JP2013037781A - Manufacturing method of transparent conductive member, and intermediate member - Google Patents

Abstract

An object of the present invention is to provide a method for producing a transparent conductive member capable of producing a transparent conductive member having both excellent transparency and conductivity with high productivity.
A method of manufacturing a transparent conductive member according to the present invention includes a step of preparing a metal foil,
Forming a graphene layer on the metal foil; forming a resin layer made of a reactive curable resin composition in an uncured or semi-cured state directly or via one or more layers on the graphene layer A step of obtaining an intermediate member, a step of obtaining a laminate by stacking a transparent base material on the resin layer of the intermediate member, and subsequently curing the resin layer, and a metal foil from the laminate Removing.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a transparent conductive member having both transparency and conductivity, and an intermediate member used in this method.

  Members having both transparency and conductivity are applied to transparent electrodes, touch panel components, and the like, and are expected to expand their applications. As such a member, a member constituted by depositing ITO on a transparent base material such as a glass base material can be cited as a representative example.

  However, since indium, which is the main component of ITO, is a rare metal, there are problems regarding cost and resource depletion.

On the other hand, in recent years, a graphene sheet has been attracting attention as a material having both high transparency and conductivity (see Patent Document 1). The graphene sheet is a sheet having a thickness of one atom formed by arranging carbon atoms in a hexagonal lattice structure in a planar shape by sp ² bonds, and the electrical resistance value at room temperature is 2/3 that of copper. It is a material excellent in both conductivity and durability that its current density resistance is 100 times or more that of copper.

  However, a method for producing a transparent conductive member in the case of applying a graphene sheet to the transparent conductive member has not been sufficiently established.

  Then, the present inventors examined the following method in order to manufacture the transparent conductive member to which a graphene sheet is applied. First, a graphene layer composed of one or more graphene sheets is formed on a metal foil such as a copper foil by a vapor deposition method or the like. The graphene layer 4 is overlaid with a transfer plastic film (transfer film), and then all the metal foil is removed by etching or the like. Thereby, the member for transfer provided with the film for transfer and the graphene layer 4 piled up on it is formed. The graphene layer in the transfer member is overlapped and bonded to a transparent substrate, and then the transfer film is peeled from the graphene layer. Thereby, a transparent conductive member provided with a transparent base material and the graphene layer laminated | stacked on this base material is obtained.

  However, in this method, it is necessary to transfer the graphene layer to the transfer film and then transfer it onto the base material, which increases the number of steps. In addition, a member that is not included in the final product, such as a transfer film, is required, which increases the production cost. There is also a problem that it is difficult to ensure adhesion between the graphene layer and the substrate.

JP 2009-107921 A

  The present invention has been made in view of the above reasons, and is used in a method for producing a transparent conductive member capable of producing a transparent conductive member having excellent transparency and conductivity with high productivity, and in this method. It is an object to provide an intermediate member.

The method for producing a transparent conductive member according to the present invention includes:
Preparing the metal foil,
Forming a graphene layer on the metal foil;
A step of obtaining an intermediate member by forming a resin layer made of a reactive curable resin composition in an uncured state or a semi-cured state directly or via one or a plurality of layers on the graphene layer,
The method includes the steps of obtaining a laminate by superimposing a transparent base material on the resin layer of the intermediate member, and subsequently curing the resin layer, and removing the metal foil from the laminate.

  In the present invention, it is preferable to form a hard coat layer made of a cured product of the resin layer by curing the resin layer.

  In the present invention, it is also preferable to form an antireflection layer containing a cured product of the resin layer by curing the resin layer.

  An intermediate member according to the present invention includes a metal foil, a graphene layer, and a resin layer, and the graphene layer is formed on the metal foil and interposed between the metal foil and the resin layer, and the resin The layer is made of a reactive curable resin composition in an uncured or semi-cured state.

  According to the present invention, a transparent conductive member having both excellent transparency and conductivity can be produced with high productivity.

(A) thru | or (e) are sectional drawings which show the 1st aspect of the manufacturing method of the transparent conductive member which concerns on embodiment of this invention. (A) thru | or (f) is sectional drawing which shows the 2nd aspect of the manufacturing method of the transparent conductive member which concerns on embodiment of this invention. (A) thru | or (e) are sectional drawings which show the 3rd aspect of the manufacturing method of the transparent conductive member which concerns on embodiment of this invention. It is the schematic which shows an example of the manufacturing apparatus applied to the manufacturing method of the transparent conductive member which concerns on embodiment of this invention. (A) is sectional drawing which shows the 1st example of the transparent conductive member manufactured by this invention, (b) is sectional drawing which shows the 2nd example of the transparent conductive member manufactured by this invention, (c) ) Is a cross-sectional view showing a third example of the transparent conductive member produced according to the present invention.

  According to the manufacturing method of the transparent conductive member by this embodiment, a transparent conductive member provided with a base material, a layer which consists of hardened material of a resin layer, and a graphene layer is obtained. The substrate and the layer made of the cured resin layer are in direct contact. The graphene layer and the cured layer of the resin layer are in direct contact with each other, or one or more layers are interposed between the graphene layer and the cured layer of the resin layer. A first example of the transparent conductive member manufactured in the present embodiment is shown in FIG. 5A, a second example is shown in FIG. 5B, and a third example is shown in FIG. 5C. .

  In the first example shown in FIG. 5A, the transparent conductive member 1 includes a base material 2, a hard coat layer 5, and a graphene layer 4. In this example, the hard coat layer 5 is a layer made of a cured product of the resin layer. The base material 2, the hard coat layer 5, and the graphene layer 4 are laminated in this order. That is, the hard coat layer 5 is laminated on the first main surface of the substrate 2, and the graphene layer 4 is laminated on the main surface of the hard coat layer 5 opposite to the substrate 2. Any element of the base material 2, the hard coat layer 5, and the graphene layer 4 has light transmittance, and the transparent conductive member 1 has light transmittance as a whole.

  Examples of the material of the substrate 2 include transparent glasses such as soda lime glass and alkali-free glass; polyester resins, polyolefin resins, polyamide resins, epoxy resins, fluororesins, cellulose resins, polycarbonate resins, acrylic resins, and the like. . The shape of the substrate 2 may be a film shape or a plate shape. In particular, when the substrate 2 is formed from a plastic film such as a polyester film, a cyclic polyolefin film, a triacetyl cellulose film, a polycarbonate film, or an acrylic film, a transparent conductive member is formed by a so-called roll-to-roll manufacturing method as will be described later. 1 can be manufactured efficiently.

  When the substrate 2 is formed from a polyester film, as the polyester, for example, an aromatic dicarboxylic acid component such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, Aromatic polyesters produced by reaction with glycol components such as ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, etc. are preferred, especially polyethylene terephthalate, polyethylene-2 1,6-naphthalene dicarboxylate is preferred. Further, the polyester may be a copolyester such as the plurality of components exemplified above.

  The base material 2 may contain organic or inorganic particles. In this case, the winding property and transportability of the base material 2 are improved. Examples of such particles include calcium carbonate particles, calcium oxide particles, aluminum oxide particles, kaolin, silicon oxide particles, zinc oxide particles, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, urea resin particles, melamine resin particles, and crosslinked silicone resin particles. Etc. The substrate 2 may also contain a colorant, an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant, a catalyst, other resins, and the like as long as the transparency is not impaired.

  The haze of the base material 2 is preferably 3% or less. In this case, the visibility of an image or the like through the transparent conductive member 1 is improved, and it becomes particularly suitable as a film for optical use. More preferably, the haze is 1.5% or less.

  Although the thickness in particular of the base material 2 is not restrict | limited, When the base material 2 is a film form, it is preferable that the thickness is the range of 25 micrometers or more and 200 micrometers or less. In particular, when the thickness of the substrate 2 is 25 μm or more and 100 μm or less, the transparent conductive member 1 can be made thinner and lighter, and interference between the front and back of the transparent conductive member 1 is suppressed. Thermal contraction when the is heated is suppressed, and problems such as deterioration of workability due to thermal contraction of the substrate 2 are suppressed.

  The hard coat layer 5 is a layer having higher hardness than the base material 2. When the transparent conductive member 1 includes the hard coat layer 5, the mechanical strength of the transparent conductive member 1 is improved. The pencil hardness of the hard coat layer 5 is preferably H or higher, more preferably 2H or higher.

  The refractive index of the hard coat layer 5 is preferably in the range of 1.45 to 1.65. When the refractive index of the hard coat layer 5 is in such a range, the occurrence of uneven interference between the hard coat layer 5 and the substrate 2 is suppressed.

  The thickness of the hard coat layer 5 is not particularly limited, but the mechanical strength of the transparent conductive member 1 is sufficiently improved if the thickness is in the range of 1 to 2 μm or more.

  The hard coat layer 5 is preferably formed from a reactive curable resin composition. For example, the hard coat layer 5 is preferably formed from at least one of a thermosetting resin composition and an active energy ray curable resin composition. Hereinafter, the reactive curable resin composition for forming the hard coat layer 5 is referred to as a first reactive curable resin composition.

  The thermosetting resin composition includes, for example, thermosetting resins such as phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, silicon resin, polysiloxane resin, and the like. contains. A crosslinking agent, a polymerization initiator, a curing agent, a curing accelerator, a solvent and the like may be used together with the thermosetting resin as necessary. The hard coat layer 5 can be formed by applying such a thermosetting resin composition and subsequently heating and thermosetting the thermosetting resin composition.

  The active energy ray-curable resin composition preferably includes a resin having an acrylate functional group. Examples of the resin having an acrylate functional group include oligomers such as (meth) acrylates of a relatively low molecular weight polyfunctional compound, prepolymers, and the like. Examples of the polyfunctional compound include polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols. The active energy ray-curable resin composition preferably further contains a reactive diluent. Examples of reactive diluents include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, and hexanediol (meth) acrylate. , Tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di The polyfunctional monomer of (meth) acrylate is mentioned.

  When the active energy ray curable resin composition is a photocurable resin composition such as an ultraviolet curable resin composition, the photocurable resin composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, thioxanthones, and the like. The photocurable resin composition may contain a photosensitizer in addition to the photopolymerization initiator or in place of the photopolymerization initiator. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone. The hard coat layer 5 can be formed by applying such a photo-curable resin composition and subsequently irradiating the photo-curable resin composition with light such as ultraviolet rays for photo-curing.

  The refractive index of the hard coat layer 5 can be easily adjusted by the composition of the resin composition for forming the hard coat layer 5. Moreover, it is also preferable that the refractive index of the hard coat layer 5 is adjusted by the hard coat layer 5 containing particles for adjusting the refractive index and the ratio thereof being adjusted.

  The particle diameter of the refractive index adjusting particles is preferably sufficiently small, that is, the refractive index adjusting particles are preferably so-called ultrafine particles. In this case, the light transmittance of the hard coat layer 5 is sufficiently maintained. Become. The particle diameter of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm to 200 nm. The particle diameter of the particles for adjusting the refractive index is the diameter of a circle (area equivalent circle) having the same area as the projected area calculated from the electron micrograph image of the particles.

  The refractive index adjusting particles are preferably particles having a relatively high refractive index, and particularly preferably particles having a refractive index of 1.6 or more. These particles are preferably metal or metal oxide particles.

  The content of the particles for adjusting the refractive index in the hard coat layer 5 is appropriately adjusted so that the refractive index of the hard coat layer 5 has an appropriate value, and in particular, for adjusting the refractive index in the hard coat layer 5. It is preferable to adjust so that the ratio of particle | grains may be 5-70 volume%.

Specific examples of the particles for adjusting the refractive index include particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony. Specific examples of the oxide include ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1. _71), SnO _2, ITO (refractive index _1.95), Y 2 _{O 3} (refractive index 1.87), _La 2 _{O 3} (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ O ₃ (refractive index 1.63) and the like.

It is also preferable that the hard coat layer 5 has antistatic performance. In this case, charging of the transparent conductive member 1 is suppressed, and adhesion of dust to the transparent conductive member 1 is suppressed. For this purpose, the hard coat layer 5 preferably contains conductive particles. The conductive particles may simultaneously function as refractive index adjusting particles. The conductive particles are preferably nanoparticles, and particularly preferably ultrafine particles having a particle size of 0.5 to 200 nm. The particle diameter of the conductive particles is also the diameter of an area equivalent circle. Examples of the material of the conductive particles include appropriate metals and metal oxides having conductivity, and specifically include oxides of one or more metals selected from indium, zinc, tin, and antimony. More specifically, indium oxide (ITO), tin oxide (SnO ₂ ), antimony / tin oxide (ATO), lead / titanium oxide (PTO), antimony oxide (Sb ₂ O ₅ ) and the like can be mentioned. .

In order to impart sufficient antistatic performance to the hard coat layer 5, it is preferable that the sheet resistance of the hard coat layer 5 is 10 ¹⁵ Ω / □ or less by containing conductive particles. The lower the sheet resistance of the hard coat layer 5, the better the antistatic property. Therefore, the lower limit is not particularly set, but there is a limit to reducing the sheet resistance, so the practical lower limit of the sheet resistance of the hard coat layer 5. Is 10 ⁶ Ω / □.

  The content of the conductive particles in the hard coat layer 5 is appropriately adjusted so that the antistatic performance of the hard coat layer 5 is at an appropriate level, but the ratio of the conductive particles in the hard coat layer 5 is particularly 5. It is preferable to adjust so that it may become -70 mass%.

  The graphene layer 4 is composed of a graphene sheet. The graphene sheet is formed by an evaporation method such as a thermal CVD method or a plasma CVD method. In this case, for example, a gas phase carbon source is supplied into the chamber, and the carbon source is heated in the chamber or subjected to plasma treatment, whereby the carbon source is decomposed and the carbon atoms are bonded to each other to form a hexagonal shape. Thus, a graphene sheet is formed.

  The carbon source for forming the graphene sheet is not particularly limited, but carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, Examples include benzene and toluene.

When the graphene layer 4 is formed by the thermal CVD method, the temperature in the chamber, the pressure of the carbon source in the chamber, and the like are appropriately adjusted. The temperature in the chamber is adjusted to a range of 300 to 2000 ° C., for example. The pressure of the carbon source in the chamber is adjusted, for example, in the range of 1.3 × 10 ^{−4 to} 1.4 × 10 ⁴ Pa, and preferably in the range of 1.3 × 10 ^{−1 to} 1.0 × 10 ⁵ Pa. It is adjusted with.

  When the graphene layer 4 is formed by a thermal CVD method, it is also preferable that hydrogen be supplied together with the carbon source into the chamber. The amount of hydrogen in this case is preferably 5% by volume or more and 40% by volume or less, more preferably 10% by volume or more and 30% by volume or less, and more preferably 15% by volume or more and 25% by volume or less. It is particularly preferable if it is present.

  The graphene layer 4 may be composed of a single-layer graphene sheet, but may be composed of a plurality of layers of graphene sheets. The graphene layer 4 is preferably made of a graphene sheet having 1 to 300 layers, particularly preferably a graphene sheet having 1 to 15 layers.

  In the second example shown in FIG. 5B, the transparent conductive member 1 includes a base material 2, a hard coat layer 5, an antireflection layer 3, and a graphene layer 4. The base material 2, the hard coat layer 5, the antireflection layer 3, and the graphene layer 4 are laminated in this order. That is, the hard coat layer 5 is laminated on the first main surface of the base material 2, and the antireflection layer 3 is laminated on the main surface of the hard coat layer 5 opposite to the base material 2. The graphene layer 4 is laminated on the main surface opposite to the substrate 2. Any element of the base material 2, the hard coat layer 5, the antireflection layer 3, and the graphene layer 4 has light transmittance, and the transparent conductive member 1 has light transmittance as a whole. In this example, the hard coat layer 5 is a layer made of a cured product of the resin layer.

  In this example, the base material 2, the hard coat layer 5, and the graphene layer 4 have the same configuration as the first example.

  The antireflection layer 3 is a layer that functions to reduce the intensity of the reflected light by causing optical interference of the reflected light. The antireflection layer 3 is preferably formed from a reactive curable resin composition. The antireflection layer 3 only needs to have a known appropriate configuration. For example, the antireflection layer 3 includes a high refractive index layer 31 and a low refractive index layer 32 laminated on the opposite side of the high refractive index layer 31 from the substrate 2. . The low refractive index layer 32 is a layer having a refractive index lower than that of the high refractive index layer 31.

  The refractive index of the high refractive index layer 31 is not particularly limited, but is, for example, in the range of 1.50 or more and 2.30 or less. The thickness of the high refractive index layer 31 is, for example, in the range of not less than 50 nm and not more than 5000 nm.

  The high refractive index layer 31 is preferably formed from a reactive curable resin composition. For example, the high refractive index layer 31 is preferably formed from at least one of a thermosetting resin composition and an active energy ray curable resin composition. Hereinafter, the reactive curable resin composition for forming the high refractive index layer 31 is referred to as a second reactive curable resin composition.

  The thermosetting resin composition for forming the high refractive index layer 31 includes, for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, Contains thermosetting resin such as polysiloxane resin. A crosslinking agent, a polymerization initiator, a curing agent, a curing accelerator, a solvent and the like may be used together with the thermosetting resin as necessary. The high refractive index layer 31 can be formed by applying such a thermosetting resin composition and subsequently heating and thermosetting the thermosetting resin composition.

  The active energy ray-curable resin composition for forming the high refractive index layer 31 preferably contains a resin having an acrylate functional group. Examples of the resin having an acrylate functional group include oligomers such as (meth) acrylates of a relatively low molecular weight polyfunctional compound, prepolymers, and the like. Examples of the polyfunctional compound include polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols. The active energy ray-curable resin composition preferably further contains a reactive diluent. Examples of reactive diluents include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, and hexanediol (meth) acrylate. , Tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di The polyfunctional monomer of (meth) acrylate is mentioned.

  When the active energy ray curable resin composition is a photocurable resin composition such as an ultraviolet curable resin composition, the photocurable resin composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, thioxanthones, and the like. The photocurable resin composition may contain a photosensitizer in addition to the photopolymerization initiator or in place of the photopolymerization initiator. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone. Such a photocurable resin composition is applied onto, for example, the substrate 2 or the anti-blocking layer, and then the photocurable resin composition is irradiated with light such as ultraviolet rays to be photocured, thereby achieving high refraction. A rate layer 31 may be formed.

  The refractive index of the high refractive index layer 31 can be easily adjusted by the composition of the resin composition for forming the high refractive index layer 31. It is also preferable that the refractive index of the high refractive index layer 31 is adjusted by the high refractive index layer 31 containing particles for adjusting the refractive index and the ratio thereof being adjusted.

  The particle diameter of the refractive index adjusting particles is preferably sufficiently small, that is, the refractive index adjusting particles are preferably so-called ultrafine particles. In this case, the light transmittance of the high refractive index layer 31 is sufficiently maintained. It becomes like this. The particle diameter of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm to 200 nm. The particle diameter of the particles for adjusting the refractive index is the diameter of a circle (area equivalent circle) having the same area as the projected area calculated from the electron micrograph image of the particles.

  The refractive index adjusting particles are preferably particles having a relatively high refractive index, and particularly preferably particles having a refractive index of 1.6 or more. These particles are preferably metal or metal oxide particles.

  The content of the refractive index adjusting particles in the high refractive index layer 31 is appropriately adjusted so that the refractive index of the high refractive index layer 31 has an appropriate value. It is preferable to adjust so that the ratio of the particle for adjustment may be 5-70 volume%.

Specific examples of the particles for adjusting the refractive index include particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony. Specific examples of the oxide include ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1. _71), SnO _2, ITO (refractive index _1.95), Y 2 _{O 3} (refractive index 1.87), _La 2 _{O 3} (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ O ₃ (refractive index 1.63) and the like.

It is also preferable that the high refractive index layer 31 has antistatic performance. In this case, charging of the transparent conductive member 1 is suppressed, and adhesion of dust to the transparent conductive member 1 is suppressed. For this purpose, the high refractive index layer 31 preferably contains conductive particles. The conductive particles may simultaneously function as refractive index adjusting particles. The conductive particles are preferably nanoparticles, and particularly preferably ultrafine particles having a particle size of 0.5 to 200 nm. The particle diameter of the conductive particles is also the diameter of an area equivalent circle. Examples of the material of the conductive particles include appropriate metals and metal oxides having conductivity, and specifically include oxides of one or more metals selected from indium, zinc, tin, and antimony. More specifically, indium oxide (ITO), tin oxide (SnO ₂ ), antimony / tin oxide (ATO), lead / titanium oxide (PTO), antimony oxide (Sb ₂ O ₅ ) and the like can be mentioned. .

In order to impart sufficient antistatic performance to the high refractive index layer 31, it is preferable that the sheet resistance of the high refractive index layer 31 is 10 ¹⁵ Ω / □ or less by containing conductive particles. The lower the sheet resistance of the high refractive index layer 31, the better the antistatic property. Therefore, the lower limit is not particularly set, but there is a limit to reducing the sheet resistance. The lower limit is 10 ⁶ Ω / □.

  The content of the conductive particles in the high refractive index layer 31 is adjusted as appropriate so that the antistatic performance of the high refractive index layer 31 is at an appropriate level. In particular, the ratio of the conductive particles in the high refractive index layer 31 Is preferably adjusted so as to be 5 to 70% by mass.

  The high refractive index layer 31 is composed of particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony, and a methacryl functional silane and an acryl functional silane. It is also preferable to contain at least one. In this case, the adhesion between the high refractive index layer 31 and the low refractive index layer 32 is improved. Examples of the methacrylic functional silane include 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane. Examples of the acrylic functional silane include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropylmethyldimethoxysilane.

  The content of the methacryl functional silane and the acrylic functional silane in the high refractive index layer 31 is not particularly limited, but the ratio of the total amount of the methacryl functional silane and the acrylic functional silane in the high refractive index layer 31 is 5 to 30 mass. % Is preferable. When the proportion is 5% by mass or more, the adhesiveness between the high refractive index layer 31 and the low refractive index layer 32 is sufficiently high, and when the proportion is 30% by mass or less, the crosslinking in the high refractive index layer 31 is performed. The density is sufficiently improved, and the hardness of the high refractive index layer 31 is sufficiently increased.

  The refractive index of the low refractive index layer 32 is preferably lower than any of the refractive indexes of the substrate 2 and the high refractive index layer 31. For example, the refractive index of the low refractive index layer 32 is in the range of 1.10 to 1.45. The thickness (actual film thickness) of the low refractive index layer 32 is, for example, in the range of not less than 20 nm and not more than 200 nm.

  The low refractive index layer 32 is also preferably formed from a reactive curable resin composition. For example, the low refractive index layer 32 is preferably formed from at least one of a thermosetting resin composition and an active energy ray curable resin composition. Hereinafter, the reactive curable resin composition for forming the low refractive index layer 32 is referred to as a third reactive curable resin composition. The low refractive index layer 32 is formed from a composition containing, for example, a binder material and particles for adjusting the refractive index used as necessary. When the binder material and the particles for adjusting the refractive index are used in combination, the refractive index of the low refractive index layer 32 is appropriately adjusted depending on the combination of the both, the blending ratio, and the like.

  As the binder material, a polymer having a main chain of at least one of silicon alkoxide resin, saturated hydrocarbon and polyether (for example, UV curable resin composition, thermosetting resin composition, etc.), fluorine atom in the polymer chain And a resin containing a unit containing.

As a silicon alkoxide resin, a silicon alkoxide represented by R _m Si (OR ′) _n (R and R ′ are alkyl groups having 1 to 10 carbon atoms, m + n = 4, m and n are integers). Examples include oligomers and polymers that are hydrolyzed condensates. Specific examples of the silicon alkoxide include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxy. Silane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, di Chill propoxysilane, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane, and the like.

  As the binder material, a reactive organosilicon compound having a plurality of groups (polymerizable double bond group or the like) that undergoes reactive crosslinking by heat or active energy rays may be used. The molecular weight of the organosilicon compound is preferably 5000 or less. Such reactive organosilicon compounds are obtained by reacting one terminal vinyl functional polysilane, both terminal vinyl functional polysilane, one terminal vinyl functional polysiloxane, both terminal vinyl functional polysiloxane, and these compounds. Examples include vinyl functional polysilanes and vinyl functional polysiloxanes. In addition to these, examples of the reactive organic silicon compound include (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane.

  As the particles for adjusting the refractive index, it is preferable to use particles having a relatively low refractive index. Examples of the material for adjusting the refractive index include silica, magnesium fluoride, lithium fluoride, aluminum fluoride, calcium fluoride, sodium fluoride, and the like. It is preferable that the refractive index adjusting particles include hollow particles. A hollow particle is a particle having a cavity surrounded by an outer shell. The refractive index of the hollow particles is preferably 1.20 to 1.45.

  The particles for adjusting the refractive index are preferably subjected to a surface treatment for improving the wettability with the binder material, if necessary.

  The particle diameter of the refractive index adjusting particles is preferably sufficiently small, that is, the refractive index adjusting particles are preferably so-called ultrafine particles. In this case, the light transmittance of the low refractive index layer 32 is sufficiently maintained. It becomes like this. The particle diameter of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm to 200 nm. The particle diameter of the particles for adjusting the refractive index is the diameter of a circle (area equivalent circle) having the same area as the projected area calculated from the electron micrograph image of the particles.

  The content of the refractive index adjusting particles in the low refractive index layer 32 is appropriately adjusted so that the refractive index value of the low refractive index layer 32 is an appropriate value. It is preferable to adjust so that the ratio of the particles for adjusting the refractive index is 20 to 99% by volume.

  The composition may further contain a water and oil repellent material. In this case, antifouling property can be imparted to the low refractive index layer 32. As the water and oil repellent material, a general wax-based material or the like can be used. In particular, when a fluorine-containing compound is used, the removability of the low refractive index layer 32, such as dirt and fingerprints, is particularly improved, and the frictional resistance of the surface of the low refractive index layer 32 is reduced. Abrasion is improved.

  The low refractive index layer 32 can be formed by curing the composition as described above by applying treatments such as heating, humidification, ultraviolet irradiation, and electron beam irradiation according to the properties of the binder material.

  The configuration of the antireflection layer 3 is not limited to the above aspect. For example, the antireflection layer 3 may have a multilayer structure of three or more layers. Further, the antireflection layer 3 may be composed of only one layer having a refractive index lower than that of the substrate 2, and in this case, the antireflection layer 3 may have the same configuration as the low refractive index layer 32 described above. Good. Further, the hard coat layer 5 may function as a part of the antireflection layer 3. That is, for example, the light reflected by the hard coat layer 5, the high refractive index layer 31, and the low refractive index layer 32 interfere with each other and cancel each other, so that the intensity of the overall reflected light at the transparent conductive member 1 is increased. It may be reduced.

  In the third example shown in FIG. 5C, the transparent conductive member 1 includes a base material 2, an antireflection layer 3, and a graphene layer 4. The base material 2, the antireflection layer 3, and the graphene layer 4 are laminated in this order. That is, the antireflection layer 3 is laminated on the first main surface of the substrate 2, and the graphene layer 4 is laminated on the main surface of the antireflection layer 3 opposite to the substrate 2. Any element of the base material 2, the antireflection layer 3, and the graphene layer 4 has light transmittance, and the transparent conductive member 1 has light transmittance as a whole.

  In this example, the base material 2 and the graphene layer 4 have the same configuration as the first example and the second example. The antireflection layer 3 has the same configuration as that of the second example. That is, the antireflection layer 3 includes a high refractive index layer 31 and a low refractive index layer 32 that is laminated on the opposite side of the high refractive index layer 31 from the substrate 2. In this example, the high refractive index layer 31 is in direct contact with the substrate 2 and the low refractive index layer 32 is in direct contact with the graphene layer. In this example, the high refractive index layer 31 is a layer made of a cured product of a resin layer.

  In the manufacturing method of the transparent conductive member 1 according to the present embodiment, a metal foil 6 is prepared, a graphene layer 4 is formed on the metal foil 6, and the graphene layer 4 is directly or via one or a plurality of layers. Then, the intermediate member 7 including the metal foil 6, the graphene layer 4, and the resin layer 9 is obtained by forming the resin layer 9 made of the reactive curable resin composition in an uncured state or a semi-cured state. The intermediate member 7 includes a metal foil 6, a graphene layer 4, and a resin layer 9. The graphene layer 4 is formed on the metal foil 6 and is interposed between the metal foil 6 and the resin layer 9. This is a member having a structure. This intermediate member 7 is configured by laminating layers other than the base material 2 among the layers constituting the transparent conductive member 1 on the metal foil 6 such as copper foil, and the outermost side opposite to the metal foil 6. The resin layer 9 is disposed on the surface. The transparent substrate 1 is stacked on the resin layer 9 of the intermediate member 7, and then the resin layer 9 is cured to obtain a laminate 8. The transparent conductive member 1 is obtained by removing the metal foil 6 from the laminate 8.

  The 1st aspect of the manufacturing method of the transparent conductive member 1 in this embodiment is demonstrated with reference to FIG. In this embodiment, the hard coat layer 5 made of a cured product of the resin layer 9 is formed by curing the resin layer 9. In this aspect, the transparent conductive member 1 of the first example is manufactured.

  In this embodiment, a metal foil 6 such as a copper foil is prepared, and the graphene layer 4 is formed on the metal foil 6 by vapor deposition or the like (FIG. 1A). On this graphene layer 4, the 1st reactive curable resin composition for forming the hard-coat layer 5 is apply | coated, or this 1st reactive curable resin composition is further semi-hardened. Thereby, the resin layer 9 which consists of a 1st reactive curable resin composition of a non-hardened state (A stage) or a semi-hardened state (B stage) is formed, and the metal foil 6, the graphene layer 4, and the resin layer 9 are formed. The intermediate member 7 provided is obtained (FIG. 1B).

  In addition, when the above layers are formed from the reactive curable resin composition, surface treatment may be performed on the surface overlapping with this layer before the layer is formed. In this case, it is possible to improve the wettability and adhesion between the layers. That is, surface treatment may be performed on the surface of the graphene layer 4 that overlaps the resin layer 9 before the resin layer 9 is formed. Examples of the surface treatment include physical surface treatment such as plasma treatment, corona discharge treatment and flame treatment, and chemical surface treatment with a coupling agent, acid and alkali.

  Subsequently, the base material 2 is overlaid on the resin layer 9 of the intermediate member 7, and the resin layer 9 is cured in this state (FIG. 1 (c) and FIG. 1 (d)). Thereby, the hard coat layer 5 is formed, the hard coat layer 5 and the base material 2 are joined, and the metal foil 6, the graphene layer 4, the hard coat layer 5, and the base material 2 are stacked in this order. A laminate 8 is obtained.

  Subsequently, the metal foil 6 such as a copper foil overlaid on the graphene layer 4 in the laminate 8 is all removed by etching or the like (FIG. 1E). Thereby, the transparent conductive member 1 is obtained. When the transparent conductive member 1 is manufactured according to this embodiment, a transfer film is not required and the manufacturing process is simplified. For this reason, the manufacturing efficiency of the transparent conductive member 1 is improved. In addition, the hard coat layer 5 and the base material 2 are easily bonded and the bonding strength is increased, whereby the transparent conductive member 1 including the graphene layer 4 is easily obtained.

  When the resin layer 9 and the substrate 2 are stacked, the adhesion of the resin layer 9 so that the adhesion between the resin layer 9 and the substrate 2 is in the range of 0.01 to 4.0 N / cm. It is preferable that the property is adjusted. In this case, the hard coat layer 5 and the base material 2 can be easily bonded and the bonding strength is sufficiently high. Depending on the composition of the first reactive curable resin composition, the adhesiveness of the resin layer 9 can be obtained by volatilizing the solvent from the first reactive curable resin composition as necessary, or by using the first reactive curable resin composition. It can be easily adjusted by advancing the curing reaction of the resin composition.

  For example, in the case where the first reactive curable resin composition is a thermosetting resin composition, the thermosetting resin composition is dried by heating, or further undergoes a curing reaction to be in a semi-cured state ( By setting it to (B stage), the adhesiveness of a thermosetting resin composition is adjusted. When the first reactive curable resin composition is an active energy ray curable resin composition, the active energy ray curable resin composition is dried by heating or irradiated with active energy rays such as ultraviolet rays. Thus, the tackiness of the active energy ray-curable resin composition is adjusted by causing the curing reaction to proceed to a semi-cured state (B stage).

  Further, when the resin layer 9 is cured, for example, when the first reactive curable resin composition is a thermosetting resin composition, the resin layer 9 is heated and the first reactive curable resin is heated. In the case where the composition is an active energy ray-curable resin composition, the resin layer 9 is irradiated with active energy rays such as ultraviolet rays, so that the curing reaction of the resin layer 9 proceeds.

  The 2nd aspect of the manufacturing method of the transparent conductive member 1 is demonstrated with reference to FIG. In this embodiment, the hard coat layer 5 made of a cured product of the resin layer 9 is formed by curing the resin layer 9. In this embodiment, the transparent conductive member 1 of the second example is manufactured.

  In this embodiment, a metal foil 6 such as a copper foil is prepared, and the graphene layer 4 is formed on the metal foil 6 by vapor deposition or the like (FIG. 2A). A third reactive curable resin composition for forming the low refractive index layer 32 is applied on the graphene layer 4, and the third reactive curable resin composition is cured by a method according to the composition. As a result, the low refractive index layer 32 is formed. A second reactive curable resin composition for forming the high refractive index layer 31 is applied on the low refractive index layer 32, and the second resin composition is cured by a technique according to the composition. Thus, the high refractive index layer 32 is formed. Thereby, the antireflection layer 3 including the low refractive index layer 32 and the high refractive index layer 31 is formed (FIG. 2B). Subsequently, the first reactive curable resin composition for forming the hard coat layer 5 is applied on the antireflection layer 3, or the first reactive curable resin composition is further semi-cured. Thereby, a resin layer 9 made of the first reactive curable resin composition in an uncured state (A stage) or a semi-cured state (B stage) is formed, and the metal foil 6, the graphene layer 4, and the antireflection layer 3 are formed. And the intermediate member 7 provided with the resin layer 9 is obtained (FIG.2 (c)).

  In addition, when the above layers are formed from the reactive curable resin composition, a surface treatment may be performed on a surface overlapping with each layer before each layer is formed. In this case, it is possible to improve the wettability and adhesion between the layers. For example, the surface treatment may be performed on the surface of the graphene layer 4 that overlaps with the antireflection layer 3 before the antireflection layer 3 is formed. When the antireflection layer 3 includes the high refractive index layer 31 and the low refractive index layer 32, the low refractive index layer 32 and the high refractive index layer 31 are sequentially formed on the graphene layer 4. In this case, the high refractive index layer 31 has a high refractive index. Before the refractive index layer 31 is formed, the surface of the low refractive index layer 32 that overlaps the high refractive index layer 31 may be subjected to surface treatment. Further, before the resin layer 9 is formed, a surface treatment may be performed on the surface of the antireflection layer 3 that overlaps the resin layer 9. Examples of the surface treatment include physical surface treatment such as plasma treatment, corona discharge treatment and flame treatment, and chemical surface treatment with a coupling agent, acid and alkali.

  Subsequently, the base material 2 is overlaid on the resin layer 9 in the intermediate member 7, and the resin layer 9 is cured in this state (FIGS. 2D and 2E). Thereby, the hard coat layer 5 is formed and the hard coat layer 5 and the base material 2 are joined, and the metal foil 6, the graphene layer 4, the antireflection layer 3, the hard coat layer 5, and the base material 2 are in this order. A laminate 8 having a laminated structure is obtained.

  Subsequently, the metal foil 6 such as a copper foil overlaid on the graphene layer 4 in the laminate 8 is all removed by etching or the like (FIG. 2 (f)). Thereby, the transparent conductive member 1 is obtained. When the transparent conductive member 1 is manufactured according to this embodiment, a transfer film is not required and the manufacturing process is simplified. For this reason, the manufacturing efficiency of the transparent conductive member 1 is improved. In addition, the hard coat layer 5 and the base material 2 are easily bonded and the bonding strength is increased, whereby the transparent conductive member 1 including the graphene layer 4 is easily obtained.

  Also in this aspect, when the resin layer 9 and the substrate 2 are overlapped, the adhesive force between the resin layer 9 and the substrate 2 is in the range of 0.01 to 4.0 N / cm. It is preferable that the adhesiveness of the resin layer 9 is adjusted. In this case, the hard coat layer 5 and the base material 2 can be easily bonded and the bonding strength is sufficiently high. Depending on the composition of the first reactive curable resin composition, the adhesiveness of the resin layer 9 can be obtained by volatilizing the solvent from the first reactive curable resin composition as necessary, or by using the first reactive curable resin composition. It can be easily adjusted by advancing the curing reaction of the resin composition.

  For example, in the case where the first reactive curable resin composition is a thermosetting resin composition, the thermosetting resin composition is dried by heating, or further undergoes a curing reaction to be in a semi-cured state ( By setting it to (B stage), the adhesiveness of a thermosetting resin composition is adjusted. When the first reactive curable resin composition is an active energy ray curable resin composition, the active energy ray curable resin composition is dried by heating or irradiated with active energy rays such as ultraviolet rays. Thus, the tackiness of the active energy ray-curable resin composition is adjusted by causing the curing reaction to proceed to a semi-cured state (B stage).

  Further, when the resin layer 9 is cured, for example, when the first reactive curable resin composition is a thermosetting resin composition, the resin layer 9 is heated and the first reactive curable resin is heated. In the case where the composition is an active energy ray-curable resin composition, the resin layer 9 is irradiated with active energy rays such as ultraviolet rays, so that the curing reaction of the resin layer 9 proceeds.

  The 3rd aspect of the manufacturing method of the transparent conductive member 1 in this embodiment is demonstrated with reference to FIG. In this embodiment, the antireflection layer 3 including a cured product of the resin layer 9 is formed by curing the resin layer 9. In this aspect, the transparent conductive member 1 of the third example is manufactured.

  In this embodiment, a metal foil 6 such as a copper foil is prepared, and the graphene layer 4 is formed on the metal foil 6 by vapor deposition or the like (FIG. 3A). A third reactive curable resin composition for forming the low refractive index layer 32 is applied on the graphene layer 4, and the third reactive curable resin composition is cured by a method according to the composition. As a result, the low refractive index layer 32 is formed. Subsequently, the second reactive curable resin composition for forming the high refractive index layer 31 is applied on the low refractive index layer 32, or the second reactive curable resin composition is further semi-cured. Is done. Thereby, the resin layer 9 made of the second reactive curable resin composition in an uncured state (A stage) or a semi-cured state (B stage) is formed, and the metal foil 6, the graphene layer 4, the low refractive index layer The intermediate member 7 provided with 32 and the resin layer 9 is obtained (FIG. 3B).

  In addition, when the above layers are formed from the reactive curable resin composition, a surface treatment may be performed on a surface overlapping with each layer before each layer is formed. In this case, it is possible to improve the wettability and adhesion between the layers. That is, surface treatment may be performed on the surface of the graphene layer 4 that overlaps the low refractive index layer 32 before the low refractive index layer 32 is formed. Further, before the resin layer 9 is formed, the surface of the low refractive index layer 32 that overlaps the resin layer 9 may be subjected to surface treatment. Examples of the surface treatment include physical surface treatment such as plasma treatment, corona discharge treatment and flame treatment, and chemical surface treatment with a coupling agent, acid and alkali.

  Subsequently, the base material 2 is overlaid on the resin layer 9 in the intermediate member 7, and the resin layer 9 is cured in this state (FIGS. 3C and 3D). Thereby, the high refractive index layer 31 is formed, and the high refractive index layer 31 and the substrate 2 are bonded. In other words, the antireflection layer 3 including the high refractive index layer 31 and the low refractive index layer 32 (the antireflection layer 3 including the high refractive index layer 31 as a part thereof) is formed. And the base material 2 are joined, and a laminate 8 having a structure in which the metal foil 6, the graphene layer 4, the antireflection layer 3, and the base material 2 are laminated in this order is obtained.

  Subsequently, all of the metal foil 6 such as a copper foil overlaid on the graphene layer 4 in the laminate 8 is removed by an etching process or the like (FIG. 3E). Thereby, the transparent conductive member 1 is obtained. When the transparent conductive member 1 is manufactured according to this embodiment, a transfer film is not required and the manufacturing process is simplified. For this reason, the manufacturing efficiency of the transparent conductive member 1 is improved. In addition, the antireflection layer 3 and the base material 2 are easily bonded and the bonding strength is increased, whereby the transparent conductive member 1 including the graphene layer 4 can be easily obtained.

  Also in this aspect, when the resin layer 9 and the substrate 2 are overlapped, the adhesive force between the resin layer 9 and the substrate 2 is in the range of 0.01 to 4.0 N / cm. It is preferable that the adhesiveness of the resin layer 9 is adjusted. In this case, the antireflection layer 3 and the base material 2 can be easily bonded and the bonding strength is sufficiently high. Depending on the composition of the second reactive curable resin composition, the adhesiveness of the resin layer 9 can be obtained by volatilizing the solvent from the second reactive curable resin composition as necessary or by using the second reactive curable resin composition. It can be easily adjusted by advancing the curing reaction of the resin composition.

  For example, in the case where the second reactive curable resin composition is a thermosetting resin composition, the thermosetting resin composition is dried by heating, or further a curing reaction is allowed to proceed to a semi-cured state ( By setting it to (B stage), the adhesiveness of a thermosetting resin composition is adjusted. When the second reactive curable resin composition is an active energy ray curable resin composition, the active energy ray curable resin composition is dried by heating or irradiated with active energy rays such as ultraviolet rays. Thus, the tackiness of the active energy ray-curable resin composition is adjusted by causing the curing reaction to proceed to a semi-cured state (B stage).

  In addition, when the resin layer 9 is cured, for example, when the second reactive curable resin composition is a thermosetting resin composition, the resin layer 9 is heated to provide a second reactive curable resin. In the case where the composition is an active energy ray-curable resin composition, the resin layer 9 is irradiated with active energy rays such as ultraviolet rays, so that the curing reaction of the resin layer 9 proceeds.

  In any of the above embodiments, when the substrate 2 is formed of a flexible plastic film, the transparent conductive member 1 can be efficiently manufactured by a so-called roll to roll manufacturing method. FIG. 4 shows a manufacturing apparatus for manufacturing the transparent conductive member 1 by a roll to roll manufacturing method.

  The manufacturing apparatus shown in FIG. 4 winds and holds a long intermediate member 7 (see FIGS. 1B, 2C, and 3B) in a roll shape and holds the intermediate member 7 in a roll shape. A first feeding machine 10 for feeding and a second feeding machine 11 for winding and holding the long base material 2 in a roll shape and feeding the base material 2 are provided.

  The manufacturing apparatus further includes a pair of pressing rolls 12. Between the two pressing rolls 12, the intermediate member 7 fed from the first feeding machine 10 and the base material 2 fed from the second feeding machine 11 are semi-cured resin layer 9 and the base material in the intermediate member 7. 2 are supplied so as to face each other. The two pressing rolls 12 bring the resin layer 9 of the intermediate member 7 and the base material 2 into close contact with each other by applying a pressing force to the intermediate member 7 and the base material 2.

  Note that the manufacturing apparatus may include appropriate equipment for applying a pressing force to the intermediate member 7 and the base material 2 instead of the pressing roll 12.

  The manufacturing apparatus further includes a curing unit 13. The curing unit 13 is a facility that functions to cure the resin layer 9 by advancing the curing reaction of the resin layer 9 in the intermediate member 7. For example, when the resin layer 9 is formed from a thermosetting resin composition in a semi-cured state (B stage), the curing unit 13 is configured by a heating furnace that heats and cures the resin layer 9. For example, when the resin layer 9 is formed from an active energy ray-curable resin composition in a semi-cured state (B stage), the curing unit 13 is cured by irradiating the resin layer 9 with active energy rays such as ultraviolet rays. It comprises an exposure apparatus that includes a light source. For this reason, the laminated body 8 in which both were integrated is formed by passing the hardening part 13 in the state which the intermediate member 7 and the base material 2 were piled up (FIG.1 (d), FIG.2 (e), And FIG. 3 (d)).

  The manufacturing apparatus further includes an etching unit 14. The etching unit 14 is a facility that functions to perform an etching process on the laminate 8 led out from the curing unit 13. For example, the etching unit 14 includes an injection device that injects an etching solution such as a ferric chloride aqueous solution toward the metal foil 6 in the laminate 8. For this reason, when the laminate 8 passes through the etching portion 14, the metal foil 6 is removed from the laminate 8 by performing an etching process, whereby the transparent conductive member 1 is obtained (FIG. 1 (e), FIG. 2 (f) and FIG. 3 (e)).

  The manufacturing apparatus further includes a post-etching processing unit 15. The post-etching processing unit 15 performs post-processing such as cleaning on the transparent conductive member 1 after the etching process. For this reason, for example, the post-etching processing unit 15 injects cleaning water onto the transparent conductive member 1. And a drying furnace 152 for heating and drying the cleaned transparent conductive member 1.

  The manufacturing apparatus further includes a winder 16. The winder 16 winds and holds the transparent conductive member 1 in a roll shape. The transparent conductive member 1 wound up by the winder 16 is transferred to the next process as necessary.

  In the roll-to-roll manufacturing method using such a manufacturing apparatus, the intermediate member 7 and the substrate 2 are pressed and brought into close contact while the intermediate member 7 and the substrate 2 are continuously conveyed. Let Subsequently, the intermediate member 7 and the base material 2 are integrated by curing the resin layer 9 of the intermediate member 7 to form the laminate 8. The transparent conductive member 1 is produced by etching the metal foil 6 of the laminate 8. Further, the transparent conductive member 1 can be rolled up after being subjected to post-etching treatment. Thereby, the transparent conductive member 1 is manufactured very efficiently.

  In addition, the structure of the manufacturing apparatus for the roll to roll (Roll to Roll) manufacturing method is not restricted to what is shown in FIG. For example, each facility constituting the manufacturing apparatus may be replaced with another facility that exhibits an equivalent function, and facilities other than the above may be added as necessary. Moreover, the manufacturing apparatus shown in FIG. 4 may be appropriately divided into a plurality of apparatuses that perform processing by a roll-to-roll manufacturing method. For example, in the manufacturing apparatus shown in FIG. 4, a winder that once winds and holds the laminate 8 in a roll shape and a feeding machine that feeds the roll laminate 8 toward the etching unit 14 are provided. The manufacturing apparatus shown in FIG. 4 may be divided.

Example 1
A graphene layer 4 was formed on a copper foil having a thickness of 70 μm by a thermal CVD method. At this time, the copper foil was placed in the chamber, and the acetylene gas was charged into the chamber at a constant rate of 200 sccm (3.38 × 10 ⁻² Pa · m ³ / sec), while the copper foil was heated at 400 ° C. for 20 hours. The graphene was produced | generated on copper foil by heat-processing for minutes. Subsequently, the copper foil was naturally cooled to grow graphene in a uniformly arranged state. The cooling rate was 600 ° C./min. Thereby, the graphene layer 4 was formed.

On this graphene layer 4, 40 parts by mass of urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-15HA), 0.8 parts by mass of photopolymerizable initiator (manufactured by BASF, trade name Irgacure 184), A first reactive curable resin composition containing 59.2 parts by mass of methyl ethyl ketone was applied, dried at 80 ° C. for 5 minutes, and then semi-cured by irradiating with ultraviolet rays (integrated amount 50 mJ / cm ² ). A semi-cured state (B stage) resin layer 9 was formed.

By laminating a PET (polyethylene terephthalate) film having a thickness of 125 μm and a refractive index of 1.65 as the base material 2 on the resin layer 9, and subsequently drying at 80 ° C. for 5 minutes, and then irradiating with ultraviolet rays (integrated amount 50 mJ / cm ² ) The resin layer 9 was cured to form a hard coat layer 5 having a thickness of 6 μm, a refractive index of 1.58, and a pencil hardness of 3H, and the hard coat layer 5 and the substrate 2 were joined to obtain a laminate 8.

  Next, the copper foil was removed by subjecting this laminate 8 to an etching process at room temperature using a ferric chloride aqueous solution, followed by washing and drying. Thereby, the transparent conductive member 1 provided with the base material 2, the hard-coat layer 5, and the graphene layer 4 was obtained.

  When the conductivity of the transparent conductive member 1 was evaluated by a surface resistance measuring device (manufactured by Mitsubishi Chemical Corporation, model number Loresta EP MCP-T360), the surface resistance value was 27Ω / □. Moreover, when the transparency (antireflection performance) of the transparent conductive member 1 was evaluated with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number NDH-2000), the total light transmittance was 88%. When the mechanical strength of the transparent conductive member 1 was evaluated by a pencil hardness test (JIS K5600), the hardness was 3H. Thus, the transparent conductive member 1 provided with the outstanding electroconductivity, transparency, and mechanical strength was obtained.

(Example 2)
A graphene layer 4 was formed on a copper foil having a thickness of 35 μm by a thermal CVD method. At this time, the copper foil was placed in the chamber, and the acetylene gas was charged into the chamber at a constant rate of 200 sccm (3.38 × 10 ⁻² Pa · m ³ / sec), while the copper foil was heated at 400 ° C. for 20 hours. The graphene was produced | generated on copper foil by heat-processing for minutes. Subsequently, the copper foil was naturally cooled to grow graphene in a uniformly arranged state. The cooling rate was 600 ° C./min. Thereby, the graphene layer 4 was formed.

  On this graphene layer 4, 2.9 parts by mass of methyl silicate (manufactured by Mitsubishi Chemical Corporation, product number MS51), 7.5 parts by mass of hollow silica sol (manufactured by JGC Catalysts and Chemicals Co., Ltd., product number CS60-IPA), isopropyl alcohol Is coated with a third reactive curable resin composition containing 59.6 parts by mass and heated at 120 ° C. for 5 minutes to form a low refractive index layer 32 having a thickness of 100 nm and a refractive index of 1.38. did.

Subsequently, 3.0 parts by mass of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product number A-DPH) and 35.0 parts by mass of zirconia sol on the low refractive index layer 32, photopolymerization start A second reactive curable resin composition containing 0.2 parts by mass of an agent (trade name Irgacure 184, manufactured by BASF) and 1.8 parts by mass of methyl ethyl ketone 6 was applied and dried at 80 ° C. for 5 minutes. Thereafter, the film was cured by irradiating with ultraviolet rays (accumulated amount: 500 mJ / cm ² ) to form a high refractive index layer 31 having a thickness of 200 nm and a refractive index of 1.70. Thereby, the antireflection layer 3 composed of the high refractive index layer 31 and the low refractive index layer 32 was formed.

Subsequently, 30 parts by mass of urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-15HA) and 0.6 parts by mass of a photopolymerizable initiator (trade name Irgacure, manufactured by BASF) are provided on the antireflection layer 3. 184), a first reactive curable resin composition containing 69.4 parts by mass of methyl ethyl ketone was applied, dried at 80 ° C. for 5 minutes, and then irradiated with ultraviolet rays (accumulated amount 50 mJ / cm ² ). The resin layer 9 in a semi-cured state (B stage) was formed by curing.

The resin layer 9 is cured by superimposing a COP (cycloolefin polymer) film having a thickness of 100 μm and a refractive index of 1.53 on the resin layer 9 as a base material 2 and subsequently irradiating with ultraviolet rays (integrated amount of 500 mJ / cm ² ). A hard coat layer 5 having a thickness of 3 μm, a refractive index of 1.58, and a pencil hardness of 2H was formed, and the hard coat layer 5 and the substrate 2 were bonded to obtain a laminate 8.

  Next, the copper foil was removed by subjecting this laminate 8 to an etching process at room temperature using a ferric chloride aqueous solution, followed by washing and drying. Thereby, the transparent conductive member 1 provided with the base material 2, the antireflection layer 3, the hard coat layer 5, and the graphene layer 4 was obtained.

  When the conductivity of the transparent conductive member 1 was evaluated by a surface resistance measuring device (manufactured by Mitsubishi Chemical Corporation, model number Loresta EP MCP-T360), the surface resistance value was 25Ω / □. Moreover, when the transparency (antireflection performance) of the transparent conductive member 1 was evaluated with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number NDH-2000), the total light transmittance was 93%. Further, when the mechanical strength of the transparent conductive member 1 was evaluated by a pencil hardness test (JIS K5600), the hardness was 2H. Thus, the transparent conductive member 1 provided with the outstanding electroconductivity, transparency, and mechanical strength was obtained.

(Example 3)
A graphene layer 4 was formed on a copper foil having a thickness of 70 μm by a thermal CVD method. At this time, the copper foil was placed in the chamber, and the acetylene gas was charged into the chamber at a constant rate of 200 sccm (3.38 × 10 ⁻² Pa · m ³ / sec), while the copper foil was heated at 400 ° C. for 20 hours. The graphene was produced | generated on copper foil by heat-processing for minutes. Subsequently, the copper foil was naturally cooled to grow graphene in a uniformly arranged state. The cooling rate was 600 ° C./min. Thereby, the graphene layer 4 was formed.

  On this graphene layer 4, 2.9 parts by mass of methyl silicate (manufactured by Mitsubishi Chemical Corporation, product number MS51), 7.5 parts by mass of hollow silica sol (manufactured by JGC Catalysts and Chemicals Co., Ltd., product number CS60-IPA), isopropyl alcohol Is coated with a third reactive curable resin composition containing 59.6 parts by mass and heated at 120 ° C. for 5 minutes to form a low refractive index layer 32 having a thickness of 100 nm and a refractive index of 1.38. did.

Subsequently, 3.0 parts by mass of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product number A-DPH) and 35.0 parts by mass of zirconia sol on the low refractive index layer 32, photopolymerization start A second reactive curable resin composition containing 0.2 parts by weight of an agent (trade name Irgacure 184, manufactured by BASF) and 61.8 parts by weight of methyl ethyl ketone was applied and dried at 80 ° C. for 5 minutes. The resin layer 9 in a semi-cured state (B stage) was formed by being semi-cured by irradiating with ultraviolet rays (integrated amount 50 mJ / cm ² ).

A PC (polycarbonate) film having a thickness of 100 μm and a refractive index of 1.59 is superimposed on the resin layer 9 as a base material 2, and subsequently the resin layer 9 is cured by irradiation with ultraviolet rays (integrated amount of 500 mJ / cm ² ) to obtain a thickness of 2 μm. A high refractive index layer 31 having a refractive index of 1.70 and a pencil hardness of 2H was formed. Thereby, while forming the antireflection layer 3 which consists of the high refractive index layer 31 and the low refractive index layer 32, this antireflection layer 3 and the base material 2 were joined, and the laminated body 8 was obtained.

  Next, the copper foil was removed by subjecting this laminate 8 to an etching process at room temperature using a ferric chloride aqueous solution, followed by washing and drying. Thereby, the transparent conductive member 1 provided with the base material 2, the antireflection layer 3, the hard coat layer 5, and the graphene layer 4 was obtained.

  When the conductivity of the transparent conductive member 1 was evaluated by a surface resistance measuring device (manufactured by Mitsubishi Chemical Corporation, model number Loresta EP MCP-T360), the surface resistance value was 32Ω / □. Further, when the transparency (antireflection performance) of the transparent conductive member 1 was evaluated by a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number NDH-2000), the total light transmittance was 94%. Further, when the mechanical strength of the transparent conductive member 1 was evaluated by a pencil hardness test (JIS K5600), the hardness was 2H. Thus, the transparent conductive member 1 provided with the outstanding electroconductivity, transparency, and mechanical strength was obtained.

DESCRIPTION OF SYMBOLS 1 Transparent conductive member 2 Base material 3 Antireflection layer 4 Graphene layer 5 Hard coat layer 6 Metal foil 7 Intermediate member 8 Laminate 9 Resin layer

Claims (4)

Preparing the metal foil,
Forming a graphene layer on the metal foil;
A step of obtaining an intermediate member by forming a resin layer made of a reactive curable resin composition in an uncured state or a semi-cured state directly or via one or a plurality of layers on the graphene layer,
A transparent conductive member comprising the steps of: obtaining a laminate by stacking a transparent base material on the resin layer of the intermediate member, and subsequently curing the resin layer; and removing the metal foil from the laminate Production method. The manufacturing method of the transparent conductive member of Claim 1 which forms the hard-coat layer which consists of the hardened | cured material of this resin layer by hardening the said resin layer. The manufacturing method of the transparent conductive member of Claim 1 which forms the antireflection layer containing the hardened | cured material of this resin layer by hardening the said resin layer. A metal foil, a graphene layer, and a resin layer, wherein the graphene layer is formed on the metal foil and interposed between the metal foil and the resin layer, and the resin layer is uncured or semi-cured An intermediate member comprising the reactive curable resin composition in a state.

Images