JP7077128B2 - Laminates, manufacturing methods thereof, transducers including the laminates, etc. - Google Patents

Description

The present invention relates to a laminate that is excellent in industrial productivity and can be efficiently produced by using a continuous coating process, a transducer member including the laminate, and the like, and relates to a transducer, an electronic component, or a display device using the laminate. ..

An electroactive polymer such as an electroactive silicone material has its mechanical and / or electrical properties, specifically, high specific dielectric constant, high insulation breaking strength, and low Young's ratio to achieve high energy density. And because it has excellent mechanical strength (specifically, tensile strength, tear strength, elongation, etc.) when used as a dielectric layer of a transducer, durability and a practical amount of displacement should be realized. It can be suitably used as a material for a transducer. For example, Applicants have disclosed that a fluoroalkyl group-containing cured organopolysiloxane has a high relative permittivity and is useful as a transducer material (Patent Document 1 or Patent Document 2).

However, in recent years, in the field of transducer materials such as actuators, electroactive polymer sheets can be easily laminated and an electrode layer can be formed between the layers, achieving both high relative permittivity and mechanical strength. There is a strong demand for improved materials, and in addition to improving the mechanical and electrical properties of polymer sheets, there is a strong need to improve the structure and production process of their laminates.

International Patent Publication No. 2014-105959 International Patent Publication No. 2015-098072

The present invention has been made to solve the above problems, and provides a laminate having an electroactive polymer sheet and a strip-shaped electrode layer that can be efficiently produced by using a continuous coating material, and a manufacturing process thereof. ..

Similarly, it is an object of the present invention to provide the use of the laminated body as a transducer material such as an actuator.

As a result of diligent studies to solve the above problems, the present inventors obtained an electroactive polymer sheet having strip-shaped electrode layers on both sides thereof as a multilayer strip-shaped coating product in a continuous coating process, and then the multilayer strip-shaped coating product. The laminated body is formed by bending and laminating the coated material, winding up and laminating, or sequentially laminating using a continuous pattern coated material, and finally crimping the upper and lower surfaces, preferably heat crimping, to perform complete fusion. We have found that the above-mentioned problems can be solved by forming the above-mentioned problem, and have reached the present invention. The laminated body may be further energized between the layers, and is preferable.

The laminated body has excellent production efficiency and can be used as a member for a transducer or the like.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminate having an electroactive polymer sheet and a strip-shaped electrode layer that can be efficiently produced by using a continuous coating material, and a manufacturing process thereof. The laminate has excellent industrial productivity, and when applied as a dielectric layer, it is suitably used as a transducer material such as an actuator because it realizes a practical displacement amount and high responsiveness in addition to durability. be able to.

It is sectional drawing of the continuous strip-shaped coating material and the pattern coating material obtained by a continuous process. It is a figure which stacks the continuous strip-shaped coating material obtained by a continuous process by folding. It is a figure which stacks the continuous strip-shaped coating material obtained by a continuous process by winding. It is sectional drawing of the continuous strip-shaped coated article including the uncoated portion of the strip-shaped electrode layer and the pattern coated article obtained by the continuous process. It is a figure which heat-bonds the layers of the laminated body which cut off the end part after laminating the continuous strip-shaped coating material obtained by the continuous process by folding. It is a figure which energized the laminated body which had the end part cut off after laminating the continuous strip-shaped coating material obtained by the continuous process by folding. In addition, in FIGS. 1 to 6, "EAP" represents an electroactive polymer sheet. The figure shows a state in which the continuous strip-shaped coating material obtained from the continuous process is laminated by folding, and then the electrode layer is further laminated and the separator on the surface is removed from the laminated body whose ends are cut off. be.

Hereinafter, the laminated body of the present invention will be described in detail.

The laminate according to the present invention is provided with strip-shaped electrode layers on both sides of the sheet, and the electroactive polymer sheet in which the strip-shaped electrode layers on both sides are arranged so as to partially overlap each other in the width direction of the sheet is folded or wound up. It is a laminate having a structure with a strip-shaped electrode layer on both sides obtained as a continuous strip-shaped coating by a continuous process, and an electroactive polymer sheet having a strip-shaped electrode layer is used. Therefore, it is excellent in industrial production efficiency.

The electroactive polymer sheet obtained as such a continuous strip-shaped coating product is obtained by coating the strip-shaped electrode layer and the electroactive polymer sheet main body in a multi-layered and strip-shaped manner on the composition as a precursor thereof. At that time, in order to allow the strip-shaped electrode layer to be appropriately arranged by folding or winding, the electroactive polymer sheet constituting the laminate has a strip-shaped electrode layer and an electrode layer in the long axis direction thereof. It is preferable that the polymer sheet has a structure in which uncoated portions are alternately formed.

In particular, it is particularly preferable that the band-shaped electrode layer is arranged to have the following features (a) to (c). The long axis direction of the sheet is the direction in which the polymer sheet is wound in the continuous strip coating, and the width direction of the sheet is the direction perpendicular to the long axis direction of the sheet. Generally, the polymer is used. It means a direction perpendicular to the plane direction with respect to the direction in which the precursor is applied onto the substrate.
(A) The strip-shaped electrode layers on the front surface and the back surface are arranged at positions where they partially overlap each other in the width direction of the sheet. (C) The shapes of the strip-shaped electrode layers on the front and back surfaces are substantially the same.

The band-shaped electrode layer can be easily formed by applying a resin (conductive paste) containing conductive inorganic particles such as silver powder.

Here, the electroactive polymer sheet preferably has the following characteristics.
[Relative permittivity]
The electroactive polymer sheet of the present invention preferably has a relative permittivity of 3 or more, more preferably 4 or more, and particularly preferably 6 or more at 1 kHz and 25 ° C.

Such an electroactive polymer sheet is preferably a silicone polymer sheet, and more preferably a silicone cured product polymer or a silicone semi-cured product polymer obtained by a curing reaction including a hydrosilylation reaction. The semi-cured product includes a reaction product in the process of curing, for example, a product capable of a multi-step curing reaction such as a dual curing type reaction product.

The electroactive polymer sheet in the present invention is
(A) Organopolysiloxane having at least two alkenyl groups having 2 to 12 carbon atoms in the molecule, which is one kind or two or more kinds.
(B) The sum of the silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5. With respect to 1 mol of the total amount of alkenyl groups in one or more kinds of organohydrogenpolysiloxane compositions. Amount to be 0 mol,
(C) Effective amount of catalyst for hydrosilylation reaction,
It may be a dielectric silicone polymer sheet obtained by curing or semi-curing a curable organopolysiloxane composition containing at least. The curable organopolysiloxane composition may be cured by heat curing, room temperature curing, or high energy ray irradiation. The conditions for each curing or curing are not particularly limited, but when the curable organopolysiloxane composition is an addition curable organopolysiloxane composition, it is held in the range of 90 ° C to 180 ° C for 30 seconds to 30 minutes. It is done by.

In the present invention, the curable organopolysiloxane composition and the dielectric sheet material proposed by the applicant in the following patent application can be used without particular limitation, and the compositions disclosed therein and the cured product thereof are the patents of the present invention. It is explicitly available as a precursor composition and an electroactive polymer sheet to form a suitable electroactive polymer sheet in the application. The curable organopolysiloxane composition of the present invention may have a multi-step curing reactivity and is preferable. By having such characteristics, it is possible to further promote curing during a heating press or the like, which will be described later.
International Patent Publication No. 2014-105959
International Patent Publication No. 2015-098072
International Patent Publication 2016-163069 International Patent Publication 2016-031242 International Patent Publication 2016-098334 International Patent Publication 2017-183541 International Patent Application Number: PCT / JP2018 / 017480
Japanese patent application number: 2017-246951
Japanese patent application number: 2017-173713

As will be described later in the manufacturing process, the laminated body of the present invention may be cut off when the curvature of the end portion of the laminated body becomes small and problems such as disconnection or rigidity become hard. Further, the layers of the laminated body may be electrically conductive, which is preferable.

The thickness of the electroactive polymer sheet is not particularly limited, but the thickness per layer is 0.1 μm to 1,000 μm, and by laminating two or more layers thereof, the thickness is 0.2 to 2,000 μm. May be.

The electroactive polymer sheet constituting such a laminate shall be a multi-layer strip-shaped coating product obtained by continuously coating each layer of the strip-shaped electrode layer on the back surface of the sheet, the electroactive polymer sheet and the strip-shaped electrode layer on the sheet surface. Is preferable, the manufacturing process thereof will be described below.

The laminated body of the present invention is the above-mentioned laminated body, and two or more laminated bodies having band-shaped electrode layers on the front surface and the back surface are prepared by the same method, and the electrode layers are bonded to each other (FIG. 7). Further may be provided with the above-mentioned structure. Such a laminated body has an advantage that multiple laminations at the time of manufacturing are easy, and a high relative permittivity and elasticity can be easily realized. The bonding of the electrode layers can be easily realized by a known means such as heat crimping.

[Manufacturing process]
The laminate of the present invention is
Step 1: A step of applying the precursor composition forming the strip-shaped electrode layer onto a peeling sheet provided with a peeling surface.
Step 2: A step of applying a precursor composition for forming an electroactive polymer sheet onto the strip-shaped electrode layer obtained in step 1.
Step 3: A precursor composition for forming a strip-shaped electrode layer on the surface of the electroactive polymer sheet obtained in step 2 so as to partially overlap each other in the width direction of the sheet with respect to the strip-shaped electrode layer obtained in step 1. The process of applying,
Step 4: A step of separating the multi-layer strip-shaped coating material obtained in Step 3 from the release sheet, and
Step 5: A step of laminating the multi-layer strip-shaped coating material separated from the release sheet by step 4 by folding or winding it in the major axis direction.
Step 6: A step of crimping the laminate,
Optionally, in addition
Step 7: A step of cutting the end portion of the laminated body of step 5 or step 6, and step 8: a step of energizing the layers of the laminated body are preferable.

In the present invention, for example, a resin (= conductive paste) containing conductive particles such as silver powder and ITO particles is applied onto a release sheet provided with a release surface to form a strip-shaped electrode layer on the back surface. A precursor composition for forming an electroactive polymer sheet such as a curable organopolysiloxane composition is applied to a substrate by die coating or the like and cured, and further contains conductive particles such as silver powder in the above arrangement. The resin may be applied on a release sheet provided with a release surface to form a strip-shaped electrode layer on the surface. Die coating is a highly productive coating method that enables high-speed coating. In addition, the strip-shaped electrode layer on each surface includes an uncoated portion in which the strip-shaped electrode layer is not formed in the long axis direction of the electroactive polymer sheet and a portion coated with the precursor composition forming the strip-shaped electrode layer. It is preferable that they are arranged so as to be provided alternately.

The precursor composition forming the strip-shaped electrode layer is preferably curing-reactive, and may have curing-reactivity in multiple stages. For example, by providing dual cure characteristics, it is possible to further promote curing during a heating press, which will be described later.

The electroactive polymer sheet can be preferably obtained by applying the above-mentioned curable organopolysiloxane composition on a substrate and curing it at room temperature, heating, or irradiation with high energy rays such as ultraviolet rays.

The material of the electrode layer includes metals such as gold, platinum, silver, palladium, copper, nickel, aluminum, titanium, zinc, zirconium, iron, cobalt, tin, lead, indium, chromium, molybdenum, and manganese, and alloys thereof. Metal oxides such as indium-tin composite oxide (ITO), antimony-tin composite oxide (ATO), ruthenium oxide, titanium oxide, zinc oxide, and tin oxide; carbon nanotubes, carbon nanohorns, carbon nanosheets, carbon fibers , And carbon materials such as carbon black; and conductive resins such as poly (ethylene-3,4-dioxythiophene) (PEDOT), polyaniline and polypyrrole can be used. It is particularly preferable to use a conductive resin and an elastomer in which the conductive filler is dispersed in the resin. These are sometimes referred to as "conductive pastes". The electrode layer may contain one of the above-mentioned conductive substances alone, or may contain two or more of them. When the electrode contains two or more kinds of conductive substances, at least one of them can function as an active material and can also function as a conductive material for reducing the resistance of the remaining electrodes. When these are dispersed or kneaded in a resin and an elastomer, known techniques (for example, a technique for kneading / dispersing a conductive filler and its defect countermeasures, a technique disclosed in the Technical Information Association (2004), etc.) are available. It can be used without any restrictions.

The laminate of the present invention is finally pressure-bonded, preferably thermocompression-bonded (= pressed) to ensure adhesion between the band-shaped electrodes. Basically, the materials fused by the heat press are the same material, so they are easily bonded, and the bonded electrodes have sufficient bonding strength. Further, a process of stretching the laminated body before or after crimping may be further provided.

The peeling surface may be referred to as a peeling liner, a release layer or a release coating layer, and preferably a release coating such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent. It is a peeling layer having a function. The base material itself may be such that fine irregularities are physically formed on the surface of the base material, or the base material itself is difficult to adhere to the strip-shaped electrode layer or the electroactive polymer sheet described above. A release sheet provided with such a release surface is sometimes called a "separator". In the present invention, the peeling surface is preferably a peeling surface made of a silicone-based release agent layer. Further, in order to prevent peeling defects such as cracking, it may be laminated on a UV peeling type die bonding sheet and finally irradiated with UV for peeling.

In the above steps 1 and 3, the precursor composition in which the strip-shaped electrode layer on each surface forms a strip-shaped electrode layer with an uncoated portion in which the strip-shaped electrode layer is not formed in the long axis direction of the electroactive polymer sheet. It is preferable that the parts coated with the object are arranged so as to be provided alternately.

The method of conducting the electrodes for each layer is as shown in FIG. 6, and by shifting the alignment in the width direction of the electrodes, the electrodes can be independently short-circuited when the built-in electrodes are penetrated.

As shown in FIG. 7, the laminated body of the present invention is a laminated body obtained by the above-mentioned manufacturing method, in which a plurality of laminated bodies having electrode layers on the front surface and the back surface are prepared, and the respective electrode layers are bonded and further laminated. You may create it.

By using the above method, it is possible to efficiently stack the sheets, which were conventionally created one by one.

Hereinafter, the present invention will be described with reference to examples of its structure and raw materials forming each functional layer, but the present invention is not limited thereto.

[Ingredients of curable organopolysiloxane composition forming a dielectric sheet]
-Component (a1): Vinyl dimethylsiloxy group blockade at both ends, 3,3,3-trifluoropropylmethylsiloxane polymer (siloxane polymerization degree including ends: about 268)
-Component (B1-1): Bis (dimethylhydrogensiloxy) diphenylsilane-Component (B1-2): Both-terminal dimethylhydrogensiloxy group-blocked diphenylsiloxane polymer (siloxane polymerization degree: about 2.5)
-Component (B2-1): A siloxane (Mw = 1.11) composed of a dimethylhydrosiloxy unit ( ^MH unit) and a ^TF3Pr unit (trifunctional siloxy unit) having a 3,3,3-trifluoropropyl group. × 103 ^, silicon atom-bonded hydrogen atom is about 0.59% by weight.)
The weight average molecular weight (Mw) of the component (B2-1) is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography) using tetrahydrofuran (THF) as a solvent.
-Component (C1): Platinum-1,3-divinyl 1,1,3,3-tetramethyldisiloxane complex both-terminal vinyldimethylsiloxy group-blocked dimethylsiloxane polymer solution (about 0.6% by weight at platinum concentration)
<Hydrosilylation reaction inhibitor>
-Component (D1): 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane <filler>
-Component (E1): Surface-treated CAB-O-SIL (R) MS75D

[Composition Examples 1 to 6: Curable Organopolysiloxane Composition to Give a Dielectric Sheet]
Table 1 composition examples are shown. In the following examples, the amount of the silicon atom-bonded hydrogen atom (Si—H) of the components (B1) and (B2) was 1.3 mol per mol of the vinyl group in the composition. Moreover, the ratio of Si—H of (B1) and (B2) is shown as B1 _H / B2 _H. Further, the degree of polymerization of the component (A) was calculated by the following formula.
[NAA1 / (NAA1 + NAA2)] DPA1 + [NAA2 / (NAA1 + NAA2)] DPA2
Here, NAA1 and NAA2 are obtained by dividing the weight ratios of (A1) and (A2) in the component (A) by the number average molecular weight, respectively, and DPA1 and DPA2 are polymerizations of (A1) and (A2), respectively. Represents the degree.

[Measurement of physical properties of the obtained material]
The silicone composition was press-cured at 150 ° C. for 15 minutes and then post-cured in an oven at 150 ° C. for 60 to 120 minutes to obtain a cured product. Based on JIS-K6249, the tear strength of the obtained cured product was measured, and the tensile strength and the elongation at break were measured to determine the Young's modulus (modulus). The thickness of the sheet was set to 2 mm for the measurement of mechanical strength. In addition, the durometer A hardness of a 6 mm thick sheet was measured.
In addition, a sheet with a thickness of about 0.1 mm was prepared under the above conditions, and the dielectric breakdown strength was measured with the electric insulating oil breakdown voltage tester PORTATEST 100A-2 manufactured by Soken Electric Co., Ltd. Similarly, a sheet having a thickness of 1 mm was prepared, and the relative permittivity was measured with a LCR meter Wayne Kerr 6530P / D2 at a temperature of 25 ° C. and a frequency in the range of 20 Hz to 1 MHz. Of these, the values at 100 KHz were used in the examples and comparative examples. Table 1 shows various physical property values.

[Example 1]
A composition for forming a band-shaped electrode layer in which 5% by mass of conductive fine particles are added to the composition selected from the above composition examples on a heat-resistant resin film (hereinafter referred to as “separator”) provided with a release layer is shown in FIG. Apply so that it becomes an "electrode". The strip-shaped electrode layer forming composition is provided with an uncoated portion as in FIG.
Then, the composition selected from the above composition examples is applied onto the strip-shaped electrode so as to be “EAP” in FIG. 4, and heated at 150 ° C. for 60 minutes to be cured.
Further, the above-mentioned composition for forming a strip-shaped electrode layer is applied onto the cured product so as to be the “surface electrode” in FIG. The strip-shaped electrode layer forming composition is provided with an uncoated portion as in FIG.

By the above method, an electroactive polymer sheet having strip-shaped electrode layers on both sides of the sheet is obtained as a multilayer strip-shaped coating product. The strip-shaped electrode layer can also be formed by using another conductive paste that provides a peelable electrode layer.

The electroactive polymer sheet provided with the strip-shaped electrode layers on both sides of the sheet is peeled off from the separator and folded in the longitudinal direction in the same manner as shown in FIG. At that time, as shown in FIG. 5, the front surface electrodes and the back surface electrodes are laminated so as to face each other. After that, when the curvature of the end portion becomes small and a problem such as disconnection or the rigidity becomes hard occurs, the end portion of the laminated body is cut off.

The above-mentioned laminated body (including the one whose end is optionally cut off) is heat-bonded as shown in FIG. 5, so that the electrodes are firmly adhered to each other. In the heat crimping step, the polymer sheet may be further cured.

An electric conductor (for example, a copper wire) is passed through the layers of the laminated body after the heat crimping to conduct the conduction.

The laminate of the present invention can be suitably used for applications requiring an elastomer or gel-like member having excellent mechanical and electrical properties, for example, for manufacturing a transducer. In particular, if the manufacturing method of the present invention is used, it is possible to efficiently stack the sheets one by one, as opposed to the conventional sheets that have been laminated one by one, and the industrial productivity is remarkably excellent. Therefore, high-performance transducer members and the like can be provided in large quantities and with high quality.

Similarly, the laminate can be used in place of the electrolyte layer or dielectric layer in the actuator element structure known as the so-called "polymer actuator" or "polymer actuator". As for other uses, there are no restrictions other than those disclosed above, and the dielectric layer film provided with a cured product obtained by curing the fluoroalkyl group-containing curable organopolysiloxane composition of the present invention is a television receiver. Computer monitors, mobile information terminal monitors, surveillance monitors, video cameras, digital cameras, mobile phones, mobile information terminals, instrument panel displays for automobiles, instrument panel displays for various equipment, devices, and equipment, automatic ticket sales It can be used for various flat panel displays (FPDs) for displaying characters, symbols, images, etc., such as machines and automatic cash deposit machines. Devices include display devices such as CRT displays, liquid crystal displays, plasma displays, organic EL displays, inorganic EL displays, LED displays, surface electrolytic displays (SED), field emission displays (FED), and touch panels using these. It can be applied. The film of the present invention may be used for the purposes of preventing scratches, stains, fingerprint adhesion, antistatic, antireflection, and peep prevention on the display surface.

Claims (12)

Step 1: A step of applying the precursor composition forming the strip-shaped electrode layer onto a peeling sheet provided with a peeling surface.
Step 2: A step of applying a precursor composition for forming an electroactive polymer sheet, which is a curing-reactive organopolysiloxane composition, onto the strip-shaped electrode layer obtained in step 1.
Step 3: A band-shaped electrode layer is formed on the surface of the electroactive polymer sheet obtained in step 2 so as to partially overlap each other in the width direction of the electroactive polymer sheet with respect to the band-shaped electrode layer obtained in step 1. Step of applying the precursor composition,
Step 4: A step of separating the multi-layer strip-shaped coating material obtained in Step 3 from the release sheet, and
Step 5: A step of laminating the multi-layer strip-shaped coating material separated from the release sheet by step 4 by folding or winding it in the major axis direction.
Step 6: A step of crimping the laminate,
A method for manufacturing a laminated body. The method for producing a laminate according to claim 1, wherein the electroactive polymer sheet is a silicone cured product polymer or a silicone semi-cured product polymer obtained by a curing reaction including a hydrosilylation reaction. In the above steps 1 to 3, the precursor in which the strip-shaped electrode layer on each surface forms a strip-shaped electrode layer with an uncoated portion in which the strip-shaped electrode layer is not formed in the long axis direction of the electroactive polymer sheet. The method for producing a laminate according to claim 1 or 2, wherein the coated portions of the body composition are arranged so as to be provided alternately. Claimed in the above steps 1 to 3, the strip-shaped electrode layers on each surface are arranged at the same position in the long axis direction of the sheet, and the shapes of the strip-shaped electrode layers on each surface are substantially the same. The method for manufacturing a laminate according to any one of items 1 to 3. After the above step 5 or step 6, further
Step 7: A step of cutting the end portion of the laminate of the above step 5 or step 6, and a step of cutting.
Step 8: A step of energizing the layers of the laminated body
The method for producing a laminate according to any one of claims 1 to 4, wherein the laminated body has the above-mentioned. The above-mentioned electroactive polymer sheet constituting the laminate is
(A) Organopolysiloxane having at least two alkenyl groups having 2 to 12 carbon atoms in the molecule, which is one kind or two or more kinds.
(B) The sum of the silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5. With respect to 1 mol of the total amount of alkenyl groups in one or more kinds of organohydrogenpolysiloxane compositions. Amount to be 0 mol,
(C) Effective amount of catalyst for hydrosilylation reaction,
The method according to any one of claims 1 to 5, which is a dielectric silicone polymer sheet obtained by curing or semi-curing a curable organopolysiloxane composition containing at least the above content by a curing reaction including a hydrosilylation reaction. Method of manufacturing a laminate of. The method for producing a laminate according to any one of claims 1 to 6, wherein the release sheet is a release sheet having a release surface made of a silicone-based release agent layer. The method for manufacturing a laminated body according to any one of claims 1 to 7 , wherein the step 6 is a heat crimping step for the laminated body. According to the method for manufacturing a laminate according to any one of claims 1 to 8, a plurality of laminates having electrode layers on the front surface and the back surface are prepared, and the electrode layers on the front surface and the back surface of each laminate are attached. A method for manufacturing a further laminated body, which comprises further laminating together . A method for manufacturing a transducer member, which comprises the method for manufacturing a laminate according to any one of claims 1 to 8 . A method for manufacturing a transducer, which comprises the method for manufacturing a laminate according to any one of claims 1 to 8 . A method for manufacturing an electronic component or a display device , which comprises the method for manufacturing a laminate according to any one of claims 1 to 8 .

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