WO2016189762A1 - 透明導電性フィルム - Google Patents
透明導電性フィルム Download PDFInfo
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- WO2016189762A1 WO2016189762A1 PCT/JP2015/080694 JP2015080694W WO2016189762A1 WO 2016189762 A1 WO2016189762 A1 WO 2016189762A1 JP 2015080694 W JP2015080694 W JP 2015080694W WO 2016189762 A1 WO2016189762 A1 WO 2016189762A1
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- transparent conductive
- layer
- conductive film
- hard coat
- thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- 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
Definitions
- the present invention relates to a transparent conductive film.
- a transparent conductive film obtained by laminating a transparent conductive layer on a transparent base film has been widely used for devices such as touch panels.
- a transparent conductive layer is etched by photolithography etc. and a wiring pattern is formed.
- the wiring pattern of the transparent conductive layer is miniaturized, there is a high possibility that even a slight scratch may cause a disconnection or a short circuit. Therefore, it is known that a hard coat layer is provided between the base film and the transparent conductive layer to increase the scratch resistance of the transparent conductive film (Patent Document 1, Patent No. 4214063).
- an optical adjustment layer (IM layer: Index Matching Layer index matching layer) is provided between the transparent conductive layer and the hard coat layer It is known that the wiring pattern is less visible (Patent Document 2, Patent No. 5425351). Since the optical adjustment layer reduces the difference in reflectance between the portion with and without the wiring pattern, the wiring pattern is less visible.
- the transparent conductive layer needs to be crystallized in order to reduce the resistance value of the transparent conductive layer, but the gas (for example, moisture) contained in the base film is released, and the gas (outgas) This may inhibit the crystallization of the transparent conductive layer.
- the gas for example, moisture
- the gas outgas
- the conventional transparent conductive film has a problem that the scratch resistance is insufficient.
- the crystallization of the transparent conductive layer is hindered. The speed became slow, and there was a problem that it was not possible to respond to crystallization in a short time necessary for mass production.
- An object of the present invention is to realize a transparent conductive film having high scratch resistance and capable of completing crystallization of a transparent conductive layer in a short time.
- the inventor of the present application when appropriately balancing the thickness of the hard coat layer and the thickness of the optical adjustment layer, increases the scratch resistance of the transparent conductive film and increases the crystallization speed of the transparent conductive layer. was completed in a short time, and the transparent conductive film of the present invention was completed.
- the transparent conductive film of the present invention is a transparent conductive film in which at least a hard coat layer, an optical adjustment layer, and a transparent conductive layer are laminated in this order on a transparent base film (FIG. 1). .
- the transparent conductive layer contains indium.
- the thickness of the hard coat layer is 250 nm to 2000 nm.
- the thickness of the optical adjustment layer is 2% to 10% of the thickness of the hard coat layer.
- the optical adjustment layer contains a metal oxide.
- the metal oxide contains silicon dioxide (SiO 2 ).
- the hard coat layer is any one of zirconium oxide ZrO 2 , silicon dioxide SiO 2 , titanium oxide TiO 2 , tin oxide SnO 2 , aluminum oxide Al 2 O 3 , or two of them. Contains inorganic fine particles of more than seeds.
- the refractive index of the hard coat layer is 1.60 to 1.70.
- an anti-peeling layer is further laminated between the hard coat layer and the optical adjustment layer (FIG. 2).
- the peel prevention layer contains an inorganic compound having a non-stoichiometric composition.
- the peel prevention layer contains silicon atoms.
- the peel preventing layer contains a silicon compound.
- the peeling prevention layer contains silicon oxide.
- the peel prevention layer has a region where the binding energy of Si2p bond is 98.0 eV or more and less than 103.0 eV.
- the thickness of the peeling prevention layer is 1.5 nm to 8 nm.
- a functional layer is further laminated on the main surface of the base film opposite to the transparent conductive layer (FIG. 3).
- the functional layer is composed of an anti-blocking hard coat layer.
- a transparent conductive film having high scratch resistance and completing the crystallization of the transparent conductive layer in a short time was realized. Crystallization of the transparent conductive layer is completed by, for example, heat treatment at 140 ° C. for 30 minutes.
- FIG. 1 is a schematic view of a transparent conductive film 10 according to the first embodiment of the present invention.
- a hard coat layer 12 In the transparent conductive film 10, a hard coat layer 12, an optical adjustment layer 13, and a transparent conductive layer 14 are laminated in this order on a transparent base film 11.
- the thickness of the hard coat layer 12 is 250 nm to 2000 nm.
- the thickness of the optical adjustment layer 13 is 2% to 10% of the thickness of the hard coat layer 12. Crystallization of the transparent conductive layer 14 is completed by, for example, heat treatment at 140 ° C. for 30 minutes.
- the degree of change in the resistance value with respect to the heating time of the transparent conductive layer 14 is adopted as a criterion for determining the completion of the crystallization of the transparent conductive layer 14. For example, if the surface resistance value after the heat treatment at 140 ° C. for 30 minutes is 1.1 times or less the surface resistance value after the heat treatment at 140 ° C. for 90 minutes, the crystallization is completed.
- FIG. 2 is a schematic view of a transparent conductive film 20 according to the second embodiment of the present invention.
- the difference from the transparent conductive film 10 of FIG. 1 is that a peeling prevention layer 15 is further laminated between the hard coat layer 12 and the optical adjustment layer 13.
- the peeling prevention layer 15 has a function of improving the adhesion between the hard coat layer 12 and the optical adjustment layer 13. As a result, the peeling prevention layer 15 improves the adhesion between the base film 11 and the optical adjustment layer 13. Details of the peeling preventing layer 15 will be described later.
- FIG. 3 is a schematic view of a transparent conductive film 30 according to the third embodiment of the present invention.
- the difference from the transparent conductive film 10 of FIG. 1 is that the functional layer 16 is laminated on the lower surface of the base film 11. Details of the functional layer 16 will be described later.
- the base film 11 is, for example, a polyester film made of polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN) or the like, a polyethylene film, a polypropylene film, a cellophane film, a diacetylcellulose film, a triacetylcellulose film, or an acetylcellulose.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- Butyrate film polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone Film, polyetherimide film, polyimide film, fluororesin film, It consists of a plastic film such as a lyamide film, an acrylic resin film, a norbornene resin film, or a cycloolefin resin film.
- the material of the base film 11 is not limited to these, polyethylene terephthalate excellent in transparency, heat resistance, and mechanical properties is particularly preferable.
- the thickness of the base film 11 is preferably 20 ⁇ m or more and 300 ⁇ m or less, but is not limited thereto. However, if the thickness of the base film 11 is less than 20 ⁇ m, handling may be difficult. Moreover, when the thickness of the base film 11 exceeds 300 ⁇ m, there is a possibility that the transparent conductive films 10, 20, 30 are too thick when mounted on a touch panel or the like.
- the in-plane heat shrinkage rate of the base film 11 is preferably ⁇ 0.5% to + 1.5%, more preferably ⁇ 0.5% to + 1.0%, and ⁇ 0.5% to + 0.7%. Is more preferable, and -0.5% to + 0.5% is most preferable.
- the heat shrinkage rate of the base film 11 exceeds 1.5%, for example, when heat is applied to the base film 11 as when the transparent conductive layer 14 is heated and crystallized, the base film 11 Is greatly contracted and an excessive compressive stress is applied to each layer, so that each layer may be easily peeled off.
- the heat shrinkage rate of the transparent conductive films 10, 20, 30 is substantially the same as the heat shrinkage rate of the base film 11.
- the surface temperature of the film-forming roll is preferably set at the time of sputtering in order not to excessively increase the thermal shrinkage of the base film 11. 20 ° C. to + 100 ° C., more preferably ⁇ 20 ° C. to + 50 ° C., and further preferably ⁇ 20 ° C. to 0 ° C.
- the heat shrinkage rate of the base film 11 tends to increase.
- the hard coat layer 12 has a function (scratch resistance) for preventing the wiring pattern formed on the transparent conductive layer 14 from being broken and short-circuited by scratching the transparent conductive film 10.
- the hard coat layer 12 may contain inorganic fine particles 17. By dispersing the inorganic fine particles 17 in the hard coat layer 12, the refractive index of the hard coat layer 12 can be adjusted, the transmittance of the transparent conductive film 10 can be improved, or the reflection hue can be more neutral (achromatic color). ).
- the hard coat layer 12 contains, for example, an organic resin, preferably contains an organic resin and inorganic fine particles 17, and more preferably consists essentially of the organic resin and inorganic fine particles 17.
- the organic resin include a curable resin.
- the curable resin include an active energy ray curable resin that is cured by irradiation with active energy rays (such as ultraviolet rays and electron beams), a thermosetting resin that is cured by heating, and preferably an active energy ray.
- active energy ray curable resin that is cured by irradiation with active energy rays (such as ultraviolet rays and electron beams)
- a thermosetting resin that is cured by heating
- preferably an active energy ray A curable resin is mentioned.
- Examples of the active energy ray-curable resin include a polymer having a functional group having a polymerizable carbon-carbon double bond in the molecule.
- Examples of such a functional group include a vinyl group and a (meth) acryloyl group (methacryloyl group and / or acryloyl group).
- Examples of the active energy ray-curable resin include (meth) acrylic resin (acrylic resin and / or methacrylic resin) containing a functional group in the side chain. These resins can be used alone or in combination of two or more.
- the material and size of the inorganic fine particles 17 contained in the hard coat layer 12 are not particularly limited.
- zirconium oxide ZrO 2 , silicon dioxide SiO 2 , titanium oxide TiO 2 , tin oxide SnO 2 , aluminum oxide Al Fine particles such as 2 O 3 are included. Two or more of these fine particles may be contained in the hard coat layer 12.
- the particle size (average particle diameter) of the inorganic fine particles 17 is preferably 10 nm to 80 nm, and more preferably 20 nm to 40 nm. If the particle size is less than 10 nm, the particles may not be uniformly dispersed in the resin.
- the hard coat layer 12 is formed by, for example, applying and drying an organic resin (for example, an acrylic resin) containing the inorganic fine particles 17 on the base film 11, but the material and the manufacturing method are not limited thereto. .
- the content ratio of the inorganic fine particles 17 is, for example, 5 parts by weight or more and 100 parts by weight or less, preferably 10 parts by weight or more and 65 parts by weight or less with respect to 100 parts by weight of the resin.
- the refractive index of the resin (hard coat layer 12) containing the inorganic fine particles 17 can be adjusted.
- the thickness of the hard coat layer 12 is preferably 250 nm to 2000 nm. If the thickness of the hard coat layer 12 is less than 250 nm, the scratch resistance may be insufficient. Since the hard coat layer 12 uses an organic solvent or a water solvent, it contains a large amount of gas. Therefore, when the thickness of the hard coat layer 12 exceeds 2000 nm, the amount of gas (typically moisture) contained in the hard coat layer 12 becomes excessive, and the gas (outgas) released from the hard coat layer 12 is optically adjusted. Barriering with the layer 13 becomes difficult, and crystallization of the transparent conductive layer 14 may be hindered.
- the refractive index of the hard coat layer 12 is not particularly limited, but is preferably 1.60 to 1.70. If the refractive index of the hard coat layer 12 deviates from this range (1.60 to 1.70), the wiring pattern formed on the transparent conductive layer 14 may be easily visible.
- the refractive index of the hard coat layer 12 is measured by an Abbe refractometer.
- the hard coat layer is applied by, for example, a phantom coat method, a die coat method, a spin coat method, a spray coat method, a gravure coat method, a roll coat method, a bar coat method, or the like. Specifically, first, a dilute solution obtained by diluting a resin component with a solvent is prepared, and then the dilute solution is applied to a substrate film and dried.
- the solvent examples include an organic solvent and an aqueous solvent, and an organic solvent is preferable.
- Organic solvents include alcohols such as ethanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), esters such as ethyl acetate and butyl acetate, and aromatic compounds such as toluene and xylene. Etc., and preferably a mixed solvent thereof is used.
- the resin component is diluted with a solvent so that the solid content concentration is, for example, 0.5 parts by weight or more and 5.0 parts by weight or less.
- the drying temperature of the diluted solution applied to the base film is, for example, 60 ° C. or more and 250 ° C. or less, and more preferably 80 ° C. or more and 200 ° C. or less. If the drying temperature is too low, the solvent remains, which may lead to film quality deterioration of the transparent conductive layer. If the drying temperature is too high, wrinkles may enter the film, which may hinder the appearance.
- the drying time is, for example, 1 minute to 60 minutes, and more preferably 2 minutes to 30 minutes. If the drying time is too short, the solvent remains, which may lead to film quality deterioration of the transparent conductive layer. If the drying time is too long, wrinkles may enter the film, which may hinder the appearance.
- the optical adjustment layer 13 is a layer for adjusting the refractive index of the transparent conductive films 10, 20 and 30.
- the optical adjustment layer 13 can optimize the optical characteristics (for example, reflection characteristics) of the transparent conductive films 10, 20, and 30.
- the difference in reflectance between the portion with the wiring pattern of the transparent conductive layer 14 and the portion without the wiring pattern is reduced, so that the wiring pattern formed on the transparent conductive layer 14 is less visible. (The wiring pattern is preferably not visually recognized).
- the optical adjustment layer 13 is formed by a dry method (dry process). Since the optical adjustment layer 13 formed by the dry method has high hardness, the scratch resistance of the transparent conductive film 10 is increased in combination with the function of the hard coat layer 12. Further, since the optical adjustment layer 13 formed by the dry method has a gas barrier property, the outgas generated from the base film 11 and the hard coat layer 12 is prevented from entering the transparent conductive layer 14, and the transparent conductive layer 14 is crystallized. Inhibition and film quality deterioration can be prevented.
- the constituent material of the optical adjustment layer 13 is not particularly limited.
- silicon monoxide (SiO), silicon dioxide (SiO 2 ), silicon oxide (SiOx: x is more than 1 and less than 2), aluminum oxide (Al 2 O 3 ), metal oxides such as zirconium oxide (ZrO 2 ) and titanium oxide (TiO 2 ) are preferred.
- silicon dioxide (SiO 2 ) (usually called silicon oxide or silica) is particularly preferable as a constituent material of the optical adjustment layer 13.
- the optical adjustment layer 13 may be a single metal oxide layer. Further, a stacked body of metal oxide layers in which a plurality of metal oxide layers having different metal atoms are stacked may be used.
- the thickness of the optical adjustment layer 13 is preferably 2% to 10% of the thickness of the hard coat layer 12.
- the gas barrier property of the optical adjustment layer 13 may be insufficient. If the gas barrier property of the optical adjustment layer 13 is insufficient, crystallization of the transparent conductive layer 14 may not be completed in a short time. If the thickness of the optical adjustment layer 13 exceeds 10% of the thickness of the hard coat layer 12, the bending resistance of the transparent conductive films 10, 20, and 30 may be deteriorated. Further, the productivity of the optical adjustment layer 13 may be reduced.
- the reason why the thickness of the optical adjustment layer 13 is linked to the thickness of the hard coat layer 12 is that the outgas from the hard coat layer 12 increases as the thickness of the hard coat layer 12 increases, so that the outgas is shielded. This is because the thickness of the optical adjustment layer 13 must also be increased. On the contrary, when the thickness of the hard coat layer 12 is thin, the outgas from the hard coat layer 12 is reduced. Therefore, the thickness of the optical adjustment layer 13 for shielding the outgas may be thin.
- the optical adjustment layer 13 is formed by a sputtering method, a vapor deposition method, a CVD method, or the like, but the manufacturing method is not limited to these.
- the optical adjustment layer 13 is particularly preferably formed by sputtering.
- a film formed by a sputtering method can stably obtain a particularly dense film among dry methods. Therefore, the optical adjustment layer 13 formed by a sputtering method has high scratch resistance.
- the sputtering method has a higher film density than, for example, a vacuum deposition method, the optical adjustment layer 13 having excellent gas barrier properties can be obtained.
- the pressure of the sputtering gas (typically argon gas) when forming the optical adjustment layer 13 is preferably 0.09 Pa to 0.5 Pa, more preferably 0.09 Pa to 0.3 Pa.
- the pressure of the sputtering gas is preferably 0.09 Pa to 0.5 Pa, more preferably 0.09 Pa to 0.3 Pa.
- the film formation can be efficiently performed by using the reactive sputtering method.
- silicon (Si) is used as a sputtering target
- argon gas is introduced as a sputtering gas
- oxygen gas is introduced as a reactive gas in an amount of 10 to 50% by pressure with respect to the argon gas.
- High silicon dioxide (SiO 2 ) film can be obtained.
- the density of the power applied to the target is preferably 1.0 W / cm 2 to 6.0 W / cm 2 .
- the power density exceeds 6.0 W / cm 2 , the surface roughness (for example, arithmetic average roughness Ra) of the optical adjustment layer 13 increases, and the surface resistance of the transparent conductive layer 14 may increase.
- the power density is less than 1.0 W / cm 2 , the film formation rate is lowered, so that the productivity of the optical adjustment layer 13 may be lowered.
- the transparent conductive layer 14 is a thin film layer mainly composed of a metal conductive oxide (for example, indium oxide), or a composite metal oxide containing a main metal (for example, indium) and one or more kinds of impurity metals (for example, tin). It is a transparent thin film layer mainly composed of an object.
- the transparent conductive layer 14 is not particularly limited in its configuration and material as long as it has optical transparency in the visible light region and has conductivity.
- Examples of the transparent conductive layer 14 include indium oxide, indium tin oxide (ITO: Indium Tin Oxide), indium zinc oxide (IZO: Indium Zinc Oxide), indium gallium zinc oxide (IGZO: Indium Gallium Zinc Oxide), etc.
- Indium tin oxide (ITO) is preferred from the viewpoint of low specific resistance and transmission hue.
- the transparent conductive layer 14 may further contain impurity metal elements such as titanium Ti, magnesium Mg, aluminum Al, gold Au, silver Ag, and copper Cu.
- the transparent conductive layer 14 is formed by sputtering, vapor deposition, or the like, but the manufacturing method is not limited to this.
- the amount of the impurity metal element (for example, tin Sn) in the transparent conductive layer 14 is 0.5% by weight to 15% by weight with respect to the total amount of indium oxide (In 2 O 3 ) and the impurity metal element (for example, tin Sn). %, Preferably 3 to 15% by weight, more preferably 5 to 13% by weight. If the tin oxide is less than 0.5% by weight, the surface resistance value of the transparent conductive layer 14 may be increased. If the tin oxide exceeds 15% by weight, the surface resistance value in the plane of the transparent conductive layer 14 may be reduced. Uniformity may be lost.
- the impurity metal element for example, tin Sn
- the transparent conductive layer 14 (for example, indium tin oxide layer) formed at a low temperature is amorphous, and can be converted from amorphous to crystalline by heat treatment. When the transparent conductive layer 14 is converted to crystalline, its surface resistance value is lowered.
- the heat treatment conditions for converting the transparent conductive layer 14 to crystalline are preferably 140 ° C. and 30 minutes or less from the viewpoint of productivity.
- the thickness of the hard coat layer 12 is as thin as 250 nm to 2000 nm, there is little outgas from the hard coat layer 12. Further, since the thickness of the optical adjustment layer 13 is 2% to 10% of the thickness of the hard coat layer 12, the gas barrier property of the optical adjustment layer 13 is high. Therefore, the crystallization of the transparent conductive layer 14 is hardly affected by the outgas from the base film 11 and the hard coat layer 12 and can be completed at 140 ° C. for 30 minutes or less.
- the arithmetic surface roughness Ra of the transparent conductive layer 14 is preferably 0.1 nm or more and 1.6 nm or less. If the arithmetic surface roughness Ra exceeds 1.6 nm, the surface resistance value of the transparent conductive layer 14 may increase. When the arithmetic surface roughness Ra is less than 0.1 nm, when the transparent conductive layer 14 is patterned by photolithography to form a wiring, the adhesion between the photoresist and the transparent conductive layer 14 decreases, and the photoresist is peeled off. There is a risk of poor etching.
- the thickness of the transparent conductive layer 14 is preferably 15 nm or more and 40 nm or less, and more preferably 15 nm or more and 35 nm or less. By setting the thickness of the transparent conductive layer 14 within the above range, the transparent conductive films 10, 20, and 30 can be suitably applied to a touch panel. If the thickness of the transparent conductive layer 14 is less than 15 nm, the surface resistance value of the transparent conductive layer 14 may increase. If the thickness of the transparent conductive layer 14 exceeds 40 nm, there is a concern that the light transmittance of the transparent conductive films 10, 20, and 30 may be reduced or cracks may be generated in the transparent conductive layer 14 due to an increase in internal stress.
- the transparent conductive layer 14 may be a laminated film in which two or more transparent conductive films are laminated.
- the peeling prevention layer 15 may be formed between the hard coat layer 12 and the optical adjustment layer 13.
- the peeling preventing layer 15 between the hard coat layer 12 and the optical adjustment layer 13
- the adhesion between the hard coat layer 12 and the optical adjustment layer 13 can be increased.
- the adhesion of the optical adjustment layer 13 can be increased.
- the anti-peeling layer 15 contains an inorganic atom, and is preferably formed from an inorganic substance such as an inorganic substance alone or an inorganic compound, more preferably from an inorganic compound.
- inorganic atoms contained in the peeling prevention layer 15 include silicon (Si), niobium (Nb), palladium (Pd), titanium (Ti), indium (In), tin (Sn), cadmium (Cd), Zinc (Zn), antimony (Sb), aluminum (Al), tungsten (W), molybdenum (Mo), chromium (Cr), tantalum (Ta), nickel (Ni), platinum (Pt), gold (Au),
- metal atoms such as silver (Ag) and copper (Cu), and preferably silicon (Si).
- the peeling prevention layer 15 is formed of a silicon simple substance or a silicon compound, and preferably is formed of a silicon compound from the viewpoint of transparency.
- the inorganic compound is preferably composed of an inorganic compound having a non-stoichiometric composition.
- Examples of the inorganic compound having a non-stoichiometric composition include inorganic nitrides such as silicon nitride (for example, SiNx, 0.1 ⁇ x ⁇ 1.3), silicon carbide (for example, SiCx, 0.1 ⁇ x ⁇ 1.0) and the like, inorganic oxides such as silicon oxide (for example, SiOx, 0.1 ⁇ x ⁇ 2.0), and the like are preferable, and silicon oxide (for example, SiOx, 0.0. 1 ⁇ x ⁇ 2.0). These inorganic compounds may have a single composition or a mixture of a plurality of compositions.
- inorganic nitrides such as silicon nitride (for example, SiNx, 0.1 ⁇ x ⁇ 1.3), silicon carbide (for example, SiCx, 0.1 ⁇ x ⁇ 1.0) and the like
- inorganic oxides such as silicon oxide (for example, SiOx, 0.1 ⁇ x ⁇ 2.0), and the like are prefer
- the anti-peeling layer 15 is made of a non-stoichiometric composition, for example, a silicon compound, by adjusting the binding energy of the Si2p orbit to an appropriate range,
- the peeling prevention function can be improved from (for example, silicon dioxide SiO 2 ).
- the element constituting the separation preventing layer 15 is preferably the same metal as the metal oxide contained in the optical adjustment layer 13 or a different metal. If the element constituting the peeling prevention layer 15 is the same metal as the metal oxide (for example, silicon dioxide SiO 2 ) contained in the optical adjustment layer 13 (silicon Si with respect to silicon dioxide SiO 2 ), the peeling prevention layer 15 and the optical Since the adhesion between the adjustment layers 13 is further improved, the same kind of metal is more preferable.
- the thickness of the peeling prevention layer 15 is preferably 1.5 nm to 8 nm. By setting the thickness of the peeling prevention layer 15 to 1.5 nm to 8 nm, both good optical characteristics and high adhesion can be achieved. When the thickness of the peeling prevention layer 15 is less than 1.5 nm, the adhesion improvement by the peeling prevention layer 15 may be insufficient. When the thickness of the peeling prevention layer 15 exceeds 8 nm, light reflection / absorption by free electrons in the peeling prevention layer 15 occurs, the light transmittance of the transparent conductive film 20 becomes low, and the transparent conductive film 20 The display on the liquid crystal panel or the like underneath may be difficult to see.
- the peeling prevention layer 15 is formed by sputtering method, vapor deposition method, CVD method, etc.
- a manufacturing method is not limited to these.
- the sputtering method is preferable from the viewpoint of film density and productivity.
- a metal target is applied with a power density of 1.0 W / cm 2 in a vacuum atmosphere of 0.2 Pa to 0.5 Pa into which argon is introduced.
- the anti-peeling layer 15 can be obtained by sputtering. At that time, it is preferable to form a film without introducing a reactive gas such as oxygen.
- the thickness of the peeling prevention layer 15 can be measured using a transmission electron microscope (TEM) image taken in the cross-sectional direction.
- TEM transmission electron microscope
- a difference in contrast occurs between the peeling prevention layer 15 and the optical adjustment layer 13.
- the difference in contrast may not be clear.
- XPS X-ray Photoelectron Spectroscopy
- ESCA Electron Spectroscopy for Chemical Analysis
- the binding energy of the Si2p orbit obtained by X-ray photoelectron spectroscopy in the peeling prevention layer 15 is, for example, 98.0 eV or more, preferably 99.0 eV or more, More preferably, it is 100.0 eV or more, More preferably, it is 102.0 eV or more, for example, less than 104.0 eV, Preferably, it is less than 103.0 eV, More preferably, it is 102.8 eV or less.
- the peel prevention layer 15 having a Si2p orbital bond energy within the above range, the adhesion of the peel prevention layer 15 can be improved.
- the peeling prevention layer 15 when the bond energy in the peeling prevention layer 15 is 99.0 eV or more and less than 103.0 eV, the peeling prevention layer 15 contains a silicon compound having a non-stoichiometric composition. Adhesion can be more reliably improved while maintaining light transmittance. Note that the distribution of the binding energy in the thickness direction inside the peeling prevention layer 15 may have a gradient that gradually increases from the peeling prevention layer 15 side toward the optical adjustment layer 13 side.
- the depth profile (measured pitch is 1 nm in terms of silicon dioxide SiO 2) by X-ray photoelectron spectroscopy. ) Is measured, and when the binding energy continuously changes, the binding energy value at a point 1 nm or more above the terminal film 11 side of the peeling prevention layer 15 (preferably a point 1 nm above) is adopted. It shall be.
- the inorganic atoms constituting the peeling prevention layer 15 and the optical adjustment layer 13 are the same (for example, when the peeling prevention layer 15 is a silicon Si compound and the optical adjustment layer 13 is silicon dioxide SiO 2 ), the optical adjustment layer 13 is used.
- the depth position where the element ratio of inorganic atoms (Si) becomes half the peak value is defined as the end portion of the peeling prevention layer 15.
- the functional layer 16 may be formed on the surface of the base film 11 opposite to the transparent conductive layer 14.
- the functional layer 16 is not particularly limited, and examples thereof include an anti-blocking hard coat layer and an optical adjustment layer.
- the anti-blocking hard coat layer is a layer for preventing the transparent conductive film 30 adjacent in the radial direction from adhering (blocking) when the long transparent conductive film 30 is wound in a roll shape.
- the optical adjustment layer 13 is a layer for improving the transmittance of the transparent conductive film 30 or making it difficult to visually recognize a pattern portion when the transparent conductive layer 14 is patterned.
- Examples and Comparative Examples Although specific embodiment of the transparent conductive film of this invention is described comparing an Example and a comparative example, this invention is not limited to these Examples.
- Example 1 has a layer structure shown in FIG.
- the base film 11 is a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m.
- the hard coat layer 12 is an acrylic resin layer having a thickness of 700 nm.
- the hard coat layer 12 contains zirconium oxide (ZrO 2 ) fine particles (inorganic fine particles 17) having an average particle diameter of 20 nm.
- the optical adjustment layer 13 is a silicon dioxide (SiO 2 ) layer having a thickness of 15 nm.
- the thickness of the optical adjustment layer 13 is 2.1% of the thickness of the hard coat layer 12.
- the transparent conductive layer 14 is an indium tin oxide (ITO) layer having a thickness of 20 nm.
- the weight ratio of tin to the total of indium oxide and tin in the transparent conductive layer 14 is 10%.
- UV curable resin composition containing acrylic resin and zirconium oxide (ZrO 2 ) fine particles (average particle size 20 nm) is methylisobutylketone (MIBK) so that the solid content concentration is 5% by weight.
- MIBK methylisobutylketone
- the obtained diluted composition was applied to one main surface of a base film 11 made of polyethylene terephthalate (PET) having a thickness of 100 ⁇ m (product name “Diafoil”, manufactured by Mitsubishi Plastics) and dried.
- PET polyethylene terephthalate
- the diluted composition was cured by irradiating ultraviolet rays to form a hard coat layer 12 having a thickness of 700 nm.
- the base film 11 on which the hard coat layer 12 was formed was wound to produce a roll of the base film 11.
- optical adjustment layer 13 (and a transparent conductive layer 14 described later) was formed using a roll-to-roll type sputtering apparatus.
- the roll of the base film 11 on which the hard coat layer 12 was formed was placed in the supply unit of the sputtering apparatus and stored for 15 hours in a vacuum state of 1 ⁇ 10 ⁇ 4 Pa or less. Then, the base film 11 was drawn out from the supply part, the base film 11 was wound around the film-forming roll, and the optical adjustment layer 13 was formed into a film by sputtering method.
- the film formation tank is set to an argon gas atmosphere of 0.2 Pa, an electric power density of 3.5 W / cm 2 is introduced while introducing oxygen gas by impedance control, and a silicon (Si) target (Sumitomo Metal Mining Co., Ltd.).
- the optical adjustment layer 13 silicon dioxide (SiO 2 ) layer having a thickness of 15 nm was formed.
- a transparent conductive layer 14 was formed following the optical adjustment layer 13.
- the base film 11 on which the optical adjustment layer 13 was formed was wound around a film-forming roll, and a 20 nm thick transparent conductive layer 14 was formed by a sputtering method.
- the argon gas Ar: oxygen gas O 2 pressure ratio is 99: 1
- the total gas pressure is 0.3 Pa
- the power density is 1.0 W / cm 2.
- a transparent conductive layer 14 was formed by sputtering an indium tin oxide target made of a sintered body of tin oxide and 90 wt% indium oxide. Then, the base film 11 was wound up in a storage part, and the roll of the transparent conductive film 10 was completed.
- Example 2 A transparent conductive film 10 of Example 2 was produced in the same manner as in Example 1 except that the thickness of the hard coat layer 12 was 300 nm and the thickness of the optical adjustment layer 13 was 12 nm. The thickness of the optical adjustment layer 13 is 4.0% of the thickness of the hard coat layer 12.
- Example 3 A transparent conductive film 10 of Example 3 was produced in the same manner as in Example 1 except that the thickness of the hard coat layer 12 was 300 nm and the thickness of the optical adjustment layer 13 was 30 nm. The thickness of the optical adjustment layer 13 is 10.0% of the thickness of the hard coat layer 12.
- Comparative Example 1 A transparent conductive film of Comparative Example 1 was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 1200 nm and the thickness of the optical adjustment layer was 12 nm. The thickness of the optical adjustment layer is 1.0% of the thickness of the hard coat layer.
- Comparative Example 2 A transparent conductive film of Comparative Example 2 was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 1600 nm and the thickness of the optical adjustment layer was 12 nm. The thickness of the optical adjustment layer is 0.75% of the thickness of the hard coat layer.
- Comparative Example 3 A transparent conductive film of Comparative Example 3 was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 200 nm and the thickness of the optical adjustment layer was 12 nm. The thickness of the optical adjustment layer is 6.0% of the thickness of the hard coat layer.
- Table 1 shows the configurations and characteristics of Examples 1 to 3 and Comparative Examples 1 to 3 of the transparent conductive film of the present invention.
- the crystallization of the transparent conductive layer is desirably completed by a heat treatment at 140 ° C. for 30 minutes from the viewpoint of productivity.
- the transparent conductive layers of Examples 1 to 3 had no problem of productivity because crystallization was completed by a heat treatment at 140 ° C. for 30 minutes (circle mark).
- the transparent conductive layers of Comparative Examples 1 and 2 had a problem in productivity because crystallization was not completed by a heat treatment at 140 ° C. for 30 minutes (X mark).
- the reason for the slow crystallization of the transparent conductive layers of Comparative Examples 1 and 2 is that the thickness of the optical adjustment layer is less than 2% of the thickness of the hard coat layer, so that the outgas from the hard coat layer is sufficiently blocked by the optical adjustment layer. This is because it penetrated into the transparent conductive layer without inhibiting crystallization.
- the transparent conductive layer of Comparative Example 3 had no problem with crystallization because crystallization was completed by heat treatment at 140 ° C. for 30 minutes (but Comparative Example 3 had a problem with scratch resistance).
- a transparent conductive film heated at 140 ° C. for 90 minutes was cut into a rectangular shape having a length of 5 cm and a width of 11 cm, and a silver paste was applied to 5 mm portions at both ends on the long side, followed by natural drying for 48 hours.
- the side of the transparent conductive film opposite to the transparent conductive layer was affixed to a glass plate with an adhesive to obtain a sample for evaluating scratch resistance.
- a 10-line pen tester manufactured by MTM Co.
- the surface of the transparent conductive layer of the sample for scratch resistance evaluation was rubbed with a length of 10 cm.
- the resistance value (R0) of the sample for scuffing evaluation before rubbing and the resistance value (R20) of the sample for scuffing evaluation after rubbing are set to the central position (5.5 cm) on the long side of the sample for scuffing evaluation.
- the position was measured by applying a tester to the silver paste portions at both ends, and the resistance change rate (R20 / R0) was determined to evaluate the scratch resistance.
- a case where the resistance change rate was 1.5 or less was evaluated as “good scratch resistance” ( ⁇ ), and a case where the resistance change rate exceeded 1.5 was evaluated as “bad scratch resistance” (X).
- Abrasion child Anticon Gold (manufactured by Contec) ⁇ Load: 127 g / cm 2 ⁇ Abrasion speed: 13 cm / sec (7.8 m / min) -Number of scratches: 20 times (10 round trips)
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Abstract
Description
図1は本発明の第1の実施形態に係る透明導電性フィルム10の模式図である。透明導電性フィルム10では、透明な基材フィルム11上に、ハードコート層12と、光学調整層13と、透明導電層14がこの順に積層されている。ハードコート層12の厚さは250nm~2000nmである。光学調整層13の厚さは、ハードコート層12の厚さの2%~10%である。透明導電層14の結晶化は、例えば、140℃、30分の熱処理により完了する。
基材フィルム11は、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート、ポリエチレンナフタレート(PEN)等からなるポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファンフィルム、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン-酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ポリアミドフィルム、アクリル樹脂フィルム、ノルボルネン系樹脂フィルム、シクロオレフィン樹脂フィルム等のプラスチックフィルムからなる。基材フィルム11の材質がこれらに限定されることはないが、透明性、耐熱性、および機械特性に優れたポリエチレンテレフタレートが、特に好ましい。
ハードコート層12は透明導電性フィルム10に傷がついて透明導電層14に形成された配線パターンが断線、ショートすることを防ぐ機能(耐擦傷性)を有する。ハードコート層12には無機微粒子17が含有されていてもよい。ハードコート層12に無機微粒子17を分散させることにより、ハードコート層12の屈折率を調整することができ、透明導電性フィルム10の透過率を向上させること、あるいは反射色相をよりニュートラル(無彩色)に近付けることができる。
光学調整層13は、透明導電性フィルム10,20,30の屈折率の調整のための層である。光学調整層13により透明導電性フィルム10,20,30の光学特性(例えば反射特性)を最適化することができる。光学調整層13を設けることにより、透明導電層14の配線パターンのある部分と配線パターンのない部分の反射率の差が小さくなるため、透明導電層14に形成された配線パターンが視認されにくくなる(配線パターンは、視認されないことが望ましい)。
透明導電層14は、金属の導電性酸化物(例えばインジウム酸化物)を主成分とする薄膜層、または主金属(例えばインジウム)と1種以上の不純物金属(例えばスズ)を含有する複合金属酸化物を主成分とする透明薄膜層である。透明導電層14は、可視光域で光透過性を有し、かつ、導電性を有するものであれば、その構成および材料が特に限定されることはない。
図2の透明導電性フィルム20のように、ハードコート層12と光学調整層13の間に剥離防止層15が形成されていてもよい。剥離防止層15をハードコート層12と光学調整層13の間に形成することにより、ハードコート層12と光学調整層13の密着性を高くすることができ、結果的に、基材フィルム11と光学調整層13の密着性を高くすることができる。
図3に示すように、基材フィルム11の、透明導電層14と反対側の面に、機能層16が形成されていてもよい。機能層16は特に限定されないが、例えばアンチブロッキングハードコート層や光学調整層などが挙げられる。アンチブロッキングハードコート層は、長尺の透明導電性フィルム30がロール状に巻回されたとき、半径方向に隣り合う透明導電性フィルム30が固着(ブロッキング)することを防止するための層である。光学調整層13は、透明導電性フィルム30の透過率を向上させる、あるいは、透明導電層14をパターニングした際のパターン部を視認しにくくするための層である。
本発明の透明導電性フィルムの具体的な実施形態について、実施例と比較例を対比しながら説明するが、本発明がこれらの実施例に限定されることはない。
実施例1は図1に示す層構成である。基材フィルム11は厚さ100μmのポリエチレンテレフタレート(PET)フィルムである。ハードコート層12は厚さ700nmのアクリル樹脂層である。ハードコート層12は、平均粒径20nmの酸化ジルコニウム(ZrO2)微粒子(無機微粒子17)を含有する。光学調整層13は厚さ15nmの二酸化ケイ素(SiO2)層である。光学調整層13の厚さは、ハードコート層12の厚さの2.1%である。透明導電層14は厚さ20nmのインジウムスズ酸化物(ITO)層である。透明導電層14中の、スズの、酸化インジウムとスズの合計に対する重量比は10%である。
アクリル樹脂と酸化ジルコニウム(ZrO2)微粒子(平均粒径20nm)とが含まれている紫外線(UV)硬化型樹脂組成物を、固形分濃度が5重量%になるようにメチルイソブチルケトン(MIBK)で希釈した。得られた希釈組成物を、厚み100μmのポリエチレンテレフタレート(PET)製の基材フィルム11(三菱樹脂製、商品名「ダイアホイル」)の一方の主面に塗布し、乾燥した。次に希釈組成物に紫外線を照射して硬化させ、厚さ700nmのハードコート層12を形成した。ハードコート層12の形成された基材フィルム11を巻回し、基材フィルム11のロールを作製した。
光学調整層13(及び後述の透明導電層14)はロール・トゥ・ロール型スパッタリング装置を用いて形成した。ハードコート層12の形成された基材フィルム11のロールをスパッタリング装置の供給部に設置し,1×10-4Pa以下の真空状態で15時間保管した。その後、供給部から基材フィルム11を繰出し、基材フィルム11を成膜ロールへ巻き付け、スパッタリング法により光学調整層13を成膜した。詳しくは、成膜槽を0.2Paのアルゴンガス雰囲気とし、インピーダンス制御によって酸素ガスを導入しながら電力密度3.5W/cm2の電力を投入して、ケイ素(Si)ターゲット(住友金属鉱山社製)をスパッタリングして、厚さ15nmの光学調整層13(二酸化ケイ素(SiO2)層)を形成した。
光学調整層13に引き続き透明導電層14を成膜した。光学調整層13が形成された基材フィルム11を成膜ロールに巻き付け、スパッタリング法により、厚さ20nmの透明導電層14を形成した。このとき、アルゴンガスAr:酸素ガスO2の圧力比が99:1で、全ガス圧が0.3Paのスパッタリング雰囲気とし、電力密度1.0W/cm2の電力を投入して、10重量%の酸化スズと90重量%の酸化インジウムの焼結体から成るインジウムスズ酸化物ターゲットをスパッタリングして透明導電層14を形成した。その後、基材フィルム11を収納部に巻き取り、透明導電性フィルム10のロールを完成させた。
ハードコート層12の厚さを300nm、光学調整層13の厚さを12nmとした以外は実施例1と同様にして、実施例2の透明導電性フィルム10を作製した。光学調整層13の厚さは、ハードコート層12の厚さの4.0%である。
ハードコート層12の厚さを300nm、光学調整層13の厚さを30nmとした以外は実施例1と同様にして、実施例3の透明導電性フィルム10を作製した。光学調整層13の厚さは、ハードコート層12の厚さの10.0%である。
ハードコート層の厚さを1200nm、光学調整層の厚さを12nmとした以外は実施例1と同様にして、比較例1の透明導電性フィルムを作製した。光学調整層の厚さは、ハードコート層の厚さの1.0%である。
ハードコート層の厚さを1600nm、光学調整層の厚さを12nmとした以外は実施例1と同様にして、比較例2の透明導電性フィルムを作製した。光学調整層の厚さは、ハードコート層の厚さの0.75%である。
ハードコート層の厚さを200nm、光学調整層の厚さを12nmとした以外は実施例1と同様にして、比較例3の透明導電性フィルムを作製した。光学調整層の厚さは、ハードコート層の厚さの6.0%である。
透明導電層の結晶化は、生産性の点から、140℃、30分の熱処理で完了することが望ましい。実施例1~3の透明導電層は、140℃、30分の熱処理で結晶化が完了していた(○印)ため生産性の問題はなかった。比較例1、2の透明導電層は、140℃、30分の熱処理で結晶化が完了していなかった(X印)ため、生産性に問題があった。比較例1、2の透明導電層の結晶化が遅い原因は、光学調整層の厚さがハードコート層の厚さの2%未満のため、ハードコート層からのアウトガスが光学調整層で十分遮断されずに透明導電層に侵入し、結晶化を阻害したためである。比較例3の透明導電層は、140℃、30分の熱処理で結晶化が完了していたので、結晶化については問題なかった(しかし比較例3は耐擦傷性に問題があった)。
実施例1~3、比較例1、2の透明導電性フィルムの耐擦傷性は問題なかった(○印)。比較例3の透明導電性フィルムの耐擦傷性は弱く問題であった(X印)。比較例3の透明導電性フィルムの耐擦傷性が不足した原因は、ハードコート層の厚さが250nm未満だったためである。
透明導電層の結晶化速度と耐擦傷性を考慮した総合的な評価は、実施例1~3は良好(○印)であるが、比較例1~3は良くない(X印)と判断された。
[厚さ]
透過型電子顕微鏡(日立製作所製HF-2000)を用いて透明導電性フィルムの断面を観察し、光学調整層、透明導電層等の厚さを測定した。
140℃、30分の熱処理後の表面抵抗値が、140℃、90分の熱処理後の表面抵抗値の1.1倍以下であるとき、結晶化が完了していると判断した。表面抵抗値はJIS K7194に準じて、4端子法を用いて測定した。
140℃で90分間加熱した透明導電性フィルムを縦5cm横11cmの長方形に切り出し、長辺側の両端部5mm部分に銀ペーストを塗着して、48時間自然乾燥させた。透明導電性フィルムの、透明導電層とは反対の側を、粘着剤付ガラス板に貼付し、擦傷性評価用サンプルを得た。10連式ペン試験機(エム・ティー・エム社製)を用いて、前記の擦傷性評価用サンプルの短辺側における中央位置(2.5cm位置)で、下記条件にて、長辺方向に10cmの長さで前記擦傷性評価用サンプルの透明導電層表面を擦った。
・擦傷子:アンティコンゴールド(コンテック社製)
・荷重:127g/cm2
・擦傷速度:13cm/秒(7.8m/分)
・擦傷回数:20回(往復10回)
11 基材フィルム
12 ハードコート層
13 光学調整層
14 透明導電層
15 剥離防止層
16 機能層
17 無機微粒子
Claims (14)
- 透明な基材フィルム上に、少なくとも、ハードコート層、光学調整層および透明導電層がこの順に積層されてなる透明導電性フィルムであって、
前記透明導電層がインジウムを含み、
前記ハードコート層の厚さが250nm~2000nmであり、
前記光学調整層の厚さが前記ハードコート層の厚さの2%~10%であることを特徴とする透明導電性フィルム。 - 前記光学調整層が金属酸化物を含むことを特徴とする請求項1に記載の透明導電性フィルム。
- 前記金属酸化物が二酸化ケイ素(SiO2)を含むことを特徴とする請求項2に記載の透明導電性フィルム。
- 前記ハードコート層が酸化ジルコニウムZrO2、二酸化ケイ素SiO2、酸化チタンTiO2、酸化スズSnO2、酸化アルミニウムAl2O3のいずれか、あるいはそれらの2種以上の無機微粒子を含むことを特徴とする請求項1~3のいずれかに記載の透明導電性フィルム。
- 前記ハードコート層の屈折率が1.60~1.70であることを特徴とする請求項1~4のいずれかに記載の透明導電性フィルム。
- 前記ハードコート層と前記光学調整層の間に更に剥離防止層が積層されていることを特徴とする請求項1~5のいずれかに記載の透明導電性フィルム。
- 前記剥離防止層が非化学量論的組成(non-stoichiometric)の無機化合物を含むことを特徴とする請求項6に記載の透明導電性フィルム。
- 前記剥離防止層がケイ素原子を含むことを特徴とする請求項6または7に記載の透明導電性フィルム。
- 前記剥離防止層がケイ素化合物を含むことを特徴とする請求項6~8のいずれかに記載の透明導電性フィルム。
- 前記剥離防止層がケイ素酸化物を含むことを特徴とする請求項6~9のいずれかに記載の透明導電性フィルム。
- 前記剥離防止層が、Si2p結合の結合エネルギーが98.0eV以上103.0eV未満の領域を有することを特徴とする、請求項8~10のいずれかに記載の透明導電性フィルム。
- 前記剥離防止層の厚さが1.5nm~8nmであることを特徴とする請求項6~11のいずれかに記載の透明導電性フィルム。
- 前記基材フィルムの、前記透明導電層とは反対側の主面に、更に機能層が積層されてなることを特徴とする請求項1~12のいずれかに記載の透明導電性フィルム。
- 前記機能層がアンチブロッキングハードコート層からなる請求項13に記載の透明導電性フィルム。
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JP2013211134A (ja) * | 2012-03-30 | 2013-10-10 | Teijin Ltd | 透明導電性積層体 |
JP2014019038A (ja) * | 2012-07-17 | 2014-02-03 | Kaneka Corp | 無機薄膜付き導電材用基板、透明電極付き基板及びその製造方法 |
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JP2009143754A (ja) * | 2007-12-12 | 2009-07-02 | Jgc Catalysts & Chemicals Ltd | 導電性繊維状中空シリカ微粒子分散質およびその製造方法 |
JP2013071380A (ja) * | 2011-09-28 | 2013-04-22 | Toppan Printing Co Ltd | 透明導電性フィルム及びタッチパネル |
JP2013211134A (ja) * | 2012-03-30 | 2013-10-10 | Teijin Ltd | 透明導電性積層体 |
JP2014019038A (ja) * | 2012-07-17 | 2014-02-03 | Kaneka Corp | 無機薄膜付き導電材用基板、透明電極付き基板及びその製造方法 |
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CN111326277A (zh) * | 2018-12-17 | 2020-06-23 | 日东电工株式会社 | 导电性薄膜 |
CN111326277B (zh) * | 2018-12-17 | 2023-08-25 | 日东电工株式会社 | 导电性薄膜 |
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