Patent Application
20170223826
The present invention relates to a laminate film which includes a transparent substrate formed of a resin film and a layered film provided on the substrate, and an electrode substrate film which is manufactured using the laminate film and is applied to a touch panel or the like, and particularly to a laminate film, an electrode substrate film in which a circuit pattern of electrodes and the like is less visible even under highly bright illumination, and a method of manufacturing the same.
In late years, “touch panels” have come to be widely used which are installed on surfaces of flat panel displays (FPD) included in a mobile phone, a portable device for electronic documents, a vending machine, a car navigation system, and the like.
The “touch panels” described above are largely divided into resistive ones and capacitive ones. The “resistive touch panel” has a main part which includes a transparent substrate formed of a resin film, an X-coordinate-(or Y-coordinate-) detecting electrode sheet and a Y-coordinate- (or X-coordinate-) detecting electrode sheet provided on the substrate, and an insulating spacer provided between these sheets. Here, although the X-coordinate-detecting electrode sheet and the Y-coordinate-detecting electrode sheet described above are spatially separated, both coordinate-detecting electrode sheets are configured to come into electrical contact with each other when pressed by a pen or the like, and to detect the position (X-coordinate and Y-coordinate) which the pen touched. The sheets are designed to trace the movement of the pen and recognize its coordinates, making it possible for the character to be inputted as a result. On the other hand, the “capacitive touch panel” has a structure where an X-coordinate- (or Y-coordinate-) detecting electrode sheet and a Y-coordinate- (or X-coordinate-) detecting electrode sheet are laminated with an insulating sheet in between, and an insulator such as glass is dispose on these. With this setup, when a finger approaches the above-described insulator such as glass, the sheets detect the position because electric capacitances of the X-coordinate-detecting electrode and the Y-coordinate-detecting electrode change.
Conventionally, transparent conductive films formed of ITO (indium oxide-tin oxide) and the like have been widely used as a conductive material for a circuit pattern of electrodes and the like (see Patent Document 1). Along with an increase in size of touch panels, mesh-structure metal thin lines as disclosed in Patent Document 2, Patent Document 3, and the like are beginning to be used.
Here, comparison between the transparent conductive film and the metal thin line described above shows the transparent conductive film has an advantage that, due to its excellent transmittance in a visible wavelength range, the circuit pattern of electrodes and the like is less visible, but the transparent conductive film has a disadvantage that it is unsuitable for the purpose of increasing the size and response speed of touch panels because its electrical resistance value is higher than that of the metal thin line. The metal thin line, on the other hand, is suitable for the purpose of increasing the size and response speed of touch panels because of its low electrical resistance value, but has a disadvantage that, due to a high reflectance in the visible wavelength range, the circuit pattern may be visible under highly bright illumination even if the metal thin line is formed into a fine mesh structure, which results in a decrease in product value.
A possible method of reducing the reflectance of the metal thin line in the visible wavelength range is to combine a metal film and a dielectric multilayered film to create an anti-reflective film. However, the method of combining the metal film and the dielectric multilayered film is not preferable because the metal thin line for the circuit pattern of electrodes and the like is formed by etching.
In such a technical background, a method has been proposed which reduces reflection on the metal film observed from the resin film side by, for example, forming a blackened layer between the resin film and the metal film by electrolytic plating or the like (see Patent Document 4), or providing a light absorbing layer (metal absorption layer) made of a metal oxide between the resin film and the metal film (see Patent Document 5).
Patent Document 1: Japanese Patent Application Publication No. 2003-151358 (see claim 2)
Patent Document 2: Japanese Patent Application Publication No. 2011-018194 (see claim 1)
Patent Document 3: Japanese Patent Application Publication No. 2013-069261 (see paragraph 0004)
Patent Document 4: Japanese Patent Application Publication No. 2014-142462 (see claim 5 and paragraph 0038)
Patent Document 5: Japanese Patent Application Publication No. 2013-225276 (see claim 1 and paragraph 0041)
However, there is a problem that provision of a blackened layer and a metal absorption layer may adversely increase reflection depending on the spectral optical characteristics of the blackened layer and the metal absorption layer proposed in Patent Documents 4 and 5, making it difficult to select a constituent material and a deposition condition.
The present invention has been made in view of this problem, and an object thereof is to provide an electrode substrate film in which a circuit pattern formed of the metal thin line described above is less visible even under highly bright illumination, to provide a laminate film used for the manufacture of this electrode substrate film, and to provide a method of manufacturing these laminate film and electrode substrate film.
Given the above situation, the present inventor repeatedly carried out deposition experiments and optical thin-film simulations for the metal absorption layer to solve the above-described problem, and has found there exist an optimum optical constants (refractive index and extinction coefficient) and film thickness condition of the metal absorption layer which make a spectral reflectance uniform and make the spectral reflectance low in a visible wavelength range (400 to 780 nm). Furthermore, it was also confirmed that it is possible to increase a line width of a metal thin line for a circuit pattern of electrodes and the like because the reflectance in the visible wavelength range can be reduced. The present invention has been completed based on such technical findings.
In summary, a first aspect of the present invention is
a laminate film including a transparent substrate formed of a resin film and a layered film provided on the transparent substrate, characterized in that
the layered film includes a metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a first layer, and a metal layer as a second layer, counted from the transparent substrate side,
optical constants of the metal absorption layer in a visible wavelength range (400 to 780 nm) satisfy conditions that
a refractive index is 2.0 to 2.2 and an extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm, and
an average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the transparent substrate and the metal absorption layer and an interface between the metal absorption layer and the metal layer is 20% or less, and a difference between a maximum transmittance and a minimum transmittance in the visible wavelength range (400 to 780 nm) is 10% or less.
A second aspect of the invention is
the laminate film described in the first aspect, characterized in that
the layered film includes a second metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a third layer, counted from the transparent substrate side, and
optical constants of the second metal absorption layer in the visible wavelength range (400 to 780 nm) satisfy conditions that
a refractive index is 2.0 to 2.2 and an extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm.
In addition, a third aspect of the invention is
the laminate film described in the first aspect or the second aspect, characterized in that
each of the metal absorption layer and the second metal absorption layer is formed of a deposition material of Ni alone or a Ni-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, or Cu alone or a Cu-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Ni, and also by a vacuum deposition method in which a reactive gas is introduced into a deposition apparatus.
A fourth aspect of the invention is
the laminate film described in the first aspect, characterized in that
a film thickness of the metal layer ranges from 50 nm to 5000 nm inclusive.
Next, a fifth aspect of the present invention is
an electrode substrate film including a transparent substrate formed of a resin film and a mesh circuit pattern provided on the transparent substrate and formed of a metal laminate thin line, the electrode substrate film characterized in that
the metal laminate thin line has a line width of 20 μm or less and includes a metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a first layer, and a metal layer as a second layer, counted from the transparent substrate side,
optical constants of the metal absorption layer in a visible wavelength range (400 to 780 nm) satisfy conditions that
a refractive index is 2.0 to 2.2 and an extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm, and
an average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the transparent substrate and the metal absorption layer and an interface between the metal absorption layer and the metal layer is 20% or less, and a difference between a maximum transmittance and a minimum transmittance in the visible wavelength range (400 to 780 nm) is 10% or less.
A sixth aspect of the invention is
the electrode substrate film described in the fifth aspect, characterized in that
the metal laminate thin line includes a second metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a third layer, counted from the transparent substrate side, and
optical constants of the second metal absorption layer in the visible wavelength range (400 to 780 nm) satisfy conditions that
a refractive index is 2.0 to 2.2 and an extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm.
Moreover, a seventh aspect of the invention is
the electrode substrate film described in the fifth aspect or the sixth aspect, characterized in that
each of the metal absorption layer and the second metal absorption layer is formed of a deposition material of Ni alone or a Ni-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, or Cu alone or a Cu-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Ni, and also by a vacuum deposition method in which a reactive gas is introduced into a deposition apparatus.
An eighth aspect of the invention is
the electrode substrate film described in the fifth aspect, characterized in that
a film thickness of the metal layer ranges from 50 nm to 5000 nm inclusive.
Next, a ninth aspect of the present invention is
a method of manufacturing a laminate film which includes a transparent substrate formed of a resin film and a layered film provided on the transparent substrate, characterized in that the method comprises:
a first step of forming, by a vacuum deposition method, a metal absorption layer a film thickness of which ranges from 20 nm to 30 nm inclusive and optical constants of which in a visible wavelength range (400 to 780 nm) satisfy conditions that
a refractive index is 2.0 to 2.2 and an extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm, the metal absorption layer being a first layer, counted from the transparent substrate side of the layered film; and
a second step of forming a metal layer by the vacuum deposition method, the metal layer being a second layer, counted from the transparent substrate side of the layered film, wherein
an average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the transparent substrate and the metal absorption layer and an interface between the metal absorption layer and the metal layer is 20% or less, and a difference between a maximum transmittance and a minimum transmittance in the visible wavelength range (400 to 780 nm) is 10% or less.
Furthermore, a tenth aspect of the invention is
the method of manufacturing a laminate film described in the ninth aspect, characterized in that the method further comprises:
a third step of forming, by the vacuum deposition method, a second metal absorption layer a film thickness of which ranges from 20 nm to 30 nm inclusive and optical constants of which in the visible wavelength range (400 to 780 nm) satisfy conditions that
a refractive index is 2.0 to 2.2 and an extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm, the second metal absorption layer being a third layer, counted from the transparent substrate side of the layered film.
An eleventh aspect of the invention is
the method of manufacturing a laminate film described in the ninth aspect or the tenth aspect, characterized in that
the metal absorption layer and the second metal absorption layer with adjusted optical constants, which are the refractive index and the extinction coefficient, are formed by introducing the deposition material according to the third aspect of the invention and a reactive gas into a deposition apparatus in which the vacuum deposition method is carried out, and by controlling a deposition condition inside the deposition apparatus.
A twelfth aspect of the invention is
the method of manufacturing a laminate film described in the eleventh aspect, characterized in that
the reactive gas includes oxygen or nitrogen gas alone, a gas mixture thereof, or a gas mixture with oxygen and nitrogen as main components.
Furthermore, a thirteenth aspect of the present invention is
a method of manufacturing an electrode substrate film which includes a transparent substrate formed of a resin film and a mesh circuit pattern provided on the transparent substrate and formed of a metal laminate thin line, characterized in that
the metal laminate thin line with a line width of 20 μm or less is formed by etching the layered film of the laminate film according to any one of the first to fourth aspects of the invention.
The electrode substrate film of the present invention including a transparent substrate formed of a resin film and a mesh circuit pattern provided on the transparent substrate and formed of a metal laminate thin line, is characterized in that
the metal laminate thin line has a line width of 20 μm or less and includes a metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a first layer, and a metal layer as a second layer, counted from the transparent substrate side,
optical constants of the metal absorption layer in a visible wavelength range (400 to 780 nm) satisfy conditions that
a refractive index is 2.0 to 2.2 and an extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm, and
an average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the transparent substrate and the metal absorption layer and an interface between the metal absorption layer and the metal layer is 20% or less, and a difference between a maximum transmittance and a minimum transmittance in the visible wavelength range (400 to 780 nm) is 10% or less.
Moreover, the average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the transparent substrate and the metal absorption layer and an interface between the metal absorption layer and the metal layer is a low value of 20% or less, and the difference between the maximum transmittance and the minimum transmittance in the visible wavelength range is a uniform value of 10% or less. For this reason, it is possible to provide an electrode substrate film in which the circuit pattern of electrodes and the like provided on the transparent substrate is less visible under highly bright illumination. Furthermore, a metal laminate thin line with a larger line width compared to a conventional one can be applied. Thus, the present invention has an effect that it can provide an electrode substrate film with a low electrical resistance value.
Further, the laminate film according to the present invention including a transparent substrate formed of a resin film and a layered film provided on the transparent substrate, is characterized in that
the layered film includes a metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a first layer, and a metal layer as a second layer, counted from the transparent substrate side,
optical constants of the metal absorption layer in a visible wavelength range (400 to 780 nm) satisfy conditions that
an average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the transparent substrate and the metal absorption layer and an interface between the metal absorption layer and the metal layer is 20% or less, and a difference between a maximum transmittance and a minimum transmittance in the visible wavelength range (400 to 780 nm) is 10% or less.
Additionally, the present invention has an effect which makes it possible to manufacture easily and reliably the electrode substrate film of the present invention by forming the layered film of the laminate film according to the present invention, by etching, into the metal laminate thin line with a line width of 20 μm or less.
An embodiment of the present invention is described below in detail with reference to the drawings.
(1) Optical Constants (Refractive Index and Extinction Coefficient) and Film Thickness Conditions for Metal Absorption Layer
(1-1) In a case of forming a metal absorption layer by a sputtering method as an example of a vacuum deposition method, the metal absorption layer mentioned above is formed while introducing a reactive gas such as oxygen or nitrogen gas into an apparatus (which is referred to as a sputtering web coater, and a sputtering target, a deposition material, is attached to a cathode inside a deposition apparatus) which carries out the sputtering method. Here, it is difficult to automatically determine a deposition condition (added amount of reactive gas such as oxygen or nitrogen gas) because it is affected by, for example, a shape of the deposition apparatus, a conveyance speed of a resin film being a transparent substrate, a deposition rate at the sputtering cathode, and a positional relationship among reactive gas discharge pipes, the sputtering cathode, and the resin film. The deposition condition described above is derived for every deposition apparatus from the added amount of reactive gas introduced and characteristic results of the deposited metal absorption layer.
(1-2) As a result of deposition experiments and optical thin-film simulations repeatedly carried out, the present inventor has found that there exist the optimum optical constants (refractive index and extinction coefficient) and film thickness condition of the metal absorption layer which make a spectral reflectance uniform and make the spectral reflectance low in a visible wavelength range (400 to 780 nm), as described above.
(1-3) A graph diagram of
Note that the deposition conditions A to E are, specifically, the deposition condition A (oxygen concentration of 0%), the deposition condition B (oxygen concentration of 11%), the deposition condition C (oxygen concentration of 23%), the deposition condition D (oxygen concentration of 28%), and, the deposition condition E (oxygen concentration of 33%).
The graph diagrams of
Hence, it is difficult to identify a metal absorption layer to be formed by the deposition material (metal material such as the Ni-based alloy) and the deposition condition (added amount of reactive gas such as oxygen or nitrogen gas). It is desirable to specify the metal absorption layer based on the optical constants thereof.
(1-4) Next, graph diagrams of
From the graph diagram of
(1-5) In view of the above, when choosing, from the graph diagrams of
Thereafter, when determining, from the graph diagrams of
the refractive index is 2.0 to 2.2 and the extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm.
(1-6) Then, in a case where the film thickness of the metal absorption layer deposited on the PET film ranges from 20 nm to 30 nm inclusive, and the optical constants (refractive index and extinction coefficient) in the visible wavelength range (400 to 780 nm) of the metal absorption layer described above satisfies the above-mentioned conditions, i.e.,
the refractive index is 2.0 to 2.2 and the extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm,
the metal absorption layer satisfies the condition that the average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the PET film and the metal absorption layer and an interface between the metal absorption layer and the metal layer (copper, for example) is 20% or less, and the flatness of the spectral reflectance property (difference between the highest reflectance and the lowest reflectance) is 10% or less. Thus, reflection on the metal layer observed on the resin film (PET film) side is reduced.
Here, the material for the metal absorption layer which possesses the property that the spectral reflectance becomes low and the spectral reflectance in the visible wavelength range becomes uniform when the metal absorption layer has a film thickness of 20 nm to 30 nm inclusive and satisfies the above-described conditions for the optical constants (refractive index and extinction coefficient) is not limited to the Ni-based alloy (Ni—W) mentioned above. For example, it has been demonstrated that the above property can also be achieved by a metal absorption layer formed of Ni alone or a Ni-based alloy containing at least one element selected from Ti, Al, V, Ta, Si, Cr, Ag, Mo, and Cu, and Cu alone or a Cu-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Ni.
(2) Laminate Film and Electrode Substrate Film According to Present Invention
(2-1) Laminate Film according to Present Invention
As illustrated in
the layered film includes a metal absorption layer 41 with a film thickness of 20 nm to 30 nm inclusive as a first layer, and a metal layer 40 as a second layer, counted from the transparent substrate 42 side,
the optical constants of the metal absorption layer 41 in the visible wavelength range (400 to 780 nm) satisfy the conditions that
the refractive index is 2.0 to 2.2 and the extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm,
and the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm, and
as illustrated in
In addition, the laminate film described above is characterized in that
the layered film includes a second metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a third layer, counted from the transparent substrate 42 side, and
the optical constants of the second metal absorption layer in the visible wavelength range (400 to 780 nm) satisfy the conditions that
the refractive index is 2.0 to 2.2 and the extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm.
(2-2) Electrode Substrate Film According to Present Invention
As illustrated in
the metal laminate thin line has a line width of 20 μm or less and includes a metal absorption layer 51 with a film thickness of 20 nm to 30 nm inclusive as a first layer, and a metal layer 50 as a second layer, counted from the transparent substrate 52 side,
the optical constants of the metal absorption layer 51 in the visible wavelength range (400 to 780 nm) satisfy the conditions that
the refractive index is 2.0 to 2.2 and the extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm, and
the average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at the interface between the transparent substrate 52 and the metal absorption layer 51 and the interface between the metal absorption layer 51 and the metal layer 50 is 20% or less, and the difference between the maximum transmittance and the minimum transmittance in the visible wavelength range (400 to 780 nm) is 10% or less.
In addition, the electrode substrate film is characterized in that
the metal laminate thin line includes a second metal absorption layer with a film thickness of 20 nm to 30 nm inclusive as a third layer, counted from the transparent substrate 52 side, and
the optical constants of the second metal absorption layer in the visible wavelength range (400 to 780 nm) satisfy the conditions that
the refractive index is 2.0 to 2.2 and the extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm.
(3) Constituent Materials for Laminate Film and Electrode Substrate Film According to Present Invention
(3-1) Resin Film Constituting Transparent Substrate
The material for the resin film applied to the laminate film and the electrode substrate film according to the present invention is not particularly limited, and its specific examples include a resin film alone selected from polyethylene terephthalate (PET), polyethersulfone (PES), polyarylates (PAR), polycarbonate (PC), polyolefins (PO), triacetyl cellulose (TAC), and a resin material of norbornene, or a composite material of a resin film alone selected from the above-mentioned resin materials and an acrylic organic film covering one or both of the surfaces of this resin film alone. In particular, typical examples of the norbornene resin material include Zeonoa (trade name) manufactured by Zeon Corporation, ARTON (trade name) manufactured by JSR Corporation, and the like.
Note that since the electrode substrate film according to the present invention is used for “touch panels” and the like, it desirably has excellent transparency in the visible wavelength range, among the resin films described above.
(3-2) Metal Absorption Layer
As described earlier, the film material for the metal absorption layer according to the present invention is preferably Ni alone or a Ni-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu, and Cu alone or a Cu-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Ni.
Besides, the metal absorption layer has a deposition material of Ni alone or the Ni-based alloy, or Cu alone or the Cu-based alloy described above, and is formed by the vacuum deposition method in which reactive gas is introduced into the deposition apparatus. The vacuum deposition method mentioned above includes magnetron sputtering, ion-beam sputtering, vacuum vapor deposition, ion plating, and CVD. In addition, the above-described reactive gas includes oxygen or nitrogen gas alone, a gas mixture of these, or a gas mixture containing argon or the like with oxygen and nitrogen as the main components.
What is more, the optical constants (refractive index and extinction coefficient) of the metal absorption layer at various wavelengths are greatly affected by the degree of reaction, i.e. the oxidation state or the degree of nitration, and are not determined only by the constituent material of the metal absorption layer.
(3-3) Metal Layer
The constituent material for the metal layer according to the present invention is not particularly limited as long as the material is a metal with a low electrical resistance value, and its examples include Cu alone or a Cu-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, and Ag, or Ag alone or a Ag-based alloy containing at least one element selected from Ti, Al, V, W, Ta, Si, Cr, and Cu. Cu alone is particularly desirable in terms of the formability and resistance value of the circuit pattern.
In addition, although the film thickness of the metal layer depends on its electrical characteristics and is not determined by optical factors, it is usually set to a film thickness at a level where transmitted light cannot be measured.
Moreover, a desirable film thickness of the metal layer is preferably 50 nm or more, and more preferably 60 nm or more in terms of electrical resistance. On the other hand, the film thickness is preferably 5 μm (5000 nm) or less, and more preferably 3 μm (3000 nm) or less in terms of formability of forming the metal layer into a wiring pattern.
(4) Deposition Apparatus Used for Carrying Out Vacuum Deposition Method
(4-1) Sputtering Web Coater
The sputtering method is taken as an example of the vacuum deposition method, and its deposition apparatus is described.
Here, this deposition apparatus is referred to as a sputtering web coater and is used in a case where a surface of a long resin film being conveyed in a roll-to-roll manner is subjected to a deposition treatment continuously and efficiently.
To be more specific, the deposition apparatus (sputtering web coater) for the long resin film conveyed in a roll-to-roll manner is provided inside a vacuum chamber 10 as illustrated in
Inside the vacuum chamber 10, for sputter deposition, pressure is reduced to an ultimate pressure of approximately 10−4 Pa and is thereafter adjusted to approximately 0.1 to 10 Pa by introducing sputtering gas. The sputtering gas used is a known gas such as argon and is further containing a gas such as oxygen or nitrogen depending on the purpose. The shape and the material for the vacuum chamber 10 are not particularly limited and various options can be adopted as long as it can withstand such a reduced pressure state. In addition, the vacuum chamber 10 has various apparatuses (not illustrated) integrated thereto such as a dry pump, turbomolecular pump, and cryocoil for reducing the pressure inside vacuum chamber 10 and maintaining the reduced pressure state.
A free roll 13 which guides the long resin film 12 and a tension sensor roll 14 which measures a tension of the long resin film 12 are disposed in this order on the conveyance path from the unwind roll 11 to the can roll 16. Meanwhile, the long resin film 12 forwarded from the tension sensor roll 14 toward the can roll 16 is adjusted relative to a peripheral speed of the can roll 16 by an upstream feed roll 15 which is driven by a motor and is provided near the can roll 16. This makes it possible to bring the long resin film 12 into close contact with an outer peripheral surface of the can roll 16.
In the same manner as described above, a downstream feed roll 21 which is driven by a motor and performs adjustment relative to the peripheral speed of the can roll 16, a tension sensor roll 22 which measures the tension of the long resin film 12, and a free roll 23 which guides the long resin film 12 are disposed in this order also on the conveyance path from the can roll 16 to the wind roll 24.
At the unwind roll 11 and the wind roll 24 described above, the tension balance of the long resin film 12 is maintained through torque control by a powder clutch or the like. Additionally, the long resin film 12 is unwound from the unwind roll 11 and wound by the wind roll 24 through the rotation of the can roll 16, and the upstream feed roll 15 and the downstream feed roll 21 which are driven by motors and rotate in synchronization with the can roll 16.
Provided near the can roll 16 are magnetron sputtering cathodes 17, 18, 19, and 20 as a means of deposition at positions facing the conveyance path (i.e., a region of the outer peripheral surface of the can roll 16 around which the long resin film 12 is wound) defined on the outer peripheral surface of the can roll 16. Reactive gas discharge pipes 25, 26, 27, 28, 29, 30, 31, and 32 which discharge reactive gas are installed in this vicinity.
When sputter deposition is to be carried out for the above-described metal absorption layer and the metal layer, a plate-shaped target can be used as illustrated in
(4-2) Reactive Sputtering
In a case where an oxide target or a nitride target is used for the purpose of forming the metal absorption layer described above, they are not suitable for mass production because the deposition rate is slow. For this reason, a metal target is employed which enables fast deposition and a method is adopted in which the above-described reactive gas is controlled when being introduced during the deposition.
Below are four known methods of controlling the reactive gas mentioned above:
(4-2-1) a method of discharging reactive gas at a constant flow rate.
(4-2-2) a method of discharging reactive gas so as to maintain a constant pressure.
(4-2-3) a method of discharging reactive gas such that the impedances of the sputtering cathodes are constant (impedance control).
(4-2-4) a method of discharging reactive gas such that the sputtering plasma intensity is constant (plasma emission control).
(5) Method of Manufacturing Electrode Substrate Film
(5-1) It is possible to obtain the electrode substrate film according to the present invention by etching the layered film of the laminate film according to the present invention and forming the layered film into a metal laminate thin line with a line width of 20 μm or less. Then, an electrode (wiring) pattern of the electrode substrate film is formed into a stripe shape or a grid shape for a touch panel. Thereby, the electrode substrate film according to the present invention can be used for a touch panel.
Moreover, since the metal laminate thin line formed into the electrode (wiring) pattern maintains a laminate structure of the laminate film according to the present invention, the average reflectance in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the transparent substrate and the metal absorption layer and an interface between the metal absorption layer and the metal layer is a low value of 20% or less, and the difference between the maximum transmittance and the minimum transmittance in the visible wavelength range is a uniform value of 10% or less. As a result, it is possible to provide an electrode substrate film in which the circuit pattern of electrodes and the like provided on the transparent substrate is very less visible even under highly bright illumination.
(5-2) Furthermore, for forming the laminate film according to the present invention into an electrode substrate film, a known subtractive method can be used.
The subtractive method is a method of creating a wiring pattern by forming a photoresist film on the surface of the layered film of the laminate film, performing exposure and development so that the photoresist film remains at an area where the wiring pattern is wished to be created, and removing, by chemical etching, the layered film at an area without the photoresist film on the surface of the layered film described above.
A hydrogen peroxide-based etching liquid and an aqueous solution of ceric ammonium nitrate can be used as an etching liquid for the chemical etching mentioned above. Furthermore, an aqueous solution of ferric chloride, an aqueous solution of copper(II) chloride, a hydrochloric acid acidified aqueous solution of permanganate salt, and an acetic acid acidified aqueous solution of permanganate salt can also be used. Note that it may be necessary to adjust the concentrations of the aqueous solution of ferric chloride, the aqueous solution of copper(II) chloride, the hydrochloric acid acidified aqueous solution of permanganate salt, and the acetic acid acidified aqueous solution of permanganate salt described above, depending on the metal absorption layer to be chemical-etched.
Hereinbelow, an example of the present invention is described in detail.
Note that an ellipsometer was used in the measurement of optical characteristics (refractive index and extinction coefficient) of the metal absorption layer, and a self-recording spectrophotometer was used in the measurement of the spectral reflectance property.
The deposition apparatus (sputtering web coater) illustrated in
Note that the can roll 16 is made of stainless steel with a diameter of 600 mm and a width of 750 mm, and a surface of the roll is plated with hard chrome. Each of the upstream feed roll 15 and the downstream feed roll 21 is made of stainless steel with a diameter of 150 mm and a width of 750 mm, and a surface of each roll is plated with hard chrome. Besides, the reactive gas discharge pipes 25, 26, 27, 28, 29, 30, 31, and 32 are installed on the upstream side and the downstream side of the cathodes 17, 18, 19, and 20. Moreover, a Ni—W target for the metal absorption layer was attached to the cathode 17, and a Cu target for the metal layer to the cathodes 18, 19, and 20.
In addition, a PET film with a width of 600 mm was used for the resin film constituting the transparent substrate, and the temperature of the can roll 16 was controlled and cooled to be at 0° C. What is more, the pressure inside the vacuum chamber 10 was reduced to 5 Pa by exhausting the gas therein through multiple dry pumps, and was further reduced to 3×10−3 Pa using multiple turbomolecular pumps and cryocoils.
(1) Manufacture of Laminate Film for Manufacturing Electrode Substrate Film
Thereafter, the conveyance speed of the resin film was set to 4 m/min. After that, 300 sccm of argon gas (sputtering gas) was introduced through the reactive gas discharge pipes 25 and 26 described above, and the power for the cathode 17 was controlled such that metal absorption layers (oxide films of Ni—W) with film thicknesses of 0 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, and 30 nm would be deposited. Here, the reactive gas (oxygen gas) was introduced as a gas mixture to the reactive gas discharge pipes 25 and 26.
The above-mentioned oxygen gas was used as the reactive gas, and the oxygen gas was controlled to a prescribed concentration using a piezo valve. The concentration conditions for the oxygen gas to be introduced were the deposition condition A (oxygen concentration of 0%), the deposition condition B (oxygen concentration of 11%), the deposition condition C (oxygen concentration of 23%), the deposition condition D (oxygen concentration of 28%), and the deposition condition E (oxygen concentration of 33%).
Note that since the deposition rate is expected to decrease depending on the amount of oxygen gas introduced, it is necessary to adjust sputtering power in order to obtain the intended film thicknesses of the metal absorption layer.
On the other hand, 300 sccm of argon gas (sputtering gas) was introduced through the reactive gas discharge pipes 27, 28, 29, 30, 31 and 32 described above, and the power for the cathodes 18, 19, and 20 was controlled such that a metal layer (Cu layer) with a film thickness of 80 nm would be formed. The laminate films of multiple kinds according to the example were manufactured by depositing the metal layer (Cu layer) with a film thickness of 80 nm on each of the metal absorption layers with film thicknesses of 0 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, and 30 nm, which were deposited under the deposition condition A (oxygen concentration of 0%) to the deposition condition E (oxygen concentration of 33%).
(2) Manufacture of Electrode Substrate Film
Next, the electrode substrate films according to the example were manufactured by the known subtractive method using the obtained laminate films of multiple kinds.
To be more specific, the electrode substrate films according to the example were manufactured by forming a photoresist film on the surface of the layered film of the laminate film described above (layered film formed of the metal absorption layer and the metal layer), performing exposure and development so that the photoresist film would remain at an area where a wiring pattern was wished to be created, and removing, by chemical etching, the layered film at an area without the photoresist film on the surface of the above-described layered film.
The circuit pattern of electrodes and the like was a stripe one with a wiring width of 5 μm and an interval of 300 μm.
Incidentally, an aqueous solution of ceric ammonium nitrate was used as the etching liquid for the chemical etching in this example. Besides, in the chemical etching, the laminate film with the photoresist film after the development was immersed in the etching liquid.
(1) Spectral reflectances of the laminate films of multiple kinds according to the example in the visible wavelength range (400 to 780 nm) attributed to reflection at an interface between the PET film and the metal absorption layer and an interface between the metal absorption layer and the metal layer were measured from the PET film side using a self-recording spectrophotometer, the laminate films being obtained by depositing metal absorption layers on the PET films so that their film thicknesses were 0 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, and 30 nm under the deposition conditions A to E described above, and thereafter depositing the metal layers (Cu layers) with a film thickness 80 nm.
The results are shown in the graph diagrams of
(2) On the other hand, the optical constants (refractive index and extinction coefficient) of the laminate films of 5 kinds according to the example in the visible wavelength range (400 to 780 nm) under the deposition conditions A to E were measured from the PET film side using an ellipsometer, the laminate films being obtained by depositing the metal absorption layers with a film thickness of 20 nm under the deposition conditions A to E, and thereafter depositing the metal layers (Cu layers) with a film thickness of 80 nm on these metal absorption layers.
The results are shown in the graph diagrams of
Note that since the optical constants are constants independent of the film thickness, the optical constant were measured for the laminate films of 5 kinds in which the metal absorption layers with a film thickness of 20 nm are deposited, as described above.
(3) When choosing, from the graph diagrams of
(4) Thereafter, when determining, from the graph diagrams of
the refractive index is 2.0 to 2.2 and the extinction coefficient is 1.8 to 2.1 at a wavelength of 400 nm,
the refractive index is 2.4 to 2.7 and the extinction coefficient is 1.9 to 2.3 at a wavelength of 500 nm,
the refractive index is 2.8 to 3.2 and the extinction coefficient is 1.9 to 2.5 at a wavelength of 600 nm,
the refractive index is 3.2 to 3.6 and the extinction coefficient is 1.7 to 2.5 at a wavelength of 700 nm, and
the refractive index is 3.5 to 3.8 and the extinction coefficient is 1.5 to 2.4 at a wavelength of 780 nm.
(5) Moreover, the aqueous solution of ceric ammonium nitrate described above was utilized as the etching liquid to examine an “etching quality” of the laminate films of multiple kinds. The metal absorption layer with a film thickness of 20 nm was etched and thereafter the periphery of the wiring pattern was checked for the “etching quality” with an optical microscope.
Etching was successfully performed for the metal absorption layers formed under the deposition condition A (oxygen concentration of 0%), the deposition condition B (oxygen concentration of 11%), the deposition condition C (oxygen concentration of 23%), and the deposition condition D (oxygen concentration of 28%) without etching residues on the periphery of the wiring pattern. However, the metal absorption layer formed under the deposition condition E (oxygen concentration of 33%) was not suitable for practical use because there were etching residues on the periphery of the wiring pattern.
Furthermore, visual check was carried out from the metal absorption layer side for the conductive substrate films including the metal absorption layers with a film thickness of 20 nm formed under the deposition conditions A, B, C, and D described above. In the checking, a conductive substrate film was placed such that a surface on the opposite side from where the conductive substrate film was visually checked was in contact with a liquid crystal display panel.
The circuit pattern of electrodes and the like was visible in the conductive substrate film with the metal absorption layer formed under the deposition condition A described above. On the other hand, the circuit pattern of electrodes and the like was less visible in the conductive substrate films with the metal absorption layers formed under the deposition conditions B, C, and D described above.
The circuit pattern of electrodes and the like was much less visible in the conductive substrate films with the metal absorption layers having a film thickness of 20 nm formed under the deposition conditions C and D described above compared to the conductive substrate film with the metal absorption layer having a film thickness of 20 nm formed under the deposition condition B described above.
It was confirmed that a conductive substrate film can be obtained in which the circuit pattern of electrodes and the like is hardly visible in an ideal case where the metal absorption layer is formed under the deposition condition C or the deposition condition D, and the its film thickness is set to 20 nm or more.
(6) Note that while the metal absorption layers according to the example are formed using the Ni—W target, they are not limited to the film material of the target as long as the optical constants are within the ranges described above, even in a case where a different Ni alloy or Cu alloy target is used.
An electrode substrate film according to the present invention is industrially applicable to a “touch panel” installed on a surface of an FPD (flat panel display) because a circuit pattern of electrodes and the like provided on a transparent substrate is less visible even under highly bright illumination.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2014-172604 | Aug 2014 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2015/073800 | 8/25/2015 | WO | 00 |
