JP2013246975A - Conductive optical member and electronic device including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high durability conductive optical member which can be patterned easily by etching.SOLUTION: A conductive optical member 1 comprises: a substrate 2; a transparent conductive layer 3 containing metal nanowire 5 and covering the substrate 2; and a transparent coating layer 4 covering the conductive layer 3. The coating layer 4 contains a resin matrix 7, and particles 6 having a porosity of 25% or less and a refractive index of 1.20-1.40 dispersed into the resin matrix 7.

Description

  The present invention relates to a conductive optical member having both transparency and conductivity, and an electronic device including the conductive optical member.

  Conventionally, conductive optical members having both transparency and conductivity have been widely applied to devices such as touch panels, organic EL, liquid crystal displays, and solar cells. As such a conductive optical member, those utilizing metal nanowires have been proposed in recent years. Moreover, in order to protect the conductive layer containing a metal nanowire, or to suppress reflection of light in the conductive layer, the conductive layer is also covered.

  For example, in Patent Document 1, a transparent conductive film (conductive layer) formed by a transparent coating film containing metal nanowires is provided on a transparent substrate, and a transparent overcoat layer is provided on the surface of the transparent conductive film and an overcoat is provided. It is disclosed that a substrate with a transparent conductive film is obtained by forming a layer using a condensate of a hydrolyzable silane compound as a matrix resin.

  However, when an overcoat layer is provided as described in Patent Document 1, an etching solution is formed even if the conductive layer is formed into an appropriate pattern shape by performing an etching process on the conductive layer in the conductive optical member. Will be blocked by the overcoat layer. For this reason, it has been difficult to pattern the conductive layer by etching.

  Patent Document 1 also discloses blending hollow silica into the overcoat layer. In that case, the etching solution easily penetrates into the overcoat layer and the conductive layer is easily etched. However, in this case, the overcoat layer easily transmits moisture, and the durability of the conductive layer is likely to be lowered.

JP 2011-204649 A

  The present invention has been made in view of the above reasons, and an object of the present invention is to provide a conductive optical member that can be easily patterned by etching and has high durability.

  The conductive optical member according to the present invention includes a base material, a metal nanowire, a transparent conductive layer that covers the base material, and a transparent coating layer that covers the conductive layer, and the coating layer is a resin. It contains a matrix and particles having a porosity of 25% or less and a refractive index of 1.20 to 1.40 dispersed in the resin matrix.

  It is preferable that the particles include at least one of sodium hexafluoroaluminate particles and magnesium fluoride particles.

  The average particle diameter of the particles is preferably smaller than the thickness of the coating layer.

  The coating layer preferably has a refractive index of less than 1.60.

  The haze of the conductive optical member is preferably 2 or less.

  It is preferable that the conductive optical member further includes an intermediate layer having a refractive index higher than that of the coating layer between the base material and the conductive layer.

  The electronic device according to the present invention includes the conductive optical member, and is configured such that the conductive optical member is visually recognized from the coating layer side.

  According to the present invention, since the coating layer easily penetrates the etching solution during the etching process, the patterning of the conductive layer by the etching process becomes easy, and further, the permeation of moisture in the coating layer is suppressed, so that the durability of the conductive optical member is improved. Improves.

It is sectional drawing which shows the electroconductive optical member in one Embodiment of this invention. It is sectional drawing which shows the touchscreen and image display apparatus in one Embodiment of this invention.

  As shown in FIG. 1, the conductive optical member 1 according to this embodiment includes a base material 2, a transparent conductive layer 3 that covers the base material 2, and a transparent coating layer 4 that covers the conductive layer 3. In the present embodiment, the intermediate layer 8 is interposed between the base material 2 and the conductive layer 3, and the conductive layer 3 covers the base material 2 through the intermediate layer 8. For this reason, as shown in FIG. 1, the conductive optical member 1 includes a substrate 2, an intermediate layer 8, a conductive layer 3, and a coating layer 4. The base material 2, the intermediate layer 8, the conductive layer 3, and the coating layer 4 are laminated in this order. That is, the intermediate layer 8 is laminated on the first main surface of the substrate 2, the conductive layer 3 is laminated on the main surface of the intermediate layer 8 opposite to the substrate 2, and the intermediate layer 8 of the conductive layer 3 is formed. The covering layer 4 is laminated on the main surface opposite to the above.

  First, the substrate 2 will be described. It is preferable that the base material 2 has a light transmittance. The light transmittance of the substrate 2 is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more.

  Although the shape in particular of the base material 2 is not restrict | limited, It is preferable that it is plate shape or a film form. In particular, from the viewpoint of improving the productivity and transportability of the conductive optical member 1, the shape of the substrate 2 is preferably a film.

  When the substrate 2 is in the form of a film, the thickness of the substrate 2 is preferably in the range of 10 μm to 500 μm. In this case, the transparency of the substrate 2 is particularly good, and the workability during production and handling of the conductive optical member 1 is also good. The thickness of the substrate 2 is preferably in the range of 25 μm to 200 μm. In particular, when the thickness of the substrate 2 is 25 μm or more and 150 μm or less, the conductive optical member 1 can be made thinner and lighter, and the occurrence of interference on the front and back of the conductive optical member 1 is suppressed. Thermal contraction when the is heated is suppressed, and problems such as deterioration of workability due to thermal contraction of the substrate 2 are suppressed.

  The material of the base material 2 is not particularly limited. Examples of the material of the substrate 2 include glass and transparent resin. Examples of transparent resins include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polymethyl methacrylate copolymer, triacetyl cellulose, polyolefin, polyamide, polyvinyl chloride, amorphous polyolefin, cycloolefin polymer, cycloolefin copolymer, etc. Can be mentioned.

  In particular, the substrate 2 is preferably formed from polyester. Among the polyester films, in particular, biaxially stretched films made of polyethylene terephthalate (PET) or polyethylene naphthalate have excellent mechanical properties, heat resistance, chemical resistance, etc., so magnetic tape, ferromagnetic thin film tape, packaging Films for electronic use, films for electronic parts, electrical insulating films, films for laminating, films to be attached to the surface of displays, and films for protecting various members. Especially for display applications, base films such as prism lens sheets, touch panels, and backlights, which are members of liquid crystal display devices, TV optical film base films, optical films used for plasma TV front optical filters, and near infrared rays It is suitable as a cut film, a base film for an electromagnetic wave shielding film, and the like.

  Examples of polyesters include aromatic dicarboxylic acid components such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, ethylene glycol, 1,4-butanediol, 1,4- Aromatic polyesters produced by reaction with glycol components such as cyclohexanedimethanol and 1,6-hexanediol are preferred. In particular, polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate and the like are preferable. In addition, the polyester may be produced by copolymerizing a plurality of the exemplified components.

  The base material 2 may contain organic or inorganic particles. In this case, the winding property and transportability of the base material 2 are improved. The particles that can be contained in the substrate 2 include calcium carbonate particles, calcium oxide particles, aluminum oxide particles, kaolin, silicon oxide particles, zinc oxide particles, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, urea resin particles, and melamine resin. Examples thereof include particles and crosslinked silicone resin particles.

  Further, the base material 2 may further contain a colorant, an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant, a catalyst, other resins, and the like as long as the transparency is not impaired.

  The haze of the substrate 2 is preferably 3% or less. In this case, the visibility of images and the like through the conductive optical member 1 is improved, and it is particularly suitable as a member for optical applications. More preferably, the haze is 1.5% or less.

  A transparent back surface coating layer 9 is preferably laminated on the second main surface of the substrate 2 opposite to the first main surface. In this case, it becomes difficult for the low molecular weight component to precipitate from the base material 2, and thus whitening of the base material 2 is suppressed. For this reason, the favorable transparency of the conductive optical member 1 is maintained.

  Although the material in particular of the back surface coating layer 9 is not restrict | limited, For example, it forms from acrylate resin, urethane acrylate resin, etc.

  Moreover, in order for the back surface coating layer 9 to sufficiently suppress the precipitation of the low molecular weight component from the base material 2, the thickness of the back surface coating layer 9 is preferably in the range of 0.5 μm or more and 10 μm or less.

  Moreover, it is preferable that the back surface coating layer 9 has antiblocking property. That is, it is preferable that blocking is suppressed by the back surface coating layer 9 when the conductive optical member 1 is rolled up and stacked. For that purpose, it is preferable that the surface of the back surface coating layer 9 is formed to be uneven. For that purpose, it is preferable that the surface of the back surface coating layer 9 is formed with irregularities by mechanical processing. Moreover, it is also preferable that an unevenness | corrugation is formed in the surface of this back surface coating layer 9 because the back surface coating layer 9 contains fillers, such as a silica particle. In this case, the back surface coating layer 9 contains, for example, acrylate resin or urethane acrylate resin in the range of 80% by mass to 95% by mass, and further silica particles having an average particle diameter of 250 nm in the range of 5% by mass to 20% by mass. It is preferable to contain.

  Moreover, it is also preferable to improve the lubricity of the electroconductive optical member 1 by the back surface coating layer 9, and for that purpose, it is also preferable that the back surface coating layer 9 contains, for example, a silicone leveling agent.

  When the back surface coating layer 9 is formed, it is preferable that the surface of the base material 2 overlapping the back surface coating layer 9 is subjected to a surface treatment before the back surface coating layer 9 is formed. In this case, it is possible to improve wettability, adhesion and the like between the substrate 2 and the back surface coating layer 9. Moreover, it is preferable that the surface of the base material 2 overlapping with the intermediate layer 8 is subjected to a surface treatment before the intermediate layer 8 is formed. In this case, it is possible to improve wettability, adhesion and the like between the substrate 2 and the intermediate layer 8. Examples of the surface treatment method include physical surface treatment such as plasma treatment, corona discharge treatment and flame treatment, and chemical surface treatment with a coupling agent, an acidic component, an alkaline component, and the like.

  Next, the intermediate layer 8 will be described. The refractive index of the intermediate layer 8 is preferably larger than the refractive index of the coating layer 4, and particularly preferably 1.60 or more. The refractive index of the intermediate layer 8 is more preferably in the range of 1.65 to 1.90, and particularly preferably in the range of 1.70 to 1.85. The thickness of the intermediate layer 8 is preferably 150 nm or less, more preferably 5 to 100 nm, and even more preferably 5 to 80 nm.

  By adjusting the refractive index and thickness of the intermediate layer 8 as described above, the color of the conductive layer 3 is less likely to appear on the appearance of the conductive optical member 1. When the conductive optical member 1 does not include the intermediate layer 8, the conductive layer 3 containing the metal nanowires 5 tends to exhibit white color. For this reason, when the conductive layer 3 is patterned, the conductive optical member 1. The pattern of the conductive layer 3 tends to appear white on the external appearance. However, when the conductive optical member 1 includes the intermediate layer 8 as described above, the conductive layer 3 and the intermediate layer 8 overlap each other, so that the color of the conductive layer 3 becomes difficult to be visually recognized from the outside of the conductive optical member 1. For this reason, the pattern of the conductive layer 3 becomes inconspicuous in appearance.

  The intermediate layer 8 is preferably formed from a reactive curable resin composition. For example, the intermediate layer 8 is preferably formed from at least one of a thermosetting resin composition and an ionizing radiation curable resin composition.

  Thermosetting resin composition contains thermosetting resin such as phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, silicon resin, polysiloxane resin, etc. To do. A crosslinking agent, a polymerization initiator, a curing agent, a curing accelerator, a solvent and the like may be used together with the thermosetting resin as necessary. The intermediate layer 8 can be formed by applying such a thermosetting resin composition onto the substrate 2, for example, and then heating and thermosetting the thermosetting resin composition.

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

  When the ionizing radiation curable resin composition is a photocurable resin composition such as an ultraviolet curable resin composition, the photocurable resin composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, thioxanthones, and the like. The photocurable resin composition may contain a photosensitizer in addition to the photopolymerization initiator or in place of the photopolymerization initiator. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone. Such a photocurable resin composition is applied onto, for example, the substrate 2, and then the photocurable resin composition is irradiated with light such as ultraviolet rays to be photocured, whereby the intermediate layer 8 can be formed. .

  The refractive index of the intermediate layer 8 can be easily adjusted by the composition of the resin composition for forming the intermediate layer 8. It is also preferable that the refractive index of the intermediate layer 8 is adjusted by the intermediate layer 8 containing particles for adjusting the refractive index and the ratio thereof being adjusted.

  The particle diameter of the refractive index adjusting particles is preferably sufficiently small, that is, the refractive index adjusting particles are preferably so-called ultrafine particles. In this case, the light transmittance of the intermediate layer 8 is sufficiently maintained. . The particle size of the particles for adjusting the refractive index is particularly preferably in the range of 0.5 nm to 150 nm. The particle diameter of the particles for adjusting the refractive index is the diameter of a circle (area equivalent circle) having the same area as the projected area calculated from the electron micrograph image of the particles.

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

  The content of the particles for adjusting the refractive index in the intermediate layer 8 is appropriately adjusted so that the refractive index of the intermediate layer 8 has an appropriate value, but the ratio of the particles for adjusting the refractive index in the intermediate layer 8 is particularly suitable. Is preferably adjusted to be 5 to 70% by volume.

Specific examples of the particles for adjusting the refractive index include particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony. Specific examples of the oxides, ZnO (refractive index 1.90), TiO2 (refractive index 2.3~2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1.71 ), SnO ₂ , ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ And O ₃ (refractive index 1.63).

  The intermediate layer 8 includes particles containing one or more oxides selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony, and at least one of methacryl functional silane and acrylic functional silane. It is also preferable to contain. In this case, the adhesion between the intermediate layer 8 and the conductive layer 3 is improved. Examples of the methacrylic functional silane include 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane. Examples of the acrylic functional silane include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropylmethyldimethoxysilane.

  Although the content of the methacryl functional silane and the acryl functional silane in the intermediate layer 8 is not particularly limited, the ratio of the total amount of the methacryl functional silane and the acrylic functional silane in the intermediate layer 8 is in the range of 5 to 30% by mass. Preferably there is. When the proportion is 5% by mass or more, the adhesion between the intermediate layer 8 and the conductive layer 3 is sufficiently high, and when the proportion is 30% by mass or less, the crosslinking density in the intermediate layer 8 is sufficiently improved. Thus, the hardness of the intermediate layer 8 becomes sufficiently high.

  The main surface of the intermediate layer 8 opposite to the substrate 2 is preferably subjected to a surface treatment before the conductive layer 3 is formed. In this case, the wettability, adhesion, etc. between the intermediate layer 8 and the conductive layer 3 can be improved. Examples of the surface treatment method include plasma surface treatment, corona discharge treatment, physical surface treatment such as flame treatment, and chemical surface treatment with a coupling agent, acid, and alkali.

  Next, the conductive layer 3 will be described. The conductive layer 3 is a transparent layer containing the metal nanowire 5. The metal nanowire 5 is a metal fiber having a nano-sized (1 to 1000 nm) diameter. Although the kind of metal which comprises the metal nanowire 5 is not restrict | limited in particular, For example, Ag, Au, Cu, Co, Al, Pt etc. are mentioned. In particular, in order to further improve the conductivity of the conductive layer 3, the metal constituting the metal nanowire 5 preferably includes at least one selected from Au, Ag, Cu and Pt, and particularly at least one selected from Ag and Cu. It is preferable to contain.

  The method for producing the metal nanowire 5 is not particularly limited, and for example, a known method such as a liquid phase method or a gas phase method can be employed. For example, as a specific example of a method for producing Ag nanowires (silver nanowires), Adv. Mater. 2002, 14, P833-837, Chem. Mater. Examples include methods disclosed in documents such as 2002, 14, P4736 to 4745, and Japanese translations of PCT publication No. 2009-505358. Moreover, as a specific example of the manufacturing method of Au nanowire (gold nanowire), the method currently disclosed by Unexamined-Japanese-Patent No. 2006-233252 etc. is mentioned. Moreover, as a method of manufacturing Cu nanowire (copper nanowire), the method currently disclosed by Unexamined-Japanese-Patent No. 2002-266007 etc. is mentioned. Moreover, as a method of manufacturing Co nanowire (cobalt nanowire), a method disclosed in Japanese Patent Application Laid-Open No. 2004-149871 can be given. In particular, Adv. Mater. 2002, 14, P 833-837, and Chem. Mater. If the manufacturing method of Ag nanowire currently disclosed by 2002, 14, P4736-4745 is employ | adopted, Ag nanowire can be manufactured simply and in large quantities by an aqueous system.

  The average diameter of the metal nanowire 5 is preferably in the range of 10 nm to 100 nm. When the average diameter is 10 nm or more, the conductivity of the conductive layer 3 is particularly high. Further, when the average particle size is 100 nm or less, the transparency of the conductive layer 3 is particularly high. The average diameter of the metal nanowire 5 is more preferably in the range of 20 nm to 100 nm, and most preferably in the range of 40 nm to 100 nm.

  The average length of the metal nanowires 5 is preferably in the range of 1 μm to 100 μm. When the average length is 1 μm or more, the conductivity of the conductive layer 3 is particularly high. Further, when the average particle diameter is 100 μm or less, the metal nanowires 5 are less likely to aggregate in the conductive layer 3, and thus the transparency of the conductive layer 3 is improved. The average length of the metal nanowire 5 is more preferably in the range of 1 μm to 50 μm, and most preferably in the range of 3 μm to 50 μm.

  In addition, the average diameter of the metal nanowire 5 is a value obtained by measuring the diameter of a sufficient number of metal nanowires 5 and arithmetically averaging the results. The average length of the metal nanowires 5 is a value obtained by measuring the length of a sufficient number of metal nanowires 5 and arithmetically averaging the results. The diameter and length of the metal nanowire 5 are derived by image analysis of an electron microscope image of the metal nanowire 5. For example, when the electron microscope image of the metal nanowire 5 is bent, the diameter (projection diameter (D)) and area (projection area (S)) of the metal nanowire 5 are calculated by image analysis. Further, the length (L = S / D) of the metal nanowire 5 is obtained by dividing the projected area (S) by the projected diameter (D). In order to derive the average diameter and the average length of the metal nanowires 5, it is preferable to measure the diameters and lengths of at least 100 metal nanowires 5. More preferably, it is measured.

  The ratio of the metal nanowires 5 in the conductive layer 3 is not particularly limited, but is preferably in the range of 0.01% by mass to 90% by mass, and further in the range of 0.1% by mass to 30% by mass. Preferably, it is most preferable if it is in the range of 0.5 to 10% by mass.

  The conductive layer 3 is formed from a composition containing, for example, metal nanowires 5 and a resin component. In this case, the conductive layer 3 can be formed by a wet film formation method.

  Examples of the resin component in the composition for forming the conductive layer 3 include cellulose resin, silicone resin, fluorine resin, acrylic resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polystyrene resin, poly Ether sulfone resin, polyarylate resin, polycarbonate resin, polyurethane resin, polyacrylonitrile resin, polyvinyl acetal resin, polyamide resin, polyimide resin, diacryl phthalate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, etc. And a copolymer formed by polymerizing two or more monomers constituting these resins.

  It is also preferred that the resin component contains a reactive curable resin. For example, at least one of a thermosetting resin and an ionizing radiation curable resin is preferably used as the reactive curable resin.

  Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, and the like. The composition may contain a crosslinking agent, a polymerization initiator, a curing agent, a curing accelerator, a solvent, and the like as necessary together with the thermosetting resin.

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

  When the ionizing radiation curable resin is a photocurable resin such as an ultraviolet curable resin, the composition preferably further contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, thioxanthones, and the like. The composition containing the photocurable resin may contain a photosensitizer in addition to the photopolymerization initiator or in place of the photopolymerization initiator. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone.

  The composition for forming the conductive layer 3 may contain a solvent as necessary. As the solvent, for example, an organic solvent is used, water is used, or an organic solvent and water are used in combination. Examples of the organic solvent include alcohols such as methanol, ethanol and isopropyl alcohol (IPA); ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; And aromatic hydrocarbons such as xylene, and mixtures thereof.

  The amount of the solvent in the composition is appropriately adjusted so that the solid content can be uniformly dissolved or dispersed in the composition. The solid content concentration in the composition is preferably in the range of 0.1 to 50 mass%, more preferably in the range of 0.5 to 30 mass%.

  The composition for forming the conductive layer 3 is applied and further formed, whereby the conductive layer 3 is formed. In applying the composition, an appropriate method such as a roll coating method, a spin coating method, or a dip coating method is employed. The method for forming the composition into a film is appropriately selected according to the type of the resin component or the like in the composition. For example, when the composition contains a thermosetting resin, the conductive layer 3 containing the metal nanowires 5 is formed by heating and thermosetting the composition. Moreover, when the composition contains an ionizing radiation curable resin, the conductive layer 3 containing the metal nanowires 5 is formed by curing the composition by irradiating the composition with ionizing radiation such as ultraviolet rays. It is formed.

  The main surface of the conductive layer 3 opposite to the substrate 2 is preferably subjected to a surface treatment before the coating layer 4 is formed. In this case, it is possible to improve wettability and adhesion between the conductive layer 3 and the coating layer 4. Examples of the surface treatment method include plasma surface treatment, corona discharge treatment, physical surface treatment such as flame treatment, and chemical surface treatment with a coupling agent, acid, and alkali.

  The refractive index of the conductive layer 3 is not particularly limited, but may be in the range of 1.35 to 1.65 so that the white color of the conductive layer 3 is not sufficiently conspicuous on the appearance of the conductive optical member 1. preferable. The thickness of the conductive layer 3 is not particularly limited, but is preferably in the range of 10 to 300 nm. The refractive index of the conductive layer 3 is easily adjusted by changing the composition of the composition for forming the conductive layer 3.

  Next, the coating layer 4 will be described. The covering layer 4 is a transparent layer that covers the transparent conductive layer 3. The coating layer 4 contains a resin matrix 7 and particles 6 having a porosity of 25% or less and a refractive index of 1.20 to 1.40. The particles 6 are dispersed in the resin matrix 7 in the coating layer 4.

  Since the coating layer 4 contains the particles 6, the conductive layer 3 is easily etched although the conductive layer 3 is covered with the coating layer 4. That is, when the coating layer 4 is exposed to the etching solution for the wet etching process, the etching solution easily enters the interface between the resin matrix 7 and the particles 6 in the coating layer 4. Becomes easy to penetrate the coating layer 4. For this reason, the etching liquid easily reaches the conductive layer 3 without being shielded by the coating layer 4, and thus the conductive layer 3 is easily etched.

  Further, since the conductive layer 3 is covered with the coating layer 4, the conductive layer 3 is protected by the coating layer 4. For this reason, damage such as scratches is less likely to occur in the conductive layer 3.

  Further, since the porosity of the particles 6 is 25% or less and the refractive index is 1.20 to 1.34, the coating layer 4 can be made to have a low refractive index, and the coating layer 4 can be treated with moisture. Becomes difficult to transmit and the durability of the conductive optical member 1 is increased. In addition, it is difficult to obtain the particles 6 having a refractive index of less than 1.20. If the particles 6 are thus made to have a low refractive index, the crystal structure of the particles 6 becomes weak or the porosity of the particles 6 is high. It will become. If it does so, the coating layer 4 will become easy to collapse at the time of an etching process, or the durability of the electroconductive optical member 1 will fall. On the other hand, when the refractive index is higher than 1.34, it is difficult to lower the refractive index of the coating layer 4, and the crystal structure of the particles 6 becomes too strong to make etching difficult. Further, when the porosity of the particles 6 is higher than 25%, moisture easily penetrates the coating layer 4, so that the durability of the conductive optical member 1 is easily lowered, and the strength of the particles 6 is lowered and etching is performed. The coating layer 4 tends to collapse during the treatment.

  The refractive index of the particles 6 is more preferably 1.24 to 1.33. Further, the porosity of the particles 6 is more preferably 0 to 20%. More preferably, the porosity of the particles 6 is 0 to 15%.

  In addition, the porosity of the particle | grains 6 is a measured value of "the density calculated from the volume measured by CT imaging | photography with a micro CT system, and the mass measured by the ultramicro balance", and the "density measured by a hydrostatic method". Derived from the difference. The value of the refractive index of the particle 6 is known from scientific chronology, various papers, and the like. Moreover, the refractive index of the particle | grains 6 is measured by well-known methods, such as the Becke method and the method using Mie scattering.

  The average particle diameter of the particles 6 is preferably not more than the thickness of the coating layer 4. In this case, the smoothness of the coating layer 4 becomes high. Moreover, it is preferable that the average particle diameter of the particle | grains 6 is the range of 10-100 nm. If the average particle diameter is 10 nm or less, the refractive index of the coating layer 4 can be sufficiently reduced without excessively increasing the blending ratio of the particles 6. For this reason, the size of the area of the interface between the particles 6 and the resin matrix 7 in the coating layer 4 is appropriately maintained, and thus the permeability of the etching solution into the coating layer 4 is appropriately maintained. Moreover, the transparency of the coating layer 4 becomes difficult to be inhibited by the particles 6 when the average particle size is 100 nm or less. The average particle diameter of the particles 6 is measured by a dynamic light scattering method.

  Examples of a preferable material of the particles 6 for satisfying the above conditions include sodium hexafluoroaluminate (cryolite), magnesium fluoride, and the like. In particular, it is preferable that the particles 6 contain at least one of sodium hexafluoroaluminate particles and magnesium fluoride particles. In this case, particles 6 satisfying the above conditions can be easily obtained.

  It is particularly preferred that the particles 6 contain sodium hexafluoroaluminate particles. In this case, an acidic etchant such as iron chloride or copper chloride is used as the etchant, so that the conductive layer 3 is further easily etched.

  Moreover, it is preferable that the ratio of the particle | grains 6 in the coating layer 4 is the range of 25-80 mass%, and it is further more preferable that it is the range of 40-70 mass%. When the ratio of the particles 6 is 25% by mass or more, the interface between the particles 6 and the resin matrix 7 is sufficiently formed in the coating layer 4, so that the etching solution is more easily penetrated into the coating layer 4. The conductive layer 3 is further easily etched. Further, when the ratio of the particles 6 is 80% or less, moisture becomes more difficult to pass through the coating layer 4, and thus the durability of the conductive optical member 1 is further improved.

  The refractive index of the coating layer 4 is preferably in the range of 1.30 to 1.50, more preferably in the range of 1.40 to 1.49. The refractive index of the covering layer 4 is preferably lower than the refractive index of the conductive layer 3. The thickness of the coating layer 4 is preferably in the range of 200 nm or less. In this case, reflection of light on the surface of the conductive layer 3 is particularly suppressed. The refractive index of the coating layer 4 is easily adjusted by changing the composition of the resin matrix 7 in the coating layer 4, the type of particles 6, the ratio of the particles 6, and the like.

  The coating layer 4 is formed from a composition containing, for example, particles 6 and a binder material for forming the resin matrix 7. In this case, the coating layer 4 can be formed by a wet film forming method.

  Examples of the binder material include polymers having a main chain of at least one of silicon alkoxide resin, saturated hydrocarbon and polyether (for example, UV curable resin composition, thermosetting resin composition, etc.), fluorine in the polymer chain. A material selected from a resin containing units containing atoms is used.

  The composition as described above is applied on the conductive layer 3, and further, the composition is subjected to treatment such as heating, humidification, ultraviolet irradiation, electron beam irradiation and the like according to the properties of the binder material. The object is cured. Thereby, the coating layer 4 is formed. In applying the composition, an appropriate method such as a roll coating method, a spin coating method, or a dip coating method is employed.

  The coating layer 4 may contain a hydrolyzable organosilane polycondensate having a fluorine-substituted alkyl group. In this case, the water resistance and alkali resistance of the coating layer 4 are improved. Furthermore, the coating layer 4 having such characteristics can be formed by a wet film formation method. For this reason, compared with the case where dry-type film-forming methods, such as a vapor deposition method, are employed, manufacturing facilities can be simplified. Moreover, the manufacturing efficiency of the conductive optical member 1 is improved.

The formation of the coating layer 4 containing a hydrolyzable organosilane polycondensate having a fluorine-substituted alkyl group by a wet film-forming method using a composition containing a binder material will be further described. In this case, it is preferable that the binder material contains at least one selected from a hydrolyzable silane compound having a fluorine-substituted alkyl group and a partial hydrolyzate thereof. Examples of the hydrolyzable silane compound having a fluorine-substituted alkyl group include a compound represented by the general formula X ₃ Si— (CF ₂ ) _n —SiX ₃ , a general formula X ₃ Si— (CH ₂ ) ₂ — (CF ₂ ). _n - the compound represented by (CH _{2) 2} -SiX _3, a compound represented by the general formula _{X 3 Si- (CF 2) n} -CF 3, the formula _{X 3 Si- (CH 2) 2} - (CF 2) Examples thereof include a compound represented by _n— CF ₃ . In these formulas, X represents a functional group having hydrolytic condensation reactivity. This X can be selected from, for example, alkoxy groups such as OCH ₃ , OCH ₂ CH ₃ , OCH (CH ₃ ) ₂ , halogens such as Cl and F, and the like. A plurality of types of X in one molecule are independently selected. n is an integer, and it is particularly preferable that n is an integer of 1 to 10. M is an integer, and it is particularly preferable that m is an integer of 0 or more and 9 or less.

  The composition may further contain a water and oil repellent material. In this case, the coating layer 4 can be imparted with antifouling properties. As the water and oil repellent material, a general wax-based material or the like can be used. In particular, when a fluorine-containing compound is used, the removability of the coating layer 4 such as dirt and fingerprints is particularly improved, and the frictional resistance of the surface of the coating layer 4 is reduced and the wear resistance of the coating layer 4 is improved.

  In a state where the conductive layer 3 is covered with the coating layer 4, the conductive layer 3 is patterned by performing a wet etching process on the conductive layer 3 as necessary. Thereby, the conductive layer 3 in the conductive optical member 1 is formed in an appropriate pattern shape.

  The patterning of the conductive layer 3 by the wet etching process is performed as follows, for example. First, an etching resist is formed on the coating layer 4 in the conductive optical member 1. Next, the area | region which is not covered with the etching resist in the coating layer 4 is exposed to etching liquid. In this region, the etching solution penetrates the coating layer 4 and reaches the conductive layer 3 as described above, whereby the conductive layer 3 and the coating layer 4 covering the conductive optical member 1 are partially removed. The In the region covered with the etching resist, the conductive layer 3 and the covering layer 4 covering the conductive layer 3 remain on the conductive optical member 1. Subsequently, the etching resist is removed from the conductive optical member 1. Thereby, the conductive layer 3 and the coating layer 4 covering the conductive layer 3 are formed in an appropriate pattern shape.

  In addition, although the conductive optical member 1 which concerns on this embodiment is provided with the base material 2, the intermediate | middle layer 8, the conductive layer 3, and the coating layer 4, the structure of the conductive optical member 1 is not restricted to this. For example, the conductive optical member 1 may not include the intermediate layer 8, and in that case, the conductive layer 3 may be directly laminated on the substrate 2. Further, the conductive optical member 1 may include additional elements other than the base material 2, the intermediate layer 8, the conductive layer 3, and the coating layer 4.

  The haze of the conductive optical member 1 is preferably 2 or less. In this case, since the transparency of the conductive optical member 1 is increased, the conductive optical member 1 is suitable for an electronic device that requires optical characteristics.

  The conductive layer 3 in the conductive optical member 1 forms an electrode or the like in an electronic device that requires optical characteristics such as a touch panel, an organic electroluminescence display panel, a plasma display panel, a liquid crystal display panel, a photoelectric conversion device, and the like. To be used.

  The conductive optical member 1 according to the present embodiment is incorporated in an electronic device as it is, for example, so that the conductive layer 3 in the conductive optical member 1 is used as an electrode or the like. Further, the conductive layer 3 may be used as an electrode or the like by peeling the member composed of the conductive layer 3 and the covering layer 4 from the conductive optical member 1 and incorporating this member into the electronic device.

  In an electronic device including the conductive optical member 1, the conductive optical member 1 is provided so that the conductive optical member 1 is visually recognized from the outside and the conductive optical member 1 is visually recognized from the coating layer 4 side. Is preferred. For example, the electronic device includes a conductive optical member 1 and a transparent cover member disposed on the side of the coating layer 4 with respect to the conductive optical member 1. It is preferable that the member 1 is configured to be visually recognized. In this case, the pattern shape of the conductive layer 3 is particularly difficult to be visually recognized from the outside.

  FIG. 2 shows a schematic configuration of an example of the touch panel 10 including the conductive optical member 1 and an example of the image display device 17 including the touch panel 10. In FIG. 2, illustration of the back surface coating layer 9 in the conductive optical member 1 is omitted.

  The image display device 17 illustrated in FIG. 2 includes an image display device 16 such as a liquid crystal display device and the touch panel 10. The touch panel 10 includes an antireflection layer 11, two conductive optical members 1 (hereinafter referred to as a first conductive optical member 101 and a second conductive optical member 102), and a transparent cover member 18. The antireflection layer 11 is formed from, for example, a known antireflection film. The cover member 18 is composed of, for example, a glass plate or an icon sheet. The antireflection layer 11, the first conductive optical member 101, the second conductive optical member 102, and the cover member 18 are laminated in this order. The antireflection layer 11 and the surface of the first conductive optical member 101 opposite to the conductive layer 3 are joined via a transparent adhesive layer (OCA (optically clear adhesive) layer) 12. The surface on the conductive layer 3 side in the first conductive optical member 101 and the surface on the opposite side to the conductive layer 3 in the second conductive optical member 102 are transparent adhesive layers (OCA (optically clear adhesive) layer). 13 is joined. The surface of the second conductive optical member 102 on the side of the conductive layer 3 and the cover member 18 are joined via a transparent adhesive layer (OCA (optically clear adhesive) layer) 14. In this touch panel 10, the conductive layer 3 in the first conductive optical member 101 and the conductive layer 3 in the second conductive optical member 102 function as electrodes.

  The outer surface of the antireflection layer 11 in the touch panel 10 and the image display device 16 are fixed by an adhesive tape 15.

  When the conductive optical member 1 is incorporated in a device such as the touch panel 10, the refractive index of the layers constituting the conductive optical member 1, that is, the refraction of the base material 2, the intermediate layer 8, the conductive layer 3, and the coating layer 4. The rate is preferably adjusted as appropriate according to the optical design of the device.

[Example 1]
A transparent polyethylene terephthalate film (thickness 125 μm) was prepared as a substrate.

  A back side coating layer was formed on this substrate as follows.

  An acrylic resin was dissolved by adding 80.84 parts by mass of methyl ethyl ketone to 10.8 parts of an acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA), thereby preparing a mixed solution. To this mixed solution, 8.0 parts by mass of particles for preventing blocking (silica particle dispersion using methyl ethyl ketone as a dispersion solvent; solid content 15%) were added and mixed at room temperature. Further, 0.36 part of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by stirring in a constant temperature atmosphere at 25 ° C. for 30 minutes. Mixed. This prepared the composition for forming a back surface side coating layer. This composition was applied to one side of the substrate with a wire bar coater # 10, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further irradiated with ultraviolet rays (ultraviolet intensity 500 mJ / cm) to be cured. It was. As a result, a back surface side coating layer having a refractive index of 1.49 and a thickness of 1100 nm was formed.

  Next, an intermediate layer was formed on the surface of the substrate opposite to the back surface side coating layer as follows.

  Acrylic resin is dissolved by adding and mixing 50.0 parts by mass of methyl ethyl ketone and 39.65 parts by mass of methyl isobutyl ketone to 1.2 parts of acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA). Thus, a mixed solution was prepared. To this mixed liquid, 9.0 parts by mass of particles for adjusting the refractive index (zirconia dispersion using methyl ethyl ketone as a dispersion solvent; solid content 20%) were added and mixed at room temperature. 0.15 part of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, product name Irgacure 184, manufactured by Ciba Geigy Co., Ltd.) was further added to this mixed solution and mixed well, followed by stirring in a constant temperature atmosphere at 25 ° C. for 30 minutes. Mixed. This prepared the composition for forming an intermediate | middle layer. This composition is applied to one side of the substrate with a wire bar coater # 4, dried at room temperature for 2 minutes, dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). It was. As a result, an intermediate layer having a refractive index of 1.70 and a thickness of 50 nm was formed.

  Next, a conductive layer was formed on the intermediate layer as follows.

  A resin-containing liquid is prepared by mixing 1.5 parts by mass of acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number A-DPH) with 22.0 parts by mass of methyl ethyl ketone and 26.35 parts by mass of methyl isobutyl ketone. did. Further, silver nanowires having an average diameter of 60 nm and an average length of 5 μm were prepared as metal nanowires. In addition, this silver nanowire was produced by the method according to the method as described in a well-known paper (Materials Chemistry and Physics vol.114 p333-338 "Preparation of Ag nanorods with high yield by polyol process"). By adding this metal nanowire to methyl ethyl ketone, a metal nanowire dispersion having a solid content of 3.0% by mass was obtained.

  50.0 parts by mass of the metal nanowire dispersion was added to the resin-containing liquid and mixed well. Furthermore, 0.15 parts by mass of a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Geigy, product name Irgacure 184) was added and mixed well, followed by stirring and mixing for 30 minutes in a constant temperature atmosphere at 25 ° C. A composition for forming a conductive layer was prepared. This composition was applied onto the intermediate layer with a wire bar coater # 10. Further, the composition on the intermediate layer was dried by allowing it to stand at room temperature (23 ° C.) for 2 minutes, and subsequently heated at 120 ° C. for 2 minutes. Subsequently, the composition was irradiated with ultraviolet rays at an intensity of 500 mJ / cm. As a result, a conductive layer having a thickness of 100 nm was formed.

  Next, the coating layer 4 was formed on the conductive layer 3 as follows.

  In order that the mass ratio of cryolite particles (sodium hexafluoroaluminate particles) in the coating layer would be 65%, a composition for forming the coating layer was prepared as follows. Acrylic resin is dissolved by adding 43.0 parts by mass of methyl ethyl ketone and 42.8 parts by mass of methyl isobutyl ketone to 1.05 parts by mass of acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA). Thus, a mixed solution was prepared. To this mixed solution, 13.0 parts by mass of sodium hexafluoroaluminate particle dispersion (solid content 15% by mass) was added and mixed at room temperature. The sodium hexafluoroaluminate (cryolite) particles contained in this sodium hexafluoroaluminate particle dispersion have an average particle size of 50 nm, a porosity of 5% or less, and a refractive index of 1.33. The dispersion solvent is methyl ethyl ketone. Further, 0.15 parts by mass of a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Irgacure 184, manufactured by Ciba Geigy Co., Ltd.) was added to this mixed solution and mixed well, followed by stirring for 30 minutes in a constant temperature atmosphere at 25 ° C. Mixed. This obtained the composition for forming a coating layer.

  This composition is applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). Thus, a coating layer having a refractive index of 1.428 and a thickness of 100 nm was formed.

  As a result, a conductive optical member having a structure in which a base material, an intermediate layer, a conductive layer, and a coating layer were sequentially laminated was obtained.

[Example 2]
In Example 1, when forming the coating layer, the mass ratio of cryolite particles (sodium hexafluoroaluminate particles) in the coating layer is 70%, so that the coating layer is formed. The composition was prepared as follows. Acrylic resin (made by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA) is dissolved by adding 0.90 parts by mass of methyl ethyl ketone 42.48 parts by mass and methyl isobutyl ketone 42.47 parts by mass. Thus, a mixed solution was prepared. To this mixed solution, 14.0 parts by mass of sodium hexafluoroaluminate particle dispersion (solid content: 15% by mass) was added and mixed at room temperature. The sodium hexafluoroaluminate (cryolite) particles contained in this sodium hexafluoroaluminate particle dispersion have an average particle size of 50 nm, a porosity of 5% or less, and a refractive index of 1.33. The dispersion solvent is methyl ethyl ketone. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer having a refractive index of 1.419 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Example 3]
In Example 1, in forming the coating layer, the mass ratio of cryolite particles (sodium hexafluoroaluminate particles) in the coating layer is 40%, so that the coating layer is formed. The composition was prepared as follows. Acrylic resin (made by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA) is dissolved in acrylic resin by adding and mixing 45.03 parts by mass of methyl ethyl ketone and 45.02 parts by mass of methyl isobutyl ketone to 1.80 parts by mass. Thus, a mixed solution was prepared. To this mixed solution, 8.0 parts by mass of sodium hexafluoroaluminate particle dispersion (solid content 15% by mass) was added and mixed at room temperature. The sodium hexafluoroaluminate (cryolite) particles contained in this sodium hexafluoroaluminate particle dispersion have an average particle size of 50 nm, a porosity of 5% or less, and a refractive index of 1.33. The dispersion solvent is methyl ethyl ketone. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer having a refractive index of 1.465 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Example 4]
In Example 1, when forming the coating layer, the mass ratio of cryolite particles (sodium hexafluoroaluminate particles) in the coating layer is 80%, so that the coating layer is formed. The composition was prepared as follows. Acrylic resin is dissolved by adding 43.0 parts by mass of methyl ethyl ketone and 40.25 parts by mass of methyl isobutyl ketone to 0.60 parts by mass of acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA). Thus, a mixed solution was prepared. To this mixed solution, 16.0 parts by mass of sodium hexafluoroaluminate particle dispersion (solid content 15% by mass) was added and mixed at room temperature. The sodium hexafluoroaluminate (cryolite) particles contained in this sodium hexafluoroaluminate particle dispersion have an average particle size of 50 nm, a porosity of 5% or less, and a refractive index of 1.33. The dispersion solvent is methyl ethyl ketone. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer having a refractive index of 1.396 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Example 5]
In Example 1, when forming the coating layer, the mass ratio of cryolite particles (sodium hexafluoroaluminate particles) in the coating layer is 25%, so that the coating layer is formed. The composition was prepared as follows. Acrylic resin (made by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA) is dissolved in acrylic resin by adding 48.0 parts by mass of methyl ethyl ketone and 44.60 parts by mass of methyl isobutyl ketone to 2.25 parts by mass. To prepare a mixed solution. To this mixed solution, 5.0 parts by mass of sodium hexafluoroaluminate particle dispersion (solid content 15% by mass) was added and mixed at room temperature. The sodium hexafluoroaluminate (cryolite) particles contained in this sodium hexafluoroaluminate particle dispersion have an average particle size of 50 nm, a porosity of 5% or less, and a refractive index of 1.33. The dispersion solvent is methyl ethyl ketone. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer having a refractive index of 1.480 and a thickness of 100 nm was obtained.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Example 6]
In Example 1, when forming the coating layer, the mass ratio of cryolite particles (sodium hexafluoroaluminate particles) in the coating layer is 85%, so that the coating layer is formed. The composition was prepared as follows. Acrylic resin is dissolved by adding 41.2 parts by mass of methyl ethyl ketone and 41.2 parts by mass of methyl isobutyl ketone to 0.45 parts by mass of acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA). Thus, a mixed solution was prepared. To this mixed solution, 17.0 parts by mass of sodium hexafluoroaluminate particle dispersion (solid content 15% by mass) was added and mixed at room temperature. The sodium hexafluoroaluminate (cryolite) particles contained in this sodium hexafluoroaluminate particle dispersion have an average particle size of 50 nm, a porosity of 5% or less, and a refractive index of 1.33. The dispersion solvent is methyl ethyl ketone. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer having a refractive index of 1.383 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Example 7]
In Example 1, when forming the coating layer, the mass ratio of cryolite particles (sodium hexafluoroaluminate particles) in the coating layer is 20%, so that the coating layer is formed. The composition was prepared as follows. Methyl ethyl ketone 46.73 parts by mass and methyl isobutyl ketone 46.72 parts by mass are added to 2.4 parts by mass of acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA), and the acrylic resin is dissolved. Thus, a mixed solution was prepared. To this mixed solution, 4.0 parts by mass of sodium hexafluoroaluminate particle dispersion (solid content: 15% by mass) was added and mixed at room temperature. The sodium hexafluoroaluminate (cryolite) particles contained in this sodium hexafluoroaluminate particle dispersion have an average particle size of 50 nm, a porosity of 5% or less, and a refractive index of 1.33. The dispersion solvent is methyl ethyl ketone. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer having a refractive index of 1.485 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Example 8]
In Example 1, instead of the sodium hexafluoroaluminate particle dispersion, a magnesium fluoride particle dispersion (solid content: 15% by mass) is used, and the mass ratio of the magnesium fluoride particles in the coating layer is 65%. A coating layer was formed. The average particle diameter of the magnesium fluoride particles contained in this magnesium fluoride particle dispersion is 20 nm, the porosity is 1% or less, the refractive index is 1.37, and the dispersion solvent is methyl ethyl ketone. As a result, a coating layer having a refractive index of 1.446 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Example 9]
In Example 4, instead of the sodium hexafluoroaluminate particle dispersion, a magnesium fluoride particle dispersion (solid content: 15% by mass) is used, and the mass ratio of the magnesium fluoride particles in the coating layer is 80%. A coating layer was formed. The average particle diameter of the magnesium fluoride particles contained in this magnesium fluoride particle dispersion is 20 nm, the porosity is 1% or less, the refractive index is 1.37, and the dispersion solvent is methyl ethyl ketone. As a result, a coating layer having a refractive index of 1.422 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 4 except for the above.

[Example 10]
In Example 5, instead of the sodium hexafluoroaluminate particle dispersion, a magnesium fluoride particle dispersion (solid content: 15% by mass) is used, and the mass ratio of the magnesium fluoride particles in the coating layer is 25%. A coating layer was formed. The average particle diameter of the magnesium fluoride particles contained in this magnesium fluoride particle dispersion is 20 nm, the porosity is 1% or less, the refractive index is 1.37, and the dispersion solvent is methyl ethyl ketone. As a result, a coating layer having a refractive index of 1.485 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 5 except for the above.

[Comparative Example 1]
In Example 1, when forming a coating layer, the composition for forming a coating layer was prepared as follows. Acrylic resin is dissolved by adding and mixing 50.0 parts by mass of methyl ethyl ketone and 46.85 parts by mass of methyl isobutyl ketone to 3.0 parts by mass of acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA). Thus, a mixed solution was prepared. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer containing no particles and having a refractive index of 1.500 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Comparative Example 2]
In Example 1, in forming the coating layer, a composition for forming the coating layer was prepared as follows so that the mass ratio of the hollow silica particles in the coating layer was 65%. Acrylic resin (made by Shin-Nakamura Chemical Co., Ltd., product number U-6LPA) is dissolved in acrylic resin by adding 45.0 parts by mass of methyl ethyl ketone and 44.05 parts by mass of methyl isobutyl ketone to 1.05 parts by mass. Thus, a mixed solution was prepared. To this mixed liquid, 9.75 parts by mass of a hollow silica particle dispersion (solid content: 20% by mass) was added and mixed at room temperature. The hollow silica particles contained in this hollow silica particle dispersion have an average particle diameter of 60 nm, a porosity of 29.5% and a refractive index of 1.33, and the dispersion solvent is methyl ethyl ketone. 0.15 parts by mass of a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Geigy, product name Irgacure 184) was added to this mixed solution and mixed well, followed by 30 minutes in a constant temperature atmosphere at 25 ° C. Stir and mix. This obtained the composition for forming a coating layer.

  This composition was applied onto the conductive layer with a wire bar coater # 4, dried at room temperature for 2 minutes, then dried at 80 ° C. for 3 minutes, and further cured by irradiation with ultraviolet rays (ultraviolet intensity 500 mJ / cm). . As a result, a coating layer having a refractive index of 1.428 and a thickness of 100 nm was formed.

  A conductive optical member was obtained in the same manner as in Example 1 except for the above.

[Evaluation test]
The following evaluation test was implemented about the electroconductive optical member obtained by each Example and the comparative example. The results are shown in Table 1 below.

(Haze measurement)
The haze of the conductive optical member obtained in each example and comparative example was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., model number NDH2000).

(Etching property evaluation)
An etching resist was formed on the coating layer in the conductive optical member obtained in each example and comparative example. Subsequently, the conductive optical member was subjected to an etching process using an etching solution (ferric chloride aqueous solution) at 35 ° C., thereby removing the conductive layer and the covering layer from the region not covered with the etching resist. At this time, the time required for the etching process for removing the conductive layer and the coating layer was measured. Based on this required time, the etching property was evaluated as follows.
○: The time required for the etching process is within 1 minute.
Δ: The time required for the etching process is longer than 1 minute.
X: Etching is impossible.

(Durability evaluation)
The film resistance of the conductive optical member obtained in each example and comparative example was measured. Subsequently, the conductive optical member obtained in each Example and Comparative Example was subjected to a high temperature and high humidity treatment in which the conductive optical member was exposed to an atmosphere of 85 ° C. and 85% RH for 250 hours. Subsequently, the film resistance of the conductive optical member was measured again.

The measurement results of the film resistance of the conductive optical member before and after the high temperature and high humidity treatment were compared, and based on this, the reliability was evaluated as follows.
5: No change in resistance value is observed before and after the high temperature and humidity resistance treatment.
4: The rate of increase in resistance value due to the high temperature and humidity resistance treatment is less than 10 times.
3: Increase rate of resistance value by high temperature and humidity resistance treatment is 10 times or more and less than 100 times.
2: The resistance value after the high temperature and humidity resistance treatment can be measured, and the increase rate of the resistance value by the high temperature and humidity resistance treatment is 100 times or more.
1: The resistance value after high temperature and humidity resistance treatment is infinite (measurable).

(Pattern visibility evaluation)
The pattern visibility was evaluated as follows by observing the appearance of the conductive optical member before and after the etching treatment by the etching property evaluation and comparing the results.
○: No difference is observed in the appearance of the conductive optical member before and after the etching treatment, and the pattern shape of the conductive layer is not visually recognized even after the etching treatment.
X: Difference in appearance of the conductive optical member before and after the etching treatment, and the pattern shape of the conductive layer is visually recognized after the etching treatment.

DESCRIPTION OF SYMBOLS 1 Conductive optical member 2 Base material 3 Conductive layer 4 Cover layer 5 Metal nanowire 6 Particle 7 Resin matrix 8 Intermediate layer

Claims (7)

Comprising a base material, a metal nanowire, a transparent conductive layer covering the base material, and a transparent coating layer covering the conductive layer;
The conductive optical member characterized in that the coating layer contains a resin matrix and particles having a porosity of 25% or less and a refractive index of 1.20 to 1.40 dispersed in the resin matrix. The conductive optical member according to claim 1, wherein the particles include at least one of sodium hexafluoroaluminate particles and magnesium fluoride particles. The conductive optical member according to claim 1, wherein an average particle diameter of the particles is smaller than a thickness of the coating layer. The conductive optical member according to any one of claims 1 to 3, wherein the refractive index of the coating layer is less than 1.60. The conductive optical member according to any one of claims 1 to 4, wherein the haze is 2 or less. The conductive optical member according to any one of claims 1 to 5, further comprising an intermediate layer having a refractive index higher than that of the coating layer between the base material and the conductive layer. An electronic device comprising the conductive optical member according to claim 1, wherein the conductive optical member is viewed from the coating layer side.

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