (B2). ｐ F ２ｐ＋１ )-R- (where R is an alkylene group having 1 to 10 carbon atoms, and p is an integer of 1 to 8) can be introduced. From the viewpoints of dielectric properties, economy, ease of production, and moldability of the resulting curable fluoroorganopolysiloxane composition, a group where p = 1, i.e., a trifluoropropyl group, is preferred. In this case, the weight ratio of the treatment components derived from hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane fixed to the filler surface should be 0 to 10. Outside this range, the affinity between component (A) or component (B) and the filler surface may be poor, resulting in reduced processability and cured physical properties.

[0051] [Other Functional Fillers] In the curable fluoroorganopolysiloxane composition of the present invention, other fillers may or may not be used as desired. Examples of such fillers include highly dielectric fillers, thermally conductive inorganic fine particles, and insulating fillers. These inorganic fine particles may have two or more functions, such as a function as a reinforcing filler.

[0052] Examples of preferred dielectric inorganic particles include one or more inorganic particles selected from the group consisting of titanium oxide, barium titanate, strontium titanate, lead titanate zirconate, and composite metal oxides in which part of the barium and titanium moieties of barium titanate are substituted with alkaline earth metals such as calcium, strontium, yttrium, neodymium, samarium, and dysprosium, zirconium, or rare earth metals. Titanium oxide, barium titanate, barium calcium titanate zirconate, and strontium titanate are more preferred, with titanium oxide and barium titanate being even more preferred. In particular, it is particularly preferred that at least a portion of the dielectric inorganic particles have a relative dielectric constant of 10 or more at room temperature and 1 kHz. The preferred upper limit of the size (average primary particle diameter) of the inorganic particles is 20,000 nm (20 μm), but considering the processability into a thin film for a transducer, which will be described later, 10,000 nm (10 μm) is more preferred. Use of such dielectric inorganic fine particles may further improve the mechanical properties and / or electrical properties, particularly the relative dielectric constant, of the fluoroorganopolysiloxane cured product.

[0053] The insulating inorganic fine particles that can be used in the present invention are generally known insulating inorganic materials, i.e., those having a volume resistivity of 10 １０ ~10 １８ There are no limitations on the inorganic material particles as long as they have a resistivity of Ω·cm, and any shape, such as particles, flakes, or fibers (including whiskers), can be used. Specific examples include ceramic spherical particles, plate-like particles, or fibers. Preferred examples include particles of alumina, iron oxide, copper oxide, metal silicates such as mica and talc, quartz, amorphous silica, and glass. These may also be treated with various surface treatment agents, as described below. These may be used alone or in combination of two or more. The incorporation of insulating inorganic fine particles into the composition can increase the mechanical strength and dielectric breakdown strength of the fluoroorganopolysiloxane cured product, and may also result in an increase in the dielectric constant.

[0054] The thermally conductive inorganic fine particles that can be used in the present invention can include metal oxide particles such as magnesium oxide, zinc oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, silver oxide, etc., and inorganic compound particles such as aluminum nitride, boron nitride, silicon carbide, silicon nitride, boron carbide, titanium carbide, diamond, diamond-like carbon, etc., and zinc oxide, boron nitride, silicon carbide, and silicon nitride are preferred.By incorporating one or more of these thermally conductive inorganic fine particles into composition, it is possible to increase the thermal conductivity of the fluoroorganopolysiloxane cured material.

[0055] The average particle size of these inorganic particles can be measured by a measurement method commonly used in the art. For example, when the average particle size is 50 nm or more and about 500 nm or less, the average primary particle size can be measured by measuring the particle size through observation with a microscope such as a transmission electron microscope (TEM), a field-emission transmission electron microscope (FE-TEM), a scanning electron microscope (SEM), or a field-emission scanning electron microscope (FE-SEM), and calculating the average value. On the other hand, when the average particle size is about 500 nm or more, the average primary particle size can be directly calculated using a laser diffraction / scattering particle size distribution analyzer or the like.

[0056] The curable organopolysiloxane composition of the present invention contains an adhesion promoter (E). In particular, the composition of the present invention cures to give a cured product having a specific crosslink density and intermolecular crosslink structure. The inclusion of an adhesion promoter here forms a chemical bond with the surface of the substrate layer or electrode layer to which the composition is applied, thereby achieving strong adhesion and conformability. On the other hand, the parameter p relating to the crosslink density / crosslink structure explained above also contributes to the formation of a chemical bond between the surface of the substrate layer or electrode layer and the crosslink structure. xl If the value does not satisfy the above range, even if the cured product contains an adhesion promoter, the adhesion to the substrate layer etc. may not be sufficiently improved.

[0057] The amount of adhesion promoter (E) used can be appropriately designed depending on the desired adhesive strength, the type of base material layer or electrode layer, and the like. However, from the viewpoint of achieving practically sufficient adhesive strength and conformability for base material layers or electrode layers made of thermoplastic resins such as polyethylene terephthalate (PET), the content of component (E) is preferably in the range of 0.1% by mass to 10% by mass, preferably 0.25% by mass to 5.0% by mass, and particularly preferably 0.5% by mass to 2.0% by mass, where the total of components (A) to (E) constituting the composition is taken as 100% by mass.

[0058] Preferred adhesion promoters are organosilicon compounds containing at least one alkoxy group bonded to a silicon atom per molecule. Examples of this alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy groups, with methoxy being particularly preferred. Examples of groups bonded to silicon atoms in organosilicon compounds other than the alkoxy group include halogen-substituted or unsubstituted monovalent hydrocarbon groups such as alkyl, alkenyl, aryl, aralkyl, and halogenated alkyl groups; glycidoxyalkyl groups such as 3-glycidoxypropyl and 4-glycidoxybutyl; epoxycyclohexylalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl and 3-(3,4-epoxycyclohexyl)propyl; epoxyalkyl groups such as 3,4-epoxybutyl and 7,8-epoxyoctyl; acrylic-containing monovalent organic groups such as 3-methacryloxypropyl; and hydrogen atoms. The organosilicon compound preferably has a group capable of reacting with an alkenyl group or a silicon-bonded hydrogen atom in the composition, specifically a silicon-bonded hydrogen atom or an alkenyl group. Furthermore, the organosilicon compound preferably has at least one epoxy-containing monovalent organic group per molecule, as this provides good adhesion to a variety of substrates.

[0059] Examples of such organosilicon compounds include organosilane compounds, organosiloxane oligomers, and alkyl silicates. The molecular structure of the organosiloxane oligomer or alkyl silicate may be linear, partially branched linear, branched, cyclic, or network, with linear, branched, or network structures being particularly preferred. Examples of organosilicon compounds include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; siloxane compounds having at least one silicon-bonded alkenyl group or one silicon-bonded hydrogen atom, and at least one silicon-bonded alkoxy group per molecule; a mixture of a silane compound or siloxane compound having at least one silicon-bonded alkoxy group with a siloxane compound having at least one silicon-bonded hydroxy group and at least one silicon-bonded alkenyl group per molecule; a reaction mixture of an amino-containing organoalkoxysilane and an epoxy-containing organoalkoxysilane; an organic compound having at least two alkoxysilyl groups per molecule and containing a bond other than a silicon-oxygen bond between the silyl groups; ａ ｎ Si(OR ｂ ) ４－ｎ (In the formula, R ａ is a monovalent epoxy group-containing organic group, and R ｂ is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. n is a number ranging from 1 to 3), or a partial hydrolysis condensate thereof; a reaction mixture of a vinyl group-containing siloxane oligomer (including those with a linear or cyclic structure) with an epoxy group-containing trialkoxysilane; methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate. This adhesion promoter is preferably a low-viscosity liquid, and although there are no limitations on its viscosity, it is preferably in the range of 1 to 500 mPa·s at 25°C. Furthermore, there are no limitations on the amount of this adhesion promoter, but it is preferably in the range of 0.01 to 10 parts by mass per 100 parts by mass of the total composition.

[0060] In the present invention, a particularly suitable adhesion promoter is, for example, a reaction mixture of a vinyl group-containing siloxane oligomer (including those having a linear or cyclic structure) and an epoxy group-containing trialkoxysilane.

[0061] [Hydrosilylation Reaction Inhibitor] The hydrosilylation reaction inhibitor is incorporated to inhibit the crosslinking reaction and chain extension reaction that occur between component (A) and component (B), thereby extending the usable life at room temperature and improving storage stability. Therefore, it is a component that is necessarily incorporated into the curable composition of the present invention in practical use.

[0062] Examples of hydrosilylation reaction inhibitors include acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds. Specific examples include alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 1-ethynyl-1-cyclohexanol, and phenylbutynol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-1-hexyn-3-yne; methylalkenylcyclosiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; and benzotriazole.

[0063] The amount of hydrosilylation reaction inhibitor to be added is an amount effective for extending the room-temperature usable life and improving the storage stability of the film-forming curable fluoroorganopolysiloxane composition of the present invention. It is typically within the range of 0.001 to 5% by mass, and preferably 0.01 to 2% by mass, per 100% by mass of component (A), but this amount can be selected appropriately depending on the type of component, the performance and content of the platinum-based catalyst, the amount of alkenyl groups in component (A), the amount of silicon-bonded hydrogen atoms in component (B), and other factors.

[0064] [Use of Solvent] The curable fluoroorganopolysiloxane composition of the present invention can be subjected to the curing reaction as is. However, when the composition or some of its components (e.g., the fluoroorganopolysiloxane resin) are solid or viscous liquid, an organic solvent can be used as needed to improve miscibility and handleability. In particular, when the curable fluoroorganopolysiloxane composition of the present invention is applied to a film, the viscosity can be adjusted using a solvent so that the overall viscosity is in the range of 100 to 50,000 mPa·s. When diluted with a solvent, the amount used can be in the range of 0 to 2,000 parts by mass relative to the sum of the above components (A) to (C) (100 parts by mass). That is, the amount of solvent in the composition of the present invention may be 0 parts by mass, which is preferred because it is a solvent-free composition. In particular, by selecting a polymer with a low degree of polymerization for the curable fluoroorganopolysiloxane composition of the present invention, a solvent-free design is possible, and no fluorine-based solvents, organic solvents, etc. remain in the film obtained by curing, which has the advantage of eliminating environmental load issues and the effects of solvents on electronic devices. Furthermore, a low-solvent composition in which the amount of solvent used is 10 parts by mass or less, preferably 5 parts by mass or less, relative to the sum of the above components (A) to (C) (100 parts by mass) may also be used, and is preferred. Furthermore, in particular, the composition used for the electrode layer may be diluted with a solvent and applied as a thin film by spray coating, as described in the examples below.

[0065] Preferably, such organic solvent is one or more organic solvents selected from (F1) organic polar solvents, (F2) low molecular weight siloxane-based solvents, and (F3) halogen-based solvents, or a mixture thereof, with those having a boiling point of 80°C or higher but lower than 200°C being preferred. Mixed solvents of different or the same type of organic solvents in any ratio may also be used. Preferably, the organic solvent includes at least one low molecular weight siloxane-based solvent selected from hexamethyldisiloxane and octamethyltrisiloxane, or a mixture thereof, which are commercially available from Dow Silicones Corporation under the names OS-10, O-20, and OS-2. Furthermore, when the fluoroalkyl group content in the curable elastomer composition is high, optionally using these low molecular weight siloxane-based solvents in combination with the above-mentioned halogen-based solvents is also encompassed within a preferred embodiment of the present invention.

[0066] [Viscosity and Thixotropy of Composition] The composition of the present invention can be used by applying it to a substrate layer or an electrode layer, etc., and curing it into a film. In particular, when its overall viscosity and thixotropy are within a certain range, it can be easily applied uniformly to the substrate layer, etc., and may be possible to improve adhesion and conformability to the substrate / electrode layer upon curing. In particular, compositions having a thixotropic index as defined below and containing an adhesion promoter are particularly preferred in that they facilitate adhesion and chemical bonding at the interface. [Overall Viscosity] The curable fluoroorganopolysiloxane composition used in the present invention has a viscosity of 25°C and a shear rate of 0.1 (S －１ The overall viscosity, as measured by a viscosity measuring device (S), is preferably in the range of 5 to 5,000,000 mPa·s, with a range of 1,000 to 2,500,000 mPa·s being particularly preferred. To achieve a preferred viscosity range, it is possible to adjust the amount of the organic solvent used, but it is also possible to use a low-solvent or solvent-free (i.e., solventless) composition. [Thixotropic Index (TI)] The curable fluoroorganopolysiloxane composition of the present invention preferably has excellent fluidity and moderate thixotropic behavior. This makes it possible to achieve a low overall viscosity and excellent uniform application properties. Specifically, the composition should have a shear rate of 0.1 (S－１ The viscosity (η) of the entire composition measured ０．１ ) and share rate 10.0 (S －１ The viscosity (η) of the entire composition measured １０．０ ) is the ratio of TI (=η ０．１ / η １０．０ ) is preferably 250 or less. From the viewpoint of uniform application, the TI of the composition is particularly preferably 100 or less, and more preferably in the range of 10 to 80. [Solids Content] In the curable fluoroorganopolysiloxane composition of the present invention, the content of components that cure to form a fluoroorganopolysiloxane cured product as a non-volatile solid (sometimes simply referred to as "solids content" in the present invention) is preferably in the range of 5 to 100 mass %, more preferably 50 to 100 mass %, 75 to 100 mass %, or 85 to 100 mass % of the total composition.

[0067] [Introduction of Dielectric Functional Groups] When the cured organopolysiloxane film of the present invention is used as an electroactive film (e.g., a dielectric film) for a transducer such as a sensor or actuator, a highly dielectric functional group may be introduced into the cured product. However, even an organopolysiloxane cured film that does not contain a highly dielectric functional group can be used as an electroactive film. The introduction of these highly dielectric functional groups and the improvement of the relative dielectric constant have been proposed, for example, in International Patent Publication WO 2014 / 105959 by the present applicant.

[0068] The introduction of a highly dielectric functional group can be carried out by using a fluoroorganopolysiloxane or organohydrogenpolysiloxane having a highly dielectric functional group as part or all of the component (A) or component (B), or by adding an organic additive having a highly dielectric functional group, a non-reactive organosilicon compound having a highly dielectric functional group, or the like, to the curable composition.From the viewpoint of improving the compatibility with the curable composition and the relative dielectric constant of the cured product, it is preferable that in the fluoroorganopolysiloxane or organohydrogenpolysiloxane of the component (A) or component (B), 10 mol% or more, preferably 20 mol% or more, more preferably 40 mol% or more of all the substituents on the silicon atoms are substituted with a highly dielectric functional group.For example, in the component (A1), (C ｐ F ２ｐ＋１ )-R- (where R is an alkylene group having 1 to 10 carbon atoms, and p is an integer of 1 or more and 8 or less) may account for 10 mol % or more, preferably 20 mol % or more, and more preferably 40 mol % or more of all substituents on silicon atoms.

[0069] The type of highly dielectric functional group introduced into the organopolysiloxane cured film is not particularly limited, but examples include a) halogen atoms and halogen atom-containing groups typified by the 3,3,3-trifluoropropyl group, b) nitrogen atom-containing groups typified by the cyanopropyl group, c) oxygen atom-containing groups typified by the carbonyl group, d) heterocyclic groups such as an imidazole group, e) boron-containing groups such as a borate ester group, f) phosphorus-containing groups such as a phosphine group, and g) sulfur-containing groups such as a thiol group, and it is preferable to use halogen atoms and halogen atom-containing groups that contain a fluorine atom.

[0070] In the present invention, the highly dielectric functional group (C) is contained in part or all of the component (A) or the component (B). ｐ F ２ｐ＋１)-R- (R is an alkylene group having 1 to 10 carbon atoms, and p is an integer of 1 to 8) is preferably incorporated. Such fluoroalkyl groups provide cured products with excellent relative dielectric constants, and the presence of fluorine atoms in each component improves the compatibility of the components, resulting in cured products with excellent transparency. Specific examples of such fluoroalkyl groups include trifluoropropyl, pentafluorobutyl, heptafluoropentyl, nonafluorohexyl, undecafluoroheptyl, tridecafluorooctyl, pentadecafluorononyl, and heptadecafluorodecyl. Among these, groups where p=1, i.e., trifluoropropyl, are preferred from the viewpoints of dielectric properties, economy, ease of production, and moldability of the resulting curable fluoroorganopolysiloxane composition.

[0071] The curable fluoroorganopolysiloxane composition of the present invention can be prepared by uniformly mixing the curable fluoroorganopolysiloxane and the curing reaction accelerator, preferably the above-mentioned components (A) to (E), and by adding other optional components as necessary and uniformly mixing them. Mixing can be carried out at room temperature using various stirrers or kneaders, but mixing can also be carried out under heating if the combination of components does not cure during mixing.

[0072] The order in which the components are mixed is not particularly limited as long as they do not cure during mixing. If the mixture is not to be used immediately after mixing, the crosslinking agent (e.g., component (B1)) and the curing reaction accelerator (e.g., component (C)) may be stored in multiple containers so that they are not contained in the same container, and the components in all containers may be mixed immediately before use.

[0073] The curing reaction of the curable fluoroorganopolysiloxane composition of the present invention, which is based on a condensation reaction such as dehydration or dealcoholization, proceeds at room temperature. However, when producing a cured fluoroorganopolysiloxane film using an industrial production process, the composition is typically heated or exposed to active energy rays. The thermal curing reaction temperature is not particularly limited, but is preferably 50°C to 200°C, more preferably 60°C to 200°C, and even more preferably 80°C to 180°C. The curing reaction time depends on the structures of the above components (A), (B), (C), and (E), but is typically 1 second to 3 hours. Generally, a cured product can be obtained by maintaining the temperature within the range of 90 to 180°C for 10 seconds to 120 minutes. The film production method will be described later.

[0074] Examples of active energy rays that can be used in the curing reaction include ultraviolet rays, electron beams, and radioactive rays, with ultraviolet rays being preferred from the viewpoint of practicality. When the curing reaction is carried out using ultraviolet rays, it is desirable to add a hydrosilylation reaction catalyst that has high activity against the ultraviolet rays used, such as a bis(2,4-pentanedionato)platinum complex or a (methylcyclopentadienyl)trimethylplatinum complex. Suitable sources of ultraviolet rays include high-pressure mercury lamps, medium-pressure mercury lamps, Xe—Hg lamps, and deep UV lamps, and the irradiation dose in this case is 100 to 8,000 mJ / cm. ２ is preferred.

[0075] [Organopolysiloxane Cured Product] The cured product obtained by curing the present composition has a storage modulus (G') of 1.0 x 10 at 23°C and 0.02 Hz under small deformation. ３ ~5.0 x 10 ４ It is preferable that the range of tensile strength and workability is within this range. If the value is lower than this range, the strength and workability will decrease, and if the value is higher than this range, the hardness will increase, which may result in a decrease in performance as a transducer.

[0076] The organopolysiloxane cured product according to the present invention is preferably a cured product having an excellent dielectric constant, in which a highly dielectric functional group, typically a trifluoropropyl group, has been introduced as part of component (A) or the like. Such a cured product is preferably in the form of a film. In particular, a cured film obtained by curing the composition of the present invention can be suitably used as a dielectric layer in a transducer, and the form of a cured organopolysiloxane film for transducers (hereinafter sometimes referred to as a "cured film for transducers") is particularly preferred.

[0077] [Laminate and Manufacturing Method Thereof] The laminate according to the present invention is a transducer or a transducer member, and has a structure obtained by laminating the above-mentioned cured film for a transducer with one or more layers selected from an electrode layer and a base layer. Here, the cured film for a transducer, which is a dielectric layer, may have a structure including electrode layers on both sides (upper and lower layers), a structure including both sides (upper and lower layers) sandwiched between base layers, or a structure including an electrode layer on one side and a base layer on the other side.

[0078] It is preferable that the interface between the cured film for a transducer according to the present invention and one or more layers selected from the electrode layer and the substrate layer is at least partially bonded by chemical bonding, and when an attempt is made to peel the laminate, cohesive failure (CF) of the cured film for a transducer preferably occurs at the interface.

[0079] The other layers constituting the laminate of the present invention may be, without particular limitation, a synthetic resin layer such as a thermoplastic resin, a metal layer, or a silicone cured material layer containing conductive particles (an electrode layer, different from the cured film for transducer of the present invention). However, when at least a portion of the electrode layer and / or substrate layer is a thermoplastic resin layer (in the case of an electrode layer, a thermoplastic resin layer containing conductive particles), applying and curing the curable organopolysiloxane composition for transducer of the present invention to at least a portion of these layers can form at least a partial chemical bond at the interface between the two layers to obtain a laminate having a bonded structure. In particular, when a thermoplastic resin layer such as PET is used as a conventional silicone cured layer, sufficient adhesion / bonding is not achieved, which can cause problems with delamination when used as a transducer member. However, the cured film for transducer of the present invention firmly bonds the two materials and achieves high conformability, which has the advantage of significantly improving the performance, reliability, and durability of the transducer member.

[0080] The thermoplastic resin layer that can be used in the laminate of the present invention is not particularly limited, and examples include thermoplastic resin film layers made of polyethylene terephthalate (PET), polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, cyclopolyolefin, nylon, etc. When heat resistance is particularly required, films of heat-resistant synthetic resins such as polyimide, polyether ether ketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide imide, and polyether sulfone are suitable. On the other hand, for applications requiring visibility, such as display devices, transparent substrates, specifically transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN, may be used. PET film is widely used industrially, and the cured transducer film of the present invention can be easily bonded to the PET film.

[0081] The substrate layer is preferably in the form of a film or sheet. There are no particular limitations on its thickness, and it can be designed to a desired thickness depending on the application. Furthermore, in order to improve the adhesion between the substrate layer or the like and the cured film for a transducer, the surface of the substrate layer may be subjected to a primer treatment, corona treatment, etching treatment, or plasma treatment in advance. However, in the present invention, since a chemical bond can be easily formed between the two, an adhesive laminate can be easily obtained without these pretreatments.

[0082] There are no particular restrictions on the method for obtaining such a laminate, but it can be easily produced by a production method including the steps of applying the curable organopolysiloxane composition for a transducer according to the present invention to at least one surface of one or more layers selected from an electrode layer and a substrate layer, and then curing the composition.

[0083] The method for applying the curable fluoroorganopolysiloxane composition to form a film can be any method known in the art, including gravure coating, offset coating, offset gravure coating, roll coating using an offset transfer roll coater, reverse roll coating, air knife coating, curtain coating using a curtain flow coater, comma coating, Mayer bar coating, and other known methods used for forming a cured layer. Furthermore, the curable organopolysiloxane composition of the present invention can also be applied in multiple layers.

[0084] The laminate according to the present invention preferably has a structure in which laminated cured organopolysiloxane films are chemically bonded at their interfaces, and this structure is formed by contacting a cured organopolysiloxane film, or a thin layer (before being completely cured) of its precursor, a curable organopolysiloxane composition, in an uncured or semi-cured state, after or before curing, and completely curing the film using a means such as heating, thereby causing a reaction between curable reactive groups to proceed at the interface of the cured film. From the standpoint of industrial production and production efficiency, this process may involve laminating layers one by one, with the curing reaction proceeding layer by layer, or it may involve previously laminating a plurality of thin layers of curable curable organopolysiloxane composition, and then completely curing the entire film using a means such as heating.

[0085] More specifically, the laminate according to the present invention can be obtained by applying a curable organopolysiloxane composition for transducers to at least one surface of one or more layers selected from an electrode layer and a substrate layer, then laminating one or more layers selected from other electrode layers and substrate layers on the coating layer of the composition in an uncured or semi-cured state, and completely curing the entire structure. Alternatively, a laminate precursor (e.g., having a configuration such as, but not limited to, electrode layer / substrate layer / (uncured composition layer) / substrate layer / electrode layer) may be prepared by laminating two or more electrode layers and three or more substrate layers and having a coating layer of the uncured curable organopolysiloxane composition for transducers between these layers, and then curing the entire structure to produce a laminate having a cured film for transducers between the layers.

[0086] This manufacturing method is particularly useful as a method for forming an electrode layer in a transducer member, and can easily provide on an industrial scale laminates, electronic components, or display device components in which the dielectric layer and the electrode layer are firmly bonded and which are less likely to suffer from peeling or defects due to insufficient adhesive strength and conformability.

[0087] The fluoroorganopolysiloxane cured film laminate of the present invention is useful as an electronic material, a display device component, or a transducer component (including sensors, speakers, actuators, and generators), and is particularly suitable for use as an electroactive film (including a highly dielectric film) with an electrode layer as an electronic component or a display device component. Furthermore, as described above, the electroactive film with high dielectric breakdown strength is suitable for transducer components such as actuators in the form of a single layer or laminate film, and since it has a structure in which the electrode layers are firmly bonded, it is particularly useful for actuator applications that operate under high voltage.

[0088] The present invention will be described below with reference to examples, but the present invention is not limited to these. The following compounds were used in the examples and comparative examples shown below. The physical properties of each composition were measured by the following method. [Viscosity of composition before curing] The viscosity of each composition before curing was measured using a viscoelasticity measuring device (manufactured by Anton Paar, model number MCR302). Measurements were carried out using a cone-plate with a diameter of 20 mm and an angle of 2°, with the shear rate varied. At 25°C and a shear rate of 0.1 (S －１ ) and 10.0 (S －１ The overall viscosity η of the composition measured ０．１ and η １０．０The values ​​were recorded for each test. The results, including the thixotropic index (TI), are shown in Tables 1 and 2. [Storage Modulus and Loss Modulus] Each curable fluoroorganopolysiloxane composition was cured at 130°C for 1 hour, and then the storage modulus was measured using a viscoelasticity measuring device (Anton Paar, Model MCR302). Samples were set to a thickness of approximately 2 mm using a Peltier element temperature control system and 8 mm diameter parallel plates. Measurements were performed at 23°C by frequency sweep under small deformation (approximately 0.2%). The storage modulus (G'), loss modulus (G''), and loss tangent at 0.02 Hz are shown in Tables 1 and 2. [Adhesion Evaluation] Approximately 1 g of the curable fluoroorganopolysiloxane composition was applied to a 200 μm thick polyethylene terephthalate film and cured at 130°C for 1 hour. The cured product was then peeled off with a spatula, and the peeling mode was visually evaluated as interfacial delamination (AF) or cohesive failure (CF) based on the presence or absence of cured residue. The results are shown in Tables 1 and 2.

[0089] Component (A): 3,3,3-trifluoropropylmethyl, dimethylsiloxane copolymer, both ends blocked with vinyldimethylsiloxy groups (vinyl group content: 0.26% by mass, siloxane polymerization degree: 193) Component (B1): dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane-methylhydrogensiloxane copolymer, both ends blocked with trimethylsiloxy groups (silicon-bonded hydrogen content: approximately 0.23% by mass) Component (B2): dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane copolymer, both ends blocked with dimethylhydrosiloxy groups (silicon-bonded hydrogen content: approximately 0.013% by mass) Component (C): dimethylsiloxane polymer solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, both ends blocked with vinyldimethylsiloxy groups (platinum concentration: approximately 0.6% by mass) Component (D1): Fumed silica treated with hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane (product name before treatment: Aerosil 200, BET specific surface area: 200 m 2 / g) Component (D2): Fumed silica treated with hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane (product name before treatment: Aerosil 50, BET specific surface area 50 m 2 / g) Component (E): Adhesion improver (= Both ends blocked with hydroxydimethylsiloxy groups, reaction product of methylvinylsiloxane and glycidoxypropyltrimethoxysilane (vinyl group content (wt%): approx. 5.6)) Component (F): 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane

[0090] [Curable fluoroorganopolysiloxane compositions according to Examples 1 to 4 and Comparative Examples 1 to 6] The above components were blended in the weight percentages shown in Table 1 to form liquid curable fluoroorganopolysiloxane compositions. xl The values ​​were set as shown in Table 1. When mixing the components, the materials were mixed under vacuum using a planetary centrifugal mixer (product name ARE-310, manufactured by Thinky Corporation). Various physical properties are also shown in Tables 1 and 2.

[0091]

[0092]

[0093] [Summary] The curable fluoroorganopolysiloxane compositions of Examples 1 to 4 were prepared by the following steps in order to achieve the object of the present invention: xl value, preferably w f By optimizing the values, the composition has an appropriate viscosity and thixotropic index, resulting in excellent uniform application properties, a storage modulus (G') appropriate for transducer components, and the peel mode between the two is cohesive failure (CF), with the PET film and the cured material chemically bonded between the layers, thereby achieving good adhesion and conformability.

[0094] On the other hand, p xl value and w fIt was confirmed that if the value is outside the optimum value, sufficient adhesion and adhesive strength will not be exhibited, resulting in interfacial peeling (AF) between the layers, or even if a certain level of adhesive strength is exhibited, the G' value of the cured product will be high, causing practical problems as a transducer component.

Claims

1. (A) One or more organopolysiloxanes having a curing reactive group containing at least two carbon-carbon double bonds in the molecule, (B1) An organohydrogenpolysiloxane having at least one silicon atom-bonded hydrogen atom in the side chain portion of the molecular chain, having no silicon atom-bonded hydrogen atom at at least one end of the molecular chain, and having at least two silicon atom-bonded hydrogen atoms in the molecule, (B2) An organohydrogenpolysiloxane having silicon atom-bonded hydrogen atoms at both ends of the molecular chain and having at least two silicon atom-bonded hydrogen atoms in the molecule, (C) An effective amount of a catalyst for hydrosilylation reaction, (D) A reinforcing filler, and (E) An adhesion promoter containing at least, and The number of silicon atom-bonded hydrogen atoms (H B1 ) in component (B1) The number of silicon atom-bonded hydrogen atoms (H B2 ) in component (B2), and the total number (Vi) of the curing reactive groups containing carbon-carbon double bonds in component (A) satisfies the following relational expression: p ｘ１ = {H B1 / H B2} / {(H B1 + H B2 ) / Vi} p defined by ｘ１ A curable organopolysiloxane composition for a transducer, characterized in that the value of is in the range of 0.1 to 6.

0.

2. 。 When the total of components (A) to (E) is 100% by mass, the content (w ｆ ), which is in the range of 5 to 40% by mass, of the curable organopolysiloxane composition for a transducer according to claim 1.

3. At least a part of component (A) is (A1) one or more kinds having at least two alkenyl groups having 2 to 12 carbon atoms in the molecule, and 10 mol% or more of all substituents on the silicon atom is (C ｐ F ２ｐ＋１ )-R- (R is an alkylene group having 1 to 10 carbon atoms, and p is an integer of 1 or more and 8 or less), and is a fluoroalkyl group-containing organopolysiloxane which is a fluoroalkyl group represented by the formula: The curable organopolysiloxane composition for a transducer according to claim 1.

4. The curable organopolysiloxane composition for a transducer according to claim 1, wherein at least a part of component (D) is inorganic oxide fine particles.

5. The cured product obtained by curing the composition has a storage elastic modulus (G') at 23°C and during minute deformation at 0.02 Hz in the range of 1.0×10 ３ to 5.0×10 ４ Pa. The curable organopolysiloxane composition for a transducer according to claim 1.

6. The overall viscosity of the composition measured at 25°C and a shear rate of 0.1 (S －１ ) is in the range of 5 to 5,000,000 mPa·s, and for the composition, the viscosity (η －１ ) of the entire composition measured at a shear rate of 0.1 (S ０．１ ) and the viscosity (η －１ ) of the entire composition measured at a shear rate of 10.0 (S １０．０ ) The thixotropic index (TI) (= η ０．１ / η １０．０ ) is 250 or less. The curable organopolysiloxane composition for a transducer according to claim 1.

7. A cured product obtained by curing the curable organopolysiloxane composition for a transducer according to any one of claims 1 to 6.

8. A film cured product for a transducer obtained by curing the curable organopolysiloxane composition for a transducer according to any one of claims 1 to 6.

9. A laminate having a structure in which a film cured product for a transducer obtained by curing the curable organopolysiloxane composition for a transducer according to any one of claims 1 to 6 is laminated with one or more layers selected from an electrode layer and a base material layer.

10. The laminate according to claim 9, wherein the film cured product for a transducer and one or more layers selected from an electrode layer and a base material layer form at least partially a chemical bond at the interface between the two layers.

11. At least a part of the electrode layer and / or the base material layer is a layer made of a thermoplastic resin, The laminate according to claim 9, having a structure in which the film cured product for a transducer and the layer made of a thermoplastic resin are bonded by forming at least partially a chemical bond at the interface between the two layers.

12. The laminate according to claim 9, wherein the cured film for a transducer has a structure in which upper and lower electrode layers or a substrate are interposed on both sides of the film.

13. A method for manufacturing a laminate according to any one of claims 9 to 12, comprising a step of applying and curing the curable organopolysiloxane composition for a transducer according to any one of claims 1 to 5 on at least one side of one or more layers selected from an electrode layer and a substrate layer.

14. A member for a transducer, comprising the laminate according to any one of claims 9 to 12.

15. A transducer, comprising the laminate according to any one of claims 9 to 12.

16. An electronic component or a display device, comprising the laminate according to any one of claims 9 to 12.