WO2013141275A1 - Stratifié conducteur transparent et panneau tactile - Google Patents

Stratifié conducteur transparent et panneau tactile Download PDF

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Publication number
WO2013141275A1
WO2013141275A1 PCT/JP2013/057990 JP2013057990W WO2013141275A1 WO 2013141275 A1 WO2013141275 A1 WO 2013141275A1 JP 2013057990 W JP2013057990 W JP 2013057990W WO 2013141275 A1 WO2013141275 A1 WO 2013141275A1
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Prior art keywords
film
transparent conductive
layer
barrier
metal
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PCT/JP2013/057990
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English (en)
Japanese (ja)
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昌哉 中山
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富士フイルム株式会社
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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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/02—Layer formed of wires, e.g. mesh
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material

Definitions

  • the present invention relates to a transparent conductive laminate and a touch panel.
  • ITO glass and ITO film are widely used as transparent conductive materials for touch panels, but indium metal is a rare metal and has low color transmittance and low resistance due to low light transmittance in the long wavelength region. Since there are problems such as the necessity of high-temperature heat treatment and low bending resistance, various alternative materials for ITO glass and ITO film have been studied.
  • conductive materials using conductive metal nanowires are known.
  • Metal nanowires are excellent in terms of transparency, low resistance, and reduction in the amount of metal used, so ITO glass and Expectation as an alternative material for ITO film is increasing.
  • ITO glass and Expectation as an alternative material for ITO film is increasing.
  • Capacitive touch panels are required to be thinner, lighter, and less expensive.
  • the substrate of the transparent substrate is changed to a film, and the cover lens (transparent protective substrate) of the touch panel is changed from a conventional glass to a film. It has been proposed to reduce the thickness, weight, and cost (for example, Patent Document 2).
  • the capacitive touch panel the transparent substrate and the cover lens (transparent protective substrate) are changed from glass to a polymer film, and the transparent conductive film having metal nanowires (
  • the touch panel becomes inoperable or malfunctions when driven under high temperature and high humidity.
  • the resistance value of the transparent conductive film which has metal nanowire rose while driving under high temperature, high humidity.
  • this resistance increase is found to be a phenomenon that occurs when a voltage is applied between line electrodes patterned in a line shape under high temperature and high humidity. Further, this resistance increase is caused by low haze, high transmittance, It has been found that this phenomenon appears prominently in a transparent conductive film using metal nanowires having an average minor axis length of 50 nm or less enabling low resistance.
  • An object of the present invention is to solve the above-described problems, and specifically, a thin and light transparent conductive laminate having low resistance and no haze even when a voltage is applied under high temperature and high humidity, and its transparent conductive It is an object of the present invention to provide a touch panel that is thin, lightweight, and has excellent visibility, which does not cause malfunction even when driven under high temperature and high humidity, by using lamination.
  • Means for solving the above-mentioned problems are the transparent conductive laminates and touch panels [1] and [9] below, and preferably the transparent conductive laminates and touch panels [2] to [10] below.
  • a transparent conductive laminate characterized by the following.
  • the pattern of the first barrier film has a transparent film made of resin on the surface opposite to the surface on which the transparent conductive film is formed, and on the side opposite to the surface adjacent to the adhesive layer of the second barrier film
  • a thin and lightweight transparent conductive laminate that does not increase resistance even when a voltage is applied under high temperature and high humidity, and has a low haze, and the transparent conductive laminate is used to drive under high temperature and high humidity.
  • FIG. 5 is a cross-sectional view taken along line X-X ′ in FIG. 4. It is a cross-sectional schematic diagram of the touch panel of a comparative example.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • FIG. 1 shows a schematic diagram of an example of the transparent conductive laminate of the present invention.
  • the transparent conductive laminate of the present invention includes a first barrier film, a patterned transparent conductive film containing metal nanowires having an average minor axis length of 5 to 50 nm formed directly on the surface of the first barrier film, An adhesive layer covering the transparent conductive film; and a second barrier film adjacent to the adhesive layer.
  • the transparent conductive film is provided on the surface of the first barrier film, but the transparent conductive film may be provided via another layer.
  • the other layer includes an embodiment in which one or more layers or films are provided on the surface of the first barrier film and a transparent conductive film is provided on the surface.
  • a transparent conductive film on the surface of the first barrier film.
  • the patterned transparent conductive film is patterned in a line shape in a conductive area and a non-conductive area, and metal nanowires having an average minor axis length of 5 to 50 nm are contained in the conductive area.
  • the water vapor transmission rates of the first and second barrier films are each 0.1 g / (m 2 ⁇ day) or less.
  • the first barrier film is formed directly (adjacent) to the pattern transparent conductive film, and the second barrier film is adjacent to the adhesive layer by adhering to the adhesive layer.
  • the first and second barrier films have a function of preventing moisture entering from the outside from entering the pattern transparent conductive film, and the water vapor permeability of the first and second barrier films is 0.1 g. / (m 2 ⁇ day) or less, is preferably 0.05 g / (m 2 ⁇ day) or less. Although there is no specific lower limit of the water vapor transmission rate, it is generally 0.000001 g / (m 2 ⁇ day) or more.
  • the first barrier film may have a transparent film made of a resin that supports the first barrier film on the surface opposite to the surface on which the patterned transparent conductive film is formed.
  • the whole including the barrier film is defined as a substrate.
  • a thing with a high light transmittance is good, 70% or more is preferable and 80% or more is more preferable.
  • Other functional layers such as an undercoat layer may be provided between the transparent film and the first barrier film.
  • Other functional layers include, for example, matting agent layers, protective layers, solvent resistant layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers. , Antifouling layer, printed layer, easy adhesion layer and the like.
  • the patterned transparent conductive film is formed directly on the surface of the first barrier film or via another layer, that is, the patterned transparent conductive film is formed on the transparent film or functional layer that supports the first barrier film. Also good.
  • the second barrier film has a transparent protective film made of a resin supporting the second barrier film on the surface opposite to the surface adjacent to the adhesive layer, and includes the second barrier film and the transparent protective film.
  • a cover film a thing with a high light transmittance is good, 70% or more is preferable and 80% or more is more preferable.
  • the surface of the transparent protective film opposite to the side on which the second barrier film is formed has a hard coat layer.
  • a hard coat layer having a hardness of 3H or more is preferable.
  • Other functional layers such as an undercoat layer may be provided between the transparent protective film and the second barrier film and between the transparent protective film and the hard coat layer.
  • Other functional layers include, for example, matting agent layers, protective layers, solvent resistant layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like. These may be a single layer or a plurality of layers. These may be a single layer or a plurality of layers. Details of the first and second barrier films will be described later.
  • the adhesive layer is composed of an adhesive.
  • the present inventor found that moisture in the outside air also entered from the adhesive layer, and found that this had an effect on the increase in resistance of the patterned transparent conductive film. For this reason, it is preferable that the water absorption rate of an adhesion layer is 2.0% or less, It is more preferable that it is 1.0% or less, It is especially preferable that it is 0.9% or less.
  • the adhesive strength of the adhesive layer is preferably 15 N / 25 mm or more, more preferably 30 to 50 N / 25 mm, and more preferably 30 to 42 N / 25 mm. It is particularly preferred. By setting the adhesive strength to 15 N / 25 mm or more, peeling between the second barrier film and the adhesive layer does not occur, and an effect of preventing moisture from entering from the interface between the second barrier film and the adhesive layer is obtained. Further, when the thickness is 30 N / 25 mm or more, a strong effect can be obtained in preventing moisture from entering from the interface between the second barrier film and the adhesive layer, and an increase in resistance of the patterned transparent conductive film can be prevented. However, when it exceeds 50 N / 25 mm, the flexibility of the transparent conductive laminate may be inferior.
  • First and second barrier films In this invention, it has the 1st barrier film adjacent to a pattern transparent conductive film, and the 2nd barrier film adjacent to an adhesion layer.
  • first and second barrier films are also referred to as “barrier films”.
  • the barrier film preferably has an inorganic barrier layer from the viewpoint of water vapor barrier performance.
  • an inorganic barrier layer is not necessarily required as long as the water vapor permeability of the barrier film satisfies 0.1 g / (m 2 ⁇ day) or less.
  • the barrier film may have a structure in which at least one inorganic barrier layer or an organic layer described later is laminated.
  • the inorganic barrier layer and the organic layer may be stacked in this order, or the organic layer and the inorganic barrier layer may be stacked in this order.
  • the uppermost layer may be an inorganic barrier layer or an organic layer.
  • first and second barrier films may be the same barrier film or different barrier films.
  • the inorganic barrier layer is usually a thin film layer made of a metal compound.
  • a method for forming the inorganic barrier layer any method can be used as long as it can form a target thin film (layer).
  • PVD physical vapor deposition method
  • CVD chemical vapor deposition methods
  • liquid phase growth method such as plating and a sol-gel method.
  • the component contained in the inorganic barrier layer is not particularly limited as long as it satisfies the above performance, but for example, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, or a metal oxycarbide, Si, Al, An oxide, nitride, carbide, oxynitride, oxycarbide, or the like containing one or more metals selected from In, Sn, Zn, Ti, Cu, Ce, and Ta can be preferably used.
  • a metal oxide, nitride or oxynitride selected from Si, Al, In, Sn, Zn and Ti is preferable, and a metal oxide, nitride or oxynitride of Si or Al is particularly preferable, Specifically, SiON (silicon nitride oxide) is preferable.
  • SiON silicon nitride oxide
  • the smoothness of the inorganic barrier layer formed according to the present invention is preferably less than 20 nm, more preferably 1 nm or less, as an average roughness (Ra value) of 1 ⁇ m square.
  • the inorganic barrier layer is preferably formed in a clean room.
  • the degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
  • the thickness of the inorganic barrier layer is not particularly limited, it is usually in the range of 5 to 500 nm, preferably 10 to 300 nm per layer.
  • the inorganic barrier layer may have a laminated structure including a plurality of sublayers. In this case, each sublayer may have the same composition or a different composition. Even in the case of a laminated structure composed of a plurality of sublayers, the preferable thickness as the total thickness of the inorganic barrier film is usually 10 to 2000 nm, more preferably 20 to 300 nm. If the total thickness of the inorganic barrier layer exceeds 300 nm, the flexibility such as the cracking of the inorganic barrier layer is likely to occur when it is bent. As disclosed in US Patent Publication No. 2004-46497, a layer in which the interface between the inorganic barrier layer and the organic layer is not clear and the composition continuously changes in the layer thickness direction may be used.
  • the organic layer in the present invention is preferably an organic layer containing an organic polymer as a main component.
  • the main component means that the first component of the component constituting the organic layer is an organic polymer, and usually 80% by mass or more of the component constituting the organic layer is an organic polymer.
  • the organic polymer include polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, and polyurethane.
  • the organic layer may be composed of a single material or a mixture, or may be a laminated structure composed of a plurality of sublayers. In this case, each sublayer may have the same composition or different compositions. Further, as disclosed in US Patent Publication No. 2004-46497, a layer in which the interface between the inorganic barrier layer and the organic layer is not clear and the composition changes continuously in the film thickness direction may be used.
  • the organic layer in the present invention is preferably formed by curing a polymerizable composition containing a polymerizable compound.
  • the polymerizable compound is preferably a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group, more preferably a compound having an ethylenically unsaturated bond at the terminal or side chain, and / or A compound having an epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred.
  • Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds, acrylamide compounds, styrene compounds, maleic anhydride, etc., (meth) acrylate compounds and / or Styrenic compounds are preferred, and (meth) acrylate compounds are more preferred.
  • (meth) acrylate compound As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
  • styrene compound styrene, ⁇ -methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.
  • the polymerizable composition when a polymerizable composition containing a polymerizable compound is applied and cured to form an organic layer, the polymerizable composition may contain a polymerization initiator.
  • a polymerization initiator for example, a polymerizable initiator described in JP 2012-025099 A can be used.
  • a method for forming the organic layer is not particularly defined, but can be formed by, for example, a solution coating method or a vacuum film forming method. Specifically, the organic layer is formed by a method described in JP2012-025099A. can do. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a method described in US Pat. No. 2,681,294. It can be applied by an extrusion coating method using a hopper.
  • a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as disclosed in Japanese Patent Application Laid-Open Nos. 2000-323273 and 2004-25732 may be used.
  • the thickness of the organic layer is not particularly limited, but is usually in the range of 10 to 3000 nm, preferably 100 to 2000 nm per layer.
  • the organic layer and the inorganic barrier layer can be laminated by repeatedly laminating the organic layer and the inorganic barrier layer sequentially in accordance with a desired layer configuration.
  • the inorganic barrier layer is formed by a vacuum film formation method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, or a plasma CVD method
  • the organic layer can also be formed by a vacuum film formation method such as the flash vapor deposition method.
  • the pressure is more preferably 100 Pa or less, more preferably 50 Pa or less, and further preferably 20 Pa or less.
  • the present invention can exhibit high barrier properties when at least two organic layers and at least two inorganic barrier layers are alternately laminated.
  • the mode of alternately laminating is that the first barrier film is laminated in the order of the organic layer / inorganic barrier layer / organic layer / inorganic barrier layer from the transparent film side supporting the first barrier film, but the inorganic barrier layer / organic layer
  • the layers may be laminated in the order of / inorganic barrier layer / organic layer.
  • the barrier film may have a functional layer.
  • the functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627.
  • Examples of functional layers other than these include matting agent layers, protective layers, solvent resistant layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers. , Antifouling layer, printed layer, easy adhesion layer and the like.
  • each of the entire first barrier film and the entire second barrier film is not particularly limited and can be appropriately selected depending on the purpose.
  • the barrier layer is an organic layer or a laminate of an organic layer and an inorganic barrier layer.
  • the thickness is preferably 50 to 10,000 nm, more preferably 100 to 5000 nm.
  • a preferable range of the total thickness of the inorganic barrier layer is 10 to 2000 nm, and more preferably 20 to 300 nm.
  • the preferred thickness of the barrier layer is in the range of 10 to 2000 nm, more preferably 20 to 300 nm. If the thickness exceeds 300 nm, as described above, the flexibility such as cracking of the inorganic barrier layer when bent is deteriorated.
  • Transparent film (support) The transparent film supports the first barrier film.
  • the light transmittance of the transparent film is preferably 65% or more, and more preferably 70% or more.
  • the material for the transparent film is not particularly limited as long as it is a flexible polymer (resin).
  • it can be selected from a polymer film (used to include both a resin and a polymer), a polymer sheet, and a polymer molded body.
  • a polymer film used to include both a resin and a polymer
  • a polymer sheet used to include both a resin and a polymer
  • a polymer molded body examples include polyethylene terephthalate (PET), polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, FRP (fiber reinforced plastic), A film containing polymethyl methacrylate resin (PMMA) or the like as a main component is included.
  • PET polyethylene terephthalate
  • PES polycarbonate
  • polyethersulfone polyester
  • acrylic resin vinyl chloride resin
  • aromatic polyamide resin polyamideimide
  • polyimide polyimide
  • FRP fiber reinforced plastic
  • the surface of the transparent film may be subjected to a surface treatment for improving adhesion with the first barrier film.
  • the surface treatment is performed by a physical or chemical method.
  • the physical method include a method of imparting an anchor effect by roughening the surface of the support by a sandblast method or the like.
  • the chemical method include a method of activating the support surface by plasma treatment or corona treatment, a method of chemically increasing adhesion to the conductive film by silane coupling agent treatment, and a method of providing an undercoat layer such as a primer layer. Etc.
  • the undercoat layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the undercoat layer may be provided with ultraviolet absorbing ability, antioxidant ability, and the like. Among these, plasma processing is particularly preferable in terms of simplicity and processing uniformity.
  • the thickness of the transparent film is not particularly limited.
  • the average thickness is preferably 0.01 mm to 10 mm, and more preferably 0.02 mm to 1 mm. However, it is not limited to this range.
  • the transparent protective film supports the second barrier film.
  • the light transmittance of the transparent protective film is preferably 65% or more, and more preferably 70% or more.
  • the material for the transparent protective film is not particularly limited as long as it is a polymer.
  • a flexible polymer may be used.
  • it can be selected from a polymer film (used to include both a resin and a polymer), a polymer sheet, and a polymer molded body.
  • Examples of usable polymer films include polyethylene terephthalate (PET), polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, FRP (fiber reinforced plastic), A film containing polymethyl methacrylate resin (PMMA) or the like as a main component is included.
  • the transparent protective film is preferably provided with a hard coat layer for preventing scratches on the surface in view of its function.
  • the material of the hard coat layer is not limited, but a material having a pencil hardness of 3H or higher and a light transmittance of 70% or higher is preferable.
  • the surface of the transparent protective film may be subjected to a surface treatment for improving adhesion with the second barrier film.
  • the surface treatment is performed by a physical or chemical method.
  • the physical method include a method of imparting an anchor effect by roughening the surface of the substrate by a sandblast method or the like.
  • the chemical method include a method of activating the substrate surface by plasma treatment or corona treatment, a method of chemically increasing adhesion to the conductive film by silane coupling agent treatment, and a method of providing an undercoat layer such as a primer layer. Etc.
  • the undercoat layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the undercoat layer may be provided with ultraviolet absorbing ability, antioxidant ability, and the like. Among these, plasma processing is particularly preferable in terms of simplicity and processing uniformity.
  • the thickness of the transparent protective film is not particularly limited.
  • the average thickness is preferably 0.01 mm to 10 mm, and more preferably 0.1 mm to 3 mm. However, it is not limited to this range.
  • the patterned transparent conductive film of the present invention refers to a transparent conductive film patterned in a conductive area and a non-conductive area.
  • the conductive area and the non-conductive area may be patterned in a line shape or may not necessarily be patterned in a line shape.
  • the non-conductive area indicates an area having a sheet resistance of 10 7 ⁇ / ⁇ or more.
  • the patterned transparent conductive film used in the present invention is formed from a composition for forming a transparent conductive film containing metal nanowires. In addition, although metal nanowire may not remain by etching etc. in the said nonelectroconductive area, it may remain.
  • the metal nanowire refers to a metal nanowire having conductivity and having a shape in which the length in the major axis direction is sufficiently longer than the diameter (length in the minor axis direction). It may be a solid fiber or a hollow fiber.
  • At least one metal selected from the group consisting of at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period, and at least one type selected from the group 2 to group 14 Metal is more preferred, at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period, and the second group, the eighth group, the ninth group, the tenth group, the eleventh group, At least one metal selected from Group 12, Group 13, and Group 14 is more preferable, and it is particularly preferable that it is included as a main component.
  • Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. And alloys thereof. Among these, silver and an alloy with silver are particularly preferable in terms of excellent conductivity. Examples of the metal used in the alloy with silver include platinum, osmium, palladium, iridium, tin, bismuth, and nickel. These may be used alone or in combination of two or more.
  • the said metal nanowire there is no restriction
  • the cross-sectional shape of the metal nanowires can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing a cross-section sliced by a microtome with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average minor axis length (sometimes referred to as “average minor axis length” or “average diameter”) of the metal nanowire is 5 to 50 nm, preferably 5 to 25 nm, and more preferably 5 to 20 nm. If the average minor axis length is less than 5 nm, the oxidation resistance may deteriorate and the durability may deteriorate. On the other hand, when the average minor axis length is 50 nm or more, scattering of the metal nanowires increases, and the haze value of the conductive film may increase. In particular, by setting the average minor axis length to 25 nm or less, the scattering of the metal nanowires can be reduced, and the haze value of the conductive film is greatly improved (reduced).
  • a touch panel using a conductive film having a small haze can eliminate the pattern appearance (bone appearance) of the conductive film and improve the visibility of the touch panel.
  • the haze value of the conductive film is preferably less than 2.5%, and particularly preferably less than 1.5% from the viewpoint of visibility.
  • the average minor axis length of the metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis length was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the shortest axis.
  • the average major axis length of the metal nanowire (sometimes referred to as “average major axis length” or “average length”) is preferably 5 ⁇ m or more, more preferably 5 ⁇ m to 40 ⁇ m, and more preferably 5 ⁇ m to 30 ⁇ m. Is more preferable. If the average major axis length is less than 5 ⁇ m, it may be difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 ⁇ m, the metal nanowires are too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
  • the average major axis length of the metal nanowires is observed, for example, using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX), and 300 metal nanowires are observed. The average major axis length was determined. In addition, when the said metal nanowire was bent, the circle
  • TEM transmission electron microscope
  • the coefficient of variation of the short axis length of the metal nanowire is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.
  • the coefficient of variation is obtained by measuring the short axis length (diameter) of 300 nanowires randomly selected from the electron microscope (TEM) image, and calculating the standard deviation and the average value for the 300 nanowires. It was.
  • the metal nanowire is not particularly limited and may be produced by any method, but is preferably produced by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved as follows. Moreover, after forming metal nanowire, it is preferable to perform a desalting process by a conventional method from a viewpoint of dispersibility and the temporal stability of an electroconductive area.
  • a method for producing metal nanowires JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, and JP2010-86714A are disclosed. Etc. can be used.
  • the solvent used for the production of the metal nanowire is preferably a hydrophilic solvent, and examples thereof include water, alcohols, polyhydric alcohols, ethers and ketones, and these may be used alone. In addition, two or more kinds may be used in combination.
  • alcohols include methanol, ethanol, normal propanol, isopropanol, and butanol.
  • the polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and the like.
  • ethers include dioxane and tetrahydrofuran.
  • ketones include acetone and methyl ethyl ketone. When heating, the heating temperature is preferably 250 ° C.
  • the boiling point means a temperature at which the vapor pressure of the reaction solvent becomes equal to the pressure in the reaction vessel. It is preferable to set the temperature to 20 ° C. or higher because formation of metal nanowires is promoted and manufacturing process time can be shortened.
  • the monodispersity of the short-axis length and long-axis length of metal nanowire improves, and it is suitable from a transparency and electroconductive viewpoint.
  • the temperature may be changed during the manufacturing process of the metal nanowires, and changing the temperature in the middle is effective in controlling nucleation, suppressing renucleation, and improving monodispersity by promoting selective growth. There may be.
  • the heating is preferably performed by adding a reducing agent.
  • the reducing agent is not particularly limited and can be appropriately selected from those usually used.
  • borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, Aromatic amines, aralkylamines, alcohols, polyhydric alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, glutathione and the like can be mentioned.
  • reducing sugars, sugar alcohols as derivatives thereof, and polyhydric alcohols are particularly preferable.
  • there is a compound that functions as a dispersant or a solvent as a function there is a compound that functions as a dispersant or a solvent as a function, and can be preferably used in the same manner.
  • a dispersant and a halogen compound or metal halide fine particles are preferable to add.
  • the timing of addition of the dispersant may be before the addition of the reducing agent, at the same time as the addition of the reducing agent, or after the addition of the reducing agent, before the addition of the metal ion or metal halide fine particles, or before the addition of the metal ion or halogen. It may be performed simultaneously with the addition of metal halide fine particles or after addition of metal ions or metal halide fine particles.
  • the step of adding the dispersant may be added before the particles are prepared and may be added in the presence of the dispersed polymer, or may be added after the particles are prepared in order to control the dispersion state.
  • the amount needs to be changed depending on the short axis length and the long axis length of the metal nanowires required. This is because the amount of dispersant added affects the amount and size of the metal particles that are the core of the metal nanowire, and the amount and size of the metal particles that are the core of the metal nanowire are the short axis of the metal nanowire. This is considered to be due to the influence on the length and the long axis length.
  • dispersant examples include amino group-containing compounds, thiol group-containing compounds, sulfide group-containing compounds, amino acids or derivatives thereof, peptide compounds, polysaccharides, polysaccharide-derived natural polymers, synthetic polymers, or these. And polymers such as gels.
  • various polymer compounds used as a dispersant are compounds included in the polymer described later.
  • polymer suitably used as a dispersant examples include gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylene amine, polyalkylene amine, partial alkyl esters of polyacrylic acid, polyvinyl pyrrolidone, and polyvinyl pyrrolidone structures, which are protective colloidal polymers.
  • a polymer having a hydrophilic group such as a copolymer containing, polyacrylic acid having an amino group or a thiol group, is preferably mentioned.
  • the polymer used as the dispersant has a weight average molecular weight (Mw) measured by GPC method of preferably 3000 or more and 300000 or less, more preferably 5000 or more and 100000 or less.
  • the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
  • the shape of the metal nanowire obtained by the kind of dispersing agent to be used can be changed.
  • the halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, or iodine, and can be appropriately selected according to the purpose.
  • sodium bromide, sodium chloride, sodium iodide, potassium iodide Compounds that can be used in combination with alkali halides such as potassium bromide, potassium chloride, potassium iodide and the following dispersants are preferred.
  • Some halogen compounds may function as a dispersant, but can be preferably used in the same manner.
  • silver halide fine particles may be used, or both a halogen compound and silver halide fine particles may be used.
  • a single substance having both functions may be used as the dispersant and the halogen compound. That is, by using a halogen compound having a function as a dispersant, the functions of both the dispersant and the halogen compound are expressed with one compound.
  • the halogen compound having a function as a dispersant include, for example, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium iodide, dodecyltrimethyl containing amino group and bromide ion or chloride ion and iodide ion.
  • the metal nanowire preferably contains as little inorganic ions as possible, such as alkali metal ions, alkaline earth metal ions, and halide ions.
  • the electrical conductivity when the metal nanowire is an aqueous dispersion is preferably 1 mS / cm or less, more preferably 0.1 mS / cm or less, and even more preferably 0.05 mS / cm or less.
  • the viscosity at 20 ° C. when the metal nanowires are dispersed in water is preferably 0.5 mPa ⁇ s to 100 mPa ⁇ s, more preferably 1 mPa ⁇ s to 50 mPa ⁇ s.
  • the aspect ratio of the metal nanowire is not particularly limited as long as it is 10 or more, and can be appropriately selected according to the purpose. More preferred is 10,000 to 100,000.
  • the aspect ratio generally means the ratio between the long side and the short side of a fibrous material (ratio of average major axis length / average minor axis length).
  • ratio of average major axis length / average minor axis length There is no restriction
  • the aspect ratio of the whole metal nanowire can be estimated by measuring the average major axis length and the average minor axis length of the metal nanowire separately.
  • the outer diameter of this tube-shaped metal nanowire is used as a diameter for calculating the said aspect ratio.
  • the metal nanowire having an aspect ratio of 10 or more is preferably contained in the coating liquid for all patterns transparent conductive film in a volume ratio of 5% or more, more preferably 50% or more, and more preferably 80% or more. It is particularly preferred that it be included.
  • the ratio of these metal nanowires may be referred to as “the ratio of metal nanowires”. If the ratio of the metal nanowires is less than 5%, the conductive material that contributes to the conductivity may decrease and the conductivity may decrease. At the same time, a voltage concentration may occur because a dense network cannot be formed. , Durability may be reduced.
  • particles having a shape other than metal nanowires are not preferable because they do not greatly contribute to conductivity and have absorption. In particular, when the particles other than the metal conductive fibers are metal and the plasmon absorption such as a spherical shape is strong, the transparency may be deteriorated.
  • the aspect ratio By setting the aspect ratio to 10 or more, a network in which metal nanowires are in contact with each other is easily formed, and a conductive layer having high conductivity can be easily obtained. Further, by setting the aspect ratio to 100,000 or less, for example, in a coating liquid when a conductive layer is provided on a substrate by coating, stable coating without risk of entanglement and aggregation of metal nanowires. Since a liquid is obtained, manufacture becomes easy. In addition, when the ratio of the metal nanowire is less than 5%, the conductive material that contributes to conductivity may decrease and conductivity may decrease, and at the same time, a dense network cannot be formed. May occur and durability may be reduced.
  • particles having a shape other than metal nanowires are not preferable because they do not greatly contribute to conductivity and have absorption.
  • the plasmon absorption such as a spherical shape is strong, the transparency may be deteriorated.
  • the ratio of the metal nanowire is, for example, when the metal nanowire is a silver nanowire, the silver nanowire aqueous dispersion is filtered to separate the silver nanowire from the other particles.
  • the ratio of metal nanowires can be determined by measuring the amount of silver remaining on the filter paper and the amount of silver transmitted through the filter paper using an ICP emission analyzer. By observing the metal nanowires remaining on the filter paper with a TEM, observing the average minor axis length of 300 metal nanowires, and examining the distribution thereof, the average minor axis length is 200 nm or less, and the average It confirms that it is a metal nanowire whose major axis length is 1 micrometer or more.
  • the filter paper measures the longest axis of particles other than metal nanowires having an average minor axis length of 200 nm or less and an average major axis length of 1 ⁇ m or more in a TEM image, and more than twice the longest axis. It is preferable to use a metal nanowire having a length equal to or shorter than the shortest length of the major axis of the metal nanowire.
  • the average minor axis length and the average major axis length of the metal nanowire can be obtained by observing a TEM image or an optical microscope image using, for example, a transmission electron microscope (TEM) or an optical microscope.
  • TEM transmission electron microscope
  • the average minor axis length and the average major axis length of the metal nanowire are obtained by observing 300 metal nanowires with a transmission electron microscope (TEM) and calculating the average value. is there.
  • the coating amount of the metal nanowires is preferably patterned transparent conductive film in 0.001 ⁇ 0.1g / cm 2, more preferably 0.002 ⁇ 0.05g / cm 2, 0.003 ⁇ 0.04g / cm 2 Is particularly preferred.
  • composition for forming transparent conductive film The composition for transparent conductive film formation which forms the said pattern transparent conductive film may be a photosensitive composition.
  • the photosensitive composition may be negative or positive.
  • examples of a composition containing at least a photosensitive composition, a sol-gel cured product, and a polymer that can be used for forming a patterned transparent conductive film will be described, but the present invention is not limited to the following examples.
  • the mass ratio of the matrix component (all components excluding the metal nanowire and the solvent contained in the pattern transparent conductive film coating solution) to the metal nanowire is 0.5 to 15 (more preferably 1.0 to 12). Particularly preferred is 2.0 to 10).
  • the mass ratio is less than 0.5, the matrix component is small, the adhesion of the metal nanowires to the substrate surface is weak, and the film strength may be weak.
  • the mass ratio exceeds 15, the pattern is transparent. The surface resistance value of the conductive film may increase.
  • the binder is a linear organic high molecular polymer, and at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) (for example, it can be appropriately selected from alkali-soluble resins having a carboxyl group, a phosphoric acid group, a sulfonic acid group, and the like. Among these, those that are soluble in an organic solvent and soluble in an aqueous alkali solution are preferable, and those that have an acid-dissociable group and become alkali-soluble when the acid-dissociable group is dissociated by the action of an acid are particularly preferable. preferable.
  • the acid dissociable group represents a functional group that can dissociate in the presence of an acid.
  • a known radical polymerization method For the production of the binder, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art, and the conditions are determined experimentally. Can be determined.
  • a polymer having a carboxylic acid in the side chain is preferable.
  • the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, As described in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial ester Maleic acid copolymers, acidic cellulose derivatives having a carboxylic acid in the side chain, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and further having a (meth) acryloyl group in the side chain A high molecular polymer is also mentioned as a preferable polymer.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly preferable.
  • a high molecular polymer having a (meth) acryloyl group in the side chain and a multi-component copolymer composed of (meth) acrylic acid / glycidyl (meth) acrylate / other monomers are also useful.
  • the polymer can be used by mixing in an arbitrary amount.
  • 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer 2-hydroxy-3-phenoxypropyl acrylate / polymethyl described in JP-A-7-140654 Methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Coalescence, etc.
  • (meth) acrylic acid and other monomers copolymerizable with the (meth) acrylic acid are suitable.
  • Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. In these, the hydrogen atom of the alkyl group and aryl group may be substituted with a substituent.
  • Examples of the alkyl (meth) acrylate or aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth).
  • the weight average molecular weight of the binder is preferably from 1,000 to 500,000, more preferably from 3,000 to 300,000, and even more preferably from 5,000 to 200,000, from the viewpoints of alkali dissolution rate, film physical properties and the like.
  • the weight average molecular weight is measured by a gel permeation chromatography method (GPC method) and can be determined using a standard polystyrene calibration curve.
  • the content of the binder is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 85% by mass, based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowires. Preferably, 20% by mass to 80% by mass is more preferable. When the content is within the preferable range, both developability and conductivity of the metal nanowire can be achieved.
  • the photopolymerizable composition means a compound that imparts a function of forming an image by exposure to the patterned transparent conductive film or gives a trigger for the function.
  • the basic component includes (a) an addition-polymerizable unsaturated compound and (b) a photopolymerization initiator that generates radicals when irradiated with light.
  • the component (a) addition-polymerizable unsaturated compound is a compound that undergoes an addition-polymerization reaction in the presence of a radical to form a polymer, and usually has a molecular end.
  • a compound having at least one, more preferably two or more, more preferably four or more, still more preferably six or more ethylenically unsaturated double bonds is used. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof.
  • Various kinds of such polymerizable compounds are known, and they can be used as the component (a).
  • particularly preferred polymerizable compounds are, from the viewpoint of film strength, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth).
  • Acrylates are particularly preferred.
  • the content of component (a) is preferably 2.6% by mass or more and 37.5% by mass or less based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowires described above. More preferably, it is 0.0 mass% or more and 20.0 mass% or less.
  • the photopolymerization initiator of component (b) is a compound that generates radicals when irradiated with light.
  • photopolymerization initiators include compounds that generate acid radicals that ultimately become acids upon irradiation with light, and compounds that generate other radicals.
  • the former is referred to as “photoacid generator”, and the latter is referred to as “photoradical generator”.
  • -Photoacid generator- Photoacid generator includes photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecoloring agent for dyes, photochromic agent, irradiation of actinic ray or radiation used for micro resist, etc.
  • known compounds that generate acid radicals and mixtures thereof can be appropriately selected and used.
  • Such a photoacid generator is not particularly limited and may be appropriately selected depending on the intended purpose.
  • quinonediazide compound triazine having at least one di- or tri-halomethyl group, or 1,3,4 -Oxadiazole, naphthoquinone-1,2-diazide-4-sulfonyl halide, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, o-nitrobenzyl sulfonate, etc. .
  • imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate which are compounds that generate sulfonic acid
  • imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate which are compounds that generate sulfonic acid
  • imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate which are compounds that generate sulfonic acid
  • oxime sulfonate which are compounds that generate sulfonic acid
  • o-nitrobenzyl sulfonate which are compounds that generate sulfonic acid
  • a group in which an acid radical is generated by irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the resin for example, US Pat. No. 3,849,137, German Patent 3914407.
  • JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 And compounds described in JP-A-63-146029, etc. can be used. Furthermore, compounds described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used as an acid radical generator.
  • triazine compound for example, compounds described in JP2011-018636A and JP2011-254046A can be used.
  • the photoacid generators compounds that generate sulfonic acid are preferable, and the following oxime sulfonate compounds are particularly preferable from the viewpoint of high sensitivity.
  • quinonediazide compound When a compound having a 1,2-naphthoquinonediazide group is used as the quinonediazide compound, high sensitivity and good developability are obtained.
  • quinonediazide compounds compounds in which D of the compounds shown below are each independently a hydrogen atom or a 1,2-naphthoquinonediazide group are preferred from the viewpoint of high sensitivity.
  • the photoradical generator is a compound that has a function of generating radicals by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.
  • the photo radical generator is preferably a compound having absorption in the wavelength region of 300 nm to 500 nm. As such a photo radical generator, many compounds are known.
  • examples thereof include organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, and acylphosphine (oxide) compounds.
  • organic peroxide compounds examples thereof include organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, and acylphosphine (oxide) compounds.
  • benzophenone compounds, acetophenone compounds, hexaarylbiimidazole compounds, oxime ester compounds, and acylphosphine (oxide) compounds are particularly preferable
  • the photo radical generator for example, the photo radical generators described in JP 2011-018636 A and JP 2011-254046 A can be used.
  • a photoinitiator may be used individually by 1 type and may use 2 or more types together,
  • the content is based on the total mass of solid content of the photopolymerizable composition containing metal nanowire,
  • the content is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and still more preferably 1% by mass to 20% by mass. In such a numerical range, when a pattern including a conductive region and a non-conductive region described later is formed on the conductive layer, good sensitivity and pattern formability can be obtained.
  • additives other than the above components include, for example, chain transfer agents, crosslinking agents, dispersants, solvents, surfactants, antioxidants, sulfurization inhibitors, metal corrosion inhibitors, viscosity modifiers, preservatives, and the like. Various additives are mentioned.
  • Chain transfer agent is used for improving the exposure sensitivity of the photopolymerizable composition.
  • chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoic acid.
  • the content of the chain transfer agent is preferably 0.01% by mass to 15% by mass, preferably 0.1% by mass to 10% by mass, based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowires. % Is more preferable, and 0.5% by mass to 5% by mass is still more preferable.
  • the crosslinking agent is a compound that forms a chemical bond by free radical or acid and heat and cures the patterned transparent conductive film, and is substituted with at least one group selected from, for example, a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
  • an epoxy compound, an oxetane compound, and a compound having an ethylenically unsaturated group are particularly preferable in terms of film properties, heat resistance, and solvent resistance.
  • the said oxetane resin can be used individually by 1 type or in mixture with an epoxy resin.
  • the reactivity is high, which is preferable from the viewpoint of improving film properties.
  • the compound which has an ethylenically unsaturated double bond group is also included by the said polymeric compound, The content is content of the polymeric compound in this invention. Should be included.
  • the content of the crosslinking agent is preferably 1 part by weight to 250 parts by weight, preferably 3 parts by weight to 200 parts by weight, when the total weight of the solid content of the photopolymerizable composition containing the metal nanowire is 100 parts by weight. Is more preferable.
  • a dispersing agent is used in order to disperse
  • the dispersant is not particularly limited as long as the metal nanowires can be dispersed, and can be appropriately selected according to the purpose.
  • a commercially available dispersant can be used as a pigment dispersant, and a polymer dispersant having a property of adsorbing to metal nanowires is particularly preferable.
  • polymer dispersant examples include polyvinyl pyrrolidone, BYK series (manufactured by Big Chemie), Solsperse series (manufactured by Nippon Lubrizol Co., Ltd.), and Ajisper series (manufactured by Ajinomoto Co., Inc.).
  • the polymer dispersant is also included in the binder, and the content thereof is as described above. It should be considered that it is included in the content of the binder.
  • the content of the dispersant is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, and particularly preferably 1 to 30 parts by weight with respect to 100 parts by weight of the binder. .
  • the content of the dispersant is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, and particularly preferably 1 to 30 parts by weight with respect to 100 parts by weight of the binder.
  • the solvent is a component used to form a coating solution for forming a composition containing the metal nanowire and the specific alkoxide compound and the photopolymerizable composition on the surface of the substrate in the form of a film. It can be appropriately selected according to, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol, water, 1-methoxy- Examples include 2-propanol, isopropyl acetate, methyl lactate, N-methylpyrrolidone (NMP), ⁇ -butyrolactone (GBL), propylene carbonate, and the like.
  • NMP N-methylpyrrolidone
  • GBL ⁇ -butyrolactone
  • This solvent may also serve as at least a part of the solvent of the metal nanowire dispersion described above. These may be used individually by 1 type and may use 2 or more types together.
  • the solid content concentration of the coating solution containing such a solvent is preferably contained in the range of 0.1% by mass to 20% by mass.
  • Metal corrosion inhibitor It is preferable to contain the metal nanowire metal corrosion inhibitor.
  • a metal corrosion inhibitor there is no restriction
  • the metal corrosion inhibitor is added to the composition for forming a transparent conductive film in a state dissolved in a suitable solvent, or added as a powder, or after forming a conductive film with a coating liquid for a patterned transparent conductive film, which will be described later, this is subjected to metal corrosion. It can be applied by dipping in an inhibitor bath.
  • a metal corrosion inhibitor it is preferable to contain 0.5% by mass to 10% by mass with respect to the metal nanowires.
  • the other matrix it is possible to use a polymer compound as a dispersant used in the production of the above-described metal nanowires as at least a part of components constituting the matrix.
  • a composition containing at least a sol-gel cured product as a matrix component can be used together with the metal nanowires.
  • the sol-gel cured product is obtained by hydrolyzing and polycondensing an alkoxide compound of an element selected from the group consisting of Si, Ti, Zr and Al (hereinafter also referred to as “specific alkoxide compound”), and further heating and drying as desired. Is obtained.
  • the specific alkoxide compound is preferably a compound represented by the following general formula (I) because it is easily available.
  • M 1 (OR 1 ) a R 2 4-a (I)
  • M 1 represents an element selected from Si, Ti and Zr
  • R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group
  • a represents an integer of 2 to 4 Show.
  • an alkyl group or an aryl group is preferable.
  • the carbon number in the case of showing an alkyl group is preferably 1 to 18, more preferably 1 to 8, and still more preferably 1 to 4.
  • a phenyl group is preferable.
  • the alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, an alkylamino group, and a mercapto group.
  • the compound represented by the general formula (I) is a low molecular compound and preferably has a molecular weight of 1000 or less.
  • the ratio of the specific alkoxide compound to the metal nanowire that is, the mass ratio of the specific alkoxide compound / metal nanowire is 0.25 / 1 to 30 / Used in the range of 1.
  • the mass ratio is less than 0.25 / 1, the transparency is inferior, and at the same time, the conductive layer is inferior in at least one of wear resistance, heat resistance, moist heat resistance and flex resistance.
  • the mass ratio is larger than 30/1, the conductive layer is inferior in conductivity and flex resistance.
  • the mass ratio is more preferably in the range of 0.5 / 1 to 20/1, more preferably in the range of 1/1 to 15/1, and most preferably in the range of 2/1 to 8/1.
  • High conductivity and high transparency It is preferable because it can stably obtain a conductive material having high properties (total light transmittance and haze), excellent wear resistance, heat resistance and moist heat resistance, and excellent flex resistance.
  • a composition containing at least a polymer as a matrix component can be used together with the metal nanowires.
  • Synthetic polymers and natural polymers are included as the polymers.
  • the synthetic polymers include polyester, polyimide, polyacryl, polyvinylon, polyethylene, polypropylene, polystyrene, polyvinyl chloride, methacrylic resin, fluorine-based resin, and phenol.
  • examples thereof include resins, melamine resins, silicone resins, synthetic rubbers, and latexes thereof.
  • the natural polymer include cellulosic resins and natural rubber.
  • a protective layer made of a protective coating material may be provided on the conductive film.
  • Protective coating materials include crosslinkers, polymerization initiators, stabilizers (eg, antioxidants and UV stabilizers for prolonging product life, and polymerization inhibitors for improving shelf life), surfactants, and the like You may include what has a special effect.
  • the protective coating material may further include a corrosion inhibitor that prevents corrosion of the metal nanowires.
  • the method for forming the protective layer is not particularly limited as long as it is a known wet coating method. Specifically, spray coating, bar coating, roll coating, die coating, ink jet coating, screen coating, dip coating and the like can be mentioned.
  • the abrasion resistance and abrasion resistance When forming the protective layer while impregnating the pattern transparent conductive film with the protective coating material, if the film thickness of the protective layer after application and drying is too thin relative to the pattern transparent conductive film before application, the abrasion resistance and abrasion resistance The function as a protective layer such as property and weather resistance is lowered, and if it is too thick, the contact resistance as a conductor increases.
  • the coating for the protective layer is preferably 30 to 150 nm after coating and drying.
  • the surface resistivity, haze, and the like can be adjusted to achieve predetermined values. 40 to 175 nm is more preferable, and 50 to 150 nm is particularly preferable.
  • the film thickness after drying of the coating material for the protective layer depends on the film thickness of the pattern transparent conductive film, the protective function by the protective layer tends to work better when the film thickness is 30 nm or more. When it is thick, it tends to be able to ensure better conductive performance.
  • a transparent conductive film coating method for forming the pattern transparent conductive film is as follows, but is not limited to the following example.
  • a coating liquid for a patterned transparent conductive film is prepared.
  • the coating solution comprises at least a metal nanowire having an average minor axis length of 5 to 50 nm and a matrix component (preferably a binder and a photosensitive compound, a sol-gel cured product, or a polymer (for forming a transparent conductive film).
  • the composition and, if necessary, other components
  • the pattern transparent conductive film coating solution is applied to a substrate surface such as a glass plate or a film.
  • the method for applying is not particularly limited and can be appropriately selected depending on the purpose.
  • spray coating method, air brush method, curtain spray method, dip coating method, roller coating method, spin coating method, ink jet method, Examples include an extrusion method.
  • the coating amount is preferably such that the metal nanowires are 0.005 to 0.5 g / m 2 .
  • the pattern transparent conductive film coating solution is applied onto a substrate to form a coating layer, and then exposed and cured.
  • an exposure method Although it can select suitably according to a use etc., the exposure method using an ultraviolet irradiation device, a ultraviolet irradiation lamp, etc. is preferable.
  • the alkali contained in the alkaline solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, Examples thereof include sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like.
  • methanol, ethanol, or a surfactant may be added as necessary.
  • a surfactant for example, an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be selected and used.
  • the addition of nonionic polyoxyethylene alkyl ether is particularly preferable because the resolution becomes high.
  • the alkali treatment is not particularly limited and may be appropriately selected depending on the intended purpose. For example, any of dip development, paddle development, and shower development can be used. By performing the alkali treatment, the conductivity of the patterned transparent conductive film can be increased.
  • the immersion time of the alkaline solution is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 seconds to 5 minutes.
  • a patterned transparent conductive film is formed by the following method.
  • Formation of the pattern transparent conductive film exposes and develops the conductive film, and includes a pattern exposure process and a development process, and further includes other processes as necessary.
  • the conductive film is patterned so as to have a desired pattern including a conductive area and a non-conductive area, and the conductive pattern member according to the present invention is manufactured.
  • a patterning method include the following methods.
  • the conductive film before patterning is also referred to as “non-patterned conductive layer”.
  • the matrix of the conductive film is non-photosensitive, it is patterned by the following methods (1) to (2).
  • a photoresist layer is provided on a non-patterned conductive layer, and a desired pattern exposure and development are performed on the photoresist layer to form the patterned resist (etching mask material).
  • This method is described, for example, in JP-T-2010-507199 (particularly, paragraphs 0212 to 0217).
  • a photocurable resin is provided on the pattern by an inkjet method or a screen printing method, and the photocurable resin layer is subjected to a desired exposure to form the pattern.
  • the resist etching mask material
  • the metal nanowires are immersed in an etchable etchant or the etchant is showered to form a conductive layer in a region not protected by the resist.
  • a patterning method for breaking or disappearing metal nanowires In the case of the method (1) or (2), it is preferable to remove the resist on the conductive film by a conventional method after the patterning is completed, because a conductive laminate having excellent transparency can be obtained.
  • the coating method is not particularly limited.
  • a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a bar coating method, a gravure coating method, a curtain coating method examples thereof include a spray coating method and a doctor coating method.
  • the printing method include letterpress (letterpress) printing, stencil (screen) printing, lithographic (offset) printing, and intaglio (gravure) printing.
  • the resist layer formed in this step may be a positive resist layer or a negative resist layer.
  • the pattern-shaped exposed region is solubilized, and a patterned resist layer is formed in the unexposed region (unsolubilized region).
  • the exposed region is A cured resist layer is formed, and by application of the solution, the unexposed portion, that is, the uncured portion of the resist layer is removed, and a patterned resist layer is formed.
  • both the metal nanowires and the binder contained in the conductive film are removed, and the substrate or the intermediate layer formed on the substrate is exposed.
  • any, such as a negative type, a positive type, a dry film type, can be used.
  • commercially available alkali-soluble photoresists can be appropriately selected and used.
  • Each positive type, negative type photoresist series, Fuji Chemical Fuji Resist series can be used, and among them, FR series, FPPR series, FMR series, FDER series, etc. can be preferably used.
  • AZ Electronic Materials photoresist series can be used, among them, RFP series, TFP series, SZP series, HKT series, SFP, series, SR series, SOP series, SZC series, CTP series, ANR series, P4000. Series, TPM606, 40XT, nXT series and the like can be preferably used. Furthermore, each photoresist made by JSR can be widely used from a high resolution type to a low resolution type.
  • the exposure step in the method for forming the patterned transparent conductive film is preferably a step of performing exposure at an oxygen concentration of 5% or less using an etching mask material containing a photopolymerization initiator.
  • the exposure is preferably performed in an atmosphere having an oxygen concentration of 5% or less, more preferably 2% or less, still more preferably 1% or less, and 0.1% or less. It is particularly preferred.
  • the exposure is performed in an atmosphere where the oxygen concentration exceeds 5%, by-products generated from the photopolymerization initiator contained in the etching mask material, or metal nanowires are disconnected by reaction with oxides such as ozone, Since the resistance value of the conductive part wiring after patterning is increased, it is not preferable.
  • the disconnection of metal nanowires in an atmosphere having a high oxygen concentration tends to be particularly noticeable when metal nanowires having a small diameter are used. Furthermore, it is not preferable to perform the exposure in an atmosphere in which the oxygen concentration exceeds 5% because the reaction efficiency in curing the etching mask material decreases and the tact time becomes longer.
  • the exposure is preferably performed in an inert gas atmosphere having an oxygen concentration of 5% or less.
  • the inert gas that can be used is not particularly limited as long as it does not interfere with the UV curing reaction when exposed using an ultraviolet irradiation device or an ultraviolet irradiation lamp.
  • nitrogen gas or argon gas is preferable, and nitrogen gas is more preferable because it is easily available and inexpensive.
  • the exposure method surface exposure (solid exposure) not using a photomask, surface exposure using a photomask, or scanning exposure using a laser beam may be performed.
  • refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used. These exposure methods can be appropriately selected as necessary.
  • solid exposure can be performed without using a photomask.
  • the light source used for the pattern exposure or exposure is selected in relation to the photosensitive wavelength range of the photoresist composition, but in general, ultraviolet rays such as g-line, h-line, i-line, and j-line are preferably used. Moreover, you may use ultraviolet LED.
  • the pattern exposure method is not particularly limited, and may be performed by surface exposure using a photomask, or may be performed by scanning exposure using a laser beam or the like. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.
  • the sample film surface temperature at the time of exposure is preferably low, preferably in the range of 0 ° C.
  • the temperature at the time of exposure is lower than 0 ° C., it is difficult to control the temperature, and if it is 80 ° C. or higher, the number of disconnections of the metal nanowires increases and the resistance increase magnification increases.
  • the solution for dissolving the metal nanowire can be appropriately selected according to the metal nanowire.
  • the metal nanowire is a silver nanowire
  • bleaching fixer, strong acid, oxidizing agent, peroxidation mainly used for bleaching and fixing process of photographic paper of silver halide color photosensitive material Examples include hydrogen.
  • bleach-fixing solution, dilute nitric acid, and hydrogen peroxide are particularly preferable.
  • the dissolution of the silver nanowire by the solution for dissolving the silver nanowire may not completely dissolve the portion of the silver nanowire provided with the solution, and if the conductivity is lost, a part of the dissolution It may remain.
  • the concentration of the diluted nitric acid is preferably 1% by mass to 20% by mass.
  • the concentration of the hydrogen peroxide is preferably 3% by mass to 30% by mass.
  • the bleach-fixing solution for example, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper-right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17
  • the processing materials and processing methods described in the 20th page, lower right column, line 20 can be preferably applied.
  • the bleach-fixing time is preferably 180 seconds or shorter, more preferably 120 seconds or shorter and 1 second or longer, and further preferably 90 seconds or shorter and 5 seconds or longer.
  • the water washing or stabilization time is preferably 180 seconds or shorter, more preferably 120 seconds or shorter and 1 second or longer.
  • the bleach-fixing solution is not particularly limited as long as it is a photographic bleach-fixing solution, and can be appropriately selected according to the purpose.
  • CP-48S, CP-49E color paper bleaching manufactured by FUJIFILM Corporation. Fixing agent), Kodak Ektacolor RA bleach-fixing solution, Dai Nippon Printing Co., Ltd. bleach-fixing solution D-J2P-02-P2, D-30P2R-01, D-22P2R-01, and the like.
  • CP-48S and CP-49E are particularly preferable.
  • a development step for removing the patterned resist (etching mask material) used in the exposure step may be included.
  • the developing step is preferably a step of removing the etching mask material by applying a solvent.
  • a positive resist it is preferably performed in a step after mask exposure and a step after etching
  • a negative resist it is preferably performed in a step after etching.
  • an alkaline solution is preferable.
  • the alkali contained in the alkaline solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, Examples thereof include sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like.
  • a commercially available developer for photoresist can be used as the solvent.
  • the immersion time of the alkaline solution is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 seconds to 5 minutes.
  • the temperature of the alkaline solution can be appropriately selected according to the purpose, but is preferably 5 ° C to 50 ° C.
  • the patterning step for forming the patterned transparent conductive film in the transparent conductive laminate of the present invention may further include other steps as necessary in addition to the exposure step and the development step. Examples of other processes include washing with water after removing the etching mask, and a drying process.
  • the conductive film may be formed on a target substrate by transfer using a transfer material.
  • a polarizing conductive film tends to be formed.
  • coating methods that maintain the randomness of the orientation of the nanowires include spray coating methods and inkjet coating methods.
  • a coating method that promotes the orientation of nanowires for example, a coating method such as a throttle die method
  • a direction different from the direction for example, a direction orthogonal to the direction
  • a treatment for reducing the orientation of the metal nanowires in the film may be performed.
  • Metal nanowires in the conductive film formed by being applied along one direction tend to be oriented along the direction. Therefore, it is preferable to perform a stretching process (for example, a stretching process with a stretching ratio of 1% or more and less than 5%) along a direction (for example, a direction orthogonal to the direction) different from the direction of application because orientation is reduced.
  • a stretching process for example, after forming a electrically conductive film on flexible substrates, such as a polymer film, it is preferable to extend
  • the surface resistance of the conductive film is preferably 1 ⁇ / ⁇ to 5,000 ⁇ / ⁇ , and more preferably 10 ⁇ / ⁇ to 500 ⁇ / ⁇ .
  • the surface resistance can be measured by, for example, a surface resistance meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation).
  • the dry film thickness of the pattern transparent conductive film is preferably 0.005 to 2 ⁇ m, more preferably 0.01 to 1 ⁇ m.
  • Adhesive layer In this invention, it has the adhesion layer formed so that a pattern transparent conductive film may be covered.
  • the adhesive layer is composed of an adhesive, and the adhesive strength of the adhesive layer is preferably 15 N / 25 mm or more (more preferably 30 to 50 N / 25 mm, particularly preferably 30 to 42 N / 25 mm).
  • it is preferable to use an adhesive whose water absorption rate of the adhesive layer is 2.0% or less (more preferably 1.0% or less, particularly preferably 0.9% or less). Although there is no specific lower limit of the water absorption rate, it is generally 0.5% or more.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer includes an adhesive in a broad sense.
  • the adhesive force of the adhesive layer may be different even in the same adhesive layer.
  • the adhesive force of the adhesive layer is 15 N / 25 mm or more. There are no particular restrictions.
  • pressure-sensitive adhesives examples include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and polyester-based pressure-sensitive adhesives. Acrylic adhesive is preferred.
  • the method for forming the adhesive layer is not particularly limited, and for example, the method described in JP2012-11637A can be used. Specifically, a coating method, a printing method, a bonding method, and the like can be mentioned. Among them, a method of installing by coating and a method of forming by sticking an adhesive sheet can be preferably used. The method of forming is more preferable.
  • the dew point temperature is preferably ⁇ 40 ° C. or lower, particularly preferably ⁇ 60 ° C. or lower.
  • the autoclave treatment has the effect of improving optical properties such as enhancing the adhesion between the adhesive layer and the barrier film and improving the transmittance and haze reduction of the transparent conductive laminate.
  • the adhesion is improved by performing ultraviolet irradiation treatment, plasma treatment, and corona treatment on the barrier film surface.
  • the thickness of the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 5 to 150 ⁇ m, more preferably 20 to 100 ⁇ m. By making the thickness of the adhesive layer 5 ⁇ m or more, it is possible to cover the steps and irregularities of the pattern transparent conductive film to be applied, and by making the thickness 150 ⁇ m or less, the transmittance of the adhesive layer can be sufficiently secured.
  • the transparent conductive laminate of the present invention may have other layers (functional layers) in addition to the substrate, conductive film, adhesive layer, barrier film, and the like.
  • the functional layer include a protective film, an undercoat layer, an adhesion layer, a cushion layer, an overcoat protective layer, a protective film layer, an antifouling layer, a water repellent layer, an oil repellent layer, and a hard coat layer.
  • an optical function can be imparted by laminating an antiglare layer, an antireflection layer, a low reflection layer, a ⁇ / 4 layer, a polarizing layer, a retardation layer, and the like. These may be a single layer or a plurality of layers.
  • the transparent conductive laminate of the present invention is applied to a touch panel.
  • the touch panel has a drive voltage of 1 V or more and is not particularly limited as long as it has the transparent conductive laminate of the present invention, and can be appropriately selected according to the purpose.
  • a surface capacitive touch panel, a projection type Examples include a capacitive touch panel and a resistive touch panel.
  • the touch panel includes a so-called touch sensor and a touch pad.
  • the layer structure of the touch panel sensor electrode part in the touch panel is a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, a single-sided jumper or a through-hole method, or a single-area layer method. Either is preferable.
  • the projected capacitive touch panel is preferably AC driven rather than DC driven, and more preferably is a drive system that requires less time to apply voltage to the electrodes.
  • FIG. 2 is a schematic view of an example of a touch panel having the transparent conductive laminate of the present invention.
  • the touch panel has a transparent conductive film on a surface opposite to the surface adjacent to the first barrier film of the transparent conductive laminate of the present invention and the first barrier film of the transparent conductive laminate. It has the laminated body laminated
  • FIG. 3 is a schematic view of another example of a touch panel having the transparent conductive laminate of the present invention.
  • a touch panel is an aspect which has a transparent film, a 3rd barrier film
  • the third barrier film may be the same barrier film as the first and second barrier films, or may be a different barrier film. In the embodiment shown in FIG. 3, even if a film substrate made of a polymer is used as the substrate and the cover film, moisture from the outside does not enter the pattern transparent conductive film. Can be prevented from malfunctioning.
  • Water vapor permeability of the third barrier film shown in FIGS. 2 and 3 (more preferably, 0.05 g / (m 2 ⁇ day) or less) preferably 0.1 g / (m 2 ⁇ day) or less be
  • the same film as the first barrier film and the second barrier film may be used, or different barrier films may be used.
  • the image display device used for the touch panel is not particularly limited, and a liquid crystal display device or an organic EL device usually used for a small electronic terminal can be used.
  • a substrate 1 was prepared by introducing an O 2 gas onto a 125 ⁇ m thick PET film using a Si 3 N 4 target and forming a 150 nm thick SiON (silicon nitride oxide) barrier film by sputtering.
  • SiON silicon nitride oxide
  • a film 2-1 having a thickness of 1 ⁇ m was formed by applying an acrylic resin on a PET film having a thickness of 125 ⁇ m.
  • an Si 2 N 4 target was used to introduce O 2 gas, and a 150 nm thick SiON film 2-2 was formed by sputtering.
  • a film 2-3 having a thickness of 1 ⁇ m is formed on the film 2-2 by applying an acrylic resin, and an O 2 gas is introduced onto the film 2-3 using a Si 3 N 4 target.
  • a barrier film composed of the films 2-1 to 2-4 was formed by forming a SiON film 4 having a thickness of 150 nm by sputtering, and the substrate 2 was manufactured.
  • a film 4-1 having a thickness of 1 ⁇ m was formed by applying an acrylic resin on a PET film having a thickness of 125 ⁇ m.
  • an O 2 gas was introduced using an Al target, and an alumina film 4-2 having a thickness of 100 nm was formed by sputtering.
  • a film 4-3 having a film thickness of 1 ⁇ m is formed on the film 4-2 by applying an acrylic resin, and O 2 gas is introduced onto the film 4-3 using an Al target, and a sputtering method is used.
  • a barrier film composed of the films 4-1 to 4-4 was formed, and the substrate 4 was manufactured.
  • a substrate 5 was produced by introducing an O 2 gas onto a PET film having a thickness of 125 ⁇ m using a Si 3 N 4 target and forming a 100 nm thick SiON barrier film by sputtering.
  • An O 2 gas was introduced onto a PET film having a thickness of 125 ⁇ m using an Al target, and an alumina barrier film having a thickness of 150 nm was formed by sputtering to produce a substrate 6.
  • a 1 ⁇ m thick film 2′-1 was formed by applying an acrylic resin on a 125 ⁇ m thick polymethyl methacrylate resin (PMMA) film.
  • PMMA polymethyl methacrylate resin
  • an O 2 gas was introduced using a Si 3 N 4 target, and a 150 nm-thick SiON film 2′-2 was formed by sputtering.
  • An acrylic resin is applied on the film 2′-2 to form a film 2′-3 having a thickness of 1 ⁇ m, and an O 2 gas is introduced onto the film 3 using a Si 3 N 4 target.
  • a cover film 2 was prepared by forming a SiON film 2′-4 having a film thickness of 150 nm by sputtering to form a barrier film composed of the films 2′-1 to 2′-4.
  • a cover film 3 was prepared by introducing an O 2 gas onto a 125 ⁇ m thick polymethyl methacrylate resin (PMMA) film using an Al target and forming a 100 nm thick alumina barrier film by sputtering.
  • PMMA polymethyl methacrylate resin
  • a cover film 4 is produced by introducing an O 2 gas onto a 125 ⁇ m thick polymethyl methacrylate resin (PMMA) film using a Si 3 N 4 target and forming a 400 nm thick SiON barrier film by sputtering. did.
  • PMMA polymethyl methacrylate resin
  • a film 6′-1 having a thickness of 1 ⁇ m was formed by applying an acrylic resin on a polymethyl methacrylate resin (PMMA) film having a thickness of 125 ⁇ m.
  • PMMA polymethyl methacrylate resin
  • an O 2 gas was introduced using an Al target, and an alumina film 6′-2 having a thickness of 100 nm was formed by sputtering.
  • a film 6′-3 having a thickness of 1 ⁇ m is formed on the film 6′-2 by applying an acrylic resin, and an O 2 gas is introduced onto the film 6′-3 using an Al target.
  • a barrier film composed of films 6′-1 to 6′-4 was formed by forming an alumina film 6′-4 with a film thickness of 100 nm by sputtering, and a cover film 6 was produced.
  • a cover film 7 is produced by introducing an O 2 gas onto a 125 ⁇ m-thick polymethyl methacrylate resin (PMMA) film using a Si 3 N 4 target and forming a 100-nm thick SiON barrier film by sputtering. did.
  • a cover film 3 was prepared by introducing an O 2 gas onto a 125 ⁇ m-thick polymethyl methacrylate resin (PMMA) film using an Al target and forming an alumina barrier film having a thickness of 150 nm by sputtering.
  • PMMA polymethyl methacrylate resin
  • each 10.5g / (m 2 ⁇ day) was 12.4g / (m 2 ⁇ day) .
  • Both water vapor transmission rates exceeded 10 g / (m 2 ⁇ day), and the water vapor transmission rate of the substrate itself and the cover film with the barrier film were measured because the water vapor transmission rate of the substrate itself was very large.
  • the result obtained can be calculated as the water vapor permeability of the barrier film.
  • the value below 0.01 g / (m ⁇ 2 > * day) which is the measurement limit of the said water-vapor-permeability measuring apparatus can be supplemented by measuring using the following method.
  • metal Ca is vapor-deposited directly on the sample, and the film and the glass substrate are sealed with a commercially available sealing material for organic EL so that the vapor-deposited Ca is on the inside, thereby producing a sealed sample.
  • the water vapor transmission rate can be obtained by holding the sealed sample at the above temperature and humidity conditions and obtaining the optical density change of the metallic Ca (the metallic luster is reduced by hydroxylation or oxidation).
  • Polyester having a thickness of 50 ⁇ m obtained by adding 0.7 part of an isocyanate-based cross-linking agent (Coronate L-45 manufactured by Nippon Polyurethane Co., Ltd., solid content: 45%) to 100 parts of the pressure-sensitive adhesive A, stirring for 15 minutes, and then removing one side with a silicone compound.
  • the film (# 50 release film) was coated so that the thickness after drying was 25 ⁇ m, and dried at 75 ° C. for 5 minutes.
  • the obtained pressure-sensitive adhesive sheet and a 38 ⁇ m-thick polyester film (# 38 release film) having one surface peel-treated with a silicone compound were bonded together. Thereafter, it was aged at 23 ° C. for 5 days to obtain a support-less pressure-sensitive adhesive sheet A having a thickness of 25 ⁇ m.
  • Polyester having a thickness of 50 ⁇ m obtained by adding 0.7 part of an isocyanate-based crosslinking agent (Coronate L-45 manufactured by Nippon Polyurethane Co., Ltd., solid content: 45%) to 100 parts of the above-mentioned adhesive B, stirring for 15 minutes, and then removing one side with a silicone compound.
  • the film (# 50 release film) was coated so that the thickness after drying was 25 ⁇ m, and dried at 75 ° C. for 5 minutes.
  • the obtained pressure-sensitive adhesive sheet and a 38 ⁇ m-thick polyester film (# 38 release film) having one surface peel-treated with a silicone compound were bonded together. Thereafter, it was aged at 23 ° C. for 5 days to obtain a support-less pressure-sensitive adhesive sheet B having a thickness of 25 ⁇ m.
  • Preparation of adhesive sheet C 10 parts of the acrylic copolymer (3) was added to 100 parts of the acrylic copolymer (2), and diluted with ethyl acetate to obtain an adhesive C having a resin solid content of 30%.
  • Polyester having a thickness of 50 ⁇ m obtained by adding 0.7 part of an isocyanate-based crosslinking agent (Coronate L-45 manufactured by Nippon Polyurethane Co., Ltd., solid content: 45%) to 100 parts of the above-mentioned pressure-sensitive adhesive, stirring for 15 minutes, and then removing one side with a silicone compound.
  • the film (# 50 release film) was coated so that the thickness after drying was 25 ⁇ m, and dried at 75 ° C. for 5 minutes.
  • the obtained pressure-sensitive adhesive sheet and a 38 ⁇ m-thick polyester film (# 38 release film) having one surface peel-treated with a silicone compound were bonded together. Thereafter, it was aged at 23 ° C. for 5 days to obtain a support-less pressure-sensitive adhesive sheet C having a thickness of 25 ⁇ m.
  • the pressure-sensitive adhesive sheet prepared above is cut out to a size of 100 mm ⁇ 100 mm, left under conditions of 60 ° C. and 90% RH for 100 hours, immediately peeled off the release film on one side of the pressure-sensitive adhesive sheet, and bonded to a 150 mm ⁇ 150 mm aluminum foil. And weigh (this mass is referred to as W1).
  • the other release film of the pressure-sensitive adhesive sheet is peeled off, dried for 2 hours at 105 ° C., and then weighed (this mass is designated as W2).
  • the adhesion strength between the barrier film and the adhesive layer was evaluated by the following method.
  • the release film on one side of the pressure-sensitive adhesive sheet prepared above is peeled off, bonded to a polyethylene terephthalate film (thickness: 25 ⁇ m), cut to a width of 25 mm and a length of 100 mm, and then the release film on the other side is peeled off.
  • a cover film having a barrier film was attached. At this time, the bonding is performed so that the barrier film faces the adhesive sheet.
  • the autoclave treatment was performed for 20 minutes under the condition of 45 ° C./0.5 MPa.
  • 180 ° peel adhesion was measured.
  • the measurement conditions for 180 ° peel adhesive strength are peeling angle: 180 °, tensile speed: 300 mm / min, temperature: 23 ° C., humidity: 50% RH, and a film made of polyethylene terephthalate from a cover film having a barrier film.
  • 180 ° peel adhesive strength was measured, and the adhesion strength between the barrier film and the pressure-sensitive adhesive layer was evaluated.
  • a silver nitrate solution 101 was prepared by dissolving 60 g of silver nitrate powder in 370 g of propylene glycol. 72.0 g of polyvinylpyrrolidone (molecular weight 55,000) was added to 4.45 kg of propylene glycol, and the temperature was raised to 90 ° C. while venting nitrogen gas through the gas phase portion of the container. This solution was designated as reaction solution 101. While maintaining the aeration of nitrogen gas, 3.00 g of the silver nitrate solution 101 was added to the reaction solution 101 that was vigorously stirred, and the mixture was heated and stirred for 1 minute. Further, a solution in which 11.8 g of tetrabutylammonium chloride was dissolved in 100 g of propylene glycol was added to this solution to obtain a reaction solution 102.
  • ultrafiltration was performed as follows. Addition and concentration of a mixed solution of distilled water and 1-propanol (volume ratio of 1: 1) to the charged solution 101 and concentration were repeated until the filtrate finally had a conductivity of 50 ⁇ S / cm or less. The obtained filtrate was concentrated to obtain a silver nanowire dispersion liquid (1) having a metal content of 0.45%.
  • the average minor axis length and the average major axis length were measured as described above. As a result, the average minor axis length was 32.5 nm and the average major axis length was 15.6 ⁇ m.
  • silver nanowire dispersion liquid (1) the silver nanowire dispersion liquid obtained by the said method is shown.
  • additive solution A After the addition of the aqueous silver nitrate solution A-1, the mixture was vigorously stirred for 180 minutes to obtain additive solution A.
  • additive solution B 42.0 g of silver nitrate powder was dissolved in 958 g of distilled water.
  • Additional liquid C 75 g of 25% aqueous ammonia was mixed with 925 g of distilled water.
  • additive liquid D 400 g of polyvinylpyrrolidone (K30) was dissolved in 1.6 kg of distilled water.
  • a silver nanowire dispersion liquid (5) was prepared as follows.
  • ultrafiltration was performed as follows. After the feed solution 102 is concentrated four times, addition and concentration of a mixed solution of distilled water and 1-propanol (volume ratio of 1: 1) to the feed solution 102 is finally performed, and finally the conductivity of the filtrate is 50 ⁇ S / cm. Repeat until: The obtained filtrate was concentrated to obtain a silver nanowire dispersion liquid (5) having a metal content of 0.45%.
  • the average minor axis length and the average major axis length were measured as described above. As a result, the average minor axis length was 17.2 nm and the average major axis length was 8.8 ⁇ m.
  • the sol-gel reaction was caused to dry at 1 degreeC for 1 minute, and the transparent conductive film 1 which consists of silver nanowire was formed.
  • the transparent conductive film 1 can be patterned using a conventional photolithography etching technique.
  • a photoresist (TMSMR-8900LB: manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied to the transparent conductive film 1, and after pattern exposure using a mask, development is performed with a developer (NMD-W: Tokyo Ohka Kogyo Co., Ltd.).
  • NMD-W Tokyo Ohka Kogyo Co., Ltd.
  • SEA-2 manufactured by Kanto Chemical Co., Inc.
  • the photoresist was stripped using a neutral stripping solution (PK-SFR8120: manufactured by Parker Corporation), and the pattern transparent conductive film 1 was prepared.
  • PK-SFR8120 manufactured by Parker Corporation
  • the space width of the conductive area of the element of the environmental resistance test and the flexibility evaluation was 50 ⁇ m.
  • a conductive area was patterned to a size of 5 cm ⁇ 5 cm.
  • an extraction electrode in which an extraction electrode of Mo (40 nm) / Al (100 nm) / Mo (40 nm) was produced by sputtering was formed on the patterned transparent conductive film 1.
  • the extraction electrode was patterned by using a shadow metal mask during sputtering film formation.
  • the surface on the barrier film side of the cover film 1 and the pattern transparent conductive film 1 were bonded together using an adhesive sheet A.
  • the bonding was performed in a glove box having a dew point temperature of ⁇ 60 ° C.
  • the transparent conductive laminate 1 was produced by subjecting the autoclave treatment to a condition of 45 ° C./0.5 MPa for 20 minutes.
  • the transparent conductive laminate 2 was prepared in the same manner as the production of the transparent conductive laminate 1, except that the aqueous dispersion of the substrate, the cover film, and the silver nanowire was changed as shown in the following table. To 21 were produced. Moreover, in the transparent conductive laminates 14, 17, 18, 19 and 20, before bonding, the surface of the barrier film of the cover film is irradiated with ultraviolet rays to be washed to enhance the adhesion between the barrier film and the adhesive layer. It was.
  • Resistance change (240 hours later + electrode resistance) / (before test + electrode resistance) AA: resistance change is less than 1.1, excellent level A: resistance change is 1.1 or more and less than 1.5, good level B: resistance change is 1.5 or more and less than 2.0, no problem level C: Resistance change is 2.0 or more, problematic level
  • ⁇ Haze> The haze value of the conductive area was measured using a haze guard plus manufactured by Gardner. The measurement was performed at the center of a 5 cm ⁇ 5 cm sample.
  • membrane is 0.1 g / (m ⁇ 2 > * day) or less respectively
  • the pattern transparent conductive film containing metal nanowire whose average short axis length is 50 nm or less It can be seen that the transparent conductive laminate in which is sealed with the first and second barrier films has good haze and excellent environmental resistance test. On the other hand, it can be seen that the comparative example which is not sealed with a barrier film having a water vapor transmission rate of 0.1 g / (m 2 ⁇ day) or less is inferior in the environmental resistance test as compared with the examples.
  • the transparent conductive laminate using metal nanowires having an average minor axis length of more than 50 nm is resistant even if a barrier film having a water vapor permeability of more than 0.1 g / (m 2 ⁇ day) is used. Although it is excellent in environmental tests, it can be seen that the haze is large and the visibility is poor. In a transparent conductive laminate using silver nanowires with an average minor axis length of 50 nm or less that has a small haze and is excellent in appearance, both sides of the patterned transparent conductive film have a water vapor transmission rate of 0.1 g / (m 2 ⁇ day) or less.
  • the environment resistance test characteristics can be improved, and both visibility and environment resistance test characteristics can be achieved. From Examples 1 to 11, by setting the adhesive force between the barrier film and the adhesive layer to 30 N / 25 mm or more and the water absorption rate of the adhesive layer to 1% or less, the environmental resistance test characteristics were further improved, and the adhesive force was 50 N / It can be seen that by setting the thickness of 25 mm or less and the thickness of the barrier film to 300 nm or less, it is possible to provide a transparent conductive laminate having further excellent flexibility.
  • the touch panel of the aspect of FIG. 3 was produced by bonding the transparent conductive film and the board
  • FIG. 12 The touch panel of the aspect of FIG. 3 was produced by bonding the transparent conductive film and the board
  • the touch panel of the aspect of FIG. 2 was produced by bonding the transparent conductive film, the pressure-sensitive adhesive sheet A, and the substrate 1 to the substrate of the transparent conductive laminate of Example 1.
  • Example 12 and 13 and Comparative Example 11 were driven at 5 V for 240 hours under an environmental condition of 85 ° C. and 90% RH.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
  • Position Input By Displaying (AREA)

Abstract

L'invention concerne un stratifié conducteur transparent comprenant : un premier film de barrière (1) ; un film conducteur transparent à motifs (2) qui contient des nanofils métalliques ayant une longueur d'axe mineur moyenne de 5-50 nm et est formé sur la surface du premier film de barrière (1) directement ou avec une autre couche étant interposée entre ; une couche adhésive (3) qui recouvre le film conducteur transparent à motifs (2) ; et un deuxième film de barrière (4) qui est agencée de manière adjacente à la couche adhésive (3). Le taux de transmission de vapeur d'eau des premier et deuxième films de barrière (1, 4) sont 0,1 g/(m2 jour) ou moins.
PCT/JP2013/057990 2012-03-23 2013-03-21 Stratifié conducteur transparent et panneau tactile WO2013141275A1 (fr)

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JP2012066919A JP5749207B2 (ja) 2012-03-23 2012-03-23 透明導電膜積層体及びタッチパネル

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WO2015045965A1 (fr) * 2013-09-30 2015-04-02 富士フイルム株式会社 Stratifié pour panneaux tactiles, et panneau tactile
WO2015045408A1 (fr) * 2013-09-30 2015-04-02 凸版印刷株式会社 Écran tactile
WO2015192520A1 (fr) * 2014-06-20 2015-12-23 京东方科技集团股份有限公司 Écran tactile, procédé de fabrication de cet écran et appareil d'affichage
CN105551582A (zh) * 2016-02-03 2016-05-04 张家港康得新光电材料有限公司 一种透明导电薄膜及具有该透明导电薄膜的触摸屏
CN106132687A (zh) * 2014-03-28 2016-11-16 富士胶片株式会社 导电膜层叠体以及使用该导电膜层叠体的触摸面板
WO2020204103A1 (fr) * 2019-04-02 2020-10-08 凸版印刷株式会社 Corps multicouche conducteur transparent formant barrière contre les gaz, son procédé de production, et dispositif

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JP6131165B2 (ja) * 2013-10-09 2017-05-17 富士フイルム株式会社 タッチパネル用積層体
JPWO2015072414A1 (ja) * 2013-11-15 2017-03-16 コニカミノルタ株式会社 タッチパネルの製造方法
JP6355012B2 (ja) * 2013-11-22 2018-07-11 大日本印刷株式会社 フィルムセンサ、フィルムセンサの製造方法、タッチ位置検出機能付き表示装置、およびフィルムセンサを作製するための積層体
KR20150077765A (ko) * 2013-12-30 2015-07-08 주식회사 동진쎄미켐 표면처리를 통한 금속 나노와이어 기반 투명 전도성 막의 패터닝 방법
FI128433B (en) * 2018-05-09 2020-05-15 Canatu Oy An electrically conductive multilayer film comprising a coating layer

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WO2011078231A1 (fr) * 2009-12-24 2011-06-30 日本写真印刷株式会社 Capteur tactile de type capacitif, dispositif électronique et procédé de fabrication d'un stratifié à film conducteur transparent

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WO2011078231A1 (fr) * 2009-12-24 2011-06-30 日本写真印刷株式会社 Capteur tactile de type capacitif, dispositif électronique et procédé de fabrication d'un stratifié à film conducteur transparent

Cited By (10)

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Publication number Priority date Publication date Assignee Title
WO2015045965A1 (fr) * 2013-09-30 2015-04-02 富士フイルム株式会社 Stratifié pour panneaux tactiles, et panneau tactile
WO2015045408A1 (fr) * 2013-09-30 2015-04-02 凸版印刷株式会社 Écran tactile
JP2015069508A (ja) * 2013-09-30 2015-04-13 凸版印刷株式会社 タッチパネル
CN106132687A (zh) * 2014-03-28 2016-11-16 富士胶片株式会社 导电膜层叠体以及使用该导电膜层叠体的触摸面板
WO2015192520A1 (fr) * 2014-06-20 2015-12-23 京东方科技集团股份有限公司 Écran tactile, procédé de fabrication de cet écran et appareil d'affichage
CN105551582A (zh) * 2016-02-03 2016-05-04 张家港康得新光电材料有限公司 一种透明导电薄膜及具有该透明导电薄膜的触摸屏
WO2020204103A1 (fr) * 2019-04-02 2020-10-08 凸版印刷株式会社 Corps multicouche conducteur transparent formant barrière contre les gaz, son procédé de production, et dispositif
JP2020168775A (ja) * 2019-04-02 2020-10-15 凸版印刷株式会社 透明導電性ガスバリア積層体及びその製造方法、並びにデバイス
CN113573886A (zh) * 2019-04-02 2021-10-29 凸版印刷株式会社 透明导电性阻气层叠体及其制造方法、以及设备
JP7287069B2 (ja) 2019-04-02 2023-06-06 凸版印刷株式会社 透明導電性ガスバリア積層体及びその製造方法、並びにデバイス

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