WO2012090735A1 - 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
- WO2012090735A1 WO2012090735A1 PCT/JP2011/079206 JP2011079206W WO2012090735A1 WO 2012090735 A1 WO2012090735 A1 WO 2012090735A1 JP 2011079206 W JP2011079206 W JP 2011079206W WO 2012090735 A1 WO2012090735 A1 WO 2012090735A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- transparent conductive
- ito film
- transparent
- ito
- Prior art date
Links
Images
Classifications
-
- 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
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
Definitions
- the present invention relates to a transparent conductive film in which a crystalline ITO film is formed as a transparent conductive layer on a flexible transparent substrate.
- the transparent conductive film of the present invention is particularly suitably used for transparent electrodes in touch panels and the like.
- a so-called conductive glass in which an indium oxide thin film is formed on glass is well known as a transparent conductive thin film, but conductive glass is inferior in flexibility and workability because the substrate is glass. Depending on the application, it may not be preferable. Therefore, in recent years, transparent conductive films based on various plastic films such as polyethylene terephthalate film have been awarded for their advantages such as excellent impact resistance and light weight in addition to flexibility and workability. It is used.
- a transparent conductive layer such as an ITO film
- sputtering film formation cannot be performed at a high temperature.
- the ITO immediately after film formation is an amorphous film (some of which may be crystallized).
- Such amorphous ITO films have problems such as strong yellowing and poor transparency, and a large resistance change after the humidification heat test.
- the amorphous ITO film can be converted into a crystalline ITO film by heating in an oxygen atmosphere in the air.
- the transparency of the ITO film is improved, the resistance change after the humidification heat test is small, and the humidification heat reliability is improved.
- the transparent conductive film using the film substrate has a problem that the transparent conductive layer is inferior in scratch resistance, and is scratched during use to increase electrical resistance or to cause disconnection.
- a transparent conductive film for a touch panel a pair of thin films facing each other via a spacer are strongly contacted at a pressing point from the one panel plate side, so that good durability characteristics that can resist this, That is, it is desired to have a hit point characteristic.
- the transparent conductive film using a film base material is generally inferior in hitting characteristics as compared with conductive glass, there is a problem that the life as a touch panel is shortened.
- a film substrate having a specific film thickness is used, and a transparent dielectric thin film whose refractive index of light is smaller than the refractive index of light of the film substrate on one side thereof, and further thereon
- a transparent conductive film is proposed in which a transparent conductive layer is sequentially formed and another transparent substrate is bonded to the other surface of the film substrate via a transparent adhesive layer (Patent Document 2).
- the transparency of the transparent conductive layer and the scratch resistance of the conductive layer can be improved, and the dot characteristics for a touch panel are improved.
- Patent Document 3 by forming a transparent conductive layer on one surface of a transparent film substrate via a plurality of dielectric thin films, the dot characteristics when using the touch panel in a bent state have been improved.
- the transparent conductive film to be used is required to have hitting characteristics under a heavy load.
- the dot characteristics and sliding durability at the screen edge are also required, but when performing input operations at the screen edge, compared to the case of the screen center.
- the transparent conductive film is in a highly bent state. Therefore, the transparent conductive film is required to have higher bending resistance in addition to the hit point characteristics under heavy load.
- an object of the present invention is to provide a transparent conductive film having excellent hit point characteristics under heavy load and excellent bending resistance.
- the present invention relates to a transparent conductive film having a transparent conductive layer made of crystalline indium-tin composite oxide (crystalline ITO) formed on a flexible transparent substrate.
- the compressive residual stress of the crystalline ITO film is preferably 0.4 to 2 GPa.
- the transparent conductive layer is preferably crystallized by heating.
- the dimensional change of the crystalline ITO film based on the amorphous ITO film before crystallization is preferably ⁇ 0.3% to ⁇ 1.5% in at least one direction in the plane.
- the present invention relates to a method for producing the transparent conductive film.
- a base material preparing step for preparing a flexible transparent base material, and forming an amorphous transparent conductive layer made of amorphous indium-tin composite oxide on the flexible transparent base material A film forming step, and a heat treatment step of heating the amorphous transparent conductive layer to convert it into a crystalline indium-tin composite oxide (crystalline ITO film).
- crystalline ITO film crystalline indium-tin composite oxide
- the transparent conductive layer is preferably compressed so that the dimensional change in at least one direction in the plane is ⁇ 0.3% to ⁇ 1.5%. Further, the compressive residual stress of the crystalline transparent conductive layer is preferably set to 0.4 to 2 GPa by applying compressive stress in the heat treatment step.
- the heating temperature in the heat treatment step is preferably 150 to 210 ° C., and the heating time is preferably 150 minutes or less.
- a crystalline ITO film having a predetermined compressive residual stress is formed on a flexible transparent substrate.
- a crystalline ITO film having a compressive residual stress has excellent hit point characteristics under heavy load, and also has high bending resistance.
- the transparent conductive film of the present invention is suitably used for touch panels, and in particular, for game machines that require hitting characteristics under heavy loads, and for touch panels for flexible displays that require high bending resistance. .
- FIG. 1 is a cross-sectional view schematically showing a transparent conductive film 101 according to the first embodiment of the present invention.
- the transparent conductive film 101 has a configuration in which a crystalline indium-tin composite oxide (ITO) film 3 is formed on a flexible transparent substrate 1 including a single transparent substrate film 11.
- the flexible transparent substrate 1 may consist of only the transparent substrate film 11, and as shown in FIG. 1, the undercoat layer 16 on the surface of the transparent substrate film 11 on which the ITO film is formed, A back coat layer 17 may be formed on the opposite surface.
- FIG. 1 shows a form in which one undercoat layer 16 and one back coat layer 17 are formed, these layers may be composed of two or more layers.
- FIG. 2 is a cross-sectional view schematically showing the transparent conductive film 102 according to the second embodiment of the present invention.
- the transparent conductive film 102 includes two or more flexible transparent substrates, and a crystalline indium tin composite oxide (ITO) film 3 is formed on the first flexible transparent substrate 1.
- ITO crystalline indium tin composite oxide
- the flexible transparent substrates 1 and 2 are preferably bonded together with an appropriate pressure-sensitive adhesive layer 5.
- FIG. 2 although the structure which has the 2 sheets of flexible transparent base materials 1 and 2 is shown in figure, the 3 or more flexible transparent base materials may be laminated
- the flexible transparent substrates 1 and 2 may be composed of only the transparent base films 11 and 12, respectively.
- FIG. 2 a form in which an undercoat layer 16 is formed on the surface of the first transparent substrate film 11 constituting the first flexible transparent substrate 1 on the side on which the ITO film is formed. Further, a back coat layer 17 is formed on the surface of the second transparent base film 12 constituting the second flexible transparent base material 2 on the opposite side to the first flexible transparent base material 1 to be bonded.
- the form currently used can also be employ
- FIG. 2 a form in which one undercoat layer 16 and one back coat layer 17 are formed is shown. However, these layers may be composed of two or more layers. Moreover, you may have a coating layer other than showing in figure.
- the transparent base film 11 constituting the flexible transparent 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
- 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 substrate film 11 is preferably about 2 to 300 ⁇ m, more preferably 6 to 200 ⁇ m. If the thickness of the film is excessively small, the mechanical strength may be insufficient, and the operation of forming the undercoat layer 16 and the transparent conductive layer (ITO film) 3 thereon may be difficult. On the other hand, if the thickness of the film is excessively large, the scratch resistance of the transparent conductive layer and the dot characteristics for touch panels may not be improved.
- an undercoat layer 16 On the surface of the transparent substrate film 11 on which the ITO film 3 is formed, an undercoat layer 16 is provided for the purpose of improving the adhesion between the flexible transparent substrate 1 and the ITO film 3 and controlling the reflection characteristics. It may be provided. There may be one undercoat layer, or two or more undercoat layers.
- the undercoat 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 undercoat layer for example, SiO 2 , MgF 2 , A1 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 undercoat layer can be formed using the above materials by vacuum deposition, sputtering, ion plating, coating, or the like.
- the surface of the flexible transparent substrate 1 is previously subjected to appropriate adhesion treatment such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, sputter etching treatment, etc. Can also be increased.
- an antiglare treatment layer or an antireflection treatment layer for the purpose of improving visibility is provided on the surface of the transparent substrate film 11 opposite to the ITO film 3 on which the ITO film 3 is formed.
- a hard coat layer for the purpose of protecting the surface can be provided.
- a cured film made of a curable resin such as a melamine resin, a urethane resin, an alkyd resin, an acrylic resin, or a silicone resin is preferably used.
- These back coat layers 17 may be provided on the transparent substrate film 11 before the transparent conductive layer 3 is formed, or may be provided after the transparent conductive layer 3 is formed.
- the flexible transparent substrate before the ITO film is formed preferably has heat shrinkability in at least one direction.
- the crystalline ITO film can be formed by heat-treating the amorphous ITO film.
- the base material has heat shrinkability, the base material shrinks during the heat-treatment, so that the ITO Since compressive stress is applied to the film, a crystalline ITO film having a desired compressive residual stress can be easily formed.
- the dimensional change rate (heat shrinkage rate) during heating of the flexible transparent substrate 1 is preferably set so that a predetermined compressive stress is applied when the ITO film is crystallized. For this reason, the preferred range of the heat shrinkage rate varies depending on the heating conditions (temperature and time) at the time of crystallization of the ITO film, but the base material before forming the ITO film conforms to, for example, JIS K7133 (1995).
- the dimensional change rate when heated at 150 ° C. for 1 hour is preferably about ⁇ 2% to + 1%, and more preferably about ⁇ 1.5% to 0%.
- the flexible transparent substrate 1 can have the above-described heat shrinkability.
- the amount of heat shrinkage can be controlled within a predetermined range by the stretching ratio of the film.
- the dimensional change rate (heat shrinkage rate) of the flexible transparent substrate varies depending on the direction
- the dimensional change rate in any one direction is preferably in the above range. Even if the substrate does not have heat shrinkability, or the dimensional change rate of the substrate is outside the above range, the amount of shrinkage can be adjusted by adjusting the conditions for heat crystallization of the ITO film. Can be controlled.
- a shrinkage stress is applied from the outside by a technique such as bonding a heat shrink film separately from the base material 1 or a heat shrinkage is controlled by applying a tension from the outside. Also by this method, a crystalline ITO film having a desired compressive residual stress can be formed.
- the transparent conductive layer 3 is mainly composed of crystalline ITO.
- the transparent conductive layer may be referred to as “crystalline ITO film” or simply “ITO film”.
- the compressive residual stress of the crystalline ITO film 3 is preferably 0.4 to 2 GPa, more preferably 0.7 to 1.6 GPa, and 0.9 to 1.55 GPa. Is more preferable, and 1.2 to 1.4 GPa is particularly preferable.
- the crystalline ITO film having a compressive residual stress means that the lattice constant is small as compared with the case where there is no distortion.
- the compressive residual stress is 0.4 GPa or more, the crystalline ITO film is excellent in hitting point characteristics and flex resistance under heavy load.
- the compressive residual stress is preferably 2 GPa or less from the viewpoint of suppressing problems such as film peeling of the ITO film and curling of the transparent conductive film.
- the compressive residual stress of the crystalline ITO film is preferably 1.6 GPa or less, more preferably 1.55 GPa or less, and 1.4 GPa More preferably, it is as follows.
- the reason why the resistance change due to humidification heat becomes large is considered that the ITO film having a large compressive residual stress is likely to be distorted or cracked at the crystal grain boundary.
- the transparent conductive film when the transparent conductive film is exposed to a high-temperature and high-humidity environment, the transparent substrate film undergoes hygroscopic expansion, so that a tensile stress is applied to the ITO film formed thereon, so It is presumed that the film breaks starting from the crack and the resistance increases.
- a crystalline ITO film can also be obtained by sputtering a ITO film at a high temperature of, for example, 200 ° C. or more on a substrate. However, considering the heat resistance of the substrate, the amorphous ITO film is once formed on the substrate. After the film is formed, the amorphous ITO film is preferably formed by heating and crystallization together with the base material.
- the amorphous ITO film is formed 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 can be suitably employed.
- the “amorphous ITO” is not limited to a completely amorphous one, and may have a small amount of crystal components.
- Whether the ITO is amorphous or not is determined by immersing the laminate in which the ITO film is formed on the base material in hydrochloric acid having a concentration of 5 wt% for 15 minutes, washing and drying, and measuring the resistance between terminals between 15 mm. It is possible to measure with. Since the amorphous ITO film disappears by etching with hydrochloric acid, the resistance increases by immersion in hydrochloric acid. In this specification, the ITO 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 amorphous ITO film 3a formed on the substrate is preferably crystallized by heating in a short time. Specifically, when heated at 150 ° C., it is preferable that crystallization can be completed within 60 minutes, more preferably within 30 minutes, and even more preferably within 20 minutes. If ITO can be crystallized on such a time scale, since the crystallization of ITO proceeds in accordance with the thermal shrinkage of the base material, compressive stress is applied at the time of crystallization and it has compressive residual stress. A crystalline ITO film is easily formed.
- Whether or not the ITO film has been crystallized 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 the amorphous ITO. If the inter-terminal resistance is within 10 k ⁇ , it is determined that it has been converted to crystalline ITO.
- the amorphous ITO film adjusts the temperature and time required for complete crystallization by adjusting the type of target used for sputtering, the ultimate vacuum during sputtering, the flow rate of introduced gas, the film forming temperature (substrate temperature), and the like. be able to.
- a metal target In—Sn target
- a metal oxide target In 2 O 3 —SnO 2 target
- the amount of SnO 2 in the metal oxide target is 0.5 wt% based on the weight of In 2 O 3 and SnO 2 added. It is preferably ⁇ 15% by weight, more preferably 1 to 10% by weight, even more preferably 2 to 6% by weight.
- the amount of Sn atoms in the metal target is 0.5 wt% to 15 wt% with respect to the weight of In atoms and Sn atoms added.
- the amount of Sn or SnO 2 in the target is preferably 1 to 10% by weight, more preferably 2 to 6% by weight. If the amount of Sn or SnO 2 in the target is too small, the durability of the ITO film may be inferior. Further, if the amount of Sn or SnO 2 is too large, the time required for crystallization tends to be long. That is, during crystallization, Sn acts as an impurity other than the amount taken into the In 2 O 3 crystal lattice, and thus tends to hinder ITO crystallization. Therefore, the amount of Sn or SnO 2 in the target is preferably within the above range.
- the degree of vacuum (degree of ultimate vacuum) in the sputtering apparatus is preferably 1 ⁇ 10 ⁇ 3 Pa or less, more preferably 1 ⁇ 10 ⁇ 4 Pa or less. It is preferable that the atmosphere is exhausted to remove impurities such as moisture in the sputtering apparatus and organic gas generated from the substrate. This is because the presence of moisture or organic gas terminates dangling bonds generated during the sputtering film formation and hinders ITO crystal growth.
- an inert gas such as Ar is introduced into the sputtering apparatus evacuated in this manner, and sputtering film formation is performed.
- a metal target In—Sn target
- sputtering is performed by introducing an oxygen gas which is a reactive gas together with an inert gas.
- 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 substrate temperature during sputtering is preferably 40 ° C. to 190 ° C., more preferably 80 ° C. to 180 ° C. If the film forming temperature is too high, appearance defects due to thermal wrinkles and thermal deterioration of the substrate may occur. On the other hand, if the film forming temperature is too low, film quality such as transparency of the ITO film may be deteriorated.
- the film thickness of the ITO film can be appropriately adjusted so that the ITO film after crystallization has a desired resistance, but it is preferably 10 to 300 nm, for example, and more preferably 15 to 100 nm. If the film thickness of the ITO film is small, the time required for crystallization tends to be long. If the film thickness of ITO is large, the specific resistance after crystallization becomes too low or the transparency is lowered. The quality of the transparent conductive film may be inferior.
- the laminated body of the flexible transparent substrate 1 and the amorphous ITO film 3a thus obtained is subjected to a heat treatment, and is converted into a crystalline ITO film by heating the amorphous ITO film. From the viewpoint of obtaining a crystalline ITO film having compressive residual stress, it is preferable that compressive stress is applied to the ITO film in this heat treatment step.
- the dimensional change in one direction of the ITO film surface is preferably ⁇ 0.3% to ⁇ 1.5%, more preferably ⁇ 0.55% to ⁇ 1.2%. More preferably, it is -0.7% to -1.05%, more preferably -0.7% to -0.9%.
- the dimensional change (%) is 100 ⁇ (L 1 ⁇ L 0 ) / when the distance L 0 between two points in one direction of the ITO film before being subjected to the heat treatment process changes to L after the heat treatment. It is defined by L 0.
- the crystalline ITO film after the heat treatment can have the predetermined compressive residual stress as described above, so that a transparent conductive film excellent in hit point characteristics and flexibility can be obtained.
- the heating temperature and heating time in the heat treatment can be appropriately set so that the ITO film is completely crystallized.
- the heating temperature is preferably 150 ° C. to 210 ° C., more preferably 160 ° C. to 200 ° C., and even more preferably 170 ° C. to 190 ° C. If the heating temperature is too low, crystallization does not proceed, or it takes a long time for crystallization and tends to be inferior in productivity. In addition, when the heating temperature is low, the amount of thermal shrinkage of the base material is small, so that an appropriate compressive stress may not be applied when the ITO film is crystallized. On the other hand, when the heating temperature is too high, the base material deteriorates, or the residual compressive stress of the ITO film becomes excessive due to the rapid thermal contraction of the base material, and the humidified heat reliability of the transparent conductive film may not be ensured.
- the heating time is preferably 150 minutes or less. If the heating time is too long, the substrate tends to deteriorate or the productivity tends to be inferior. On the other hand, if the heating time is too short, crystallization of ITO does not proceed, or the thermal contraction of the substrate becomes insufficient, and an appropriate compressive stress may not be applied to the ITO film. From this viewpoint, the heating time is preferably 5 to 60 minutes, and more preferably 5 to 30 minutes. If the ITO film is heated and crystallized on such a time scale, the stress due to the shrinkage of the substrate is transmitted to the ITO, and a crystalline ITO film having a compressive residual stress is easily formed. Note that the above heating temperature and heating time are examples, and an appropriate heating temperature and heating time can be selected depending on the characteristics of the amorphous ITO film.
- the laminate in which the amorphous ITO film 3a before crystallization is formed on the flexible transparent substrate 1 is 150.
- the dimensional change when heated at 1 ° C. for 1 hour is preferably about ⁇ 2% to + 1%, more preferably about ⁇ 1.5% to 0%, and ⁇ 1.2% to ⁇ 0. More preferably, it is about 3%.
- the dimensional change rate of the laminate of the amorphous ITO film and the flexible transparent substrate is flexible. It is substantially the same as the dimensional change rate of the transparent substrate.
- the compressive stress is applied to the ITO film in addition to the heat shrinkage force of the base material as described above, for example, when the ITO film is heated and crystallized, separately from the base material 1, the heat is applied to the ITO film surface or the base material. It can also be realized by applying a shrinkage stress from the outside by a technique such as bonding a shrink film. It is also possible to control the amount of shrinkage by applying a tension from the outside using a base material having a large amount of shrinkage (the dimensional change rate is negative and the absolute value is large).
- the dimensional change rate (heat shrinkage rate) of the flexible transparent substrate varies depending on the direction
- the dimensional change rate in any one direction is preferably in the above range. Even if the substrate does not have heat shrinkability or the dimensional change rate is outside the above range, the amount of shrinkage is controlled by adjusting the conditions for heat crystallization of the ITO film. be able to.
- the heating conditions during the heat treatment are preferably selected so that the base material thermally shrinks in accordance with the ITO crystallization time scale in addition to the viewpoint of crystallizing the ITO. That is, as the crystallization of ITO proceeds, or if the base material heat shrinks after crystallization of ITO, compressive stress is applied to the crystalline ITO film. can get.
- Such heating conditions vary depending on the thermal deformation profile of the base material, but by confirming in advance the thermal deformation profile of the base material or the base material after the formation of the amorphous ITO film by thermal analysis such as TMA, It is possible to select heating conditions that cause the base material to thermally shrink in accordance with the time scale of the crystal.
- FIGS. 7 and 8 show examples in which the relationship between the crystallization of ITO and the thermal deformation of the substrate is schematically analyzed using TMA.
- FIGS. 7 and 8 show a PET film having a total thickness of 130 ⁇ m (hard coat layer) with an amorphous ITO film having a thickness of 20 nm formed on one surface of a PET film having a thickness of 25 ⁇ m and an adhesive layer having a thickness of 25 ⁇ m on the other surface.
- the thickness change behavior of the transparent conductive film having a thickness of 5 ⁇ m was analyzed by TMA.
- the horizontal axis represents time, and the vertical axis represents temperature and dimensional change rate.
- the measurement conditions were as follows: sample width: 4 mm, load: 20 mN / 4 mm, initial length: 10 mm, temperature increase rate and temperature decrease rate: 5 ° C./min, retention time: 60 minutes, FIG. 7 and FIG.
- the measurement results at 190 ° C. and 150 ° C. are shown.
- Example 6 where crystallization was performed, the residual compressive stress of the ITO film was 0.57 GPa. From this, it is considered that the schematic analysis using TMA reproduces the tendency of the dimensional change behavior when the ITO film is actually crystallized. Based on the analysis result of TMA, the ITO crystal It can be said that the heating conditions such that the base material contracts can be selected according to the time scale.
- the ITO film crystals may have a predetermined particle size distribution.
- the crystal content having a maximum particle size of 300 nm or less is preferably 95 area% or more, and it is more preferable that no crystal having a maximum particle size exceeding 300 nm exists.
- the crystal content having a maximum particle size of 200 nm or less exceeds 50 area%.
- the crystal content having a maximum grain size of 100 nm or less exceeds 5 area%, and the maximum grain size of the remaining crystals is present in a distribution width of more than 100 nm and 200 nm, and the crystal content of 100 nm or less is 10 areas. % Or more is particularly preferable.
- the maximum crystal grain size is preferably 10 nm or more, and more preferably 30 nm or more.
- the maximum crystal grain size and distribution are determined by observing the surface of the conductive thin film with a field emission transmission electron microscope (FE-TEM).
- the maximum crystal grain size is the largest diagonal or diameter in each observed polygonal or oval region.
- the content of the crystal having the maximum grain size is specifically the area ratio of the crystal having each grain size per unit area (1.5 ⁇ m ⁇ 1.5 ⁇ m) in the electron microscope image. .
- the material configuration of the conductive thin film and the method for forming the thin film may be appropriately selected.
- SnO 2 content in ITO an In 2 O 3 and SnO 2 content relative to SnO 2 and the weight plus
- SnO 2 content in the ITO is preferably 2 wt% or more, more preferably 3 wt% or more.
- an inorganic film formed by a vacuum evaporation method preferably an SiO 2 thin film formed by a vacuum evaporation method
- an anchor layer serving as an underlayer of ITO film formation that is, an anchor layer closest to the ITO film.
- the transparent conductive film 102 according to the second embodiment of the present invention including two or more flexible transparent base materials will be described focusing on differences from the first embodiment.
- the transparent conductive film 102 according to the second embodiment includes two or more flexible transparent substrates.
- the first flexible transparent substrate 1 is a substrate for forming an ITO film, and an undercoat layer 16 and the like are formed on the first transparent substrate film 11 as necessary.
- the 2nd flexible transparent base material is bonded together to the 1st flexible transparent base material through suitable adhesion means, such as adhesive layer 5.
- the second flexible transparent substrate is obtained by forming the back coat layer 17 and the like on the second transparent substrate film 12 as necessary.
- the transparent substrate films 11 and 12 those similar to those described above with reference to the first embodiment are preferably used.
- the form which has two flexible transparent base materials is illustrated in FIG. 2, the form which has three or more flexible transparent base materials may also be employ
- the crystalline ITO film has a compressive residual stress similar to that described above with respect to the first embodiment.
- such a crystalline ITO film is preferably formed by once forming an amorphous ITO film and then heating and crystallizing the amorphous ITO film together with a substrate.
- the plurality of transparent substrate films 11 and 12 are preferably bonded together via the pressure-sensitive adhesive layer 5.
- the constituent material of the pressure-sensitive adhesive layer 5 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.
- the pressure-sensitive adhesive layer 5 may have a function of improving the scratch resistance of the transparent conductive layer 3 provided on the transparent substrate film 11 and the hitting point characteristics for a touch panel due to, for example, the cushion effect. From the viewpoint of more effectively exerting this function, it is preferable to set the elastic modulus of the pressure-sensitive adhesive layer 5 in the range of 1 to 100 N / cm 2 and the thickness in the range of 1 ⁇ m or more (more preferably 5 to 100 ⁇ m). If it exists in this range, the said effect will fully be exhibited and the adhesive force of transparent bases will also become sufficient.
- FIGS. 3A to 3C are schematic cross-sectional views conceptually showing the manufacturing process of the transparent conductive film 102.
- FIGS. 3A to 3C illustration of the undercoat layer and the back coat layer is omitted.
- the bonding of the transparent substrate films 11 and 12 through the pressure-sensitive adhesive layer 5 is performed before the ITO film is formed (FIG. 3A), after the amorphous ITO film is formed and before the heat crystallization (FIG. 3B), and the amorphous ITO film is heated. This can be done either after crystallization (FIG. 3C).
- the formation of amorphous ITO film by sputtering or the like is performed continuously by the roll-to-roll method, whereas the heat crystallization of the ITO film heats the film cut into a single wafer in batch mode. Often processed. Therefore, as shown in FIGS. 3A and 3B, in the embodiment in which the substrates are bonded before the crystallization of the ITO film, the bonding can be continuously performed by a roll-to-roll method.
- the amorphous ITO film 3a is formed on the first flexible transparent substrate 1 before bonding the substrates, a plurality of transparent substrate films are bonded in advance.
- the thickness of the substrate during sputtering film formation is reduced. Therefore, since the winding diameter of the roll wound body is reduced and the film forming length that can be continuously formed by the winding type sputtering apparatus is increased, it is preferable from the viewpoint of productivity.
- the amorphous ITO film 3a is formed on the flexible transparent substrate on which a plurality of substrates are bonded. Formed (FIG. 3A (c)) and crystallization is performed. Therefore, the thickness, dimensional change rate, and the like of the base material in which the two (or two or more) flexible transparent base materials after bonding are regarded as one body are within the above-described range with respect to the first embodiment. It is preferable to do so.
- the film was heated during the formation of the amorphous ITO film (FIG. 3B (b)).
- the 1st flexible transparent base material and the 2nd flexible transparent base material which is not provided for ITO film-forming are pasted together (Drawing 3B (c)), and crystallization is performed 3B (d)).
- the thickness, the dimensional change rate, and the like when the flexible transparent base material after bonding is regarded as an integral body are within the above-described range with respect to the first embodiment.
- the ITO film is crystallized in the heat treatment step after two or more flexible transparent substrates are bonded together.
- compressive stress is applied to the ITO film as the base material shrinks.
- the dimensional change of each flexible transparent substrate is different, there may be a problem such as peeling between the substrates in the heat treatment step or curling of the transparent conductive film.
- each flexible transparent substrate before being subjected to the heat treatment step preferably has an absolute value of a difference in dimensional change rate when heated at 150 ° C. for 1 hour, of 0.5% or less, More preferably, it is 0.3% or less.
- the first flexible transparent substrate 1 is heated when it is used for forming the ITO film, whereas the second flexible transparent substrate 2 is used.
- the difference in dimensional change in the heat treatment step may become large because the thermal histories of the two differ greatly.
- the second flexible transparent substrate 2 before being bonded to the first flexible transparent substrate 1 It is preferable to stabilize the dimensions by heat treatment in advance.
- the heating conditions for dimensional stabilization are appropriately set so that the difference in the dimensional change rate is small. For example, it is preferable to perform heating at 130 ° C. to 160 ° C. for about 0.5 minutes to 3 minutes.
- a flexible transparent base material including a single transparent base film as in the first embodiment As shown in FIG. 3C, when the transparent base films 11 and 12 are bonded together after heat crystallization of the ITO film, a flexible transparent base material including a single transparent base film as in the first embodiment. A crystalline ITO film 3 is formed on 1 (FIG. 3C (c)). Then, the 2nd transparent base film 12 is bonded together through the adhesive layer 5 (FIG. 3C (d)).
- the transparent conductive film of the present invention as described above is suitably used for forming transparent electrodes and touch panels of various devices.
- the transparent conductive film of the present invention is suitable for a resistive touch panel because the transparent conductive layer is excellent in hitting characteristics under heavy loads and bending resistance, and is particularly suitable for touch panels of game machines and flexible displays. Is preferably used.
- the resistance value was measured by a two-terminal method.
- the surface resistance was measured by a four-probe method according to JIS K7194 (1994).
- ⁇ Dimensional change rate> Two marks (scratches) are formed at an interval of about 80 mm in the transport direction (hereinafter referred to as “MD direction”) during sputtering film formation on the ITO film surface of the laminate in which an amorphous ITO film is formed on a substrate. Then, the distance L 0 between the gauge points before heat crystallization and the distance L between the gauge points after heating were measured with a two-dimensional measuring machine to obtain a dimensional change rate (%).
- 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. 4 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).
- the transparent conductive film was cut into a 60 mm ⁇ 140 mm rectangle with the MD direction as the long side.
- a silver paste was screen printed with a width of 5 mm on both short sides and dried at room temperature for 24 hours to form a silver electrode.
- the transparent conductive film on which the silver electrode is formed and the ITO conductive glass manufactured by Nippon Soda Co., Ltd.
- the ITO film 22 having a surface roughness Ra 0.9 nm is formed on the glass 21 through the spacer 8 having a thickness of 180 ⁇ m.
- a touch panel as schematically shown in FIG. 5 was prepared by arranging the ITO forming surfaces so as to face each other.
- the outline of linearity measurement is as shown in FIG.
- the position of the pen displayed on the screen is determined from the resistance value of the contact portion between the upper panel and the lower panel by being pressed with the pen.
- the resistance value is determined on the assumption that the output voltage distribution on the upper and lower panel surfaces is a theoretical line (ideal line), but if the voltage value deviates from the theoretical line as shown in the figure, the actual value
- the pen position on the screen determined by the pen position and the resistance value does not synchronize well.
- the deviation from the theoretical line is linearity, and the larger the value, the larger the deviation between the actual pen position and the pen position on the screen. That is, the smaller the linearity after the durability test, the better the durability.
- the test piece was curved along a cork polar with a hole diameter of 17 mm ⁇ with the ITO forming surface facing out, and held for 10 seconds at a load of 1.0 kg. Then, after repeatedly repeating the same bending using a cork polar with a hole diameter of 15.5 mm ⁇ , 14 mm ⁇ , 12.5 mm ⁇ , and 11 mm ⁇ and holding for 10 seconds with a load of 1.0 kg, the resistance R 11T was measured. Then, the rate of change R 11T / R o relative to the initial resistance was obtained.
- test piece was further bent along a cork polar with a hole diameter of 9.5 mm ⁇ and held for 10 seconds with a load of 1.0 kg, and then the resistance R 9.5T was measured, and the rate of change R 9. 5T / Ro was determined.
- the transparent conductive film was put into a constant temperature and humidity chamber at 60 ° C. and 95% humidity for 500 hours, and the surface resistance was measured by a four-probe method to evaluate the resistance fluctuation under humidification heat.
- the resistance variation under humidification heat is represented by the ratio (R / R 1 ) of the surface resistance R after humidification heat to the initial surface resistance R 1 .
- Example 1 In Example 1, after forming an amorphous ITO film on a PET film (first flexible transparent substrate) having a thickness of 25 ⁇ m on which two undercoat layers were formed, a hard film having a thickness of 5 ⁇ m was formed as a back coat layer. A 125 ⁇ m-thick PET film (second flexible transparent substrate) on which a coat layer was formed was bonded via a 25 ⁇ m-thick adhesive layer. Thereafter, the ITO film was heated and crystallized to produce a transparent conductive film in which a crystalline transparent conductive layer having a thickness of 20 nm was formed on a substrate having a total thickness of 180 ⁇ m. This is based on the same process as shown in FIG. 3B, and details of each process are as follows.
- undercoat layer As a first transparent substrate, a biaxially stretched polyethylene terephthalate film having a thickness of 25 ⁇ m (trade name “Diafoil” manufactured by Mitsubishi Chemical Polyester, glass transition temperature 80 ° C., refractive index 1.66, 150 ° C. in the MD direction when heated at 1 hour) Two undercoat layers were formed on this PET film using a dimensional change rate of -0.80%.
- 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) is diluted with methyl ethyl ketone so that the solid content concentration becomes 1% by weight, and this solution is applied onto the first undercoat layer.
- the film was 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. Even after the undercoat layer was formed, the dimensional change rate in the MD direction when the substrate was heated at 150 ° C. for 1 hour was ⁇ 0.80%, which was not changed before the undercoat layer was formed.
- 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 is applied onto the second transparent substrate film, heated at 100 ° C. for 3 minutes and dried, and then irradiated with ultraviolet light with an integrated light quantity of 300 mJ / cm 2 with a high-pressure mercury lamp to form a hard coat having a thickness of 5 ⁇ m. A layer was formed.
- the PET film on which the hard coat layer was formed was transported by a roll transporter, it was heated in a heating furnace at 150 ° C. for 1 minute to stabilize the dimensions. Subsequently, after cooling at room temperature to release the residual stress, the dimensional change rate in the MD direction when heated at 150 ° C. for 1 hour was measured. The dimensional change rate of the PET film with a hard coat layer after dimensional stabilization was ⁇ It was 0.45%.
- the acrylic pressure-sensitive adhesive solution is applied to the surface of the PET film with a hard coat layer after dimensional stabilization, on which the hard coat layer is not formed, and is cured by heating at 155 ° C. for 1 minute, and has a thickness of 25 ⁇ m. An agent layer was formed. Subsequently, the separator which attached the silicone layer to the adhesive layer surface was bonded together by roll bonding. The dimensional change rate in the MD direction at the time of heating at 150 ° C. for 1 hour with this hard-coated PET bag with adhesive was ⁇ 0.45%.
- the obtained laminate was obtained by forming an amorphous ITO film having a thickness of 20 nm on a flexible transparent substrate having a total thickness of 180 ⁇ m.
- Example 2 to 6 and Comparative Examples 1 and 2 In Examples 2 to 6 and Comparative Examples 1 and 2, a transparent conductive film having a crystalline ITO film was obtained in the same manner as in Example 1 except that the heating conditions for crystallization of the ITO film were changed as shown in Table 1. A conductive film was produced.
- Example 7 a transparent conductive film was produced in the same manner as in Example 1. However, when the amorphous ITO film was formed by sputtering and the dimension of the PET film with a hard coat layer was stabilized, the conveyance tension was increased. This was different from Example 1 in that it was increased and the heating temperature in the heat treatment step was set to 150 ° C.
- the transport tension during sputtering film formation was set to twice that of Example 1, and an amorphous ITO film was formed in a situation where the PET film was stretched.
- the dimensional change rate in the MD direction when heated at 150 ° C. for 1 hour was measured to be ⁇ 0.85%.
- the transport tension when the PET film with a hard coat layer was heated in a heating furnace to stabilize the dimensions while being transported by a roll transporter was set to 8 times that of Example 1. After dimensional stabilization, cooling at room temperature to release the residual stress, and measuring the dimensional change rate in the MD direction when heated at 150 ° C. for 1 hour, the dimensional change rate of the PET film with a hard coat layer after dimensional stabilization was ⁇ 0.85%.
- Example 8 amorphous ITO was formed on the undercoat layer forming surface of a PET film having a total thickness of 180 ⁇ m in which two undercoat layers were formed on one surface and a hard coat layer having a thickness of 5 ⁇ m was formed on the other surface. After forming the film, heat crystallization was performed to produce a transparent conductive film in which a crystalline transparent conductive layer having a thickness of 20 nm was formed on a substrate having a total thickness of 180 ⁇ m.
- An amorphous ITO film having a thickness of 20 nm was formed on the undercoat layer forming surface of this substrate in the same manner as in Example 1 by sputtering.
- a 300 mm square sheet was cut out from this laminated body and heated in a heating bath at 150 ° C. for 1 hour, Crystallization was performed to obtain a transparent conductive film having a crystalline ITO film. Note that the dimensional change rate in the MD direction at the time of heating at 150 ° C. for 1 hour after the ITO film was formed and before crystallization was ⁇ 0.59%.
- Example 9 In Example 9, an amorphous ITO film was formed on a PET film (first flexible transparent substrate) having a thickness of 25 ⁇ m on which two undercoat layers were formed, and the ITO film was heated and crystallized. Thereafter, a 125 ⁇ m thick PET film (second flexible transparent substrate) on which a 5 ⁇ m thick hard coat layer was formed was bonded via a 25 ⁇ m thick adhesive layer. This is due to a process similar to that shown in FIG. 3C.
- an amorphous ITO film was formed on the first flexible transparent substrate, and the second flexible transparent substrate on which the hard coat layer was formed.
- the pressure-sensitive adhesive layer was formed.
- a laminated body in which an amorphous ITO film is formed on the first flexible transparent substrate without bonding the first flexible transparent substrate and the second flexible transparent substrate is 300 mm.
- the four sheets were cut out and heated in a heating bath at 180 ° C. for 1 hour to crystallize the ITO film. Thereafter, the first flexible transparent substrate on which the crystalline ITO film is formed is bonded to a second flexible transparent substrate with an adhesive layer cut into a 300 mm square sheet, A transparent conductive film having a total thickness of 180 ⁇ m was obtained.
- Example 10 a transparent conductive film having a total thickness of 180 ⁇ m having a crystalline ITO film was produced in the same manner as in Example 9 except that the heating temperature in crystallization of the ITO film was changed to 150 ° C. .
- Table 1 shows the conditions of each example and comparative example, and the evaluation results of the transparent conductive film.
- the thickness of the base material in Table 1 represents the thickness in the crystallization process.
- all the total thickness of the transparent conductive film of each Example used for evaluation and a comparative example was 180 micrometers.
- the transparent conductive film of each example in which the ITO film has a predetermined residual compressive stress is superior in bending resistance and heavy load spot characteristics as compared with the transparent conductive film of the comparative example. I understand.
- the residual compressive stress of the ITO film increases, the resistance change due to humidification heat tends to increase. Therefore, it can be said that it is more preferable that the residual compressive stress of the ITO film is set to an appropriate range in consideration of the balance between bending resistance, heavy load spot characteristics and humidification heat reliability.
- crystallization shrinkage can be achieved by increasing the temperature of the heat treatment step regardless of the thickness of the substrate at the time of crystallization.
- Example 7 since a high stress is applied in the MD direction of the base material during the sputtering of the amorphous ITO film, and the stress is released after the film formation, the amorphous ITO film as compared with Example 6 It is considered that a high compressive stress is applied to.
- the residual compressive stresses of the crystalline ITO films in the transparent conductive films of Example 6 and Example 7 are substantially the same, and the durability is also substantially the same. From this result, it can be said that in order to increase the durability of the ITO film, it is more important to apply a compressive stress during the subsequent heat crystallization than to apply a compressive stress to the ITO film in an amorphous state. .
- ⁇ Crystal grain size distribution of ITO film> A 300 ⁇ m ⁇ 300 ⁇ m square test piece was cut out from the transparent conductive films of Example 3 and Example 6, and fixed to an ultramicrotome sample holder so that the ITO film surface was in front. Next, a microtome knife was installed at an extremely acute angle with respect to the ITO film surface, and an observation sample was obtained by cutting at a set thickness of 70 nm so that the cut surface was substantially parallel to the ITO film surface. An observation field of 1.5 ⁇ m ⁇ 1.5 ⁇ m was selected from a site on the ITO film surface side of this observation sample where there was no significant damage to the thin film, and a transmission electron microscope (manufactured by Hitachi, model number “H-7650”) was used.
- Transparent conductive film crystalline ITO film
- Amorphous ITO film Adhesive layers 11, 12 Transparent substrate film 16 Undercoat layer 17 Back coat layer 101 Transparent conductive film 102 Transparent conductive film
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
(透明基体フィルム)
可撓性透明基材1を構成する透明基体フィルム11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。
透明基体フィルム11のITO膜3を製膜する側の面には、可撓性透明基材1とITO膜3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ダーコート層16が設けられていてもよい。アンダーコート層は1層でもよいし、2層あるいはそれ以上設けてもよい。アンダーコート層は、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。アンダーコート層を形成する材料としては、例えば、無機物として、SiO2、MgF2、A12O3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。アンダーコート層は、上記の材料を用いて、真空蒸着法、スパッタ法、イオンプレーティング法、塗工法などにより形成できる。
透明基体フィルム11のITO膜3を製膜するのと反対側の面には、背面コート層17として、例えば視認性の向上を目的とした防眩処理層や反射防止処理層を設けたり、外表面の保護を目的としたハードコート層を設けることができる。ハードコート層には、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、アクリル系樹脂、シリコーン系樹脂などの硬化型樹脂からなる硬化被膜が好ましく用いられる。これらの背面コート層17は、透明導電層3を製膜する前に透明基体フィルム11上に設けてもよいし、透明導電層3の製膜後に設けてもよい。
透明導電層3は結晶性のITOを主成分とするものである。以下、透明導電層を「結晶性ITO膜」あるいは単に「ITO膜」と記載する場合がある。本発明において、結晶性ITO膜3の圧縮残留応力は、0.4~2GPaであることが好ましく、0.7~1.6GPaであることがより好ましく、0.9~1.55GPaであることがさらに好ましく、1.2~1.4GPaであることが特に好ましい。結晶性ITO膜が圧縮残留応力を有するとは、歪みがない場合に比して格子定数が小さいことを意味する。圧縮残留応力が0.4GPa以上である場合に、結晶性ITO膜は、重荷重での打点特性および耐屈曲性に優れる。一方、ITO膜の膜剥がれや、透明導電性フィルムのカールの発生等の不具合を抑止する観点からは、圧縮残留応力は2GPa以下であることが好ましい。
アモルファスITO膜は気相法によって形成される。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を好適に採用し得る。なお、「アモルファスITO」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。ITOがアモルファスであるか否かの判定は、基材上にITO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が可能である。アモルファスITO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、ITO膜がアモルファスであるものとする。
このようにして得られた可撓性透明基材1とアモルファスITO膜3aとの積層体は熱処理に供され、アモルファスITO膜が加熱されることにより結晶性ITO膜に転化される。圧縮残留応力を有する結晶性ITO膜を得る観点からは、この熱処理工程において、ITO膜に圧縮応力が付与されることが好ましい。具体的には、ITO膜の膜面の一方向における寸法変化は、-0.3%~-1.5%であることが好ましく、-0.55%~-1.2%であることがより好ましく、-0.7%~-1.05%であることがさらに好ましく、-0.7%~-0.9%であることが特に好ましい。なお、寸法変化(%)は、熱処理工程に供する前のITO膜の一方向における2点間の距離L0が、熱処理熱後にLに変化した場合において、100×(L1-L0)/L0で定義される。寸法変化を前記範囲とすることにより、熱処理後の結晶性ITO膜が、前述のような所定の圧縮残留応力を有し得るため、打点特性や屈曲性に優れる透明導電性フィルムが得られうる。
次に、2枚以上の可撓性透明基材を含む本発明の第2の実施形態にかかる透明導電性フィルム102について、第1の実施形態とは異なる点を中心に説明する。
複数の透明基体フィルム11、12は粘着剤層5を介して貼り合わせられることが好ましい。粘着剤層5の構成材料としては、透明性を有するものであれば特に制限なく使用できる。例えば、アクリル系ポリマー、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリビニルエーテル、酢酸ビニル/塩化ビニルコポリマー、変性ポリオレフィン、エポキシ系、フッ素系、天然ゴム、合成ゴム等のゴム系などのポリマーをベースポリマーとするものを適宜に選択して用いることができる。特に、光学的透明性に優れ、適度な濡れ性、凝集性及び接着性等の粘着特性を示し、耐候性や耐熱性等にも優れるという点からは、アクリル系粘着剤が好ましく用いられる。
図3A~Cは、透明導電性フィルム102の製造工程を概念的に表す模式的断面図である。なお、図3A~Cにおいては、アンダーコート層や背面コート層の図示は省略されている。粘着剤層5を介しての透明基体フィルム11、12の貼り合わせは、ITO膜の形成前(図3A)、アモルファスITO膜を形成後、加熱結晶化前(図3B)、アモルファスITO膜の加熱結晶化後(図3C)、のいずれにおいても行い得る。
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。
抵抗値は二端子法により測定した。表面抵抗は、JIS K7194(1994年)に準じて四探針法により測定した。
基材上にアモルファスITO膜が形成された積層体のITO膜面に、スパッタ製膜時の搬送方向(以下、「MD方向」)に約80mmの間隔で2点の標点(傷)を形成し、加熱結晶化前の標点間距離L0および、加熱後の標点間距離Lを、二次元測長機により測定して、寸法変化率(%)を求めた。
残留応力は、X線散乱法により、ITO膜の結晶格子歪みから間接的に求めた。
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。
(タッチパネルの作製)
透明導電性フィルムを、MD方向を長辺とする60mm×140mmの長方形に切り出した。その両短辺上に銀ペーストを幅5mmでスクリーン印刷し、室温で24時間乾燥して、銀電極を形成した。銀電極が形成された透明導電性フィルムとガラス21上に表面粗さRa=0.9nmのITO膜22が形成されたITO導電ガラス(日本曹達製)とを、厚み180μmのスペーサ8を介してITO形成面同士が対向するように配置して、図5に模式的に示すようなタッチパネルを作製した。
作製したタッチパネルの上部電極(透明導電性フィルム)側の上方2cmの高さから、1.5kgの荷重をかけたペン先R=0.8mmのポリアセタール製ペンを自由落下させた。この操作を1mm間隔で直線状に計10点行った。この10点の落下試験を1セットとし、1セットの試験後および5セットの試験後のリニアリティを測定した。
透明導電性フィルムの短辺上に形成された銀電極間に5Vの電圧を印加し、一方の電極(端子A)および他方の電極(端子B)間の出力電圧を測定した。リニアリティは、測定開始位置Aでの出力電圧をEA、測定終了位置Bでの出力電圧をEB、AB間の距離をLAB、開始位置Aからの距離Xの測定点での出力電圧をEX、理論値をEXXとすると、以下の計算から、求められる。
EXX={X・(EB-EA)/LAB}+EA
リニアリティ(%)=〔(EXX-EX)/(EB-EA)〕×100
(タッチパネルの作製)
スペーサの厚みを180μmから100μmに変更した以外は、上記の重荷重ペン打点耐久性の場合と同様にして、図5に模式的に示すようなタッチパネルを形成した。
作製したタッチパネルの上部電極(透明導電性フィルム)側から、ペン先R=0.8mmのポリアセタール製ペンを荷重250gで50000回(25000往復)の摺動を行った。タッチパネル端部(銀電極)からの距離1.66mmの位置で摺動を行った場合と距離1.39mmの位置で摺動を行った場合のそれぞれの試料について、上記重荷重ペン打点耐久性の場合と同様にして、リニアリティを測定した。
(試験片の作製)
透明導電性フィルムを、MD方向を長辺とする10mm×150mmの長方形に切り出し、両短辺上に銀ペーストを幅5mmでスクリーン印刷し、室温で24時間乾燥して、銀電極を形成した。この試験片の抵抗(初期抵抗R0)を二端子法により求めた。
試験片を、ITO形成面を外側にして穴開け径17mmφのコルクポーラーに沿って湾曲させ、1.0kgの荷重で10秒間保持した。その後、順次、穴開け径15.5mmφ、14mmφ、12.5mmφ、11mmφのコルクポーラーを用いて同様に湾曲させて1.0kgの荷重で10秒間保持することを繰り返した後、抵抗R11Tを測定し、初期抵抗に対する変化率R11T/Roを求めた。その後、さらに穴開け径9.5mmφのコルクポーラーに沿って試験片を湾曲させ、1.0kgの荷重で10秒間保持した後、抵抗R9.5Tを測定し、初期抵抗に対する変化率R9.5T/Roを求めた。
試験片を、ITO形成面を内側にしてコルクポーラーに沿って湾曲させた以外は、上記の引張屈曲性試験と同様にして、穴開け径17mmφ、15.5mmφ、14mmφ、12.5mmφ、11mmφのコルクポーラーに沿って湾曲させた後の抵抗R11C、およびさらに穴開け9.5mmφのコルクポーラーに沿って湾曲させた後の抵抗R9.5Cを測定し、初期抵抗に対する変化率R11C/RoおよびR9.5C/Roを求めた。
透明導電性フィルムを60℃湿度95%の恒温恒湿器に500時間投入して、四探針法により表面抵抗を測定して、加湿熱下での抵抗変動を評価した。加湿熱下での抵抗変動は、初期表面抵抗R1に対する、加湿熱後の表面抵抗Rの比(R/R1)で表される。
実施例1においては、2層のアンダーコート層が形成された厚み25μmのPETフィルム(第1の可撓性透明基材)上にアモルファスITO膜を形成した後、背面コート層として厚み5μmのハードコート層が形成された厚み125μmのPETフィルム(第2の可撓性透明基材)を厚み25μmの粘着剤層を介して貼り合わせた。その後、ITO膜の加熱結晶化を行い、合計厚みが180μmの基材上に厚み20nmの結晶性透明導電層が形成された透明導電性フィルムを作製した。これは図3Bに示すのと同様の工程によるものであり、各工程の詳細は下記の通りである。
第1の透明基体として、厚み25μmの二軸延伸ポリエチレンテレフタレートフィルム(三菱化学ポリエステル製 商品名「ダイアホイル」、ガラス転移温度80℃、屈折率1.66、150℃1時間加熱時のMD方向の寸法変化率-0.80%)を用い、このPETフィルム上に、2層の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のアモルファスITO膜を形成した。アモルファスITO膜形成後の積層体を室温で冷却して残留応力を開放した後に、150℃1時間加熱時のMD方向の寸法変化率を測定したところ、-0.45%であった。
第2の透明基体フィルムとして、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 U43 125μm」)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ITO膜が形成されたPETフィルムのITOが形成されていない側の面を連続的に貼り合わせた。得られた積層体は、合計厚み180μmの可撓性透明基材上に厚み20nmのアモルファスITO膜が形成されたものであった。
上記の積層体から300mm四方の枚葉体を切り出し、200℃の加熱槽内で1時間加熱して、ITO膜の結晶化を行い、結晶性ITO膜を有する透明導電性フィルムを得た。
実施例2~6および比較例1、2においては、ITO膜の結晶化における加熱条件を表1のように変更した以外は、上記実施例1と同様にして、結晶性ITO膜を有する透明導電性フィルムが作製された。
実施例7においては、実施例1と同様にして、透明導電性フィルムが作製されたが、アモルファスITO膜をスパッタ製膜する際、およびハードコート層付きPETフィルムを寸法安定化する際の搬送張力を大きくした点、および熱処理工程における加熱温度を150℃とした点において、実施例1とは異なっていた。
実施例8においては、一方の面に2層のアンダーコート層が形成され、他方の面に厚み5μmのハードコート層が形成された合計厚み180μmのPETフィルムのアンダーコート層形成面上にアモルファスITO膜を形成した後、加熱結晶化を行い、この合計厚みが180μmの基材上に厚み20nmの結晶性透明導電層が形成された透明導電性フィルムを作製した。
厚み175μm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 U43 175μm」、ガラス転移温度80℃、屈折率1.66、150℃1時間加熱時のMD方向の寸法変化率-0.9%)の一方の面に、実施例1と同様にして、2層のアンダーコート層を形成した。その後、PETフィルムの他方の面に、実施例1と同様にして、厚み5μmのハードコート層を形成した。なお、アンダーコート層およびハードコート層を形成後の基材の150℃1時間加熱時のMD方向の寸法変化率は-0.65%であった。
実施例9においては、2層のアンダーコート層が形成された厚み25μmのPETフィルム(第1の可撓性透明基材)上にアモルファスITO膜を形成し、ITO膜の加熱結晶化を行った後、厚み5μmのハードコート層が形成された厚み125μmのPETフィルム(第2の可撓性透明基材)を厚み25μmの粘着剤層を介して貼り合わせた。これは図3Cに示すのと同様の工程によるものである。
実施例10においては、ITO膜の結晶化における加熱温度を150℃に変更した以外は、上記実施例9と同様にして、結晶性ITO膜を有する合計厚み180μmの透明導電性フィルムが作製された。
実施例3および実施例6の透明導電性フィルムから300μm×300μmの正方形の試験片を切り出し、ITO膜面が手前となるように、ウルトラミクロトームの試料ホルダに固定した。次いで、ITO膜面に対して極鋭角にミクロトームナイフを設置し、切断面がITO膜面と略平行となるように、設定厚み70nmで切削して観察試料を得た。この観察試料のITO膜表面側でかつ薄膜の著しい損傷がない部位から1.5μm×1.5μmの観察視野を選択し、透過型電子顕微鏡(日立製、型番「H-7650」)を用い、加速電圧100kVにて観察した。観察写真(倍率:50000倍)から、視野1.5μm四方で観察される全ての結晶粒の最大粒径を求め、最大粒径が30~100nm、100nmを超え200nm、200nmを超え300nm以下の結晶の面積比率を求めた。面積比率(%)を表2に示す。
3 透明導電層(結晶性ITO膜)
3a アモルファスITO膜
5 粘着剤層
11、12 透明基体フィルム
16 アンダーコート層
17 背面コート層
101 透明導電性フィルム
102 透明導電性フィルム
Claims (6)
- 可撓性透明基材、および可撓性透明基材上に形成された結晶性のインジウム・スズ複合酸化物からなる透明導電層を備え、
前記透明導電層の圧縮残留応力が0.4~2GPaである、透明導電性フィルム。 - 前記透明導電層は、加熱により結晶化されたものであり、面内の少なくとも一方向における結晶化前に対する寸法変化が、-0.3%~-1.5%である、請求項1に記載の透明導電性フィルム。
- 可撓性透明基材、および可撓性透明基材上に形成された結晶性のインジウム・スズ複合酸化物からなる透明導電層を有する透明導電性フィルムの製造方法であって、
可撓性透明基材を準備する基材準備工程、
可撓性透明基材上に、非晶質のインジウム・スズ複合酸化物からなる非晶質透明導電層を形成する製膜工程、および
前記非晶質透明導電層を加熱して、結晶性のインジウム・スズ複合酸化物に転化する熱処理工程、を有し、
前記熱処理工程において、少なくとも面内の一方向において透明導電層に圧縮応力が付与されることを特徴とする透明導電性フィルムの製造方法。 - 前記熱処理工程において、透明導電層を面内の少なくとも一方向における寸法変化が-0.3%~-1.5%となるように圧縮する、請求項3に記載の透明導電性フィルムの製造方法。
- 前記圧縮応力の付与によって、結晶性透明導電層の圧縮残留応力を0.4~2GPaとすることを特徴とする、請求項3または4に記載の透明導電性フィルムの製造方法。
- 前記熱処理工程における加熱温度が150℃~210℃であり、加熱時間が150分以下である、請求項3~5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。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147034467A KR101991545B1 (ko) | 2010-12-27 | 2011-12-16 | 투명 도전성 필름 및 그 제조 방법 |
KR1020177024557A KR20170103998A (ko) | 2010-12-27 | 2011-12-16 | 투명 도전성 필름 및 그 제조 방법 |
CN201180063189.3A CN103314127B (zh) | 2010-12-27 | 2011-12-16 | 透明导电性薄膜及其制造方法 |
KR1020137013909A KR20130114171A (ko) | 2010-12-27 | 2011-12-16 | 투명 도전성 필름 및 그 제조 방법 |
US13/976,839 US9305680B2 (en) | 2010-12-27 | 2011-12-16 | Transparent conductive film and manufacturing method therefor |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010290499 | 2010-12-27 | ||
JP2010-290499 | 2010-12-27 | ||
JP2011-050469 | 2011-03-08 | ||
JP2011050469A JP6023402B2 (ja) | 2010-12-27 | 2011-03-08 | 透明導電性フィルムおよびその製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012090735A1 true WO2012090735A1 (ja) | 2012-07-05 |
Family
ID=46382848
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/079206 WO2012090735A1 (ja) | 2010-12-27 | 2011-12-16 | 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) | US9305680B2 (ja) |
JP (1) | JP6023402B2 (ja) |
KR (3) | KR101991545B1 (ja) |
CN (2) | CN103314127B (ja) |
TW (2) | TWI556268B (ja) |
WO (1) | WO2012090735A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI620665B (zh) * | 2012-12-07 | 2018-04-11 | Nitto Denko Corp | Laminated body |
JP2021002478A (ja) * | 2019-06-21 | 2021-01-07 | 日東電工株式会社 | 透明導電性フィルム |
US11091671B2 (en) * | 2013-10-23 | 2021-08-17 | Lg Chem, Ltd. | High-refractive adhesive film and touch panel including the same |
WO2021200710A1 (ja) * | 2020-03-31 | 2021-10-07 | 東洋紡株式会社 | 透明導電性フィルム |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104303240B (zh) * | 2012-05-17 | 2017-03-01 | 株式会社钟化 | 带有透明电极的基板及其制造方法以及触摸面板 |
JP6261988B2 (ja) | 2013-01-16 | 2018-01-17 | 日東電工株式会社 | 透明導電フィルムおよびその製造方法 |
JP6261987B2 (ja) * | 2013-01-16 | 2018-01-17 | 日東電工株式会社 | 透明導電フィルムおよびその製造方法 |
JP5805799B2 (ja) * | 2013-05-15 | 2015-11-10 | 日本写真印刷株式会社 | タッチセンサおよびタッチセンサモジュール |
WO2014185330A1 (ja) * | 2013-05-15 | 2014-11-20 | 日本写真印刷株式会社 | 透明導電体 |
CN104465475B (zh) * | 2013-09-22 | 2017-08-04 | 昆山工研院新型平板显示技术中心有限公司 | 柔性显示器件的制备方法及柔性显示器件 |
WO2015080496A1 (ko) * | 2013-11-27 | 2015-06-04 | 주식회사 엘지화학 | 전도성 구조체 전구체, 전도성 구조체 및 이의 제조방법 |
JP6207633B2 (ja) | 2014-04-30 | 2017-10-04 | 日東電工株式会社 | 透明導電性フィルム |
WO2015178298A1 (ja) * | 2014-05-20 | 2015-11-26 | 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 |
JP6240789B2 (ja) * | 2014-09-08 | 2017-11-29 | 富士フイルム株式会社 | タッチパネル用導電フィルムおよびタッチパネル |
JP5957133B2 (ja) * | 2014-11-20 | 2016-07-27 | 日東電工株式会社 | 保護フィルム付き透明導電性フィルム |
WO2016121316A1 (ja) * | 2015-01-26 | 2016-08-04 | 日本曹達株式会社 | 導電膜付き基材 |
KR101582913B1 (ko) * | 2015-03-16 | 2016-01-08 | 연세대학교 산학협력단 | 플렉서블 기판 상의 박막 적층 방법 |
WO2017014307A1 (ja) * | 2015-07-23 | 2017-01-26 | 富士フイルム株式会社 | 積層体 |
EP3333681A4 (en) * | 2015-08-05 | 2019-03-27 | Shenzhen Royole Technologies Co., Ltd. | TOUCH FILM, ORGANIC LIGHT EMITTING DIODE DISPLAY PANEL AND METHOD FOR PREPARING TOUCH FILM |
US10551596B2 (en) * | 2016-06-29 | 2020-02-04 | Ams Sensors Singapore Pte. Ltd. | Optical and optoelectronic assemblies including micro-spacers, and methods of manufacturing the same |
KR102425042B1 (ko) * | 2016-06-30 | 2022-07-25 | 닛토덴코 가부시키가이샤 | 전자파 투과성 금속 부재, 이것을 사용한 물품, 및 전자파 투과성 금속 필름의 제조 방법 |
EP3521867B1 (en) * | 2016-09-28 | 2022-10-12 | Mitsubishi Gas Chemical Company, Inc. | Optical lens |
JP6961174B2 (ja) * | 2016-09-28 | 2021-11-05 | 三菱瓦斯化学株式会社 | 光学フィルム、位相差フィルム、偏光板 |
US10981366B2 (en) * | 2016-09-28 | 2021-04-20 | Mitsubishi Gas Chemical Company, Inc. | Optical polyester film and transparent conductive film |
US10613042B2 (en) | 2017-09-28 | 2020-04-07 | International Business Machines Corporation | Measuring and analyzing residual stresses and their gradients in materials using high resolution grazing incidence X-ray diffraction |
WO2019130841A1 (ja) * | 2017-12-28 | 2019-07-04 | 日東電工株式会社 | 光透過性導電フィルム、その製造方法、調光フィルム、および、調光部材 |
JP7280036B2 (ja) * | 2018-12-17 | 2023-05-23 | 日東電工株式会社 | 導電性フィルムの製造方法 |
JP2020167047A (ja) * | 2019-03-29 | 2020-10-08 | 日東電工株式会社 | ヒータ |
KR20220155281A (ko) * | 2020-03-19 | 2022-11-22 | 닛토덴코 가부시키가이샤 | 투명 도전성 필름, 및 투명 도전성 필름의 제조 방법 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006286308A (ja) * | 2005-03-31 | 2006-10-19 | Toppan Printing Co Ltd | 透明導電膜積層体およびその製造方法 |
JP2007133839A (ja) * | 2005-11-07 | 2007-05-31 | Hs Planning:Kk | 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 |
JP2007234397A (ja) * | 2006-03-01 | 2007-09-13 | Ulvac Japan Ltd | 透明電極及びその形成方法 |
JP2008103208A (ja) * | 2006-10-19 | 2008-05-01 | Fujikura Ltd | 透明導電性基板の製造方法および電極基板の製造方法 |
WO2010035598A1 (ja) * | 2008-09-26 | 2010-04-01 | 東洋紡績株式会社 | 透明導電性フィルム及びタッチパネル |
WO2012005300A1 (ja) * | 2010-07-06 | 2012-01-12 | 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 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6179647A (ja) | 1984-09-28 | 1986-04-23 | 帝人株式会社 | 透明導電性積層体及びその製造方法 |
EP0385475A3 (en) * | 1989-03-02 | 1991-04-03 | Asahi Glass Company Ltd. | Method of forming a transparent conductive film |
JPH0329216A (ja) * | 1989-03-28 | 1991-02-07 | Asahi Glass Co Ltd | 透明電導膜の形成方法 |
JPH0315536A (ja) | 1989-06-13 | 1991-01-23 | Matsushita Electric Works Ltd | 配線基板の製造方法 |
JP2763472B2 (ja) | 1993-01-23 | 1998-06-11 | 日東電工株式会社 | 透明導電性積層体とタツチパネル |
JPH0859867A (ja) * | 1994-08-19 | 1996-03-05 | Oji Kako Kk | 透明導電性フィルム |
US6351068B2 (en) * | 1995-12-20 | 2002-02-26 | Mitsui Chemicals, Inc. | Transparent conductive laminate and electroluminescence light-emitting element using same |
JPH11335815A (ja) * | 1998-05-20 | 1999-12-07 | Nippon Sheet Glass Co Ltd | 透明導電膜付き基板および成膜装置 |
JP2000238178A (ja) * | 1999-02-24 | 2000-09-05 | Teijin Ltd | 透明導電積層体 |
JP2000282225A (ja) * | 1999-04-01 | 2000-10-10 | Nippon Sheet Glass Co Ltd | 透明導電膜形成方法及び該方法より形成された透明導電膜 |
JP4004025B2 (ja) | 2001-02-13 | 2007-11-07 | 日東電工株式会社 | 透明導電性積層体およびタッチパネル |
KR100505536B1 (ko) * | 2002-03-27 | 2005-08-04 | 스미토모 긴조쿠 고잔 가부시키가이샤 | 투명한 도전성 박막, 그것의 제조방법, 그것의 제조를위한 소결 타겟, 디스플레이 패널용의 투명한 전기전도성기재, 및 유기 전기루미네선스 디바이스 |
JP3785109B2 (ja) * | 2002-04-08 | 2006-06-14 | 日東電工株式会社 | 透明導電積層体の製造方法 |
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 |
JP2009020199A (ja) * | 2007-07-10 | 2009-01-29 | Mitsubishi Electric Corp | 表示パネル及びその製造方法 |
JP4914317B2 (ja) * | 2007-09-14 | 2012-04-11 | グンゼ株式会社 | タッチパネル装置。 |
JP4966924B2 (ja) | 2008-07-16 | 2012-07-04 | 日東電工株式会社 | 透明導電性フィルム、透明導電性積層体及びタッチパネル、並びに透明導電性フィルムの製造方法 |
WO2012005290A1 (ja) | 2010-07-06 | 2012-01-12 | 日東電工株式会社 | 透明導電性フィルムの製造方法 |
-
2011
- 2011-03-08 JP JP2011050469A patent/JP6023402B2/ja active Active
- 2011-12-16 CN CN201180063189.3A patent/CN103314127B/zh active Active
- 2011-12-16 WO PCT/JP2011/079206 patent/WO2012090735A1/ja active Application Filing
- 2011-12-16 KR KR1020147034467A patent/KR101991545B1/ko active IP Right Grant
- 2011-12-16 KR KR1020137013909A patent/KR20130114171A/ko not_active Application Discontinuation
- 2011-12-16 US US13/976,839 patent/US9305680B2/en not_active Expired - Fee Related
- 2011-12-16 KR KR1020177024557A patent/KR20170103998A/ko not_active Application Discontinuation
- 2011-12-16 CN CN201510435735.1A patent/CN105070353B/zh active Active
- 2011-12-27 TW TW103136899A patent/TWI556268B/zh active
- 2011-12-27 TW TW100149008A patent/TWI461305B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006286308A (ja) * | 2005-03-31 | 2006-10-19 | Toppan Printing Co Ltd | 透明導電膜積層体およびその製造方法 |
JP2007133839A (ja) * | 2005-11-07 | 2007-05-31 | Hs Planning:Kk | 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 |
JP2007234397A (ja) * | 2006-03-01 | 2007-09-13 | Ulvac Japan Ltd | 透明電極及びその形成方法 |
JP2008103208A (ja) * | 2006-10-19 | 2008-05-01 | Fujikura Ltd | 透明導電性基板の製造方法および電極基板の製造方法 |
WO2010035598A1 (ja) * | 2008-09-26 | 2010-04-01 | 東洋紡績株式会社 | 透明導電性フィルム及びタッチパネル |
WO2012005300A1 (ja) * | 2010-07-06 | 2012-01-12 | 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 |
Non-Patent Citations (1)
Title |
---|
T.J.VINK ET AL.: "On the homogeneity of sputter-deposited ITO films. Part I. Stress and microstructure", THIN SOLID FILMS, vol. 266, no. 2, 1995, pages 145 - 151, XP004000478, DOI: doi:10.1016/0040-6090(95)06818-X * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI620665B (zh) * | 2012-12-07 | 2018-04-11 | Nitto Denko Corp | Laminated body |
US11091671B2 (en) * | 2013-10-23 | 2021-08-17 | Lg Chem, Ltd. | High-refractive adhesive film and touch panel including the same |
JP2021002478A (ja) * | 2019-06-21 | 2021-01-07 | 日東電工株式会社 | 透明導電性フィルム |
WO2021001691A3 (ja) * | 2019-06-21 | 2021-03-04 | 日東電工株式会社 | 透明導電性フィルム |
WO2021200710A1 (ja) * | 2020-03-31 | 2021-10-07 | 東洋紡株式会社 | 透明導電性フィルム |
JPWO2021200710A1 (ja) * | 2020-03-31 | 2021-10-07 | ||
JP7060850B2 (ja) | 2020-03-31 | 2022-04-27 | 東洋紡株式会社 | 透明導電性フィルム |
Also Published As
Publication number | Publication date |
---|---|
KR20140146234A (ko) | 2014-12-24 |
US20130280554A1 (en) | 2013-10-24 |
TW201505040A (zh) | 2015-02-01 |
CN105070353A (zh) | 2015-11-18 |
KR20170103998A (ko) | 2017-09-13 |
TWI556268B (zh) | 2016-11-01 |
KR20130114171A (ko) | 2013-10-16 |
CN103314127B (zh) | 2016-03-16 |
JP2012150779A (ja) | 2012-08-09 |
KR101991545B1 (ko) | 2019-06-20 |
JP6023402B2 (ja) | 2016-11-09 |
US9305680B2 (en) | 2016-04-05 |
TW201236877A (en) | 2012-09-16 |
TWI461305B (zh) | 2014-11-21 |
CN103314127A (zh) | 2013-09-18 |
CN105070353B (zh) | 2017-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
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 | |
JP6006368B2 (ja) | 透明導電性フィルムの製造方法 | |
JP5543907B2 (ja) | 透明導電性フィルムおよびその製造方法 | |
US9588606B2 (en) | Transparent conductive film and manufacturing method therefor | |
WO2012029830A1 (ja) | ガラス-樹脂積層体、およびそれを巻き取ったガラスロール、並びにガラスロールの製造方法 | |
JP2006327098A (ja) | 透明フィルムおよびその製造方法 | |
CN110197739B (zh) | 透明导电性薄膜层叠体及透明导电性薄膜的制造方法 | |
TW201916064A (zh) | 結晶化膜 | |
JP2019079637A (ja) | 透明導電性フィルムおよび透明導電性フィルム積層体 | |
JP2022109930A (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 | |
JPH0915627A (ja) | 液晶表示素子 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180063189.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11853096 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137013909 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13976839 Country of ref document: US |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11853096 Country of ref document: EP Kind code of ref document: A1 |