Laminated body composed of cured polyorganosiloxane film, its use and method for producing the same

Abstract

The present invention provides a laminate, its use and manufacturing method, wherein the laminate is a laminate formed by stacking two or more layers of polyorganosiloxane cured films obtained by curing curable polyorganosiloxane compositions having different compositions due to different required functions such as dielectric layers and electrode layers, and the problem of peeling and defects caused by insufficient bonding strength and followability at the interface of the cured films constituting the laminate is not easy to occur. A laminate having a structure in which two or more layers of polyorganosiloxane cured films with different compositions are stacked, and the cured films after stacking have a structure formed by chemical bonding at their interface, and at least a portion of the functional groups participating in the curing reaction of the two or more polyorganosiloxane cured films are common. Preferably, the compositions all contain hydrosilylation-reactive groups, and the SiH / Vi ratios in the compositions are different, and the cured films after stacking have a structure formed by chemical bonding at their interface through a hydrosilylation reaction.

Description

Technical Field

[0001] The present invention relates to a laminated body formed by laminating at least two polyorganosiloxane cured film layers, its use, and its production method and production apparatus. Background Art

[0002] Cured polyorganosiloxanes with a polysiloxane skeleton exhibit excellent transparency, electrical insulation, heat resistance, and cold resistance. They can be improved in electrical activity as desired by introducing high-dielectric functional groups such as fluoroalkyl groups. They can also be easily processed into films or sheets. Consequently, 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 polyorganosiloxanes are classified according to their curing mechanism into hydrosilylation-curable, condensation-curable, and peroxide-curable types. In particular, cured polyorganosiloxane films using hydrosilylation-curable curable polyorganosiloxane compositions are widely used because they cure rapidly by standing at room temperature or heating and do not produce byproducts.

[0003] On the other hand, when using cured polyorganosiloxane films as electronic materials for touch panels and electronic components for display devices, particularly transducer materials for sensors and actuators, it is necessary to provide an electrode layer on the electroactive film serving as the dielectric layer. For example, Non-Patent Documents 1 and 2 propose forming an electrode layer having excellent followability to the dielectric layer by adding a conductive filler to a highly flexible organosilicone elastomer matrix.

[0004] However, when an electrode layer containing a conductive filler is formed on a cured polyorganosiloxane film serving as an electroactive membrane, interfacial delamination between the dielectric layer and the electrode layer may occur, particularly with displacement of the dielectric layer (e.g., expansion and contraction of an actuator, etc.), leading to poor electrical conduction and reduced reliability of the actuator. The applicants of this case and others proposed, in Patent Document 3 and others, coating a curable polyorganosiloxane composition containing a conductive filler on a cured polyorganosiloxane film serving as an electroactive membrane, thereby forming an electrode layer serving as the cured polyorganosiloxane film on the electroactive membrane (= dielectric layer). However, this method does not completely solve the problem of delamination associated with insufficient followability of the electrode surface in transducer materials used in actuators, etc., and there is still room for improvement.

[0005] Prior art literature

[0006] Non-patent literature

[0007] Non-patent literature 1: Kujawski, M.; Pearse, JD; Smela, E. Carbon 2010, 48, 2409-2417.

[0008] Non-patent document 2: Rosset, S.; Shea, HR Appl. Phys. A 2013, 110, 281-307.

[0009] Patent Literature

[0010] Patent Document 1: International Patent Publication No. WO2014 / 105959 Summary of the Invention

[0011] Problems to be solved by the invention

[0012] The present invention has been made to solve the above-mentioned problems, and its object is to provide a laminated body comprising two or more cured polyorganosiloxane films obtained by curing curable polyorganosiloxane compositions having different compositions due to different required functions, such as a dielectric layer and an electrode layer, and a use and method for producing the laminated body, wherein the laminated body is less likely to cause problems such as peeling and defects at the interfaces of the cured films constituting the laminated body due to insufficient adhesive strength and followability.

[0013] Solutions for solving problems

[0014] The present inventors conducted intensive research and found that the above-mentioned problems can be solved by a laminate having a structure in which two or more layers of cured polyorganosiloxane films having different compositions are laminated, wherein the laminated cured polyorganosiloxane films have a structure in which chemical bonds are formed at their interfaces, and the two or more cured polyorganosiloxane films are obtained by curing a curable polyorganosiloxane composition having at least a portion of the functional groups participating in the curing reaction in common, thereby completing the present invention.

[0015] Here, at least one of the stacked cured polyorganosiloxane films may be an electrode layer formed by curing a composition containing conductive fine particles; the other layer may be a dielectric layer formed by curing a composition containing dielectric functional groups or containing no conductive fine particles. Furthermore, preferably, the compositions having different compositions providing the stacked cured polyorganosiloxanes both contain curing-reactive groups that cure via a hydrosilylation reaction, and the amount of silicon-bonded hydrogen atoms in this component differs per 1 mol of the total carbon-carbon double bonds in the compositions, so that the stacked cured polyorganosiloxane films have a structure formed by chemical bonding via a hydrosilylation reaction at their interfaces.

[0016] Beneficial effects

[0017] The present invention provides a laminate comprising two or more layers of cured polyorganosiloxane films having different compositions prior to curing, which is alternatingly laminated. The laminate is less likely to experience delamination or defects at the interfaces of the cured films due to insufficient adhesive strength and compliant properties. In particular, the present invention provides a laminate comprising alternating layers of cured polyorganosiloxane films that are cured by a hydrosilylation reaction and function as electrode layers and dielectric layers, and its use and production method are excellent. The laminate is less likely to experience delamination or electrical conduction failure at the interfaces of the films, and exhibits excellent reliability in applications such as actuators. DETAILED DESCRIPTION

[0018] [Laminated body]

[0019] The laminate of the present invention is characterized in that it has a structure in which two or more layers of polyorganosiloxane cured films having different compositions are stacked, and the stacked polyorganosiloxane cured films have a structure formed by chemical bonding at their interfaces, and the two or more layers of the polyorganosiloxane cured films are obtained by curing a curable polyorganosiloxane composition having at least a portion of the functional groups participating in the curing reaction in common. The polyorganosiloxane cured film can be stacked in three or more layers, as long as its compositions before curing are different from each other, or three or more different polyorganosiloxane cured films can be stacked. The laminate of the present invention can have a multilayer structure of two or more layers, as long as at least a portion thereof has a structure formed by stacking two polyorganosiloxane cured films having different compositions, and it is not a problem for other stacked portions to have a structure formed by stacking the same type of polyorganosiloxane cured film (for example, a partial structure in which a cured film having the function of a dielectric layer is stacked in order to increase the thickness). In particular, a structure in which two types of cured polyorganosiloxane films having different compositions (for example, cured films serving as dielectric layers and electrode layers) are alternately laminated is particularly preferred in part or all of the laminate.

[0020] As an example, when polyorganosiloxane cured films L1, L2, L3, etc., having different compositions before curing, are stacked, and their interfaces are represented by " / ", it is preferred to illustrate the overall or partial configuration of the stack as described below. It should be noted that []n refers to a stacked structure in which the structure within the brackets is repeated n times or more, where n is independently a number greater than 0. Furthermore, " / " indicates that the layers are opposed in the stacking direction of the stack (generally, the thickness direction perpendicular to the surface of each functional layer).

[0021] 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.

[0022] In the case where the laminate of the present invention is used for transducer (sensor, actuator, generator) purposes, it is preferred that the polyorganosiloxane cured material film as the electrode layer is stacked on at least one side of the polyorganosiloxane cured material film as the dielectric layer, and the polyorganosiloxane cured material film after stacking has a structure formed by chemical bonding at its interface. Specifically, in the composition of the above-mentioned laminate, L1 is the polyorganosiloxane cured material film as the dielectric layer, and L2 is the polyorganosiloxane cured material film as the electrode layer, preferably having a structure represented by L2 / [L1 / L2]n / L1 / L2, these layers are alternately stacked, and the entire or partial structure of the electrode layer is configured on the outside. It should be noted that the dielectric layer as L1 can be replaced by a multilayer structure of one or more layers such as L1 / [L1 / ]n. Of course, the multilayer dielectric layer can also have a structure formed by chemical bonding at its interface and is preferred.

[0023] Moreover, in addition to the electrode layer, the single-layer or multi-layer dielectric layer, the laminate of the present invention may also have a pressure-sensitive adhesive layer used for the purpose of being arranged in the transducer, and a non-silicone thermoplastic resin layer that may arbitrarily have a peeling surface. In particular, when used as a component for an electronic device, the structure of the laminate can be exemplified by the combination described below. In the present invention, it is preferred that the dielectric layer and the electrode layer, the dielectric layer and the pressure-sensitive adhesive layer, or the electrode layer and the pressure-sensitive adhesive layer have a structure formed by chemical bonding at their interface (" / "). It should be noted that the following combinations are examples and are of course not limited thereto. As shown in some examples, it is also not necessary to have a symmetrical laminate. Moreover, in the examples, the examples of each functional layer are as follows, and " / " has the same meaning as above.

[0024] (L1) A single-layer or multi-layer high dielectric sheet comprising a cured polymer having dielectric functional groups: (EAP).

[0025] (L2) Silicone-based pressure-sensitive adhesive layer: (PSA).

[0026] (L3) Electrode layer: (EL).

[0027] (L4) Non-silicone-based thermoplastic resin layer: (PF).

[0028] Example 1: PSA / EAP / PSA.

[0029] Example 2: PSA / EL / EAP / EL / PSA.

[0030] Example 3: PSA / PF / EAP / PF / PSA.

[0031] Example 4: PSA / EL / PF / EAP / PF / EL / PSA.

[0032] Example 5: PSA / PF / EL / EAP / EL / PF / PSA.

[0033] Example 6: PF / PSA / EL / EAP / EL / PSA / PF.

[0034] Example 7: EL / PSA / EAP / PSA / EL.

[0035] Example 8: PF / PSA / EL / EAP / PF / PSA / EL.

[0036] Example 9: EL / PSA / EAP / EL.

[0037] Example 10: EL / PSA / EAP / EL / PSA.

[0038] Example 11: PF / PSA / EAP / PF.

[0039] Example 12: PF / PSA / EAP / PF / PSA.

[0040] Example 13: EL / PSA / PF / EAP / PF / PSA / EL.

[0041] It should be noted that the laminates in Examples 7 and 13, which have an electrode layer formed on a PSA, can be shipped as peelable laminates containing a separator on the PSA, and then the separator can be peeled off to form an electrode layer on the PSA. Furthermore, the laminates in Examples 6 and 11, in which a non-silicone thermoplastic resin layer forms an outer layer, can be handled as electronic device components containing these resin layers or as peelable laminates having a peelable surface on the inner surface of the laminate of these resin layers.

[0042] In the present invention, a particularly preferred embodiment is a laminate structure in which a single or multiple dielectric layers (EAP) and an electrode layer (EL) are chemically bonded at their interfaces. Furthermore, as represented by (EL / EAP / )nEL, these layers are alternately stacked, with all or part of the electrode layer positioned on the outside. Here, n is a number greater than 1, and any number of layers can be stacked repeatedly, depending on the thickness of the laminate required for a transducer or the like.

[0043] The laminate of the present invention is characterized in that the polyorganosiloxane cured product films with different compositions before curing have a structure formed by chemical bonding at their interfaces. In the present invention, the structure is formed by the reaction of the curing-reactive functional groups contained in each film or its precursor at the interfaces of the films with different compositions before curing. Therefore, at least a part of the functional groups participating in the curing reaction of the above-mentioned polyorganosiloxane cured product films is required to be common. It should be noted that the type of curing reaction described later is not limited and can be one or more reactions. It is particularly preferred that the polyorganosiloxane cured product films after lamination have a structure formed by chemical bonding at their interfaces by a hydrosilylation reaction based on an alkenyl group and a silicon atom-bonded hydrogen atom. It should be noted that such bonding can be preferably achieved by adjusting the content of the silicon atom-bonded hydrogen atom in the composition described later, coating of the curable polyorganosiloxane composition, and a curing manufacturing method or a combination thereof.

[0044] The composition and physical properties of the cured polyorganosiloxane film constituting the laminate are not particularly limited, but at least one of them preferably has a volume resistivity of 10 2 Ω·cm or less, preferably containing conductive fine particles described below (particularly preferably containing at least one conductive carbon fine particle selected from conductive carbon black, graphite, and vapor-grown carbon (VGCF)). Such a conductive cured polyorganosiloxane film is suitable for an electrode layer.

[0045] At least one of the polyorganosiloxane cured films constituting the laminate preferably has a shear storage modulus (G′) of 5.0×10 4 Pa~1.5×10 5 Pa. A cured polyorganosiloxane film having such a shear storage modulus is particularly suitable for an electrode layer.

[0046] As other mechanical properties, the compressive residual strain (%) of the cured polyorganosiloxane film of the present invention is preferably less than 10%, more preferably less than 5%, and particularly preferably 4% or less.

[0047] Furthermore, when the composition providing the polyorganosiloxane cured film of the present invention is heat-molded into a 2.0 mm thick sheet, it can be designed to have the following mechanical properties measured in accordance with JIS K 6249. Compositions providing such properties are particularly suitable for dielectric layers, but are not limited thereto.

[0048] (1) The Young's modulus (MPa) at room temperature can be set to 0.001 MPa to 10 MPa, preferably 0.001 MPa to 2 MPa, and particularly preferably within the range of 0.001 MPa to 1.5 MPa.

[0049] (2) The tear strength (N / mm) can be set to 1 N / mm or more at room temperature, and is particularly preferably in the range of 2 N / mm or more.

[0050] (3) The tensile strength (MPa) can be set to 1 MPa or more at room temperature, and is particularly preferably in the range of 2 MPa or more.

[0051] (4) The elongation at break (%) can be 50% or more, and a particularly preferred range is 100% to 1000%.

[0052] [Polyorganosiloxane cured film]

[0053] The cured polyorganosiloxane material of the present invention is formed by curing a curable polyorganosiloxane composition into a film. The curing reaction mechanism is not particularly limited, but examples include: hydrosilylation curing (cure by alkenyl groups bonding to silicon-bonded hydrogen atoms); dehydration condensation curing and dealcoholization condensation curing (cure by silanol groups and / or silicon-bonded alkoxy groups); peroxide curing (cure by organic peroxides); and free radical curing (cure by high-energy radiation exposure to mercapto groups, etc.). From the perspective of faster overall curing and easier reaction control, hydrosilylation curing, peroxide curing, free radical curing, and combinations thereof are preferred, with hydrosilylation curing and curable polyorganosiloxane compositions being preferred. These curing reactions are carried out by heating, high-energy radiation exposure, or a combination thereof.

[0054] In the present invention, the curable polyorganosiloxane composition that provides the cured polyorganosiloxane film preferably contains at least:

[0055] (A) a polyorganosiloxane having at least two curing reactive groups containing a carbon-carbon double bond in the molecule;

[0056] (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in its molecule, wherein the silicon-bonded hydrogen atoms in this component are present in an amount of 0.5 mol to 2.5 mol per 1 mol of the total amount of alkenyl groups in the composition; and

[0057] (C) an effective amount of a catalyst for the hydrosilylation reaction.

[0058] It should be noted that, in the composition for providing a cured polyorganosiloxane film used as a dielectric layer, the component (A) is more preferably a polyorganosiloxane mixture containing the following components:

[0059] (a1) a linear or branched polyorganosiloxane having alkenyl groups only at the molecular chain ends; and

[0060] (a2) An alkenyl-containing polyorganosiloxane resin having at least one branched siloxane unit in the molecule and a vinyl group (CH2=CH-) content within a range of 1.0% by mass to 5.0% by mass.

[0061] The above-mentioned component (A) is a polyorganosiloxane having a curing reactive group containing a carbon-carbon double bond. Examples thereof include linear, branched, cyclic or resinous (network) polyorganosiloxanes containing a curing reactive group selected from the following groups in the molecule: alkenyl groups having 2 to 20 carbon atoms, such as vinyl groups; and (meth)acryloyl-containing groups, such as 3-acryloyloxypropyl groups and 3-methacryloyloxypropyl groups.

[0062] The polyorganosiloxane as component (A) may also contain a group selected from a monovalent hydrocarbon group that does not have a carbon-carbon double bond in the molecule, a hydroxyl group, and an alkoxy group having 1 to 3 carbon atoms. In addition, with respect to the monovalent hydrocarbon group, a portion of its hydrogen atoms may be substituted by a halogen atom or a hydroxyl group, and when used as a dielectric layer, a dielectric functional group described later may be introduced. Industrially, methyl, phenyl, hydroxyl, alkoxy, and dielectric functional groups described later are preferred. It should be noted that when component (A) contains a hydroxyl group or the like, the component has condensation reactivity in addition to hydrosilylation reaction curing properties.

[0063] When used in a dielectric layer, component (A) may preferably be a polyorganosiloxane represented by the following average composition formula or a mixture thereof.

[0064] R 1 a R 2 b SiO (4-a-b) / 2

[0065] Where R 1 It is the aforementioned curing reactive group containing a carbon-carbon double bond.

[0066] R 2 It is a group selected from the above-mentioned monovalent hydrocarbon group not having a carbon-carbon double bond, hydroxyl group, and alkoxy group.

[0067] a and b are numbers that satisfy the following conditions: 1 ≤ a + b ≤ 3 and 0.001 ≤ a / (a ​​+ b) ≤ 0.33, and preferably 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 at least the lower limit of the above range, the flexibility of the cured product increases, while on the other hand, when a + b is at most the upper limit of the above range, the mechanical strength of the cured product increases. When a / (a ​​+ b) is at least the lower limit of the above range, the mechanical strength of the cured product increases, while when a / (a ​​+ b) is at most the upper limit of the above range, the flexibility of the cured product increases.

[0068] When used in a dielectric layer, the component (A) of the present invention is particularly preferably a polyorganosiloxane mixture containing the following components.

[0069] (a1) a linear or branched polyorganosiloxane having alkenyl groups only at the molecular chain ends; and

[0070] (a2) An alkenyl-containing polyorganosiloxane resin having at least one branched siloxane unit in the molecule and a vinyl group (CH2=CH-) content within a range of 1.0% by mass to 5.0% by mass.

[0071] Component (a1) has a siloxane unit represented by the following formula at the end of its molecular chain.

[0072] (Alk)R 2 2SiO 1 / 2

[0073] (wherein Alk is an alkenyl group having 2 or more carbon atoms) The other siloxane units are essentially composed only of R 2 2SiO 2 / 2 A linear or branched polyorganosiloxane composed of siloxane units represented by 2 represents the same groups as described above. In addition, the degree of siloxane polymerization of component (A1-1) is in the range of 7 to 1002, including the terminal siloxane unit, and can be in the range of 102 to 902. Such component (A1-1) is particularly preferably one in which both ends of the molecular chain are connected by (Alk)R 2 2SiO 1 / 2 It is a linear polyorganosiloxane terminated with a siloxane unit.

[0074] Component (a2) is an alkenyl group-containing polyorganosiloxane resin.

[0075] Examples of the alkenyl group-containing polyorganosiloxane resins represented by the following average unit formulas are given.

[0076] (RSiO 3 / 2 )o(R2SiO 2 / 2 )p(R3SiO 1 / 2 )q(SiO 4 / 2 )r(XO 1 / 2 )s

[0077] In the above formula, R is a group selected from an alkenyl group and a monovalent hydrocarbon group without a carbon-carbon double bond, and X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among all R, it is preferred that R is an alkenyl group, especially R3SiO 1 / 2 At least a portion of the R groups on the siloxane units represented by are alkenyl groups.

[0078] 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 in the range of 0 to 10, q / (o+r) is a number in the range of 0 to 5, (o+r) / (o+p+q+r) is a number in the range of 0.3 to 0.9, and s / (o+p+q+r) is a number in the range of 0 to 0.4.

[0079] As the component (a2), an alkenyl group-containing MQ polyorganosiloxane resin represented by the following formula is particularly preferably exemplified.

[0080] {(Alk)R 2 2SiO 1 / 2}q1(R 2 3SiO 1 / 2 )q2(SiO 4 / 2 )r

[0081] (where Alk, R 2 The same group as described 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 of 1.0% by mass to 5.0% by mass of the vinyl group (CH2=CH-) in the polyorganosiloxane resin.

[0082] By using a component (a1) having alkenyl groups only at the ends of their molecular chains and a component (a2) having a certain amount of alkenyl groups as a polyorganosiloxane resin in combination, a cured reaction product having excellent curability as the composition as a whole and excellent mechanical strength and flexibility can be provided, thereby providing a polyorganosiloxane cured product film particularly suitable for adhesive layers or dielectric layers in the above-mentioned electronic components and the like.

[0083] Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in its molecule, and functions as a crosslinking agent for component (A).

[0084] Examples of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, methylhydrogenpolysiloxane terminated at both ends of the molecular chain by trimethylsiloxy groups, dimethylsiloxane / methylhydrogensiloxane copolymer terminated at both ends of the molecular chain by trimethylsiloxy groups, dimethylpolysiloxane terminated at both ends of the molecular chain by dimethylhydrogensiloxy groups, dimethylsiloxane / methylhydrogensiloxane copolymer terminated at both ends of the molecular chain by dimethylhydrogensiloxy groups, methylhydrogensiloxane / diphenylsiloxane copolymer terminated at both ends of the molecular chain by trimethylsiloxy groups, methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer terminated at both ends of the molecular chain by trimethylsiloxy groups, hydrolysis-condensation products of trimethoxysilane, (CH3)2HSiO 1 / 2 unit and SiO 4 / 2 Copolymer composed of units, (CH3)2HSiO 1 / 2 unit, SiO 4 / 2 Unit and (C6H5)SiO 3 / 2 Copolymers composed of units and mixtures of two or more thereof.

[0085] Regarding the amount of component (B) used, the amount of silicon-bonded hydrogen atoms is in the range of 0.1 to 10 moles relative to 1 mole of carbon-carbon double bonds in the composition, preferably relative to 1 mole of carbon-carbon double bonds in component (A), preferably in the range of 0.5 to 2.5 moles, and particularly preferably in the range of 0.5 to 2.0 moles. When the amount of component (B) used is below the lower limit, it may cause poor curing. If the content of component (B) exceeds the upper limit, the mechanical strength of the cured product becomes too high, and sometimes it is impossible to obtain the physical properties preferred as an electrode layer, dielectric layer or adhesive layer. However, when the purpose is to improve the bonding strength of the polyorganosiloxane cured film of the present invention to an adherend such as glass, it does not prevent the use of silicon-bonded hydrogen atoms in the range of more than 20 moles relative to 1 mole of carbon-carbon double bonds in component (A).

[0086] Preferably, the polyorganosiloxane cured film after lamination of the present invention has a structure that is chemically bonded by a hydrosilylation reaction between the component (A) and the component (B) at its interface. Here, the reaction between the component (A) and the component (B) at the interface is preferably carried out under the following circumstances: at the interface of two cured films or their precursors (including uncured / semi-cured coating states), the silicon atom-bonded hydrogen atoms (hereinafter sometimes abbreviated as "SiH / Vi ratio") in the organohydrogenpolysiloxane component relative to the total amount of 1 mole of carbon-carbon double bonds in the cured film or the curable composition providing the cured product are different. On the other hand, if the SiH / Vi ratios of the two are consistent, the reaction of the curing reactive functional groups asked at the interface cannot be promoted, and sufficient chemical bonds cannot be formed sometimes.

[0087] Preferably, when using curable polyorganosiloxane 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 is excessive), and the SiH / Vi ratio in composition (II) is greater than 0.5 mol and less than 1.0 mol (i.e., SiH is insufficient). Thus, at the interface of the cured film formed by curing the two, the reaction between the common curing-reactive functional groups is promoted, forming a strong chemical bond. It should be noted that, with respect to the SiH / Vi ratios of compositions (I) and (II), [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. It should be noted that the composition (I) with excess SiH may be the dielectric layer, and the composition (II) with insufficient SiH may be the electrode layer, or vice versa (composition (I): electrode layer, composition (II): dielectric layer), without particular limitation.

[0088] It should be noted that in the present invention, it is preferred to form a strong chemical bond between the polyorganosiloxane cured film serving as the electrode layer and the dielectric layer. Therefore, when the above-mentioned 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 particles. Specifically, regarding the composition (II) forming the electrode layer, the 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 dielectric layer forming composition (I) does not contain conductive fine particles, and its SiH / Vi ratio ([SiH / Vi] DEAP ), particularly preferably [SiH / Vi]Elec / [SiH / Vi] DEAP The values ​​of are in the ranges of 0.33 to 0.85, 0.50 to 0.75, and 0.58 to 0.67. In other words, it is particularly preferred that the composition forming the dielectric layer be a composition having a certain excess of SiH.

[0089] Component (C) is a catalyst that promotes the hydrosilylation reaction of component (A) and component (B). Examples thereof include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, nickel-based catalysts, iridium-based catalysts, ruthenium-based catalysts, and iron-based catalysts, preferably platinum-based catalysts. Examples of the platinum-based catalysts include platinum fine powder, chloroplatinic acid, alcoholic 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. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes of platinum are preferred, and are preferably added in the form of alkenylsiloxane solutions of the complexes. In addition, from the perspective of improving workability and the pot life of the composition, microparticles containing platinum in hydrosilylation reaction catalysts dispersed or encapsulated in thermoplastic resins may also be used. Note that, as a catalyst for promoting the hydrosilylation reaction, a non-platinum metal catalyst such as iron, ruthenium, or iron / cobalt can be used.

[0090] Furthermore, the hydrosilylation reaction catalyst as component (C) may be a hydrosilylation reaction catalyst that is inactive without irradiation with high-energy rays but becomes active in the composition upon irradiation with high-energy rays, a so-called high-energy ray-activated catalyst or a photoactivated catalyst. By using such a component (C), the composition as a whole can achieve the following properties: curing even at low temperatures triggered by irradiation with high-energy rays, excellent storage stability, and easy reaction control, resulting in excellent workability.

[0091] Examples of high-energy rays include ultraviolet rays, gamma rays, X-rays, α-rays, and electron beams. In particular, ultraviolet rays, X-rays, and electron beams irradiated by commercially available electron beam irradiation devices are mentioned. Ultraviolet rays are preferred from the perspective of catalyst activation efficiency, and ultraviolet rays with a wavelength of 280 nm to 380 nm are preferred from the perspective of industrial utilization. Furthermore, the irradiation dose varies depending on the type of high-energy ray-activated catalyst. In the case of ultraviolet rays, the cumulative irradiation dose at a wavelength of 365 nm is preferably 100 mJ / cm 2 ~100J / cm 2 within the range.

[0092] 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(acetylacetylacetonate)platinum (IV), trimethyl(3,5-pentamethylcyclopentadienyl)trimethylplatinum (IV), and trimethyl(1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum (IV). -heptanedione) platinum (IV), trimethyl (methylacetoacetate) platinum (IV), bis(2,4-pentanedione) platinum (II), bis(2,4-hexanedione) platinum (II), bis(2,4-heptanedione) platinum (II), bis(3,5-heptanedione) platinum (II), bis(1-phenyl-1,3-butanedione) platinum (II), bis(1,3-diphenyl-1,3-propanedione) platinum (II), and bis(hexafluoroacetylacetonate) platinum (II). Among them, (methylcyclopentadienyl)trimethyl platinum (IV) and bis(2,4-pentanedione) platinum (II) are preferred from the perspective of versatility and ease of acquisition.

[0093] The amount of component (C) used is an effective amount and is not particularly limited, as long as it is an amount that promotes the curing of the curable polyorganosiloxane composition of the present invention. Specifically, the metal atoms in the catalyst are calculated in units of mass, relative to the sum of components (A) to (C) (the total is set to 100% by mass), and the platinum metal atoms in component (C) are preferably in an amount within the range of 0.1ppm to 500ppm. This is because: if the content of component (C) is below the lower limit of the above range, curing may become insufficient, and if the content of component (C) exceeds the upper limit of the above range, in addition to being uneconomical, it may also have an adverse effect on the coloration and transparency of the resulting cured product.

[0094] [Use of functional fillers and functions of cured films]

[0095] In the present invention, the polyorganosiloxane cured product film after lamination is a polyorganosiloxane cured product film obtained by curing a curable polyorganosiloxane composition having different compositions, and in order to realize its function, it is preferably combined with a functional filler. In particular, the polyorganosiloxane cured product film as a dielectric layer is not only different from the preferred SiH / Vi ratio described, but also different from the polyorganosiloxane cured product film as an electrode layer, and is greatly different in terms of not containing conductive particles. Generally, the curable polyorganosiloxane composition provided as the cured product film of the electrode layer includes (E) conductive particles, and the curable polyorganosiloxane composition provided as the cured product film of the dielectric layer preferably includes (F) reinforcing filler, does not contain conductive particles, and can arbitrarily further introduce a high dielectric functional group. It should be noted that the functional filler can also be subjected to the surface treatment of hydrophobization. As the surface treatment agent used for hydrophobization, at least one surface treatment agent selected from the group consisting of an organic titanium compound, an organic silicon compound, an organic zirconium compound, an organic aluminum compound, and an organic phosphorus compound can be listed.

[0096] [(E) Conductive fine particles]

[0097] There are no particular limitations on the conductive fine particles, as long as they impart conductivity to the cured polyorganosiloxane film. A cured film containing these conductive fine particles can be preferably used as an electrode layer. It should be noted that electrode layers containing conductive fine particles are proposed, for example, in International Patent Publication No. WO2014 / 105959 by the applicant of this application.

[0098] Specifically, conductive carbon 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; further examples include antimony-doped tin oxide, phosphorus-doped tin oxide, needle-shaped titanium oxide coated with tin oxide / antimony, tin oxide, indium oxide, antimony oxide, zinc antimonate, and pigments such as carbon or graphite whiskers coated with tin oxide; pigments coated with at least one conductive metal oxide selected from the group consisting of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), and phosphorus-doped tin oxide nickel oxide; and conductive pigments containing tin oxide and phosphorus on the surface of titanium dioxide particles. These pigments may also be treated with various surface treatment agents. These pigments may be used alone or in combination of two or more. Furthermore, in order to uniformly disperse these conductive fine particles in the curable polyorganosiloxane composition, they may be kneaded in advance with part or all of component (A) or component (B) used in the composition and incorporated into the curable polyorganosiloxane composition as a mixture.

[0099] Moreover, the conductive inorganic particles can also be particles of conductive materials such as metal coated on the surface of fibers such as glass fibers, silica alumina fibers, alumina fibers, carbon fibers, and needle-shaped reinforcing materials such as aluminum borate whiskers and potassium titanate whiskers, glass beads, talc, mica, graphite, wollastonite, and dolomite.

[0100] [(F) Reinforcing fillers]

[0101] The curable polyorganosiloxane composition that provides a cured film serving as a dielectric layer preferably contains reinforcing fine particles or a composite 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 curing reaction.

[0102] From the perspective of mechanical strength of the cured product, the reinforcing fine particles are preferably one or more reinforcing inorganic fine particles having an average primary particle size of less than 50 nm. Examples include fumed silica, wet silica, ground silica, calcium carbonate, diatomaceous earth, finely ground quartz, various metal oxide powders other than aluminum oxide / zinc oxide, glass fiber, carbon fiber, etc., and these particles may be treated with one or more organosilicon compounds described below. The shape of the reinforcing fine particles is not particularly limited, and any shape, such as particles, plates, needles, or fibers, may be used.

[0103] As a preferred example, from the perspective of improving the mechanical strength of the dielectric layer, fumed silica or its metal oxide complex can be used, with an average primary particle size of 10 nm or less, partially agglomerated, and with different BET surface areas, as described below, and having hydrophilic or hydrophobic properties. Furthermore, from the perspective of improving dispersibility, the fumed silica or its metal oxide complex is preferably treated with disilazane or a silane coupling agent, described below. Two or more of these reinforcing inorganic particles may also be used in combination.

[0104] In the present invention, the reinforcing filler used in the dielectric layer comprises the following components:

[0105] (F1) Surface treated with one or more organosilicon compounds, with an average BET specific surface area exceeding 100 m 2 / g of reinforcing microparticles or their complexes; and

[0106] (F2) Surface treated with one or more organic silicon compounds, with an average BET specific surface area of ​​10m 2 / g~100m 2 / g range of reinforcing particles or their complexes, and

[0107] The mass ratio of component (F1) to component (F2) is within the range of 50:50 to 99:1, and may be within the range of 70:30 to 97:3, and preferably within the range of 70:30 to 95:5. If the mass ratio deviates from the above range, the viscosity of the curable polyorganosiloxane composition before curing may increase, or the mechanical strength and dielectric breakdown strength after curing may decrease.

[0108] By incorporating reinforcing fillers (components (F1) and (F2)) into the composition, the mechanical strength and dielectric breakdown strength of the cured polyorganosiloxane material formed by curing the curable polyorganosiloxane composition of the present invention can be increased. The amount of these fillers added, as the sum of components (F1) and (F2), relative to the sum of components that form non-volatile solids in the composition through the curing reaction, is in the range of 10% to 40% by mass, preferably 15% to 35% by mass, and particularly preferably 15% to 30% by mass. Exceeding the upper limit of the aforementioned mass % range may make uniform, thin-film coating difficult, while below the lower limit of the aforementioned mass % range may result in insufficient physical properties of the cured curable polyorganosiloxane composition.

[0109] The reinforcing fillers (F1) and (F2) are preferably surface-treated with one or more organosilicon compounds. This surface treatment with an organosilicon compound is a hydrophobic treatment, which allows the reinforcing filler treated with the organosilicon compound to be uniformly dispersed in the polyorganosiloxane composition at a high filling rate. Furthermore, this suppresses the increase in the viscosity of the composition, improving moldability.

[0110] Examples of organosilicon compounds include low molecular weight organosilicon compounds such as silane, silazane, siloxane, or the like; and organosilicon polymers or oligomers such as polysiloxane, polycarbosiloxane, or the like. Preferably, the organosilicon compound used for surface treatment contains at least one selected from hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane.

[0111] In the surface treatment, the ratio of the surface treatment agent to the total amount of the filler is preferably in the range of 0.1% to 50% by mass, and more preferably in the range of 0.3% to 40% by mass. It should be noted that the treatment amount refers to the charge ratio of the filler to the surface treatment agent, and the excess treatment agent is preferably removed after the treatment. Furthermore, additives to promote or assist the reaction may be used during the treatment as needed.

[0112] In the surface treatment, whether the components of the surface treatment agent are chemically or physically fixed to the filler surface is an important parameter. For example, the fixed amount of the surface treatment agent can be analyzed by reacting excess tetraethoxysilane with a composition containing a filler under alkaline conditions and detecting the reaction product by gas chromatography. The amount of the component of the surface treatment agent fixed on the surface of the above-mentioned filler can be 1.0 mass parts or more relative to 100 mass parts of the filler amount, preferably 3.0 mass parts or more. Among them, in the case where hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane are used as the organosilicon compounds for the surface treatment of the (F1) component and the (F2) component related to the present invention, the fixed ratio of each on the filler surface can be changed as needed. For example, in the present invention, as described above, a high dielectric functional group can be introduced into a part or all of component (A) or component (B) by (C 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). From the viewpoint of dielectric properties, economy, ease of preparation, and molding processability of the resulting curable polyorganosiloxane composition, a preferred group is a group in which p=1, i.e., a trifluoropropyl group. 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 on the filler surface can be from 0 to 10, preferably from 0 to 5. If it deviates from this range, the affinity of component (A) or component (B) to the filler surface deteriorates, and there is a possibility that the processability and physical properties after curing will be reduced.

[0113] [Other functional fillers]

[0114] In the curable polyorganosiloxane composition of the present invention, other fillers may be used or not used as desired, and examples thereof include high dielectric fillers, thermally conductive inorganic fine particles, and insulating fillers. These inorganic fine particles may also have two or more functions, such as serving as reinforcing fillers.

[0115] As the example of preferred dielectric inorganic particles, one or more inorganic particles can be listed in the group consisting of a composite metal oxide selected from the barium and titanium parts of titanium oxide, such as titanium oxide, barium titanate, strontium titanate, lead zirconate titanate and barium titanate, substituted with alkaline earth metals, zirconium or rare earth metals such as calcium, strontium, yttrium, neodymium, samarium, dysprosium, more preferably titanium oxide, barium titanate, barium calcium zirconate titanate and strontium titanate, further preferably titanium oxide, barium titanate. In particular, dielectric inorganic particles are particularly preferably dielectric inorganic particles having a relative dielectric constant of more than 10 at room temperature and 1kHz of at least a portion thereof. It should be noted that the upper limit of the preferred size (average primary particle size) of the inorganic particles is 20000nm (20 μm), but if the processability of the transducer film described later is considered, 10000nm (10 μm) is more preferably used. By using the dielectric inorganic fine particles, the mechanical properties and / or electrical properties of the polyorganosiloxane cured product may be further improved, particularly the relative dielectric constant.

[0116] The insulating inorganic fine particles that can be used in the present invention are any generally known insulating inorganic materials, that is, any materials having a volume resistivity of 10 10 Ω·cm~10 18 There is no restriction on the particles of inorganic materials with a resistance of Ω·cm, and any shape among particle, sheet, fiber (including whisker) can be used. Specifically, spherical particles, plate-like particles or fibers of ceramics can be listed, and particles of metal silicates such as aluminum oxide, iron oxide, copper oxide, mica, talc, quartz, amorphous silica, glass, etc. can be listed as preferred examples of use. In addition, these can also be treated with various surface treatment agents described later. They can be used alone or in combination of two or more. By incorporating insulating inorganic particles into the composition, the mechanical strength and dielectric breakdown strength of the polyorganosiloxane cured product can be increased, and an increase in relative dielectric constant can sometimes be seen.

[0117] 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, silicon nitride, boron 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, the thermal conductivity of the cured polyorganosiloxane can be increased.

[0118] The mensuration of the average particle size of these inorganic particles can be carried out by common measuring method in described field.For example, when average particle size is more than 50nm and below about 500nm, particle diameter is measured by microscopic observations such as transmission electron microscope (TEM), field emission transmission electron microscope (FE-TEM), scanning electron microscope (SEM), field emission scanning electron microscope (FE-SEM), by obtaining average value, average primary particle diameter can be measured.On the other hand, when average particle size is more than about 500nm, the value of average primary particle diameter can be directly obtained by laser diffraction / scattering type particle size distribution measuring device etc.

[0119] [Use of solvent]

[0120] The curable polyorganosiloxane composition of the present invention can be used directly for the curing reaction. However, when the composition or a portion of its components (e.g., polyorganosiloxane resin) is solid or viscous, an organic solvent may be used as needed to improve its miscibility and operability. In particular, when the curable polyorganosiloxane composition of the present invention is applied as a film, a solvent may be used to adjust the viscosity within the range of 100 mPa·s to 50,000 mPa·s. When diluted with a solvent, the solvent may be used within the range of 0 to 2,000 parts by mass relative to the sum of the above-mentioned components (A) to (C) (100 parts by mass). That is, in the composition of the present invention, the solvent may be 0 parts by mass, preferably a solvent-free type. In particular, by selecting a polymer with a low degree of polymerization in the curable polyorganosiloxane composition of the present invention, there are the following advantages: it can be designed to be solvent-free, and no fluorinated solvents, organic solvents, etc. remain in the film obtained by curing, which can eliminate the problem of environmental load and the impact of solvents on electronic devices. In addition, a low-solvent type composition can be used, wherein 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-mentioned components (A) to (C) (100 parts by mass). Furthermore, the electrode layer composition can be diluted with a solvent as described in the examples below and applied as a thin film by spray coating.

[0121] Preferably, the organic solvent is one or more organic solvents selected from the following solvents or a mixed solvent thereof:

[0122] (E1) an organic polar solvent;

[0123] (E2) a low molecular weight siloxane solvent; and

[0124] (E3) halogen-based solvents,

[0125] An organic solvent with a boiling point of 80°C or higher and less than 200°C is preferably used. It should be noted that a mixed solvent of different types or the same type of organic solvents in varying ratios may also be used. Preferably, the organic solvent comprises at least one low molecular weight siloxane-based solvent selected from hexamethyldisiloxane and octamethyltrisiloxane, and a mixed solvent thereof, which are commercially available from Dow Silicones Corporation as OST-10, OST-20, and OST-2. Furthermore, when the curable elastomer composition has a high fluoroalkyl content, the optional combined use of these low molecular weight siloxane-based solvents and the aforementioned halogen-based solvents is also included in a preferred embodiment of the present invention.

[0126] [Overall viscosity]

[0127] In the case of the curable polyorganosiloxane composition used in the present invention, the curable polyorganosiloxane composition is subjected to a temperature of 25° C. and a shear rate of 10.0 (S -1 ) is preferably within the range of 5 mPa·s to 500,000 mPa·s, particularly preferably within the range of 1,000 mPa·s to 10,000 mPa·s. The amount of the organic solvent used can be adjusted to achieve the preferred viscosity range, but a low-solvent type or solvent-free (= solvent-free) type can also be used. It should be noted that the electrode layer composition can be diluted with a solvent as described in the examples below and applied as a thin film by spraying, and this is preferred.

[0128] [Thixotropic ratio]

[0129] Preferably, the curable polyorganosiloxane composition of the present invention has excellent fluidity and does not exhibit thixotropic behavior. This allows for low overall viscosity and excellent uniform coating properties. Specifically, the composition preferably has a thixotropic ratio of 10.0 or less, which is defined as the thixotropic ratio at 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 ) is the ratio of the viscosity of the entire composition measured under ).

[0130] [Solid content]

[0131] In the curable polyorganosiloxane composition of the present invention, the content of the component that cures to form a polyorganosiloxane cured product as a non-volatile solid component (sometimes simply referred to as "solid content" in the present invention) is preferably in the range of 5% to 100% by mass of the entire composition, more preferably in the range of 50% to 100% by mass, 75% to 100% by mass, or 85% to 100% by mass.

[0132] [Introduction of dielectric functional groups]

[0133] When the polyorganosiloxane cured product film of the present invention is used as an electroactive film (e.g., a dielectric film) for a transducer such as an actuator, a high dielectric functional group may be introduced into the cured product. However, even a polyorganosiloxane cured product film that does not contain a high dielectric functional group can be used as an electroactive film. It should be noted that the introduction of these high dielectric functional groups and the improvement of the relative dielectric constant have been proposed, for example, in International Patent Publication No. WO2014 / 105959 of the applicant of this case.

[0134] The introduction of high dielectric functional groups can be achieved by using a polyorganosiloxane or organohydrogenpolysiloxane having high dielectric functional groups as part or all of component (A) or component (B), or by adding an organic additive having high dielectric functional groups, a non-reactive organosilicon compound having high dielectric functional groups, or the like to the curable composition. From the perspective of improving miscibility with the curable composition and the relative 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 polyorganosiloxane or organohydrogenpolysiloxane as component (A) or component (B) are substituted with high dielectric functional groups.

[0135] The type of high dielectric functional group introduced into the polyorganosiloxane cured film is not particularly limited. Preferably, the following can be exemplified: a) halogen atoms and halogen atom-containing groups represented by 3,3,3-trifluoropropyl, etc., b) nitrogen atom-containing groups represented by cyanopropyl, etc., c) oxygen atom-containing groups represented by carbonyl, etc., d) heterocyclic groups such as imidazole, e) boron-containing groups such as borate, f) phosphorus-containing groups such as phosphine, and g) sulfur-containing groups such as thiol. Halogen atoms and halogen atom-containing groups containing fluorine atoms are preferably used.

[0136] In the present invention, it is preferred that a high dielectric functional group is introduced into a part or all of component (A) or component (B) by (C 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). Such a fluoroalkyl group provides a cured product having an excellent relative dielectric constant, and each component has a fluorine atom, thereby improving the compatibility of the components and providing a cured product having excellent transparency. Specific examples of such a fluoroalkyl group are trifluoropropyl, pentafluorobutyl, heptafluoropentyl, nonafluorohexyl, undecafluoroheptyl, tridecafluorooctyl, pentafluorononyl, and heptadecafluorodecyl. Among them, from the viewpoints of dielectric properties, economy, ease of preparation, and molding processability of the resulting curable polyorganosiloxane composition, the preferred group is a group with p=1, i.e., a trifluoropropyl group.

[0137] In addition to the aforementioned components, other components may be added to the curable polyorganosiloxane composition of the present invention as needed, provided they do not impair the objectives of the present invention. Examples of other components include hydrosilylation inhibitors, mold release agents, insulating additives, adhesion enhancers, heat resistance enhancers, fillers, pigments, and other conventionally known additives. Specific examples of these are the same as those disclosed in the aforementioned International Patent Publication No. WO2014 / 105959.

[0138] The curable polyorganosiloxane composition of the present invention can be prepared by uniformly mixing the curable polyorganosiloxane with a component that accelerates the curing reaction, preferably the components (A) to (C) described above. Furthermore, any other optional components may be added and uniformly mixed as needed. Mixing can be performed at room temperature using various stirrers or kneaders. However, for combinations of components that do not cure during mixing, mixing may also be performed under heating.

[0139] If the mixture does not cure during mixing, the order of mixing the components is not particularly limited. After mixing, if not used immediately, the crosslinking agent (e.g., component (B)) and the curing reaction accelerating component (e.g., component (C)) can be stored in separate containers so that they are not in the same container. The components in all containers can be mixed immediately before use.

[0140] The curing reaction of the curable polyorganosiloxane composition of the present invention is carried out at room temperature in a curing reaction based on a condensation reaction such as dehydration and dealcoholization. However, in the case of producing a polyorganosiloxane cured film by an industrial production process, it is usually achieved by heating the composition or exposing it to active energy rays. The curing reaction temperature based on heat is not particularly limited, but is preferably 50°C or higher and 200°C or lower, more preferably 60°C or higher and 200°C or lower, and further preferably 80°C or higher and 180°C or lower. In addition, the time taken for the curing reaction depends on the structure of the above-mentioned components (A), (B), and (C), but is usually 1 second or higher and 3 hours or lower. In general, a cured product can be obtained by maintaining the temperature within the range of 90°C to 180°C for 10 seconds to 30 minutes. It should be noted that the method for preparing the film will be described later.

[0141] As active energy rays that can be used for curing reaction, can list out: ultraviolet ray, electron beam and radiation etc., preferably ultraviolet ray in terms of practicality.When utilizing ultraviolet ray to carry out curing reaction, it is desirable to add a hydrosilylation reaction catalyst with high activity relative to the ultraviolet ray used, such as bis(2,4-pentanedionatoic acid) platinum complex, (methylcyclopentadienyl) trimethylplatinum complex.As ultraviolet generation source, preferably high pressure mercury lamp, medium pressure mercury lamp, Xe-Hg lamp and deep ultraviolet lamp (Deep UV Lamp) etc., the irradiation amount at this moment is preferably 100mJ / cm 2 ~8000mJ / cm 2 .

[0142] [Method for producing laminate]

[0143] The laminate of the present invention can be obtained by a method for producing a laminate comprising the following steps: the laminate having a structure in which two or more cured polyorganosiloxane films having different compositions are laminated, wherein the laminated cured polyorganosiloxane films have a structure in which the interfaces thereof are chemically bonded.

[0144] Step I: a step of obtaining a cured polyorganosiloxane film by curing one of two or more curable polyorganosiloxane compositions having at least a portion of functional groups participating in the curing reaction in common and having different compositions into a film form.

[0145] Step II: Simultaneously with or after step I, a curable polyorganosiloxane composition different from that in step I is applied in the form of a film on the cured polyorganosiloxane film of step I or its precursor, and a curing reaction is carried out to thereby laminate a different cured polyorganosiloxane film on the cured polyorganosiloxane film of step I.

[0146] Here, it is preferred that the polyorganosiloxane cured product film in the above-mentioned step I is a dielectric layer, and the polyorganosiloxane cured product film in the above-mentioned step II is an electrode layer, but the reverse may also be true.

[0147] In step I or step II, as a method for coating the curable polyorganosiloxane composition into a film, gravure coating, offset coating, indirect gravure coating, roll coating using an offset transfer roll coater, reverse roll coating, air knife coating, curtain coating using a curtain flow coater, comma blade coating, Mayer bar coating, and other well-known methods for forming a cured layer can be used without limitation. Furthermore, the curable polyorganosiloxane composition of the present invention can also be applied in multiple layers.

[0148] The laminate of the present invention has a chemically bonded structure at the interface of the laminated polyorganosiloxane films. This structure is formed by contacting the cured polyorganosiloxane films, or thin layers of uncured or semi-cured curable polyorganosiloxane compositions (pre-cured state), which are their precursors, after or before curing, and then completely curing them using heating or other methods. This reaction between the curable reactive groups proceeds at the interface of the cured films. From the perspective of industrial production and production efficiency, this process can be performed by allowing the curing reaction to proceed in each layer before lamination, or by pre-laminating multiple thin layers of curable polyorganosiloxane compositions with curing reactions and then completely curing the entire film using heating or other methods.

[0149] Preferably, the following method for producing a laminate can be exemplified, characterized in that the above-mentioned step II includes the step of applying a curable polyorganosiloxane composition different from that in step I into a film form, further laminating another cured polyorganosiloxane film or its precursor on the coating layer of the curable polyorganosiloxane composition while the coating layer is in an uncured or semi-cured state, and arbitrarily repeating the same step two or more times to form a laminate in which a cured polyorganosiloxane film or its precursor and an uncured or semi-cured coating layer of the curable polyorganosiloxane composition are laminated together, and then allowing the curing reaction of the coating layer of the curable polyorganosiloxane composition different from that in step I to complete and cure, thereby laminating a different cured polyorganosiloxane film on the cured polyorganosiloxane film of step I. In this case, for example, a curable polyorganosiloxane composition containing conductive fine particles is applied in a film-like form on a cured polyorganosiloxane film serving as a dielectric layer, and a cured polyorganosiloxane film serving as a dielectric layer is further laminated in an uncured or semi-cured state, and the same procedure as below is repeated.

[0150] Dielectric layer (cured film) / uncured or semi-cured electrode layer / Dielectric layer (cured film) / uncured or semi-cured electrode layer / ...

[0151] After the laminate precursor is formed as described above, the entire laminate is cured by heating or the like, thereby obtaining a laminate in which cured dielectric layers and electrode layers are alternately laminated and the interfaces of the two layers are chemically bonded.

[0152] The manufacturing method is particularly useful as a method for forming an electrode layer in a transducer component, and can easily provide a laminated body, electronic component, or display device component in which the dielectric layer and the electrode layer are firmly bonded and are less likely to cause peeling and defects due to insufficient bonding strength and followability.

[0153] The laminate of the polyorganosiloxane cured product film of the present invention is useful as an electronic material, a component for a display device, or a component for a transducer (including a sensor, a speaker, an actuator, and a generator). In particular, it can be used as an electroactive film (including a high dielectric film) having an electrode layer, and is preferably used as a component of an electronic component or a display device. Moreover, as described above, the electroactive film with high dielectric breakdown strength is preferably a transducer component for an actuator, etc. in the form of a single layer or a laminated film, and because it has a structure formed by firmly bonding the electrode layers, it is particularly useful in applications in actuators that are activated at high voltages.

[0154] Example

[0155] The present invention will be described below with reference to the following examples, but the present invention is not limited to these examples. The following compounds were used in the following examples and comparative examples. In addition, the physical properties of each cured film were measured by the following methods.

[0156] [Shore A hardness]

[0157] Regarding the cured film as the electrode layer (ELEC), the curable organosiloxane composition was heated at a curing temperature of 150°C for 1 hour, and regarding the cured film as the dielectric layer (DEAP), the curable polyorganosiloxane composition was heated at a curing temperature of 110°C for 1 hour to prepare a cured film. It should be noted that the thickness of the cured sample was set to about 6 mm. The Shore A hardness of each cured film obtained was measured using DD2 (manufactured by Polymer Metering Co., Ltd.) according to the method of JIS K6249. The results are shown in Table 1. It should be noted that in the case of insufficient curing or excessive softness, it is set to "unable to measure" according to the respective reasons.

[0158] [Elastic modulus]

[0159] The elastic modulus of each curable polyorganosiloxane composition providing the electrode layer was measured using a viscoelasticity measuring instrument (manufactured by Anton Paar, Model MCR302). A Peltier element temperature control system and parallel plates with a diameter of 15 mm were used to set the sample 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 to allow curing. The storage modulus (G') 60 minutes after the start of the temperature increase is shown in Table 1 as the elastic modulus.

[0160] [Volume resistivity measurement]

[0161] Measurement equipment: Loresta GP (Mitsubishi Chemical Analytech) was used for measurements at room temperature. A PSP (Mitsubishi Chemical Analytech) probe was used. As described below, measurements were taken at at least 14 locations on an electrode layer formed on a polyorganosiloxane cured film serving as a dielectric layer. The values ​​calculated using the average of the stabilized readings, electrode thickness, and a correction factor are shown in Table 1.

[0162] Component (a1): a dimethylsiloxane polymer (vinyl content: 0.24% by mass, siloxane polymerization degree: 300) end-capped at both ends with vinyldimethylsiloxy groups.

[0163] Component (a2): a copolymer of 3,3,3-trifluoropropylmethyl and dimethylsiloxane (vinyl content: 0.26% by mass, siloxane polymerization degree: 193) end-capped with vinyldimethylsiloxy groups at both ends.

[0164] Component (b1): a dimethylsiloxy-methylhydrosiloxy-siloxane copolymer (silicon atom-bonded hydrogen content: 0.71% by mass) terminated at both ends by trimethylsiloxy groups.

[0165] Component (b2): a dimethylsiloxane polymer terminated at both ends with dimethylhydrogensiloxy groups (content of silicon-bonded water: 0.02% by mass).

[0166] Component (b3): ​​a dimethylsiloxane / 3,3,3-trifluoropropylmethylsiloxane / methylhydrogensiloxane copolymer (content of silicon-bonded hydrogen: approximately 0.23% by mass) terminated at both ends with trimethylsiloxy groups.

[0167] Component (b4): a dimethylsiloxane / 3,3,3-trifluoropropylmethylsiloxane copolymer (content of silicon-bonded hydrogen: approximately 0.014% by mass) terminated at both ends with dimethylhydrogensiloxy groups.

[0168] Component (c1): a solution of a dimethylsiloxane polymer terminated at both ends with vinyldimethylsiloxy groups of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (about 0.6% by mass in terms of platinum concentration).

[0169] Component (d): Acetylene black (manufactured by Denka Co., Ltd., 100% pressed product).

[0170] 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).

[0171] 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).

[0172] Component (e3): fumed silica treated with hexamethyldisilazane (product name before treatment: AEROSIL 200, BET specific surface area 200 m 2 / g).

[0173] Component (e4): fumed silica treated with hexamethyldisilazane (product name before treatment: AEROSIL 50, BET specific surface area 50 m 2 / g).

[0174] Component (f1): 1-ethynyl-1-cyclohexanol.

[0175] Component (f2): 1,3,5,7-Tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane.

[0176] [Curable polyorganosiloxane compositions providing electrode layers of Examples 1 to 3 and Comparative Examples 1 to 7]

[0177] The liquid curable polyorganosiloxane composition was prepared by blending the above components in the weight percentages shown in Table 1. The amount of silicon-bonded hydrogen atoms (Si—H) in component (b) per 1 mol of the unsaturated hydrocarbon groups in the composition was as shown in Table 1: (SiH / Vi) ELECThe components were mixed using a rotary / revolution mixer (product name ARE-310, manufactured by Thinky Co., Ltd.) with materials other than the catalyst component (c1). After adding component (c1), the mixture was further mixed using a rotary / revolution mixer under vacuum. Various physical properties are also shown in Table 1.

[0178] [Curable Polyorganosiloxane Composition 1 for Providing Dielectric Layers of Examples 1, 3, and Comparative Examples 1 to 7] <For DEAP Sheet Example 1>

[0179] A liquid curable polyorganosiloxane composition was prepared by blending 68.34 mass % of the above-mentioned component (a2), 5.06 mass % of the component (b3), 5.06 mass % of the component (b4), 0.10 mass % of the component (c1), 18.69 mass % of the component (e1), 2.46 mass % of the component (e2), and 0.28 mass % of the component (f2). The ratio of silicon-bonded hydrogen atoms (Si—H) of the component (b) per 1 mol of the unsaturated hydrocarbon groups in the composition was (SiH / Vi): DEAP The amount used was about 1.2 mol. The hardness of the obtained polyorganosiloxane cured product was Shore A 37.

[0180] [Curable Polyorganosiloxane Composition 2 for Providing a Dielectric Layer of Example 2] <For DEAP Sheet Example 2>

[0181] A liquid curable polyorganosiloxane composition was prepared by blending 70.59 mass % of the above-mentioned component (a1), 0.99 mass % of the component (b1), 3.83 mass % of the component (b2), 0.10 mass % of the component (c1), 20.10 mass % of the component (e3), 4.35 mass % of the component (e4), and 0.04 mass % of the component (f1). The ratio of silicon-bonded hydrogen atoms (Si—H) of the component (b) per 1 mol of the unsaturated hydrocarbon groups in the composition was (SiH / Vi): DEAP The amount used was about 1.2 mol. The hardness of the obtained polyorganosiloxane cured product was Shore A39.

[0182] [Formation of Dielectric Layer (Film) in Examples / Comparative Examples]

[0183] The curable polyorganosiloxane composition providing the dielectric layer was applied as a thin film on a PET substrate having a release layer (release liner) using a coater and cured in an oven at 110° C. for 60 minutes to prepare a film having a thickness of 0.1 mm.

[0184] [Formation of Electrode Layer in Examples / Comparative Examples]

[0185] The curable polyorganosiloxane composition for providing the electrode layer described in Table 1 was diluted using a low molecular weight siloxane solvent (OST-20, manufactured by DOWSILICONES) in such a way that the electrode material concentration became 10% by weight. A circular cover was attached to one side of the dielectric layer (film) having a thickness of 0.1 mm produced above, and the diluted solution was sprayed from above the cover in such a way that 16 circular electrodes having a diameter of 13.5 mm were formed. After coating, the mixture was placed at 60°C under vacuum for about 12 hours. Thereafter, a PET substrate having a peeling layer (peeling liner) was covered on the electrode and pressed at room temperature. The film of the substrate PET was peeled off and heated at 120°C for 60 minutes to form an electrode having a thickness of 10 μm-13 μm.

[0186] [Evaluation of Adhesion Between Dielectric Layer and Electrode Layer: Peel Test]

[0187] A tape (manufactured by Nitto Denko, trade name: NITOFLON (registered trademark) 0.08) was applied to the circular electrode layer formed on one side of the dielectric layer (film) by the above method. After leaving it at room temperature for 10 minutes, it was peeled off and the adhesion between the dielectric layer and the electrode layer was evaluated. At this time, if the electrode layer could not be peeled off together with the tape and almost remained on the dielectric layer (film), it was evaluated as "usable". If the electrode layer was peeled off together with the tape, it was evaluated as "unusable" and recorded in Table 1. It should be noted that when the electrode layer was peeled off from the surface of the dielectric layer to the tape side and transferred, it is considered that sufficient chemical bonding was not formed at the interface between the electrode layer and the surface of the dielectric layer, and the adhesion and bonding strength were weak.

[0188] [Table 1]

[0189]

[0190]

[0191] The dielectric layer / electrode layer in Examples 1 to 3 did not peel off during the peel test, demonstrating a structure in which the two layers were firmly bonded. On the other hand, in Comparative Examples 1 to 7, where the SiH / Vi ratios of the two layers were not designed within the preferred range, the electrode layer peeled off during the peel test, suggesting insufficient adhesion and followability.

Claims

1. A laminate having a structure comprising two or more layers of cured polyorganosiloxane films having different compositions, wherein the two or more cured polyorganosiloxane films are obtained by curing a curable polyorganosiloxane composition having at least a portion of the functional groups participating in the curing reaction in common, wherein: The curable polyorganosiloxane composition that provides a polyorganosiloxane cured film upon curing contains at least: (A) a polyorganosiloxane having at least two curing reactive groups containing a carbon-carbon double bond in the molecule; (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in its molecule, wherein the silicon-bonded hydrogen atoms in this component are present in an amount of 0.5 mol to 2.5 mol per 1 mol of the total amount of carbon-carbon double bonds in the composition; and (C) an effective amount of a catalyst for a hydrosilylation reaction, The laminated cured polyorganosiloxane film has a structure formed by chemical bonding at its interface through a hydrosilylation reaction between the component (A) and the component (B), and is a cured polyorganosiloxane film obtained by curing curable polyorganosiloxane compositions having different compositions. One aspect of the polyorganosiloxane cured film is a cured film obtained by curing a curable polyorganosiloxane composition having an amount of silicon-bonded hydrogen atoms in an organohydrogenpolysiloxane component exceeding 1.0 mol and not more than 2.0 mol per 1 mol of the total amount of carbon-carbon double bonds in the composition, wherein the cured film contains conductive fine particles, and the amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane component per 1 mol of the total amount of carbon-carbon double bonds in the composition [SiH / Vi] is: Elec is 0.7 mol or more and 0.8 mol or less, The other polyorganosiloxane cured film is a cured film obtained by curing a curable polyorganosiloxane composition (II) in which the amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane component is 0.5 mol or more and 1.0 mol or less per 1 mol of the total amount of carbon-carbon double bonds in the composition, the cured film being a dielectric layer and not containing conductive fine particles, wherein the amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane component per 1 mol of the total amount of carbon-carbon double bonds in the composition is [SiH / Vi]: DEAP , [SiH / Vi] Elec / [SiH / Vi] DEAP The value of is in the range of 0.58 to 0.

67.

2. The laminate according to claim 1, wherein The volume resistivity of at least one side of the laminated polyorganosiloxane cured film is 10 2 Ω·cm or less.

3. The laminate according to claim 1 or 2, wherein The shear storage modulus G' at 120°C of at least one of the laminated polyorganosiloxane cured films is within the range of 5.0×10 4 Pa~1.5×10 5 Within the range of Pa.

4. The laminate according to any one of claims 1 to 3, wherein At least one of the laminated polyorganosiloxane cured films contains conductive fine particles.

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

6. The laminate according to any one of claims 1 to 5, wherein At least one of the laminated polyorganosiloxane cured films is an electrode layer, and the other is a dielectric layer.

7. The laminate according to any one of claims 1 to 6, wherein The cured polyorganosiloxane film as the electrode layer is laminated on at least one side of the cured polyorganosiloxane film as the dielectric layer, and the laminated cured polyorganosiloxane films have a chemically bonded structure at their interfaces. 8 . A transducer member, comprising the laminate according to claim 1 . 9 . A transducer comprising the laminate according to claim 1 . 10 . An electronic component or a display device, comprising the laminate according to claim 1 .

11. A method for manufacturing a laminate according to any one of claims 1 to 7, comprising: Step I: a step of curing one of two or more curable polyorganosiloxane compositions having at least a portion of functional groups participating in a curing reaction in common and having different compositions into a film-like form, thereby obtaining a cured polyorganosiloxane film; Step II: Simultaneously with or after step I, a curable polyorganosiloxane composition different from that in step I is applied in the form of a film on the cured polyorganosiloxane film of step I or its precursor, and a curing reaction is carried out to thereby laminate a different cured polyorganosiloxane film on the cured polyorganosiloxane film of step I.

12. The method for producing a laminate according to claim 11, wherein: The polyorganosiloxane cured product film obtained in the above-mentioned step I is a dielectric layer, and the polyorganosiloxane cured product film obtained in the above-mentioned step II is an electrode layer.

13. The method for producing a laminate according to claim 11 or 12, wherein: The above-mentioned step II includes the steps of: applying a curable polyorganosiloxane composition different from that in step I into a film form, further laminating another cured polyorganosiloxane film or its precursor on the coating layer of the curable polyorganosiloxane composition while the coating layer is in an uncured or semi-cured state, and arbitrarily repeating the same step two or more times to form a stacked product comprising one or more stacked layers of a cured polyorganosiloxane film or its precursor and an uncured or semi-cured coating layer of the curable polyorganosiloxane composition; and then allowing the curing reaction of the coating layer of the curable polyorganosiloxane composition different from that in step I to proceed to completion and curing, thereby laminating a different cured polyorganosiloxane film on the cured polyorganosiloxane film of step I. 14 . A method for forming an electrode layer in a transducer member, comprising the method for manufacturing a laminate according to claim 11 .

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