Gel-like composition, member, electronic component, electronic device, and method for producing gel-like composition

Abstract

As a solution, the present application provides a gel-like composition containing a vinyl chloride resin and a plasticizer, which is in a gel state at 20°C. The plasticizer is at least one selected from the group consisting of isophthalate esters, terephthalate esters, fumarate esters, acetyl ricinoleate esters, citrate esters, acetyl citrate esters, adipate esters selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleate esters and their derivatives, and salts thereof. The present application provides an electronic element having a first electrode and a second electrode, and a polymer layer disposed between the first electrode and the second electrode and containing the gel-like composition.

Description

Technical Field

[0001] This invention relates to a gel-like composition, component, electronic element, electronic machine, and method for producing the gel-like composition. Background Technology

[0002] Patent documents 1-5 disclose derivatives of gel-like substances containing polyvinyl chloride and dibutyl adipate that can be used as actuators or sensors. Patent document 6 discloses an actuator comprising a PVC gel sheet containing polyvinyl chloride, diethyl adipate, dioctyl adipate, diethyl sebacate, dioctyl sebacate, or diethyl succinate.

[0003] (Existing technical literature)

[0004] (Patent Documents)

[0005] (Patent Document 1) Japanese Patent No. 5392669

[0006] (Patent Document 2) Japanese Patent No. 5914003

[0007] (Patent Document 3) Japanese Patent Application Publication No. 2021-112018

[0008] (Patent Document 4) Japanese Patent Application Publication No. 2021-164395

[0009] (Patent Document 5) Japanese Patent Application Publication No. 2021-161365

[0010] (Patent Document 6) Japanese Patent Application Publication No. 2021-161364 Summary of the Invention

[0011] In a first aspect of the invention, a gel-like composition is provided, comprising a vinyl chloride-based resin and a plasticizer. The gel-like composition is in a gel state at 20°C. The plasticizer may be at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetylacetic acid esters, citrates, acetylacetic acid esters, adipates selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleates, and their derivatives, as well as their salts.

[0012] The plasticizer may be at least one selected from the group consisting of di-2-ethylhexyl isophthalate (DOIP), di-2-ethylhexyl terephthalate (DOTP), dibutyl fumarate (DBF), di-2-ethylhexyl fumarate (DOF), methyl acetylacetonate (MAR), tributyl acetylacetonate (ATBC), diethyl fumarate (DEF), diethyl maleate (DEM), dibutyl maleate (DBM), triethyl citrate (TEC), tributyl citrate (TBC), and their derivatives and salts.

[0013] The adhesive force of the gel-like composition, measured as the force for peeling the contacted sample and anode, using an aluminum electrode as the anode and applying a voltage of 300 V to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm, is 0.5 N / cm. 2 above.

[0014] The gel composition, using a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an opening ratio of 62% as the anode, can exhibit a change of more than 0.5 μm when a voltage of 300 V is applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm.

[0015] The plasticizer may be at least one selected from the group consisting of di-2-ethylhexyl isophthalate (DOIP) and its derivatives and salts thereof. The gel composition (i) may contain up to 1000 parts by weight of plasticizer relative to 100 parts by weight of vinyl chloride resin. Alternatively / the gel composition (ii) may contain more than 200 parts by weight of plasticizer relative to 100 parts by weight of vinyl chloride resin.

[0016] The plasticizer may be at least one selected from the group consisting of di-2-ethylhexyl terephthalate (DOTP) and its derivatives and salts thereof. The gel composition may contain 200 or more parts by weight of plasticizer relative to 100 parts by weight of vinyl chloride resin.

[0017] In a second aspect of the invention, a component is provided, formed from any of the aforementioned compositions.

[0018] In a third aspect of the invention, an electronic component is provided, comprising a first electrode and a second electrode, and a polymer layer. The polymer layer is disposed between the first electrode and the second electrode and contains a gel-like composition according to any one of claims 1 to 6.

[0019] In a fourth aspect of the invention, a method for producing a gel-like composition is provided, comprising a mixing step and a removal step. In the mixing step, a vinyl chloride resin, a plasticizer, and a solvent may be mixed. In the removal step, the mixture of the vinyl chloride resin, plasticizer, and solvent obtained in the mixing step may be dried, and a portion of the solvent may be removed from the mixture. The mixture may contain 100 to 1000 parts by weight of plasticizer relative to 100 parts by weight of vinyl chloride resin. The plasticizer may be at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetylacetic acid esters, citrates, acetylacetic acid esters, adipates selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleates, and their derivatives and salts.

[0020] In a fifth aspect of the invention, the total mass of the vinyl chloride resin and the plasticizer relative to the mass of the mixture may be 80% by mass or more. The plasticizer may be at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetylacetic acid esters, citrates, acetylacetic acid esters, adipates selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleates, and their derivatives and salts.

[0021] In a sixth aspect of the invention, a gel-like composition is provided, comprising a vinyl chloride-based resin and a plasticizer, which is in a gel state at 20°C. The adhesive force (N / cm) of the gel-like composition is... 2 The product of the change in the sample (μm) and the change in the sample size is 20 μmN / cm. 2 The above describes the adhesive force, measured using an aluminum electrode as the anode and a 300 V voltage applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm. The sample variation was measured using a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an opening ratio of 62%, applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm and a 300 V voltage applied.

[0022] In a seventh aspect of the invention, a gel-like composition is provided, comprising a vinyl chloride-based resin and a plasticizer, which is in a gel state at 20°C. The adhesive strength (N / cm) of the gel-like composition is... 2 The change in viscosity (excluding the change in sample size (μm)) / adhesion ratio is 1.5 μm / cm. 2 / N or higher. Adhesive force was measured as the force required to peel the sample from the contacting anode when an aluminum electrode was used as the anode and a voltage of 300 V was applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm. The change in sample size was measured when a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an opening ratio of 62% was used as the anode and a voltage of 300 V was applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm.

[0023] Furthermore, the description of the invention does not list all the essential features of the invention. In addition, sub-combinations of their feature groups can also constitute an invention. Attached Figure Description

[0024] Figure 1 This is a simplified representation of the system configuration of actuator 100.

[0025] Figure 2 This is a simplified representation of the system configuration of sensor 200.

[0026] Figure 3 This is a simplified example of the method for manufacturing polymer layer 116. Detailed Implementation

[0027] The present invention will now be described through embodiments thereof, but these embodiments do not limit the invention as defined in the claims. Not all combinations of features described in the embodiments are necessarily necessary for the solution of the invention. Furthermore, the embodiments will be described with reference to the accompanying drawings; however, in the accompanying drawings, sometimes the same or similar parts are labeled with the same reference numerals, and repeated descriptions are omitted.

[0028] (Summary of Actuator 100)

[0029] Figure 1 This is a schematic representation of the system configuration of actuator 100. Actuator 100 converts electrical energy into mechanical energy.

[0030] In this embodiment, the actuator 100 includes, for example, a piezoelectric element 110, a drive device 120, and wiring 130. In this embodiment, the piezoelectric element 110 includes, for example, a cathode 112, an anode 114, and a polymer layer 116. Furthermore, in this embodiment, the polymer layer is a component formed from a gel composition. More specifically, the piezoelectric element 110 includes two cathodes 112, one anode 114, and two polymer layers 116. In this embodiment, the cathodes 112, polymer layers 116, anodes 114, polymer layers 116, and cathodes 112 are arranged sequentially.

[0031] In this embodiment, the piezoelectric element 110 utilizes the inverse piezoelectric effect of the polymer layer 116 to convert electrical energy into mechanical energy. As described above, in this embodiment, the piezoelectric element 110 includes a pair of cathodes 112 and an anode 114, and a polymer layer 116 disposed between the pair of cathodes 112 and anodes 114. In one embodiment, a portion of the polymer layer 116 is disposed between the pair of cathodes 112 and anodes 114. For example, one end of the polymer layer 116 and its vicinity are disposed between the pair of cathodes 112 and anodes 114. In another embodiment, the entire polymer layer 116 is disposed between the pair of cathodes 112 and anodes 114.

[0032] A pair of cathodes 112 and anodes 114 apply a voltage to a polymer layer 116 disposed between the pair of cathodes 112 and anodes 114. The polymer layer 116 deforms according to the magnitude of the applied voltage. The voltage can be applied while being adjusted appropriately, and can be 10 to 500 V, preferably 20 to 400 V.

[0033] The cathode 112 and anode 114 can be any components capable of applying voltage to the polymer layer 116, and there are no particular limitations on the material and structure of the cathode 112 and anode 114. Examples of the structure of the cathode 112 and anode 114 include: shape, planar dimensions, thickness, etc. Examples of the shape of the cathode 112 and anode 114 include: plate-shaped, foil-shaped, comb-shaped, mesh-shaped, etc.

[0034] At least one of the cathode 112 and anode 114 may have a comb-like or mesh-like shape. In particular, by having the anode 114 in a mesh-like shape, the polymer layer 116 can be allowed to enter the gaps in the mesh and shrink. The cathode 112 and / or anode 114 having a comb-like or mesh-like shape can be easily deformed. As a result, the power consumption of the actuator 100 is reduced.

[0035] In this embodiment, polymer layer 116 is a polymer layer containing vinyl chloride-based resin and plasticizer. Polymer layer 116 is in a gel state at 20°C. The term "gel state" generally refers to a state called "gel," which is a mixed system of two or more components. For example, a "gel" has intermediate properties between solid and liquid, and can be a swollen body of polymers that have absorbed polymers or solvents. Furthermore, for example, a "gel" can be considered as a state in which the polymer chains are linked together in a very long network.

[0036] In one embodiment, the polymer layer 116 comprises a piezoelectric element. The polymer layer 116 may also be a piezoelectric element. Thus, when pressure is applied to the polymer layer 116, a voltage proportional to the magnitude of the pressure is generated. Furthermore, when a voltage is applied to the polymer layer 116, the polymer layer 116 can deform. The piezoelectric element may be a dielectric material.

[0037] In another embodiment, the polymer layer 116 has adhesive properties. Adhesiveness is an indicator of the degree of stickiness of a material surface. The polymer layer 116 may contain an adhesive piezoelectric element, or may be an adhesive piezoelectric element. In yet another embodiment, the polymer layer 116 may also have optical path bending properties. Details of the polymer layer 116 will be described later.

[0038] In this embodiment, the drive device 120 controls the operation of the actuator 100. In one embodiment, the drive device 120 controls the timing of applying voltage to the piezoelectric element 110. In another embodiment, the drive device 120 controls the magnitude of the voltage applied to the piezoelectric element 110. In this embodiment, the wiring 130 electrically connects the piezoelectric element 110 and the drive device 120.

[0039] Actuator 100 may be an example of an electronic device. Piezoelectric element 110 may be an example of an electronic component. Polymer layer 160 may be an example of a gel-like composition. Cathode 112 may be an example of one of the first electrode and the second electrode. Anode 114 may be an example of the other of the first electrode and the second electrode.

[0040] (An example of another implementation)

[0041] In this embodiment, the piezoelectric element 110 is described in detail as having two cathodes 112, one anode 114, and two polymer layers 116, with the cathodes 112, polymer layers 116, anodes 114, polymer layers 116, and cathodes 112 arranged sequentially. However, the piezoelectric element 110 is not limited to this embodiment. For example, the structure of the piezoelectric element 110, the number of each part constituting the piezoelectric element 110, and / or the shape of each part constituting the piezoelectric element 110 are not limited to this embodiment.

[0042] In another embodiment, the piezoelectric element 110 includes one or more (sometimes referred to as more than one) unit units comprising a cathode 112, a polymer layer 116, and an anode 114. In the unit unit, the cathode 112, polymer layer 116, and anode 114 are arranged, for example, sequentially. In the unit unit, the polymer layer 116 may be in contact with the cathode 112 and the anode 114. The unit unit may have a sheet-like, thin-film, or layered component different from the polymer layer 116 between the cathode 112 and the anode 114. When the piezoelectric element 110 has multiple individual unit units, adjacent unit units may share a single cathode 112, and adjacent unit units may also share a single anode 114. When the piezoelectric element 110 has multiple individual unit units, the multiple unit units may be combined to form the outermost layer of the piezoelectric element 110 as the cathode 112, and the multiple unit units may also be combined to form the outermost layer of the piezoelectric element 110 as the anode 114.

[0043] In another embodiment, a plurality of polymer layers 116 may be disposed between the cathode 112 and the anode 114. The piezoelectric element 110, for example, has a plurality of independent polymer layers 116 between the cathode 112 and the anode 114. Each polymer layer 116 may have a substantially polygonal columnar, polygonal pyramidal, cylindrical, conical, elliptical columnar, or elliptical cone shape, or a shape similar to these shapes.

[0044] In this embodiment, details of the actuator 100, as an example of an electronic machine, have been described. However, the electronic machine is not limited to the actuator 100 described in this embodiment. In another embodiment, the electronic machine may be any machine that utilizes the inverse piezoelectric effect or the piezoelectric effect of the polymer layer 116.

[0045] The electronic device can be any type of actuator utilizing the inverse piezoelectric effect of polymer layer 116, or it can be a machine equipped with such an actuator. A machine equipped with an actuator can be a machine that uses the actuator as a power source. Examples of machines that use the actuator as a power source include: artificial muscles, robotic suits, robotic arms, variable-focus lenses, vibration generating devices, and tactile displays. Examples of vibration generating devices include: loudspeakers, vibrating loudspeakers, and bone conduction loudspeakers.

[0046] The electronic device can be any type of sensor utilizing the piezoelectric effect of polymer layer 116, or it can be a machine equipped with such a sensor. Details of the sensor will be explained later.

[0047] In this embodiment, an example of the use of polymer layer 116 is described using the piezoelectric effect or inverse piezoelectric effect. However, the use of polymer layer 116 is not limited to this embodiment. In another embodiment, the adhesive properties of polymer layer 116 are utilized. Polymer layer 116 is used, for example, as an adsorbent material, adhesive material, etc. Polymer layer 116 can also be part of an air purifier or an electrostatic flocking device. In yet another embodiment, the optical path bending properties of polymer layer 116 are utilized. Polymer layer 116 is used, for example, as part of an optical scanning device or a display.

[0048] (Overview of Sensor 200)

[0049] Figure 2 This is a simplified representation of the system configuration of sensor 200. Sensor 200 converts mechanical energy into electrical energy.

[0050] In this embodiment, the sensor 200 includes, for example, a piezoelectric element 210, a detection device 220, and wiring 230. In this embodiment, the piezoelectric element 210 includes, for example, a cathode 112, an anode 114, and a polymer layer 116. More specifically, the piezoelectric element 110 includes one cathode 112, one anode 114, and one polymer layer 116. In this embodiment, the cathode 112, the polymer layer 116, and the anode 114 are arranged sequentially.

[0051] In this embodiment, the piezoelectric element 210 utilizes the piezoelectric effect of the polymer layer 116 to convert mechanical energy into electrical energy. As described above, in this embodiment, the piezoelectric element 210 includes a pair of cathodes 112 and an anode 114, and a polymer layer 116 disposed between the pair of cathodes 112 and anodes 114. In one embodiment, a portion of the polymer layer 116 is disposed between the pair of cathodes 112 and anodes 114. For example, one end of the polymer layer 116 and its vicinity are disposed between the pair of cathodes 112 and anodes 114. In another embodiment, the entire polymer layer 116 is disposed between the pair of cathodes 112 and anodes 114.

[0052] In this embodiment, when pressure is applied to the polymer layer 116 disposed between a pair of cathodes 112 and anodes 114, a potential difference (sometimes referred to as voltage) is generated between the pair of cathodes 112 and anodes 114. The pair of cathodes 112 and anodes 114 are connected to the detection device 220 via wiring 230. For example, the cathodes 112 are electrically connected to one input terminal of the detection device 220, and the anodes 114 are electrically connected to the other input terminal of the detection device 220.

[0053] The cathode 112 and anode 114 can be any conductive components, and there are no particular limitations on their material and structure. Examples of the structure of the cathode 112 and anode 114 include: shape, planar dimensions, thickness, etc. Examples of the shape of the cathode 112 and anode 114 include: plate-shaped, foil-shaped, comb-shaped, mesh-shaped, etc.

[0054] At least one of the cathode 112 and anode 114 may have a comb-like or mesh-like shape. In particular, the anode 114 may have a mesh-like shape. The cathode 112 and / or anode 114 having a comb-like or mesh-like shape can be easily deformed. As a result, the polymer layer 116 can easily enter the gaps in the mesh, and the sensitivity of the sensor 200 is improved.

[0055] In this embodiment, the detection device 220 detects the voltage generated between a pair of cathodes 112 and anodes 114. The detection device 220 can determine the magnitude of the voltage using any known method. In this embodiment, the wiring 230 electrically connects the piezoelectric element 210 and the detection device 220.

[0056] Sensor 200 may be an example of an electronic device. Piezoelectric element 210 may be an example of an electronic component.

[0057] (An example of another implementation)

[0058] In this embodiment, the piezoelectric element 210 is described in detail, taking as an example a piezoelectric element 210 comprising one cathode 112, one anode 114, and one polymer layer 116, with the cathode 112, polymer layer 116, and anode 114 arranged sequentially. However, the piezoelectric element 210 is not limited to this embodiment. For example, the structure of the piezoelectric element 210, the number of each part constituting the piezoelectric element 210, and / or the shape of each part constituting the piezoelectric element 210 are not limited to this embodiment. The piezoelectric element 210 may have the same configuration as other embodiments of the piezoelectric element 210 described.

[0059] (Details of polymer layer 116)

[0060] In this embodiment, the polymer layer 116 contains a gel-like composition (sometimes referred to as a gel-like composition). The polymer layer 116 may also be a gel-like composition. The gel-like composition, for example, contains a vinyl chloride-based resin and a plasticizer. The gel-like composition, for example, is in a gel state at 20°C. Preferably, the gel-like composition is in a gel state at a temperature between -10°C and 50°C, more preferably at a temperature between 5°C and 35°C.

[0061] (A. Composition of the gel-like composition)

[0062] (vinyl chloride-based resin)

[0063] In this embodiment, the vinyl chloride-based resin may be (i) a homopolymer of vinyl chloride monomer, (ii) a copolymer of vinyl chloride monomer and one or more other polymerizable monomers, or (iii) a chloride of these (i) and (ii) polymers or copolymers. The other polymerizable monomers are any compounds capable of copolymerizing with vinyl chloride monomer, and their specific details are not particularly limited. When the vinyl chloride-based resin is a copolymer, the types of the other polymerizable monomers can be selected to facilitate molding into sheets, films, or layers when a plasticizer is added.

[0064] Other polymerizable monomers may be compounds containing vinyl unsaturated groups. Compounds containing vinyl unsaturated groups may be compounds with one vinyl unsaturated group per molecule or compounds with multiple vinyl unsaturated groups per molecule.

[0065] Examples of compounds containing vinyl unsaturated groups include: ethylene, propylene, vinylidene chloride, vinyl acetate, vinyl carboxylate monomers, aromatic vinyl monomers, conjugated diene monomers, vinyl unsaturated monocarboxylic acid esters, vinyl unsaturated polycarboxylic acid esters, vinyl unsaturated monocarboxylic acid esters, vinyl unsaturated dicarboxylic acid esters, vinyl unsaturated ethers, epoxy-containing monomers, alcohol-containing hydroxyl monomers, alkoxy-containing monomers, nitrile-containing monomers, amide-containing monomers, and amino-containing monomers.

[0066] Vinyl chloride resins may also be substantially free of impurities (sometimes referred to as unavoidable impurities) introduced into the raw materials and / or manufacturing process of vinyl chloride resins.

[0067] The K-value of vinyl chloride resins is not particularly limited, and can be in the range of 40 to 110, preferably 45 to 105. The K-value is determined according to JIS K 7367-2. Examples of commercially available vinyl chloride resins with such K-values ​​include: TK-2500HS, TK-2000E (manufactured by Shin-Etsu Chemical Co., Ltd.), VICIR S2000 (manufactured by Cires Co., Ltd.), and VICIRS5000 (manufactured by Cires Co., Ltd.).

[0068] (Plasticizer)

[0069] (Types of plasticizers)

[0070] In this embodiment, the plasticizer may be at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetylacetic acid esters, citrates, acetylacetic acid esters, adipic acid esters selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleates, and their derivatives and salts. Thus, the gel composition containing the plasticizer and the vinyl chloride resin can become a piezoelectric material.

[0071] As described above, Patent Documents 1-5 disclose the preparation of PVC gels containing polyvinyl chloride and dibutyl adipate (sometimes referred to as dibutyl adipate). While Patent Documents 1-5 describe the use of various compounds as plasticizers, as examples, only PVC gels containing dibutyl adipate as a plasticizer are disclosed. Furthermore, Patent Documents 1-5 neither describe nor suggest a relationship between the amount of plasticizer added and the degree of the reverse piezoelectric effect of the PVC gel. Moreover, Patent Documents 1-5 neither describe nor suggest a relationship between the type and / or amount of plasticizer added and the adhesiveness of the PVC gel.

[0072] Patent Document 6 discloses the production of PVC gel sheets containing polyvinyl chloride, and diethyl adipate, dioctyl adipate, diethyl sebacate, dioctyl sebacate, or diethyl succinate. Furthermore, while Patent Document 6 describes producing PVC gel sheets by varying the concentration of the plasticizer, it does not describe specific experimental results. In addition, Patent Document 6 neither describes nor implies a relationship between the amount of plasticizer added and the degree of the reverse piezoelectric effect of the PVC gel. Moreover, Patent Document 6 neither describes nor implies a relationship between the type and / or amount of plasticizer and the adhesiveness of the PVC gel.

[0073] The inventors have discovered that when the plasticizer is at least one selected from the group consisting of adipates, maleates, and their derivatives and salts selected from di-2-ethylhexyl adipate (DOA) and diisononyl adipate (DINA), a gel composition containing the plasticizer and the vinyl chloride resin can become a piezoelectric material. Furthermore, the inventors have discovered that the gel composition exhibits excellent adhesive properties.

[0074] Furthermore, the inventors changed the amount of plasticizer added to each of the gel compositions and observed changes in the degree of reverse piezoelectric effect and the degree of adhesion of each gel composition. As a result, the inventors found that, depending on the type of plasticizer, (i) the variation pattern of the degree of reverse piezoelectric effect of the gel composition when the amount of plasticizer added changes, (ii) the variation pattern of the degree of adhesion of the gel composition when the amount of plasticizer added changes, (iii) the variation pattern of the degree of reverse piezoelectric effect × adhesion of the gel composition when the amount of plasticizer added changes, and / or (iv) the variation pattern of (degree of reverse piezoelectric effect / adhesion) of the gel composition when the amount of plasticizer added changes. It should be noted that the degree of reverse piezoelectric effect can also represent the degree of piezoelectric effect.

[0075] Specifically, the inventors have discovered that there are plasticizers of the type in which the degree of the reverse piezoelectric effect of the gel composition increases with increasing addition amount, and plasticizers of the type in which the degree of the reverse piezoelectric effect of the gel composition decreases with increasing addition amount. Furthermore, the inventors have discovered that, depending on the type of plasticizer, the degree of the reverse piezoelectric effect of the gel composition sometimes has a maximum or minimum value.

[0076] The inventors have discovered that there are plasticizers of the type that increase the adhesiveness of the gel composition with increasing addition amount, and plasticizers of the type that decrease the adhesiveness of the gel composition with increasing addition amount. Furthermore, the inventors have discovered that, depending on the type of plasticizer, the adhesiveness of the gel composition sometimes has a maximum or minimum value.

[0077] The inventors have discovered plasticizers of various types, including those where the degree of reverse piezoelectric effect × adhesiveness of the gel-like composition substantially increases with increasing addition amount, those that temporarily increase with increasing addition amount but then become constant, and those that temporarily increase with increasing addition amount and then decrease. Furthermore, the inventors have found that, depending on the type of plasticizer, the degree of reverse piezoelectric effect × adhesiveness of the gel-like composition sometimes has a maximum or minimum value.

[0078] The inventors have discovered plasticizers of various types, including those whose degree of reverse piezoelectric effect / adhesion of the gel composition generally increases with increasing addition amount, those whose degree of increase is temporary but then becomes constant with increasing addition amount, and those whose degree of increase is temporary and then decreases with increasing addition amount. Furthermore, the inventors have found that, depending on the type of plasticizer, the degree of reverse piezoelectric effect / adhesion of the gel composition sometimes has a maximum or minimum value.

[0079] Plasticizers may contain (i) esters of isophthalic acid, terephthalic acid, fumaric acid, acetylated ricinoleic acid, acetylated citric acid, citric acid, adipic acid, or maleic acid, and (ii) esters of alcohols (linear, branched, or cyclic, which may contain aromatics or substituents) having 1 to 20 carbon atoms, or salts of such esters. Examples of salts of such esters include carbonates, phosphates, and sulfates.

[0080] The plasticizer is preferably selected from at least one of the group consisting of di-2-ethylhexyl isophthalate (DOIP), di-2-ethylhexyl terephthalate (DOTP), dibutyl fumarate (DBF), di-2-ethylhexyl fumarate (DOF), methyl acetylacetonate (MAR), acetylacetonate tributyl citrate (ATBC), diethyl fumarate (DEF), diethyl maleate (DEM), dibutyl maleate (DBM), triethyl citrate (TEC), tributyl citrate (TBC), and their derivatives and salts.

[0081] When the plasticizers are di-2-ethylhexyl isophthalate (DOIP), di-2-ethylhexyl terephthalate (DOTP), diethyl fumarate (DEF), diethyl maleate (DEM), dibutyl maleate (DBM), triethyl citrate (TEC), and tributyl citrate (TBC), a gel composition with greater adhesiveness can be obtained compared to a gel composition containing di-2-ethylhexyl phthalate (DOP), a structural isomer of these compounds, as a plasticizer. Furthermore, compared to using DOP as a plasticizer, it is easier to balance the degree of reverse piezoelectric effect and the degree of adhesiveness.

[0082] Specifically, in gel compositions containing DOP as a plasticizer, the degree of reverse piezoelectric effect increases with increasing plasticizer content, while the degree of adhesiveness decreases sharply. Therefore, balancing the degree of reverse piezoelectric effect and adhesiveness using DOP as a plasticizer is relatively difficult. In contrast, in gel compositions containing DOIP as a plasticizer, the degree of reverse piezoelectric effect increases with increasing plasticizer content, while the degree of adhesiveness decreases relatively slowly. Furthermore, in gel compositions containing DOTP as a plasticizer, both the degree of reverse piezoelectric effect and adhesiveness increase with increasing plasticizer content. Moreover, the degree of adhesiveness exhibits a maximum value.

[0083] Gel compositions containing DEF, DEM, DBM, TEC, or TBC as plasticizers also showed a trend that the degree of reverse piezoelectric effect of the gel composition generally increased with increasing plasticizer content. Furthermore, the degree of adhesiveness of the gel composition tended to remain roughly constant or decrease relatively slowly.

[0084] Therefore, when using DOTP and DOIP as plasticizers, it is relatively easy to produce gel compositions with high adhesiveness. In particular, when using DOTP as a plasticizer, it is possible to produce gel compositions with relatively high degree of reverse piezoelectric effect and relatively high adhesiveness.

[0085] When the plasticizer is dibutyl fumarate (DBF), di-2-ethylhexyl fumarate (DOF), methyl acetylacetonate (MAR), tributyl acetylacetonate (ATBC), diethyl fumarate (DEF), diethyl maleate (DEM), dibutyl maleate (DBM), triethyl citrate (TEC), and / or tributyl citrate (TBC), a gel-like composition with high adhesiveness can be obtained. When the plasticizer is dibutyl fumarate (DBF), di-2-ethylhexyl fumarate (DOF), methyl acetylacetonate (MAR), and / or tributyl acetylacetonate (ATBC), for example, compared to the case where the plasticizer is dibutyl adipate (DBA) used in Patent Documents 1-6, a gel-like composition with even greater adhesiveness can be obtained. As a result, the balance between the degree of reverse piezoelectric effect and the degree of adhesiveness can be easily adjusted.

[0086] (Plasticizer content)

[0087] The gel-like composition may contain a plasticizer in an amount of 100 to 1000 parts by weight, preferably 200 to 800 parts by weight, and more preferably 250 to 700 parts by weight, relative to 100 parts by weight of vinyl chloride-based resin. This allows for the preparation of a composition that exhibits a gel state at 20°C. When the plasticizer content is above the lower limit of the aforementioned range, a piezoelectric material exhibiting a gel state at 20°C can be obtained. When the plasticizer content is below the upper limit of the aforementioned range, the composition has suitable viscosity and / or elasticity, allowing for the preparation of sheet-like, film-like, or layered gel-like compositions.

[0088] When the plasticizer is DOIP, the gel composition may contain 200 to 800 parts by mass, preferably 250 to 500 parts by mass, relative to 100 parts by mass of vinyl chloride resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0089] When the plasticizer is DOTP, the gel composition may contain 200 parts by mass or more of plasticizer relative to 100 parts by mass of vinyl chloride-based resin. The gel composition may contain 250 parts by mass or more of plasticizer relative to 100 parts by mass of vinyl chloride-based resin, or it may contain 300 parts by mass or more of plasticizer relative to 100 parts by mass of vinyl chloride-based resin. This allows for the preparation of gel compositions with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0090] When the plasticizer is DOTP, the gel composition may contain 800 parts by weight or less, preferably 700 parts by weight or less, of plasticizer relative to 100 parts by weight of vinyl chloride-based resin. The gel composition may contain 650 parts by weight or less of plasticizer relative to 100 parts by weight of vinyl chloride-based resin, or 600 parts by weight or less of plasticizer relative to 100 parts by weight of vinyl chloride-based resin, or less than 600 parts by weight of plasticizer relative to 100 parts by weight of vinyl chloride-based resin. The gel composition may contain 500 parts by weight or less of plasticizer relative to 100 parts by weight of vinyl chloride-based resin. Therefore, a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness can be obtained.

[0091] When the plasticizer is DBF, the gel composition may contain 200 to 800 parts by mass, preferably 250 to 500 parts by mass, relative to 100 parts by mass of the vinyl chloride-based resin. The gel composition may contain 400 parts by mass or more of plasticizer relative to the vinyl chloride-based resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0092] When the plasticizer is DOF, the gel composition may contain 200 to 800 parts by mass, preferably 250 to 600 parts by mass, relative to 100 parts by mass of the vinyl chloride-based resin. The gel composition may contain 300 parts by mass or more of plasticizer relative to the vinyl chloride-based resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0093] When the plasticizer is MAR, the gel composition may contain 200 to 800 parts by weight, preferably 250 to 500 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. The gel composition may contain 300 parts by weight or more of plasticizer relative to the vinyl chloride resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0094] When the plasticizer is ATBC, the gel composition may contain 200 to 800 parts by weight, preferably 250 to 500 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. The gel composition may also contain 300 to 400 parts by weight of the plasticizer relative to the vinyl chloride resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0095] When the plasticizer is DEF, the gel composition may contain 200 to 800 parts by mass, preferably 250 to 500 parts by mass, relative to 100 parts by mass of the vinyl chloride-based resin. The gel composition may contain 300 parts by mass or more of plasticizer relative to the vinyl chloride-based resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0096] When the plasticizer is DEM, the gel composition may contain 200 to 800 parts by weight, preferably 250 to 500 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. The gel composition may contain 300 parts by weight or more of plasticizer relative to the vinyl chloride resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0097] When the plasticizer is DBM, the gel composition may contain 200 to 800 parts by mass, preferably 250 to 500 parts by mass, relative to 100 parts by mass of the vinyl chloride-based resin. The gel composition may contain 300 parts by mass or more of plasticizer relative to the vinyl chloride-based resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0098] When the plasticizer is TEC, the gel composition may contain 200 to 800 parts by weight, preferably 250 to 500 parts by weight, relative to 100 parts by weight of the vinyl chloride-based resin. The gel composition may contain 300 parts by weight or more of plasticizer relative to the vinyl chloride-based resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0099] When the plasticizer is TBC, the gel composition may contain 200 to 800 parts by weight, preferably 250 to 500 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. The gel composition may contain 300 parts by weight or more of plasticizer relative to the vinyl chloride resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0100] When the plasticizer is DOA, the gel composition may contain 200 to 800 parts by mass, preferably 250 to 600 parts by mass, relative to 100 parts by mass of the vinyl chloride-based resin. The gel composition may contain 300 parts by mass or more of plasticizer relative to the vinyl chloride-based resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0101] When the plasticizer is DINA, the gel composition may contain 200 to 800 parts by weight, preferably 250 to 600 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. The gel composition may contain 300 parts by weight or more of plasticizer relative to the vinyl chloride resin. This results in a gel composition with a relatively high degree of reverse piezoelectric effect and high adhesiveness.

[0102] (Other additives) In the composition, the two-component system of polyvinyl chloride and plasticizer is preferably 100% by mass, but other arbitrary additives including solvents may also be added up to 20% by mass.

[0103] (B. Physical properties of the gel-like composition)

[0104] (The degree of inverse piezoelectric effect)

[0105] As described above, the gel composition containing the plasticizer is a piezoelectric material, and actuators and / or sensors can be realized by utilizing the inverse piezoelectric effect and / or piezoelectric effect of the gel composition. The degree of the inverse piezoelectric effect of the gel composition can be evaluated, for example, based on the amount of deformation (μm) of the sample measured by the following steps.

[0106] According to this embodiment, firstly, a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm is cut from the gel-like composition to be measured. Next, an aluminum strip electrode with a height of 7.5 cm, a width of 2.5 cm, and a thickness of 0.008 cm is prepared as the cathode. Similarly, a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an opening ratio of 62% is prepared as the anode.

[0107] Next, the cathode is placed on a smooth, horizontally positioned measuring stage. A sample is then placed on the cathode, and an anode mesh and aluminum strip are slowly placed on the sample. Next, using a laser displacement meter (Keyence, model LK-G30), the distance between the laser sensor and the aluminum strip on the anode mesh is measured without applying voltage to the anode and cathode.

[0108] Next, a voltage application device (Matsusada Precision, model HARb-1P30-LFPs) is used to apply voltage to the anode and cathode. The applied voltage is, for example, 100 V or 300 V. Then, a laser displacement meter (Keyence, model LK-G30) is used to measure the distance between the laser sensor and the aluminum strip on the anode mesh while the voltage is applied to the anode and cathode.

[0109] Next, the difference in thickness of the sample before and after applying voltage to the anode and cathode is calculated. From this, the deformation (μm) of the sample before and after applying voltage to the anode and cathode (as described above, for example, 100 V or 300 V) is derived.

[0110] Using a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an aperture ratio of 62% as the anode, when a voltage of 300 V is applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm, the change in the sample is, for example, 0.5 μm or more. This change can also be 10 μm or more, preferably 20 μm or more. Therefore, for example, actuators with low power consumption and / or sensors with high sensitivity can be realized.

[0111] (Degree of adhesion)

[0112] As described above, the gel composition containing the plasticizer has relatively high adhesiveness. The degree of adhesiveness of the gel composition can be evaluated, for example, based on the adhesive force measured by the steps described below.

[0113] According to this embodiment, firstly, a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm is cut from the gel-like composition to be measured. Next, an aluminum strip electrode with a height of 2 cm, a width of 3.5 cm, and a thickness of 0.009 cm is prepared as the cathode. Similarly, an aluminum electrode is prepared as the anode.

[0114] Next, an anode is installed in the detection section of the force gauge (manufactured by Kyowa Electric Co., Ltd., model LTS-500GA). Furthermore, a cathode is placed on a horizontally arranged, smooth measuring stage, and the sample is placed on the cathode. Then, the distance between the anode mounted on the detection section and the sample is adjusted, and the anode is slowly placed onto the sample. The force gauge is installed on a Z-axis lifting stage (manufactured by Chuo Seiki Co., Ltd., ALV104-HP), and the distance between it and the sample is adjusted by its lifting and lowering.

[0115] Next, a voltage is applied to the anode and cathode using a voltage application device (manufactured by Matsusada Precision, model HARb-1P30-LFPs). The applied voltage is, for example, 100 V or 300 V.

[0116] Next, the force gauge is slowly raised. The force gauge is raised until the sample peels off from the anode, and the force pulling on the force gauge during peeling is measured. Similarly, the force pulling on the force gauge when the sample peels off from the anode at 0 V is measured as the adhesive force. The difference between the adhesive force at each applied voltage and the adhesive force at 0 V is derived as the adhesive force.

[0117] Using an aluminum electrode as the anode, and with a voltage of 300 V applied to a sample 1.5 cm high, 1.5 cm wide, and 0.03 cm thick, the adhesive force, measured as the force used to peel the sample from the anode, was, for example, 0.5 N / cm. 2 The adhesive force can also be 1 N / cm. 2 The above is preferably 2 N / cm 2 The above. Therefore, for example, it is possible to realize actuators that consume little power and / or sensors with high sensitivity.

[0118] The variation (μm) and adhesion (N / cm) of the sample 2 The product of these two quantities, when measured at 300 V, can be 20 μmN / cm. 2 The above is preferably 36 μmN / cm 2 The above is further preferred to be 50 μmN / cm. 2 The above. When measured at 100 V, it can be 0.3 μmN / cm. 2 The above is preferably 1.3 μmN / cm 2 The above is further preferred to be 2.0 μmN / cm. 2 The above. Therefore, for example, it is possible to improve both the degree of reverse piezoelectric effect and the adhesive force of the gel composition in a balanced manner without bias towards one side. Furthermore, it is possible to realize actuators with low power consumption and / or sensors with high sensitivity. Additionally, the change in amount (μm) and adhesive force (N / cm) 2 The requirement of multiplying by ) is an example of a more preferred implementation, but not a necessary requirement.

[0119] The change in the sample (μm) divided by the adhesion (N / cm) 2 The change in viscosity (%), when measured at 300 V, can be 0.4 μmcm. 2 / N or higher, preferably 1.5 μmcm 2 / N or higher, more preferably 3.0 μmcm 2 / N or higher. When measured at 100 V, it can be 0.5 μmcm. 2 / N or higher, preferably 1.5 μmcm 2 / N or higher, more preferably 3.0 μmcm 2 / N or more. Therefore, for example, it is possible to increase the amount of change in adhesive force per unit, and to improve the inverse piezoelectric effect when the adhesive force is adjusted to a constant value. Furthermore, it is possible to realize actuators with low power consumption and / or sensors with high sensitivity. Additionally, the change in force (μm) / adhesive force (N / cm) 2 The requirement of the ratio is an example of a more preferred implementation, but not a necessary requirement.

[0120] (C. Method for manufacturing gel-like compositions)

[0121] use Figure 3 The method for preparing polymer layer 116 (more specifically, a gel composition) is described in detail. Figure 3 This is a simplified example of the method for manufacturing polymer layer 116.

[0122] (Solution casting method)

[0123] according to Figure 3 In the illustrated embodiment, firstly, in step 322 (sometimes simplified to step S), the vinyl chloride resin, plasticizer, and solvent are mixed. This yields a mixture of the vinyl chloride resin, plasticizer, and solvent (sometimes referred to as a precursor solution).

[0124] Examples of solvents include cyclic ether compounds and cyclic ketone compounds. Examples of cyclic ether compounds include tetrahydrofuran (THF) and dioxane. Examples of cyclic ketone compounds include cyclohexanone.

[0125] The precursor solution contains, for example, a plasticizer in an amount of 100 to 1000 parts by weight relative to 100 parts by weight of a vinyl chloride resin.

[0126] The precursor solution may contain, for example, a solvent of 1000 to 3000 parts by mass relative to 100 parts by mass of the vinyl chloride resin. Alternatively, the precursor solution may contain a solvent of 1500 to 2500 parts by mass relative to 100 parts by mass of the vinyl chloride resin. In this case, it is preferable to uniformly mix the vinyl chloride resin and the plasticizer by stirring for approximately 1 hour to 2 weeks, preferably 12 hours to 10 days, as needed. Furthermore, there are no particular limitations on the stirring conditions, as long as uniform mixing is achieved; stirring can be performed at 50 to 2000 rpm, preferably 100 to 1000 rpm.

[0127] Next, in S324, the precursor solution is added to a suitable culture dish to achieve the desired thickness. Then, in S326, a drying process of the precursor solution is performed. This removes a portion of the solvent from the precursor solution. The drying process is performed, for example, at a temperature between 5°C and 35°C. During the drying process, for example, by performing the process at said temperature for more than one day, preferably more than one week or about three weeks, a gel-like polymer forming component can be formed. The thickness of the component can be appropriately adjusted according to the purpose, preferably 0.01 to 0.1 cm.

[0128] Gelation is performed in the drying process to obtain a gel-like composition containing a vinyl chloride-based resin and a plasticizer. The mass ratio of the solvent to the mass of the dried gel composition can be less than 1% by mass or less than 0.1% by mass.

[0129] In this embodiment, an example of a method for producing a gel-like composition is described using a pre-prepared vinyl chloride-based resin to carry out S322. However, the method for producing a gel-like composition is not limited to this embodiment. In another embodiment, before carrying out S322, a step of removing at least a portion of the impurities contained in the vinyl chloride-based resin may be further performed. Unavoidable impurities can be exemplified as such. In this case, in S322, a precursor solution is prepared by mixing the impurity-removed vinyl chloride-based resin, a plasticizer, and a solvent.

[0130] The total mass of the vinyl chloride resin and plasticizer relative to the mass of the mixture can be 80% by mass or more, or 90% by mass or more. Alternatively, the total mass of the vinyl chloride resin and plasticizer relative to the mass of the mixture can be 80% by mass or more but less than 100% by mass.

[0131] Example

[0132] The following examples illustrate the present invention. However, the present invention is not limited to the manufacturing examples, synthesis examples, or embodiments described below. Furthermore, unless otherwise specified, "parts" refers to "parts by mass," and "%" refers to "% by mass."

[0133] (Example 1)

[0134] First, 30 g of tetrahydrofuran (THF; manufactured by Fujifilm and Koko Pure Chemical Industries, Ltd., Grade 204-08745, purity 99.5%) and 4 g of di-2-ethylhexyl isophthalate (DOIP; manufactured by CG EASTER Co., Ltd., product name DOIP, purity ≥ 99%) were added to the inside of the reaction vessel. Using a magnetic stirrer, THF and DOIP were stirred at 500 rpm, while simultaneously adding 2 g of polyvinyl chloride (PVC; manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name TK-2500HS, K value 84.4, purity ≥ 99.5%) in small, repeated additions. Then, the mixture of THF, DOIP, and PVC was stirred for one week at 500 rpm.

[0135] Next, the mixed solution was added to the interior of a 7.6 cm diameter petri dish. The petri dish was then left to stand at a temperature between 5°C and 35°C for 2 weeks. This yielded a gel-like composition with a diameter of 7.6 cm and a thickness of 0.3 mm.

[0136] (Examples 2-4)

[0137] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in each example are shown in Tables 1 to 4 (also collectively referred to as "Table 1 et al").

[0138] (Example 5)

[0139] Except for using di-2-ethylhexyl terephthalate (DOTP; manufactured by ADEKA Corporation, product name ADKCIZER D-810, purity ≥ 99%) as a plasticizer, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 5 are shown in Table 1, etc.

[0140] (Examples 6-9)

[0141] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 5. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0142] (Example 10)

[0143] Except for the use of dibutyl fumarate (DBF; manufactured by Tokyo Chemical Industry Co., Ltd., product code F0116, purity ≥ 98%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 10 are shown in Table 1, etc.

[0144] (Examples 11-13)

[0145] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 10. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0146] (Example 14)

[0147] Except for the use of di-2-ethylhexyl fumarate (DOF; manufactured by Tokyo Chemical Industry Co., Ltd., product code F0117, purity ≥ 98%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 14 are shown in Table 1, etc.

[0148] (Examples 15-18)

[0149] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 14. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0150] (Example 19)

[0151] Except for the use of methyl acetylacetonate (MAR; manufactured by Tokyo Chemical Industry Co., Ltd., product code A0879, purity ≥ 80%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 19 are shown in Table 1, etc.

[0152] (Examples 20-22)

[0153] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 19. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0154] (Example 23)

[0155] Except for the use of acetylated tributyl citrate (ATBC; manufactured by Taoka Chemical Industry Co., Ltd., product name ATBC, purity ≥ 99%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 23 are shown in Table 1, etc.

[0156] (Examples 24-26)

[0157] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 23. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0158] (Example 27)

[0159] Except for the use of diethyl fumarate (DEF; manufactured by Tokyo Chemical Industry Co., Ltd., product code F0068, purity ≥ 98%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 27 are shown in Table 1, etc.

[0160] (Examples 28-30)

[0161] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 27. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0162] (Example 31)

[0163] Except for the use of diethyl maleate (DEM; manufactured by Tokyo Chemical Industry Co., Ltd., product code M0010, purity ≥90%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 31 are shown in Table 1, etc.

[0164] (Examples 32-34)

[0165] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 31. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0166] (Example 35)

[0167] Except for the use of dibutyl maleate (DBM; manufactured by Tokyo Chemical Industry Co., Ltd., product code M0009, purity ≥ 95%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 35 are shown in Table 1, etc.

[0168] (Examples 36-38)

[0169] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 35. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0170] (Example 39)

[0171] Except for the use of triethyl citrate (TEC; manufactured by Tokyo Chemical Industry Co., Ltd., product code C0367, purity ≥ 99%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 39 are shown in Table 1, etc.

[0172] (Examples 40-42)

[0173] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 39. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0174] (Example 43)

[0175] Except for the use of tributyl citrate (TBC; manufactured by Tokyo Chemical Industry Co., Ltd., product code C0366, purity ≥ 98%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 43 are shown in Table 1, etc.

[0176] (Examples 44-46)

[0177] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 43. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0178] (Example 47)

[0179] Except for the use of di-2-ethylhexyl adipic acid (DOA; manufactured by Tokyo Chemical Industry Co., Ltd., product code A0163, purity ≥ 98%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 47 are shown in Table 1, etc.

[0180] (Examples 48-51)

[0181] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared following the same steps as in Example 47. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0182] (Example 52)

[0183] Except for the use of diisononyl adipate (DINA; manufactured by Shin Nippon Rikka Co., Ltd., product name SANSO CIZERDINA, purity ≥ 99%) as a plasticizer, and the different amounts of PVC, plasticizer, and THF added, the gel composition was prepared following the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 52 are shown in Table 1, etc.

[0184] (Examples 53-56)

[0185] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 52. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 1, etc.

[0186] (Example 57)

[0187] Except for the use of TK-2500PE (manufactured by Shin-Etsu Chemical Industry Co., Ltd., K value = 88) as PVC, dibutyl fumarate (DBF; manufactured by Tokyo Chemical Industry Co., Ltd., product code F0116, purity ≥ 98%) as plasticizer, and the different amounts of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 57 are shown in Tables 5 and 6 (also collectively referred to as "Tables 5 et al.").

[0188] (Examples 58-60)

[0189] Except for the different amounts of PVC, plasticizer, and / or THF added, the gel composition was prepared following the same steps as in Example 57. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 5, etc.

[0190] (Example 61)

[0191] Except for the use of VICIR S5000 (manufactured by Cires Corporation, K value 99) as PVC, dibutyl fumarate (DBF; manufactured by Tokyo Chemical Industry Co., Ltd., product code F0116, purity ≥ 98%) as plasticizer, and the different amounts of plasticizer and / or THF added, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Example 61 are shown in Table 5, etc.

[0192] (Examples 62-64)

[0193] Except for the different amounts of PVC, plasticizer, and / or THF added, the gel composition was prepared following the same steps as in Example 61. The amounts of PVC, plasticizer, and THF added in each example are shown in Table 5, etc.

[0194] (Comparative Example 1)

[0195] Except for using di-2-ethylhexyl phthalate (DOP; manufactured by CG EASTER Co., Ltd., product name DOP, purity ≥ 99%) as a plasticizer, the gel composition was prepared according to the same steps as in Example 1. The amounts of PVC, plasticizer, and THF added in Comparative Example 1 are shown in Table 1, etc.

[0196] (Comparative Examples 2-4)

[0197] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same procedure as Comparative Example 1. The amounts of PVC, plasticizer, and THF added in each comparative example are shown in Table 1, etc.

[0198] (Comparative Example 5)

[0199] Except for using dibutyl adipic acid (DBA; manufactured by Fujifilm and Koh Genuine Chemicals Co., Ltd., Premium Grade 043-19421, 99% purity) as a plasticizer, the gel composition was prepared according to the same procedure as in Example 1. The amounts of PVC, plasticizer, and THF added in Comparative Example 5 are shown in Table 1, etc.

[0200] (Comparative Examples 6-8)

[0201] Except for the differences in the amount of plasticizer and / or THF added, the gel composition was prepared according to the same procedure as Comparative Example 5. The amounts of PVC, plasticizer, and THF added in each comparative example are shown in Table 1, etc.

[0202] (Evaluate)

[0203] For the gel compositions prepared in each embodiment and comparative example, the changes and adhesive forces were measured. The changes and adhesive forces were measured for both cases where a voltage of 100 V was applied to the gel composition and cases where a voltage of 300 V was applied to the gel composition. Table 1, etc., shows the changes and adhesive forces of each embodiment and comparative example when a voltage of 100 V was applied to the gel composition, and the changes and adhesive forces of each embodiment and comparative example when a voltage of 300 V was applied to the gel composition.

[0204] As shown in Examples 1-26, when the plasticizer is at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetylacetic acid esters, acetylacetic acid citrates and their derivatives and salts, the gel composition containing the plasticizer and the vinyl chloride resin is a piezoelectric material. Furthermore, it is known that the gel composition has excellent adhesive properties.

[0205] A comparison of Examples 1-9 and Comparative Examples 1-4 shows that, when the plasticizer is di-2-ethylhexyl isophthalate (DOIP) and / or di-2-ethylhexyl terephthalate (DOTP), a gel composition with greater adhesiveness can be obtained compared to a gel composition containing di-2-ethylhexyl phthalate (DOP), a structural isomer of these compounds, as the plasticizer. Furthermore, it is found that, with increasing amounts of plasticizer added, the degree of reverse piezoelectric effect and the adhesiveness of the gel composition increase in gel compositions containing DOTP as the plasticizer. Therefore, it is evident that using DOTP as the plasticizer results in a gel composition with both a relatively large degree of reverse piezoelectric effect and relatively high adhesiveness.

[0206] A comparison of Examples 10-56 and Comparative Examples 5-8 shows that when the plasticizer is dibutyl fumarate (DBF), di-2-ethylhexyl fumarate (DOF), methyl acetylacetonate (MAR), tributyl acetylacetonate (ATBC), diethyl fumarate (DEF), diethyl maleate (DEM), dibutyl maleate (DBM), triethyl citrate (TEC), tributyl citrate (TBC), di-2-ethylhexyl adipate (DOA), and / or diisononyl adipate (DINA), a gel-like composition with a high degree of adhesion can be obtained. Furthermore, it is evident that, compared to the case where the plasticizer is dibutyl adipate (DBA), the gel-like composition exhibits a relatively greater degree of reverse piezoelectric effect and a higher degree of adhesion.

[0207] A comparison of Examples 5-56 and Comparative Examples 1-8 shows that when the plasticizer is di-2-ethylhexyl terephthalate (DOTP), dibutyl fumarate (DBF), di-2-ethylhexyl fumarate (DOF), methyl acetylacetonate (MAR), tributyl acetylacetonate (ATBC), diethyl fumarate (DEF), diethyl maleate (DEM), dibutyl maleate (DBM), triethyl citrate (TEC), tributyl citrate (TBC), di-2-ethylhexyl adipate (DOA), and / or diisononyl adipate (DINA), a gel-like composition with a large product of the degree of reverse piezoelectric effect and the degree of adhesion (especially when 300 V is applied) can be obtained.

[0208] [Table 1]

[0209]

[0210] [Table 2]

[0211]

[0212] [Table 3]

[0213]

[0214] [Table 4]

[0215]

[0216] [Table 5]

[0217]

[0218] [Table 6]

[0219]

[0220] The present invention has been described above using embodiments, but the technical scope of the present invention is not limited to the scope described in the embodiments. It will be apparent to those skilled in the art that various changes or modifications can be made to the embodiments. Furthermore, to the extent that there is no technical conflict, the matters described for a particular embodiment can be applied to other embodiments. In addition, each constituent element may have the same features as other constituent elements with the same name but different reference numerals. As will be clear from the claims, forms with such changes or modifications are also included within the technical scope of the present invention.

[0221] It should be noted that the execution order of actions, steps, and processes in the apparatus, system, program, and method shown in the claims, specification, and drawings can be performed in any order unless specifically stated as "before," "before," etc., or the output of a previous process is not used in a subsequent process. Even if the flow of actions in the claims, specification, and drawings is described using terms such as "firstly," "next," etc., for convenience, this does not mean that they must be performed in that order.

[0222] Explanation of reference numerals in the attached figures

[0223] 100: Actuator

[0224] 110: Piezoelectric element

[0225] 112: Cathode

[0226] 114: Anode

[0227] 116: Polymer layer

[0228] 120: Drive unit

[0229] 130: Wiring

[0230] 200: Sensor

[0231] 210: Piezoelectric element

[0232] 220: Detection device

[0233] 230: Wiring

Claims

1. A gel-like composition comprising a vinyl chloride-based resin and a plasticizer, which is in a gel state at 20°C; and The plasticizer is at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetylacetic acid esters, citrates, acetylacetic acid esters, adipic acid esters selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleates, and their derivatives and salts.

2. The gel-like composition according to claim 1, wherein, The plasticizer is selected from at least one of the group consisting of di-2-ethylhexyl isophthalate (DOIP), di-2-ethylhexyl terephthalate (DOTP), dibutyl fumarate (DBF), di-2-ethylhexyl fumarate (DOF), methyl acetylacetonate (MAR), acetylacetonate tributyl citrate (ATBC), diethyl fumarate (DEF), diethyl maleate (DEM), dibutyl maleate (DBM), triethyl citrate (TEC), tributyl citrate (TBC), and their derivatives and salts.

3. The gel-like composition according to claim 1, wherein, Using an aluminum electrode as the anode, and with a voltage of 300 V applied to a sample 1.5 cm high, 1.5 cm wide, and 0.03 cm thick, the adhesive force, measured as the force used to peel the sample from the anode, was 0.5 N / cm. 2 above.

4. The gel-like composition according to claim 1, wherein, Using a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an opening ratio of 62% as the anode, when a voltage of 300V is applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm, the change in the sample is greater than 0.5 μm.

5. The gel-like composition according to claim 1, wherein, The plasticizer is selected from at least one of the group consisting of di-2-ethylhexyl isophthalate (DOIP) and its derivatives and salts thereof; the gel composition (i) contains less than 1000 parts by weight of the plasticizer relative to 100 parts by weight of the vinyl chloride resin, or (ii) contains more than 200 parts by weight of the plasticizer relative to 100 parts by weight of the vinyl chloride resin.

6. The gel-like composition according to claim 1, wherein, The plasticizer is selected from at least one of the group consisting of di-2-ethylhexyl terephthalate (DOTP) and its derivatives and salts thereof; the gel composition contains more than 200 parts by weight of the plasticizer relative to 100 parts by weight of the vinyl chloride resin.

7. A component formed from the composition according to any one of claims 1 to 6.

8. An electronic component comprising: The first electrode and the second electrode; and A polymer layer disposed between the first electrode and the second electrode, and containing a gel-like composition according to any one of claims 1 to 6.

9. An electronic machine comprising the electronic components according to claim 8.

10. A method for producing a gel-like composition, comprising the following steps: Mixed vinyl chloride resins, plasticizers and solvents; and The mixture of the vinyl chloride resin, the plasticizer, and the solvent obtained in the mixing step is dried to remove a portion of the solvent from the mixture; and The mixture contains, relative to 100 parts by weight and less than 1000 parts by weight of the plasticizer, amounting to 1000 parts by weight of the vinyl chloride-based resin. The plasticizer is at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetyl ricinoleate, acetyl citrate, citrates, adipic acid esters selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleates, and their derivatives and salts.

11. The method for producing a gel-like composition according to claim 10, wherein, The total mass of the vinyl chloride resin and the plasticizer is 80% or more by mass relative to the mass of the mixture; The plasticizer is at least one selected from the group consisting of isophthalates, terephthalates, fumarates, acetylacetic acid esters, citrates, acetylacetic acid esters, adipic acid esters selected from di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), maleates, and their derivatives and salts.

12. A gel-like composition comprising a vinyl chloride-based resin and a plasticizer, which is in a gel state at 20°C; and Using an aluminum electrode as the anode, the adhesion force (N / cm²) was measured as the force used to peel the sample and the anode from the contact surface under a voltage of 300 V applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm. 2 The product of this product and the change in sample size (μm) when a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an opening ratio of 62% is applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm is used as the anode is 20 μmN / cm. 2 above.

13. A gel-like composition comprising a vinyl chloride-based resin and a plasticizer, which is in a gel state at 20°C; and Using an aluminum electrode as the anode, the adhesion force (N / cm²) was measured as the force used to peel the sample and the anode from the contact surface under a voltage of 300 V applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm. 2 The change in adhesion was calculated by dividing the change by the change in adhesion when a stainless steel mesh electrode with a wire diameter of 0.18 mm, a mesh size of 0.67 mm, and an opening ratio of 62% was applied to a sample with a height of 1.5 cm, a width of 1.5 cm, and a thickness of 0.03 cm. The resulting change / adhesion ratio was 1.5 μm / cm². 2 / N or more.

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