Silicone polymer, elastomer and electrical element

Abstract

To provide an elastomer having a high dielectric constant, a low elastic modulus, and large breaking elongation, to provide a silicone polymer for producing the elastomer, and to provide an electrical element using the elastomer.SOLUTION: A silicone polymer includes a main chain comprising siloxane bond, and a side chain bonded to the main chain. One or more high dielectric constant functional groups, one or more hydrosilyl groups and one or more alkene groups are introduced to the terminal of the side chain and / or the main chain. An elastomer is obtained by bridging the silicone polymer with hydrosilylation reaction. An electrical element includes an elastomer layer comprising the elastomer, a first electrode formed on the one surface of the elastomer layer, and a second electrode formed on the other surface of the elastomer layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a silicone polymer, an elastomer, and an electric element, and more particularly to an elastomer having a high dielectric constant, a low modulus of elasticity, and a large elongation at break, a silicone polymer for producing such an elastomer, and an electric element using such an elastomer. [Background technology]

[0002] Dielectric elastomers are used in the dielectric layers of various electrical elements such as sensors and actuators. To improve the sensitivity and output of sensors and actuators that use dielectric elastomers, it is necessary to increase the dielectric constant of the dielectric elastomer, decrease the modulus of elasticity, and increase the elongation at break. Of these, to increase the dielectric constant of an elastomer, it is necessary to incorporate functional groups with a large dielectric constant (e.g., cyclic carbonate groups, cyano groups, etc.) into the polymer and crosslink such a polymer.

[0003] Various proposals have been made regarding such dielectric elastomers. For example, Patent Document 1 discloses a silicone elastomer obtained by reacting a silicone polymer having a cyano group and a hydroxy group in the side chain with a diisocyanate (crosslinking agent). The same document states: (A) When a highly polar cyano group is introduced into the side chain of a silicone elastomer, the relative dielectric constant of the silicone elastomer is improved, and (B) When the hydroxyl group introduced into the side chain of the silicone polymer reacts with the isocyanate group of the diisocyanate, adjacent silicone polymers are crosslinked via urethane bonds, resulting in an elastomer. is stated.

[0004] As described in Patent Document 1, when a functional group with a high dielectric constant (high polarity) is incorporated into a polymer and the polymer is crosslinked using a crosslinking agent, an elastomer with a high dielectric constant can be obtained. On the other hand, in order to achieve a low modulus of elasticity and a large elongation at break, it is necessary to reduce the crosslink density. However, conventional methods have had limitations in reducing the crosslink density. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2024-046163 Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide a novel elastomer having a high dielectric constant. Another problem to be solved by the present invention is to provide a novel elastomer that has a low modulus of elasticity and a large elongation at break in addition to a high dielectric constant.

[0007] Another problem that the present invention aims to solve is to provide a silicone polymer for producing such elastomers. Another object of the present invention is to provide an electric element using such an elastomer. [Means for solving the problem]

[0008] In order to solve the above problems, the silicone polymer according to the present invention comprises: a main chain formed of siloxane bonds; a side chain attached to the main chain; Equipped with At least one high dielectric constant functional group, at least one hydrosilyl group, and at least one alkene group are introduced into the side chains and / or the ends of the main chain.

[0009] The elastomer according to the present invention is obtained by crosslinking the silicone polymer according to the present invention through a hydrosilylation reaction.

[0010] The electric element according to the present invention comprises: an elastomer layer made of the elastomer according to the present invention; a first electrode formed on one surface of the elastomer layer; a second electrode formed on the other surface of the elastomer layer; It is equipped with: [Effects of the Invention]

[0011] When a silicone polymer having a high dielectric constant functional group, a hydrosilyl group, and an alkene group in the polymer chain is crosslinked by a hydrosilylation reaction, an elastomer with a high dielectric constant, a low modulus, and a large elongation at break is obtained. Moreover, the obtained elastomer functions as a low modulus elastomer even when the crosslink density is low. The silicone polymer of the present invention has hydrosilyl groups and alkene groups in the polymer chain, which allows for efficient crosslinking between polymer chains without significant deformation or movement of the silicone polymer molecules. Furthermore, the efficiency of the crosslinking reaction can be increased, making it possible to produce crosslinked products with low crosslink density. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Configuration 1] a main chain formed of siloxane bonds; a side chain attached to the main chain; Equipped with At least one high dielectric constant functional group, at least one hydrosilyl group, and at least one alkene group are introduced into the side chains and / or the ends of the main chain. Silicone polymer. However, the "high relative dielectric constant functional group" refers to a functional group having a dielectric constant E of 8 or more.

[0013] [Configuration 2] 2. The silicone polymer of claim 1 further comprising methylalkyl silicone units (—O—Si(Me)(R)—) copolymerized into the backbone. however, R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'); R' is an alkyl group having one or more carbon atoms, Each R" is an alkylene group having one or more carbon atoms.

[0014] [Configuration 3] The silicone polymer according to aspect 1 or 2, which satisfies the following formulae (0) to (4): 30.0mol%≦X≦99.0mol%…(0) 0.1 mol%≦Y≦25.0 mol% …(1) 0.1 mol%≦Z≦25.0 mol% …(2) 0.0 mol%≦U≦60.0 mol% …(3) 0.90≦Y / Z≦1.60 …(4) however, X=x×100 / (x+y+z+u), Y=y×100 / (x+y+z+u), Z=z×100 / (x+y+z+u), U=u×100 / (x+y+z+u), "x" is the total number of moles of the high dielectric constant functional groups, "y" is the total number of moles of the hydrosilyl groups; "z" is the total number of moles of the alkene groups; "u" is the total number of moles of methylalkyl silicone units (-O-Si(Me)(R)-) copolymerized into the main chain; R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'); R' is an alkyl group having one or more carbon atoms, Each R" is an alkylene group having one or more carbon atoms.

[0015] [Configuration 4] A silicone polymer according to any one of configurations 1 to 3, which satisfies a composition formula represented by formula (5) described below.

[0016] [Configuration 5] 5. The silicone polymer according to any one of configurations 1 to 4, wherein a branched structure derived from trialkoxysilane and / or tetraalkoxysilane is introduced into the main chain.

[0017] [Configuration 6] 6. The silicone polymer of any one of claims 1 to 5, having a weight average molecular weight of 2500 or greater.

[0018] [Configuration 7] 2. The silicone polymer according to claim 1, wherein the high dielectric constant functional group comprises at least one selected from the group consisting of a cyclic carbonate group, a cyano group, a trifluoropropyl group, a lactam group, a lactone group, an amide group, a sulfoxide group, and a sulfone group.

[0019] [Configuration 8] An elastomer obtained by crosslinking the silicone polymers according to any one of configurations 1 to 7 through a hydrosilylation reaction.

[0020] [Configuration 9] The elastic modulus is 0.10 MPa or more and 10.0 MPa or less, and / or Crosslink density is 0.1mmol / g or more and 1.0mmol / g or less 9. The elastomer of claim 8.

[0021] [Configuration 10] An elastomer layer made of the elastomer according to configuration 8 or 9; a first electrode formed on one surface of the elastomer layer; a second electrode formed on the other surface of the elastomer layer; An electrical element comprising:

[0022] [Configuration 11] a first step of simultaneously or stepwise carrying out hydrolysis and polycondensation of 1 to n alkoxysilanes (n≧2) in a solvent to obtain a solution containing a silicone polymer; a second step of separating the silicone polymer from the solution; Equipped with (A) The first to nth alkoxysilanes are Dialkoxysilane A, At least one alkoxysilane selected from the group consisting of dialkoxysilane B, monoalkoxysilane, and trialkoxysilane; Including, (B) Among the functional groups other than alkoxy groups bonded to the first to nth alkoxysilanes, At least one of the functional groups is a high dielectric constant functional group; at least one is a hydrosilyl group, At least one of the functional groups contains an alkene group. A method for producing silicone polymers.

[0023] [Configuration 12] 12. The method for producing a silicone polymer according to claim 11, wherein the first to nth alkoxysilanes further include at least one tetraalkoxysilane.

[0024] An embodiment of the present invention will be described in detail below. [1. Silicone polymer] The silicone polymer according to the present invention comprises: a main chain formed of siloxane bonds; a side chain attached to the main chain; It is equipped with:

[0025] [1.1. Main chain and side chain] The main chain is formed by hydrolysis and condensation polymerization of dialkoxysilane, and therefore consists of siloxane bonds (-Si-O-Si-). The main chain is bonded with a side chain derived from a functional group other than the alkoxy group contained in the dialkoxysilane.

[0026] To cap the silanol groups (-Si-OH) at the ends of the main chain, a monoalkoxysilane may be used in addition to the dialkoxysilane. In this case, a terminal functional group derived from a functional group other than the alkoxy group contained in the monoalkoxysilane is bonded to the end of the main chain. Furthermore, in order to introduce a branched structure into the main chain, trialkoxysilane and / or tetraalkoxysilane may be used in combination with dialkoxysilane. When trialkoxysilane is used to introduce a branched structure, a side chain derived from a functional group other than the alkoxy group contained in the trialkoxysilane is bonded to the branch point.

[0027] [1.2. Functional groups] The silicone polymer of the present invention differs from conventional polymers in that at least one high dielectric constant functional group, at least one hydrosilyl group, and at least one alkene group are introduced into the side chains and / or the ends of the main chain.

[0028] [1.2.1. High-dielectric-constant functional groups] "A high dielectric constant functional group is introduced into the side chain and / or the end of the main chain" means (a) A high dielectric constant functional group is directly bonded to a Si atom located in the middle or at the end of the main chain, or (b) A high dielectric constant functional group is bonded to a Si atom located in the middle or at the end of the main chain via a divalent functional group. This refers to

[0029] The high dielectric constant functional group is a functional group necessary for increasing the dielectric constant of the silicone polymer and the elastomer obtained by crosslinking the silicone polymer. The silicone polymer may have one high-dielectric-constant functional group per molecule, or may have two or more high-dielectric-constant functional groups per molecule. When the silicone polymer has two or more high-dielectric-constant functional groups per molecule, the types of the high-dielectric-constant functional groups may be the same or different.

[0030] The high-dielectric-constant functional group may be introduced into a side chain or into the end of the main chain. It is particularly preferable that the high-dielectric-constant functional group be introduced into a side chain. This is because it facilitates the introduction of a large amount of high-dielectric-constant functional groups into one molecule. The greater the amount of high-dielectric-constant functional group introduced into the silicone polymer, the higher the dielectric constant of the silicone polymer and the elastomer obtained by crosslinking it.

[0031] The term "high dielectric constant functional group" refers to a functional group having a dielectric constant E of 8 or more. The "dielectric constant E" of a functional group is (a) Using the molecular weight and relative dielectric constant data of the real compound, the real compound is divided into functional group moieties and alkyl moieties, the molecular weight of each moiety is calculated, and an E value for each moiety is assigned to each functional group moiety and alkyl moiety. (b) Determine the E value of each part using the least squares method so that the calculated relative permittivity of the actual compound (=Σ(molecular weight of each part × E value of each part)) matches the measured value of the relative permittivity of the actual compound. This refers to the E value of the functional group site obtained by

[0032] Examples of high dielectric constant functional groups include cyclic carbonate groups, cyano groups, trifluoropropyl groups, lactam groups, lactone groups, amide groups, sulfoxide groups, sulfone groups, etc. The silicone polymer may contain any one of these high dielectric constant functional groups, or may contain two or more of them. The high dielectric constant functional group is preferably a cyclic carbonate group and / or a cyano group, since materials containing these functional groups have a proven track record as components of electronic functional materials and have been confirmed to be electrically stable.

[0033] When the high dielectric constant functional group is a cyclic carbonate group, the number of atoms constituting the ring contained in the cyclic carbonate group is not particularly limited, and an optimum number can be selected depending on the purpose. Generally, the more atoms that make up the ring, the less likely the ring is to open, improving the ring's stability. On the other hand, if the number of atoms that make up the ring is excessive, the degree of freedom in the conformation that the ring can take increases. When the ring is small, the carbonate group's conformation has high ring tension, so it can only take conformations with large polarization of the carbonate group. In contrast, when the ring is large, the degree of freedom in the conformation that the ring can take increases, and it can also take conformations with small polarization of the carbonate group. As a result, when the ring is large, the average polarization of the entire ring becomes smaller, which can ultimately result in a smaller dielectric constant. Therefore, the cyclic carbonate group preferably has a 4-membered ring, a 5-membered ring, or a 6-membered ring, and particularly preferably has a 5-membered ring.

[0034] Examples of cyclic carbonate groups include an ethylene carbonate group (-C3H3O3), a propylene carbonate group (-C4H5O3), and a butylene carbonate group (-C5H7O3).

[0035] When the high dielectric constant functional group is bonded to the Si atom via a divalent functional group, the type of the divalent functional group is not particularly limited. (a) an alkylene group having one or more carbon atoms; (b) Ether (-O-), thioether (-S-), carbonyl group (-C(O)-), Alkylene group with one or more carbon atoms containing a carboxyl group (-COOH) or a carboxylic acid ester (-R"-COOR') etc. Here, the term "an alkylene group containing an ether, a thioether, or a carbonyl group" means (a) a functional group in which an ether, thioether, or carbonyl group is bonded to a carbon atom located on the high dielectric constant functional group side of an alkylene group, or (b) A functional group in which an ether, thioether, or carbonyl group is inserted between adjacent carbon atoms constituting an alkylene group. This refers to The term "alkylene group containing a carboxy group or a carboxylic acid ester" refers to a functional group in which a hydrogen atom of an alkylene group is substituted with a carboxy group (-COOH) or a carboxylic acid ester (-R"-COOR').

[0036] [1.2.2. Hydrosilyl group] "A hydrosilyl group is introduced at the end of the side chain and / or the main chain" means (a) A hydrogen atom is bonded to the Si atom located in the middle of the main chain, or (b) A hydrogen atom is bonded to the silicon atom located at the end of the main chain. This refers to

[0037] The hydrosilyl group (-Si-H) is a functional group necessary for the hydrosilylation reaction to occur with an alkene group. When a hydrosilylation reaction occurs between silicone polymer A having a hydrosilyl group and silicone polymer B having an alkene group, silicone polymer A and silicone polymer B can be crosslinked. The silicone polymer may have one hydrosilyl group per molecule, or may have two or more hydrosilyl groups per molecule.

[0038] [1.2.3. Alkene group] "An alkene group is introduced into the terminal of the side chain and / or the main chain" means (a) An alkene group is bonded directly to a silicon atom located in the middle or at the end of the main chain, or (b) An alkene group is bonded to a silicon atom located in the middle or at the end of the main chain via a divalent functional group. This refers to

[0039] The alkene group is a functional group necessary for causing a hydrosilylation reaction with a hydrosilyl group. The silicone polymer may have one alkene group per molecule, or may have two or more alkene groups per molecule. When the silicone polymer has two or more alkene groups per molecule, the types of alkene groups may be the same or different.

[0040] An alkene group is represented by the general formula: -C(R3)=C(R4)(R5), where R3 and R4 are each a hydrogen atom or an alkyl group having one or more carbon atoms. Examples of functional groups containing an alkene group include -CH=CH2, -CH2-CH=CH2, and -CH2-CH2-CH=CH2. When the alkene group is bonded to the Si atom via a divalent functional group, the type of the divalent functional group is not particularly limited. Details of the divalent functional group are as described above, so further explanation is omitted.

[0041] [1.3. Methyl alkyl silicone unit] The silicone polymer may further comprise methyl alkyl silicone units copolymerized into the backbone. Here, the term "methyl alkyl silicone unit" refers to a structure represented by -O-Si(Me)(R)-. however, R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'); R' is an alkyl group having one or more carbon atoms, Each R" is an alkylene group having one or more carbon atoms. R may contain a methyl group (-Me).

[0042] The methyl alkyl silicone unit is not necessarily required. However, if the silicone polymer contains the methyl alkyl silicone unit, the silicone polymer tends to have a high molecular weight. This is thought to be because dialkoxysilanes containing methyl groups have less bulky side chains and less steric hindrance than dialkoxysilanes containing certain high dielectric constant functional groups or alkene groups.

[0043] [1.4. Branching Structure] The silicone polymer may have a branched structure derived from trialkoxysilane and / or tetraalkoxysilane introduced into the main chain. Here, the trialkoxysilane may be one having a high dielectric constant functional group, a hydrosilyl group, or an alkene group, or one having none of a high dielectric constant functional group, a hydrosilyl group, or an alkene group.

[0044] When synthesizing a silicone polymer, if trialkoxysilane and / or tetraalkoxysilane is further added to the raw materials, a branched structure derived from the trialkoxysilane and / or tetraalkoxysilane can be introduced into the main chain. The branched structure is not essential, but if the silicone polymer has a branched structure, the strength of the silicone polymer and the elastomer obtained by crosslinking the silicone polymer can be increased.

[0045] [1.5. Composition] In the present invention, the composition of the silicone polymer is not particularly limited, and an optimum composition can be selected depending on the purpose. It is particularly preferable that the silicone polymer satisfies the following formulas (0) to (4):

[0046] 30.0mol%≦X≦99.0mol%…(0) 0.1 mol%≦Y≦25.0 mol% …(1) 0.1 mol%≦Z≦25.0 mol% …(2) 0.0 mol%≦U≦60.0 mol% …(3) 0.90≦Y / Z≦1.60 …(4)

[0047] however, X=x×100 / (x+y+z+u), Y=y×100 / (x+y+z+u), Z=z×100 / (x+y+z+u), U=u×100 / (x+y+z+u), "x" is the total number of moles of the high dielectric constant functional groups, "y" is the total number of moles of the hydrosilyl groups; "z" is the total number of moles of the alkene groups; "u" is the total number of moles of methylalkyl silicone units (-O-Si(Me)(R)-) copolymerized into the main chain; R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'); R' is an alkyl group having one or more carbon atoms, Each R" is an alkylene group having one or more carbon atoms. R may contain a methyl group (-Me).

[0048] [1.5.1. Content of high dielectric constant functional groups X] Formula (0) represents a suitable range for the high dielectric constant functional group. If X is too small, the dielectric constant of the elastomer obtained by crosslinking the silicone polymer may become excessively small. Therefore, X is preferably 30.0 mol% or more. X is more preferably 40.0 mol% or more, 50.0 mol% or more, 60.0 mol% or more, or 70.0 mol% or more.

[0049] On the other hand, if X is too large, the crosslink density may be excessively reduced when the silicone polymer is crosslinked. Therefore, X is preferably 99.0 mol% or less. X is more preferably 97.0 mol% or less, 95.0 mol% or less, or 90.0 mol% or less.

[0050] [1.5.2. Hydrosilyl group content Y] Formula (1) represents a suitable range for the hydrosilyl group content Y. If Y is too small, the crosslinking density may be excessively reduced when the silicone polymer is crosslinked. Therefore, Y is preferably 0.1 mol% or more. Y is more preferably 0.5 mol% or more, 1.0 mol% or more, 2.0 mol% or more, or 3.0 mol% or more.

[0051] On the other hand, if Y is too large, the content of high-dielectric-constant functional groups will be relatively low, and the dielectric constant of the elastomer obtained by crosslinking the silicone polymer may be excessively reduced. Therefore, Y is preferably 25.0 mol% or less. Y is preferably 20.0 mol% or less, 15.0 mol% or less, or 10.0 mol% or less.

[0052] [1.5.3. Alkene group content Z] Formula (2) represents a suitable range for the alkene group content Z. If Z is too small, the crosslink density may be excessively reduced when the silicone polymer is crosslinked. Therefore, Z is preferably 0.1 mol% or more. Z is more preferably 0.5 mol% or more, 1.0 mol% or more, 2.0 mol% or more, or 3.0 mol% or more.

[0053] On the other hand, if Z is too large, the content of high-dielectric-constant functional groups becomes relatively small, which may result in an excessive decrease in the dielectric constant of the elastomer. Therefore, Z is preferably 25.0 mol% or less. Z is more preferably 20.0 mol% or less, 15.0 mol% or less, or 10.0 mol% or less.

[0054] [1.5.4. Methyl alkyl silicone unit content U] Formula (3) represents a suitable range for the content U of methyl alkyl silicone units. U may be 0 mol%. However, the larger U, the more likely it is that the silicone polymer will have a high molecular weight. Furthermore, the greater the flexibility of the silicone polymer, the more likely it is that the elastic modulus of the elastomer will decrease. To achieve this effect, U is preferably 0.1 mol% or more. U is more preferably 0.5 mol% or more, 1.0 mol% or more, 2.0 mol% or more, or 3.0 mol% or more.

[0055] On the other hand, if U becomes too large, the content of high-dielectric-constant functional groups becomes relatively small, which may result in an excessive decrease in the dielectric constant of the elastomer. Therefore, U is preferably 60.0 mol% or less. U is more preferably 50.0 mol% or less, 40.0 mol% or less, 30.0 mol% or less, 20.0 mol% or less, 15.0 mol% or less, or 10.0 mol% or less.

[0056] [1.5.5. Y / Z Ratio] Formula (4) represents the preferred range of the ratio (Y / Z) of the number of moles of hydrosilyl groups Y to the number of moles of alkene groups Z. If Y / Z is too small, the hydrosilyl groups will be relatively insufficient, and the crosslink density may be excessively reduced. Therefore, Y / Z is preferably 0.90 or more. Y / Z is more preferably 1.00 or more. On the other hand, if Y / Z becomes too large, the alkene group becomes relatively insufficient, and the crosslink density may be excessively reduced. Therefore, Y / Z is preferably 1.60 or less. Y / Z is more preferably 1.57 or less.

[0057] 1.5.6. Suitable Composition It is particularly preferable that the silicone polymer satisfies the composition formula represented by the following formula (5): Note that formula (5) is a composition formula that represents the ratio of units derived from the alkoxysilane used as a raw material, and is not a structural formula that specifies the molecular structure.

[0058] [ka]

[0059] however, q1+q2+n+m+k+p=100mol%, 30.0 mol%≦n≦99.0 mol%, 0.5 mol%≦m+q1≦25.0 mol%, 0.5 mol%≦k+q2≦25.0 mol%, 0 mol%≦p≦20.0 mol%, q=q1+q2+q3>0, q1≧0, q2≧0, q3≧0, R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'), R' is an alkyl group having one or more carbon atoms, R" is an alkylene group having one or more carbon atoms, X d is the high dielectric constant functional group, L is, respectively, (a) None, (b) an alkylene group having one or more carbon atoms, or (c) an alkylene group having one or more carbon atoms, including an ether (-O-), a thioether (-S-), a carbonyl group (-C(O)-), a carboxyl group (-COOH), or a carboxylic acid ester (-R"-COOR'); -[Si(R)2-R t ] q are -[Si(R)2-H] respectively. q1 , -[Si(R)2-L-CH=CH2] q2 , and -[H] q3 At least one selected from the group consisting of: R may also be a methyl group (-Me).

[0060] In formula (5), n represents the ratio of units derived from dialkoxysilane containing a high dielectric constant functional group such as an ethylene carbonate group (-C3H3O3) or a cyano group. m represents the ratio of units derived from a dialkoxysilane containing a hydrosilyl group. k represents the ratio of units derived from a dialkoxysilane containing a vinyl group. p represents the ratio of units derived from dialkoxysilane containing a methyl group (-Me). q represents the sum of q1, q2, and q3. q1 represents the ratio of units derived from monoalkoxysilane containing a hydrosilyl group. q2 represents the ratio of units derived from monoalkoxysilane containing a vinyl group. q3 represents the ratio of silanol groups.

[0061] As mentioned above, if m+q1 is too small, the crosslink density may be excessively reduced. Therefore, m+q1 is preferably 0.5 mol% or more. m+q1 is more preferably 1.0 mol% or more, 2.0 mol% or more, or 3.0 mol% or more. On the other hand, if m+q1 is too large, the relative dielectric constant of the elastomer may be excessively reduced. Therefore, m+q1 is preferably 25.0 mol% or less. m+q1 is more preferably 20.0 mol% or less, 15.0 mol% or less, 10.0 mol% or less, or 5.0 mol% or less.

[0062] Similarly, if k+q2 is too small, the crosslink density may be excessively reduced. Therefore, k+q2 is preferably 0.5 mol% or more. k+q2 is more preferably 1.0 mol% or more, 2.0 mol% or more, or 3.0 mol% or more. On the other hand, if k+q2 is too large, the relative dielectric constant of the elastomer may be excessively reduced. Therefore, k+q2 is preferably 25.0 mol% or less. k+q2 is more preferably 20.0 mol% or less, 15.0 mol% or less, 10.0 mol% or less, or 5.0 mol% or less.

[0063] The preferred ranges of n and p are the same as the preferred ranges of X and U, respectively, and therefore will not be described here.

[0064] Each of q1 and q2 may be 0 mol %. In this case, silanol groups (—Si—OH) remain at the terminals of the main chain. On the other hand, when q1 + q2 exceeds 0 mol %, all or part of the silanol groups at the terminals of the main chain can be blocked with monoalkoxysilane.

[0065] Capping the main chain end with a monoalkoxysilane containing a vinyl group or a hydrosilyl group may facilitate the crosslinking reaction between polymer chains. To achieve this effect, q1+q2 is preferably 0.1 mol% or more. q1+q2 is more preferably 1.0 mol% or more, or 2.0 mol% or more. On the other hand, if q1+q2 becomes too large, the molecular weight of the silicone polymer may be excessively reduced. Therefore, q1+q2 is preferably 5.0 mol% or less. q1+q2 is more preferably 4.5 mol% or less.

[0066] [1.6. Weight average molecular weight] Optimizing the manufacturing conditions for silicone polymers allows the production of silicone polymers with high weight-average molecular weights. Generally, the higher the weight-average molecular weight of a silicone polymer, the more easily the crosslinking reaction between polymer chains proceeds. To achieve this effect, the weight-average molecular weight is preferably 2,500 or more. The weight-average molecular weight is more preferably 5,000 or more, 7,500 or more, or 10,000 or more.

[0067] On the other hand, if the weight-average molecular weight is too large, the silicone polymer may become insoluble in the solvent, making it difficult to produce an elastomer. Therefore, the weight-average molecular weight is preferably 70,000 or less. The weight-average molecular weight is more preferably 65,000 or less, or even 60,000 or less.

[0068] [2. Elastomer] The elastomer according to the present invention is obtained by crosslinking the silicone polymers according to the present invention through a hydrosilylation reaction. The silicone polymer according to the present invention has a hydrosilyl group and an alkene group in one molecule, and therefore polymer chains can be crosslinked without the use of a crosslinking agent.

[0069] 2.1. Structure The elastomer according to the present invention is Silicone polymer A according to the present invention; Silicone polymer B according to the present invention; a crosslinking group that crosslinks Si atom A contained in silicone polymer A with Si atom B contained in silicone polymer B; It is equipped with: The crosslinking group has a structure represented by the following formula (6):

[0070] [ka]

[0071] however, R1 to R3 each represent a hydrogen atom or an alkyl group having one or more carbon atoms; L is (a) None, (b) an alkylene group having one or more carbon atoms, or (c) Alkylene groups having one or more carbon atoms, including ether (-O-), thioether (-S-), carbonyl group (-C(O)-), carboxyl group (-COOH), or carboxylic acid ester (-R"-COOR').

[0072] The crosslinking group is formed by a hydrosilylation reaction between a hydrosilyl group contained in silicone polymer A and an alkene group contained in silicone polymer B. Therefore, the crosslinking group has a structure represented by formula (6). Details of the divalent functional group contained in L in formula (6) are as described above, so further explanation is omitted.

[0073] [2.2. Characteristics] 2.2.1. Elastic Modulus When producing an elastomer, the elastic modulus of the elastomer can be controlled by optimizing the production conditions (particularly the type and composition ratio of alkoxysilane). The elastic modulus of the elastomer is not particularly limited, and an optimal value can be selected depending on the purpose. Generally, if the modulus of elasticity of an elastomer is too small, the elastomer becomes too soft and may be difficult to use as a dielectric layer for an electrical element. Therefore, the modulus of elasticity is preferably 0.10 MPa or more. The modulus of elasticity is more preferably 0.15 MPa or more, or even 0.20 MPa or more.

[0074] On the other hand, if the elastic modulus of the elastomer is too high, the elongation becomes too small, which may result in a decrease in sensitivity and output when used as a dielectric layer in an electric element. Therefore, the elastic modulus is preferably 10.0 MPa or less. The elastic modulus is more preferably 5.0 MPa or less, 3.0 MPa or less, or 1.0 MPa or less.

[0075] [2.2.2. Crosslink density] When producing an elastomer, optimizing the production conditions allows the crosslink density of the elastomer to be controlled. The crosslink density of the elastomer is not particularly limited, and an optimal value can be selected depending on the purpose. Generally, if the crosslink density of an elastomer is too low, the elastomer becomes too soft and may be difficult to use as a dielectric layer in an electrical element. If the crosslink density is even lower, the elastomer may not be able to be solidified by crosslinking, making it difficult to form an elastomer. Therefore, the crosslink density is preferably 0.1 mmol / g or higher. The crosslink density is more preferably 0.12 mmol / g or higher.

[0076] On the other hand, if the crosslink density of the elastomer is too high, the elongation becomes too small, which may result in a decrease in sensitivity and output when used as a dielectric layer in an electric element. Therefore, the crosslink density is preferably 1.0 mmol / g or less. The crosslink density is more preferably 0.8 mmol / g or less, 0.5 mmol / g or less, or 0.4 mmol / g or less. The elastomer of the present invention has a high crosslinking reaction efficiency, so that it can be produced even with a crosslinked body having a lower crosslink density than conventional elastomers. Furthermore, as the crosslink density decreases, the elongation at break also increases.

[0077] 2.2.3. Dielectric constant The elastomer according to the present invention exhibits a high dielectric constant because it contains high-dielectric-constant functional groups in its molecule. When the manufacturing conditions are optimized, the dielectric constant becomes 8 or more. When the manufacturing conditions are further optimized, the dielectric constant becomes 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 35 or more.

[0078] [3. Electrical Elements] The electric element according to the present invention comprises: an elastomer layer made of the elastomer according to the present invention; a first electrode formed on one surface of the elastomer layer; a second electrode formed on the other surface of the elastomer layer; It is equipped with:

[0079] 3.1. Elastomer Layer The elastomer layer is made of the elastomer according to the present invention. The shape, thickness, etc. of the elastomer layer are not particularly limited, and an optimum shape or thickness can be selected depending on the purpose. The thickness of the elastomer layer is usually 10 μm to 10 mm. The details of the elastomer are as described above, and therefore will not be described here.

[0080] [3.2. 1st electrode, 2nd electrode] The first electrode is formed on one side of the elastomer layer, and the second electrode is formed on the other side of the elastomer layer. The shapes, thicknesses, etc. of the first and second electrodes are not particularly limited, and can be selected optimally depending on the purpose.

[0081] The materials for the first electrode and the second electrode are not particularly limited, and an optimum material can be selected depending on the purpose. Examples of the materials for the first electrode and the second electrode include: (a) Metals (gold, aluminum, platinum, etc.), (b) Composite material of conductive filler and resin etc.

[0082] Examples of the conductive filler include: (a) Carbon materials such as carbon black, CNT, and graphite; (b) Particulate or needle-shaped silver etc. Examples of resins include silicone resin, acrylic resin, thermosetting elastomer (rubber), and thermoplastic elastomer.

[0083] [3.3. Usage] 3.3.1. Sensors When the electrical characteristics of the electric element according to the present invention are monitored with a bias applied to the electrodes, the distance between the electrodes changes when the elastomer layer is deformed by an external force. As a result, the capacitance of the elastomer layer changes. This is because the change in the distance between the electrodes is proportional to the change in impedance. Therefore, the electric element according to the present invention can be used as a sensor for detecting changes in external force as electrical changes.

[0084] The higher the dielectric constant of the elastomer layer, the greater the electrical change, and therefore the higher the dielectric constant, the more sensitive the sensor. Furthermore, the smaller the modulus of elasticity of the elastomer layer, the greater the deformation of the elastomer layer in response to an external force. This results in a greater change in the distance between the electrodes, and a greater electrical change. In other words, the smaller the modulus of elasticity of the elastomer, the greater the amount of force that can be detected. The electric element according to the present invention is made of an organic material, and therefore is softer than conventional inorganic sensors, and serves as a sensor device with good affinity to humans.

[0085] 3.3.2. Actuators The structure of the actuator is similar to that of the sensor, but the method of use is different. When a voltage is applied between the electrodes of the electric element of the present invention, an attractive force acts between the electrodes due to Maxwell stress. As a result, the distance between the electrodes shortens, and at the same time, a force acts in the planar direction of the elastomer layer to push the elastomer layer apart. This deformation can be used as an actuator. The electric element according to the present invention is made of organic matter, and therefore is an actuator device that is lighter, softer, and more human-friendly than conventional inorganic actuators (for example, motors).

[0086] 4. Silicone Polymer Manufacturing Method The method for producing a silicone polymer according to the present invention comprises the steps of: a first step of simultaneously or stepwise carrying out hydrolysis and polycondensation of 1 to n alkoxysilanes (n≧2) in a solvent to obtain a solution containing the silicone polymer according to the present invention; a second step of separating the silicone polymer from the solution; It is equipped with:

[0087] [4.1. 1st step] First, hydrolysis and polycondensation of 1st to nth alkoxysilanes (n≧2) are carried out simultaneously or stepwise in a solvent, thereby obtaining a solution containing the silicone polymer according to the present invention.

[0088] [4.1.1. Types of alkoxysilanes] In the present invention, the first to nth alkoxysilanes are Dialkoxysilane A, At least one alkoxysilane selected from the group consisting of dialkoxysilane B, monoalkoxysilane, and trialkoxysilane; Includes. The first to n-th alkoxysilanes may further include at least one tetraalkoxysilane.

[0089] Dialkoxysilane A is an essential component for forming the main chain of the silicone polymer. When multiple dialkoxysilanes are contained in the 1st to nth alkoxysilanes, the one with the largest content is defined as "dialkoxysilane A." Dialkoxysilane A preferably has at least one selected from the group consisting of a high-dielectric-constant functional group, a hydrosilyl group, and an alkene group. Dialkoxysilane A particularly preferably has a cyclic carbonate group or a cyano group as the high-dielectric-constant functional group. In addition, if it is possible to introduce the necessary functional groups into the silicone polymer using other alkoxysilanes, dialkoxysilane A may not have any of the high dielectric constant functional groups, hydrosilyl groups, or alkene groups.

[0090] Dialkoxysilane B is a component for forming the main chain of the silicone polymer and has a structure different from that of dialkoxysilane A. The first to n-th alkoxysilanes may contain any one type of dialkoxysilane B, or may contain two or more types. Dialkoxysilane B may contain at least one selected from the group consisting of a high dielectric constant functional group, a hydrosilyl group, and an alkene group, or may not contain any of these. An example of the latter is a dialkoxysilane for copolymerizing a methylalkylsilicone unit (-O-Si(Me)(R)-) in the main chain. If the necessary functional groups can be introduced into the silicone polymer using another alkoxysilane, the use of dialkoxysilane B can be omitted.

[0091] The monoalkoxysilane is a component for blocking the silanol group (-Si-OH) at the end of the main chain. The first to nth alkoxysilanes may contain any one type of monoalkoxysilane, or may contain two or more types. The monoalkoxysilane may have at least one selected from the group consisting of a high dielectric constant functional group, a hydrosilyl group, and an alkene group, or may not have any of these. If it is not necessary to block the ends of the main chain, or if the necessary functional groups can be introduced into the silicone polymer using other alkoxysilanes, the use of monoalkoxysilanes can be omitted.

[0092] The trialkoxysilane is a component for introducing a branched structure into the main chain. The first to nth alkoxysilanes may contain any one type of trialkoxysilane, or may contain two or more types. The trialkoxysilane may or may not contain a high dielectric constant functional group, a hydrosilyl group, or an alkene group. If it is not necessary to introduce a branched structure into the main chain, or if the necessary functional groups can be introduced into the silicone polymer using another alkoxysilane, the use of trialkoxysilane can be omitted.

[0093] The tetraalkoxysilane is a component for introducing a branched structure into the main chain. The first to nth alkoxysilanes may contain any one type of tetraalkoxysilane, or may contain two or more types. If it is not necessary to introduce a branched structure into the main chain, the use of tetraalkoxysilane can be omitted.

[0094] [4.1.2. Functional groups] The first to nth alkoxysilanes for producing the silicone polymer have a total of at least three functional groups other than alkoxy groups. Among the functional groups other than the alkoxy groups bonded to the first to nth alkoxysilanes, At least one of the functional groups is a high dielectric constant functional group; at least one is a hydrosilyl group, At least one of the functional groups contains an alkene group.

[0095] When there are four or more functional groups other than alkoxy groups bonded to the first to nth alkoxysilanes, the types of the remaining functional groups are not particularly limited. That is, the remaining functional group may be a functional group containing a high dielectric constant functional group, a hydrosilyl group, or a functional group containing an alkene group, or may be a functional group other than these (for example, a methyl group).

[0096] [4.1.3. Specific examples of alkoxysilanes] [A. Dialkoxysilane] An example of a dialkoxysilane is shown in the following formula (7): The raw material may contain one or more dialkoxysilanes represented by formula (7).

[0097] [ka]

[0098] however, F1 and F2 each represent one of the functional groups represented by the following formulae (a) to (e): A1 and A2 are functional groups represented by the following formula (d) or (e), respectively:

[0099] [ka]

[0100] R1 to R3 each represent a hydrogen atom or an alkyl group having one or more carbon atoms; X d is a high dielectric constant functional group, L is (a) None, (b) an alkylene group having one or more carbon atoms, or (c) an alkylene group having one or more carbon atoms, including an ether (-O-), a thioether (-S-), a carbonyl group (-C(O)-), a carboxyl group (-COOH), or a carboxylic acid ester (-R"-COOR'); R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'); R' is an alkyl group having one or more carbon atoms, Each R" is an alkylene group having one or more carbon atoms. R may also be a methyl group (-Me).

[0101] [B. Monoalkoxysilane] An example of a monoalkoxysilane is shown in the following formula (8): The raw material may contain one type of monoalkoxysilane represented by formula (8), or may contain two or more types.

[0102] [ka]

[0103] however, F1, F2, and F3 each represent one of the functional groups represented by formulas (a) to (e), A1 is a functional group represented by formula (d) or formula (e).

[0104] [C. Trialkoxysilane] An example of trialkoxysilane is shown in the following formula (9): The raw material may contain any one type of trialkoxysilane represented by formula (9), or may contain two or more types.

[0105] [ka]

[0106] however, F1 is any one of functional groups represented by formulas (a) to (e), A1, A2, and A3 are each a functional group represented by formula (d) or formula (e).

[0107] [D. Tetraalkoxysilane] An example of a tetraalkoxysilane is shown in the following formula (10): The raw material may contain any one type of tetraalkoxysilane represented by formula (10), or may contain two or more types.

[0108] [ka]

[0109] however, A1, A2, A3, and A4 are each a functional group represented by formula (d) or formula (e).

[0110] [4.1.4. Formulation] The combination of the first to n-th alkoxysilanes and their blending amounts are preferably selected so as to obtain a silicone polymer having the desired composition.

[0111] 4.1.5. Hydrolysis and Polycondensation When a catalyst is added to a raw material solution containing 1 to n alkoxysilanes, catalytic hydrolysis of the silicone ester and subsequent dehydration polycondensation reaction occur, resulting in the silicone polymer according to the present invention. The type of catalyst is not particularly limited, and an optimum catalyst can be selected depending on the purpose. Examples of the catalyst include an aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, and phosphonic acid.

[0112] The order of addition of the first to nth alkoxysilanes to the raw material solution and the order of reaction are not particularly limited, and an optimal order can be selected depending on the purpose. For example, all of the first to n-th alkoxysilanes may be added to a solvent to form a raw material solution, and the first to n-th alkoxysilanes may be reacted simultaneously in the raw material solution. Alternatively, the first to n-th alkoxysilanes may be added stepwise to a solvent, and the first to n-th alkoxysilanes may be reacted stepwise.

[0113] The method for reacting the first to n-th alkoxysilanes stepwise is not particularly limited. The first method of reacting in a stepwise manner is, for example, (a) adding some of the first to n-th alkoxysilanes (e.g., dialkoxysilanes) to a solvent and reacting them to generate polysiloxanes in the solution; (b) The remaining alkoxysilane (e.g., monoalkoxysilane) is added to the solution containing polysiloxane and further reacted. There is a way.

[0114] The second method of reacting in stages is, for example, (a) adding some of the first to n-th alkoxysilanes (including dialkoxysilanes) to a solvent and reacting them to produce polysiloxane A in solution A; (b) Separately, the remaining alkoxysilane (including dialkoxysilane) is added to the solvent and reacted to produce polysiloxane B in solution B, (c) Mixing solution A containing polysiloxane A with solution B containing polysiloxane B to further react polysiloxane A with polysiloxane B. There is a way.

[0115] The following formula (11) shows an example of a synthetic reaction for the silicone polymer according to the present invention. Formula (11) is: (a) a dialkoxysilane having a cyclic carbonate group, which is a type of high dielectric constant functional group; (b) vinyl-containing dialkoxysilanes and monoalkoxysilanes; (c) a dialkoxysilane having a hydrosilyl group; In formula (11), k, m, n, and q each represent the proportion of units derived from each monomer.

[0116] [ka]

[0117] Specific examples of other combinations of alkoxysilanes other than those mentioned above include the following combinations.

[0118] Example 1: (a) a dialkoxysilane having a high dielectric constant functional group such as a cyclic carbonate group or a cyano group; (b) a dialkoxysilane or monoalkoxysilane having a vinyl group; (c) a dialkoxysilane and / or a monoalkoxysilane having a hydrosilyl group; A combination of.

[0119] Example 2: (a) a dialkoxysilane having a high dielectric constant functional group such as a cyclic carbonate group or a cyano group; (b) a dialkoxysilane and / or a monoalkoxysilane having a vinyl group; (c) a dialkoxysilane and / or a monoalkoxysilane having a hydrosilyl group; (d) Dialkoxysilane with a methyl group A combination of.

[0120] Example 3: (a) a dialkoxysilane having a high dielectric constant functional group such as a cyclic carbonate group or a cyano group; (b) a dialkoxysilane and / or a monoalkoxysilane having a vinyl group; (c) a dialkoxysilane and / or a monoalkoxysilane having a hydrosilyl group; (d) trialkoxysilane and / or tetraalkoxysilane A combination of.

[0121] Example 4: (a) a dialkoxysilane having a high dielectric constant functional group such as a cyclic carbonate group or a cyano group; (b) a dialkoxysilane and / or a monoalkoxysilane having a vinyl group; (c) a dialkoxysilane and / or a monoalkoxysilane having a hydrosilyl group; (d) a dialkoxysilane having a methyl group; (e) trialkoxysilane and / or tetraalkoxysilane A combination of.

[0122] [4.2. 2nd step] The silicone polymer is then separated from the solution, thereby obtaining the silicone polymer according to the present invention. The method for separating the silicone polymer is not particularly limited, and an optimum method can be selected depending on the type of silicone polymer.

[0123] 5. Elastomer manufacturing method The elastomer according to the present invention can be obtained by subjecting the silicone polymer according to the present invention to a hydrosilylation reaction. In this case, any one type of silicone polymer may be reacted, or two or more types of silicone polymers may be reacted. The following formula (12) shows an example of a synthesis reaction for the elastomer according to the present invention, in which the high dielectric constant functional group is a cyclic carbonate group.

[0124] [ka]

[0125] [6. Effect] Traditionally, thermosetting polymers have been produced by combining two types of cross-linking functional groups A and B through a cross-linking reaction and then curing them. Typical examples include epoxy resin, urethane resin, and silicone resin. In these cases, polymer A, which has functional group A, and polymer B, which has functional group B, are prepared separately, and then cured by mixing and cross-linking these polymers. The reason for preparing the polymers separately is that if polymer A, which has functional group A, and polymer B, which has functional group B, are mixed together, the cross-linking reaction will proceed. Therefore, they must be mixed just before curing.

[0126] Conventional silicone polymers having functional groups with large polarization (high dielectric constant functional groups), such as cyclic carbonate groups and cyano groups, have also been produced by similar methods. See, for example, Patent Document 1. However, using conventional methods, it has been difficult to obtain crosslinked bodies with low elastic modulus and low crosslink density.

[0127] The higher the dielectric constant of the elastomer material, the higher the deformation of the actuator and the sensitivity of the sensor. Therefore, elastomer materials with a high dielectric constant are in demand. Furthermore, if the modulus of elasticity of an elastomer is too high when used as a sensor, a large stress is required for sensing, resulting in reduced sensitivity. Similarly, if the modulus of elasticity of an elastomer is too high when used as an actuator, the amount of displacement will be small. Therefore, elastomer materials with a low modulus of elasticity are required.

[0128] In contrast, when a silicone polymer having a high dielectric constant functional group, a hydrosilyl group, and an alkene group in the polymer chain is crosslinked by a hydrosilylation reaction, an elastomer with a high dielectric constant, a low modulus of elasticity, and a large elongation at break is obtained. Moreover, the obtained elastomer functions as a low modulus elastomer even when the crosslinking density is low. This is thought to be due to the high efficiency of the crosslinking reaction.

[0129] In other words, when introducing different crosslinking groups onto different polymers, a crosslinking reaction between polymer chains will not occur unless the two types of polymers are adjacent to each other. For example, the polymer next to polymer A with functional group A may be polymer B with functional group B, or polymer A with functional group A. In the former case, a crosslinking reaction will occur, but in the latter case, no crosslinking reaction will occur. As a result, functional groups that cannot participate in the crosslinking reaction will be generated. In contrast, the silicone polymer of the present invention has hydrosilyl groups and alkene groups within the polymer chain, which allows for efficient crosslinking between adjacent polymer chains without significant deformation or movement of the silicone polymer molecules. Furthermore, the efficiency of the crosslinking reaction can be increased, making it possible to produce crosslinked bodies with low crosslink density.

[0130] The silicone polymer according to the present invention exhibits a high relative dielectric constant because it contains functional groups with high polarization (such as cyclic carbonate groups and cyano groups) in its side chains. Furthermore, the silicone main skeleton has a glass transition temperature lower than room temperature, and the polymer main chain has high mobility at room temperature, so the orientation of the functional groups in an electric field is not hindered, and the elastomer according to the present invention therefore exhibits large orientation polarization. Furthermore, since the silicone polymer according to the present invention has a flexible main chain skeleton with high mobility, it becomes an elastomer with a low modulus of elasticity by crosslinking it.

[0131] Furthermore, since the silicone skeleton has high electrical insulation properties, the elastomer exhibits high electrical resistance even when functional groups with high polarization are introduced into the side chains of the silicone skeleton. Furthermore, the crosslinked structure formed by the hydrosilylation reaction is a chemical structure consisting of an alkylsilicone skeleton, and no polar groups that would reduce the insulating properties are introduced into the crosslinked structure during the reaction. As a result, the elastomer of the present invention exhibits higher electrical resistance than conventional elastomers.

[0132] The silicone polymer of the present invention provides an elastomer that has a low modulus of elasticity, high electrical resistance, a high dielectric constant, and is capable of being formed into a thin film. Furthermore, the elastomer of the present invention functions as an elastomer even when the crosslinking density is low. Therefore, when used as a dielectric layer in various electrical devices, the electrical devices can have high output and high sensitivity. [Example]

[0133] (Examples 1 to 6, Comparative Examples 1 and 2) 1. Sample Preparation 1.1. Reagents The following monomers were used to prepare the silicone polymer: (a) 4-[2-(dimethoxymethylsilyl)ethyl]-1,3-dioxolan-2-one (hereinafter referred to as "carbonate monomer") (b) Dimethoxymethylsilane (hereinafter referred to as "SiH monomer") (c) Dimethylethoxyvinylsilane (hereinafter referred to as "terminal vinyl monomer") (d) Dimethoxymethylvinylsilane (hereinafter referred to as "vinyl monomer") (e) Dimethoxydimethylsilane (hereinafter referred to as "methyl monomer") (f) Dimethylethoxysilane (hereinafter referred to as "SiH terminal monomer")

[0134] 1.2. Preparation of silicone polymer 1.2.1. Example 1 0.5 g (2.3 mmol) of carbonate monomer, 16.5 μL (0.13 mmol) of SiH monomer, 22 μL (0.13 mmol) of terminal vinyl monomer, and 0.5 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere.

[0135] To this was added 150 μL of a 1.4 M sulfuric acid solution, which was then cooled and stirred for 30 minutes, followed by stirring at room temperature for an additional 1.5 hours. While stirring at room temperature, the pressure was reduced using a rotary pump for 2 hours to remove volatiles. The solid was dissolved in 3 mL of acetonitrile and reprecipitated in 20 mL of a 1:1 hexane / ether mixed solvent (volume ratio), a process repeated five times. Further evaporation and vacuum drying yielded 278.4 mg of silicone polymer. The synthesis reaction is shown in Equation (13) below.

[0136] [ka]

[0137] 1.2.2. Example 2 0.5 g (2.3 mmol) of carbonate monomer, 35 μL (0.28 mmol) of SiH monomer, 23.4 μL (0.14 mmol) of vinyl-terminated monomer, 21.1 μL (0.14 mmol) of vinyl monomer, and 0.5 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15°C under a nitrogen atmosphere. The procedure was then repeated as in Example 1 to obtain 241.4 mg of silicone polymer. The synthesis reaction formula is shown in the following formula (14).

[0138] [ka]

[0139] 1.2.3. Example 3 0.5 g (2.3 mmol) of carbonate monomer, 60.1 μL (0.49 mmol) of SiH monomer, 26.7 μL (0.16 mmol) of vinyl-terminated monomer, 48.2 μL (0.32 mmol) of vinyl monomer, and 0.5 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15°C under a nitrogen atmosphere. The procedure was then repeated as in Example 2 to obtain 298 mg of silicone polymer. See formula (14).

[0140] 1.2.4. Example 4 0.5 g (2.3 mmol) of carbonate monomer, 19.8 μL (0.19 mmol) of SiH monomer, 22 μL (0.13 mmol) of vinyl-terminated monomer, and 0.5 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere. The procedure was then repeated as in Example 1 to obtain 208.1 mg of a silicone polymer. See formula (13).

[0141] 1.2.5. Example 5 0.5 g (2.3 mmol) of carbonate monomer, 23.1 μL (0.16 mmol) of SiH monomer, 22 μL (0.13 mmol) of vinyl-terminated monomer, and 0.5 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere. The procedure was then repeated as in Example 1 to obtain 219.7 mg of silicone polymer. See formula (13).

[0142] 1.2.6. Example 6 0.5 g (2.3 mmol) of carbonate monomer, 26.4 μL (0.21 mmol) of SiH monomer, 22 μL (0.13 mmol) of vinyl-terminated monomer, and 0.5 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere. The procedure was then repeated as in Example 1 to obtain 257.5 mg of silicone polymer. See formula (13).

[0143] 1.2.7. Comparative Example 1A: Preparation of a Silicone Polymer with Vinyl Groups 2.0 g (9.1 mmol) of carbonate monomer, 270 μL (1.8 mmol) of terminal vinyl monomer, 135 μL (0.91 mmol) of vinyl monomer, and 2 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere.

[0144] To this was added 580 μL of aqueous sulfuric acid (1.4 M), and the mixture was cooled and stirred for 30 minutes, followed by stirring at room temperature for an additional 1.5 hours. While stirring at room temperature, the pressure was reduced using a rotary pump for 2 hours to remove volatiles. The solid was dissolved in 6 mL of acetonitrile, and reprecipitated by adding phosphate buffer (a mixture of 20 mL of 1 M pH 6 phosphate buffer and 10 mL of water). The solid was then dissolved in 6 mL of acetonitrile and reprecipitated with 30 mL of water, a process repeated three times. The mixture was then vacuum dried to obtain 708 mg of silicone polymer 1A. The synthesis reaction is shown in the following formula (15):

[0145] [ka]

[0146] 1.2.8. Comparative Example 1B: Preparation of a Silicone Polymer with Hydrosilyl Groups Carbonate monomer: 1.0 g (4.5 mmol), SiH monomer: 96 mg (0.91 mmol), methyl monomer: 55 mg (0.45 mmol), terminal SiH monomer: 124 μL (0.91 mmol), and dimethoxyethane: 1 mL were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere.

[0147] To this was added 290 μL of a 1.4 M sulfuric acid solution, which was then cooled and stirred for 30 minutes, followed by stirring at room temperature for an additional 1.5 hours. While stirring at room temperature, the pressure was reduced using a rotary pump for 1 hour to remove volatiles. The solid was dissolved in 6 mL of acetonitrile and reprecipitated in 30 mL of water, a process repeated three times. The mixture was then dried in vacuo to obtain 708 mg of silicone polymer 1B. The synthesis reaction is shown in the following formula (16):

[0148] [ka]

[0149] 1.2.9. Comparative Example 2A: Preparation of a Silicone Polymer with Vinyl Groups Carbonate monomer: 1.0 g (4.5 mmol), methyl monomer: 63 μL (0.45 mmol), terminal vinyl monomer: 135 μL (0.91 mmol), and dimethoxyethane: 1 mL were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere.

[0150] To this was added 290 μL of a 1.4 M sulfuric acid solution, which was then cooled and stirred for 30 minutes, followed by stirring at room temperature for an additional 1.5 hours. While stirring at room temperature, the pressure was reduced using a rotary pump for 12 hours to remove volatiles. The solid was dissolved in 6 mL of acetonitrile and reprecipitated in 30 mL of water, a process repeated three times. The mixture was then dried under vacuum to obtain 850 mg of silicone polymer 2A. The synthesis reaction is shown in the following formula (17):

[0151] [ka]

[0152] 1.2.10. Comparative Example 2B: Preparation of a Silicone Polymer with Hydrosilyl Groups 1.0 g (4.5 mmol) of carbonate monomer, 55 mg (0.45 mmol) of methyl monomer, 96 mg (0.91 mmol) of SiH monomer, and 1 mL of dimethoxyethane were placed in a Schlenk tube and cooled to −15° C. under a nitrogen atmosphere.

[0153] To this was added 290 μL of a 1.4 M sulfuric acid solution, which was then cooled and stirred for 30 minutes, followed by stirring at room temperature for an additional 1.5 hours. While stirring at room temperature, the pressure was reduced using a rotary pump for 2 hours to remove volatiles. The solid was dissolved in 6 mL of acetonitrile and reprecipitated in 30 mL of water, a process repeated three times. The mixture was then dried in vacuo to obtain 625 mg of silicone polymer 2B. The synthesis reaction is shown in Equation (18) below.

[0154] [ka]

[0155] [1.3. Preparation of elastomer (crosslinked film)] 1.3.1. Examples 1 to 6 25 mg of silicone polymer was dissolved in 60 μL of acetone, to which 2 μL of Karstedt catalyst (0.2% platinum / xylene) was added. The solution was poured into a 20 mm diameter polytetrafluoroethylene dish and allowed to dry. The solution was then heated at 70°C for 10 hours under a nitrogen atmosphere to obtain a crosslinked membrane.

[0156] 1.3.2. Comparative Example 1 17.1 mg of silicone polymer 1A and 9.8 mg of silicone polymer 1B were dissolved in 60 μL of acetone, and 2 μL of Karstedt catalyst was added thereto. Then, in the same manner as in Example 1, a crosslinked membrane was obtained.

[0157] 1.3.3. Comparative Example 2 13.7 mg of silicone polymer 2A and 11.3 mg of silicone polymer 2B were dissolved in 60 μL of acetone, and 2 μL of Karstedt catalyst was added thereto. Then, in the same manner as in Example 1, a crosslinked membrane was obtained.

[0158] 2. Test Method 2.1. Evaluation of silicone polymers [2.1.1. Molecular weight] 5 mg of silicone polymer was dissolved in 1.5 mL of acetone. This was filtered through a 0.2 μm syringe filter and subjected to GPC measurement using acetone as the solvent (Shodex α-M column, differential refractive index meter). Based on the GPC measurement results, the molecular weight distribution calculated as polymethyl methacrylate (PMMA) was calculated. Furthermore, the number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated from the molecular weight distribution.

[0159] [2.1.2. Copolymerization component analysis] The silicone polymer was dissolved in deuterated acetonitrile and 1H-NMR was measured using an NMR spectrometer. The molar ratio of the copolymerization components was calculated from the integral ratio of the carbonate ring protons, the hydrosilane Si-H protons, the vinyl group protons, and the Si-methyl group protons. The molar equivalents of the vinyl group and hydrosilane in the polymer were calculated from the copolymerization ratio. Furthermore, the crosslink density was calculated from the molar equivalents of vinyl groups and hydrosilane in the polymer, assuming that the vinyl groups and hydrosilane form a crosslinked structure through a 100% hydrosilylation reaction.

[0160] 2.2. Elastomer Evaluation 2.2.1. Tensile test The crosslinked membrane (thickness: approximately 100 μm) was cut into 5 mm wide strips. Tensile tests were performed using the resulting strip specimens. The tests were performed at a rate of 10 mm / min using a load-displacement measuring unit (FSA-0.5K2-500N) and a digital force gauge (ZTA-2N), and the breaking elongation, breaking strength, and elastic modulus were determined.

[0161] 2.2.2. Electrical characteristics Gold was deposited on the top and bottom of the crosslinked film by magnetron sputtering.The dielectric constant and dielectric loss tangent of the resulting sample were measured at 1 kHz using an impedance analyzer (Keysight, HP4194A).

[0162] [3. Results] The results are shown in Tables 1 and 2. From Tables 1 and 2, the following can be seen. (1) As the crosslink density increased, the elastic modulus of the elastomer increased and the elongation at break decreased. (2) The dielectric constant of commercially available silicone rubber is approximately 3 to 3.5. In contrast, the dielectric constants of the elastomers obtained in Examples 1 to 6 were as high as approximately 30 to 40.

[0163] (3) Examples 1 to 6 are elastomers obtained by crosslinking silicones that simultaneously contain vinyl and hydrosilyl groups in the molecular chain. It was found that the method according to the present invention can produce elastomers even with a crosslink density of 0.13 mmol / g (Example 4).

[0164] (4) Example 1 had a crosslink density of 0.18 mmol / g, which was higher than that of Example 4. However, Example 1 had a breaking elongation of over 100% and an elastic modulus of 0.25 MPa, making it a softer elastomer than Example 4. The reasons for this are thought to be as follows. The Si-H in the polymer is unstable, and some of it may react with water or oxygen in the atmosphere to become Si-OH, losing its cross-linking ability and becoming inactive. Therefore, the amount of Si-H participating in cross-linking in the polymer may be less than the amount of Si-H estimated by NMR. The Si-H amount estimated by NMR in Example 4 was 0.31 mmol / g, while that in Example 1 was 0.18 mmol / g, meaning that the Si-H amount in Example 4 was greater. If a certain proportion of these Si-H groups lost their crosslinking ability, the crosslink density would change depending on the amount of remaining Si-H groups.

[0165] For example, assuming that half of the Si-H groups in Example 4 are deactivated, the amount of remaining Si-H groups in Example 4 is estimated to be 0.155 mmol / g, while the amount of vinyl groups is 0.13 mmol / g. In this case, the actual crosslink density of Example 4 is estimated to be 0.13 mmol / g, regardless of whether or not there is deactivation. On the other hand, assuming that half of the Si-H groups are deactivated in Example 1 as well, the amount of remaining Si-H groups is estimated to be 0.09 mmol / g, while the amount of vinyl groups is 0.26 mmol / g in Example 1. Therefore, the actual crosslink density of Example 1 is estimated to be 0.09 mmol / g, not 0.18 mmol / g. That is, depending on the amount of remaining Si-H, the actual crosslink density may be in the reverse order from the estimated crosslink density values ​​listed in Table 1. It is believed that this is the reason why the softness of the elastomer is reversed.

[0166] (5) In Comparative Example 2, the elastic modulus was less than 0.1 MPa, even though the crosslink density was 0.37 mmol / g. In addition, Comparative Example 2 was too soft, so the electrical properties could not be evaluated. This result indicates that the methods of Comparative Examples 1 and 2 (methods of crosslinking a polymer having a vinyl group with a polymer having a hydrosilyl group) cannot substantially produce elastomers with a crosslink density of 0.37 mmol / g or less.

[0167] (6) In both Example 2 and Comparative Example 1, the calculated crosslink density was approximately 0.5 mmol / g. However, the elastic modulus and breaking strength of Example 2 were both greater than those of Comparative Example 1. Therefore, it is considered that the actual crosslink density of Example 2 is greater than that of Comparative Example 1. This result is considered to indicate that the efficiency of the crosslinking reaction is improved when the method of the present invention is used.

[0168] [Table 1]

[0169] [Table 2]

[0170] (Examples 11 to 15, Comparative Examples 11 to 13) 1. Sample Preparation 1.1. Reagents The following monomers were used to prepare the silicone polymer: (a) 3-cyanopropylmethyldimethoxysilane (hereinafter referred to as "CN monomer") (b) Dimethoxy(methyl)silane (hereinafter referred to as "SiH monomer") (c) Dimethylethoxyvinylsilane (hereinafter referred to as "terminal vinyl monomer") (d) Dimethoxydimethylsilane (hereinafter referred to as "methyl monomer") (e) Ethoxydimethylsilane (hereinafter referred to as "terminal SiH monomer")

[0171] 1.2. Preparation of silicone polymer 1.2.1. Example 11A Under a nitrogen atmosphere, a 20 mL Schlenk tube was charged with 2.08 g (12 mmol) of CN monomer, 10 mg (0.1 mmol) of SiH monomer, 13 mg (0.1 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol, and cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated aqueous sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 2 hours. The mixture was then stirred at room temperature for 3 hours while evacuating. The reaction mixture was ice-cooled at 0°C and neutralized with phosphate buffer (pH 6, concentration 1 M).

[0172] 16 mL of ethyl acetate and 4 mL of water were added to the reaction solution, and the mixture was centrifuged at 4800 rpm for 5 minutes, after which the aqueous layer was removed. Approximately 4 mL of water was added to the solids, and the mixture was centrifuged at 4800 rpm for 5 minutes, after which the aqueous layer was removed. This procedure was repeated three times. The solvent was then removed using a rotary evaporator. After overnight vacuum drying, 1.44 g of a colorless, transparent, oily polymer was obtained. The synthesis reaction formula is shown in the following formula (19).

[0173] [ka]

[0174] 1.2.2. Example 11B Under a nitrogen atmosphere, 2.08 g (12 mmol) of CN monomer, 42 mg (0.4 mmol) of SiH monomer, 52 mg (0.4 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol were placed in a 20 mL Schlenk tube and cooled for 10 minutes in an ice bath at -10°C. Then, in the same manner as in Example 11A, 1.46 g of a colorless, transparent, oily polymer was obtained.

[0175] 1.2.3. Example 12 Under a nitrogen atmosphere, 2.08 g (12 mmol) of CN monomer, 74 mg (0.7 mmol) of SiH monomer, 91 mg (0.7 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol were placed in a 20 mL Schlenk tube and cooled for 10 minutes in an ice bath at -10°C. Then, in the same manner as in Example 11A, 1.46 g of a colorless, transparent, oily polymer was obtained.

[0176] 1.2.4. Example 13 Under a nitrogen atmosphere, a 20 mL Schlenk tube was charged with 2.08 g (12 mmol) of CN monomer, 106 mg (1.0 mmol) of SiH monomer, 130.1 mg (1.0 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol, and the mixture was cooled in an ice bath at -10°C for 10 minutes. An ice-cooled concentrated aqueous sulfuric acid solution (49 μL / 510 μL of water) was added to the mixture, and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 3 hours. The procedure was then repeated as in Example 11A, yielding 1.47 g of a colorless, transparent, oily polymer.

[0177] 1.2.5. Example 14 Under a nitrogen atmosphere, a 20 mL Schlenk flask was charged with 1.73 g (10 mmol) of CN monomer, 240 mg (2.0 mmol) of methyl monomer, 106 mg (1.0 mmol) of SiH monomer, 130 mg (1.0 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol, and the mixture was cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 2.5 hours. The procedure was repeated as in Example 11A, yielding 1.42 g of a colorless, transparent, oily polymer. The synthesis reaction formula is shown in the following formula (20).

[0178] [ka]

[0179] 1.2.6. Example 15 Under a nitrogen atmosphere, a 20 mL Schlenk flask was charged with 692 mg (4.0 mmol) of CN monomer, 961 mg (8.0 mmol) of methyl monomer, 106 mg (1.0 mmol) of SiH monomer, 130 mg (1.0 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol, and the mixture was cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 2.5 hours. The procedure was then repeated as in Example 11A, yielding 0.94 g of a colorless, transparent, oily polymer.

[0180] [1.2.7. Comparative Example 11A] Under a nitrogen atmosphere, a 20 mL Schlenk tube was charged with 1.66 g (9.6 mmol) of CN monomer, 256 mg (2.4 mmol) of SiH monomer, 550 μL (4.0 mmol) of terminal SiH monomer, and 2 mL of 2-propanol, and cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 3 hours. The mixture was then stirred at room temperature for 2 hours while evacuating. The procedure was repeated in the same manner as in Example 11A, yielding 1.37 g of a colorless, transparent, oily polymer. The synthesis reaction formula is shown in the following formula (21).

[0181] [ka]

[0182] [1.2.8. Comparative Example 11B] Under a nitrogen atmosphere, 2.08 g (12 mmol) of CN monomer, 130 mg (1.0 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol were placed in a 20 mL Schlenk tube and cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 3 hours. The procedure was repeated as in Example 11A, yielding 1.43 g of a colorless, transparent, oily polymer. The synthesis reaction formula is shown in the following formula (22).

[0183] [ka]

[0184] [1.2.9. Comparative Example 12A] Under a nitrogen atmosphere, a 20 mL Schlenk tube was charged with 1.87 g (10.8 mmol) of CN monomer, 128 mg (1.2 mmol) of SiH monomer, 550 μL (4.0 mmol) of terminal SiH monomer, and 2 mL of 2-propanol, and the mixture was cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated aqueous sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 3 hours. The mixture was then stirred at room temperature for 2 hours while evacuating. The procedure was repeated in the same manner as in Example 11A, yielding 1.44 g of a colorless, transparent, oily polymer.

[0185] 1.2.10. Comparative Example 12B Under a nitrogen atmosphere, 2.08 g (12 mmol) of CN monomer, 520 mg (4.0 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol were placed in a 20 mL Schlenk tube and cooled in an ice bath at -10°C for 10 minutes. To this was added an ice-cooled concentrated aqueous sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by reaction at room temperature for 3 hours. The procedure was then repeated as in Example 11A to obtain 1.49 g of a colorless, transparent, oily polymer.

[0186] 1.2.11. Comparative Example 13A Under a nitrogen atmosphere, a 20 mL Schlenk flask was charged with 779 mg (4.5 mmol) of CN monomer, 540 mg (4.5 mmol) of methyl monomer, 106 mg (1.0 mmol) of SiH monomer, 550 μL (4.0 mmol) of terminal SiH monomer, and 2 mL of 2-propanol, and cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated aqueous sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 3 hours. The mixture was then stirred at room temperature for 2 hours while evacuating. The procedure was repeated in the same manner as in Example 11A, yielding 917 mg of a colorless, transparent, oily polymer. The synthesis reaction formula is shown in the following formula (23).

[0187] [ka]

[0188] [1.2.8. Comparative Example 13B] Under a nitrogen atmosphere, a 20 mL Schlenk flask was charged with 865 mg (5.0 mmol) of CN monomer, 600 mg (5.0 mmol) of methyl monomer, 520 mg (4.0 mmol) of vinyl-terminated monomer, and 2 mL of 2-propanol, and the mixture was cooled in a -10°C ice bath for 10 minutes. To this was added an ice-cooled concentrated sulfuric acid solution (49 μL / 510 μL of water), and the mixture was stirred at -10°C for 30 minutes, followed by a reaction at room temperature for 3 hours. The procedure was then repeated as in Example 11A, yielding 882 mg of a colorless, transparent, oily polymer. The synthesis reaction scheme is shown in the following formula (24).

[0189] [ka]

[0190] [1.3. Preparation of elastomer (crosslinked film)] 1.3.1. Examples 11 to 15 150 mg of each of the polymers of Examples 11A, 12, and 15 was dissolved in 400 μL of tetrahydrofuran (THF). 2 μL of a solution of platinum catalyst diluted 1 / 10 with xylene (Pt amount: 0.027 μmol) was added and stirred. The platinum catalyst used was a xylene solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt amount: approximately 2%, manufactured by Aldrich, Karstedt catalyst). The resulting solution was applied to an aluminum substrate or a PVA / PET film and thermally cured at 70°C for 10 hours in a nitrogen atmosphere to obtain a crosslinked film.

[0191] The films in Examples 12 to 15 were solidified to form crosslinked films, whereas the film in Example 11A was insufficiently solidified due to its low crosslink density. Therefore, the same procedure was performed on a mixture of 75 mg of the polymer of Example 11A and 75 mg of the polymer of Example 11B, which solidified to give a crosslinked membrane.

[0192] 1.3.2. Comparative Example 11 57 mg of the polymer of Comparative Example 11A and 93 mg of the polymer of Comparative Example 11B were dissolved in 400 μL of THF. Then, a crosslinked membrane was obtained in the same manner as in Examples 12 to 15.

[0193] 1.3.3. Comparative Example 12 79 mg of the polymer of Comparative Example 12A and 71 mg of the polymer of Comparative Example 12B were dissolved in 400 μL of THF. Then, a crosslinked membrane was obtained in the same manner as in Examples 12 to 15.

[0194] 1.3.4. Comparative Example 13 69 mg of the polymer of Comparative Example 13A and 81 mg of the polymer of Comparative Example 13B were dissolved in 400 μL of THF. Then, a crosslinked membrane was obtained in the same manner as in Examples 12 to 15.

[0195] 2. Test Method 2.1. Evaluation of silicone polymers [2.1.1. Molecular weight] 5 mg of silicone polymer was dissolved in 2.0 mL of chloroform. This was filtered through a 0.2 μm filter and subjected to GPC measurement. Based on the GPC measurement results, the molecular weight distribution in terms of polystyrene was determined. Furthermore, the weight average molecular weight (Mw) was determined from the molecular weight distribution.

[0196] [2.1.2. Copolymerization component analysis] The silicone polymer was dissolved in deuterated chloroform and 1H-NMR was measured using an NMR spectrometer. The molar ratio of the copolymerization components was calculated from the integral ratio of the alkyl protons of the cyanoalkyl group, the Si-H protons of the hydrosilane, the protons of the vinyl group, and the protons of the Si-methyl group. The molar equivalents of the vinyl group and hydrosilane in the polymer were calculated from the copolymerization ratio. Furthermore, the crosslink density was calculated from the molar equivalents of vinyl groups and hydrosilane in the polymer, assuming that the vinyl groups and hydrosilane form a crosslinked structure through a 100% hydrosilylation reaction.

[0197] 2.2. Elastomer Evaluation 2.2.1. Tensile test The crosslinked film (thickness: approximately 100 μm) was cut into strips approximately 20 mm x 5 mm wide. Tensile tests were performed using the resulting strip specimens. Using a load-displacement measuring unit (IMADA Co., Ltd., FSA-0.5K2-500N) and a digital force gauge (ZTA-2N), the tensile test was performed at a tension speed of 10 mm / min and a gauge length of 10 mm, and the breaking elongation, breaking strength, and elastic modulus were determined.

[0198] 2.2.2. Electrical characteristics Gold was deposited on the top and bottom of the crosslinked film by magnetron sputtering. The dielectric constant and dielectric loss tangent of the resulting sample at 1 kHz were measured using an impedance analyzer (Keysight, HP4194A). Furthermore, a voltage of 5 V was applied to the crosslinked film for 10 minutes using an insulation resistance meter (Advantest, R8340A), and the volume resistivity of the crosslinked film was then measured.

[0199] [3. Results] The results are shown in Tables 3 and 4. The following can be seen from Tables 3 and 4. (1) The higher the crosslink density, the higher the elastic modulus and the lower the elongation. (2) The relative dielectric constant of silicone rubber is approximately 3 to 3.5. In contrast, the relative dielectric constants of the crosslinked films obtained in Examples 12 to 15 were as high as 8 to 22.

[0200] (3) The polymer of Example 11A (crosslink density: 0.052 mmol / g) did not solidify by itself, but it was able to solidify when mixed with the polymer of Example 11B (crosslink density: 0.19 mmol / g). This result is thought to indicate that the silicone polymer of the present invention will solidify if its crosslink density is approximately the average of the two polymers (approximately 0.12 mmol / g).

[0201] (4) In Comparative Example 11, although the crosslink density was 0.33 mmol / g, the elastic modulus was 0.14 MPa, and the sample was too soft to evaluate its electrical properties. This result is thought to indicate that conventional crosslinking methods cannot substantially produce elastomers with crosslink densities of less than 0.33 mmol / g. (5) The elastomer of Example 11 was soft due to its low crosslink density, and therefore its elongation exceeded 100% and its breaking strength was a low value of 0.093 MPa.

[0202] (6) Example 13 and Comparative Example 12 had almost the same calculated crosslink density. However, the elastic modulus and breaking strength of Example 13 were greater than those of Comparative Example 12. This result is thought to indicate that the actual crosslink density of Example 13 was greater than that of Comparative Example 12, i.e., the crosslinking reaction rate of Example 13 was higher than that of Comparative Example 12.

[0203] [Table 3]

[0204] [Table 4]

[0205] Example 21 [1. Test Method] [1.1. Calculation of the dielectric constant E] Using the molecular weight and dielectric constant data of the actual compound, the actual compound was divided into functional group and alkyl groups, and the molecular weight of each group was calculated. Next, an E value was assigned to each functional group and alkyl group, and the calculated dielectric constant of the compound was calculated using the following formula. Calculated relative permittivity of the actual compound = Σ (molecular weight of each part × E value of each part) The E value of each part was determined by the least squares method so that the measured value of the relative permittivity of the actual compound and the calculated relative permittivity of the actual compound would match.

[0206] [1.2. Predicting the relative permittivity of silicone materials using E values] Using the E value of the functional group site and the same dielectric constant calculation method as in [1.1.], the dielectric constant of materials in which various functional groups were introduced via alkyl groups into the side chains of silicone polymers was calculated.

[0207] [2. Results] [2.1. Dielectric constant E] Table 5 shows the relative dielectric constant of each compound used to calculate the E value. Table 6 shows the E values ​​of various functional groups. Table 6 shows that CN groups, closed-ring carbonate groups (cyclic carbonate groups), lactone groups, lactam groups, amide groups, sulfoxide groups, sulfone groups, etc. have high E values. For the trifluoropropyl group, we performed the same calculation as above using the literature value (=7.15, Reference 1) of the relative dielectric constant εr of a silicone material containing trifluoropropyl groups: poly(3,3,3-trifluoropropylmethylsiloxane), to calculate the E value of the trifluoropropyl group. As a result, the E value of the trifluoropropyl group was found to be 12.40. [Reference 1] "SILICONE FLUIDS: STABLE, INERT MEDIA ENGNEERING AND DESIGN PROPERTIES FOR: Heat Transfer, Mechanical, Lubrication, Smart Fluid, Dielectric and Optical Applications Updated Hydrophilic and Organic Silicones," Gelest, Inc. (2012). https: / / s3.amazonaws,com / gelest / product-brochures / Inert-Silicones.pdf

[0208] [Table 5]

[0209] [Table 6]

[0210] 2.2. Estimation of the relative permittivity of silicone materials using E values Tables 7 and 8 show estimated values ​​of the dielectric constant of various silicone materials. For example, when a CN group is bonded to the silicone polymer via an alkylene group with n=3, the dielectric constant is estimated to be 12.44. When an ethylene carbonate group is bonded to the silicone polymer via an alkylene group with n=2, the dielectric constant is estimated to be 42.78. These estimated values ​​are in good agreement with experimental results.

[0211] [Table 7]

[0212] [Table 8]

[0213] Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments, and various modifications are possible within the scope of the gist of the present invention. [Industrial Applicability]

[0214] The elastomers according to the present invention can be used as dielectric layers in various sensors and actuators.

Claims

1. a main chain formed of siloxane bonds; a side chain attached to the main chain; Equipped with At least one high dielectric constant functional group, at least one hydrosilyl group, and at least one alkene group are introduced into the side chains and / or the ends of the main chain. Silicone polymer. However, the "high relative dielectric constant functional group" refers to a functional group having a dielectric constant E of 8 or more.

2. 2. The silicone polymer of claim 1, further comprising methylalkylsilicone units (-O-Si(Me)(R)-) copolymerized into the backbone. however, R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'); R' is an alkyl group having one or more carbon atoms, Each R" is an alkylene group having one or more carbon atoms.

3. The silicone polymer according to claim 1, which satisfies the following formulas (0) to (4): 30.0mol%≦X≦99.0mol%…(0) 0.1mol%≦Y≦25.0mol%…(1) 0.1mol%≦Z≦25.0mol%…(2) 0.0mol%≦U≦60.0mol%…(3) 0.90≦Y / Z≦1.60 (4) however, X=x×100 / (x+y+z+u), Y=y×100 / (x+y+z+u), Z=z×100 / (x+y+z+u), U=u×100 / (x+y+z+u), "x" is the total number of moles of the high dielectric constant functional groups, "y" is the total number of moles of the hydrosilyl groups, "z" is the total number of moles of the alkene groups; "u" is the total number of moles of methylalkyl silicone units (-O-Si(Me)(R)-) copolymerized into the main chain, R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'); R' is an alkyl group having one or more carbon atoms, Each R" is an alkylene group having one or more carbon atoms.

4. 2. The silicone polymer according to claim 1, which satisfies the composition formula represented by the following formula (5): 【Chemistry 1】 however, q 1 +q 2 +n+m+k+p=100mol%、 30.0 mol%≦n≦99.0 mol%, 0.5mol%≦m+q 1 ≦25.0mol%、 0.5mol%≦k+q 2 ≦25.0mol%、 0 mol%≦p≦20.0 mol%, q=q 1 +q 2 +q 3 >0、q 1 ≧0、q 2 ≧0、q 3 ≧0、 R is an alkyl group (-R'), an alkyl ether group (-R"-O-R'), an alkyl thioether group (-R"-S-R'), an alkyl carbonyl group (-R"-C(O)-R'), an alkyl carboxy group (-R"-COOH), or a carboxylic acid ester (-R"-COOR'), R' is an alkyl group having one or more carbon atoms; R" is an alkylene group having one or more carbon atoms, X d is the high dielectric constant functional group, L is, respectively, (a) None, (b) an alkylene group having one or more carbon atoms, or (c) an alkylene group having one or more carbon atoms, including an ether (—O—), a thioether (—S—), a carbonyl group (—C(O)—), a carboxyl group (—COOH), or a carboxylic acid ester (—R″-COOR′); -[Si(R) 2 -R t ] q are respectively -[Si(R) 2 -H] q1 , -[Si(R) 2 -L-CH=CH 2 ] q2 , and -[H] q3 At least one selected from the group consisting of:

5. 2. The silicone polymer according to claim 1, wherein a branched structure derived from trialkoxysilane and / or tetraalkoxysilane is introduced into the main chain.

6. 2. The silicone polymer according to claim 1, having a weight average molecular weight of 2,500 or more.

7. 2. The silicone polymer according to claim 1, wherein the high dielectric constant functional group comprises at least one selected from the group consisting of a cyclic carbonate group, a cyano group, a trifluoropropyl group, a lactam group, a lactone group, an amide group, a sulfoxide group, and a sulfone group.

8. An elastomer obtained by crosslinking the silicone polymers according to claim 1 through a hydrosilylation reaction.

9. The elastic modulus is 0.10 MPa or more and 10.0 MPa or less, and / or The crosslink density is 0.1 mmol / g or more and 1.0 mmol / g or less.

9. The elastomer of claim 8.

10. an elastomer layer made of the elastomer according to claim 8; a first electrode formed on one surface of the elastomer layer; a second electrode formed on the other surface of the elastomer layer; An electrical element comprising:

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