WO2013164890A1 - Graphene laminate - Google Patents

Graphene laminate Download PDF

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Publication number
WO2013164890A1
WO2013164890A1 PCT/JP2012/061602 JP2012061602W WO2013164890A1 WO 2013164890 A1 WO2013164890 A1 WO 2013164890A1 JP 2012061602 W JP2012061602 W JP 2012061602W WO 2013164890 A1 WO2013164890 A1 WO 2013164890A1
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Prior art keywords
graphene
film
adhesive layer
graphene film
pressure
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PCT/JP2012/061602
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French (fr)
Japanese (ja)
Inventor
正治 長谷川
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グラフェンプラットフォーム株式会社
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Priority to PCT/JP2012/061602 priority Critical patent/WO2013164890A1/en
Publication of WO2013164890A1 publication Critical patent/WO2013164890A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating

Definitions

  • the present invention relates to a graphene laminate in which graphene used in products such as transparent electrodes, conductive thin films, heat dissipation / heating elements, displays, organic LEDs, and solar cells can be directly attached to these products.
  • Graphene is composed of carbon atoms in layers or sheets, has electrical, mechanical and chemical stability, and has excellent electrical conductivity. It is attracting attention as a basic element. Graphene has been found to be easily adsorbed by molecules such as gas due to the structure of carbon atoms forming a hexagonal plane. This is due to the van der Waals force acting between the carbon atom of graphene and other molecules, and the force is about a few tenths of a chemical bond. It is expected that this adsorption function will be used because the pressure of carbon atoms is a considerable pressure when integrated.
  • a hydrophilic oxide layer is formed on a silicon wafer on which a hydrophobic metal catalyst layer is formed, and the graphene layer is formed into a metal by using chemical vapor deposition. Some are formed by growing in a film shape on the upper surface of the catalyst layer (see, for example, Patent Document 1).
  • Patent Document 1 when a graphene member on which a graphene layer is formed is transferred to another member, it is necessary to remove the metal catalyst layer by an etching process, and thus an etching process facility is required. This is troublesome and difficult to handle.
  • the present invention has been made paying attention to such problems, and an object of the present invention is to provide a graphene laminate including a graphene layer that is easy to handle.
  • the graphene laminate of the present invention is At least one graphene film in which carbon atoms are covalently bonded; and An adhesive layer with physical adhesive strength; A base material having a predetermined strength; With The graphene film is adhered to at least a part of one surface of the adhesive layer, and the base material is adhered to the other surface of the adhesive layer. According to this feature, since the graphene film is adhered to one surface of the adhesive layer and the base material is adhered to the other surface of the adhesive layer, the graphene is attached to the base material having a predetermined strength via the adhesive layer. Since the film is formed, the graphene film can be easily handled.
  • the graphene laminate is temporarily held by another member at the adhesive layer portion where the graphene film is not formed. Therefore, positioning to another member to which the graphene film is attached is facilitated.
  • the adhesive layer is configured so that the adhesive force can be lost or reduced.
  • the graphene film can be peeled from the substrate by the physical adhesive force disappearing or decreasing. In this case, if the graphene film side of the base material is brought into close contact with another member, and then the physical adhesive force of the adhesive layer disappears, the base material and the graphene film can be separated, and the graphene film With the adsorption function, a graphene film can be attached to another member.
  • the adhesive force of the adhesive layer is characterized in that it disappears or is reduced by light irradiation.
  • the graphene film can be peeled from the base material by irradiating light with the adhesive force of the adhesive layer disappearing or decreasing.
  • the pressure-sensitive adhesive layer can use a pressure-sensitive adhesive that loses its adhesive strength when irradiated with light such as ultraviolet rays.
  • the adhesive strength of the adhesive layer is characterized in that it disappears or is reduced by irradiation with ultraviolet rays.
  • the graphene film can be peeled from the base material by irradiating or reducing the adhesive force of the adhesive layer by irradiating ultraviolet rays.
  • the adhesive force of the adhesive layer is characterized in that it disappears or is reduced by heat or a solvent.
  • the graphene film can be peeled from the base material by the adhesive force of the adhesive layer disappearing or being reduced by heat or a solvent.
  • the base material is characterized by having flexibility or elasticity. According to this feature, since the base material has flexibility or elasticity, the shape of the base material can be changed in accordance with the shape of the object to which the graphene film is attached.
  • the base material is formed of a resin film. According to this feature, since the base material is made of a resin film, the shape of the base material can be changed in accordance with the shape of the object to which the graphene film is attached.
  • the substrate is characterized by having at least one of thermosetting, thermoplastic, heat-shrinkable, biodegradable, and water-soluble functions.
  • the substrate can be provided with at least one of thermosetting, thermoplastic, heat-shrinkable, biodegradable, and water-soluble functions in accordance with the shape of other members to be used. .
  • the base material is characterized by being composed of at least one of glass, metal, and ceramics. According to this feature, since the base material is made of glass, metal, or ceramics, the base material can have a predetermined strength.
  • the base material is characterized by having translucency. According to this feature, since the substrate has translucency, the adhesive layer can be irradiated with light or ultraviolet light from the substrate side.
  • a protective member for protecting the graphene film is provided. According to this feature, the graphene film can be protected by the protective member, so that handling becomes easy.
  • the protective member is characterized by being processed so as to be peelable from the graphene film. According to this feature, since the protective member is processed so as to be peelable from the graphene film, the protective member is easily peeled from the graphene film.
  • FIG. 1 shows a configuration diagram of a graphene laminate in the example
  • FIG. 1 (a) shows a plan view
  • FIG. 1 (b) shows a cross-sectional view.
  • a graphene laminate 1 includes at least one graphene film 2 in which carbon atoms are covalently bonded, an adhesive layer 3 having a physical adhesive force, and a base material 4 having a predetermined strength.
  • the graphene film 2 is adhered to at least a part of one surface of the layer 3, and the substrate 4 is adhered to the other surface of the adhesive layer 3.
  • the graphene laminate 1 is laminated in three layers by forming the adhesive layer 3 on the upper surface of the substrate 4 and further forming the graphene film 2 on the upper surface of the adhesive layer 3.
  • the graphene laminate 1 in the present example includes an adhesive layer 3 having a physical adhesive force larger than the van der Waals force acting between the carbon atom of the graphene film 2 and other molecules.
  • the graphene film 2 and the substrate 4 are physically adhered by the adhesive layer 3 by providing the adhesive layer 3 having a physical adhesive force larger than the adsorption force that the graphene film 2 adsorbs to other objects. I am letting.
  • the graphene film 2 can be peeled from the base material 4 by configuring the adhesive layer 3 so that the adhesive strength can be lost or reduced.
  • the graphene laminated body which can affix the graphene film 2 on other products directly can be comprised.
  • the base material 4 for example, a substrate having a predetermined strength such as a resin film, glass, metal, ceramics, or the like can be used, and a deformable material having flexibility or elasticity can be used.
  • the shape of the base material can be changed in accordance with the shape of the object to which the graphene film is attached.
  • the substrate 4 may be provided with at least one of thermosetting, thermoplasticity, heat shrinkability, biodegradability, and water solubility.
  • the graphene film 2 is formed on the base material 4 having a predetermined strength via the adhesive layer 3, it is possible to easily handle a graphene film that is difficult to handle.
  • a pressure-sensitive adhesive, an adhesive, or the like that can be configured to lose or reduce the pressure-sensitive adhesive force can be used.
  • an adhesive that loses its adhesive strength when irradiated with light such as ultraviolet rays an adhesive that loses or decreases its adhesive strength when heated or cooled, or is immersed in a solvent such as water
  • An adhesive that loses or reduces its power can be used.
  • the pressure-sensitive adhesive whose adhesive strength is lost or reduced by heating is at least a urea resin type, a melamine resin type, a phenol resin type, an epoxy resin type, a cyanoacrylate type, a polyurethane type, an acrylic resin type, and an EVA resin.
  • a resin composition can be used.
  • the pressure sensitive adhesive whose viscosity is lost or reduced by cooling is at least a urea resin type, a melamine resin type, a phenol resin type, an epoxy resin type, a cyanoacrylate type, a polyurethane type, an acrylic resin type, an acrylic resin.
  • a resin composition comprising any one of a system pressure sensitive system, a rubber pressure sensitive system, and other pressure sensitive adhesives and composed of one or a plurality of pressure sensitive adhesives can be used.
  • a resin composition comprising one or more of resin-based emulsion, water-soluble isocyanate-based, synthetic rubber-based latex, and other water-soluble adhesives can be used.
  • the graphene laminate is temporarily attached to another member in the adhesive layer 3 where the graphene film 2 is not formed. Therefore, positioning to another member to which the graphene film 2 is attached becomes easy.
  • the graphene film 2 may be formed on the entire upper surface of the adhesive layer 3.
  • the adhesive layer 3 may be formed on at least a part of the upper surface of the base material 4, the portion of the base material 4 on which the adhesive layer 3 is not formed can be gripped with tweezers or the like. Handling of the laminated body 1 becomes easy.
  • the adhesive layer 3 may be formed on the entire upper surface of the substrate 4.
  • the graphene laminate 1 in this example can be configured by forming the graphene film 2 on the adhesive sheet 11.
  • the graphene film 2 is formed on the metal film 7 (for example, copper Cu, nickel Ni, aluminum AL, iron Fe, cobalt Co, etc.) as a catalyst by using chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • FIG. 2A a two-layer roll sheet 8 composed of the metal film 7 and the graphene film 2 is prepared.
  • CVD chemical vapor deposition
  • thermal CVD film formation, plasma CVD, or the like can be used.
  • the two-layer roll sheet 8 on which the graphene film 2 is formed is cut into a two-layer rectangular sheet 9 having an arbitrary size as shown in FIG.
  • an adhesive sheet 11 is attached to the graphene film 2 side of a two-layer rectangular sheet 9 using a laminator 10.
  • the graphene film 2, the metal film 7 and the adhesive sheet 11 composed of the two-layer rectangular sheet 9 and the adhesive sheet 11 are acidic. Is immersed in a water tank 12 filled with an etching solution 13. Thereby, the metal film 7 is melted by the etching solution 13, and only the graphene film 2 and the adhesive sheet 11 remain.
  • the base material 4 and the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 11 use acid-resistant materials that can withstand the etching solution 13. Further, as shown in FIG. 3 (e), the graphene film 2 and the pressure-sensitive adhesive sheet 11 are washed with the neutralizing solution 14 to complete the production of the graphene laminate 1.
  • the graphene laminate 1 in the present example can be formed by the steps as described above.
  • the graphene film 2 can be directly formed on the adhesive sheet 11 instead of forming the graphene film 2 on the metal film 7. Furthermore, as another method of forming the graphene film 2 on the pressure-sensitive adhesive sheet 11, the pressure-sensitive adhesive sheet 11 is attached to the member on which the graphene film 2 is formed, and the pressure-sensitive adhesive sheet 11 is peeled off from the member. It can be formed by transferring the graphene film 2. As another method for forming the graphene film 2 on the pressure-sensitive adhesive sheet 11, graphite powder obtained by pulverizing graphite is dispersed by ultrasonic waves, dissolved in a solvent, and the solvent is volatilized and applied to the pressure-sensitive adhesive sheet 11. Then, it can also be formed by removing the solvent by removing it.
  • the graphene film 2 is formed on the surface of the pressure-sensitive adhesive sheet 11 and is exposed, so that the graphene film 2 is not damaged when shipped or handled. Therefore, a protective member for protecting the graphene film 2 on the surface of the graphene laminate 1 may be provided.
  • the graphene laminate 1 can be provided with a protective film 15 as a protective member on the graphene film 2 side as shown in FIG.
  • a resin film such as a silicone film, a fluorine film, or a polyethylene film can be used.
  • the surfaces of these films may be subjected to embossing or the like for facilitating peeling from the graphene film 2.
  • a light shielding film may be further formed on the surface of the film by aluminum vapor deposition or the like.
  • the protective film 15 includes gas barrier properties (functions that block moisture, oxygen, etc.), light shielding properties (functions that block visible light, ultraviolet rays, etc.), releasability (functions that make the protective film 15 easy to peel off from the graphene film 2). Etc. are desirable.
  • the graphene film 2 can be further protected by packing it in a case or a packing bag 16 as a protective member.
  • the packing bag 16 can prevent oxidation of graphene by filling a vacuum state or an inert gas such as nitrogen or argon.
  • the packaging bag 16 desirably has gas barrier properties (function of blocking moisture, oxygen, etc.), light shielding properties (function of blocking visible light, ultraviolet rays, etc.) and the like.
  • FIG. 5A shows a case where the graphene laminate 1 of the above-described embodiment is formed in a rectangular sheet shape 1A
  • FIG. 5B shows the graphene laminate 1 of the above-described embodiment of A4 size
  • FIG. 5 (c) shows a case where the graphene laminate 1C is formed as a narrow roll-like shape 5 as shown in FIG.
  • FIG.5 (d) shows the case where the graphene laminated body 1D is formed by making the graphene laminated body 1 of the Example mentioned above into the roll shape 6 of the width
  • FIG.5 (e) is the implementation mentioned above.
  • the graphene laminated body 1 of an example has shown the modification of the rectangular sheet form 1E.
  • the rectangular sheet-like shape 1 ⁇ / b> E may partially expose the adhesive layer 3 of the graphene laminate 1 by removing a part of the graphene film 2. Since the graphene laminate can be temporarily held by another member at the portion of the adhesive layer 3 where the graphene film 2 is not formed, positioning to the other member to which the graphene film 2 is attached becomes easy. .
  • the graphene film 2 of the graphene laminated body 1 in the present embodiment can be transferred to the object 17 of another member by the following method.
  • the graphene laminate 1A taken out from the packing bag 16 is cut into an arbitrary size, and the protective film 15 is peeled off. Then, with the graphene film 2 side facing upward, the object 17 is placed thereon, and the graphene laminate 1A is brought into contact with the object 17. Thereafter, the graphene laminate 1A and the object 17 are pressed and bonded together. Then, after the graphene laminate 1A is peeled off after the adhesiveness of the adhesive layer 3 is lost or reduced by various peeling methods described later, only the graphene film 2 can be left on the object 17.
  • the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 11 uses a material whose adhesive strength is reduced by reacting with ultraviolet rays, and the graphene film 2, the object 17 and the pressure-sensitive adhesive sheet 11 are transferred to a roller.
  • 18 shows an example in which the pressure-sensitive adhesive sheet 11 is gradually peeled from one end while being irradiated with ultraviolet rays by the ultraviolet irradiation device 19 while being sandwiched by 18.
  • the substrate 4 of the pressure-sensitive adhesive sheet 11 has translucency to transmit light, and the pressure-sensitive adhesive polymer is taken into the photocrosslinking structure by irradiating the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 11 with ultraviolet light.
  • the pressure-sensitive adhesive sheet 11 is adhered to the graphene film 2 side, and then the physical adhesive force disappears by irradiating the pressure-sensitive adhesive layer 3 with ultraviolet rays, the pressure-sensitive adhesive sheet 11 and the graphene film 2 can be separated.
  • the graphene film 2 can be attached to the object 17 by the adsorption function of the graphene film 2.
  • the substrate 4 of the adhesive sheet 11 may not have translucency.
  • the ultraviolet irradiation device 19 is irradiated from the object 17 side,
  • the adhesive layer 3 can be irradiated with ultraviolet rays.
  • the pressure-sensitive adhesive of the pressure-sensitive adhesive sheet 11 has a pressure-sensitive adhesive force lowered by heating to a temperature equal to or higher than a predetermined temperature or cooling to a temperature equal to or lower than a predetermined temperature.
  • the graphene film 2, the object 17, and the pressure-sensitive adhesive sheet 11 are sandwiched between rollers 20 having heating / cooling functions, and the pressure-sensitive adhesive sheet 11 is gradually peeled from one end.
  • the graphene film 2 is separated from the pressure-sensitive adhesive sheet 11 due to expansion of the foaming agent.
  • the base material 4 is provided with a thermosetting function, since the base material 4 is cured when heated, it can be more easily peeled off.
  • a pressure-sensitive adhesive of the pressure-sensitive adhesive sheet 11 when using a material whose adhesive strength is reduced by cooling to a temperature equal to or lower than a predetermined temperature, the molecular movement of the pressure-sensitive adhesive composition is eliminated by cooling and the adhesiveness is lost. .
  • the physical adhesive force of the adhesive layer 3 disappears by making the graphene film 2 side of the adhesive sheet 11 adhere to the object 17 and then heating or cooling the adhesive sheet 11, the adhesive sheet 11 and the graphene film 2 And the graphene film 2 can be attached to the object 17 by the adsorption function of the graphene film 2.
  • the peeling method shown in FIG.7 (c) uses the water-soluble thing for the adhesive of the adhesive sheet 11,
  • the graphene film 2, the target object 17, and the adhesive sheet 11 are put into the water tank 21 filled with water.
  • An example in which the pressure-sensitive adhesive sheet 11 is peeled off by immersion is shown.
  • the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 3 dissolves in water and loses the pressure-sensitive adhesiveness.
  • the adhesive sheet 11 which consists of the adhesion layer 3 and the base material 4 can be dissolved by making the base material 4 also have a water-soluble function.
  • the pressure-sensitive adhesive sheet 11 has flexibility and elasticity even when the graphene film 2 is transferred to the object 22 having a convex portion.
  • the graphene film 2 can be transferred regardless of the shape of the object 22 by the above-described peeling process of the pressure-sensitive adhesive sheet 11.
  • the substrate 4 of the pressure-sensitive adhesive sheet 11 is made of a thermoplastic film
  • the graphene laminate 1 is mounted on a heating and pressurizing tank
  • the graphene laminate 1 is heated to a predetermined temperature
  • the object 22 Then, a pressure medium such as air or liquid is injected into the tank and the graphene laminate 1 is pressed against the object 22 to press the object 22 according to the shape of the object 22 and pressurize the object 22.
  • the graphene laminated body 1 can be stuck.
  • the tank is cut off from the graphene laminate 1 and the object 22, the adhesiveness of the adhesive layer 3 is lost by the above-described various peeling methods, and the adhesive sheet 11 is peeled off, so that the graphene film 2 is attached to the object 22. You can turn it on.
  • the pressure-sensitive adhesive sheet 11 has a heat shrinkability, so that the recess
  • the graphene film 2 can be transferred regardless of the shape of the object 24 by the above-described peeling process of the pressure-sensitive adhesive sheet 11.
  • the substrate 4 of the pressure-sensitive adhesive sheet 11 is made of a heat-shrinkable film, and as shown in FIG. 9A, the graphene film 2 is on the inside and the graphene laminate 1A is on the cylinder, and the inside The object 24 is put in the box.
  • the graphene laminate 1A is wound around the outside of the object 24 with the graphene film 2 inside.
  • the pressure-sensitive adhesive sheet 11 of the graphene laminated body 1 ⁇ / b> A is contracted by heating around the graphene laminated body 1 ⁇ / b> A with warm air such as a dryer, and the pressure-sensitive adhesive sheet 11 is closely attached to the object 24.
  • membrane 2 can be affixed on the target object 24 by making the adhesiveness of the adhesion layer 3 lose
  • the object to be molded includes, for example, resin, ceramic material before sintering (green sheet, etc.), iron-based (ferrite, etc.), carbon-based, ceramic-based, other various powder systems, low melting point, etc. Glass etc. can be used.
  • the graphene laminate 1 When molding these objects with a mold or the like, by attaching the above-described graphene laminate 1 to a corresponding position of the mold (a position corresponding to a position where the object is to be attached), The graphene laminate 1 is brought into close contact with the molded object. Then, the graphene film
  • FIG. Examples of the molding method of the object include injection molding, blow molding, vacuum molding, foam molding, polymerization molding (heating, UV (ultraviolet light), EB (electron beam), etc.), hot emboss molding, imprint molding, and the like. .
  • the graphene laminate 1 When the graphene laminate 1 is attached to the mold when molding by these molding methods, the graphene laminate 1 can be applied simultaneously with the molding, and after the adhesive sheet 11 has disappeared, the adhesive sheet 11 is removed. By peeling off, the object on which the graphene film 2 is formed can be molded.
  • the base material 4 is made of glass
  • the adhesive layer 3 can be made of an adhesive that loses its adhesive strength when irradiated with light such as ultraviolet rays.
  • the adhesive force can be lost by irradiating the adhesive layer 3 of the adhesive sheet 11 with ultraviolet rays from the glass side.
  • the base material 4 can be decomposed by microorganisms after being peeled from the graphene film 2, thereby reducing the burden on the natural environment. Can do.

Abstract

A graphene laminate provided with an easily-handleable graphene layer can be obtained by having the graphene laminate configured of a graphene film in which carbon atoms are covalently bonded to each other, an adhesive layer having physical adhesiveness, and a base having a predetermined strength such that the graphene film is adhered to at least a part of one surface of the adhesive layer and the base layer is adhered to the other surface of the adhesive layer.

Description

グラフェン積層体Graphene stack
　本発明は、透明電極、導電性薄膜、放熱・発熱素子、ディスプレイ、有機ＬＥＤ、太陽電池等の製品で利用するグラフェンを、これらの製品に直接貼り付けることができるグラフェン積層体に関する。 The present invention relates to a graphene laminate in which graphene used in products such as transparent electrodes, conductive thin films, heat dissipation / heating elements, displays, organic LEDs, and solar cells can be directly attached to these products.
　近年、グラフェンに関する研究が活発に行われており、ここ数年で大面積グラフェンの製造技術は飛躍的に発展している。グラフェンは、炭素原子が層またはシート状に構成されているものであり、電気的、機械的及び化学的な安定性を備えており、かつ優れた導電性を有しているので、電子回路の基本要素として注目されている。また、グラフェンは、六角網平面を形成する炭素原子の構造により気体などの分子が吸着しやすいことが判明している。これは、グラフェンの炭素原子と他の分子との間にファンデルワールス力が働くことによるものであり、その力は化学結合の数十分の１程度であるが、六角網目構造で並ぶ個々の炭素原子の力を積算するとかなりの圧力となるため、この吸着機能を利用することが期待されている。 In recent years, research on graphene has been actively conducted, and the technology for producing large-area graphene has been dramatically improved in recent years. Graphene is composed of carbon atoms in layers or sheets, has electrical, mechanical and chemical stability, and has excellent electrical conductivity. It is attracting attention as a basic element. Graphene has been found to be easily adsorbed by molecules such as gas due to the structure of carbon atoms forming a hexagonal plane. This is due to the van der Waals force acting between the carbon atom of graphene and other molecules, and the force is about a few tenths of a chemical bond. It is expected that this adsorption function will be used because the pressure of carbon atoms is a considerable pressure when integrated.
　このようなグラフェンの従来の製造方法としては、疎水性を有する金属触媒層が形成されたシリコンウエハに、親水性を有する酸化層を形成し、化学気相蒸着法を用いて、グラフェン層を金属触媒層の上面に膜状に成長させて形成しているものがある（例えば、特許文献１参照）。 As a conventional method for manufacturing such graphene, a hydrophilic oxide layer is formed on a silicon wafer on which a hydrophobic metal catalyst layer is formed, and the graphene layer is formed into a metal by using chemical vapor deposition. Some are formed by growing in a film shape on the upper surface of the catalyst layer (see, for example, Patent Document 1).
特開２０１１－０６３５０６号公報（段落００３２～００４０、図１）Japanese Unexamined Patent Publication No. 2011-063506 (paragraphs 0032 to 0040, FIG. 1)
　しかしながら、特許文献１にあっては、グラフェン層が形成されたグラフェン部材を、他の部材に転写する場合には、金属触媒層をエッチング工程により除去する必要があるため、エッチング工程の設備が必要になり、手間がかかり、取り扱いにくいという問題がある。 However, in Patent Document 1, when a graphene member on which a graphene layer is formed is transferred to another member, it is necessary to remove the metal catalyst layer by an etching process, and thus an etching process facility is required. This is troublesome and difficult to handle.
　本発明は、このような問題点に着目してなされたもので、取り扱いやすいグラフェン層を備えるグラフェン積層体を提供することを目的とする。 The present invention has been made paying attention to such problems, and an object of the present invention is to provide a graphene laminate including a graphene layer that is easy to handle.
　前記課題を解決するために、本発明のグラフェン積層体は、
　炭素原子が共有結合された少なくとも一層のグラフェン膜と、
　物理的粘着力を備える粘着層と、
　所定の強度を備える基材と、
　を備え、
　前記粘着層の一方面の少なくとも一部に、前記グラフェン膜が粘着され、前記粘着層の他方面に前記基材が粘着されていることを特徴としている。
　この特徴によれば、粘着層の一方面に、グラフェン膜が粘着され、前記粘着層の他方面に基材が粘着されているため、所定の強度を備える基材に、粘着層を介してグラフェン膜が形成されるので、グラフェン膜を取り扱いやすくすることができる。また、粘着層の一方面の少なくとも一部に、グラフェン膜を粘着させておくことで、グラフェン膜が形成されていない粘着層の部分で、他の部材にグラフェン積層体を一時的に仮保持させることができるので、グラフェン膜を貼付する他の部材への位置決めが容易となる。 In order to solve the above problems, the graphene laminate of the present invention is
At least one graphene film in which carbon atoms are covalently bonded; and
An adhesive layer with physical adhesive strength;
A base material having a predetermined strength;
With
The graphene film is adhered to at least a part of one surface of the adhesive layer, and the base material is adhered to the other surface of the adhesive layer.
According to this feature, since the graphene film is adhered to one surface of the adhesive layer and the base material is adhered to the other surface of the adhesive layer, the graphene is attached to the base material having a predetermined strength via the adhesive layer. Since the film is formed, the graphene film can be easily handled. In addition, by adhering the graphene film to at least a part of one surface of the adhesive layer, the graphene laminate is temporarily held by another member at the adhesive layer portion where the graphene film is not formed. Therefore, positioning to another member to which the graphene film is attached is facilitated.
　本発明のグラフェン積層体において、
　前記粘着層は、前記粘着力が消失または減少可能に構成されていることを特徴としている。
　この特徴によれば、物理的粘着力が消失または減少されることで、グラフェン膜を基材から剥離することができる。この場合、他の部材に、基材のグラフェン膜側を密着させ、その後、粘着層の物理的粘着力が消失させれば、基材とグラフェン膜とを分離することができ、また、グラフェン膜の吸着機能により、他の部材にグラフェン膜を貼りつけることができる。 In the graphene laminate of the present invention,
The adhesive layer is configured so that the adhesive force can be lost or reduced.
According to this feature, the graphene film can be peeled from the substrate by the physical adhesive force disappearing or decreasing. In this case, if the graphene film side of the base material is brought into close contact with another member, and then the physical adhesive force of the adhesive layer disappears, the base material and the graphene film can be separated, and the graphene film With the adsorption function, a graphene film can be attached to another member.
　本発明のグラフェン積層体において、
　前記粘着層の前記粘着力は、光の照射により消失または減少されることを特徴としている。
　この特徴によれば、光を照射させることで粘着層の粘着力が消失または減少されることで、グラフェン膜を基材から剥離することができる。例えば、粘着層は、紫外線などの光を照射させることで粘着力が消失される粘着剤を利用することができる。 In the graphene laminate of the present invention,
The adhesive force of the adhesive layer is characterized in that it disappears or is reduced by light irradiation.
According to this feature, the graphene film can be peeled from the base material by irradiating light with the adhesive force of the adhesive layer disappearing or decreasing. For example, the pressure-sensitive adhesive layer can use a pressure-sensitive adhesive that loses its adhesive strength when irradiated with light such as ultraviolet rays.
　本発明のグラフェン積層体において、
　前記粘着層の前記粘着力は、紫外線の照射により消失または減少されることを特徴としている。
　この特徴によれば、紫外線を照射させることで粘着層の粘着力が消失または減少されることで、グラフェン膜を基材から剥離することができる。 In the graphene laminate of the present invention,
The adhesive strength of the adhesive layer is characterized in that it disappears or is reduced by irradiation with ultraviolet rays.
According to this feature, the graphene film can be peeled from the base material by irradiating or reducing the adhesive force of the adhesive layer by irradiating ultraviolet rays.
　本発明のグラフェン積層体において、
　前記粘着層の前記粘着力は、熱または溶媒により消失または減少されることを特徴としている。
　この特徴によれば、熱または溶媒により粘着層の粘着力が消失または減少されることで、グラフェン膜を基材から剥離することができる。例えば、加熱または冷却することで粘着力が消失または減少される粘着剤を利用したり、水などの溶媒に浸すことで粘着力が消失または減少される粘着剤を利用したりすることができる。 In the graphene laminate of the present invention,
The adhesive force of the adhesive layer is characterized in that it disappears or is reduced by heat or a solvent.
According to this feature, the graphene film can be peeled from the base material by the adhesive force of the adhesive layer disappearing or being reduced by heat or a solvent. For example, it is possible to use an adhesive whose adhesive strength is lost or reduced by heating or cooling, or an adhesive whose adhesive strength is lost or reduced by immersion in a solvent such as water.
　本発明のグラフェン積層体において、
　前記基材は、可撓性または弾性を備えることを特徴としている。
　この特徴によれば、基材は、可撓性または弾性を備えるため、グラフェン膜を貼り付ける対象物の形状に合わせて基材の形状を変形させることができる。 In the graphene laminate of the present invention,
The base material is characterized by having flexibility or elasticity.
According to this feature, since the base material has flexibility or elasticity, the shape of the base material can be changed in accordance with the shape of the object to which the graphene film is attached.
　本発明のグラフェン積層体において、
　前記基材は、樹脂製のフィルムにより構成されていることを特徴としている。
　この特徴によれば、基材は、樹脂製のフィルムにより構成されているため、グラフェン膜を貼り付ける対象物の形状に合わせて基材の形状を変形させることができる。 In the graphene laminate of the present invention,
The base material is formed of a resin film.
According to this feature, since the base material is made of a resin film, the shape of the base material can be changed in accordance with the shape of the object to which the graphene film is attached.
　本発明のグラフェン積層体において、
　前記基材は、熱硬化性、熱可塑性、熱収縮性、生分解性、水溶性の少なくともいずれかの機能を備えることを特徴としている。
　この特徴によれば、使用する他の部材の形状等に合わせて、基材を、熱硬化性、熱可塑性、熱収縮性、生分解性、水溶性の少なくともいずれかの機能を備えるようにできる。 In the graphene laminate of the present invention,
The substrate is characterized by having at least one of thermosetting, thermoplastic, heat-shrinkable, biodegradable, and water-soluble functions.
According to this feature, the substrate can be provided with at least one of thermosetting, thermoplastic, heat-shrinkable, biodegradable, and water-soluble functions in accordance with the shape of other members to be used. .
　本発明のグラフェン積層体において、
　前記基材は、ガラス、金属、セラミックスの少なくともいずれかで構成されていることを特徴としている。
　この特徴によれば、基材は、ガラス、金属、セラミックスにより構成されているため、基材が所定の強度を備えるようにできる。 In the graphene laminate of the present invention,
The base material is characterized by being composed of at least one of glass, metal, and ceramics.
According to this feature, since the base material is made of glass, metal, or ceramics, the base material can have a predetermined strength.
　本発明のグラフェン積層体において、
　前記基材は、透光性を備えることを特徴としている。
　この特徴によれば、基材は透光性を備えるため、粘着層に対して基材側より、光や紫外線を照射させることができる。 In the graphene laminate of the present invention,
The base material is characterized by having translucency.
According to this feature, since the substrate has translucency, the adhesive layer can be irradiated with light or ultraviolet light from the substrate side.
　本発明のグラフェン積層体において、
　前記グラフェン膜を保護する保護部材を備えることを特徴としている。
　この特徴によれば、保護部材によりグラフェン膜を保護することができるので、取り扱いが容易となる。 In the graphene laminate of the present invention,
A protective member for protecting the graphene film is provided.
According to this feature, the graphene film can be protected by the protective member, so that handling becomes easy.
　本発明のグラフェン積層体において、
　前記保護部材は、前記グラフェン膜から剥離可能な加工が施されていることを特徴としている。
　この特徴によれば、保護部材がグラフェン膜から剥離可能な加工が施されているため、保護部材をグラフェン膜から剥離しやすくなる。 In the graphene laminate of the present invention,
The protective member is characterized by being processed so as to be peelable from the graphene film.
According to this feature, since the protective member is processed so as to be peelable from the graphene film, the protective member is easily peeled from the graphene film.
実施例におけるグラフェン積層体の平面図（ａ）および断面図（ｂ）である。It is the top view (a) and sectional drawing (b) of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の製造工程を示す説明図（ａ）～（ｃ）である。It is explanatory drawing (a)-(c) which shows the manufacturing process of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の製造工程を示す説明図（ｄ）および（ｅ）である。It is explanatory drawing (d) and (e) which show the manufacturing process of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の外観図である。It is an external view of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の他の外観図である。It is another external view of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の使用例を示す説明図である。It is explanatory drawing which shows the usage example of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の剥離法を示す説明図（ａ）～（ｃ）である。It is explanatory drawing (a)-(c) which shows the peeling method of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の他の使用例を示す説明図（ａ）、（ｂ）である。It is explanatory drawing (a) which shows the other usage example of the graphene laminated body in an Example. 実施例におけるグラフェン積層体の他の使用例を示す説明図（ａ）～（ｃ）である。It is explanatory drawing (a)-(c) which shows the other usage example of the graphene laminated body in an Example.
　本発明に係るグラフェン積層体を実施するための形態を実施例に基づいて以下に説明する。 Embodiments for carrying out a graphene laminate according to the present invention will be described below based on examples.
　実施例に係るグラフェン積層体につき、図１から図９を参照して説明する。 The graphene laminate according to the example will be described with reference to FIGS.
　図１は、実施例におけるグラフェン積層体の構成図を示し、図１（ａ）は平面図、図１（ｂ）は断面図を示している。 FIG. 1 shows a configuration diagram of a graphene laminate in the example, FIG. 1 (a) shows a plan view, and FIG. 1 (b) shows a cross-sectional view.
　図１において、グラフェン積層体１は、炭素原子が共有結合された少なくとも一層のグラフェン膜２と、物理的粘着力を備える粘着層３と、所定の強度を備える基材４と、を備え、粘着層３の一方面の少なくとも一部に、グラフェン膜２が粘着され、粘着層３の他方面に基材４が粘着されている。このため、グラフェン積層体１は、基材４の上面に粘着層３が形成され、さらに粘着層３の上面にグラフェン膜２が形成されることにより、３層に積層されている。本実施例におけるグラフェン積層体１は、グラフェン膜２の炭素原子と他の分子との間に働くファンデルワールス力よりも大きい物理的粘着力を備える粘着層３を備えている。すなわち、グラフェン膜２が他の対象物に吸着する吸着力よりも大きい物理的粘着力を備える粘着層３を備えることで、粘着層３により、グラフェン膜２と基材４とを物理的に粘着させている。また、粘着層３を、粘着力が消失または減少可能に構成しておくことで、グラフェン膜２を基材４から剥離することができる。これにより、グラフェン膜２を、他の製品に直接貼る付けることができるグラフェン積層体を構成できる。 In FIG. 1, a graphene laminate 1 includes at least one graphene film 2 in which carbon atoms are covalently bonded, an adhesive layer 3 having a physical adhesive force, and a base material 4 having a predetermined strength. The graphene film 2 is adhered to at least a part of one surface of the layer 3, and the substrate 4 is adhered to the other surface of the adhesive layer 3. For this reason, the graphene laminate 1 is laminated in three layers by forming the adhesive layer 3 on the upper surface of the substrate 4 and further forming the graphene film 2 on the upper surface of the adhesive layer 3. The graphene laminate 1 in the present example includes an adhesive layer 3 having a physical adhesive force larger than the van der Waals force acting between the carbon atom of the graphene film 2 and other molecules. That is, the graphene film 2 and the substrate 4 are physically adhered by the adhesive layer 3 by providing the adhesive layer 3 having a physical adhesive force larger than the adsorption force that the graphene film 2 adsorbs to other objects. I am letting. Moreover, the graphene film 2 can be peeled from the base material 4 by configuring the adhesive layer 3 so that the adhesive strength can be lost or reduced. Thereby, the graphene laminated body which can affix the graphene film 2 on other products directly can be comprised.
　本実施例において、基材４としては、例えば、樹脂製のフィルム、ガラス、金属、セラミックスなどの所定の強度を備える基板を利用することができ、また、可撓性または弾性を備える変形自在な素材を用いることで、グラフェン膜を貼り付ける対象物の形状に合わせて基材の形状を変形させることができる。また、基材４としては、熱硬化性、熱可塑性、熱収縮性、生分解性、水溶性のいずれかを少なくとも備えるようにしてもよい。また、所定の強度を備える基材４に、粘着層３を介してグラフェン膜２が形成されるので、取り扱いにくいグラフェン膜を取り扱いやすくすることができる。 In the present embodiment, as the base material 4, for example, a substrate having a predetermined strength such as a resin film, glass, metal, ceramics, or the like can be used, and a deformable material having flexibility or elasticity can be used. By using the material, the shape of the base material can be changed in accordance with the shape of the object to which the graphene film is attached. Further, the substrate 4 may be provided with at least one of thermosetting, thermoplasticity, heat shrinkability, biodegradability, and water solubility. In addition, since the graphene film 2 is formed on the base material 4 having a predetermined strength via the adhesive layer 3, it is possible to easily handle a graphene film that is difficult to handle.
　本実施例において、粘着層３としては、粘着力が消失または減少可能に構成されるような粘着剤、接着剤等を利用することができる。例えば、紫外線などの光を照射させることで粘着力が消失される粘着剤、加熱または冷却することで粘着力が消失または減少される粘着剤を利用したり、水などの溶媒に浸すことで粘着力が消失または減少される粘着剤を利用したりすることができる。例えば、紫外線などの光を照射させることで粘着力が消失される粘着剤としては、少なくとも、ユリア樹脂系、メラミン樹脂系、フェノール樹脂系、エポキシ樹脂系、シアノアクリレート系、ポリウレタン系、アクリル樹脂系、その他の紫外線にて反応する粘着剤のいずれかを含有し、一種類または複数から構成される樹脂組成物を利用できる。また、加熱することで粘着力が消失または減少される粘着剤としては、少なくとも、ユリア樹脂系、メラミン樹脂系、フェノール樹脂系、エポキシ樹脂系、シアノアクリレート系、ポリウレタン系、アクリル樹脂系、ＥＶＡ樹脂ホットメルト系、合成ゴムホットメルト系、その他ホットメルト系、アクリル樹脂系感圧系、ゴム系感圧系、その他の感圧系粘着剤のいずれかを含有し、一種類または複数から構成される樹脂組成物を利用することができる。また、冷却することで粘着力が消失または減少される粘着剤としては、少なくとも、ユリア樹脂系、メラミン樹脂系、フェノール樹脂系、エポキシ樹脂系、シアノアクリレート系、ポリウレタン系、アクリル樹脂系、アクリル樹脂系感圧系、ゴム系感圧系、その他の感圧系粘着剤のいずれかを含有し、一種類または複数から構成される樹脂組成物を利用することができる。また、水などの溶媒に浸すことで粘着力が消失または減少される粘着剤としては、少なくとも、酢酸ビニル系樹脂系エマルション、酢酸ビニル共重合系エマルション、ＥＶＡ樹脂系エマルション、アクリル樹脂系エマルション、その他樹脂系エマルション、水溶性イソシアネート系、合成ゴム系ラテックス、その他の水溶性着剤のいずれかを含有し、一種類または複数から構成される樹脂組成物を利用することができる。 In this embodiment, as the pressure-sensitive adhesive layer 3, a pressure-sensitive adhesive, an adhesive, or the like that can be configured to lose or reduce the pressure-sensitive adhesive force can be used. For example, an adhesive that loses its adhesive strength when irradiated with light such as ultraviolet rays, an adhesive that loses or decreases its adhesive strength when heated or cooled, or is immersed in a solvent such as water An adhesive that loses or reduces its power can be used. For example, at least urea resin, melamine resin, phenol resin, epoxy resin, cyanoacrylate, polyurethane, acrylic resin as adhesive that loses adhesive strength when irradiated with light such as ultraviolet rays In addition, a resin composition comprising any one or a plurality of other pressure-sensitive adhesives that react with ultraviolet rays can be used. In addition, the pressure-sensitive adhesive whose adhesive strength is lost or reduced by heating is at least a urea resin type, a melamine resin type, a phenol resin type, an epoxy resin type, a cyanoacrylate type, a polyurethane type, an acrylic resin type, and an EVA resin. Contains one or more of hot melt, synthetic rubber, hot melt, other hot melt, acrylic resin pressure sensitive, rubber pressure sensitive, and other pressure sensitive adhesives A resin composition can be used. In addition, the pressure sensitive adhesive whose viscosity is lost or reduced by cooling is at least a urea resin type, a melamine resin type, a phenol resin type, an epoxy resin type, a cyanoacrylate type, a polyurethane type, an acrylic resin type, an acrylic resin. A resin composition comprising any one of a system pressure sensitive system, a rubber pressure sensitive system, and other pressure sensitive adhesives and composed of one or a plurality of pressure sensitive adhesives can be used. In addition, as an adhesive whose adhesive strength disappears or decreases by being immersed in a solvent such as water, at least vinyl acetate resin emulsion, vinyl acetate copolymer emulsion, EVA resin emulsion, acrylic resin emulsion, and others A resin composition comprising one or more of resin-based emulsion, water-soluble isocyanate-based, synthetic rubber-based latex, and other water-soluble adhesives can be used.
　また、粘着層３の一方面の少なくとも一部に、グラフェン膜２を粘着させておくことで、グラフェン膜２が形成されていない粘着層３の部分で、他の部材にグラフェン積層体を一時的に仮保持させることができるので、グラフェン膜２を貼付する他の部材への位置決めが容易となる。また、粘着層３上面の全面にグラフェン膜２を形成してもよい。また、基材４の上面の少なくとも一部に、粘着層３を形成しておくことで、粘着層３が形成されていない基材４の部分を、ピンセット等で把持することができるので、グラフェン積層体１の取扱いが容易となる。また、基材４の上面の全面に粘着層３を形成するようにしてもよい。 In addition, by adhering the graphene film 2 to at least a part of one surface of the adhesive layer 3, the graphene laminate is temporarily attached to another member in the adhesive layer 3 where the graphene film 2 is not formed. Therefore, positioning to another member to which the graphene film 2 is attached becomes easy. Further, the graphene film 2 may be formed on the entire upper surface of the adhesive layer 3. Further, by forming the adhesive layer 3 on at least a part of the upper surface of the base material 4, the portion of the base material 4 on which the adhesive layer 3 is not formed can be gripped with tweezers or the like. Handling of the laminated body 1 becomes easy. Further, the adhesive layer 3 may be formed on the entire upper surface of the substrate 4.
　また、基材４および粘着層３は、粘着シート１１として構成できるので、本実施例におけるグラフェン積層体１は、粘着シート１１にグラフェン膜２が形成されることで構成するようにできる。 Moreover, since the base material 4 and the adhesive layer 3 can be configured as an adhesive sheet 11, the graphene laminate 1 in this example can be configured by forming the graphene film 2 on the adhesive sheet 11.
　つぎに、本実施例におけるグラフェン積層体の製造工程の一例を図２および図３を参照して説明する。まず、触媒としての金属膜７（例えば銅Ｃｕ、ニッケルＮｉ、アルミニウムＡＬ、鉄Ｆｅ、コバルトＣｏ等）に、化学気相蒸着法（ＣＶＤ）を用いてグラフェン膜２を成膜する。そして図２（ａ）に示すように、金属膜７およびグラフェン膜２から構成される２層のロール状シート８を作成しておく。化学気相蒸着法（ＣＶＤ）としては、熱ＣＶＤ成膜やプラズマＣＶＤ法などを利用できる。つぎに、グラフェン膜２が形成された２層のロール状シート８を、図２（ｂ）に示すように、任意の大きさの２層の矩形状シート９に切り分け、図２（ｃ）に示すように、ラミネーター１０を用いて２層の矩形状シート９のグラフェン膜２側に粘着シート１１を貼り付ける。 Next, an example of the manufacturing process of the graphene laminate in the present embodiment will be described with reference to FIGS. First, the graphene film 2 is formed on the metal film 7 (for example, copper Cu, nickel Ni, aluminum AL, iron Fe, cobalt Co, etc.) as a catalyst by using chemical vapor deposition (CVD). Then, as shown in FIG. 2A, a two-layer roll sheet 8 composed of the metal film 7 and the graphene film 2 is prepared. As chemical vapor deposition (CVD), thermal CVD film formation, plasma CVD, or the like can be used. Next, the two-layer roll sheet 8 on which the graphene film 2 is formed is cut into a two-layer rectangular sheet 9 having an arbitrary size as shown in FIG. As shown, an adhesive sheet 11 is attached to the graphene film 2 side of a two-layer rectangular sheet 9 using a laminator 10.
　つぎに、金属膜７を除去するため、図３（ｄ）に示されるように、２層の矩形状シート９と粘着シート１１とからなるグラフェン膜２、金属膜７および粘着シート１１は、酸性であるエッチング液１３を満した水槽１２に浸漬させる。これにより、エッチング液１３により金属膜７が溶かされ、グラフェン膜２および粘着シート１１のみが残る。なお、粘着シート１１の基材４および粘着層３は、エッチング液１３に耐えうるような耐酸性の素材を利用する。さらに図３（ｅ）に示されるように、グラフェン膜２および粘着シート１１が中和液１４により洗浄されてグラフェン積層体１の製造が完了する。 Next, in order to remove the metal film 7, as shown in FIG. 3D, the graphene film 2, the metal film 7 and the adhesive sheet 11 composed of the two-layer rectangular sheet 9 and the adhesive sheet 11 are acidic. Is immersed in a water tank 12 filled with an etching solution 13. Thereby, the metal film 7 is melted by the etching solution 13, and only the graphene film 2 and the adhesive sheet 11 remain. The base material 4 and the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 11 use acid-resistant materials that can withstand the etching solution 13. Further, as shown in FIG. 3 (e), the graphene film 2 and the pressure-sensitive adhesive sheet 11 are washed with the neutralizing solution 14 to complete the production of the graphene laminate 1.
　以上説明したような工程で、本実施例におけるグラフェン積層体１を形成することができる。 The graphene laminate 1 in the present example can be formed by the steps as described above.
　また、上述したプラズマＣＶＤ法を利用する場合には、金属膜７にグラフェン膜２を成膜する代わりに、粘着シート１１に、直接グラフェン膜２を成膜することができる。さらに、粘着シート１１にグラフェン膜２を形成する他の方法としては、グラフェン膜２が形成された部材に粘着シート１１を貼り付け、この粘着シート１１を部材より引き剥がすことで、粘着シート１１にグラフェン膜２を転写することで形成できる。また、粘着シート１１にグラフェン膜２を形成する他の方法としては、グラファイトを粉砕させたグラファイトの紛体を超音波等で分散させ、溶媒に溶かし込み、この溶媒を揮発させて粘着シート１１に塗布し、その後、溶媒を飛ばして除去することでも形成できる。 Further, when the plasma CVD method described above is used, the graphene film 2 can be directly formed on the adhesive sheet 11 instead of forming the graphene film 2 on the metal film 7. Furthermore, as another method of forming the graphene film 2 on the pressure-sensitive adhesive sheet 11, the pressure-sensitive adhesive sheet 11 is attached to the member on which the graphene film 2 is formed, and the pressure-sensitive adhesive sheet 11 is peeled off from the member. It can be formed by transferring the graphene film 2. As another method for forming the graphene film 2 on the pressure-sensitive adhesive sheet 11, graphite powder obtained by pulverizing graphite is dispersed by ultrasonic waves, dissolved in a solvent, and the solvent is volatilized and applied to the pressure-sensitive adhesive sheet 11. Then, it can also be formed by removing the solvent by removing it.
　上述したように形成されたグラフェン積層体１は、グラフェン膜２が粘着シート１１の表面に形成され、剥き出した状態のため、出荷する際や取扱いの際には、グラフェン膜２を傷つけないようにする必要があるので、グラフェン積層体１の表面のグラフェン膜２を保護する保護部材を設けるようにしてもよい。 In the graphene laminate 1 formed as described above, the graphene film 2 is formed on the surface of the pressure-sensitive adhesive sheet 11 and is exposed, so that the graphene film 2 is not damaged when shipped or handled. Therefore, a protective member for protecting the graphene film 2 on the surface of the graphene laminate 1 may be provided.
　そこで、グラフェン積層体１は、図４に示すように、グラフェン膜２側に、保護部材としての保護膜１５を備えるようにできる。保護膜１５の材質としては、シリコーン系フィルム、フッ素系フィルム、ポリエチレン系フィルム等の樹脂製のフィルムを利用することができる。それらフィルムの表面は、グラフェン膜２から剥離しやすくするためのエンボス加工等を施しておいてもよい。また、アルミ蒸着等によりさらにフィルムの表面に遮光膜を形成しておいてもよい。保護膜１５としては、ガスバリア性（水分、酸素等を遮断する機能）、遮光性（可視光線、紫外線等を遮断する機能）、離型性（保護膜１５をグラフェン膜２から剥がしやすくする機能）等を備えることが望ましい。 Therefore, the graphene laminate 1 can be provided with a protective film 15 as a protective member on the graphene film 2 side as shown in FIG. As the material of the protective film 15, a resin film such as a silicone film, a fluorine film, or a polyethylene film can be used. The surfaces of these films may be subjected to embossing or the like for facilitating peeling from the graphene film 2. Further, a light shielding film may be further formed on the surface of the film by aluminum vapor deposition or the like. The protective film 15 includes gas barrier properties (functions that block moisture, oxygen, etc.), light shielding properties (functions that block visible light, ultraviolet rays, etc.), releasability (functions that make the protective film 15 easy to peel off from the graphene film 2). Etc. are desirable.
　さらに、グラフェン積層体１を出荷する際には、保護部材として、ケースまたは梱包袋１６等にパック詰めしておくことで、さらにグラフェン膜２を保護することができる。また、梱包袋１６は、真空状態、または窒素やアルゴンなどの不活性ガスを充填しておくことで、グラフェンの酸化を防止することができる。梱包袋１６としては、ガスバリア性（水分、酸素等を遮断する機能）、遮光性（可視光線、紫外線等を遮断する機能）等を備えることが望ましい。 Furthermore, when the graphene laminate 1 is shipped, the graphene film 2 can be further protected by packing it in a case or a packing bag 16 as a protective member. Moreover, the packing bag 16 can prevent oxidation of graphene by filling a vacuum state or an inert gas such as nitrogen or argon. The packaging bag 16 desirably has gas barrier properties (function of blocking moisture, oxygen, etc.), light shielding properties (function of blocking visible light, ultraviolet rays, etc.) and the like.
　上述した実施例においては、グラフェン積層体１を矩形状のシート状に形成する場合を例に説明してきたが、グラフェン膜２および粘着シート１１の長さおよび形状を適宜調整することで、図５に示されるような様々な形状に成形しておくことが可能である。図５（ａ）～（ｅ）に示すように、実施例に係るグラフェン積層体１は、様々な形状に成形できる。図５（ａ）は、上述した実施例のグラフェン積層体１を矩形状のシート状１Ａに形成した場合を示し、図５（ｂ）は、上述した実施例のグラフェン積層体１をＡ４サイズの大型の矩形状のシート状１Ｂに形成した場合を示し、図５（ｃ）は、上述した実施例のグラフェン積層体１を幅狭のロール状５としてグラフェン積層体１Ｃを形成した場合を示し、図５（ｄ）は、上述した実施例のグラフェン積層体１をＡ４サイズの幅の幅大のロール状６としてグラフェン積層体１Ｄを形成した場合を示し、図５（ｅ）は、上述した実施例のグラフェン積層体１を矩形状のシート状１Ｅの変形例を示している。図５（ｅ）に示すように、矩形状のシート状１Ｅは、グラフェン膜２の一部を除去することで、グラフェン積層体１の粘着層３を一部表面に剥き出しとしておいてもよい。グラフェン膜２が形成されていない粘着層３の部分で、他の部材にグラフェン積層体を一時的に仮保持させることができるので、グラフェン膜２を貼付する他の部材への位置決めが容易となる。 In the embodiment described above, the case where the graphene laminated body 1 is formed in a rectangular sheet shape has been described as an example. However, by appropriately adjusting the length and shape of the graphene film 2 and the pressure-sensitive adhesive sheet 11, FIG. Can be formed into various shapes as shown in FIG. As shown in FIGS. 5A to 5E, the graphene laminate 1 according to the embodiment can be formed into various shapes. FIG. 5A shows a case where the graphene laminate 1 of the above-described embodiment is formed in a rectangular sheet shape 1A, and FIG. 5B shows the graphene laminate 1 of the above-described embodiment of A4 size. FIG. 5 (c) shows a case where the graphene laminate 1C is formed as a narrow roll-like shape 5 as shown in FIG. 5 (c). FIG.5 (d) shows the case where the graphene laminated body 1D is formed by making the graphene laminated body 1 of the Example mentioned above into the roll shape 6 of the width | variety of A4 size, and FIG.5 (e) is the implementation mentioned above. The graphene laminated body 1 of an example has shown the modification of the rectangular sheet form 1E. As shown in FIG. 5 (e), the rectangular sheet-like shape 1 </ b> E may partially expose the adhesive layer 3 of the graphene laminate 1 by removing a part of the graphene film 2. Since the graphene laminate can be temporarily held by another member at the portion of the adhesive layer 3 where the graphene film 2 is not formed, positioning to the other member to which the graphene film 2 is attached becomes easy. .
　次に、グラフェン積層体１の使用方法について図６から図９を参照して説明する。本実施例におけるグラフェン積層体１のグラフェン膜２は、以下に示すような方法で、他の部材の対象物１７に転写することができる。 Next, a method of using the graphene laminate 1 will be described with reference to FIGS. The graphene film 2 of the graphene laminated body 1 in the present embodiment can be transferred to the object 17 of another member by the following method.
　図６に示されるように、梱包袋１６から取り出されたグラフェン積層体１Ａを任意の大きさにカットし、保護膜１５を剥がす。そしてグラフェン膜２側を上向きにして、その上に、対象物１７を載置し、対象物１７にグラフェン積層体１Ａを接触させる。その後、グラフェン積層体１Ａと対象物１７を加圧して貼り合わせる。その後、後述する各種剥離法により粘着層３の粘着性を消失または減少させてから、グラフェン積層体１Ａを剥がすと対象物１７にグラフェン膜２のみを残すことができる。 As shown in FIG. 6, the graphene laminate 1A taken out from the packing bag 16 is cut into an arbitrary size, and the protective film 15 is peeled off. Then, with the graphene film 2 side facing upward, the object 17 is placed thereon, and the graphene laminate 1A is brought into contact with the object 17. Thereafter, the graphene laminate 1A and the object 17 are pressed and bonded together. Then, after the graphene laminate 1A is peeled off after the adhesiveness of the adhesive layer 3 is lost or reduced by various peeling methods described later, only the graphene film 2 can be left on the object 17.
　続いて、グラフェン膜２から粘着シート１１を剥離させる各種剥離法について図７を用いて説明する。 Subsequently, various peeling methods for peeling the adhesive sheet 11 from the graphene film 2 will be described with reference to FIG.
　図７（ａ）に示す剥離法は、粘着シート１１の粘着層３に、紫外線に反応して粘着力が低下するものが用いられており、グラフェン膜２、対象物１７および粘着シート１１をローラー１８で挟持しつつ、粘着シート１１に紫外線照射装置１９で紫外線を照射しながら粘着シート１１を一端から漸次剥離させる例を示したものである。この場合、粘着シート１１の基板４は、光を透過させる透光性を備えており、粘着シート１１の粘着層３に紫外線を照射することで、粘着剤ポリマーが光架橋構造に取り込まれ、体積収縮が起り、粘着力が消失される。粘着シート１１のグラフェン膜２側を密着させ、その後、粘着層３に紫外線を照射して物理的粘着力が消失させれば、粘着シート１１とグラフェン膜２とを分離することができ、また、グラフェン膜２の吸着機能により、対象物１７にグラフェン膜２を貼りつけることができる。また、対象物１７が透光性を備える場合には、粘着シート１１の基板４は透光性を備えなくてもよく、この場合、紫外線照射装置１９を、対象物１７側から照射させて、粘着層３に紫外線を照射することができる。 In the peeling method shown in FIG. 7 (a), the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 11 uses a material whose adhesive strength is reduced by reacting with ultraviolet rays, and the graphene film 2, the object 17 and the pressure-sensitive adhesive sheet 11 are transferred to a roller. 18 shows an example in which the pressure-sensitive adhesive sheet 11 is gradually peeled from one end while being irradiated with ultraviolet rays by the ultraviolet irradiation device 19 while being sandwiched by 18. In this case, the substrate 4 of the pressure-sensitive adhesive sheet 11 has translucency to transmit light, and the pressure-sensitive adhesive polymer is taken into the photocrosslinking structure by irradiating the pressure-sensitive adhesive layer 3 of the pressure-sensitive adhesive sheet 11 with ultraviolet light. Shrinkage occurs and the adhesive strength disappears. If the pressure-sensitive adhesive sheet 11 is adhered to the graphene film 2 side, and then the physical adhesive force disappears by irradiating the pressure-sensitive adhesive layer 3 with ultraviolet rays, the pressure-sensitive adhesive sheet 11 and the graphene film 2 can be separated. The graphene film 2 can be attached to the object 17 by the adsorption function of the graphene film 2. When the object 17 has translucency, the substrate 4 of the adhesive sheet 11 may not have translucency. In this case, the ultraviolet irradiation device 19 is irradiated from the object 17 side, The adhesive layer 3 can be irradiated with ultraviolet rays.
　図７（ｂ）に示す剥離法は、粘着シート１１の粘着剤に、所定温度以上の温度に加熱または所定温度以下の温度に冷却することで、粘着力が低下するものが用いられており、グラフェン膜２、対象物１７および粘着シート１１を加熱／冷却機能を有するローラー２０で挟持し、粘着シート１１を一端から漸次剥離させる例を示している。この場合、粘着シート１１の粘着剤として、所定温度以上の温度で加熱すると粘着力が低下するものを利用する場合、内包する発泡剤が膨張することで、粘着シート１１からグラフェン膜２が分離される。この場合、基材４としては、熱硬化性の機能を備えるものにしておくことで、加熱した際に基材４が硬化するため、より剥がしやすくすることができる。また、粘着シート１１の粘着剤として、所定温度以下の温度に冷却することで、粘着力が低下するものを利用する場合、冷却することで粘着剤組成物の分子運動が無くなり粘着性を消失する。粘着シート１１のグラフェン膜２側を対象物１７に密着させ、その後、粘着シート１１を加熱または冷却することで、粘着層３の物理的粘着力が消失させれば、粘着シート１１とグラフェン膜２とを分離することができ、また、グラフェン膜２の吸着機能により、対象物１７にグラフェン膜２を貼りつけることができる。 In the peeling method shown in FIG. 7 (b), the pressure-sensitive adhesive of the pressure-sensitive adhesive sheet 11 has a pressure-sensitive adhesive force lowered by heating to a temperature equal to or higher than a predetermined temperature or cooling to a temperature equal to or lower than a predetermined temperature. In this example, the graphene film 2, the object 17, and the pressure-sensitive adhesive sheet 11 are sandwiched between rollers 20 having heating / cooling functions, and the pressure-sensitive adhesive sheet 11 is gradually peeled from one end. In this case, when a pressure-sensitive adhesive having a pressure-sensitive adhesive strength that is reduced when heated at a temperature equal to or higher than a predetermined temperature is used as the pressure-sensitive adhesive of the pressure-sensitive adhesive sheet 11, the graphene film 2 is separated from the pressure-sensitive adhesive sheet 11 due to expansion of the foaming agent. The In this case, as the base material 4 is provided with a thermosetting function, since the base material 4 is cured when heated, it can be more easily peeled off. Moreover, as a pressure-sensitive adhesive of the pressure-sensitive adhesive sheet 11, when using a material whose adhesive strength is reduced by cooling to a temperature equal to or lower than a predetermined temperature, the molecular movement of the pressure-sensitive adhesive composition is eliminated by cooling and the adhesiveness is lost. . If the physical adhesive force of the adhesive layer 3 disappears by making the graphene film 2 side of the adhesive sheet 11 adhere to the object 17 and then heating or cooling the adhesive sheet 11, the adhesive sheet 11 and the graphene film 2 And the graphene film 2 can be attached to the object 17 by the adsorption function of the graphene film 2.
　また図７（ｃ）に示す剥離法は、粘着シート１１の粘着剤に、水溶性のものが用いられており、グラフェン膜２、対象物１７および粘着シート１１を、水を満たした水槽２１に浸漬させて、粘着シート１１を剥離させる例を示している。この場合、粘着シート１１の粘着剤として、水溶性の粘着剤を利用することで、粘着層３の粘着剤が水へ溶解し粘着性を消失する。粘着シート１１のグラフェン膜２側を対象物１７に密着させ、その後、粘着シート１１を水に含浸させることで、粘着層３の物理的粘着力が消失させれば、粘着シート１１とグラフェン膜２とを分離することができ、また、グラフェン膜２の吸着機能により、対象物１７にグラフェン膜２を貼りつけることができる。さらに、基材４も水溶性の機能を備えるようにしておくことで、粘着層３および基材４からなる粘着シート１１を溶解させることができる。 Moreover, the peeling method shown in FIG.7 (c) uses the water-soluble thing for the adhesive of the adhesive sheet 11, The graphene film 2, the target object 17, and the adhesive sheet 11 are put into the water tank 21 filled with water. An example in which the pressure-sensitive adhesive sheet 11 is peeled off by immersion is shown. In this case, by using a water-soluble pressure-sensitive adhesive as the pressure-sensitive adhesive of the pressure-sensitive adhesive sheet 11, the pressure-sensitive adhesive of the pressure-sensitive adhesive layer 3 dissolves in water and loses the pressure-sensitive adhesiveness. If the physical adhesive force of the adhesive layer 3 disappears by adhering the graphene film 2 side of the adhesive sheet 11 to the object 17 and then impregnating the adhesive sheet 11 with water, the adhesive sheet 11 and the graphene film 2 And the graphene film 2 can be attached to the object 17 by the adsorption function of the graphene film 2. Furthermore, the adhesive sheet 11 which consists of the adhesion layer 3 and the base material 4 can be dissolved by making the base material 4 also have a water-soluble function.
　また、図８（ａ）および（ｂ）に示されるように、凸部を有する対象物２２にグラフェン膜２を転写する場合であっても、粘着シート１１が可撓性、弾性力を備えることで凸部の形状に沿って密着可能であり、前述した粘着シート１１の剥離工程により対象物２２の形状に関わらずグラフェン膜２を転写することができる。この場合、例えば、粘着シート１１の基板４を熱可塑性のフィルムで構成し、グラフェン積層体１を加熱および加圧用のタンクに装着させて、グラフェン積層体１を所定温度まで加熱し、対象物２２に接触させた後に、タンクに空気又は液体などの加圧媒体を注入して、対象物２２にグラフェン積層体１を押し付けることで、対象物２２の形状に添わせ加圧することで対象物２２とグラフェン積層体１とを密着させることができる。その後、グラフェン積層体１および対象物２２から、タンクを切り離し、上述した各種剥離法により、粘着層３の粘着性を消失させ、粘着シート１１を剥がすことで、対象物２２にグラフェン膜２を貼りつけることができる。 In addition, as shown in FIGS. 8A and 8B, the pressure-sensitive adhesive sheet 11 has flexibility and elasticity even when the graphene film 2 is transferred to the object 22 having a convex portion. The graphene film 2 can be transferred regardless of the shape of the object 22 by the above-described peeling process of the pressure-sensitive adhesive sheet 11. In this case, for example, the substrate 4 of the pressure-sensitive adhesive sheet 11 is made of a thermoplastic film, the graphene laminate 1 is mounted on a heating and pressurizing tank, the graphene laminate 1 is heated to a predetermined temperature, and the object 22 Then, a pressure medium such as air or liquid is injected into the tank and the graphene laminate 1 is pressed against the object 22 to press the object 22 according to the shape of the object 22 and pressurize the object 22. The graphene laminated body 1 can be stuck. Thereafter, the tank is cut off from the graphene laminate 1 and the object 22, the adhesiveness of the adhesive layer 3 is lost by the above-described various peeling methods, and the adhesive sheet 11 is peeled off, so that the graphene film 2 is attached to the object 22. You can turn it on.
　また、図９（ａ）～（ｃ）に示されるように、凹部を有する対象物２４にグラフェン膜２を転写する場合であっても、粘着シート１１が熱収縮性を備えることで、凹部の形状に沿って密着可能であり、前述した粘着シート１１の剥離工程により対象物２４の形状に関わらずグラフェン膜２を転写することができる。この場合、例えば、粘着シート１１の基板４を熱収縮性のフィルムで構成し、図９（ａ）に示すように、グラフェン膜２を内側にしてグラフェン積層体１Ａを円筒上にして、その内側に対象物２４を入れる。もしくは、対象物２４の外側に、グラフェン膜２を内側にしてグラフェン積層体１Ａを巻きつける。その後、図９（ｂ）に示すように、グラフェン積層体１Ａの周りをドライヤーなどの温風で加熱してグラフェン積層体１Ａの粘着シート１１を収縮させて、粘着シート１１を対象物２４に密着させる。その後、上述した各種剥離法により、粘着層３の粘着性を消失させ、粘着シート１１を剥がすことで、対象物２４にグラフェン膜２を貼りつけることができる。 Further, as shown in FIGS. 9A to 9C, even when the graphene film 2 is transferred to the object 24 having a recess, the pressure-sensitive adhesive sheet 11 has a heat shrinkability, so that the recess The graphene film 2 can be transferred regardless of the shape of the object 24 by the above-described peeling process of the pressure-sensitive adhesive sheet 11. In this case, for example, the substrate 4 of the pressure-sensitive adhesive sheet 11 is made of a heat-shrinkable film, and as shown in FIG. 9A, the graphene film 2 is on the inside and the graphene laminate 1A is on the cylinder, and the inside The object 24 is put in the box. Alternatively, the graphene laminate 1A is wound around the outside of the object 24 with the graphene film 2 inside. Thereafter, as shown in FIG. 9B, the pressure-sensitive adhesive sheet 11 of the graphene laminated body 1 </ b> A is contracted by heating around the graphene laminated body 1 </ b> A with warm air such as a dryer, and the pressure-sensitive adhesive sheet 11 is closely attached to the object 24. Let Then, the graphene film | membrane 2 can be affixed on the target object 24 by making the adhesiveness of the adhesion layer 3 lose | disappear, and peeling the adhesive sheet 11 by the various peeling method mentioned above.
　また、上述した使用例においては、既に成形された対象物に対して、グラフェン膜２を貼りつける例を示しているが、他の使用例として、例えば、対象物そのものを成形する際に、グラフェン膜２を転写することもできる。この場合、成形する対象物としては、例えば、樹脂、焼結前のセラミックス素材（グリーンシート等）、鉄系（フェライト等）、カーボン系、セラミックス系、その他様々な紛体系による成形物、低融点ガラス等を利用できる。これらの対象物を金型等で成形する際に、上述したグラフェン積層体１を、その金型の対応する位置（対象物の貼付したい位置に対応する位置）に装着させて成形することで、成形した対象物にグラフェン積層体１を密着させる。その後、上述した各種剥離法により、粘着層３の粘着性を消失させ、粘着シート１１を剥がすことで、成形された対象物にグラフェン膜２を貼りつけることができる。対象物の成形方法としては、例えば、射出成型、ブロー成形、真空成型、発砲成形、重合成形（加熱、ＵＶ（紫外線）、ＥＢ（電子線）等）、ホットエンボス成形、インプリント成形等がある。これらの成形方法で成形する際に、金型にグラフェン積層体１を装着しておけば、成形と同時にグラフェン積層体１を貼付でき、その後粘着シート１１の粘着性を消失後、粘着シート１１を剥がすことで、グラフェン膜２が形成された対象物を成形することができる。 Moreover, in the usage example mentioned above, although the example which affixes the graphene film 2 with respect to the already shape | molded target object is shown, as another usage example, when shape | molding the target object itself, for example, graphene The film 2 can also be transferred. In this case, the object to be molded includes, for example, resin, ceramic material before sintering (green sheet, etc.), iron-based (ferrite, etc.), carbon-based, ceramic-based, other various powder systems, low melting point, etc. Glass etc. can be used. When molding these objects with a mold or the like, by attaching the above-described graphene laminate 1 to a corresponding position of the mold (a position corresponding to a position where the object is to be attached), The graphene laminate 1 is brought into close contact with the molded object. Then, the graphene film | membrane 2 can be affixed on the shape | molded target object by making the adhesiveness of the adhesion layer 3 lose | disappear by the various peeling method mentioned above, and peeling the adhesive sheet 11. FIG. Examples of the molding method of the object include injection molding, blow molding, vacuum molding, foam molding, polymerization molding (heating, UV (ultraviolet light), EB (electron beam), etc.), hot emboss molding, imprint molding, and the like. . When the graphene laminate 1 is attached to the mold when molding by these molding methods, the graphene laminate 1 can be applied simultaneously with the molding, and after the adhesive sheet 11 has disappeared, the adhesive sheet 11 is removed. By peeling off, the object on which the graphene film 2 is formed can be molded.
　以上、本発明の実施例を図面により説明してきたが、具体的な構成はこれら実施例に限られるものではなく、本発明の要旨を逸脱しない範囲における変更や追加があっても本発明に含まれる。 Although the embodiments of the present invention have been described with reference to the drawings, the specific configuration is not limited to these embodiments, and modifications and additions within the scope of the present invention are included in the present invention. It is.
　上述した実施例における基材４と粘着層３との材質や機能の組み合わせは、自由に設定することができる。例えば、基材４をガラスとし、粘着層３として、紫外線などの光を照射させることで粘着力が消失される粘着剤を用いることができる。この場合、ガラスは透光性を備えるので、ガラス側から粘着シート１１の粘着層３に紫外線を照射することで、粘着力を消失させることができる。 The combination of materials and functions of the base material 4 and the adhesive layer 3 in the above-described embodiments can be freely set. For example, the base material 4 is made of glass, and the adhesive layer 3 can be made of an adhesive that loses its adhesive strength when irradiated with light such as ultraviolet rays. In this case, since glass has translucency, the adhesive force can be lost by irradiating the adhesive layer 3 of the adhesive sheet 11 with ultraviolet rays from the glass side.
　また、基材４を生分解性の機能を備えるようにしておくことで、基材４をグラフェン膜２から剥離した後に、微生物などによって分解させることができ、自然環境への負担を少なくすることができる。 In addition, by providing the base material 4 with a biodegradable function, the base material 4 can be decomposed by microorganisms after being peeled from the graphene film 2, thereby reducing the burden on the natural environment. Can do.
１、１Ａ～１Ｅ　　グラフェン積層体
２　　　　　　　　グラフェン膜
３　　　　　　　　粘着層
４　　　　　　　　基材
５　　　　　　　　幅狭のロール状
６　　　　　　　　幅大のロール状
７　　　　　　　　金属膜
８　　　　　　　　２層のロール状シート
９　　　　　　　　２層の矩形状シート
１０　　　　　　　ラミネーター
１１　　　　　　　粘着シート
１２、２１　　　　水槽
１３　　　　　　　エッチング液
１４　　　　　　　中和液
１５　　　　　　　保護膜
１６　　　　　　　梱包袋
１７、２２、２４　対象物
１８　　　　　　　ローラー
１９　　　　　　　紫外線照射装置
２０　　　　　　　加熱／冷却機能を有するローラー DESCRIPTION OF SYMBOLS 1, 1A-1E Graphene laminated body 2 Graphene film 3 Adhesion layer 4 Base material 5 Narrow roll shape 6 Wide roll shape 7 Metal film 8 Two-layer roll sheet 9 Two-layer rectangular sheet 10 Laminator 11 Adhesion Sheets 12 and 21 Water tank 13 Etching solution 14 Neutralization solution 15 Protective film 16 Packaging bags 17, 22, and 24 Object 18 Roller 19 Ultraviolet irradiation device 20 Roller having heating / cooling function

Claims (12)

  1. 　炭素原子が共有結合された少なくとも一層のグラフェン膜と、
    　物理的粘着力を備える粘着層と、
    　所定の強度を備える基材と、
    　を備え、
    　前記粘着層の一方面の少なくとも一部に、前記グラフェン膜が粘着され、前記粘着層の他方面に前記基材が粘着されていることを特徴とするグラフェン積層体。     At least one graphene film in which carbon atoms are covalently bonded; and
    An adhesive layer with physical adhesive strength;
    A base material having a predetermined strength;
    With
    The graphene laminate, wherein the graphene film is adhered to at least a part of one surface of the adhesive layer, and the base material is adhered to the other surface of the adhesive layer.
  2. 　前記粘着層は、前記粘着力が消失または減少可能に構成されていることを特徴とする請求項１に記載のグラフェン積層体。 The graphene laminate according to claim 1, wherein the adhesive layer is configured such that the adhesive force can be lost or reduced.
  3. 　前記粘着層の前記粘着力は、光の照射により消失または減少されることを特徴とする請求項１または２に記載のグラフェン積層体。 The graphene laminate according to claim 1 or 2, wherein the adhesive force of the adhesive layer disappears or is reduced by light irradiation.
  4. 　前記粘着層の前記粘着力は、紫外線の照射により消失または減少されることを特徴とする請求項１ないし３のいずれかに記載のグラフェン積層体。 The graphene laminate according to any one of claims 1 to 3, wherein the adhesive force of the adhesive layer disappears or is reduced by irradiation with ultraviolet rays.
  5. 　前記粘着層の前記粘着力は、熱または溶媒により消失または減少されることを特徴とする請求項１ないし４のいずれかに記載のグラフェン積層体。 The graphene laminate according to any one of claims 1 to 4, wherein the adhesive force of the adhesive layer disappears or is reduced by heat or a solvent.
  6. 　前記基材は、可撓性または弾性を備えることを特徴とする請求項１ないし５のいずれかに記載のグラフェン積層体。 The graphene laminate according to any one of claims 1 to 5, wherein the base material has flexibility or elasticity.
  7. 　前記基材は、樹脂製のフィルムにより構成されていることを特徴とする請求項１ないし６のいずれかに記載のグラフェン積層体。 The graphene laminate according to any one of claims 1 to 6, wherein the substrate is made of a resin film.
  8. 　前記基材は、熱硬化性、熱可塑性、熱収縮性、生分解性、水溶性の少なくともいずれかの機能を備えることを特徴とする請求項１ないし７のいずれかに記載のグラフェン積層体。 The graphene laminate according to any one of claims 1 to 7, wherein the base material has at least one of thermosetting, thermoplastic, heat-shrinkable, biodegradable, and water-soluble functions.
  9. 　前記基材は、ガラス、金属、セラミックスの少なくともいずれかで構成されていることを特徴とする請求項１ないし８のいずれかに記載のグラフェン積層体。 The graphene laminate according to any one of claims 1 to 8, wherein the substrate is made of at least one of glass, metal, and ceramics.
  10. 　前記基材は、透光性を備えることを特徴とする請求項３または４に記載のグラフェン積層体。 The graphene laminate according to claim 3 or 4, wherein the substrate has translucency.
  11. 　前記グラフェン膜を保護する保護部材を備えることを特徴とする請求項１ないし１０のいずれかに記載のグラフェン積層体。 The graphene laminate according to any one of claims 1 to 10, further comprising a protective member that protects the graphene film.
  12. 　前記保護部材は、前記グラフェン膜から剥離可能な加工が施されていることを特徴とする請求項１１に記載のグラフェン積層体。 The graphene laminate according to claim 11, wherein the protective member is processed to be peelable from the graphene film.
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