Organopolysiloxane composition applied for transducer, cured material, film cured material, lamination body and manufacturing process thereof, transducer member, transducer, electronic component

Abstract

[The technical problem to be solved] The purpose of this invention is to provide a laminate, its use and manufacturing method. The laminate system is a laminate formed by stacking an organic polysiloxane curable film as a dielectric layer and an electrode layer / substrate layer. It improves the adhesion of the interface of the curable film and is less likely to cause peeling and defects caused by insufficient adhesion strength and followability. Technical means to solve the problem A curable organopolysiloxane composition for a converter contains (A) a polysiloxane having a C=C type curable reactive group, (B1) a side-chain SiH type organohydrogen polysiloxane, (B2) a terminal SiH type organohydrogen polysiloxane, (C) a catalyst for hydrosiliconization reaction, (D) a reinforcing filler, and (E) a tackifier, wherein the value of px1={HB1 / HB2} / {(HB1+HB2) / Vi} is in the range of 0.1 to 6.0 with respect to the number of Si-H atoms in components (B1) and (B2) and the total number of curable reactive groups in component (A).

Description

[Technical Field]

[0001] This invention relates to an organic polysiloxane composition for a converter, a laminate consisting of a cured film thereof, its use, and a method of manufacturing thereof. [Previous Technology]

[0002] Organopolysiloxane curables with a polysiloxane backbone exhibit excellent transparency, electrical insulation, heat resistance, and cold resistance. They can be infused with high-dielectric functional groups such as fluoroalkyl groups to improve electroactivity, and are easily processed into thin films or sheets. Therefore, they are exemplified by adhesive films used in various electrical / electronic devices and electroactive films used in actuators and other converter devices, and can be used for a wide range of applications. These organopolysiloxane curables can be classified according to their curing mechanism into hydrosilicification reaction curing type, condensation reaction curing type, and peroxide curing type. In particular, organopolysiloxane curable films using hydrosilicification reaction curing type compositions are more commonly used because they can be rapidly cured by being placed at room temperature or heated without producing byproducts.

[0003] On the other hand, when using organopolysiloxane cured films as electronic materials for touch panels, electronic components for display devices, and especially as converter materials for sensors, actuators, etc., it is necessary to provide an electrode layer on the electroactive thin film that serves as the dielectric layer. For example, Non-Patent Documents 1 and 2 propose forming an electrode layer with excellent conformability to the dielectric layer by forming an electrode layer formed by adding a conductive filler to a polysiloxane elastomer matrix with excellent flexibility.

[0004] Furthermore, the inventors have proposed that this type of organopolysiloxane cured film can also be used for substrates and electrode layers with low conformability. For example, Patent Documents 1 and 2 propose that the organopolysiloxane cured film can be sandwiched into a thin film substrate as a pressure-sensitive adhesive layer and a dielectric layer. However, there is still room for improvement in the fabrication and use of laminates containing organopolysiloxane cured films in the following aspects: the adhesion of each interface through pressure-sensitive adhesion, surface treatment of the substrate, etc., is not sufficient, or the process efficiency is poor. (Preferred Art Documents - Non-Patent Documents)

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

[0006] [Patent Document 1] International Publication (WO) No. 2016 / 098334 Booklet [Patent Document 2] International Publication (WO) No. 2016 / 163069 [Summary of the Invention]

[0007] The problem that the invention aims to solve

[0008] This invention was made to solve the above-mentioned problems, and its purpose is to provide a laminate, its use, and a manufacturing method thereof. This laminate system laminates an organopolysiloxane cured film with improved adhesion between the dielectric layer and the electrode layer or substrate layer. At the interface of the cured film constituting the laminate, problems such as peeling and defects caused by insufficient adhesive strength and conformability are less likely to occur. Technical means to solve the problem.

[0009] Through diligent research, the inventors discovered that when the value of the parameter determining the crosslinking density in the organopolysiloxane composition, namely pxl, and more preferably the value of the mass % (wf) of the reinforcing filler in the composition, is within a specific range, the above-mentioned problems can be solved, thereby completing the present invention.

[0010] Specifically, the above-mentioned problem is solved by a curable organopolysiloxane composition for converters, characterized by containing at least: (A) one or more organopolysiloxanes having at least two alkenyl groups having 2 to 12 carbon atoms in one or more molecules; (B1) an organohydrogen polysiloxane having at least one silicon atom bonded to a hydrogen atom at the side chain of the molecular chain, having no silicon atom bonded to a hydrogen atom at at least one end of the molecular chain, and having at least two silicon atom bonded to hydrogen atoms within the molecule; (B2) an organohydrogen polysiloxane having silicon atom bonded to hydrogen atoms at both ends of the molecular chain, and having at least two silicon atom bonded to hydrogen atoms within the molecule; (C) an effective amount of catalyst for hydrosilylation reaction; (D) a reinforcing filler; and (E) a tackifier; and utilizing the number of silicon atom bonded to hydrogen atoms (HB1) in component (B1). The number of silicon atoms bonded to hydrogen atoms in component (B2) (HB2) and the total number of hardening reactive groups containing carbon-carbon double bonds in component (A) (Vi) are defined by the following relationship: px1={HB1 / HB2} / {(HB1+HB2) / Vi}, with the value of px1 ranging from 0.1 to 6.0.

[0011] Here, when the total of components (A) to (E) is set to 100% by mass, the content (wf) of component (D) is preferably in the range of 5% to 40% by mass, and more preferably at least a portion of component (A) is an alkenyl group having at least two carbon atoms in one or more molecules (A1), and at least 10 mol% of all substituents on the silicon atom are fluoroalkyl organopolysiloxanes represented by (CpF2p+1)-R- (R is an alkyl group having 1 to 10 carbon atoms, and p is an integer between 1 and 8).

[0012] Furthermore, the above-mentioned problems are better solved by a converter thin film cured by curing the above-mentioned components, a laminate having a structure formed by stacking the converter thin film cured by stacking, a laminate having a structure formed by stacking one or more layers selected from electrode layers and substrate layers, and a converter containing the laminate. Effects of the Invention

[0013] According to the present invention, a laminate, its use and manufacturing method can be provided, wherein the laminate system laminates an organic polysiloxane curable film with improved adhesion between the dielectric layer and the electrode layer or the substrate layer, and at the interface of the curable film constituting the laminate, it is not easy to generate peeling or defects caused by insufficient adhesion strength and followability.

[0014] In particular, the converter of the present invention uses a curable organopolysiloxane composition, which forms a laminate with a structure in which chemical bonds are formed at least locally at the interface of the two layers by coating the composition before curing onto at least one side of the electrode layer or the substrate layer and curing it. Therefore, it has the following advantages: a laminate in which the cured film, the electrode layer and / or the substrate layer are bonded with sufficient strength in a practically necessary manner can be manufactured efficiently without additional bonding steps or pretreatment, and a laminate with excellent reliability for use as a converter and its manufacturing method can be provided.

Implementation Method

[0016] First, the curable organopolysiloxane composition for the converter of the present invention will be described in detail. Hereinafter, "converter" in this specification refers to all electronic devices that have the function of converting mechanical energy into electrical energy, and includes the concept of sensors, speakers, actuators, and generators. The curable organopolysiloxane composition of the present invention has better pre-curing and post-curing characteristics in terms of its cured form, especially the cured film, as a component constituting the above-mentioned converter.

[0017] The composition of the present invention contains at least: (A) one or more organopolysiloxanes having at least two alkenyl groups having 2 to 12 carbon atoms in one or more molecules; (B1) an organohydrogen polysiloxane having at least one silicon atom bonded to a hydrogen atom at the side chain of the molecular chain, having no silicon atom bonded to a hydrogen atom at at least one end of the molecular chain, and having at least two silicon atom bonded to hydrogen atoms within the molecule; (B2) an organohydrogen polysiloxane having silicon atom bonded to hydrogen atoms at both ends of the molecular chain, and having at least two silicon atom bonded to hydrogen atoms within the molecule; (C) an effective amount of catalyst for hydrosiliconization reaction; (D) a reinforcing filler; and (E) a tackifier; and may optionally contain hydrosiliconization reaction inhibitors, other organic solvents and other arbitrary additives.

[0018] The composition of the present invention is a hardening type composition that utilizes the hydrogenation reaction of alkenyl groups and silicon atoms to bond hydrogen atoms. It has the advantages of relatively fast overall hardening and easy control of the reaction. The hardening reaction is carried out under heating, high-energy line irradiation, or a combination thereof.

[0019] The above-mentioned component (A) is an organopolysiloxane having a curing reactive group containing a carbon-carbon double bond. Examples include linear, branched, cyclic, or resinous (network) organopolysiloxanes containing the following curing reactive groups in the molecule, wherein the curing reactive groups are selected from alkenyl groups such as vinyl with 2 to 20 carbon atoms; 3-propenyloxypropyl, 3-methacryloxypropyl, etc., containing (meth)acrylic acid groups.

[0020] The organopolysiloxane as component (A) may contain a group selected from monovalent hydrocarbon groups, hydroxyl groups, and alkoxy groups having 1 to 3 carbon atoms that do not have a carbon-carbon double bond within the molecule. Furthermore, some hydrogen atoms of the monovalent hydrocarbon group may be replaced by halogen atoms or hydroxyl groups, and when used as a dielectric layer, it may also incorporate the dielectric functional groups described later. Industrially preferred are methyl, phenyl, hydroxyl, alkoxy, and the dielectric functional groups described later. Additionally, if component (A) contains hydroxyl groups, etc., in addition to the curing property of hydrogen silane reaction, the component also has condensation reactivity.

[0021] When used in a dielectric layer, component (A) is preferably an organic polysiloxane or a mixture thereof represented by the following average composition formula: R1aR2bSiO(4-ab) / 2. In the formula, R1 is the aforementioned curing reactive group containing a carbon-carbon double bond, and R2 is a group selected from the aforementioned monovalent hydrocarbon group, hydroxyl group, and alkoxy group that does not have a carbon-carbon double bond. a and b are numbers satisfying the following conditions: 1≦a+b≦3 and 0.001≦a / (a+b)≦0.33, preferably satisfying the following conditions: 1.5≦a+b≦2.5 and 0.005≦a / (a+b)≦0.2. The reason is that when a+b is above the lower limit of the above range, the softness of the hardened material will increase. On the other hand, when a+b is below the upper limit of the above range, the mechanical strength of the hardened material will increase. When a / (a+b) is above the lower limit of the above range, the mechanical strength of the hardened material will increase. On the other hand, when a / (a+b) is below the upper limit of the above range, the softness of the hardened material will increase.

[0022] Here, when using component (A), the value of px1, which is related to the crosslinking density and crosslinking structure of the composition described later, should be selected or designed in a manner that the amount (Vi) of the alkenyl group or other hardening reactive groups containing carbon-carbon double bonds in component (A) is in the range of 0.1 to 6.0, more preferably 0.5 to 6.0, even more preferably 1.0 to 6.0, and even more preferably 1.5 to 5.5.

[0023] In this invention, component (A) is preferably introduced intramolecularly as a fluoroalkyl group represented by (CpF2p+1)-R- (R is an alkyl group with 1 to 10 carbon atoms, and p is an integer from 1 to 8). Considering dielectric properties, economy, ease of manufacture, and the molding and processability of the obtained curable organopolysiloxane composition, a group with p=1, i.e., trifluoropropyl, is preferred.

[0024] Preferably, at least part or all of component (A1) is an organofluoroalkyl polysiloxane having at least two alkenyl groups having 2 to 12 carbon atoms in one or more molecules, and at least 10 mol% of all substituents on the silicon atom are fluoroalkyl groups represented by (CpF2p+1)-R- (R is an alkenyl group having 1 to 10 carbon atoms, and p is an integer between 1 and 8). By using this component (A1) as a main agent, a fluorinated organofluoropolysiloxane cured film with excellent dielectric properties can be obtained.

[0025] Furthermore, when the cured film formed by curing this composition is used as the dielectric layer of a converter, component (A) of the present invention is preferably (a1-1) a straight-chain or branched fluoroorganopolysiloxane having only an alkenyl group at the end of the molecular chain, or (a1-2) an alkenyl-containing fluoroorganopolysiloxane resin having at least one branched siloxane unit within the molecule, with an ethylene (CH2=CH-) group content in the range of 1.0 to 5.0% by mass, or a mixture of such fluoroorganopolysiloxanes.

[0026] Component (a1-1) is a linear or branched fluoroorganopolysiloxane whose molecular chain ends have siloxane units represented by (Alk)R22SiO1 / 2 (where Alk is an alkenyl group with 2 or more carbon atoms), and other siloxane units are substantially composed only of siloxane units represented by R22SiO2 / 2. Additionally, R2 represents the same group as described above. Furthermore, including the terminal siloxane units, the degree of polymerization of component (a1-1) is in the range of 7 to 1002, or possibly in the range of 102 to 902. This component (a1-1) is preferably a linear fluoroorganopolysiloxane whose molecular chain ends are capped with siloxane units represented by (Alk)R22SiO1 / 2.

[0027] Component (a1-2) is an alkenyl-containing fluorinated organosiloxane resin, which can be exemplified by an alkenyl-containing fluorinated organosiloxane resin represented by the average unit formula: (RSiO3 / 2)o(R2SiO2 / 2)p(R3SiO1 / 2)q(SiO4 / 2)r(XO1 / 2)s. In the above formula, R is selected from alkenyl groups and monovalent hydrocarbon groups that do not have carbon-carbon double bonds, and X is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms. Among all R, at least in the range of 1.0 to 5.0% by mass of ethylene (CH2=CH-) group content in the fluorinated organosiloxane resin, R is alkenyl, and preferably at least a portion of R on the silicate unit represented by R3SiO1 / 2 is alkenyl.

[0028] 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.

[0029] As a component (a1-2), it is particularly preferred to exemplify an alkenyl-containing MQ fluoroorganic polysiloxane resin represented by {(Alk)R22SiO1 / 2}q1(R23SiO1 / 2)q2(SiO4 / 2)r (where Alk and R2 are the same groups 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 fluoroorganic polysiloxane resin in which the ethylene (CH2=CH-) group content satisfies the range of 1.0 to 5.0% by mass).

[0030] The components (a1-1) with alkenyl groups only at the ends of the molecular chains and the components (a1-2) with a certain amount of alkenyl groups as fluorinated organopolysiloxane resins can be used simultaneously to form a curing reactant with excellent curability, mechanical strength and flexibility as a whole, thereby providing a fluorinated organopolysiloxane curing film that is particularly suitable for adhesive layers or dielectric layers of the aforementioned electronic components.

[0031] Component (B) is an organohydrogen polysiloxane having at least two silicon-bonded hydrogen atoms in its molecule, and functions as a (B1) crosslinking agent or (B2) chain extender of component (A). Specifically, component (B1) is an organohydrogen polysiloxane having at least one silicon-bonded hydrogen atom at the side chain of its molecular chain, having no silicon-bonded hydrogen atom at at least one end of its molecular chain, and having at least two silicon-bonded hydrogen atoms in its molecule. It differs from component (B2) in that it does not have silicon-bonded hydrogen atoms at both ends. Preferably, it is a structure in which the two ends of the molecular chain are capped with functional groups that are non-reactive to hydrogenation reactions (especially reactions with the aforementioned component (A)). Component (B1) has hydrogen atoms bonded to the silicon atoms constituting the main chain of the siloxane molecule (i.e., hydrogen atoms bonded to the side chain sites). Therefore, intermolecular cross-linking structures are formed between the hydrogen atoms on the side chains and the hardening reactive groups in component (A). On the other hand, the chain elongation effect of the cross-linked product is limited. Furthermore, component (B2) is an organohydrogen polysiloxane with silicon atoms bonded to hydrogen atoms at both ends of the molecular chain and at least two silicon atoms bonded to hydrogen atoms within the molecule, preferably having two silicon atoms bonded to hydrogen atoms (i.e., only at both ends of the molecular chain). This component (B2) reacts with the hardening reactive groups in component (A) to introduce a long siloxane molecular structure into the cross-linked product, thereby imparting appropriate softness and elasticity to the cross-linked product.

[0032] Examples of this component (B1) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris(dimethylhydrosiloxy)methylsilane, tris(dimethylhydrosiloxy)phenylsilane, methylhydropolysiloxane with both ends of the molecular chain capped by trimethylsiloxy groups, dimethylsiloxane-methylhydrosiloxane copolymer with both ends of the molecular chain capped by trimethylsiloxy groups, methylhydrosiloxane-diphenylsiloxane copolymer with both ends of the molecular chain capped by trimethylsiloxy groups, and others with both ends of the molecular chain capped by trimethylsiloxy groups. The following are copolymers of trimethylsiloxy-terminated methylhydrosiloxane-diphenylsiloxane-dimethylsiloxane, copolymers of methylhydrosiloxane-dimethylsiloxane-trifluoropropylmethylsiloxane with trimethylsiloxy-terminated ends, hydrolytic condensates of trimethoxysilane, copolymers composed of (CH3)2HSiO1 / 2 units and SiO4 / 2 units, copolymers composed of (CH3)2HSiO1 / 2 units, SiO4 / 2 units and (C6H5)SiO3 / 2 units, and mixtures of two or more of these.

[0033] Examples of such component (B2) include dimethylsiloxanes whose molecular chains are capped at both ends by dimethylhydrosiloxy groups, dimethylsiloxane-diphenylsiloxane copolymers whose molecular chains are capped at both ends by dimethylhydrosiloxy groups, dimethylsiloxane-trifluoropropylmethylsiloxane copolymers whose molecular chains are capped at both ends by dimethylhydrosiloxy groups, dimethylsiloxane-methylhydrosiloxane copolymers whose molecular chains are capped at both ends by dimethylhydrosiloxy groups, and mixtures of two or more of these.

[0034] [Parameter pxl] The curable organopolysiloxane composition for converters of the present invention is characterized in that the value of pxl for components (A), (B1), and (B2) is within a specified range, as defined by the following parameter. px1 is a parameter used to describe the crosslinking density and intermolecular crosslinking structure of the cured product obtained by curing this composition. It is defined by the following relationship: px1 = {HB1 / HB2} / {(HB1+HB2) / Vi}, using the number of silicon atoms bonded to hydrogen atoms (HB1) in component (B1), the number of silicon atoms bonded to hydrogen atoms (HB2) in component (B2), and the total number of curing reactive groups containing carbon-carbon double bonds (Vi) in component (A). The types and amounts of components (A), (B1), and (B2) must be in the range of px1 values ​​from 0.1 to 6.0. Furthermore, considering the performance of the cured product formed by curing this composition, especially the cured film, as a component for a converter and its adhesion to the substrate layer or electrode layer, the value of px1 is preferably in the range of 0.5 to 6.0, more preferably in the range of 1.0 to 6.0, and even more preferably in the range of 1.5 to 6.0. On the one hand, if the value of px1 exceeds the aforementioned upper limit, the adhesion of the cured product will decrease, or the storage modulus will not be suitable for the purpose of this invention. On the other hand, if the value of px1 is less than the aforementioned lower limit, there may be insufficient cross-linking or curing reaction.

[0035] The technical meaning of pxl will be explained. This composition contains two organohydrogen polysiloxanes. Component (B1) functions as a crosslinking agent, and component (B2) functions as a chain extender. {HB1 / HB2} represents the ratio of Si-H in the crosslinking agent and the chain extender. If such ratio is within a specific range, a crosslinked structure is formed with a moderately long intermolecular distance for the curing reactive groups in component (A), thereby easily achieving moderate hardness and a rubber-like storage modulus. Furthermore, if the value of pxl obtained by dividing the above {HB1 / HB2} by the value of (HB1+[HB2) / Vi, which represents the "SiH / Vi ratio" of the composition as a whole, is in the range of 0.1 to 6.0, the storage modulus of the film cured as a crosslinked material, its conformability to thermoplastic resins or electrode layers, and its adhesion are improved. In addition, in this invention, a two-layer chemically bonded structure can be achieved by using the tackifier as component (E).

[0036] In addition, the amounts of components (B1) and (B2) used need to meet the above ranges. Preferably, the sum of silicon-bonded hydrogen atoms of components (B1) and (B2) is in the range of 0.1 to 10 mol relative to 1 mol of carbon-carbon double bond in component (A), more preferably in the range of 0.5 to 2.5 mol, and even more preferably in the range of 0.5 to 2.0 mol.

[0037] Component (C) is a catalyst used to promote the hydrosiliconization reaction of components (A) and (B). Examples of catalysts 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 micropowder, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, platinum-alkenyl silicate complexes, platinum-olefin complexes, platinum-carbonyl complexes, and catalysts that disperse or encapsulate these platinum-based catalysts using thermoplastic resins such as silicone resin, polycarbonate resin, and acrylic resin. Platinum-alkenyl silicate complexes are particularly preferred. A platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is particularly preferred, and it is more preferably added in the form of an alkenyl silicate solution of this complex. Furthermore, from the viewpoint of improving operability and the shelf life of the composition, particulate platinum-containing silicon hydrocracking catalysts dispersed or encapsulated using thermoplastic resins can also be used. In addition, non-platinum metal catalysts such as iron, ruthenium, and iron / cobalt can also be used as catalysts to promote the silicon hydrocracking reaction.

[0038] Furthermore, the catalyst for the hydrosiliconization reaction, which is component (C), can be a hydrosiliconization reaction catalyst that does not exhibit activity without irradiation with a high-energy line, but exhibits activity in the composition by irradiation with a high-energy line; this is called a high-energy line activated catalyst or a photoactivated catalyst. By using this component (C), the composition as a whole can be hardened at low temperatures by using irradiation with a high-energy line as an inducing factor, exhibits excellent storage stability, and is easy to control the reaction, thus achieving excellent workability.

[0039] Examples of high-energy rays include ultraviolet light, gamma rays, X-rays, alpha rays, and electron beams. Examples of high-energy rays include ultraviolet light, X-rays, and electron beams irradiated by commercially available electron beam irradiation devices. From the viewpoint of catalyst activation efficiency, ultraviolet light is preferred; from the viewpoint of industrial use, ultraviolet light with a wavelength in the range of 280 to 380 nm is preferred. Furthermore, the irradiation dose varies depending on the type of high-energy-energy-energy-active catalyst; when using ultraviolet light, the cumulative irradiation dose at a wavelength of 365 nm is preferably in the range of 100 mJ / cm² to 100 J / cm².

[0040] Specific examples of ingredient (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(acetylpyruvate)platinum (IV), trimethyl(3,5-heptadiene)platinum (IV), and trimethyl(3,5-heptadiene)platinum (IV). Platinum (IV) of 2,4-pentanedione, platinum (IV) of trimethyl(methylacetic acid), platinum (II) of bis(2,4-pentanedione), platinum (II) of bis(2,4-hexanedione), platinum (II) of bis(2,4-heptadecanedione), platinum (II) of bis(3,5-heptadecanedione), platinum (II) of bis(1-phenyl-1,3-butanedione), platinum (II) of bis(1,3-diphenyl-1,3-propanedione), platinum (II) of bis(hexafluoroacetylpyruvate), among which, from the viewpoint of versatility and ease of acquisition, (methylcyclopentadienyl)trimethylplatinum (IV) and platinum (II) of bis(2,4-pentanedione) are preferred.

[0041] The amount of component (C) used is an effective amount and is not particularly limited, as long as it is an amount that can promote the curing of the curable organopolysiloxane composition of the present invention. Specifically, relative to the sum of components (A) to (C) (taking the whole as 100% by mass), the amount of metal atoms in the catalyst, expressed in mass units, is 0.01 to 1,000 ppm, preferably 0.1 to 500 ppm of platinum metal atoms in component (C). The reason for this is that if the content of component (C) is less than the lower limit of the above range, curing may be insufficient, and if it exceeds the upper limit of the above range, in addition to being detrimental to cost savings, it may also have an adverse effect on transparency, such as the coloring of the obtained cured product.

[0042] The curable organopolysiloxane composition of the present invention includes (D) a reinforcing filler. When the composition is cured to obtain a cured film for a converter as a dielectric layer, the reinforcing filler as component (D) is preferably at least partially composed of inorganic oxide particles represented by silicon dioxide, and preferably contains, within a certain range, reinforcing fillers as component (D) or composites thereof that have been surface-treated with one or more organosilicone compounds and have different average BET specific surface areas, relative to the sum of components (A) to (F) in the composition that will form a non-volatile solid portion through the curing reaction.

[0043] Here, considering the mechanical strength of the hardened material, the reinforcing microparticles are preferably one or more types of reinforcing inorganic microparticles with an average primary particle size of less than 50 nm. Examples include fumed silica, wet silica, pulverized silica, calcium carbonate, diatomaceous earth, micronized quartz, various metal oxide powders other than alumina / zinc oxide, glass fiber, and carbon fiber. These can be treated with one or more of the following organosilicon compounds. Their shape is not particularly limited; any shape, such as particle-like, plate-like, needle-like, or fibrous, can be used.

[0044] As a preferred example, considering the viewpoint of improving the mechanical strength of the dielectric layer, an example can be a hydrophilic or hydrophobic fumed silica or its metal oxide composite with an average primary particle size of 10 nm or less, localized aggregation, and different BET specific surface areas as described below. Furthermore, considering the viewpoint of improving dispersibility, it is preferable to treat the fumed silica or its metal oxide composite with silazane or the silane coupling agent described below. Two or more of these reinforcing inorganic particles can also be used in combination.

[0045] In this invention, the reinforcing filler material for the dielectric layer comprises: (D1) reinforcing microparticles or composites thereof that have been surface-treated with one or more organosilicon compounds and have an average BET specific surface area exceeding 100 m² / g; and (D2) reinforcing microparticles or composites thereof that have been surface-treated with one or more organosilicon compounds and have an average BET specific surface area in the range of 10 to 100 m² / g. The mass ratio of component (D1) to component (D2) is in the range of 50:50 to 99:1, or in the range of 70:30 to 97:3, preferably in the range of 70:30 to 95:5. When the mass ratio exceeds the above range, the viscosity of the curable fluoroorganopolysiloxane composition before curing may increase, or the mechanical strength and insulation breaking strength after curing may decrease.

[0046] By mixing the above-mentioned (D1) and (D2) components, i.e. reinforcing filler materials, into the composition, the mechanical strength and insulation failure strength of the organopolysiloxane hardened product formed by hardening the organopolysiloxane composition of the present invention can be enhanced.

[0047] [Content (wf) of Component (D)] Preferably, when the sum of the components that will form a non-volatile solid portion through the curing reaction, i.e., the total of components (A) to (E), is set to 100% by mass, the content (wf) of component (D) is in the range of 5 to 40% by mass, and more preferably in the range of 10 to 30% by mass. Dielectric films for converter applications require deformability and adequate resilience. If the content (wf) of component (D) exceeds the above-mentioned upper limit, the viscosity of the composition tends to increase, becoming high-viscosity and making it difficult to achieve uniform coating on the film. In addition, the storage modulus after curing tends to increase, becoming too stiff, and thus failing to fully realize the performance for converter applications. On the other hand, when it is less than the lower limit of the above-mentioned mass percentage range, the physical properties of the curable organopolysiloxane composition after curing may be insufficient.

[0048] More preferably, when the total of components (A) to (E) is set to 100% by mass, the sum of component (D1) and component (D2) is in the range of 5% to 40% by mass, or in the range of 5.0% to 35% by mass, and more preferably in the range of 6.5% to 30% by mass. When the sum exceeds the upper limit of the above-mentioned mass percentage range, it is sometimes difficult to achieve a uniform and thin film coating, and the storage modulus after curing becomes high. When the sum is less than the lower limit of the above-mentioned mass percentage range, the physical properties of the curable organopolysiloxane composition after curing may be insufficient.

[0049] The aforementioned components (D1) and (D2), i.e., the reinforcing filler, are preferably surface-treated with one or more organosilicon compounds. The surface treatment with the organosilicon compound is a hydrophobic treatment, allowing the reinforcing filler to be surface-treated with this organosilicon compound to achieve a high filling rate and uniform dispersion within the fluoroorganopolysiloxane composition. Furthermore, it can suppress the increase in viscosity of the composition and improve molding processability.

[0050] Examples of organosilicone compounds include low molecular weight organosilicone compounds such as silanes, silazines, siloxanes, or similar compounds, as well as organosilicone polymers or oligomers such as polysiloxanes, polycarbosiloxanes, or similar compounds. Preferably, the organosilicone compound used in surface treatment contains at least one selected from hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane.

[0051] 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% by mass to 50% by mass, more preferably in the range of 0.3% by mass to 40% by mass. Furthermore, the treatment amount is the ratio of filler to surface treatment agent, preferably such that any remaining treatment agent is removed after treatment. In addition, additives that promote or assist the reaction may be added as needed during the treatment.

[0052] In the surface treatment, whether the components of the surface treatment agent are chemically or physically fixed to the surface of the filler is an important parameter. For example, the amount of surface treatment agent fixed can be analyzed by reacting excess tetraethoxysilane with the composition containing the filler under alkaline conditions and detecting the reaction products using gas chromatography. The amount of surface treatment agent fixed to the surface of the filler is 1.0 part by mass or more, preferably 3.0 part by mass or more, relative to 100 parts by mass of filler. When hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane are used as the organosilicone compounds in the surface treatment of components (D1) and (D2) of the present invention, the fixation ratio of each on the surface of the filler can be changed as needed. For example, in this invention, as described above, a fluoroalkyl group represented by (CpF2p+1)-R- (where R is an alkyl group with 1 to 10 carbon atoms and p is an integer from 1 to 8) can be introduced into part or all of component (A) or component (B1) and component (B2) as a high dielectric functional group. Considering dielectric properties, economy, ease of manufacture, and the molding and processability of the resulting curable fluoroorganopolysiloxane composition, a group with p=1, i.e., trifluoropropyl, is preferred. In this case, the weight ratio of the treated components from hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane fixed on the filler surface is preferably 0 to 10. Beyond this range, the affinity between component (A) or component (B) and the filler surface will deteriorate, and processability and post-curing properties may decrease.

[0053] [Other functional fillers] In the curable fluoroorganopolysiloxane composition of the present invention, other filler materials may be used or not used as needed. Examples include high dielectric fillers, thermally conductive inorganic microparticles, insulating fillers, etc. These inorganic microparticles sometimes have two or more functions, such as serving as reinforcing filler materials.

[0054] Examples of preferred dielectric inorganic particles include one or more inorganic particles selected from the group consisting of titanium oxide, barium titanate, strontium titanate, lead zirconate titanate, and composite metal oxides in which a portion of the barium and titanium portions of barium titanate is replaced by alkaline earth metals such as calcium, strontium, yttrium, neodymium, samarium, and dysprosium, zirconium, or rare earth metals. More preferably, titanium oxide, barium titanate, barium zirconate calcium titanate, and strontium titanate are used, and even more preferably, titanium oxide and barium titanate are used. It is particularly preferred that at least a portion of the dielectric inorganic particles are dielectric inorganic particles with a dielectric constant of 10 or more at 1 kHz at room temperature. Furthermore, the upper limit of the preferred size (average primary particle size) of the inorganic particles is 20,000 nm (20 µm), but considering the processability of the thin film for the converter described below, it is more preferably 10,000 nm (10 µm). By using this dielectric inorganic microparticle, it is sometimes possible to further improve the mechanical and / or electrical properties of fluorinated organosiloxane cured materials, especially the dielectric constant.

[0055] As the insulating inorganic microparticles that can be used in this invention, any well-known insulating inorganic material, i.e., particles of inorganic materials with a volume resistivity of 10¹⁰ to 10¹⁸ Ω·cm, is acceptable and is not limited in shape. The shape can be any of particle, flake, or fiber (including whiskers). Specifically, examples include spherical particles, plate-like particles, or fibers of ceramics. Preferred examples include metal silicates such as alumina, iron oxide, copper oxide, mica, or talc, as well as particles of quartz, amorphous silica, and glass. Furthermore, the latter can be treated with various surface treatment agents described below. These can be used alone or in combination of two or more. By mixing insulating inorganic microparticles into the composition, the mechanical strength and insulation breaking strength of the cured fluorinated organopolysiloxane can sometimes be increased, as well as the dielectric constant.

[0056] Examples of thermally conductive inorganic microparticles that can be used in this invention include metal oxide particles such as magnesium oxide, zinc oxide, nickel oxide, vanadium oxide, copper oxide, iron oxide, and silver oxide, as well as inorganic compound particles such as aluminum nitride, boron nitride, silicon carbide, titanium carbide, diamond, and diamond-like carbon. Zinc oxide, boron nitride, silicon carbide, and silicon nitride are preferred. By mixing one or more of these thermally conductive inorganic microparticles into the composition, the thermal conductivity of the fluorinated organopolysiloxane cured material can be increased.

[0057] When determining the average particle size of these inorganic particles, conventional measurement methods can be used in the field. For example, when the average particle size is 50 nm or more but less than about 500 nm, microscopic observation can be performed using a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a scanning electron microscope (SEM), or a field emission scanning electron microscope (FE-SEM) to measure the particle size, and the average primary particle size can be determined by calculating the average value. On the other hand, when the average particle size is about 500 nm or more, the value of the average primary particle size can be directly calculated using a laser diffraction / scattering particle size distribution measuring device.

[0058] The curable organopolysiloxane composition of the present invention contains (E) a tackifier. In particular, the composition of the present invention cures to form a cured product with a specific crosslinking density and intermolecular crosslinking structure. Due to the presence of the tackifier, chemical bonds can be formed with the surface of the substrate layer or electrode layer coated with the composition, thereby achieving strong adhesion and conformability. On the other hand, when the value of the parameter pxl related to the crosslinking density / crosslinking structure described above does not meet the aforementioned range, even a cured product containing a tackifier may sometimes fail to sufficiently improve adhesion to the substrate layer, etc.

[0059] (E) The amount of tackifier used can be appropriately designed according to the required adhesion, the type of substrate layer or electrode layer, etc. Considering the viewpoint of achieving practically sufficient adhesive strength and conformability for substrate layers and electrode layers formed of thermoplastic resins such as polyethylene terephthalate (PET), it is preferable that when the total of components (A) to (E) constituting the composition is set to 100% by mass, the content of component (E) is 0.1% by mass to 10% by mass, more preferably 0.25% by mass to 5.0% by mass, and even more preferably in the range of 0.5% by mass to 2.0% by mass.

[0060] As a thickener, it is preferably an organosilicone compound having at least one alkoxy group bonded to a silicon atom in one molecule. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy, with methoxy being particularly preferred. In addition, examples of groups other than the alkoxy group in the organosilicone compound that are bonded to the silicon atom include halogen-substituted or unsubstituted monovalent hydrocarbon groups such as alkyl, alkenyl, aryl, aralkyl, and haloalkyl; glycidoxyalkyl groups such as 3-glycidoxypropyl and 4-glycidoxybutyl; epoxycyclohexylalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl and 3-(3,4-epoxycyclohexyl)propyl; epoxyalkyl groups such as 3,4-epoxybutyl and 7,8-epoxyoctyl; monovalent organic groups containing an acrylic group such as 3-methacryloxypropyl; and hydrogen atoms. The organosilicone compound preferably has a group that can react with the alkenyl or silicon-bonded hydrogen atom in the composition; specifically, it preferably has a silicon-bonded hydrogen atom or an alkenyl group. Furthermore, considering good adhesion to various substrates, the organosilicone compound is preferably one molecule containing at least one monovalent organic group with an epoxy group.

[0061] Examples of such organosilicone compounds include organosilane compounds, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of such organosiloxane oligomers or alkyl silicates include linear, partially branched linear, branched, cyclic, and network structures, with linear, branched, and network structures being particularly preferred. Examples of organosilicone compounds include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; siloxane compounds in which at least one silicon atom is bonded to an alkenyl group or a silicon atom is bonded to a hydrogen atom and a silicon atom is bonded to an alkoxy group; and silicon compounds in which at least one silicon atom is bonded to an alkoxy group. A mixture of alkane or siloxane compounds and a molecule of a siloxane compound having at least one silicon atom bonded to a hydroxyl group and a silicon atom bonded to an alkenyl group; a reaction mixture of an organoalkoxysilane containing an amino group and an organoalkoxysilane containing an epoxy group; an organic compound having at least two alkoxysilyl groups in a molecule and the silicon groups being bonded by a bond other than a silicon-oxygen bond; an epoxy-containing silane or its partially hydrolyzed condensate represented by the general formula: RanSi(ORb)4-n (where Ra is a monovalent epoxy-containing organic group, Rb is an alkyl or hydrogen atom having 1 to 6 carbon atoms, and n is a number in the range of 1 to 3); a reaction mixture of a vinyl-containing siloxane oligomer (including those with chain or cyclic structures) and an epoxy-containing trialkoxysilane; polymethyl silicate; polyethyl silicate; and epoxy-containing polyethyl silicate. The thickener is preferably a low-viscosity liquid, and its viscosity is not limited, but is preferably in the range of 1 to 500 mPa·s at 25°C. Furthermore, the content of the thickener is not limited, but is preferably in the range of 0.01 to 10 parts by mass relative to 100 parts by mass of the total composition.

[0062] In this invention, a preferred tackifier may be, for example, a reaction mixture of a vinyl-containing silica oligomer (including those with chain or cyclic structures) and an epoxy-containing trialkoxysilane.

[0063] [Silicosis Reaction Inhibitor] The silicosis reaction inhibitor is formulated to inhibit the cross-linking reaction and chain elongation reaction between component (A) and component (B), thereby extending the usable time at room temperature and improving storage stability. Therefore, it is a component that will inevitably be mixed in practical application for the curing composition of the present invention.

[0064] Examples of inhibitors for hydrosiliconization reactions include acetylene compounds, enyne compounds, organonitrogen compounds, organophosphorus compounds, and oxime compounds. Specifically, examples include acetylenols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 1-acetylen-1-cyclohexanol, and phenylbutanol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-1-hexyn-3-yne; methylenylcyclosiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; and benzotriazole.

[0065] The amount of the silane hydrocracking reaction inhibitor is the effective amount for extending the usable time of the curable fluoroorganopolysiloxane composition for film formation of the present invention at room temperature and improving its storage stability. Generally, the amount of each component (A) is 100% by mass, ranging from 0.001% to 5% by mass, preferably from 0.01% to 2% by mass, and can be appropriately selected according to the type of component, the performance and content of the platinum catalyst, the amount of alkenyl groups in component (A), and the amount of silicon atoms bonded to hydrogen atoms in component (B).

[0066] [Use of Solvents] The curable fluoroorganopolysiloxane composition of the present invention can be directly used in the curing reaction. However, when the composition or a portion thereof (e.g., fluoroorganopolysiloxane resin) is in a solid or viscous liquid state, an organic solvent may be used as needed to improve its miscibility and workability. In particular, when the curable fluoroorganopolysiloxane composition of the present invention is coated into a film, a solvent may be used to adjust the viscosity to make the overall viscosity in the range of 100 to 50,000 mPa·s. When diluting with a solvent, the solvent may be used in the range of 0 to 2000 parts by mass relative to the sum of the components (A) to (C) above (100 parts by mass). That is, in the composition of the present invention, the solvent may be 0 parts by mass, making it solvent-free. In particular, in the curable fluorinated organopolysiloxane composition of the present invention, by selecting polymers with low polymerization degrees, it can be designed to be solvent-free, thereby having the advantage that no fluorinated solvents, organic solvents, etc. remain in the film obtained after curing, solving the problem of environmental pollution and eliminating the influence of solvents on electronic devices. Furthermore, relative to the sum of the components (A) to (C) above (100 parts by mass), the amount of solvent used can be, and preferably, less than 10 parts by mass, and more preferably less than 5 parts by mass, of a low-solvent composition. In addition, the composition used, especially for the electrode layer, can be diluted with solvent as described in the embodiments below, and coated into a thin film by spraying.

[0067] Preferably, the organic solvent is one or more organic solvents selected from (F1) organic polar solvents, (F2) low molecular weight silicate solvents, and (F3) halogen solvents, or a mixture thereof, preferably having a boiling point of 80°C or higher and less than 200°C. Alternatively, it can be a mixture of different types or the same type of organic solvent but with different ratios. The aforementioned organic solvent is preferably one containing at least one low molecular weight silicate solvent selected from hexamethyldisiloxane and octamethyltrisiloxane, or a mixture thereof, which can be purchased from Dow Organic Silicones under the names OS-10, O-20, and OS-2. Furthermore, when the fluoroalkyl content in the curable elastomer composition is high, the simultaneous use of these low molecular weight silicate solvents and the aforementioned halogen solvents is also included in the preferred embodiments of the present invention.

[0068] [Viscosity and Thixotropy of the Composition] The composition of the present invention can be coated onto a substrate layer or electrode layer and cured into a thin film for use. In particular, when its overall viscosity and thixotropy are within a certain range, it is easy to coat uniformly onto a substrate layer, etc., and can improve the adhesion and conformability to the substrate / electrode layer during curing. In particular, compositions having a thixotropic index as defined below and containing a tackifier are especially advantageous in terms of easy formation of interfacial adhesion and chemical bonds. [Overall Viscosity] The overall viscosity of the curable fluoroorganopolysiloxane composition used in the present invention, measured at 25°C and a shear rate of 0.1 (s⁻¹), is preferably in the range of 5 to 5,000,000 mPa·s, and more preferably in the range of 1,000 to 2,500,000 mPa·s. For the purpose of setting a better viscosity range, the amount of the above-mentioned organic solvent can be adjusted, but it can also be set as a low-solvent type or a solvent-free type (= solvent-free type). [Thixotropic Index (TI)] The curable fluoroorganopolysiloxane composition of the present invention preferably has excellent flowability and moderate thixotropic behavior. Therefore, it is possible to achieve properties of low overall viscosity and excellent uniform coating. Specifically, the ratio of the overall viscosity of the composition (η0.1) measured at a shear rate of 0.1 (S-1) to the overall viscosity of the composition (η10.0) measured at a shear rate of 10.0 (S-1), i.e., TI (=η0.1 / η10.0), is preferably 250 or less. Considering the viewpoint of uniform coating, the TI of this composition is particularly preferably 100 or less, and more preferably in the range of 10 to 80. [Amount of solid component] In the curable fluoroorganopolysiloxane composition of the present invention, the content of the non-volatile solid component formed after curing, namely the cured fluoroorganopolysiloxane (sometimes referred to as "solid component" in the present invention), is preferably in the range of 5 to 100% by mass of the total composition, more preferably in the range of 50 to 100% by mass, 75 to 100% by mass, or 85 to 100% by mass.

[0069] [Introduction of Dielectric Functional Groups] When the organopolysiloxane cured film of the present invention is used as an electroactive film (e.g., a dielectric film) for use in transducers such as sensors and actuators, high dielectric functional groups can be introduced into the cured film. However, even organopolysiloxane cured films without high dielectric functional groups can be used as electroactive films. Furthermore, regarding the introduction of such high dielectric functional groups and the increase of dielectric constant, for example, the applicant of this case has made proposals in International Patent Publication No. WO2014 / 105959.

[0070] The introduction of high dielectric functional groups can be carried out by using a fluorinated organosiloxane or an organohydrosiloxane having high dielectric functional groups as part or all of the aforementioned component (A) or component (B); adding an organic additive having high dielectric functional groups, a non-reactive organosilicone compound having high dielectric functional groups, etc., to the aforementioned curing composition. Considering the miscibility with the curing composition and the increase in the dielectric constant of the cured product, in the aforementioned component (A) or component (B), i.e., the fluorinated organosiloxane or the organohydrosiloxane, it is preferable that 10 mol% or more, more preferably 20 mol% or more, and more preferably 40 mol% or more of all substituents on the silicon atoms are replaced by high dielectric functional groups. For example, in the aforementioned component (A1), 10 mol% or more, preferably 20 mol% or more, and more preferably 40 mol% or more of all substituents on the silicon atom are fluoroalkyl groups represented by (CpF2p+1)-R- (R is an alkyl group with 1 to 10 carbon atoms, and p is an integer from 1 to 8).

[0071] There are no particular restrictions on the types of high dielectric functional groups introduced into the organopolysiloxane curable film. Examples include a) halogen atoms and groups containing halogen atoms, such as 3,3,3-trifluoropropyl; b) nitrogen-containing groups, such as cyanopropyl; c) oxygen-containing groups, such as carbonyl; d) heterocyclic groups such as imidazole; e) boron-containing groups such as boron ester; f) phosphorus-containing groups such as phosphine; and g) sulfur-containing groups such as thiol. Halogen atoms containing fluorine atoms and groups containing halogen atoms are preferred.

[0072] In this invention, it is preferable that component (A) or component (B) contains, in part or all of a fluoroalkyl group represented by (CpF2p+1)-R- (R is an alkyl group with 1 to 10 carbon atoms, and p is an integer from 1 to 8) as a high dielectric functional group. Such fluoroalkyl groups can produce cured products with excellent dielectric constants, and because each component has fluorine atoms, the compatibility of each component can be improved, resulting in cured products with excellent transparency. Specific examples of such fluoroalkyl groups include trifluoropropyl, pentafluorobutyl, heptafluoropentyl, nonafluorohexyl, undecafluoroheptyl, tridecafluorooctyl, pentadecylfluorononyl, and heptadecafluorodecyl. Among these, considering dielectric properties, economy, ease of manufacture, and the molding and processability of the resulting cured fluoroorganopolysiloxane composition, a p=1 group, i.e., trifluoropropyl, is preferred.

[0073] The curable fluoroorganopolysiloxane composition of the present invention can be prepared by uniformly mixing a curable fluoroorganopolysiloxane and a component that promotes the curing reaction, preferably the above-mentioned components (A) to (E), and adding any other arbitrary components as needed. Although various mixers or kneaders can be used for mixing at room temperature, if the combination of components that will not harden during mixing is present, it can also be mixed under heat.

[0074] If the mixture will not be cured, there are no particular restrictions on the order of mixing the components. If the mixture is not to be used immediately after mixing, the crosslinking agent (e.g., component (B1)) and the component that promotes the curing reaction (e.g., component (C)) can be stored separately in multiple containers, and should not be stored in the same container. The components in all containers should be mixed just before use.

[0075] Regarding the curing reaction of the curable fluoroorganopolysiloxane composition of the present invention, the curing reaction based on condensation reactions such as dehydration and de-alcoholization is carried out at room temperature. However, when producing fluoroorganopolysiloxane cured films by industrial production processes, it is usually achieved by heating the composition or exposing it to an active energy line. The temperature at which the curing reaction is carried out using heat is not particularly limited, but it is preferably 50°C to 200°C, more preferably 60°C to 200°C, and even more preferably 80°C to 180°C. In addition, the time taken for the curing reaction depends on the structure of the components (A), (B), (C), and (E) above, but is usually 1 second to 3 hours. Generally, a cured product can be obtained by maintaining the temperature in the range of 90 to 180°C for 10 seconds to 120 minutes. Furthermore, the method for manufacturing the film is described below.

[0076] Examples of active energy beams that can be used in the hardening reaction include ultraviolet light, electron beams, and radiation. From a practical point of view, ultraviolet light is preferred. When using ultraviolet light to carry out the hardening reaction, it is preferable to add a catalyst for silane hydrocracking that is highly active to the ultraviolet light used, such as bis(2,4-pentanedione)platinum complex or (methylcyclopentadienyl)trimethylplatinum complex. As the ultraviolet light source, high-pressure mercury lamps, medium-pressure mercury lamps, Xe-Hg lamps, and deep ultraviolet lamps are preferred, and the irradiation dose is preferably 100 to 8,000 mJ / cm2.

[0077] [Organopolysiloxane cured material] The storage modulus (G') of the cured material formed by curing this composition at 23°C and 0.02 Hz under minute deformation is preferably in the range of 1.0 × 10³ to 5.0 × 10⁴ Pa. If it is lower than this value, the strength and processability will decrease; if it is higher than this value, the hardness will increase, resulting in a decrease in the performance of the converter.

[0078] The organopolysiloxane curable of the present invention is preferably a curable containing a high-dielectric functional group represented by trifluoropropyl as part of component (A) and having an excellent dielectric constant. This curable is preferably in the form of a thin film. In particular, the curable film obtained by curing the composition of the present invention is suitable for use as a dielectric layer in a converter, and is especially preferably in the form of an organopolysiloxane curable film for converters (hereinafter sometimes referred to as "curable film for converters").

[0079] [Laminated Body and Manufacturing Method Thereof] The laminated body of the present invention is a converter or a converter component, having a structure formed by laminating the aforementioned converter thin film curing material and one or more layers selected from electrode layers and substrate layers. Here, the converter thin film curing material, which serves as the dielectric layer, may have an electrode layer on both sides (upper and lower layers), or it may have a structure where both sides (upper and lower layers) are sandwiched by substrate layers, or it may have an electrode layer on one side and a substrate layer on the other side.

[0080] The interface between the converter film curing material of the present invention and one or more layers selected from the electrode layer and the substrate layer is preferably adhered at least partially by chemical bonds, and preferably, when the laminate is to be peeled off, the interface will undergo cohesive destruction (CF) of the converter film curing material.

[0081] Other layers constituting the laminate of the present invention may be synthetic resin layers such as thermoplastic resin, metal layers, or polysiloxane curable layers containing conductive particles (which are electrode layers and are different from the thin film curable material for converters of the present invention). There are no particular limitations. When at least a portion of the electrode layers and / or the substrate layer are thermoplastic resin layers (which are thermoplastic resin layers containing conductive particles when they are electrode layers), a laminate having a structure in which chemical bonds are formed at least partially at the interface of the two layers and the laminate is bonded together can be obtained by coating at least a portion of the curable organic polysiloxane composition for converters of the present invention onto at least a portion of the layers and curing it. In particular, when thermoplastic resin layers such as PET are conventional polysiloxane curing layers, sufficient adhesion / adhesion cannot be achieved, resulting in interlayer delamination when used as converter components. However, the converter film curing material of the present invention has the following advantages: it can significantly improve the performance, reliability and durability of the converter component in terms of firmly bonding the two and achieving a high degree of conformity.

[0082] There are no particular limitations on the thermoplastic resin layer that can be used in the laminate of the present invention. Examples of thermoplastic resin film layers formed from polyethylene terephthalate (PET), polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, cyclic polyolefins, nylon, etc. are also possible. In particular, when heat resistance is required, films of heat-resistant synthetic resins such as polyimide, polyetherketone ether, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide-imide, and polyether ether are preferred. On the other hand, for applications requiring visibility, such as display devices, transparent substrates can be used, specifically transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN. In addition, PET film is commonly used in industry, and the converter film curing material of the present invention can be easily adhered to the PET film.

[0083] The aforementioned substrate layer is preferably in the form of a thin film or sheet. Its thickness is not particularly limited and can be designed to the desired thickness according to the application. Furthermore, in order to improve the adhesion between the substrate layer and the converter film curing material, a primer treatment, corona treatment, etching treatment, or plasma treatment can be performed on the surface of the substrate layer beforehand. However, in this invention, since chemical bonds can be easily formed between the two, it has the advantage that an adhesive laminate can be easily obtained even without such pretreatment.

[0084] There are no particular limitations on the method of obtaining such a laminate. It can be easily manufactured by a manufacturing method having the steps of coating at least one side of a layer selected from an electrode layer and a substrate layer with a curable organopolysiloxane composition of the converter of the present invention and curing it.

[0085] There are no particular limitations on the method for coating the curable fluoroorganopolysiloxane composition into a thin film. Gravure printing coating, offset printing coating, gravure offset printing, roller coating using offset transfer rollers, reverse roller coating, air knife coating, curtain coating using curtain flow coating, comma blade coating, Mayer rod coating, and other well-known methods for forming a curable layer can be used. Furthermore, the curable fluoroorganopolysiloxane composition of the present invention can also be coated in multiple layers.

[0086] Preferably, the laminated body of the present invention is a laminated organopolysiloxane curable film having a chemically bonded structure at its interface. This structure is formed by contacting a thin layer of curable organopolysiloxane composition in an uncured or semi-cured state (before complete curing) with the organopolysiloxane curable film after curing or before curing, or as a precursor, and then using methods such as heating to fully cure it, thereby allowing the curable reactive groups at the interface of the curable film to react with each other. From the viewpoint of industrial production and production efficiency, this process can be performed by curing reaction on each layer, or multiple layers of curable reactive organopolysiloxane composition can be laminated first, and then the whole can be fully cured by methods such as heating.

[0087] More specifically, the laminate of the present invention can be obtained by coating at least one side of a converter-compatible curable organopolysiloxane composition selected from one or more layers selected from electrode layers and substrate layers, and then further depositing other layers selected from one or more layers selected from electrode layers and substrate layers on the coating layer of the composition in an uncured or semi-cured state, and then completely curing the whole. Alternatively, a laminate precursor with a converter-compatible thin film cured between the layers can be produced by laminating two or more layers selected from electrode layers and substrate layers, and having a coating layer formed by an uncured converter-compatible curable organopolysiloxane composition between these layers (e.g., having a configuration of electrode layer / substrate layer / (uncured composition layer) / substrate layer / electrode layer, etc., but not limited thereto), and then curing the whole, thereby producing a laminate with a converter-compatible thin film cured between the layers.

[0088] This manufacturing method is particularly useful as a method for forming electrode layers in components for converters. It can easily provide, in industry, components of laminates, electronic parts or display devices that are firmly bonded to the dielectric layer and the electrode layer and are less prone to peeling or defects caused by insufficient adhesion strength and followability.

[0089] The laminated fluoroorganopolysiloxane cured film of the present invention is suitable as a component for electronic materials, display devices, or converters (including sensors, speakers, actuators, and generators), and is particularly preferred as an electroactive thin film (including high-dielectric thin films) with an electrode layer for use as a component for electronic parts or display devices. Furthermore, as described above, the electroactive thin film with high insulation breaking strength, in the form of a single-layer or laminated film, is suitable for converter components such as actuators, and because it has a structure that firmly bonds the electrode layer, it is particularly useful for applications involving actuators that start under high voltage. Examples

[0090] The present invention is illustrated by the following examples, but the present invention is not limited thereto. The following examples and comparative examples use the following compounds. In addition, the physical properties of each component were determined by the following method. [Viscosity of the component before curing] The viscosity of each component before curing was measured using a viscoelasticity measuring device (Anton-Paar, model MCR302). A cone plate with a diameter of 20 mm and a 2° angle was used, and the shear rate was varied. The overall viscosity η0.1 and η10.0 of the component were recorded at 25°C and shear rates of 0.1 (S-1) and 10.0 (S-1), respectively. The results, including the thixotropic index (TI) value, are shown in Tables 1 and 2. [Storage modulus and loss modulus] After each curable fluoroorganopolysiloxane component was cured at 130°C for 1 hour, the storage modulus was measured using a viscoelasticity measuring device (Anton-Paar, model MCR302). A Peltier element temperature control system and an 8 mm diameter parallel plate were used, with the sample set at a thickness of approximately 2 mm. Frequency sweep measurements were performed at 23 °C with minimal deformation (approximately 0.2%). The storage modulus (G'), loss modulus (G''), and loss tangent at 0.02 Hz are shown in Tables 1 and 2. [Evaluation of Adhesion] Approximately 1 g of the curable fluoroorganopolysiloxane composition was coated onto a 200 µm thick polyethylene terephthalate film and cured at 130 °C for 1 hour. The cured material was then peeled off with a scraper, and the peeling mode (interfacial peeling (AF) or cohesive failure (CF) was visually evaluated based on the presence or absence of cured material residue. The results are shown in Tables 1 and 2.

[0091] ･ Component (A): 3,3,3-trifluoropropylmethyl-dimethylsiloxane copolymer with both ends capped with vinyl dimethylsiloxy groups (vinyl content: 0.26% by mass, degree of polymerization of siloxane: 193) ･ Component (B1): Dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane-methylhydrosiloxane copolymer with both ends capped with trimethylsiloxy groups (content of silicon-bonded hydrogen: approximately 0.23% by mass) ･ Component (B2): Dimethylsiloxane-3,3,3-trifluoropropylmethylsiloxane copolymer with both ends capped with dimethylhydrosiloxy groups (content of silicon-bonded hydrogen: approximately 0.013% by mass) ･ Composition (C): A solution of dimethylsiloxane polymers with both ends of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisilazane complex capped with vinyldimethylsiloxy groups (platinum concentration approximately 0.6% by mass). • Composition (D1): Fumed silica treated with hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane (untreated product name: AEROSIL 200, BET specific surface area 200 m² / g). • Composition (D2): Fumed silica treated with hexamethyldisilazane and 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane (untreated product name: AEROSIL 50, BET specific surface area 50 m² / g). Component (E): Tackifier (=Reaction product of methyl vinyl siloxane with hydroxydimethylsiloxy groups at both ends and glycidoxypropyltrimethoxysilane (vinyl content (wt%) approximately 5.6%)) Component (F): 1,3,5,7-Tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane

[0092] [Cureable Fluoroorganopolysiloxane Compositions of Examples 1 to 4 and Comparative Examples 1 to 6] As a liquid curable fluoroorganopolysiloxane composition, the above-mentioned components were formulated as shown in Table 1 by weight % . The pxl values ​​in the composition were set as shown in Table 1. During mixing of the components, the materials were prepared by mixing under vacuum using a rotary mixer (product name ARE-310, manufactured by THINKY Co., Ltd.). Various physical properties are also shown in Tables 1 and 2.

[0093]

Table 1

[0094]

Table 2

[0095] [Summary] In order to achieve the purpose of the present invention, the curable fluoroorganopolysiloxane compositions of Examples 1 to 4 have moderate viscosity and thixotropic index by optimizing the pxl value, preferably the wf value, thus exhibiting excellent uniform coating properties, a suitable storage modulus (G') for use as a converter component, and a cohesive breaking (CF) peel mode between the two. The PET film and the curing material are chemically bonded between the layers, achieving good adhesion and followability.

[0096] On the other hand, if the pxl value and wf value deviate from the optimal value, sufficient adhesion and adhesive strength cannot be displayed, and interlayer peeling (AF) occurs. Or even if a certain adhesive strength is displayed, the G' value of the hardened material becomes high, and practical problems can be identified as a component for converter. [Simplified Explanation of the Diagram]

[0015] None

Claims

1. A curable organopolysiloxane composition for a converter, characterized by containing at least: (A) one or more organopolysiloxanes having at least two curable reactive groups containing carbon-carbon double bonds in one or more molecules; (B1) an organohydrogen polysiloxane having at least one silicon atom bonded to a hydrogen atom at the side chain of the molecular chain, having no silicon atom bonded to a hydrogen atom at at least one end of the molecular chain, and having at least two silicon atom bonded to hydrogen atoms within the molecule; (B2) an organohydrogen polysiloxane having silicon atom bonded to hydrogen atoms at both ends of the molecular chain, and having at least two silicon atom bonded to hydrogen atoms within the molecule; (C) an effective amount of a catalyst for hydrosilylation reaction; (D) a reinforcing filler; and (E) a tackifier; and utilizing the number of silicon atom bonded to hydrogen atoms (HB1) in component (B1). The number of silicon atoms bonded to hydrogen atoms (HB2) in component (B2) and the total number of hardening reactive groups containing carbon-carbon double bonds (Vi) in component (A) are defined by the following relationship: px1={HB1 / HB2} / {(HB1+HB2) / Vi}, where the value of px1 is in the range of 0.1 to 6.

0. At least a portion of component (A) is (A1) one or more alkenyl groups having at least two carbon atoms of 2 to 12 in one molecule, and at least 10 mol% of all substituents on the silicon atom are fluoroalkyl organopolysiloxanes represented by (CpF2p+1)-R- (R is an alkyl group of 1 to 10 carbon atoms, and p is an integer from 1 to 8).

2. The converter of claim 1 uses a curable organopolysiloxane composition, wherein when the total of components (A) to (E) is set to 100% by mass, the content (wf) of component (D) is in the range of 5% to 40% by mass.

3. The converter of claim 1 or 2 uses a curable organic polysiloxane composition, wherein at least a portion of component (D) is inorganic oxide microparticles.

4. The converter of claim 1 or 2 uses a curable organopolysiloxane composition, wherein the storage modulus (G') of the cured product obtained by curing the composition is in the range of 1.0 × 10³ to 5.0 × 10⁴ Pa when subjected to minute deformation at 23 °C and 0.02 Hz.

5. The converter using a curable organopolysiloxane composition as requested in claim 1 or 2, wherein the overall viscosity of the composition, measured at 25°C and a shear rate of 0.1 (S⁻¹), is in the range of 5 to 5,000,000 mPa·s, and the thixotropic index (TI) (=η⁰.1 / η⁰.0) is 250 or less, representing the ratio of the overall viscosity of the composition (η⁰.1) measured at a shear rate of 0.1 (S⁻¹) to the overall viscosity of the composition (η⁻¹⁰.0) measured at a shear rate of 10.0 (S⁻¹).

6. A curable material formed by curing a converter as claimed in any one of claims 1 to 5 with a curable organopolysiloxane composition.

7. A converter film curing material, which is formed by curing a converter curing organic polysiloxane composition as claimed in any one of claims 1 to 5.

8. A laminate having the following structure: the laminate is formed by curing a converter film formed by curing a converter using a curable organopolysiloxane composition as claimed in any one of claims 1 to 5, and one or more layers selected from electrode layers and substrate layers.

9. The laminate of claim 8, wherein the converter thin film curing material and one or more layers selected from electrode layers and substrate layers form chemical bonds at least partially at the interface of the two layers.

10. The laminate of claim 8 or 9, having the following structure: at least a portion of the electrode layer and / or the substrate layer is a layer formed of thermoplastic resin, and the converter film curing material and the layer formed of thermoplastic resin are at least partially bonded together by chemical bonds at the interface of the two layers.

11. The laminate of claim 8 or 9, having the following structure: a converter thin film curing material is sandwiched between upper and lower electrode layers or a substrate on both sides of the thin film.

12. A method for manufacturing a laminate, the laminate system being a laminate of any one of claims 8 to 11, the method comprising the steps of: coating at least one side of at least one side of a layer selected from an electrode layer and a substrate layer with a curable organopolysiloxane composition for a converter as of any one of claims 1 to 4 and curing it.

13. A converter component comprising a laminate as claimed in any one of claims 8 to 10.

14. A converter comprising a stack as claimed in any one of claims 8 to 10.

15. An electronic component comprising a laminate as claimed in any one of claims 8 to 10.