WO2012005300A1 - 透明導電性フィルムおよびその製造方法 - Google Patents
透明導電性フィルムおよびその製造方法 Download PDFInfo
- Publication number
- WO2012005300A1 WO2012005300A1 PCT/JP2011/065493 JP2011065493W WO2012005300A1 WO 2012005300 A1 WO2012005300 A1 WO 2012005300A1 JP 2011065493 W JP2011065493 W JP 2011065493W WO 2012005300 A1 WO2012005300 A1 WO 2012005300A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- composite oxide
- transparent conductive
- indium
- amorphous
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Definitions
- the present invention relates to a transparent conductive film in which a crystalline transparent conductive thin film is formed on a transparent film substrate, and a method for producing the transparent conductive film.
- Transparent conductive films in which a transparent conductive thin film is formed on a transparent film substrate are widely used for solar cells, inorganic EL elements, transparent electrodes for organic EL elements, electromagnetic shielding materials, touch panels, and the like.
- the rate of mounting touch panels on mobile phones, portable game devices, and the like has increased, and the demand for transparent conductive films for electrostatic touch panels capable of multipoint detection is rapidly expanding.
- a film in which a conductive metal oxide film such as indium-tin composite oxide (ITO) is formed on a flexible transparent substrate such as a polyethylene terephthalate film Widely used.
- the ITO film uses the same oxide target as the ITO film composition formed on the substrate or a metal target made of an In—Sn alloy, and an inert gas (Ar gas) alone, and if necessary
- a reactive gas such as oxygen is introduced to form a film by sputtering.
- an indium-based composite oxide film such as ITO
- a transparent film substrate made of a polymer molding such as a polyethylene terephthalate film
- it is made by sputtering at a high temperature because there is a restriction due to the heat resistance of the substrate. Can not do the membrane. Therefore, the indium composite oxide film immediately after film formation is an amorphous film (some of which may be crystallized).
- Such an amorphous indium composite oxide film has problems such as strong yellowing and inferior transparency and a large resistance change after the humidification heat test.
- the manufacturing process of the transparent conductive film in which the crystalline indium composite oxide film is formed on the transparent film substrate includes the step of forming the amorphous indium composite oxide film on the transparent substrate, and the indium system. It is roughly divided into a process in which the complex oxide film is heated and crystallized. Conventionally, in order to form an amorphous indium-based composite oxide film, a winding-type sputtering device has been used, and a method of forming a thin film on the surface of a substrate while continuously running a long substrate is employed. Has been. That is, the formation of the amorphous indium composite oxide film on the substrate is performed by a roll-to-roll method to form a wound body of a long transparent conductive laminate.
- the crystallization of the indium composite oxide film is performed in a batch manner mainly because it takes a long time to crystallize the amorphous indium composite oxide film.
- supplying a long transparent conductive film in which a crystalline indium-based composite oxide film is formed on a transparent film substrate has a great merit in the subsequent touch panel formation.
- the subsequent touch panel formation process can be performed by a roll-to-roll method, so that the touch panel formation process is simplified, leading to mass productivity and cost reduction. Can contribute.
- the indium composite oxide film is crystallized, it is possible to subsequently perform a process for forming a touch panel without being wound around a wound body.
- an object of the present invention is to provide a long transparent conductive film in which a crystalline indium composite oxide film is formed on a transparent film substrate.
- the present inventors have attempted to crystallize a wound body in which an amorphous indium composite oxide film is formed in a heating furnace while being wound. It was. However, according to such a method, the wound body is tightened due to a dimensional change of the base film, and the transparent conductive film is deformed such as wrinkles, or the film quality in the film surface is poor. A defect such as uniformity occurred.
- the present invention is a method for producing a long transparent conductive film in which a crystalline indium-based composite oxide film is formed on a transparent film substrate, which contains indium and a tetravalent metal.
- Amorphous laminate forming step in which an amorphous film of a composite oxide is formed on the long transparent film substrate by sputtering, and a long transparent film base on which the amorphous film is formed.
- the material has a crystallization process in which the material is continuously conveyed into a heating furnace and the amorphous film is crystallized.
- the temperature in the heating furnace in the crystallization step is preferably 170 ° C. to 220 ° C.
- the change rate of the film length in the said crystallization process is + 2.5% or less.
- the stress in the transport direction applied to the long transparent film substrate in the heating furnace is preferably 1.1 MPa to 13 MPa.
- the heating time in the crystallization step is preferably 10 seconds to 30 minutes.
- the amorphous laminate forming step it is preferable that an amorphous indium composite oxide film that can be crystallized by heating at a temperature of 180 ° C. for 60 minutes is formed on the transparent film substrate. . Therefore, before the amorphous film is formed, evacuation is preferably performed until the degree of vacuum in the sputtering apparatus becomes 1 ⁇ 10 ⁇ 3 Pa or less.
- the indium-based composite oxide preferably contains 15 parts by weight or less of tetravalent metal with respect to 100 parts by weight of the total of indium and tetravalent metal.
- a wound body of a long transparent conductive film in which an indium composite oxide film having a small resistance change due to heating or humidification heat is formed is obtained. It is done.
- the compressive residual stress of the indium composite oxide film after heating the transparent conductive film cut out from the wound body into a sheet to 60 ° C. for 60 minutes is preferably 0.4 to 1.6 GPa.
- the dimensional change rate in the longitudinal direction of the film when heated at 150 ° C. for 60 minutes is preferably 0% to ⁇ 1.5%.
- an amorphous film can be crystallized while a film is being conveyed, a long transparent conductive film on which a crystalline indium composite oxide film is formed is efficiently produced. be able to.
- Such a long film is once wound up as a wound body and used for subsequent formation of a touch panel or the like.
- subsequent steps such as a touch panel formation step can be continuously performed following the crystallization step.
- the crystallization process is a relatively short heating process. Is possible. Therefore, the crystallization process is optimized and the productivity of the transparent conductive film can be improved. Furthermore, by controlling the film transport tension in the crystallization step and suppressing the elongation of the film, it is possible to obtain a transparent conductive film with low resistance and high reliability of heating and humidification with high productivity.
- the transparent conductive film 10 has a configuration in which a crystalline indium composite oxide film 4 is formed on a transparent film substrate 1. Between the transparent film substrate 1 and the crystalline indium composite oxide film 4, for the purpose of improving the adhesion between the substrate and the indium composite oxide film, controlling the reflection characteristics by the refractive index, etc. Anchor layers 2 and 3 may be provided.
- the crystalline indium composite oxide film 4 is formed by first forming an amorphous indium composite oxide film 4 'on the substrate 1, and heating and crystallizing the amorphous film together with the substrate. Is done. Conventionally, this crystallization process has been performed by heating a single wafer batchwise. However, in the present invention, heating and crystallization are performed while a long film is being conveyed. A wound body of the scale-like transparent conductive film 10 is obtained.
- the indium composite oxide film is referred to as an “amorphous laminate” before crystallization
- a film after the indium composite oxide film is crystallized may be referred to as a “crystalline stack”.
- a long amorphous laminate 20 in which an amorphous indium composite oxide film 4 ′ is formed on the transparent film substrate 1 is formed (amorphous laminate formation step).
- anchor layers 2 and 3 are provided on the base material 1 as necessary, and an amorphous indium composite oxide film 4 ′ is formed thereon.
- the material of the transparent film substrate 1 is not particularly limited as long as it has flexibility and transparency, and an appropriate material can be used.
- acrylic resins polyvinyl chloride resins
- polystyrene resins polyvinyl resins
- polyvinyl resins examples thereof include alcohol resins, polyarylate resins, polyphenylene sulfide resins, polyvinylidene chloride resins, and (meth) acrylic resins.
- polyester resins, polycarbonate resins, polyolefin resins and the like are particularly preferable.
- the thickness of the transparent film substrate 1 is preferably about 2 to 300 ⁇ m, and more preferably 6 to 200 ⁇ m. If the thickness of the substrate is excessively small, the film is likely to be deformed by the stress during film conveyance, and thus the film quality of the transparent conductive layer formed thereon may be deteriorated. On the other hand, when the thickness of the substrate is excessively large, problems such as an increase in the thickness of a device on which a touch panel or the like is mounted are caused.
- the substrate preferably has a higher glass transition temperature.
- the glass transition temperature of the substrate is preferably 170 ° C. or lower, and more preferably 160 ° C. or lower.
- a film containing a crystalline polymer is preferably used as the transparent film substrate 1.
- the Young's modulus rapidly decreases and plastic deformation occurs. For this reason, the amorphous polymer film is likely to be stretched when heated to near the glass transition temperature under conveyance tension.
- a crystalline polymer film that is partially crystallized such as polyethylene terephthalate (PET)
- PET polyethylene terephthalate
- the elongation at the time of heating can be suppressed by using, for example, a stretched film. That is, when the stretched amorphous polymer film is heated to near the glass transition temperature, the orientation of the molecules is relaxed and thus tends to shrink. By balancing the heat shrinkage and the elongation due to the film transport tension, the deformation of the base material when the indium composite oxide film is crystallized is suppressed.
- Anchor layer The main surface of the transparent film substrate 1 on which the indium-based composite oxide film 4 ′ is formed is intended to improve the adhesion between the base material and the indium-based composite oxide film and to control the reflection characteristics.
- Anchor layers 2 and 3 may be provided. One anchor layer may be provided, or two or more anchor layers may be provided as shown in FIG.
- the anchor layer is formed of an inorganic material, an organic material, or a mixture of an inorganic material and an organic material.
- a material for forming the anchor layer for example, SiO 2 , MgF 2 , Al 2 O 3 or the like is preferably used as an inorganic substance.
- organic substances include organic substances such as acrylic resins, urethane resins, melamine resins, alkyd resins, and siloxane polymers.
- a thermosetting resin made of a mixture of a melamine resin, an alkyd resin, and an organic silane condensate as the organic substance.
- the anchor layer can be formed by vacuum deposition, sputtering, ion plating, coating, or the like using the above materials.
- the surface of the base material or anchor layer is previously subjected to appropriate adhesion treatment such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching treatment, etc. Adhesiveness of the composite oxide can also be improved.
- amorphous indium composite oxide film 4 ′ is formed on the transparent film substrate by a vapor phase method.
- the vapor phase method include an electron beam vapor deposition method, a sputtering method, and an ion plating method.
- the sputtering method is preferable from the viewpoint of obtaining a uniform thin film, and a DC magnetron sputtering method is preferably employed.
- the “amorphous indium composite oxide” is not limited to a completely amorphous material, and may contain a small amount of a crystal component.
- the indium composite oxide is amorphous or not is determined by immersing the laminate in which the indium composite oxide film is formed on the base material in hydrochloric acid having a concentration of 5 wt% for 15 minutes, and then washing and drying.
- the inter-terminal resistance between 15 mm is measured by a tester. Since the amorphous indium-based composite oxide film is etched away by hydrochloric acid and disappears, the resistance increases by immersion in hydrochloric acid.
- an indium composite oxide film is assumed to be amorphous when the resistance between terminals of 15 mm exceeds 10 k ⁇ after immersion in hydrochloric acid, washing with water, and drying.
- the formation of the amorphous indium composite oxide film 4 ′ is performed while transporting the base material as in the roll-to-roll method, for example. It is preferable.
- the amorphous film is formed by the roll-to-roll method, for example, using a take-up type sputtering apparatus, and performing sputter film formation while the base material is unwound from a long roll of base material and continuously run.
- the base material on which the amorphous indium composite oxide film is formed is wound in a roll shape.
- the amorphous indium composite oxide film 4 ′ formed on the substrate is preferably crystallized by heating in a short time. Specifically, when heated at 180 ° C., it is preferable that crystallization can be completed within 60 minutes, more preferably within 30 minutes, and even more preferably within 20 minutes. Whether or not the crystallization is completed can be judged from the resistance between terminals of 15 mm by dipping in hydrochloric acid, washing with water and drying as in the case of amorphous. If the terminal-to-terminal resistance is within 10 k ⁇ , it is judged that it has been converted into a crystalline indium composite oxide.
- the amorphous indium composite oxide film that can be crystallized by heating for a short time is adjusted by, for example, the type of target used for sputtering, the ultimate vacuum during sputtering, the flow rate of introduced gas during sputtering, and the like. be able to.
- a metal target indium-quadrivalent metal target
- a metal oxide target an In 2 O 3-quadrivalent metal oxide target
- the amount of the tetravalent metal oxide in the metal oxide target exceeds 0 and is 15% by weight with respect to the weight of In 2 O 3 and the tetravalent metal oxide. It is preferably 1 to 12% by weight, more preferably 6 to 12% by weight, still more preferably 7 to 12% by weight, and 8 to 12% by weight. More preferably, it is 9 to 12% by weight, more preferably 9 to 10% by weight.
- the amount of tetravalent metal atoms in the metal target exceeds 0 and is 15% by weight with respect to the weight of In atoms and tetravalent metal atoms added. It is preferably 1 to 12% by weight, more preferably 6 to 12% by weight, still more preferably 7 to 12% by weight, and 8 to 12% by weight. More preferably, it is 9 to 12% by weight, more preferably 9 to 10% by weight. If the amount of tetravalent metal or tetravalent metal oxide is too large, the time required for crystallization tends to be long.
- the tetravalent metal functions as an impurity except for the amount taken into the In 2 O 3 crystal lattice, it tends to prevent crystallization of the indium composite oxide.
- the amount of tetravalent metal or tetravalent metal oxide in the target is preferably within the above range.
- the amount of tetravalent metal or tetravalent metal oxide in the target is the amount obtained by adding In atoms and tetravalent metal atoms or In 2 O.
- Examples of the tetravalent metal constituting the indium-based composite oxide include group 14 elements such as Sn, Si, Ge and Pb, group 4 elements such as Zr, Hf and Ti, and lanthanoids such as Ce.
- group 14 elements such as Sn, Si, Ge and Pb
- group 4 elements such as Zr, Hf and Ti
- lanthanoids such as Ce.
- Sn, Zr, Ce, Hf, and Ti are preferable from the viewpoint of reducing the resistance of the indium composite oxide film, and Sn is most preferable from the viewpoint of material cost and film formability.
- the degree of vacuum in the sputtering apparatus is preferably 1 ⁇ 10 ⁇ 3 Pa or less, more preferably 1 ⁇ 10 ⁇ 4 Pa or less.
- the atmosphere in which impurities such as moisture in the sputtering apparatus and organic gas generated from the substrate are removed is preferable to set the atmosphere in which impurities such as moisture in the sputtering apparatus and organic gas generated from the substrate are removed. This is because the presence of moisture or organic gas terminates dangling bonds generated during sputtering film formation and hinders the crystal growth of the indium composite oxide.
- the indium composite oxide can be crystallized satisfactorily even when the content of tetravalent metal is high (for example, 6% by weight or more). it can.
- an oxygen gas which is a reactive gas
- an inert gas such as Ar
- the amount of oxygen introduced into the inert gas is preferably 0.1% by volume to 15% by volume, and more preferably 0.1% by volume to 10% by volume.
- the pressure during film formation is preferably 0.05 Pa to 1.0 Pa, more preferably 0.1 Pa to 0.7 Pa. If the film forming pressure is too high, the film forming speed tends to decrease. Conversely, if the pressure is too low, the discharge tends to become unstable.
- the temperature at the time of sputtering film formation is preferably 40 ° C.
- the film forming temperature is too high, appearance defects due to thermal wrinkles and thermal deterioration of the substrate film may occur. Conversely, when the film forming temperature is too low, film quality such as transparency of the transparent conductive film may be deteriorated.
- the thickness of the indium-based composite oxide film can be appropriately adjusted so that the indium-based composite oxide film after crystallization has a desired resistance, but is preferably, for example, 10 to 300 nm, preferably 15 to 100 nm. More preferably. If the film thickness of the indium composite oxide film is small, the time required for crystallization tends to be long. If the film thickness of the indium composite oxide film is large, the specific resistance after crystallization is too low or transparent. In some cases, the quality as a transparent conductive film for a touch panel is inferior.
- the amorphous laminate 20 in which the amorphous indium composite oxide film is formed on the base material may be subjected to the crystallization process as it is or once has a predetermined diameter.
- the wound body may be formed by being wound in a roll shape with a predetermined tension around the core.
- the amorphous laminate obtained in this manner is subjected to a crystallization step, and the amorphous indium composite oxide film 4 'is crystallized by heating.
- the formation of the amorphous indium composite oxide film on the substrate and the crystallization process are performed as a continuous series of processes. Done.
- a step film feeding step
- a process crystalstallization process
- the crystalline laminate 20 is heated while being transported to crystallize the indium composite oxide film is performed as a series of processes.
- the amorphous laminate is heated while being transported under a predetermined tension, and the indium composite oxide film is crystallized.
- the rate of change of the film length in the crystallization step is preferably + 2.5% or less, more preferably + 2.0% or less, and + 1.5% or less. More preferred is + 1.0% or less.
- the “film length” refers to the length in the film transport direction (MD direction). The dimensional change of the film in the crystallization process is obtained from the maximum value of the rate of change of the film length in the crystallization process, based on the film length before the crystallization process.
- the inventors of the present invention formed an amorphous indium-based composite oxide film that can be crystallized in a short time on a biaxially stretched PET film under the sputtering conditions as described above.
- ITO indium-tin composite oxide
- the indium composite oxide film is crystallized by heating at a high temperature in a short time. It was confirmed that crystallization can be performed continuously by a method of heating while conveying a film, such as a roll-to-roll method.
- the indium-based composite oxide film crystallized under such conditions significantly increases the resistance compared to the indium-based composite oxide film that is crystallized by heating the single wafer in batch mode. It has been found that heating reliability and humidification reliability may not be sufficient. As a result of studying these causes, there is a certain difference between the transport tension of the transparent conductive laminate and the heating reliability of the crystalline indium composite oxide film when the indium composite oxide film is heated and crystallized. Correlation is observed, and by reducing the transport tension, it is possible to obtain a crystalline indium-based composite oxide film with higher heating reliability and humidification reliability, that is, a resistance value change that is small even with heating and humidification. all right.
- FIG. 2 shows the maximum dimensional change rate when an amorphous laminate is heated under a predetermined load by a thermomechanical analysis (TMA) apparatus, and heat crystallization under the same tension and temperature conditions as TMA.
- TMA thermomechanical analysis
- membrane performed was plotted.
- a 20-nm-thick amorphous ITO film weight ratio of indium oxide and tin oxide 97: 3
- the temperature raising condition of TMA was 10 ° C./min, and heating was performed from room temperature to 200 ° C.
- the resistance change is a ratio R / R 0 between the surface resistance value R 0 of the ITO film heated and crystallized in the TMA apparatus and the surface resistance value R of the ITO film after being further heated at 150 ° C. for 90 minutes. is there.
- a linear relationship is observed between the maximum elongation during heating by TMA and the resistance change R / R 0 of the indium composite oxide film, and the resistance change increases as the elongation increases. Tend to be larger.
- the rate of change of the film length after heating with respect to the film length before heating is +2.5. % Or less, more preferably + 2.0% or less. If the change rate of the film length is + 2.5% or less, the resistance change R / R 0 when heating the crystalline indium-based composite oxide film at 150 ° C. for 90 minutes is set to 1.5 or less, and the heating reliability is improved. Can be increased.
- the length of the film changes due to thermal expansion, thermal contraction, elastic deformation and plastic deformation due to stress, but after the crystallization process, Elongation due to thermal expansion or elastic deformation due to stress tends to return to an original state due to a decrease in the temperature of the film or release of stress due to the transport tension. Therefore, in order to evaluate the rate of change in the length of the film in the crystallization step, it is preferable to obtain, for example, the peripheral speed ratio between the film transport roll on the upstream side of the heating furnace and the film transport roll on the downstream side of the heating furnace. Moreover, it can replace with the peripheral speed ratio of a roll, and can also calculate the rate of change of film length by TMA measurement.
- the rate of change of the film length by TMA can be measured by TMA using an amorphous laminate cut into strips and adjusting the weight so that the same stress as the transport tension in the crystallization step is applied.
- the dimensional change rate H 0,60 when the amorphous laminate before being subjected to the crystallization step was heated at 150 ° C. for 60 minutes
- the difference ⁇ H 60 (H 1,60 ⁇ H 0,60 ) from the dimensional change rate H 1,60 when the transparent conductive laminate after crystallization is heated at 150 ° C. for 60 minutes, or crystallization
- the dimensional change rate H 0,90 when the amorphous laminate before being subjected to the process was heated at 150 ° C. for 90 minutes, and the transparent conductive laminate after crystallization was heated at 150 ° C. for 90 minutes.
- the thermal deformation history in the crystallization process can also be evaluated.
- FIG. 4 shows a plot of the relationship between ⁇ H and the maximum value of the dimensional change rate when the heating test measurement by TMA is performed with the weight adjusted as in the case of FIG. 2 described above.
- FIG. 4 shows that there is also a linear relationship between ⁇ H 90 and the maximum value of the dimensional change rate by TMA. That is, when FIG. 2 to FIG. 4 are combined, the difference ⁇ H 90 in the dimensional change rate before and after crystallization, the maximum value of the dimensional change rate in the TMA heating test performed under the same stress conditions as in the crystallization step, and the heating It can be seen that there is a linear relationship between the resistance change R / R0 of the crystalline ITO film before and after. Therefore, it can be seen from the value of ⁇ H 90 that the rate of change of the length of the film in the crystallization process can be estimated, and the resistance change R / R 0 during heating of the transparent conductive film can be predicted.
- the dimensional change rate H 0,90 when the amorphous laminate before being subjected to the crystallization process is heated at 150 ° C. for 90 minutes.
- To + 1.5% is preferable, ⁇ 0.25% to + 1.3% is more preferable, and 0% to + 1% is more preferable.
- the dimensional change rate H 0,60 when the amorphous laminate before being subjected to the crystallization process is heated at 150 ° C.
- the difference ⁇ H 60 (H 1,60 ⁇ H 0,60 ) from the dimensional change rate H 1 when heated for 60 minutes is preferably ⁇ 0.4% to + 1.5%, and ⁇ 0. It is more preferably 25% to + 1.3%, and further preferably 0% to + 1%.
- a small ⁇ H 90 or ⁇ H 60 means that the elongation percentage of the film in the crystallization process is large. If ⁇ H 90 or ⁇ H 60 is smaller than ⁇ 0.4%, the resistance value of the crystalline indium composite oxide tends to increase or the heating reliability tends to decrease. On the other hand, when ⁇ H 90 or ⁇ H 60 is greater than + 1.5%, heat wrinkles tend to occur due to instability of film conveyance, and the appearance of the transparent conductive film is deteriorated. There is.
- the measurement of the dimensional change rate and the measurement by TMA are performed on the base material alone before forming the indium composite oxide film, instead of using the transparent conductive laminate on which the indium composite oxide film is formed. You can also.
- tension conditions suitable for the crystallization process can be estimated in advance without actually performing crystallization of the indium composite oxide film by the roll-to-roll method. That is, in a general transparent conductive laminate, an indium composite oxide film having a thickness of several nanometers to several tens of nanometers is formed on a base material having a thickness of several tens to 100 micrometers.
- the thermal deformation behavior of the laminate is dominated by the thermal deformation behavior of the base material, and the presence or absence of the indium-based composite oxide film hardly affects the thermal deformation behavior. Therefore, if the TMA test of the base material is performed or the base material is heated under application of a predetermined stress, and the dimensional change rate difference ⁇ H before and after it is evaluated, the thermal deformation behavior of the base material is evaluated, It is possible to estimate tension conditions suitable for the crystallization process.
- the long amorphous laminate 10 is once wound to form the amorphous wound body 21, and the long amorphous laminate is formed from the wound body. And a step in which the indium composite oxide film is crystallized by heating while the long amorphous laminated body 20 drawn out from the wound body is conveyed.
- (crystallization step) is performed as a series of steps by a roll-to-roll method will be described as an example.
- FIG. 5 shows an example of a manufacturing system for performing crystallization by the roll-to-roll method, and conceptually explains the process of crystallizing the indium-based composite oxide film.
- a wound body 21 of an amorphous laminate in which an amorphous indium composite oxide film is formed on a transparent film substrate has a heating furnace 100 between a film feeding section 50 and a film winding section 60. It is set on the film feed stand 51 of the film transport / heating device. Crystallization of the indium-based composite oxide film is carried out from the wound body 21 by a process (film feeding process) in which a long amorphous multilayer is continuously fed out from the wound body 21 of the amorphous laminate.
- the long amorphous laminate 20 is heated while being transported to crystallize the indium composite oxide film (crystallization step), and the crystallized laminate 10 after crystallization is rolled. It is performed by a roll-to-roll method by carrying out a series of steps (winding step) wound around.
- the long amorphous laminate 20 is continuously drawn out from the wound body 21 of the amorphous laminate set on the feed stand 51 of the feed section 50 (film feeding process). .
- the amorphous indium-based composite oxide film is crystallized by being heated by the heating furnace 100 provided in the film conveyance path while the amorphous laminated body fed out from the wound body is conveyed (crystals). Process).
- the crystalline laminate 10 after heating and crystallization is wound into a roll shape by the winding unit 60 to form a wound body 11 of a transparent conductive film (winding step).
- a plurality of rolls are provided to configure the film conveyance path.
- drive rolls 81a and 82a linked with a motor or the like tension is applied to the film with the rotational force, and the film is continuously conveyed.
- the drive rolls 81a and 82a form nip roll pairs 81 and 82, respectively, with the rolls 81b and 82b, but the drive rolls do not have to constitute a nip roll pair.
- tension detecting means such as tension pickup rolls 71 to 73 on the transport path.
- the rotational speed (peripheral speed) of the drive rolls 81a and 82a and the rotational torque of the take-up stand 61 are controlled by an appropriate tension control mechanism so that the transport tension detected by the tension detection means becomes a predetermined value. Is done.
- the tension detecting means appropriate means such as a combination of a dancer roll and a cylinder can be adopted in addition to the tension pickup roll.
- the rate of change of the film length in the crystallization process is preferably + 2.5% or less.
- the rate of change of the film length can be obtained from the ratio of the peripheral speeds of the nip roll 81 provided on the upstream side of the heating furnace and the nip roll 82 provided on the downstream side of the heating furnace, for example.
- the roll drive is controlled so that the peripheral speed ratio between the upstream roll of the heating furnace and the downstream roll of the heating furnace is within the above range. That's fine.
- control can also be performed so that the peripheral speed ratio of the roll is constant. In this case, the film being transported may flutter due to thermal expansion of the film in the heating furnace 100, or in the furnace. Problems such as film loosening may occur.
- a method of controlling the peripheral speed of the drive roll 82a provided on the downstream side of the heating furnace is adopted by an appropriate tension control mechanism so that the tension in the furnace becomes constant.
- the tension control mechanism reduces the peripheral speed of the drive roll 82a and the tension is higher than the set value.
- This is a mechanism for performing feedback so as to increase the peripheral speed of the drive roll 82a.
- 5 shows a form in which a tension pickup roll 72 as a tension detecting means is provided on the upstream side of the heating furnace 100, the tension control means is disposed on the downstream side of the heating furnace. Alternatively, it may be arranged both upstream and downstream of the heating furnace 100.
- a manufacturing system what is equipped with the mechanism heated while conveying a film like a conventionally well-known film drying apparatus and a film stretching apparatus can also be diverted as it is.
- a manufacturing system can be configured by diverting various components used in a film drying device, a film stretching device, and the like.
- the furnace temperature of the heating furnace 100 is a temperature suitable for crystallizing the amorphous indium composite oxide film, for example, 120 ° C. to 260 ° C., preferably 150 ° C. to 220 ° C., more preferably 170 ° C. to 220 ° C. Adjusted to ° C.
- the temperature in the furnace is too low, crystallization does not proceed, or a long time is required for crystallization, so that the productivity tends to be inferior.
- the temperature in the furnace is too high, the elastic modulus (Young's modulus) of the base material decreases and plastic deformation tends to occur, so that the film tends to be stretched due to tension.
- the temperature in the furnace can be adjusted by an appropriate heating means such as an air circulation type fence temperature oven through which hot air or cold air circulates, a heater using microwaves or far infrared rays, a roll heated for temperature adjustment, a heat pipe roll, etc. .
- an appropriate heating means such as an air circulation type fence temperature oven through which hot air or cold air circulates, a heater using microwaves or far infrared rays, a roll heated for temperature adjustment, a heat pipe roll, etc.
- the heating temperature does not need to be constant in the furnace, and may have a temperature profile that increases or decreases in steps.
- the furnace can be divided into a plurality of zones, and the set temperature can be changed for each zone.
- the temperature near the entrance and exit of the heating furnace is used to prevent the film from undergoing sudden dimensional changes due to temperature changes at the entrance and exit of the heating furnace and causing wrinkles and poor conveyance.
- a preheating zone or a cooling zone can be provided so that the change is moderate.
- the heating time in the furnace is a time suitable for crystallization of the amorphous film at the furnace temperature, for example, 10 seconds to 30 minutes, preferably 25 seconds to 20 minutes, more preferably 30 seconds to 15 minutes. Adjusted to If the heating time is too long, the productivity may be inferior and the film may be easily stretched. On the other hand, if the heating time is too short, crystallization may be insufficient.
- the heating time can be adjusted by the length of the film conveyance path (furnace length) in the heating furnace and the film conveyance speed.
- FIG. 5 shows a float conveyance type heating furnace in which hot air blowing nozzles (floating nozzles) 111 to 115 and 121 to 124 are alternately arranged above and below the film conveyance path.
- the float transport method When the float transport method is adopted for transporting the film in the heating furnace, if the transport tension in the furnace is too small, the film will rub against the nozzle due to film fluttering or looseness due to the film's own weight. In addition, the surface of the indium composite oxide film may be damaged. In order to prevent such damage, it is preferable to control the amount of hot air blown out and the conveyance tension.
- the transport tension is adjusted so that the elongation rate of the film falls within the above range. It is preferable.
- the preferred range of the transport tension varies depending on the thickness of the substrate, Young's modulus, linear expansion coefficient, etc.
- the transport tension per unit width of the film is 25 N / m. It is preferably ⁇ 300 N / m, more preferably 30 N / m to 200 N / m, and even more preferably 35 N / m to 150 N / m.
- the stress applied to the film during conveyance is preferably 1.1 MPa to 13 MPa, more preferably 1.1 MPa to 8.7 MPa, and further preferably 1.1 MPa to 6.0 MPa. preferable.
- the tenter transport method is a method that can transport the film without applying tension in the transport direction of the film, and thus can be said to be a preferable transport method from the viewpoint of suppressing dimensional changes in the crystallization process.
- the distance between clips (or the distance between pins) in the width direction may be expanded to absorb slack.
- the film is stretched in the width direction, whereby the resistance of the crystalline indium composite oxide film may increase or the heating reliability may be poor.
- the distance between the clips is such that the elongation of the film in the width direction (TD) is preferably + 2.5% or less, more preferably + 2.0% or less, still more preferably + 1.5% or less, particularly preferably. Is preferably adjusted to be + 1.0% or less.
- the crystalline laminate 10 in which the indium composite oxide film is crystallized by heating in the heating furnace is conveyed to the winding unit 60.
- a winding core having a predetermined diameter is set on the winding base 61 of the winding unit 60, and the crystalline laminate 10 is wound around the winding core in a roll shape with a predetermined tension.
- a wound body 11 of a conductive film is obtained.
- the tension (winding tension) applied to the film when it is wound around the core is preferably 20 N / m or more, and more preferably 30 N / m or more. If the winding tension is too small, the film may not be wound well on the core, or the film may be damaged due to winding deviation.
- the preferable range of the winding tension is often larger than the film transport tension for suppressing the elongation of the film in the crystallization step.
- the tension cutting means a nip roll 82 as shown in FIG. 5, a suction roll, or a group of rolls arranged so that the film transport path is S-shaped can be used.
- a tension detecting means such as a tension pickup roll 72 is arranged between the tension cutting means and the winding unit 60, and an appropriate tension control means so that the winding tension becomes constant by an appropriate tension control mechanism.
- the rotational torque of the winding mount 61 is adjusted.
- the amorphous laminated body Formation and crystallization may be performed as a series of steps. Further, after the crystallization step, before forming the wound body 11, other steps such as forming another layer on the crystalline laminate may be provided.
- an amorphous indium composite oxide film that can be crystallized by heating in a short time is formed. Therefore, the time required for crystallization is shortened, the crystallization of the indium composite oxide film can be performed by the roll-to-roll method, and the long shape in which the crystalline indium composite oxide film is formed. A wound body of a transparent conductive film is obtained. Moreover, by suppressing the elongation of the film in the crystallization step, it is possible to obtain a transparent conductive film in which a crystalline indium composite oxide film having low resistance and excellent heating reliability is formed.
- the ratio R / R 0 with the surface resistance value R of the indium composite oxide film before and after heating the transparent conductive film at 150 ° C. for 90 minutes is 1.0 or more and 1.5 or less. preferable.
- R / R 0 is more preferably 1.4 or less, and more preferably 1.3 or less.
- a long transparent conductive film wound body in which a crystalline indium composite oxide film is formed on a transparent film substrate is obtained.
- Single-wafer transparent conductive film cut out from the revolving body is heat-shrinkable compared to conventional transparent conductive films in which single-wafer bodies are heated batchwise to crystallize an indium composite oxide film. Tends to occur. This is considered to be related to the elongation of the film in the crystallization process.
- the transparent conductive film after the indium composite oxide film is crystallized is heated under tension release, it is presumed that heat shrinkage easily occurs.
- the tension (stress) at the time of conveyance is released, the elongation in the film conveyance direction due to elastic deformation tends to return to the original, whereas the elongation due to plastic deformation remains after the tension is released. Since it remains, the transparent film substrate after the indium composite oxide film is crystallized is considered to be in a stretched state.
- the dimensional change rate of the transparent conductive film after crystallization is negative and its absolute value is large, that is, when the thermal contraction of the transparent conductive film after crystallization is large
- a resistance change is likely to occur when the transparent conductive film is heated or humidified.
- the test piece cut out from the transparent conductive film after crystallization is subjected to a heating test, and then further humidification / heating test is performed, the resistance value of the indium composite oxide film is significantly increased There is. Therefore, from the viewpoint of obtaining a transparent conductive film having a small resistance change due to heating and humidification, the single wafer cut out from the transparent conductive film after crystallization by the roll-to-roll method is 60 ° C.
- the dimensional change rate h 150 when heated is preferably ⁇ 0.85% or more, and more preferably ⁇ 0.70% or more. Further, the dimensional change rate h 140 when heated at 140 ° C. for 60 minutes is preferably ⁇ 0.75% or more, and more preferably ⁇ 0.60% or more. In order to reduce the absolute value of the heating dimensional change rate, it is preferable that the rate of change of the film length in the crystallization step is within the above-mentioned range.
- the cause of the decrease in humidification heat durability was analyzed from the structural aspect of the crystalline film, and the indium-based composite oxide film has a high compressive residual stress, which is one cause of the decrease in humidification heat durability. It was estimated. That the crystalline indium composite oxide film has a compressive residual stress means that the lattice constant is smaller than that of a crystalline indium composite oxide without distortion.
- the amorphous laminate carried into the heating furnace under tension is an indium-based composite oxide that causes elongation due to a decrease in Young's modulus and thermal expansion of the film substrate as the temperature of the laminate increases. Crystallization of the film proceeds, and after completion of crystallization, the film is carried out of the heating furnace.
- the transparent conductive film after crystallization carried out of the furnace tends to shrink due to a decrease in temperature and release of tension. It is considered that compressive stress is applied to the crystalline indium composite oxide film during the shrinkage, and the compressive stress remains in the film.
- the transparent conductive film having the indium composite oxide film having the residual compressive stress is further heated under stress release and causes thermal shrinkage, the indium composite oxide film also has a compressive stress. Is granted. Therefore, it is considered that the residual compressive stress of the indium composite oxide film is further increased.
- a transparent conductive film having a large residual compressive stress is likely to cause an increase in resistance of the crystalline indium composite oxide film due to humidification heat. This is considered to be because a crystalline indium composite oxide film having a large compressive residual stress is likely to be distorted or cracked at the crystal grain boundary. That is, when the transparent conductive film is exposed to a high-temperature and high-humidity environment, the transparent film base material undergoes hygroscopic expansion, so that a tensile stress is applied to the indium composite oxide film formed thereon, It is presumed that the resistance rises due to the film breakage starting from the strain and cracks of the grain boundaries.
- the transparent conductive film is compressed into an indium composite oxide film along with the dimensional change of the transparent conductive film during heating. Since stress is applied, distortion and cracks are likely to occur at the crystal grain boundaries, and it is considered that film breakdown is likely to occur when this is exposed to a humid heat environment.
- the residual compression of the indium composite oxide film after the test piece of the transparent conductive film cut out from the wound body of the long transparent conductive film according to the present invention is heated at 150 ° C. for 60 minutes.
- the stress is preferably 2 GPa or less, more preferably 1.6 GPa or less, further preferably 1.4 GPa or less, and particularly preferably 1.2 GPa or less.
- the residual compressive stress of the indium-based composite oxide film is small, the bending resistance of the transparent conductive film is reduced, or when it is incorporated in a resistive film type touch panel, it is resistant to loads such as pen input. It may not be obtained. Therefore, the residual compressive stress of the indium composite oxide film of the transparent conductive film of the present invention obtained by the roll-to-roll method is preferably 0.4 GPa or more.
- the residual compressive stress of the indium composite oxide film after the transparent conductive film is heated at 150 ° C. for 60 minutes is preferably 0.4 GPa or more.
- the compressive residual stress of the crystalline indium-based composite oxide film is, as will be described in detail later, the lattice strain ⁇ obtained from the diffraction peak in powder X-ray diffraction, the elastic modulus (Young's modulus) E, and Poisson It can be calculated based on the ratio ⁇ .
- the lattice strain ⁇ is preferably obtained from a peak having a large diffraction angle 2 ⁇ .
- the transparent conductive film obtained by the production method of the present invention is suitably used for forming transparent electrodes and touch panels of various devices.
- a wound body of a long transparent conductive film on which a crystalline indium composite oxide film is formed can be obtained. Lamination and processing of metal layers and the like by the method becomes possible. Therefore, according to the present invention, not only the productivity of the transparent conductive film itself can be improved, but also the productivity of touch panels and the like thereafter can be improved.
- the transparent conductive film of the present invention can also be used as it is for transparent electrodes and touch panels of various devices.
- a laminate 30 is formed in which a transparent substrate 31 is bonded to the transparent film substrate 1 of the transparent conductive film 10 using an appropriate adhesive means 33 such as an adhesive layer. May be. Bonding of the base material 1 and the transparent base 31 may be performed either before or after the indium composite oxide film is formed on the base material 1. The smaller the substrate thickness at the time of indium-based composite oxide film formation, the smaller the winding diameter of the roll wound body, and the longer the film forming length that can be continuously formed by the winding type sputtering device, and the better the productivity. .
- the bonding of the substrate 1 and the transparent substrate 31 is performed after the indium composite oxide film is formed. Further, the bonding of the base material 1 and the transparent substrate 31 may be performed before or after the indium composite oxide film is crystallized, but the yellowing of the adhesive due to the crystallization being performed at a high temperature or From the viewpoint of suppressing poor appearance and reduced reliability associated with the precipitation of low molecular weight components such as oligomers from the substrate, it is preferable that bonding is performed after crystallization.
- the base 1 and the transparent base 31 of the transparent conductive film are generally bonded together.
- the base material and the transparent substrate may be bonded by an appropriate bonding means such as a nip roll before being wound into a roll. .
- both heating dimensions The rate of change may be different. If the difference between the two heating dimensional change rates is large, warping or curling may occur when the laminate 30 is heated. Therefore, it is also preferable to adjust the dimensional change rate by a method such as heat-treating the transparent substrate 31 before being bonded to the transparent film substrate in order to suppress the warpage and curling of the laminate 30. .
- substrate are bonded together after crystallization of an indium type complex oxide film
- the transparent substrate 31 in addition to various resin films similar to those used for the transparent film substrate, a rigid substrate such as glass can also be used. Further, as shown in FIG. 6, the transparent substrate 31 has a functional layer 32 such as an easy-adhesion layer, a hard coat layer, an antireflection layer, and an optical interference layer on the side opposite to the surface on which the adhesive layer 33 is formed. Also good.
- a functional layer 32 such as an easy-adhesion layer, a hard coat layer, an antireflection layer, and an optical interference layer on the side opposite to the surface on which the adhesive layer 33 is formed. Also good.
- an adhesive layer is preferable.
- the constituent material of the pressure-sensitive adhesive layer can be used without particular limitation as long as it has transparency.
- acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy polymers, fluorine polymers, natural rubber, synthetic rubber and other rubber polymers Can be appropriately selected and used.
- an acrylic pressure-sensitive adhesive is preferably used from the viewpoint that it is excellent in optical transparency, exhibits adhesive properties such as appropriate wettability, cohesiveness and adhesiveness, and is excellent in weather resistance and heat resistance.
- a laminated body in which an amorphous indium composite oxide film is formed on a substrate is put into a heating oven at 180 ° C., and each laminated body after 2 minutes, 10 minutes, 30 minutes, and 60 minutes after loading. The completion of crystallization was judged by measuring the resistance value after immersion in hydrochloric acid with a tester.
- the crystal lattice spacing d of the ITO film was calculated from the peak of the obtained diffraction image (peak of the (622) plane of ITO) angle 2 ⁇ and the wavelength ⁇ of the X-ray source, and the lattice strain ⁇ was calculated based on d. . In the calculation, the following formulas (1) and (2) were used.
- d 0 is the value obtained from the ICDD (The International Centre for Diffraction Data ) database.
- the angle ⁇ between the film surface normal and the ITO crystal surface normal shown in FIG. 7 is 45 °, 50 °, 55 °, 60 °, 65 °, 70 °, 77 °, 90
- the lattice strain ⁇ at each ⁇ was calculated for each of the degrees.
- the angle ⁇ formed by the film surface normal and the ITO crystal surface normal was adjusted by rotating the sample about the TD direction (the direction orthogonal to the MD direction) as the rotation axis.
- the residual stress ⁇ in the in-plane direction of the ITO film was determined by the following equation (3) from the slope of a straight line plotting the relationship between sin 2 ⁇ and lattice strain ⁇ .
- E is the Young's modulus (116 GPa) of ITO
- ⁇ is the Poisson's ratio (0.35).
- ⁇ Dimensional change rate of transparent conductive film> A strip-shaped test piece of 100 mm ⁇ 10 mm having a long side in the MD direction was cut out from the transparent conductive films of Examples and Comparative Examples, and the dimensional change rate h 140 when heated at 140 ° C. for 60 minutes and at 150 ° C. The dimensional change rate h 150 when heated for 60 minutes was determined. The dimensional change rate was measured by measuring the distances L 0 and L 1 between the gauge points before and after heating with a three-dimensional measuring machine in the same manner as described above.
- Example 1 (Formation of anchor layer) Two undercoat layers are formed on a biaxially stretched polyethylene terephthalate film (trade name “Diafoil” manufactured by Mitsubishi Plastics, glass transition temperature 80 ° C., refractive index 1.66) having a thickness of 23 ⁇ m by a roll-to-roll method. Formed. First, a thermosetting resin composition containing melamine resin: alkyd resin: organosilane condensate in a weight ratio of 2: 2: 1 in solid content was diluted with methyl ethyl ketone so that the solid content concentration was 8% by weight. . This solution was applied to one main surface of a PET film and heat-cured at 150 ° C. for 2 minutes to form a first undercoat layer having a thickness of 150 nm and a refractive index of 1.54.
- a siloxane-based thermosetting resin (trade name “Colcoat P” manufactured by Colcoat) was diluted with methyl ethyl ketone so that the solid content concentration was 1% by weight. This solution was applied on the first undercoat layer and cured by heating at 150 ° C. for 1 minute to form a SiO 2 thin film (second undercoat layer) having a film thickness of 30 nm and a refractive index of 1.45.
- a sintered body containing indium oxide and tin oxide in a weight ratio of 97: 3 as a target material was attached to a parallel plate type take-up magnetron sputtering apparatus. While transporting the PET film base material on which the two undercoat layers were formed, dehydration and degassing were performed, and the air was exhausted to 5 ⁇ 10 ⁇ 3 Pa. In this state, argon gas and oxygen gas were introduced at a flow rate ratio of 98%: 2% so that the heating temperature of the substrate was 120 ° C. and the pressure was 4 ⁇ 10 ⁇ 1 Pa. Film formation was performed to form an amorphous ITO film having a thickness of 20 nm on the substrate.
- the base material on which the amorphous ITO film was formed was continuously wound around a winding core to form a wound body of an amorphous laminate.
- the surface resistance of this amorphous ITO film was 450 ⁇ / ⁇ .
- ITO crystallization Using a film heating / conveying apparatus having a float conveying type heating furnace as shown in FIG. 5, the laminated body is continuously fed out from the wound body of the amorphous laminated body and conveyed in the heating furnace. The ITO film was crystallized by heating at. The laminated body after crystallization was wound around the core again to form a wound body of a transparent conductive film on which a crystalline ITO film was formed.
- the furnace length of the heating furnace was 20 m
- the heating temperature was 200 ° C.
- the film conveyance speed was 20 m / min (heating time when passing through the furnace: 1 minute).
- the conveying tension in the furnace was set so that the tension per unit width of the film was 28 N / m. It was confirmed that the obtained transparent conductive film had a higher transmittance than the amorphous ITO film before heating and was crystallized. Moreover, it was confirmed from the resistance value after being immersed in hydrochloric acid that crystallization was completed.
- Example 2 a wound body of a transparent conductive film on which a crystalline ITO film was formed was formed in the same manner as in Example 1, but the transport tension per unit width in the furnace in the crystallization process was It was different from Example 1 only in that it was set to 51 N / m.
- Example 3 In Example 3, a wound body of a transparent conductive film on which a crystalline ITO film was formed was formed in the same manner as in Example 1, but the transport tension per unit width in the furnace in the crystallization process was It was different from Example 1 only in that it was set to 65 N / m.
- Example 4 the wound body of the transparent conductive film on which the crystalline ITO film was formed was formed in the same manner as in Example 1, but the transport tension per unit width in the furnace in the crystallization process was It was different from Example 1 only in that it was set to 101 N / m.
- Example 5 In Example 5, a sintered body containing indium oxide and tin oxide at a weight ratio of 90:10 was used as a target material, and 5 ⁇ 10 ⁇ 4 Pa at the time of dehydration and degassing before sputtering film formation.
- a transparent conductive laminate in which an amorphous ITO film is formed on a biaxially stretched polyethylene terephthalate film on which an undercoat layer has been formed is obtained under the same sputtering conditions as in Example 1 except that evacuation is performed until It was.
- the surface resistance of this amorphous ITO film was 450 ⁇ / ⁇ .
- ITO was crystallized by the roll-to-roll method in the same manner as in Example 1, but the film conveyance speed was 6.7 m / min (when passing through the furnace). Heating time: 3 minutes), and the conditions of the crystallization step were different from Example 1 in that the conveyance tension was set to 65 N / m. It was confirmed that the obtained transparent conductive film had a higher transmittance than the amorphous laminate before heating and was crystallized. Moreover, it was confirmed from the resistance value after being immersed in hydrochloric acid that crystallization was completed.
- Example 6 In Example 6, an undercoat layer was formed under the same sputtering conditions as in Example 1 except that evacuation was performed to 5 ⁇ 10 ⁇ 4 Pa at the time of dehydration and degassing before sputtering film formation. A transparent conductive laminate having an amorphous ITO film formed on a biaxially stretched polyethylene terephthalate film was obtained. The surface resistance of this amorphous ITO film was 450 ⁇ / ⁇ . When a heating test of the amorphous ITO film was performed, it was confirmed that crystallization was completed after heating at 180 ° C. for 2 minutes.
- Example 1 Using this amorphous laminate, ITO was crystallized by the roll-to-roll method in the same manner as in Example 1. However, Example 1 differs from Example 1 in that the conveyance tension was set to 101 N / m. The conditions of the crystallization process were different. It was confirmed that the obtained transparent conductive film had a higher transmittance than the amorphous laminate before heating and was crystallized.
- Comparative Example 1 In Comparative Example 1, a wound body of a transparent conductive film on which a crystalline ITO film was formed was formed in the same manner as in Example 6, but the conveyance tension per unit width in the furnace in the crystallization process was It was different from Example 6 only in that it was set to 120 N / m.
- Comparative Example 2 a wound body of a transparent conductive film on which a crystalline ITO film was formed was formed in the same manner as in Example 1, but the transport tension per unit width in the furnace in the crystallization process was It was different from Example 1 only in that it was set at 138 N / m.
- Example 7 the wound body of the transparent conductive film on which the crystalline ITO film was formed was formed in the same manner as in Example 5, but the transport tension per unit width in the furnace in the crystallization process was It was different from Example 5 only in that it was set to 51 N / m.
- Table 1 shows the manufacturing conditions of the above Examples and Comparative Examples, and the evaluation results of the transmittance of the transparent conductive film after heating, the crystallinity of the ITO film, and the surface resistance.
- Table 2 shows the heating conditions (crystallization conditions) in each example and comparative example, and the evaluation results of the ITO film after heating.
- the properties of the transparent conductive film after crystallization were the same at the inner periphery (near the core) and the outer periphery of the wound body.
- the indium composite oxide film can be crystallized by heating the film while being conveyed. Further, when heating is performed while the film is being conveyed, a long transparent conductive film with little variation in quality in the longitudinal direction is obtained.
- hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by Ciba Geigy) as a photopolymerization initiator to 100 parts by weight of acrylic / urethane resin (trade name “Unidic 17-806” manufactured by DIC)
- a hard coat coating solution was prepared by diluting with toluene so that the solid content was 50% by weight. This solution was applied onto a PET film, heated at 100 ° C. for 3 minutes and dried, and then irradiated with ultraviolet light having an integrated light amount of 300 mJ / cm 2 with a high-pressure mercury lamp to form a hard coat layer having a thickness of 5 ⁇ m. .
- the acrylic pressure-sensitive adhesive solution was applied to the surface of the PET film with a hard coat layer on which the hard coat layer was not formed, and heat-cured at 155 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m. . Subsequently, the separator which attached the silicone layer to the adhesive layer surface was bonded by roll bonding.
- Heating dimensional change rate A 100 mm ⁇ 10 mm strip-shaped test piece having a long side in the MD direction was cut out from the obtained laminate, and the dimensional change rate when heated at 140 ° C. for 60 minutes and the dimensional change when heated at 150 ° C. for 60 minutes. The rate was measured. All samples had values similar to the dimensional change rates h 140 and h 150 of the transparent conductive film alone.
- Heating test A sheet test piece was cut out from the laminate, and the ratio of surface resistance before and after heating when heated at 140 ° C. for 60 minutes (R 1,140 / R 0 ) and before and after heating when heated at 150 ° C. for 60 minutes The surface resistance ratio (R 1,150 / R 0 ) was determined. Further, the residual stress ⁇ 150 of the ITO film of the sample after heating at 150 ° C. for 60 minutes was determined by the X-ray scattering method described above.
- Table 2 shows the compressive residual stress ⁇ 0 of the ITO film before the heating test and the compressive residual stress ⁇ 150 of the ITO film after heating at 150 ° C. for 60 minutes.
- Table 3 shows the surface resistance ratios R 2,140 / R 1,140 and R 2,0 / R 0 before and after the thermal test. Further, the dimensional change rate h 140 when the transparent conductive film was heated at 140 ° C.
- FIG. 8 shows a graph plotting the relationship between the surface resistance ratios R 2,140 / R 1,140 when subjected to the thermal test.
- the transparent conductive film having a small absolute value of the heating dimensional change rate h 140 at 140 ° C. is either after the heating test or after being subjected to the humidification heat test. However, an increase in the resistance value is suppressed. The same tendency can be seen from the ratio of the heating dimensional change rate h 150 at 150 ° C. and the resistance before and after the 150 ° C. heating test. Moreover, according to FIG. 8, it turns out that there is a correlation between the heating dimensional change rate and the resistance change. Furthermore, according to Table 2, it can be seen that there is a high correlation between the resistance change before and after the heating test and the residual compressive stress ⁇ 150 of the indium composite oxide film. From this, the residual compressive stress of the indium composite oxide film increases due to dimensional change (shrinkage) when the transparent conductive film after the indium composite oxide film is crystallized is further heated. Was thought to contribute to increased resistance.
- the compressive stress is applied to the indium composite oxide film due to the shrinkage of the base material when the transparent conductive film is heated, and the residual compressive stress increases, and the residual compressive stress of the indium composite oxide film increases. It can be seen that there is a tendency for resistance changes to occur when large transparent conductive films are exposed to humid heat environments. From this, it was considered that the compressive strain generated in the indium composite oxide film due to the shrinkage during heating was the cause of the resistance change.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
- Manufacturing Of Electric Cables (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
透明フィルム基材1は、可撓性および透明性を有するものであれば、その材質に特に限定はなく、適宜なものを使用することができる。具体的には、ポリエステル系樹脂、アセテート系樹脂、ポリエーテルスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、ポリアリレート系樹脂、ポリフェニレンサルファイド系樹脂、ポリ塩化ビニリデン系樹脂、(メタ)アクリル系樹脂などが挙げられる。これらの中でも、特に好ましいものは、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリオレフィン系樹脂などである。
透明フィルム基材1のインジウム系複合酸化物膜4’が製膜される側の主面には、基材とインジウム系複合酸化物膜との密着性の向上や、反射特性の制御等を目的としてアンカー層2,3が設けられていてもよい。アンカー層は1層でもよいし、図2に示すように2層あるいはそれ以上設けられていてもよい。アンカー層は、無機物、有機物、あるいは無機物と有機物との混合物により形成される。アンカー層を形成するための材料としては、例えば、無機物として、SiO2、MgF2、Al2O3などが好ましく用いられる。また有機物としてはアクリル樹脂、ウレタン樹脂、メラミン樹脂、アルキド樹脂、シロキサン系ポリマーなどの有機物が挙げられる。特に、有機物として、メラミン樹脂とアルキド樹脂と有機シラン縮合物の混合物からなる熱硬化型樹脂を使用することが好ましい。アンカー層は、上記の材料を用いて、真空蒸着法、スパッタリング法、イオンプレーティング法、塗工法などにより形成できる。
透明フィルム基材上に気相法により非晶質インジウム系複合酸化物膜4’が形成される。気相法としては、電子ビーム蒸着法、スパッタ法、イオンプレーティング法等があげられるが、均一な薄膜が得られる点からスパッタ法が好ましく、DCマグネトロンスパッタ法が好適に採用される。なお、「非晶質インジウム系複合酸化物」とは、完全に非晶質であるものに限られず、少量の結晶成分を有していてもよい。インジウム系複合酸化物が非晶質であるか否かの判定は、基材上にインジウム系複合酸化物膜が形成された積層体を濃度5wt%の塩酸に15分間浸漬した後、水洗・乾燥し、15mm間の端子間抵抗をテスタにて測定することによりおこなわれる。非晶質インジウム系複合酸化物膜は塩酸によりエッチングされて消失するために、塩酸への浸漬により抵抗が増大する。本明細書においては、塩酸への浸漬・水洗・乾燥後に、15mm間の端子間抵抗が10kΩを超える場合に、インジウム系複合酸化物膜が非晶質であるものとする。
実施例での評価は、以下の方法によりおこなったものである。
<表面抵抗>
表面抵抗は、JIS K7194(1994年)に準じて四端子法により測定した。
(加熱試験)
結晶化後の透明導電性フィルムからフィルム片を切り出して、150℃の加熱槽内で90分間加熱して、加熱前の表面抵抗(R0)と加熱後の表面抵抗(R)との比R/R0を求めた。
結晶化工程に供される前の非晶質積層体を、MD方向を長辺とする100mm×10mmの短冊状の試験片に切り出し、MD方向に約80mmの間隔で2点の標点(傷)を形成して、標点間の距離L0を三次元測長機により測定した。その後、150℃の加熱槽内で90分間試験片の加熱を行い、加熱後の標点間距離L1を測定した。L0およびL1から寸法変化率H0,90(%)=100×(L1-L0)/L0を算出した。結晶化後の結晶質積層体についても同様にして90分間加熱した際の寸法変化率H1,90を求め、これらの寸法変化率の差から、結晶化前後での寸法変化率の差ΔH90=(H1,90-H0,90)を算出した。また、150℃の加熱槽内での加熱時間を60分として同様の試験を行い、非晶質積層体の加熱寸法変化率H0,60と結晶化後の結晶質積層体の加熱寸法変化率H1,60との差ΔH60=(H1,60-H0,60)を算出した。
ヘイズメーター(スガ試験機製)を用いて、JIS K-7105に準じ、全光線透過率を測定した。
基材上に非晶質インジウム系複合酸化物膜が形成された積層体を180℃の加熱オーブン中に投入し、投入後2分、10分、30分、60分後のそれぞれの積層体について、塩酸に浸漬後の抵抗値をテスタで測定することにより、結晶化の完了を判断した。
結晶化工程における張力は、フィルム搬送経路中の加熱炉の上流に設けられたテンションピックアップロールにより検出された張力の値を用いた。また、その張力およびフィルムの厚みから、フィルムに付与される応力を算出した。結晶化工程でのフィルムの伸び率は、フィルム搬送経路中の加熱炉の上流に設けられた駆動式のニップロールと、加熱炉の下流側に設けられた駆動式のニップロールとの周速比から算出した。
X線散乱法により測定された結晶格子歪みから、上記実施例および比較例のITO膜の残留応力を間接的に求めた。
株式会社リガク製の粉末X線回折装置により、測定散乱角2θ=59~62°の範囲で0.04°おきに回折強度を測定した。各測定角度における積算時間(露光時間)は100秒とした。
ここで、λはX線源(Cu Kα線)の波長(=0.15418nm)であり、d0は無応力状態のITOの格子面間隔(=0.15241nm)である。なお、d0はICDD(The International Centre for Diffraction Data)データベースから取得した値である。
上記式において、EはITOのヤング率(116GPa)、νはポアソン比(0.35)である。これらの値は、D. G. Neerinckand T. J. Vink, “Depth profiling of thin ITO films by grazing incidence X-ray diffraction”, Thin Solid Films, 278 (1996), PP 12-17.に記載されている既知の実測値である。
実施例および比較例の透明導電性フィルムからMD方向を長辺とする100mm×10mmの短冊状の試験片を切り出して、140℃で60分間加熱した際の寸法変化率h140、および150℃で60分間加熱した際の寸法変化率h150を求めた。寸法変化率の測定は、先に記載したのと同様に、加熱前と加熱後の標点間距離L0およびL1を三次元測長機で測定することによって求めた。
(アンカー層の形成)
ロール・トゥー・ロール法により、厚み23μmの二軸延伸ポリエチレンテレフタレートフィルム(三菱樹脂製 商品名「ダイアホイル」、ガラス転移温度80℃、屈折率1.66)上に、2層のアンダーコート層を形成した。まず、メラミン樹脂:アルキド樹脂:有機シラン縮合物を、固形分で2:2:1の重量比で含む熱硬化型樹脂組成物を、固形分濃度が8重量%となるようにメチルエチルケトンで希釈した。この溶液を、PETフィルムの一方主面に塗布し、150℃で2分間加熱硬化させ、膜厚150nm、屈折率1.54の第1アンダーコート層を形成した。
平行平板型の巻き取り式マグネトロンスパッタ装置に、ターゲット材料として、酸化インジウムと酸化スズとを97:3の重量比で含有する焼結体を装着した。2層のアンダーコート層が形成されたPETフィルム基材を搬送しながら、脱水、脱ガスを行い、5×10-3Paとなるまで排気した。この状態で、基材の加熱温度を120℃とし、圧力が4×10-1Paとなるように、98%:2%の流量比でアルゴンガスおよび酸素ガスを導入して、DCスパッタ法により製膜を行い、基材上に厚み20nmの非晶質ITO膜を形成した。非晶質ITO膜が形成された基材は、連続的に巻芯に巻取られ、非晶質積層体の巻回体が形成された。この非晶質ITO膜の表面抵抗は、450Ω/□であった。非晶質ITO膜の加熱試験を行ったところ、180℃で10分間の加熱後に結晶化が完了していることが確認された。
図5に示すようなフロート搬送式の加熱炉を有するフィルム加熱・搬送装置を用いて、前記の非晶質積層体の巻回体から、積層体を連続的に繰出し、搬送しながら加熱炉内で加熱することでITO膜の結晶化を行った。結晶化後の積層体を再度巻芯に巻取られ、結晶ITO膜が形成された透明導電性フィルムの巻回体が形成された。
実施例2においては、実施例1と同様にして、結晶ITO膜が形成された透明導電性フィルムの巻回体が形成されたが、結晶化工程における炉内での単位幅あたりの搬送張力が51N/mに設定された点のみにおいて、実施例1とは異なっていた。
実施例3においては、実施例1と同様にして、結晶ITO膜が形成された透明導電性フィルムの巻回体が形成されたが、結晶化工程における炉内での単位幅あたりの搬送張力が65N/mに設定された点のみにおいて、実施例1とは異なっていた。
実施例4においては、実施例1と同様にして、結晶ITO膜が形成された透明導電性フィルムの巻回体が形成されたが、結晶化工程における炉内での単位幅あたりの搬送張力が101N/mに設定された点のみにおいて、実施例1とは異なっていた。
実施例5においては、ターゲット材料として、酸化インジウムと酸化スズとを90:10の重量比で含有する焼結体を用い、スパッタ製膜を行う前の脱水、脱ガス時に5×10-4Paとなるまで排気をおこなった以外は実施例1と同様のスパッタ条件により、アンダーコート層が形成された二軸延伸ポリエチレンテレフタレートフィルム上に非晶質ITO膜が形成された透明導電性積層体を得た。この非晶質ITO膜の表面抵抗は、450Ω/□であった。非晶質ITO膜の加熱試験を行ったところ、180℃で30分間の加熱後に結晶化が完了していることが確認された。
実施例6においては、スパッタ製膜を行う前の脱水、脱ガス時に5×10-4Paとなるまで排気をおこなった以外は、実施例1と同様のスパッタ条件により、アンダーコート層が形成された二軸延伸ポリエチレンテレフタレートフィルム上に非晶質ITO膜が形成された透明導電性積層体を得た。この非晶質ITO膜の表面抵抗は、450Ω/□であった。非晶質ITO膜の加熱試験を行ったところ、180℃で2分間の加熱後に結晶化が完了していることが確認された。
比較例1においては、実施例6と同様にして、結晶ITO膜が形成された透明導電性フィルムの巻回体が形成されたが、結晶化工程における炉内での単位幅あたりの搬送張力が120N/mに設定された点のみにおいて、実施例6とは異なっていた。
比較例2においては、実施例1と同様にして、結晶ITO膜が形成された透明導電性フィルムの巻回体が形成されたが、結晶化工程における炉内での単位幅あたりの搬送張力が138N/mに設定された点のみにおいて、実施例1とは異なっていた。
実施例7においては、実施例5と同様にして、結晶ITO膜が形成された透明導電性フィルムの巻回体が形成されたが、結晶化工程における炉内での単位幅あたりの搬送張力が51N/mに設定された点のみにおいて、実施例5とは異なっていた。
下記のように、実施例および比較例の透明導電性フィルムがハードコート層付きのPETフィルムと貼り合わされた積層体を作製して、加熱および加湿熱による特性変化を評価した。なお、加熱および加湿熱による特性変化は、透明導電性フィルム単体で行うこともできる。しかしながら、上記の実施例および比較例の透明導電性フィルムは、基材厚みが23μmと小さく、加熱および加湿熱試験後にITO膜面を凸とする反りが生じ、表面抵抗等の測定値のバラつきが大きくなる場合があった。そのため、以下では、厚みの大きいPETフィルムとの積層体にて評価を行った。
厚みが125μmの二軸延伸ポリエチレンテレフタレートフィルム(東レ製、商品名「ルミラー U34」、150℃60分加熱時のMD方向の寸法変化率:-1.0%)を用い、ロール・トゥー・ロール法により、以下のようにハードコート層を形成した。
撹拌ミキサー、温度計、窒素ガス導入管、冷却機を備えた重合槽に、ブチルアクリレート100重量部、アクリル酸5 重量部および2-ヒドロキシエチルアクリレート0.075重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.2 重量部、重合溶媒として酢酸エチル200重量部を仕込み、十分に窒素置換した後、窒素気流下で撹拌しながら重合槽内の温度を55℃付近に保って10時間重合反応を行い、アクリル系ポリマー溶液を調整した。このアクリル系ポリマー溶液の固形分100重量部に、過酸化物としてジベンゾイルパーオキシド(日本油脂製 商品名「ナイパーBMT」)0.2重量部、イソシアネート系架橋剤としてトリメチロールプロパン/トリレンジイソシアネートのアダクト体(日本ポリウレタンエ業製、商品名「コロネートL」)0.5 重量部、シランカップリング剤(信越化学工業製、商品名「KBM403」)0.075重量部を均一に混合撹拌して、粘着剤溶液(固形分10.9重量%)を調製した。
ロール貼合により、粘着剤層付きハードコートPETフィルムからセパレータを剥離しながら、その露出面に実施例で得られた透明導電性フィルムのITO膜が形成されていない側の面を連続的に貼り合わせて、図6に模式的に示す積層構成を有する積層体30を得た。
得られた積層体からMD方向を長辺とする100mm×10mmの短冊状の試験片を切り出して、140℃で60分間加熱した際の寸法変化率および150℃で60分間加熱した際の寸法変化率を測定した。いずれの試料も、透明導電性フィルム単体での寸法変化率h140およびh150と同様の値であった。
積層体から枚葉の試験片を切り出して、140℃で60分間加熱した際の加熱前後での表面抵抗の比(R1,140/R0)および150℃で60分間加熱した際の加熱前後での表面抵抗の比(R1,150/R0)を求めた。また、150℃で60分間加熱後の試料のITO膜の残留応力σ150を、前述のX線散乱法により求めた。
前述の140℃で60分間加熱後の試料、および結晶化後の透明導電性フィルムから切り出された後加熱試験に供されていない試料のそれぞれを、温度60℃湿度95%の恒温恒湿槽に500時間投入した後の表面抵抗を測定して、加湿熱による変化を評価した。加湿熱による表面抵抗の変化は、加湿熱試験前の表面抵抗に対する、加湿熱試験後の表面抵抗の比(R2,140/R1,140、およびR2,0/R0)の値により評価した。なお、R2,140は140℃で60分間加熱後の試料を加湿熱試験に供した後の表面抵抗であり、R2,0は加熱試験に供していない試料を加湿熱試験に供した後の表面抵抗である。
2,3 アンカー層
4 結晶質膜
4’ 非晶質膜
10 結晶質積層体(透明導電性フィルム)
20 非晶質積層体
50 繰出部
51 繰出架台
60 巻取部
61 巻取架台
71~73 テンションピックアップロール
81,82 ニップロール対
81a 駆動ロール
82a 駆動ロール
100 加熱炉
Claims (8)
- 長尺状透明フィルム基材上に結晶質のインジウム系複合酸化物膜が形成された長尺状透明導電性フィルムを製造する方法であって、
インジウムと4価金属とを含有するインジウム系複合酸化物の非晶質膜が、スパッタ法により前記長尺状透明フィルム基材上に形成される非晶質積層体形成工程、および
前記非晶質膜が形成された長尺状透明フィルム基材が、170℃~220℃の加熱炉内に連続的に搬送され、前記非晶質膜が結晶化される、結晶化工程、を有し、
前記結晶化工程におけるフィルム長さの変化率が+2.5%以下である、透明導電性フィルムの製造方法。 - 前記結晶化工程において、加熱炉内の長尺状透明フィルム基材に付与される搬送方向の応力が、1.1MPa~13MPaである、請求項1に記載の透明導電性フィルムの製造方法。
- 前記結晶化工程における加熱時間が10秒~30分である、請求項1または2に記載の透明導電性フィルムの製造方法。
- 前記インジウム系複合酸化物は、インジウムと4価金属との合計100重量部に対して0重量部を超え15重量部以下の4価金属を含有する、請求項1~3のいずれか1項に記載の透明導電性フィルムの製造方法。
- 前記非晶質積層体形成工程において、前記非晶質膜が形成される前に、スパッタ装置内の真空度が1×10-3Pa以下となるまで排気が行われる、請求項1~4のいずれか1項に記載の透明導電性フィルムの製造方法。
- 長尺状透明フィルム基材上に結晶質インジウム系複合酸化物膜が形成された長尺状透明導電性フィルムがロール状に巻回されている透明導電性フィルムの巻回体であって、
前記インジウム系複合酸化物は、インジウムと4価金属とを含有し、
前記透明導電性フィルムを枚葉体に切り出して150℃で60分間加熱した際に、前記インジウム系複合酸化物膜の圧縮残留応力が0.4GPa~1.6GPaである、透明導電性フィルム巻回体。 - 前記透明導電性フィルムを枚葉体に切り出して150℃で60分間加熱した際に、長尺フィルムの長手方向における寸法変化率が0%~-1.5%である、請求項6に記載の透明導電性フィルム巻回体。
- 前記インジウム系複合酸化物は、インジウムと4価金属との合計100重量部に対して0を超え15重量部以下の4価金属を含有する、請求項6または7に記載の透明導電性フィルム巻回体。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157012159A KR20150059798A (ko) | 2010-07-06 | 2011-07-06 | 투명 도전성 필름 및 그 제조 방법 |
KR1020137003070A KR20130025969A (ko) | 2010-07-06 | 2011-07-06 | 투명 도전성 필름 및 그 제조 방법 |
US13/808,487 US20130149555A1 (en) | 2010-07-06 | 2011-07-06 | Transparent conductive film and manufacturing method therefor |
CN201180033556.5A CN102985585B (zh) | 2010-07-06 | 2011-07-06 | 透明导电性薄膜及其制造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-154219 | 2010-07-06 | ||
JP2010154219 | 2010-07-06 | ||
JP2011-050457 | 2011-03-08 | ||
JP2011050457 | 2011-03-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012005300A1 true WO2012005300A1 (ja) | 2012-01-12 |
Family
ID=45441277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/065493 WO2012005300A1 (ja) | 2010-07-06 | 2011-07-06 | 透明導電性フィルムおよびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130149555A1 (ja) |
JP (2) | JP5944629B2 (ja) |
KR (2) | KR20130025969A (ja) |
CN (1) | CN102985585B (ja) |
TW (2) | TW201221363A (ja) |
WO (1) | WO2012005300A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012090735A1 (ja) * | 2010-12-27 | 2012-07-05 | 日東電工株式会社 | 透明導電性フィルムおよびその製造方法 |
CN103578609A (zh) * | 2012-08-09 | 2014-02-12 | 日东电工株式会社 | 导电性膜 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6435597B2 (ja) * | 2013-09-13 | 2018-12-12 | 東ソー株式会社 | 透明導電性フィルム及びその製造方法 |
CN104347191A (zh) * | 2014-02-28 | 2015-02-11 | 深圳市骏达光电股份有限公司 | 一种透明导电薄膜缩水方法 |
CN106460153B (zh) * | 2014-04-30 | 2019-05-10 | 日东电工株式会社 | 透明导电性膜及其制造方法 |
KR102314238B1 (ko) * | 2014-04-30 | 2021-10-18 | 닛토덴코 가부시키가이샤 | 투명 도전성 필름 및 그 제조 방법 |
JP6211557B2 (ja) * | 2014-04-30 | 2017-10-11 | 日東電工株式会社 | 透明導電性フィルム及びその製造方法 |
KR20170008196A (ko) * | 2014-05-20 | 2017-01-23 | 닛토덴코 가부시키가이샤 | 투명 도전성 필름 및 그 제조 방법 |
WO2016018052A1 (ko) * | 2014-07-29 | 2016-02-04 | 주식회사 엘지화학 | 전도성 적층체 및 이의 제조방법 |
JP6842031B2 (ja) * | 2016-08-23 | 2021-03-17 | 住友金属鉱山株式会社 | ロールツーロール方式の表面処理装置並びにこれを用いた成膜方法及び成膜装置 |
JP6689174B2 (ja) * | 2016-10-31 | 2020-04-28 | 日東電工株式会社 | 透明導電性フィルム及びそれを用いたタッチパネル |
KR101841946B1 (ko) * | 2017-02-24 | 2018-03-26 | 동우 화인켐 주식회사 | 장력 제어를 이용한 터치 센서 필름 제조방법 |
JP2019059170A (ja) * | 2017-09-27 | 2019-04-18 | 日東電工株式会社 | 結晶化フィルム |
JP6999899B2 (ja) * | 2017-11-24 | 2022-01-19 | 日本電気硝子株式会社 | 透明導電膜付きガラスロール及び透明導電膜付きガラスシートの製造方法 |
JP2020167047A (ja) * | 2019-03-29 | 2020-10-08 | 日東電工株式会社 | ヒータ |
CN112092256B (zh) * | 2019-12-26 | 2022-02-15 | 深圳市中欧新材料有限公司 | 一种导电膜生产用温度可调节的加热装置 |
CN113140833B (zh) * | 2021-04-14 | 2022-08-09 | 酷驰(深圳)新能源科技有限公司 | 一种具有加热功能的电池模组 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63454A (ja) * | 1986-06-20 | 1988-01-05 | Konica Corp | 透明導電性フイルムの製造方法 |
JPH02221365A (ja) * | 1989-02-22 | 1990-09-04 | Nitto Denko Corp | 誘明導電性積層体の製造方法 |
JP2004149845A (ja) * | 2002-10-30 | 2004-05-27 | Sony Corp | 走行式真空成膜装置 |
JP2005325399A (ja) * | 2004-05-13 | 2005-11-24 | Nippon Zeon Co Ltd | 積層フィルムの製造方法 |
WO2008102868A1 (ja) * | 2007-02-23 | 2008-08-28 | Konica Minolta Holdings, Inc. | 透明導電膜を有するロール状樹脂フィルムの製造方法及びこれを用いる有機エレクトロルミネッセンス素子 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4056422A (en) * | 1975-06-06 | 1977-11-01 | General Binding Corporation | Two stage oven laminator method |
JPH063454A (ja) * | 1992-06-23 | 1994-01-11 | Olympus Optical Co Ltd | 内部増幅型固体撮像素子 |
JPH08227623A (ja) * | 1995-02-21 | 1996-09-03 | Oji Kako Kk | 透明導電性フィルムの製造方法 |
JP4296462B2 (ja) * | 2000-11-27 | 2009-07-15 | 東洋紡績株式会社 | 透明導電性フィルム、透明導電性シートおよびタッチパネル |
US6811815B2 (en) * | 2002-06-14 | 2004-11-02 | Avery Dennison Corporation | Method for roll-to-roll deposition of optically transparent and high conductivity metallic thin films |
US8728285B2 (en) * | 2003-05-23 | 2014-05-20 | Demaray, Llc | Transparent conductive oxides |
JP4428698B2 (ja) * | 2004-03-31 | 2010-03-10 | 出光興産株式会社 | 酸化インジウム−酸化セリウム系スパッタリングターゲット及び透明導電膜及び透明導電膜の製造方法 |
JP4882262B2 (ja) * | 2005-03-31 | 2012-02-22 | 凸版印刷株式会社 | 透明導電膜積層体の製造方法 |
JP4754955B2 (ja) * | 2005-11-07 | 2011-08-24 | 有限会社エイチエスプランニング | タッチパネル用導電性フィルム及びタッチパネル用導電性フィルム製造方法 |
JP5506011B2 (ja) * | 2007-03-02 | 2014-05-28 | 日東電工株式会社 | 粘着剤層付き透明導電性フィルムおよびその製造方法 |
KR20120108062A (ko) * | 2007-06-26 | 2012-10-04 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 아모르퍼스 복합 산화막, 결정질 복합 산화막, 아모르퍼스 복합 산화막의 제조 방법, 결정질 복합 산화막의 제조 방법 및 복합 산화물 소결체 |
JP5122670B2 (ja) * | 2010-11-05 | 2013-01-16 | 日東電工株式会社 | 透明導電性フィルムの製造方法 |
-
2011
- 2011-07-06 JP JP2011150223A patent/JP5944629B2/ja active Active
- 2011-07-06 US US13/808,487 patent/US20130149555A1/en not_active Abandoned
- 2011-07-06 TW TW100123967A patent/TW201221363A/zh unknown
- 2011-07-06 WO PCT/JP2011/065493 patent/WO2012005300A1/ja active Application Filing
- 2011-07-06 KR KR1020137003070A patent/KR20130025969A/ko active Search and Examination
- 2011-07-06 KR KR1020157012159A patent/KR20150059798A/ko active Search and Examination
- 2011-07-06 CN CN201180033556.5A patent/CN102985585B/zh active Active
- 2011-07-06 TW TW103134141A patent/TW201505039A/zh unknown
-
2015
- 2015-05-18 JP JP2015101096A patent/JP6006368B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63454A (ja) * | 1986-06-20 | 1988-01-05 | Konica Corp | 透明導電性フイルムの製造方法 |
JPH02221365A (ja) * | 1989-02-22 | 1990-09-04 | Nitto Denko Corp | 誘明導電性積層体の製造方法 |
JP2004149845A (ja) * | 2002-10-30 | 2004-05-27 | Sony Corp | 走行式真空成膜装置 |
JP2005325399A (ja) * | 2004-05-13 | 2005-11-24 | Nippon Zeon Co Ltd | 積層フィルムの製造方法 |
WO2008102868A1 (ja) * | 2007-02-23 | 2008-08-28 | Konica Minolta Holdings, Inc. | 透明導電膜を有するロール状樹脂フィルムの製造方法及びこれを用いる有機エレクトロルミネッセンス素子 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012090735A1 (ja) * | 2010-12-27 | 2012-07-05 | 日東電工株式会社 | 透明導電性フィルムおよびその製造方法 |
US9305680B2 (en) | 2010-12-27 | 2016-04-05 | Nitto Denko Corporation | Transparent conductive film and manufacturing method therefor |
CN103578609A (zh) * | 2012-08-09 | 2014-02-12 | 日东电工株式会社 | 导电性膜 |
US9304635B2 (en) | 2012-08-09 | 2016-04-05 | Nitto Denko Corporation | Conductive film |
Also Published As
Publication number | Publication date |
---|---|
US20130149555A1 (en) | 2013-06-13 |
JP5944629B2 (ja) | 2016-07-05 |
JP2015193934A (ja) | 2015-11-05 |
TW201505039A (zh) | 2015-02-01 |
CN102985585B (zh) | 2015-09-30 |
CN102985585A (zh) | 2013-03-20 |
JP2012199215A (ja) | 2012-10-18 |
KR20150059798A (ko) | 2015-06-02 |
TWI560071B (ja) | 2016-12-01 |
TW201221363A (en) | 2012-06-01 |
TWI560725B (ja) | 2016-12-01 |
KR20130025969A (ko) | 2013-03-12 |
JP6006368B2 (ja) | 2016-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6006368B2 (ja) | 透明導電性フィルムの製造方法 | |
JP5679925B2 (ja) | 透明導電性フィルムの製造方法 | |
JP6023402B2 (ja) | 透明導電性フィルムおよびその製造方法 | |
JP6181806B2 (ja) | 透明導電性フィルムおよびその製造方法 | |
JP2015146243A (ja) | 透明導電性フィルムおよびこの製造方法 | |
TWI780239B (zh) | 透明導電性膜 | |
JP7272488B2 (ja) | 透明導電性フィルム | |
TW201916064A (zh) | 結晶化膜 | |
JP2023159680A (ja) | 透明導電性フィルム | |
CN111372776A (zh) | 透明导电性薄膜 | |
WO2023063128A1 (ja) | 位相差層付偏光板およびそれを用いた画像表示装置 | |
JP2012207265A (ja) | ディスプレイ用フィルム基板の製造方法 | |
TWI847024B (zh) | 透明導電性薄膜 | |
CN115776942A (zh) | 透明导电性薄膜 | |
JP2023043359A (ja) | 積層体 | |
CN115769315A (zh) | 透明导电性薄膜 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180033556.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11803634 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137003070 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13808487 Country of ref document: US |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11803634 Country of ref document: EP Kind code of ref document: A1 |