Laminate made of cured organopolysiloxane film, its uses, and its manufacturing method

Abstract

[Problem] The present invention provides: a multilayer body in which two or more cured organopolysiloxane films are stacked, said cured organopolysiloxane films being obtained by curing curable organopolysiloxane compositions that have different compositions for achieving different functions required, for example, for a dielectric layer and an electrode layer, said multilayer body being not susceptible to the occurrence of problems such as defects or separation at the interface between the cured films, which constitute the multilayer body, due to insufficiency of bonding strength or followability; a use of this multilayer body; and a method for producing this multilayer body. [Solution] A multilayer body which has a structure wherein two or more cured organopolysiloxane films are stacked, said cured organopolysiloxane films having different compositions and at least some common functional groups that are involved in the curing reaction, and wherein the stacked cured films are chemically bonded to each other at the interface. It is preferable that the compositions contain a hydrosilylatable group, while having different SiH / Vi ratios, and the stacked cured films are chemically bonded to each other at the interface by means of hydrosilylation.

Description

[Technical Field]

[0001] The present invention relates to a laminate in which at least two types of cured organopolysiloxane films are laminated, uses thereof, a method and an apparatus for producing the same. [Background technology]

[0002] Cured organopolysiloxanes having a polysiloxane skeleton exhibit excellent transparency, electrical insulation, heat resistance, cold resistance, and the like. Their electrical activity can be improved by optionally incorporating highly dielectric functional groups such as fluoroalkyl groups. Furthermore, they can be easily processed into films or sheets. Because of this, they are used in a variety of applications, including adhesive films for various electrical and electronic devices and electroactive films for transducer devices such as actuators. These cured organopolysiloxanes are classified according to their curing mechanism: hydrosilylation reaction-curable, condensation reaction-curable, peroxide-curable, and the like. 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 and the like, an electronic component for display devices, and particularly as a transducer material for sensors, actuators, etc., an electrode layer must be provided on the electroactive film as a dielectric layer. For example, Non-Patent Documents 1 and 2 propose forming an electrode layer with excellent conformity to the dielectric layer by adding a conductive filler to a silicone elastomer matrix with excellent flexibility.

[0004] However, when attempting to form an electrode layer containing a conductive filler on an organopolysiloxane cured film, which is an electroactive film, interfacial peeling between the dielectric layer and the electrode layer can occur, particularly with displacement of the dielectric layer (e.g., expansion and contraction of an actuator, etc.), leading to poor electrical conductivity and reduced reliability as an actuator. In Patent Document 3 and elsewhere, the present applicants have proposed forming an electrode layer made of a cured organopolysiloxane film on an electroactive film (=dielectric layer) by applying a curable organopolysiloxane composition containing a conductive filler to the cured organopolysiloxane film, which is an electroactive film. However, when used as a transducer material for actuators, etc., this does not completely solve the problem of peeling caused by insufficient conformability of the electrode surface, and there is still room for improvement. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Kujawski, M.; Pearse, J.D.; Smela, E. Carbon 2010, 48, 2409-2417. [Non-patent document 2] Rosset, S.; Shea, HR Appl. Phys. A 2013, 110, 281-307. [Patent documents]

[0006] [Patent Document 1] International Patent Publication No. WO2014 / 105959 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made to solve the above-mentioned problems, and its object is to provide a laminate comprising two or more organopolysiloxane cured films obtained by curing curable organopolysiloxane compositions whose compositions differ from each other because different functions are required for the dielectric layer and the electrode layer, and which is less likely to suffer from peeling or defects at the interface between the cured films that make up the laminate due to insufficient adhesive strength and conformability, as well as uses and a production method for the laminate. [Means for solving the problem]

[0008] As a result of extensive investigation, the present inventors have found that the above-mentioned problems can be solved by a laminate having a structure in which two or more layers of organopolysiloxane cured films obtained by curing curable organopolysiloxane compositions that are different from each other in composition but share at least some of the functional groups involved in the curing reaction are laminated together, and in which the laminated organopolysiloxane cured films have a structure in which the laminated cured organopolysiloxane films are chemically bonded at their interfaces, thereby completing the present invention.

[0009] At least one of the laminated cured organopolysiloxane films may be an electrode layer formed by curing a composition containing conductive fine particles, and the other may be a dielectric layer formed by curing a composition containing dielectric functional groups or a composition not containing conductive fine particles. Furthermore, the compositions having different compositions that give the cured organopolysiloxane films to be laminated on each other preferably both contain curing reactive groups that cure by a hydrosilylation reaction and differ in the amount of silicon-bonded hydrogen atoms in this component per mole of the total number of carbon-carbon double bonds in the composition, so that the laminated cured organopolysiloxane films have a structure in which they are chemically bonded at their interfaces by a hydrosilylation reaction. [Effects of the Invention]

[0010] The present invention provides a laminate in which two or more cured organopolysiloxane films having different compositions before curing are alternately laminated, which is less susceptible to peeling or defects at the interfaces of the cured films due to insufficient adhesive strength and conformability, as well as uses and a manufacturing method thereof. In particular, the present invention provides a laminate in which cured organopolysiloxane films that are cured by a hydrosilylation reaction and function as an electrode layer and a dielectric layer, respectively, are alternately laminated, which is less susceptible to interfacial peeling between the films, and which has excellent reliability in applications such as actuators and which prevent poor electrical conductivity, and a manufacturing method thereof. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Laminate] The laminate of the present invention comprises a structure in which two or more layers of cured organopolysiloxane films are laminated together, each layer being obtained by curing a curable organopolysiloxane composition that has different compositions but shares at least some of the functional groups involved in the curing reaction, and the laminated cured organopolysiloxane films are chemically bonded at their interfaces. Three or more layers of cured organopolysiloxane films may be laminated together, and three or more different types of cured organopolysiloxane films may be laminated together, as long as their pre-curing compositions are different. The laminate of the present invention may have a multilayer structure of two or more layers. As long as at least a portion of the laminate comprises two types of cured organopolysiloxane films with different compositions, the remaining laminated portions may comprise a structure in which the same type of cured organopolysiloxane films are laminated together (for example, a partial structure in which a cured film functioning as a dielectric layer is laminated to increase thickness). In particular, it is particularly preferable that the laminate has a structure in which two types of cured organopolysiloxane films with different compositions (for example, cured films that are dielectric layers and electrode layers) are alternately laminated in part or all of the laminate.

[0012] As an example, when organopolysiloxane cured films L1, L2, L3, etc., each having a different pre-curing composition, are laminated, and the interface is represented by " / ", the following overall or partial laminate structure can be suitably exemplified. Note that [ ]n means a laminate structure in which the structure within the brackets is repeated n or more times, and n is independently a number greater than or equal to 0. Furthermore, " / " means that each layer faces each other in the stacking direction of the laminate (generally the thickness direction perpendicular to the surface of each functional layer). L1 / L2;L1 / [L2 / L1]n / L2 / L1;L2 / [L1 / L2]n / L1 / L2;L2 / L1 / [L1 / ]n / L2;L1 / L2 / L3;L1 / L2 / L3 / L4

[0013] When the laminate according to the present invention is used for transducers (sensors, actuators, generators), it is preferable that an organopolysiloxane cured film serving as an electrode layer is laminated on at least one side of an organopolysiloxane cured film serving as a dielectric layer, and that the laminated organopolysiloxane cured films have a chemically bonded structure at their interfaces. Specifically, in the configuration of the above-mentioned laminate, L1 is an organopolysiloxane cured film serving as a dielectric layer, L2 is an organopolysiloxane cured film serving as an electrode layer, and the laminate preferably has a whole or partial structure represented by L2 / [L1 / L2]n / L1 / L2, in which these layers are alternately laminated and the electrode layers are disposed on the outside. Note that the dielectric layer L1 may be replaced by a multilayer structure of one or more layers, such as L1 / [L1 / ]n. Needless to say, the multilayer dielectric layer may have a chemically bonded structure at its interfaces, and this is preferred.

[0014] Furthermore, the laminate according to the present invention may comprise, in addition to the electrode layer and the single-layer or multi-layer dielectric layer, a pressure-sensitive adhesive layer for use in placement within a transducer, and a non-silicone thermoplastic resin layer that may optionally have a release surface. In particular, when used as a component for an electronic device, the laminate structure may include the following combinations, and in the present invention, it is preferable that the dielectric layer and electrode layer, the dielectric layer and pressure-sensitive adhesive layer, or the electrode layer and pressure-sensitive adhesive layer have a structure in which they are chemically bonded at their interface (" / "). It goes without saying that the following combinations are merely examples and are not limited to these, and the laminate need not necessarily be symmetrical as shown in some of the examples. Furthermore, in the examples, examples of each functional layer are as follows, with " / " having the same meaning as above: (L1) Highly dielectric sheet containing a single or multiple layer of a cured polymer having a dielectric functional group: (EAP) (L2) Silicone-based pressure-sensitive adhesive layer: (PSA) (L3) Electrode layer: (EL) (L4) Non-silicone thermoplastic resin layer: (PF)

[0015] Example 1: PSA / EAP / PSA Example 2: PSA / EL / EAP / EL / PSA Example 3: PSA / PF / EAP / PF / PSA Example 4: PSA / EL / PF / EAP / PF / EL / PSA Example 5: PSA / PF / EL / EAP / EL / PF / PSA Example 6: PF / PSA / EL / EAP / EL / PSA / PF Example 7: EL / PSA / EAP / PSA / EL Example 8: PF / PSA / EL / EAP / PF / PSA / EL Example 9: EL / PSA / EAP / EL Example 10: EL / PSA / EAP / EL / PSA Example 11: PF / PSA / EAP / PF Example 12: PF / PSA / EAP / PF / PSA Example 13: EL / PSA / PF / EAP / PF / PSA / EL It should be noted that laminates in which an electrode layer is formed on a PSA, such as those in Examples 7 and 13, may be shipped as a peelable laminate containing a separator on the PSA, and the separator may be peeled off later to form an electrode layer on the PSA. Furthermore, laminates in Examples 6 and 11 in which non-silicone thermoplastic resin layers form outer layers may be treated as electronic device components including these resin layers, or may be treated as peelable laminates with a release surface provided on the inner surface of these resin layers within the laminate.

[0016] In the present invention, a particularly preferred embodiment is a laminate having a structure in which a single or multiple dielectric layers (EAP) and electrode layers (EL) are chemically bonded at their interfaces, and which has a whole or partial structure in which these layers are alternately stacked with electrode layers disposed on the outside, such as (EL / EAP / )nEL, where n is a number equal to or greater than 1, and the layers may be stacked any number of times depending on the thickness of the laminate required for a transducer or the like.

[0017] The laminate of the present invention is characterized by a structure in which cured organopolysiloxane films with different compositions before curing are chemically bonded at their interface. In the present invention, this structure is formed by the reaction of curing-reactive functional groups contained in each film or its precursor at the interface between films with different compositions before curing. Therefore, the cured organopolysiloxane films must share at least some of the functional groups involved in the curing reaction. The type of curing reaction described below is not limited and may be one or more types. However, it is particularly preferable for the laminated cured organopolysiloxane films to have a structure in which the cured organopolysiloxane films are chemically bonded at their interface by a hydrosilylation reaction between alkenyl groups and silicon-bonded hydrogen atoms. Such bonding can be achieved by adjusting the content of silicon-bonded hydrogen atoms in the composition, by a production method involving application and curing of a curable organopolysiloxane composition, or by a combination thereof, as described below.

[0018] The organopolysiloxane cured film constituting the laminate is not particularly limited in composition or physical properties, but at least one of the films should have a volume resistivity of 10 2 The resistivity is preferably Ω·cm or less, and the film preferably contains conductive fine particles (particularly preferably fine particles containing at least one type of conductive carbon selected from conductive carbon black, graphite, and vapor grown carbon (VGCF)) as described below. A cured organopolysiloxane film with such conductivity is suitable for an electrode layer.

[0019] At least one of the organopolysiloxane cured films constituting the laminate has a shear storage modulus (G') at 120°C of 5.0 x 10 4 ~1.5×10 5 It is preferable that the shear storage modulus is in the range of Pa. A cured organopolysiloxane film having such a shear storage modulus is particularly suitable for an electrode layer.

[0020] As for other mechanical properties, the compressive set (%) of the organopolysiloxane cured film according to the present invention is preferably less than 10%, more preferably less than 5%, and particularly preferably 4% or less.

[0021] Furthermore, when the composition that provides the organopolysiloxane cured film according to the present invention is hot-formed into a sheet having a thickness of 2.0 mm, it can be designed to have the following mechanical properties measured in accordance with JIS K 6249. Compositions that provide such properties are particularly suitable for, but are not limited to, dielectric layers. (1) The Young's modulus (MPa) at room temperature can be set to 0.001 to 10 MPa, preferably 0.001 to 2 MPa, and particularly preferably 0.001 to 1.5 MPa. (2) The tear strength (N / mm) can be set to 1 N / mm or more at room temperature, and a particularly preferred range is 2 N / mm or more. (3) The tensile strength (MPa) at room temperature can be 1 MPa or more, and a particularly preferred range is 2 MPa or more. (4) The elongation at break (%) can be 50% or more, and a particularly preferable range is 100 to The range is 1000%.

[0022] [Organopolysiloxane cured film] The organopolysiloxane cured product of the present invention is obtained by curing a curable organopolysiloxane composition into a film. The curing reaction mechanism is not particularly limited, but examples include hydrosilylation reaction curing between alkenyl groups and silicon-bonded hydrogen atoms; dehydration condensation reaction curing between silanol groups and / or silicon-bonded alkoxy groups, dealcoholization condensation reaction curing; peroxide curing using an organic peroxide; and radical reaction curing by high-energy radiation irradiation of mercapto groups, etc. Hydrosilylation reaction curing, peroxide curing, radical reaction curing, or a combination thereof is preferred, as the entire product cures relatively quickly and the reaction can be easily controlled. A hydrosilylation reaction-curable curable organopolysiloxane composition is preferred. These curing reactions proceed by heating, high-energy radiation irradiation, or a combination thereof.

[0023] Preferably, in the present invention, the curable organopolysiloxane composition that provides the organopolysiloxane cured film is (A) an organopolysiloxane having a curing reactive group containing at least two carbon-carbon double bonds in the molecule; (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, in an amount such that the number of silicon-bonded hydrogen atoms in this component is 0.5 to 2.5 moles per mole of total alkenyl groups in the composition; and (C) an effective amount of a hydrosilylation catalyst; It contains at least the following. In the composition for producing the organopolysiloxane cured film used as the dielectric layer, the component (A) is preferably (a1) a linear or branched organopolysiloxane having alkenyl groups only at the molecular chain terminals, and (a2) More preferably, the organopolysiloxane mixture contains an alkenyl group-containing organopolysiloxane resin that has at least one branched siloxane unit in the molecule and has a vinyl (CH2=CH-) group content in the range of 1.0 to 5.0 mass %.

[0024] 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.

[0025] 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 a hydroxyl group. When used as a dielectric layer, a dielectric functional group, as described below, may be incorporated. 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 exhibits condensation reactivity in addition to hydrosilylation reaction curability.

[0026] When used in a dielectric layer, component (A) preferably has the following average composition formula: R 1 a R 2 b SiO (4-a―b) / 2 or a mixture thereof. In the formula, R 1 is a curing reactive group containing a carbon-carbon double bond as described above, R 2is a group selected from the above monovalent hydrocarbon groups having no carbon-carbon double bond, hydroxyl groups, and alkoxy groups, a and b are numbers that satisfy the following conditions: 1≦a+b≦3 and 0.001≦a / (a+b)≦0.33, and preferably 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;

[0027] When used in a dielectric layer, component (A) according to the present invention is particularly preferably (a1) a linear or branched organopolysiloxane having alkenyl groups only at the molecular chain terminals, and (a2) An alkenyl group-containing organopolysiloxane resin having at least one branched siloxane unit in the molecule and having a vinyl (CH2=CH-) group content in the range of 1.0 to 5.0 mass%. The organopolysiloxane mixture comprises:

[0028] Component (a1) has a molecular chain terminal (Alk)R 2 2SiO 1 / 2 (wherein Alk is an alkenyl group having 2 or more carbon atoms), and other siloxane units are substantially represented by R 2 2SiO 2 / 2 It is a linear or branched organopolysiloxane 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. It is particularly preferable that both ends of the molecular chain of component (A1-1) are (Alk)R 2 2SiO 1 / 2It is a linear organopolysiloxane terminated with a siloxane unit represented by the formula:

[0029] Component (a2) is an alkenyl group-containing organopolysiloxane resin, Average unit formula: (RSiO 3 / 2 )o(R2SiO 2 / 2 )p(R3SiO 1 / 2 )q(SiO 4 / 2 )r(XO 1 / 2 )s Examples of the alkenyl group-containing organopolysiloxane resin include those represented by the following formula: In the above formula, R is a group selected from an alkenyl group and the above-mentioned monovalent hydrocarbon group having no carbon-carbon double bond, and X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, provided that, among all R, at least R is an alkenyl group in the range in which the content of vinyl (CH2=CH-) groups in the organopolysiloxane resin is 1.0 to 5.0 mass%, and in particular, R3SiO 1 / 2 Preferably, at least some of the R on the siloxane unit represented by the formula: is an alkenyl group.

[0030] 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.

[0031] As component (a2), particularly preferred are {(Alk)R 2 2SiO 1 / 2}q1(R 2 3SiO 1 / 2 )q2(SiO 4 / 2 )r (In the formula, Alk, R 2is the same group as 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 a number in the range such that the content of vinyl (CH2=CH-) groups in the organopolysiloxane resin is in the range of 1.0 to 5.0 mass%. Examples include alkenyl group-containing MQ organopolysiloxane resins represented by the following formula:

[0032] The combined use of component (a1) having alkenyl groups only at the molecular chain terminals and component (a2), which is an organopolysiloxane resin having a certain amount of alkenyl groups, provides a cured reaction product that exhibits excellent curability as a whole composition and excellent mechanical strength and flexibility, making it possible to provide an organopolysiloxane cured film that is particularly suitable for adhesive layers or dielectric layers in the above-mentioned electronic components, etc.

[0033] Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule, and functions as a crosslinking agent for component (A).

[0034] Examples of such component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, methylhydrogenpolysiloxane terminated at both molecular chain ends with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer terminated at both molecular chain ends with trimethylsiloxy groups, and dimethylhydrogenpolysiloxane terminated at both molecular chain ends with trimethylsiloxy groups. Hydrogensiloxy-capped dimethylpolysiloxane, dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer at both molecular chain ends, methylhydrogensiloxane-diphenylsiloxane copolymer at both molecular chain ends, methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer at both molecular chain ends, trimethylsiloxy-terminated methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer, hydrolysis condensate of trimethoxysilane, (CH3)2HSiO 1 / 2 Units and SiO 4 / 2A copolymer consisting of (CH3)2HSiO units 1 / 2 Units and SiO 4 / 2 Units and (C6H5)SiO 3 / 2 Examples include copolymers consisting of units and mixtures of two or more of these.

[0035] The amount of component (B) used in the composition is preferably an amount that provides 0.1 to 10 moles of silicon-bonded hydrogen atoms per mole of carbon-carbon double bonds in component (A), more preferably an amount that provides 0.5 to 2.5 moles, and particularly preferably an amount that provides 0.5 to 2.0 moles. Using component (B) in an amount below the lower limit may result in poor curing, while using component (B) in an amount above the upper limit may result in the cured product having too high a mechanical strength, making it impossible to achieve suitable physical properties for an electrode layer, dielectric layer, or adhesive layer. However, when the objective is to improve the adhesive strength of the organopolysiloxane cured film of the present invention to an adherend such as glass, this does not preclude use in an amount that provides more than 20 moles of silicon-bonded hydrogen atoms per mole of carbon-carbon double bonds in component (A).

[0036] Preferably, the laminated organopolysiloxane cured films of the present invention have different compositions and are chemically bonded at their interface by a hydrosilylation reaction between the aforementioned components (A) and (B). The reaction between components (A) and (B) at the interface proceeds favorably when the ratio of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane component to the total number of carbon-carbon double bonds in the cured film or the curable composition that gives rise to it (hereinafter sometimes abbreviated as "SiH / Vi ratio") differs at the interface between the two cured films or their precursors (including uncured / semi-cured coated states). Conversely, if the SiH / Vi ratios of both films are the same, the reaction of the curing-reactive functional groups at the interface may not be promoted, resulting in insufficient chemical bonding.

[0037] Preferably, when using curable organopolysiloxane compositions (I) and (II) having different compositions, the SiH / Vi ratio in composition (I) is greater than 1.0 mol and less than 2.0 mol (i.e., SiH excess), and the SiH / Vi ratio in composition (II) is greater than 0.5 mol and less than 1.0 mol (i.e., SiH deficiency), thereby promoting the reaction between the common curing reactive functional groups at the interface of the cured film obtained by curing both compositions, and forming a strong chemical bond. Note that the SiH / Vi ratio of compositions (I) and (II) is [SiH / Vi] II / [SiH / Vi] I The value of is preferably in the range of 0.33 to 0.85, particularly preferably in the range of 0.50 to 0.75, or 0.58 to 0.67. The SiH-excess composition (I) may be the dielectric layer and the SiH-deficient composition (II) may be the electrode layer, but the reverse (composition (I): electrode layer, composition (II): dielectric layer) may also be possible, and is not particularly limited.

[0038] In the present invention, a strong chemical bond is preferably formed between the electrode layer and the organopolysiloxane cured film that is the dielectric layer. Therefore, when the above composition (I) provides the dielectric layer and the composition (II) provides the electrode layer, the difference in composition is determined not only by the SiH / Vi ratio but also by the presence or absence of conductive fine particles. Specifically, the composition (II) that forms the electrode layer contains conductive fine particles, and its SiH / Vi ratio ([SiH / Vi] Elec ) is 0.5 mol or more and 1.0 mol or less, preferably 0.6 mol or more and 0.9 mol or less, more preferably 0.7 mol or more and 0.8 mol or less, and the composition (I) for forming the dielectric layer does not contain conductive fine particles, and its SiH / Vi ratio ([SiH / Vi] DEAP ) for [SiH / Vi] Elec / [SiH / Vi] DEAP It is particularly preferable that the value of is in the range of 0.33 to 0.85, 0.50 to 0.75, or 0.58 to 0.67. That is, it is particularly preferable that the composition forming the dielectric layer has a certain degree of excess SiH.

[0039] 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, and the complex is preferably 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 that promote the hydrosilylation reaction.

[0040] Furthermore, the hydrosilylation catalyst of component (C) may 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 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.

[0041] 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 ~100J / cm 2 It is preferable that the range is within the range of

[0042] 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), trimethyl(3,5-heptamethylcyclopentadienyl)trimethylplatinum(IV), Examples of suitable platinum 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.

[0043] The amount of component (C) used is an effective amount, and is not particularly limited, as long as it 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 in the range of 0.1 to 500 ppm, based on the sum of components (A) to (C) (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.

[0044] [Use of functional fillers and the function of cured films] In the present invention, the laminated cured organopolysiloxane films are obtained by curing curable organopolysiloxane compositions having different compositions, and it is preferable to incorporate a functional filler to achieve this function. In particular, the cured organopolysiloxane film serving as the dielectric layer differs significantly in composition not only by the preferred SiH / Vi ratio described above, but also by the absence of conductive fine particles, unlike the cured organopolysiloxane film serving as the electrode layer. Generally, the curable organopolysiloxane composition providing the cured film serving as the electrode layer preferably contains (E) conductive fine particles, while the curable organopolysiloxane composition providing the cured film serving as the dielectric layer preferably contains (F) a reinforcing filler, but does not contain conductive fine particles and may optionally further contain a highly dielectric functional group. The functional filler may be surface-treated for hydrophobicity. The surface treatment agent for hydrophobization includes at least one surface treatment agent selected from the group consisting of organotitanium compounds, organosilicon compounds, organozirconium compounds, organoaluminum compounds, and organophosphorus compounds.

[0045] [(E) Conductive fine particles] The conductive fine particles are not particularly limited as long as they can impart conductivity to the organopolysiloxane cured film, and a cured film containing them can be suitably used as an electrode layer. Note that electrode layers containing conductive fine particles have been proposed, for example, in International Patent Publication WO2014 / 105959 filed by the present applicant.

[0046] Specific examples include conductive carbons such as conductive carbon black, graphite, and vapor-grown carbon (VGCF); metal powders such as platinum, gold, silver, copper, nickel, tin, zinc, iron, and aluminum; antimony-doped tin oxide, phosphorus-doped tin oxide, acicular titanium oxide coated with tin oxide / antimony, tin oxide, indium oxide, antimony oxide, zinc antimonate; pigments in which the surface of carbon or graphite whiskers is coated with tin oxide or the like; pigments in which titanium dioxide particles are coated with at least one conductive metal oxide selected from the group consisting of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), phosphorus-doped tin oxide, and nickel oxide; and conductive pigments containing tin oxide and phosphorus on the surface, which may be treated with various surface treatment agents. These may be used alone or in combination of two or more. Furthermore, in order to disperse these conductive fine particles uniformly in the curable organopolysiloxane composition, they may be kneaded in advance with some or all of component (A) or component (B) used in the composition, and then incorporated into the curable organopolysiloxane composition in the form of a compound.

[0047] Furthermore, the conductive inorganic fine particles may be fibers such as glass fibers, silica alumina fibers, alumina fibers, and carbon fibers, needle-shaped reinforcing materials such as aluminum borate whiskers and potassium titanate whiskers, and inorganic fillers such as glass beads, talc, mica, graphite, wollastonite, and dolomite, the surfaces of which are coated with a conductive material such as a metal.

[0048] [(F) Reinforcing filler] The curable organopolysiloxane composition that provides the cured film that is the dielectric layer preferably contains reinforcing microparticles or composites thereof that have been surface-treated with one or more organosilicon compounds and have different average BET specific surface areas, within a certain range relative to the sum of the components in the composition that form non-volatile solids upon a curing reaction.

[0049] 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, such as 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., which may be treated with one or more organosilicon compounds as described below. There are no particular limitations on the shape of the fine particles, and any shape, such as particulate, plate-like, needle-like, or fibrous, may be used.

[0050] 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, of either hydrophilic or hydrophobic nature. 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.

[0051] In the present invention, the reinforcing filler used in the dielectric layer is (F1) Surface-treated with one or more organic silicon compounds, with an average BET specific surface area of ​​100m 2 / g or more of reinforcing fine particles or composites thereof (F2) Surface-treated with one or more organic silicon compounds, with an average BET specific surface area of ​​10 to 100 m 2 / g of reinforcing microparticles or composites thereof, and The mass ratio of component (F1) to component (F2) is in the range of 50:50 to 99:1, may be in the range of 70:30 to 97:3, and is preferably in the range of 70:30 to 95:5. If the mass ratio is outside this range, the viscosity of the curable organopolysiloxane composition before curing may increase, and the mechanical strength and dielectric breakdown strength after curing may decrease.

[0052] The incorporation of the reinforcing fillers (components (F1) and (F2)) into the composition increases the mechanical strength and dielectric breakdown strength of the organopolysiloxane cured product obtained by curing the curable organopolysiloxane composition of the present invention. The amount of these fillers, as the sum of components (F1) and (F2), based on the sum of the components in the composition that form nonvolatile solids upon curing reaction, is within the range of 10 to 40 mass%, or may be within the range of 15 to 35 mass%, with the range of 15 to 30 mass% being particularly preferred. If the upper limit of the above mass% range is exceeded, it may be difficult to apply the composition in a uniform, thin film form. If the mass% range is below the lower limit of the above mass% range, the cured physical properties of the curable organopolysiloxane composition may be insufficient.

[0053] The reinforcing fillers (components (F1) and (F2)) 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 uniformly dispersed at a high filling rate in organopolysiloxane compositions. Furthermore, an increase in the viscosity of the composition is suppressed, improving moldability.

[0054] 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.

[0055] 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.

[0056] 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 1.0 part by mass or more, 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 (F1) and (F2) of 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) is contained in part or all of component (A) or component (B). 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 organopolysiloxane composition, a group where p=1, i.e., a trifluoropropyl group, is preferred. In this case, the weight ratio of the treatment component derived from hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane fixed to the filler surface is 0 to 10, preferably 0 to 5. 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.

[0057] [Other functional fillers] In the curable organopolysiloxane 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 the function as a reinforcing filler.

[0058] Preferred examples of dielectric inorganic fine particles include one or more inorganic fine particles selected from the group consisting of titanium oxide, barium titanate, strontium titanate, lead titanate zirconate, and composite metal oxides in which a portion 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. It is particularly preferred that at least a portion of the dielectric inorganic fine 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 fine particles is 20,000 nm (20 μm), but 10,000 nm (10 μm) is more preferred in consideration of the processability into thin films for transducers, as described below. Use of the dielectric inorganic fine particles may further improve the mechanical properties and / or electrical properties, particularly the relative dielectric constant, of the organopolysiloxane cured product.

[0059] 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 18There are no limitations on the inorganic 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 spherical, plate-like ceramic 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. The incorporation of insulating inorganic fine particles into the composition can increase the mechanical strength and dielectric breakdown strength of the organopolysiloxane cured product, and may also result in an increase in the dielectric constant.

[0060] Examples of thermally conductive inorganic fine particles that can be used in the present invention include metal oxide particles such as magnesium oxide, zinc oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, and silver oxide, and inorganic compound particles such as aluminum nitride, boron nitride, silicon carbide, titanium carbide, diamond, and diamond-like carbon, with zinc oxide, boron nitride, silicon carbide, and silicon nitride being preferred. By incorporating one or more of these thermally conductive inorganic fine particles into the composition, it is possible to increase the thermal conductivity of the organopolysiloxane cured product.

[0061] 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 approximately 500 nm or less, the average primary particle size can be measured by measuring the particle size through microscopic observation using a transmission electron microscope (TEM), field-emission transmission electron microscope (FE-TEM), scanning electron microscope (SEM), field-emission scanning electron microscope (FE-SEM), or the like, and calculating the average value. On the other hand, when the average particle size is approximately 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.

[0062] [Use of solvents] The curable organopolysiloxane composition of the present invention can be subjected to a curing reaction as is. However, when the composition or some of its components (e.g., organopolysiloxane resin) are solid or viscous liquid, an organic solvent can be used as needed to improve its miscibility and ease of handling. In particular, when the curable organopolysiloxane composition of the present invention is applied to a film, the viscosity can be adjusted using a solvent to achieve an overall viscosity of 100 to 50,000 mPa·s. When diluted with a solvent, the amount can be 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 solvent content of the composition of the present invention can be 0 parts by mass, which is preferable as a solvent-free composition. In particular, by selecting a polymer with a low degree of polymerization for the curable organopolysiloxane composition of the present invention, a solvent-free design is possible. This eliminates residual fluorine-based solvents, organic solvents, etc. in the cured film, thereby eliminating environmental impact and the impact of solvents on electronic devices. The composition may be 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 (100 parts by mass) of the components (A) to (C). 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.

[0063] Preferably, such organic solvent is (E1) organic polar solvent, (E2) a low molecular weight siloxane solvent, and (E3) Halogenated solvents The organic solvent is one or more organic solvents selected from the group consisting of hexamethyldisiloxane and octamethyltrisiloxane, or a mixture thereof, preferably having a boiling point of 80°C or higher but lower than 200°C. Mixtures of different organic solvents, either of the same or different types, in any ratio may also be used. Preferably, the organic solvent comprises at least one low molecular weight siloxane solvent selected from hexamethyldisiloxane and octamethyltrisiloxane, or a mixture thereof, which are commercially available from Dow Silicones Corporation under the names OST-10, OST-20, and OST-2. Furthermore, when the fluoroalkyl group content in the curable elastomer composition is high, optionally using these low molecular weight siloxane solvents in combination with the above-mentioned halogen-based solvents is also encompassed within a preferred embodiment of the present invention.

[0064] [Overall viscosity] The curable organopolysiloxane composition used in the present invention has a shear rate of 10.0 (S -1 The overall viscosity measured by the ion exchange method is preferably in the range of 5 to 500,000 mPa·s, and particularly preferably in the range of 1,000 to 10,000 mPa·s. To achieve a preferred viscosity range, the amount of the organic solvent used can be adjusted, but a low-solvent or solvent-free (i.e., solventless) composition can also be used. 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, and this is preferred. [Thixotropy ratio] The curable organopolysiloxane composition of the present invention preferably has excellent flowability and does not exhibit thixotropic behavior. This makes it possible to achieve low overall viscosity and excellent uniform application properties. Specifically, the composition has a shear rate of 0.1 (S -1 The viscosity of the entire composition measured at a shear rate of 10.0 (S -1 )(S -1 It is particularly preferable that the thixotropy ratio, which is the ratio of the viscosity of the entire composition measured by the method (2) to the viscosity of the entire composition measured by the method (3), is 10.0 or less. [Solid content] In the curable organopolysiloxane composition of the present invention, the content of components that cure to form a non-volatile solid organopolysiloxane cured product (sometimes simply referred to as "solid 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 entire composition.

[0065] [Introduction of dielectric functional groups] When the organopolysiloxane cured film according to the present invention is used as an electroactive film (e.g., a dielectric film) for a transducer such as an 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 such 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.

[0066] The introduction of the highly dielectric functional group can be achieved by using an organopolysiloxane 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 standpoint of improving miscibility with the curable composition and the dielectric constant of the cured product, it is preferred that 10 mol % or more, preferably 20 mol % or more, and more preferably 40 mol % or more of all substituents on silicon atoms in the organopolysiloxane or organohydrogenpolysiloxane of component (A) or component (B) be substituted with the highly dielectric functional group.

[0067] 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. Preferably, halogen atoms and halogen atom-containing groups containing a fluorine atom are used.

[0068] In the present invention, the highly dielectric functional group (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) 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. Of these, the group where p=1, i.e., trifluoropropyl, is preferred from the viewpoints of dielectric properties, economy, ease of production, and moldability of the resulting curable organopolysiloxane composition.

[0069] In addition to the above-described components, other components may be added to the curable organopolysiloxane composition of the present invention as needed, provided that the purpose of the present invention is not impaired. Examples of other components include hydrosilylation reaction inhibitors, mold release agents, insulating additives, adhesion improvers, heat resistance improvers, fillers, pigments, and various other conventionally known additives. Specific examples of these are similar to those proposed in, for example, International Patent Publication WO 2014 / 105959.

[0070] The curable organopolysiloxane composition of the present invention can be prepared by uniformly mixing the curable organopolysiloxane and the curing reaction accelerator, preferably the above-mentioned components (A) to (C), 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.

[0071] The order in which the components are mixed is not particularly limited as long as they do not harden during mixing. If the mixture is not to be used immediately after mixing, the crosslinking agent (e.g., component (B)) and the curing reaction accelerator (e.g., component (C)) can be stored in multiple containers so that they are not in the same container, and the components in all containers can be mixed immediately before use.

[0072] The curing reaction of the curable organopolysiloxane 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 organopolysiloxane film using an industrial production process, the composition is typically heated or exposed to active energy rays. The temperature for the thermal curing reaction 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 time required for the curing reaction depends on the structures of the above components (A), (B), and (C), but is typically 1 second to 3 hours. A cured product can generally be obtained by maintaining the temperature within the range of 90 to 180°C for 10 seconds to 30 minutes. The film production method will be described later.

[0073] 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.

[0074] [Method of manufacturing laminate] The laminate according to the present invention has a structure in which two or more layers of cured organopolysiloxane films having different compositions are laminated together, and the laminated cured organopolysiloxane films are chemically bonded at their interfaces. Step I: A step of obtaining a cured organopolysiloxane film by curing one type of curable organopolysiloxane composition out of two or more types of curable organopolysiloxane compositions that share at least a portion of the functional groups involved in the curing reaction but differ in composition, into a film form; Step II: Simultaneously with or after Step I, a curable organopolysiloxane composition different from that used in Step I is applied in the form of a film onto the organopolysiloxane cured film obtained in Step I or onto a precursor thereof, and a curing reaction is allowed to proceed, thereby laminating a different organopolysiloxane cured film onto the organopolysiloxane cured film obtained in Step I. The laminate can be obtained by a method for manufacturing a laminate comprising the steps of:

[0075] Here, it is preferable that the organopolysiloxane cured film in the above step I is the dielectric layer and the organopolysiloxane cured film in the above step II is the electrode layer, but the reverse may also be true.

[0076] In Step I or Step II, the method for applying the curable organopolysiloxane 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 or the like, reverse roll coating, air knife coating, curtain coating using a curtain flow coater or the like, comma coating, Mayer bar coating, and other known methods used for forming a cured layer. The curable organopolysiloxane composition of the present invention can also be applied in multiple layers.

[0077] The laminate according to the present invention 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 it is completely cured) of its precursor, a curable organopolysiloxane composition, in an uncured or semi-cured state, with the cured organopolysiloxane film after or before it is cured, 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 multiple thin layers of curable curable organopolysiloxane composition, and then completely curing the entire film using a means such as heating.

[0078] A preferred example of a method for producing a laminate includes a step of applying a curable organopolysiloxane composition different from that used in step I in the form of a film in step II, and then laminating another organopolysiloxane cured film or a precursor thereof on the coating layer of the curable organopolysiloxane composition while the coating layer is in an uncured or semi-cured state, and optionally repeating a similar step two or more times to form a laminate in which an organopolysiloxane cured film or a precursor thereof and one or more coating layers of the curable organopolysiloxane composition in an uncured or semi-cured state are laminated, and then completely curing the coating layer of the curable organopolysiloxane composition different from that used in step I, thereby laminating a different organopolysiloxane cured film on the organopolysiloxane cured film used in step I. In this case, for example, a curable organopolysiloxane composition containing conductive fine particles is applied in the form of a film onto an organopolysiloxane cured film that is a dielectric layer, and in an uncured or semi-cured state, another organopolysiloxane cured film that is a dielectric layer is laminated thereon, and the same procedure is repeated thereafter to form a dielectric layer. Dielectric layer (cured film) / Uncured or semi-cured electrode layer / Dielectric layer (cured film) / Uncured or semi-cured electrode layer / After forming such a laminate precursor, the entire structure is cured by heating or the like, thereby obtaining a laminate in which cured dielectric layers and electrode layers are alternately stacked and the interfaces of both layers are chemically bonded.

[0079] 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.

[0080] The organopolysiloxane 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 because it has a structure in which the electrode layers are firmly bonded, it is particularly useful for actuator applications that operate under high voltage. [Example]

[0081] The present invention will be described below with reference to examples, but is not limited to these examples. The following compounds were used in the examples and comparative examples shown below. The physical properties of each cured film were measured by the following methods. [Shore A hardness] Cured films were prepared by heating each curable organopolysiloxane composition for 1 hour at a curing temperature of 150°C for the electrode layer (ELEC) and at a curing temperature of 110°C for the dielectric layer (DEAP). The thickness of the cured samples was approximately 6 mm. The Shore A hardness of each of the resulting cured films was measured using a DD2 (manufactured by Kobunshi Keiki Co., Ltd.) according to JIS K 6249. The results are shown in Table 1. Insufficient curing or excessive softness were deemed "unmeasurable" for various reasons. Elasticity Modulus The elastic modulus of each curable organopolysiloxane composition used to form the electrode layer was measured using a viscoelasticity measuring device (Anton Paar, model MCR302). Using a Peltier element temperature control system and a 15 mm diameter parallel plate, the sample was set to a thickness of 500 μm. The temperature was raised from 25°C to 120°C over 2.8 minutes, and then maintained at 120°C for curing. The storage modulus (G') 60 minutes after the start of the temperature rise was taken as the elastic modulus and is shown in Table 1. [Volume resistivity measurement] Measurements were taken at room temperature using a measuring device called Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). A PSP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used as the probe. As described below, measurements were taken on at least 14 electrodes on an electrode layer fabricated on an organopolysiloxane cured film, which is a dielectric layer. The average value of the stable readings, as well as the value calculated using the electrode thickness and a correction factor, are shown in Table 1.

[0082] Component (a1): Dimethylsiloxane polymer with both ends blocked with vinyldimethylsiloxy groups (vinyl group content: 0.24% by mass, siloxane polymerization degree: 300) Component (a2): Both ends blocked with vinyldimethylsiloxy groups, 3,3,3-trifluoropropylmethyl, dimethylsiloxane copolymer (vinyl group content: 0.26% by mass, siloxane polymerization degree: 193) Component (b1): Both ends blocked with trimethylsiloxy groups, dimethylsiloxy-methylhydrosiloxy-siloxane copolymer (silicon-bonded hydrogen content: 0.71% by mass) Component (b2): Dimethylsiloxane polymer with both ends blocked by dimethylhydrosiloxy groups (silicon atom-bound water content: 0.02% by mass) Component (b3): ​​Both ends blocked with trimethylsiloxy groups, dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane-methylhydrogensiloxane copolymer (silicon-bonded hydrogen content: approximately 0.23% by mass) Component (b4): Dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane copolymer, both ends blocked with dimethylhydrosiloxy groups (silicon-bonded hydrogen content: approximately 0.014% by mass) Component (c1): A solution of platinum-1,3-divinyl 1,1,3,3-tetramethyldisiloxane complex in a dimethylsiloxane polymer terminated at both ends with vinyldimethylsiloxy groups (platinum concentration: approximately 0.6% by mass) Component (d): Acetylene black (manufactured by Denka, 100% pressed product) · Component (e1): 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 m2 / g) · Component (e2): 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 m2 / g) · Component (e3): Fumed silica treated with hexamethyldisilazane (Product name before treatment: Aerosil 200, BET specific surface area 200m 2 / g) · Component (e4): Fumed silica treated with hexamethyldisilazane (Product name before treatment: Aerosil 50, BET specific surface area 50m 2 / g) · Component (f1): 1-Ethynyl-1-cyclohexanol · Component (f2): 1,3,5,7-Tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane

[0083] [Curable organopolysiloxane composition for providing electrode layers according to Examples 1 to 3 and Comparative Examples 1 to 7] As a liquid curable organopolysiloxane composition, the above components were blended in weight % as shown in Table 1. At that time, per mole of unsaturated hydrocarbon groups in the composition, the silicon-bonded hydrogen atoms (Si-H) of component (b) were in the amounts shown in Table 1: (SiH / Vi) ELEC and used. In mixing each component, materials other than component (c1) which is a catalyst were mixed with a rotation-revolution mixer (Product name ARE-310, manufactured by Shinchi Co., Ltd.), and after adding component (c1), they were further mixed and prepared with a rotation-revolution mixer under vacuum. Various physical properties are also shown in Table 1.

[0084] [Curable organopolysiloxane composition 1 for providing dielectric layers according to Examples 1, 3 and Comparative Examples 1 to 7]<Used in Example 1 of DEAP sheet> As a liquid curable organopolysiloxane composition, the above component (a2) is blended and prepared to be 68.34% by mass, component (b3) is 5.06% by mass, component (b4) is 5.06% by mass, component (c1) is 0.10% by mass, component (e1) is 18.69% by mass, component (e2) is 2.46% by mass, and component (f2) is 0.28% by mass. At that time, per mole of unsaturated hydrocarbon groups in the composition, the silicon atom-bonded hydrogen atoms (Si-H) of component (b): (SiH / Vi) DEAP was used in an amount such that it was about 1.2 moles. The hardness of the obtained organopolysiloxane cured product was Shore A 37.

[0085] [Curable organopolysiloxane composition 2 for providing a dielectric layer according to Example 2]<Used in DEAP sheet Example 2> As a liquid curable organopolysiloxane composition, the above component (a1) was blended and prepared to be 70.59% by mass, component (b1) was 0.99% by mass, component (b2) was 3.83% by mass, component (c1) was 0.10% by mass, component (e3) was 20.10% by mass, component (e4) was 4.35% by mass, and component (f1) was 0.04% by mass. At that time, per mole of unsaturated hydrocarbon groups in the composition, the silicon atom-bonded hydrogen atoms (Si-H) of component (b): (SiH / Vi) DEAP was used in an amount such that it was about 1.2 moles. The hardness of the obtained organopolysiloxane cured product was Shore A 39.

[0086] [Formation of dielectric layer (film) in Examples / Comparative Examples] A curable organopolysiloxane composition for providing a dielectric layer was applied in a thin film form onto a PET substrate provided with a release layer (release liner) using a coater, and cured in an oven at 110 °C for 60 minutes to produce a film with a thickness of 0.1 mm.

[0087] [Formation of electrode layer in Examples / Comparative Examples] The curable organopolysiloxane composition that produces the electrode layer shown in Table 1 was diluted with a low-molecular-weight siloxane solvent (OST-20, manufactured by Dow Silicones) to a concentration of 10 wt% electrode material. A circular mask was attached to one side of the 0.1 mm-thick dielectric layer (film) prepared above, and the diluted solution was sprayed onto the mask to form 16 circular electrodes with a diameter of 13.5 mm. After application, the mixture was left at 60°C under vacuum for approximately 12 hours. A PET substrate with a release layer (release liner) was then placed on the electrode and pressed at room temperature. The PET substrate film was peeled off, and the mixture was heated at 120°C for 60 minutes to form electrodes with a thickness of 10-13 μm.

[0088] [Evaluation of adhesion between dielectric layer and electrode layer: peel test] Using the method described above, tape (manufactured by Nitto Denko, product name: Nitoflon (registered trademark) 0.08) was applied to the circular electrode layer formed on one side of the dielectric layer (film), and after leaving it at room temperature for 10 minutes, it was peeled off to evaluate the adhesion between the dielectric layer and the electrode layer. If the electrode layer was not peeled off with the tape and most of the electrode layer remained on the dielectric layer (film), it was rated as "usable." If the electrode layer was peeled off with the tape, it was rated as "unusable," and this was entered in Table 1. Note that if the electrode layer was peeled off from the dielectric layer surface and transferred to the tape, it is considered that sufficient chemical bonding was not formed at the interface between the electrode layer and the dielectric layer surface, and the adhesion and bonding strength were weak.

[0089] [Table 1]

[0090] In the dielectric layer / electrode layer of Examples 1 to 3, the electrode layer did not peel off in the peel test, and the two had a structure in which they were firmly adhered to each other. On the other hand, in Comparative Examples 1 to 7, in which the SiH / Vi ratios of both layers were not designed to be within the preferred range, the electrode layer peeled off in the peel test, and it is considered that the adhesion and followability between the two were insufficient.

Claims

1. A laminate having a structure in which two or more layers of organopolysiloxane cured films obtained by curing curable organopolysiloxane compositions, each having a different composition but having at least a portion of the functional groups participating in the curing reaction in common, are laminated, and the laminated organopolysiloxane cured films are chemically bonded at their interfaces, A curable organopolysiloxane composition that provides a cured organopolysiloxane film upon curing, (A) an organopolysiloxane having a curing reactive group containing at least two carbon-carbon double bonds in the molecule; (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, in an amount such that the number of silicon-bonded hydrogen atoms in this component is 0.5 to 2.5 moles per mole of total carbon-carbon double bonds in the composition; and (C) an effective amount of a hydrosilylation catalyst; and the laminated cured organopolysiloxane film has a structure in which the components (A) and (B) are chemically bonded at their interface by a hydrosilylation reaction between the components (A) and (B), and further the laminated cured organopolysiloxane films are obtained by curing curable organopolysiloxane compositions having different compositions, one of the organopolysiloxane cured films contains conductive fine particles, and the molar amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane component, [SiH / Vi]Elec, per mole of the total number of carbon-carbon double bonds in the composition is 0.5 moles or more and 1.0 moles or less; a laminate in which the other organopolysiloxane cured film is a dielectric layer, does not contain conductive fine particles, the amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane component, [SiH / Vi] DEAP, per mole of the total number of carbon-carbon double bonds in the composition is greater than 1.0 mole and not more than 2.0 moles, and the value of [SiH / Vi] Elec / [SiH / Vi] DEAP is in the range of 0.33 to 0.

85.

2. At least one of the laminated organopolysiloxane cured films has a volume resistivity of 10 ２ The laminate according to claim 1, having a resistivity of Ω·cm or less.

3. At least one of the laminated organopolysiloxane cured films has a shear storage modulus (G') at 120°C of 5.0 x 10 ４ ~1.5 x 10 ５ The laminate according to claim 1 or claim 2, wherein the modulus is in the range of Pa.

4. 2. The laminate according to claim 1, wherein the conductive fine particles are fine particles containing at least one type of conductive carbon selected from the group consisting of conductive carbon black, graphite, and vapor grown carbon (VGCF).

5. A transducer member comprising the laminate according to any one of claims 1 to 4.

6. A transducer comprising the laminate according to any one of claims 1 to 4.

7. An electronic component or a display device comprising the laminate according to any one of claims 1 to 4.

8. Step I: A step of obtaining a cured organopolysiloxane film by curing one type of curable organopolysiloxane composition out of two or more types of curable organopolysiloxane compositions that share at least a portion of the functional groups involved in the curing reaction but differ in composition, into a film form; Step II: Simultaneously with or after Step I, a curable organopolysiloxane composition different from that used in Step I is applied in the form of a film onto the organopolysiloxane cured film obtained in Step I or onto a precursor thereof, and a curing reaction is allowed to proceed, thereby laminating a different organopolysiloxane cured film onto the organopolysiloxane cured film obtained in Step I. The method for producing a laminate according to any one of claims 1 to 4, comprising:

9. 9. The method for producing a laminate according to claim 8, wherein the cured organopolysiloxane film produced in step I is a dielectric layer, and the cured organopolysiloxane film produced in step II is an electrode layer.

10. 10. The method for producing a laminate according to claim 8 or 9, wherein in step II, a curable organopolysiloxane composition different from that used in step I is applied in the form of a film, and then, while the coating layer of the curable organopolysiloxane composition is in an uncured or semi-cured state, another organopolysiloxane cured film or a precursor thereof is laminated on the coating layer. This similar process is optionally repeated two or more times to form a laminate in which an organopolysiloxane cured film or a precursor thereof and one or more coating layers of the curable organopolysiloxane composition in an uncured or semi-cured state are laminated, and then the curing reaction of the coating layer of the curable organopolysiloxane composition different from that used in step I is allowed to proceed to completion and cured, thereby laminating a different organopolysiloxane cured film on the organopolysiloxane cured film used in step I.

11. A method for forming an electrode layer in a transducer member, comprising the method for producing a laminate according to any one of claims 8 to 10.

Images