CN107405880B - Film for laminating transparent conductive layer, method for producing same, and transparent conductive film - Google Patents
Film for laminating transparent conductive layer, method for producing same, and transparent conductive film Download PDFInfo
- Publication number
- CN107405880B CN107405880B CN201680017089.XA CN201680017089A CN107405880B CN 107405880 B CN107405880 B CN 107405880B CN 201680017089 A CN201680017089 A CN 201680017089A CN 107405880 B CN107405880 B CN 107405880B
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- Prior art keywords
- layer
- transparent conductive
- transparent
- film
- laminating
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- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
Abstract
The invention provides a film for laminating a transparent conductive layer, which is a film for laminating a transparent conductive layer, wherein a composite layer of a metal layer having an opening and a transparent resin layer provided in the opening is laminated on a transparent gas barrier layer on a transparent resin film substrate, and wherein the transparent resin film substrate having the transparent gas barrier layer has a water vapor permeability of 1.0 × 10 at 40 ℃ × 90% RH specified in JIS K7129, a water vapor permeability of 40 ℃ ×% RH of the transparent resin film substrate is provided‑3(g/m2Day) or less, and a water vapor transmission rate of 20 (g/m) at 40 ℃ × 90% RH defined in JIS K7129 corresponding to 100 μm of the transparent resin layer2Day) below.
Description
Technical Field
The invention relates to a film for laminating a transparent conductive layer, a method for manufacturing the same, and a transparent conductive film.
Background
In recent years, with the development of printed electronic devices, electronic devices mainly using organic materials, such as organic thin film solar cells and organic EL lighting, which are expected to be widespread in the future, have been increasing in area and flexibility. From the viewpoint of producing high-performance and large-area electronic devices, transparent conductive films used as light-transmissive electrodes in these electronic devices are required to have a low resistivity in order to improve power loss (in the case of an electronic device for power generation such as a solar cell, the conversion efficiency that determines the performance of the cell is reduced as the distance from the collector electrode becomes farther due to the high resistivity of the transparent conductive layer, the current density is reduced as the distance from the voltage-applied electrode becomes farther in the case of an electronic device for light emission such as organic EL lighting, and the luminance distribution is generated as the current density is reduced as the distance from the voltage-applied electrode becomes farther in the case of an electronic device for light emission such as organic EL lighting, and the like) that are generally caused by the high resistivity of the transparent conductive layer during device operation (collecting or applying voltage). In addition, from the viewpoint of maintaining device performance and flexibility and providing a long-life electronic device, gas barrier properties are required in order to suppress deterioration of materials such as an active layer and metal wiring materials in the electronic device due to water vapor, oxygen, and the like that have passed through the transparent conductive layer of the transparent conductive film.
Among these, for the requirements relating to the reduction of resistance of the surface of the transparent conductive layer (including the elimination of short-circuiting between the transparent conductive layer and the driving layer portion in the electronic device due to the structure (height difference) in which an auxiliary metal electrode layer is provided to the transparent conductive layer and the auxiliary metal electrode layer is provided), for example, patent document 1 discloses a structure in which a metal thin wire having a lower resistance value than that of the transparent conductive layer and a pattern layer of a metal paste are provided as an auxiliary electrode on the transparent conductive layer, and discloses a transparent electrode substrate in which a transparent conductive film having a transparent resin film in an opening portion on a transparent substrate formed of a plastic resin film is laminated on a layer formed of a metal film as a method for eliminating the problem of the occurrence of short-circuiting and the like.
In addition, regarding the requirement of gas barrier properties, patent document 2 discloses a barrier transparent conductive film in which a transparent barrier layer, a transparent resin layer, and a transparent conductive layer are sequentially laminated on a transparent film substrate.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4615250
Patent document 2: international publication No. 2011/046011
Disclosure of Invention
Problems to be solved by the invention
However, in patent document 1, this structure has a serious problem that, for example, the gas barrier properties required for an active layer and the like in an electronic device such as an organic thin-film solar cell and an organic EL lighting cannot be satisfied only with a resin base material, and moisture permeates through a transparent conductive substrate on the side in contact with the air to deteriorate the active layer and the like in the electronic device, which causes a reduction in the device life including deterioration of the device performance.
In addition, in patent document 2, although the transparent gas barrier layer suppresses the permeation of moisture from the surface of the transparent film substrate on the side in contact with the atmosphere, the gas barrier property in which moisture permeates from the end face of the transparent resin layer constituting the transparent conductive film, which is in direct contact with the atmosphere, to the inside of the device is not considered, and there is a problem that the device performance deteriorates with time and the device life is shortened due to the permeation of moisture from the end face of the transparent resin layer to the active layer and the like constituting the electronic device.
In view of the above problems, an object of the present invention is to provide a film for laminating a transparent conductive layer, which realizes reduction in resistance of the surface of the transparent conductive layer of the transparent conductive film and reduction in surface roughness of the transparent conductive layer, and which suppresses transmission of water vapor through the transparent conductive layer of the transparent conductive film, a method for producing the same, and a transparent conductive film. Another object of the present invention is to provide an organic thin-film solar cell and an organic EL lighting device which have less deterioration in device performance and a longer life by using the transparent conductive film of the present invention as a light-transmissive electrode.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found a film for laminating a transparent conductive layer, which is obtained by laminating a composite layer of a metal layer having an opening and a transparent resin layer provided in the opening on a transparent gas barrier layer provided on a transparent resin film substrate, wherein the water vapor permeability of the transparent resin film substrate having a transparent gas barrier layer and the water vapor permeability of the transparent resin layer are respectively set to specific ranges, whereby the transmission of water vapor from the transparent resin film substrate can be suppressed, and the transmission of water vapor from the end face of the transparent resin layer can be suppressed, and further, have found that the transparent conductive film obtained by laminating a transparent conductive layer on the film for laminating a transparent conductive layer can be used as a light-transmitting electrode of an electronic device, whereby the resistance of the transparent conductive layer can be reduced and the deterioration of the device performance can be reduced, and the life can be prolonged, thus, the present invention has been completed. In the present invention, the "transparent resin film base containing a transparent gas barrier layer" means a transparent resin film base in which a transparent gas barrier layer is laminated on at least one surface of the transparent resin film base.
That is, the present invention provides the following (1) to (11).
(1) A film for laminating a transparent conductive layer, which is obtained by laminating a composite layer of at least a metal layer having an opening and a transparent resin layer provided in the opening on a transparent gas barrier layer provided on a transparent resin film base material,
the transparent resin film substrate having the transparent gas barrier layer has a water vapor transmission rate of 1.0 × 10 at 40 ℃ × 90% RH as defined in JIS K7129-3(g/m2Day) or less, and a water vapor transmission rate of 20 (g/m) at 40 ℃ × 90% RH specified in JIS K7129 corresponding to 100 μm of the transparent resin layer2Day) below.
(2) The film for laminating a transparent conductive layer according to the above (1), wherein the transparent resin layer is formed of polyethylene, polypropylene, polystyrene, polyvinyl chloride, or polyvinylidene chloride.
(3) The film for laminating a transparent conductive layer according to the above (1), wherein the transparent gas barrier layer is formed of a silicon oxynitride layer, an inorganic oxide layer, or an inorganic nitride layer.
(4) The film for laminating a transparent conductive layer according to the above (1), wherein a root mean square roughness Rq of the surface of the composite layer including a height difference between the metal layer and the transparent resin layer, which roughness is defined in JIS-B0601-1994, is 200nm or less.
(5) A transparent conductive film obtained by laminating a transparent conductive layer on the composite layer of the film for laminating a transparent conductive layer according to any one of (1) to (4) above.
(6) The transparent conductive film according to item (5) above, wherein the transparent conductive layer comprises a transparent conductive oxide or a conductive organic polymer.
(7) The transparent conductive film according to (6), wherein the transparent conductive oxide is Indium Tin Oxide (ITO) or Gallium Zinc Oxide (GZO), and the conductive organic polymer is poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate) [ PEDOT: PSS ].
(8) The transparent conductive film according to any one of (5) to (7) above, wherein the surface resistivity of the transparent conductive layer of the transparent conductive film is 5(Ω/□) or less.
(9) An electronic device comprising at least one of opposing electrodes formed of the transparent conductive film, wherein the transparent conductive film is the transparent conductive film according to any one of (5) to (8) above.
(10) A method for producing a film for laminating a transparent conductive layer, which is a film for laminating a transparent conductive layer, comprising a transparent gas barrier layer on a transparent resin film base material and a composite layer of at least a metal layer having an opening and a transparent resin layer provided in the opening, the method comprising the following steps (A) and (B):
(A) forming a composite layer by forming the metal layer having the opening on the transfer substrate and forming the transparent resin layer in the opening;
(B) and transferring the composite layer to the transparent gas barrier layer.
(11) The method for producing a transparent conductive film according to item (10) above, comprising: and a step of further laminating a transparent conductive layer on the composite layer of the film for laminating a transparent conductive layer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a film for laminating a transparent conductive layer, which realizes reduction in resistance of the surface of the transparent conductive layer of the transparent conductive film and reduction in surface roughness of the transparent conductive layer, and which suppresses transmission of water vapor through the transparent conductive layer of the transparent conductive film, a method for producing the same, and a transparent conductive film. Further, by using the transparent conductive film of the present invention as a light-transmissive electrode, an organic thin-film solar cell and an organic EL lighting with less deterioration in device performance and a long lifetime can be provided.
Drawings
Fig. 1 is a cross-sectional view showing an example of a film for laminating a transparent conductive layer and a transparent conductive film of the present invention.
Fig. 2 is a schematic view showing an example of the steps of the manufacturing method of the present invention in the order of steps.
Fig. 3 is a drawing for explaining a sample for evaluation of calcium corrosion test prepared in an example of the present invention and a comparative example, (a) is a cross-sectional view of the sample for evaluation of calcium corrosion test, and (b) is a plan view showing a corrosion image of a calcium layer after corrosion has progressed.
Description of the symbols
1: transparent conductive film
1 a: film for laminating transparent conductive layer
1 b: transparent conductive layer
2: transparent resin film substrate
3: transparent gas barrier layer
4: composite layer
5: metal layer (auxiliary electrode layer)
6: transparent resin layer
7: base material for transfer printing
8: sealing adhesive material layer
9: glass substrate
10: calcium layer
10 a: calcium layer left end (front square part)
10 b: calcium layer left end (rear square part)
10 c: calcium layer left end (center part)
10 d: erosion distance
10 k: corrosion zone
10 p: direction of corrosion development
11: sample for calcium corrosion test evaluation
Detailed Description
[ film for laminating transparent conductive layer ]
The film for laminating a transparent conductive layer of the present invention is a film for laminating a transparent conductive layer, which is obtained by laminating a composite layer of at least a metal layer having an opening and a transparent resin layer provided in the opening on a transparent gas barrier layer provided on a transparent resin film substrate, wherein the transparent resin film substrate having the transparent gas barrier layer has a water vapor permeability of 1.0 × 10 at 40 ℃ × 90% RH as defined in JIS K7129-3(g/m2Day) or less, and a water vapor transmission rate of 20 (g/m) at 40 ℃ × 90% RH specified in JIS K7129 corresponding to 100 μm of the transparent resin layer2Day) below.
Fig. 1 is a cross-sectional view showing an example of a film for laminating a transparent conductive layer and a transparent conductive film of the present invention. The film 1a for laminating a transparent conductive layer is formed by laminating a transparent gas barrier layer 3 and a composite layer 4 on a transparent resin film substrate 2, the composite layer 4 is composed of a metal layer 5 having an opening and a transparent resin layer 6 provided in the opening, and the transparent conductive film 1 is further formed by laminating a transparent conductive layer 1b on the composite layer 4.
The transparent resin film substrate comprising a transparent gas barrier layer constituting a film for laminating a transparent conductive layer is set to have a water vapor transmission rate of 1.0 × 10 at 40 ℃ of × 90% RH-3(g/m2Day) or less, and the water vapor permeability of the transparent resin layer constituting the film for laminating a transparent conductive layer corresponding to a film thickness of 100 μm is set to 20 (g/m) at 40 ℃ and × 90% RH (100% RH)2Day), it is possible to suppress the transmission of water vapor in the atmosphere from the end portion of the transparent resin layer constituting the composite layer. As a result, for example, when the transparent conductive layer is formed as a transparent conductive film by laminating the transparent conductive layer on the composite layer of the film for laminating a transparent conductive layer, water vapor can be suppressed from passing through the transparent conductive layer.
In addition, when a transparent conductive layer is formed by laminating a transparent conductive layer, the surface resistance of the transparent conductive layer can be lowered (the surface resistivity can be lowered) by providing a metal layer (auxiliary electrode layer) of the composite layer.
For example, in an electronic device in which at least one of the opposing electrodes is formed of a transparent conductive film, when the transparent conductive film in which the transparent conductive layer is laminated on the composite layer of the film for laminating a transparent conductive layer according to the present invention is used as a light-transmitting electrode, since water vapor that transmits through the transparent conductive layer is suppressed, deterioration with time due to water vapor can be minimized in an active layer or the like that forms an adjacent electronic device, and a long life can be achieved.
(evaluation of Water vapor Transmission Rate)
In the present invention, the water vapor transmission rate was evaluated in accordance with the specification of JIS K7129.
The transparent resin film substrate having a transparent gas barrier layer used in the present invention was measured for its water vapor transmission rate of × 90% RH at 40 ℃ using a water vapor transmission rate meter (manufactured by Mocon corporation, equipment name: AQUATRAN).
The transparent resin layer used in the present invention was measured for its water vapor permeability at 40 ℃ of × 90% RH using a water vapor permeability meter (Lyssy L80-5000, manufactured by Systechinstruments Co., Ltd.) and the obtained value was converted to a value (g/m) at a film thickness of 100 μm2Day). The film thickness of 100 μm means that when the film thickness is measured with another film thickness, the water vapor transmission rate is inversely proportional to the film thickness, and therefore, a value equivalent to 100 μm can be adopted. In this regard, the water vapor transmission rate per unit film thickness is a physical property inherent to the material.
Although it is difficult to directly measure the water vapor transmission rate from the thin end face, it is considered that the lower the water vapor transmission rate, the lower the water vapor transmission rate at the end face, because the water vapor transmission rate is a physical property inherent to a general material as described above. Therefore, it is considered that there is no problem in discussing the water vapor transmission rate of the end face by relatively comparing the normal water vapor transmission rates.
(transparent resin film substrate)
The transparent resin film substrate used in the present invention can be appropriately selected when a transparent gas barrier layer is laminated so that the water vapor transmission rate under high humidity conditions of 40 ℃ × 90% RH on the transparent resin film substrate surface side not having the transparent gas barrier layer is 1.0 × 10 in total-3(g/m2Day) below.
The transparent resin film substrate is not particularly limited as long as it is excellent in flexibility and transparency, and examples thereof include: polyimide, polyamide, polyamideimide, polyphenylene oxide, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclic olefin polymer, aromatic polymer, and the like. Among them, as the polyester, there can be mentioned: polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polyarylate, and the like. Examples of the cyclic olefin polymer include: norbornene polymer, monocyclic cyclic olefin polymer, cyclic conjugated diene polymer, vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. Among such transparent resin film substrates, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) which are biaxially stretched are particularly preferable from the viewpoint of cost and heat resistance.
The thickness of the transparent film resin substrate is preferably 10 to 500. mu.m, more preferably 10 to 300. mu.m, and still more preferably 10 to 100. mu.m. Within this range, the mechanical strength and transparency of the transparent resin film substrate can be ensured.
(transparent gas barrier layer)
The transparent gas barrier layer used in the present invention is provided between the transparent resin film substrate 2 and the composite layer 4 in fig. 1, for example, and has a function of preventing water vapor from passing through the composite layer 4 and the transparent conductive layer 1b as a result of suppressing water vapor in the atmosphere that has passed through the transparent resin film substrate 2. In the present invention, when the transparent resin film substrate is laminated, it is necessary to appropriately select a gas barrier material and the number of layers described later so as not to have such permeability, depending on the transparent resin film substrateThe transparent resin film substrate side of the clear gas barrier layer had a water vapor transmission rate of 1.0 × 10 under high humidity conditions of 40 ℃ and 90% RH-3(g/m2Day) below.
Examples of the transparent gas barrier layer include: inorganic vapor deposited films such as vapor deposited films of inorganic compounds and vapor deposited films of metals; a layer obtained by subjecting a layer containing a polymer compound (hereinafter, sometimes referred to as a "polymer layer") to a modification treatment such as ion implantation; and so on.
As the raw material of the vapor deposited film of the inorganic compound, there can be mentioned: inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; an inorganic carbide; an inorganic sulfide; inorganic nitrogen oxides such as silicon oxynitride; inorganic oxides of carbon; an inorganic carbonitride; inorganic oxycarbonitrides, and the like.
As the raw material of the metal deposition film, there may be mentioned: aluminum, magnesium, zinc, tin, and the like. These raw materials may be used alone in 1 kind, or in combination of 2 or more kinds.
Examples of the polymer compound used in the polymer layer include: silicon-containing polymer compounds such as polyorganosiloxane and polysilazane compounds, polyimide, polyamide, polyamideimide, polyphenylene oxide, polyether ketone, polyether ether ketone, polyolefin, and polyester. These polymer compounds may be used alone in 1 kind, or in combination with 2 or more kinds. Among these polymer compounds, a silicon-containing polymer compound having more excellent gas barrier properties is preferable. Examples of the silicon-containing polymer compound include: polysilazane compounds, polyorganosiloxane compounds, polysilane compounds, polyorganosiloxane compounds, and the like. Among them, polysilazane compounds are preferable from the viewpoint of forming a barrier layer having excellent gas barrier properties.
Among the above, from the viewpoint of gas barrier properties, an inorganic deposited film using an inorganic oxide, an inorganic nitride, or a metal as a raw material is preferable, and from the viewpoint of transparency, an inorganic deposited film using an inorganic oxide or an inorganic nitride as a raw material is preferable. Further, from the viewpoint of having interlayer adhesiveness, gas barrier properties, and bending resistance, a vapor deposited film of an inorganic compound or a silicon oxynitride layer formed of a layer containing oxygen, nitrogen, and silicon as main constituent atoms, which is formed by modifying a layer containing a polysilazane compound, can be preferably used.
The transparent gas barrier layer can be formed by, for example, subjecting a layer containing a polysilazane compound to plasma ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, or the like. As ions to be implanted by the plasma ion implantation treatment, there can be mentioned: hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, krypton, and the like.
Specific examples of the plasma ion implantation treatment include: a method of implanting ions present in plasma generated using an external electric field into a layer containing a polysilazane compound; alternatively, a method in which plasma is generated only by an electric field generated by a negative high voltage pulse applied to a layer formed of a material for forming a gas barrier layer without using an external electric field, and ions present in the plasma are implanted into a layer containing a polysilazane compound.
The plasma treatment is a method of modifying a layer containing a silicon-containing polymer by exposing the layer containing a polysilazane compound to plasma. For example, the plasma treatment can be performed according to the method described in Japanese patent laid-open No. 2012-106421. The ultraviolet irradiation treatment is a method of modifying a layer containing a silicon-containing polymer by irradiating a layer containing a polysilazane compound with ultraviolet light. For example, the ultraviolet ray modification treatment can be carried out according to the method described in Japanese patent laid-open publication No. 2013-226757. Among them, the ion implantation treatment is preferable because the ion implantation treatment can efficiently modify the surface of the layer containing the polysilazane compound into the inside thereof without roughening the surface, and can form a gas barrier layer having more excellent gas barrier properties.
The transparent gas barrier layer may be 1 layer, or 2 or more layers may be stacked. When 2 or more layers are stacked, the layers may be the same or different.
The thickness of the transparent gas barrier layer is preferably 20nm to 50 μm, more preferably 30nm to 1 μm, and still more preferably 40 to 500 nm. When the film thickness of the transparent gas barrier layer is in this range, not only excellent gas barrier properties and adhesion properties can be obtained, but also flexibility and film strength can be achieved.
Further, the water vapor transmission rate of the transparent gas barrier layer (including a plurality of layers) alone under a high humidity condition of × 90% RH at 40 ℃ is preferably 0.1 (g/m)2Day) or less, more preferably 0.05 (g/m)2Day) or less, and more preferably 0.01 (g/m)2Day) below. In the case of such a water vapor transmission rate, water vapor that has passed through the transparent resin film substrate can be blocked, and, for example, water vapor can be inhibited from passing through the adjacent composite layers used in the present invention.
The transparent resin film substrate having the transparent gas barrier layer used in the present invention, that is, the laminate of the transparent resin film substrate 2 and the transparent gas barrier layer 3 in fig. 1 has a water vapor transmission rate of 1.0 × 10 at 40 ℃ of × 90% RH-3(g/m2Day) the water vapor transmission rate exceeds 1.0 × 10-3(g/m2Day), the transparent conductive layer is deteriorated by the permeation of water vapor in the atmosphere, and the surface resistivity is increased, and when the transparent conductive layer is used as a light-transmitting electrode of an electronic device, the active layer and the like in the device are deteriorated with time, and the lifetime of the device is shortened, and the water vapor transmission rate is preferably 7.0 × 10-4(g/m2Day), more preferably 5.0 × 10-4(g/m2Day), more preferably 1.0 × 10-4(g/m2Day) below. When the water vapor permeability is within the above range and the water vapor permeability of the transparent resin layer described later is within the range of the present invention, for example, when a transparent conductive layer is laminated on a composite layer of the film for laminating a transparent conductive layer to form a transparent conductive film, the surface resistivity can be maintained without deteriorating the transparent conductive layer. In addition, when used as a light-transmissive electrode of an electronic device, deterioration with time of an active layer and the like in the device can be suppressed, and the device can have a long life.
Composite layer
The composite layer of the present invention has a function of suppressing lowering of resistance (lowering of surface resistivity) of the transparent conductive layer and permeation of water vapor in the atmosphere when the transparent conductive layer is laminated on the film for laminating a transparent conductive layer to form a transparent conductive film.
As shown in fig. 1, the composite layer 4 is formed on the transparent gas barrier layer 3, for example, and is composed of a metal layer 5 having an opening and a transparent resin layer 6 provided in the opening.
(Metal layer)
When a transparent conductive layer is formed by laminating a transparent conductive layer on the film for laminating a transparent conductive layer of the present invention, a metal layer may be provided in order to lower the surface resistivity of the transparent conductive layer. In order to prevent the transmittance of the transparent conductive layer from being lowered, a metal layer (hereinafter, the patterned metal layer may be referred to as an "auxiliary electrode layer") having at least an opening (aperture ratio) described later is usually used by patterning, and a solid layer formed only of a metal layer is not used.
The material for forming the auxiliary electrode layer is not particularly limited, and when patterning is performed by a method such as photolithography, there are included: and a single metal such as gold, silver, copper, aluminum, nickel, or platinum, or a 2-to 3-membered aluminum alloy such as aluminum-silicon, aluminum-copper, or aluminum-titanium-palladium. Among these materials, silver, copper, and aluminum alloys are preferable, and copper and aluminum alloys are more preferable from the viewpoint of cost, etching properties, and corrosion resistance.
In addition, a conductive paste containing conductive fine particles may be used. As the conductive paste, a conductive paste in which conductive fine particles such as metal fine particles, carbon fine particles, and ruthenium oxide fine particles are dispersed in a solvent containing a binder can be used. The auxiliary electrode layer can be obtained by printing and curing the conductive paste.
The material of the metal fine particles is preferably silver, copper, gold, or the like from the viewpoint of conductivity, and silver, copper, nickel, iron, cobalt, or the like from the viewpoint of price. Further, platinum, rhodium, ruthenium, palladium, and the like are preferable from the viewpoint of corrosion resistance and chemical resistance. The carbon fine particles are inferior to the metal fine particles in conductivity, but are inexpensive and excellent in corrosion resistance and chemical resistance. In addition, ruthenium oxide (RuO)2) The fine particles are more expensive than the carbon fine particles, but are excellentThe conductive material having corrosion resistance of (3) can be used as an auxiliary electrode layer.
The auxiliary electrode layer may be a single layer or a multilayer structure. The multilayer structure may be a multilayer structure formed by stacking layers made of the same material, or a multilayer structure formed by stacking layers made of at least 2 or more materials.
The multilayer structure is more preferably a 2-layer structure formed by laminating layers made of different materials. Such a multilayer structure is preferable because, for example, when a silver pattern layer is formed first and a copper pattern layer is formed thereon, the high conductivity of silver can be maintained and the corrosion resistance can be improved.
The pattern of the auxiliary electrode layer of the present invention is not particularly limited, and examples thereof include: lattice, honeycomb, comb-like, strip-like (stripe-like), linear, curved, wavy (sinusoidal, etc.), polygonal, circular, elliptical, amorphous, and the like. Among them, a lattice-like, honeycomb-like, or comb-like pattern is preferable.
The thickness of the auxiliary electrode layer is preferably 100nm to 20 μm, more preferably 100nm to 15 μm, and still more preferably 100nm to 10 μm.
The aperture ratio of the opening of the auxiliary electrode layer pattern (the portion where the auxiliary electrode layer is not formed) is preferably 80% or more and less than 100%, more preferably 90% or more and less than 100%, and still more preferably 95% or more and less than 100%, from the viewpoint of transparency (light transmittance). The aperture ratio is a ratio of the total area of the openings to the area of the entire region where the auxiliary electrode layer pattern including the openings is formed.
The line width of the auxiliary electrode layer is preferably 1 to 100 μm, more preferably 3 to 75 μm, and further preferably 5 to 50 μm. When the line width is in this range, the aperture ratio is large, the transmittance can be secured, and a stable transparent conductive film with low resistance can be obtained.
(transparent resin layer)
For example, in fig. 1, the transparent resin layer used in the present invention is provided in the opening (transparent resin layer 6) of the metal layer (auxiliary electrode layer) 5, and has a function of suppressing the transmission of water vapor from the end portion of the composite layer 4 in contact with the atmosphere.
Further, by making the thickness of the auxiliary electrode layer the same as that of the transparent resin layer and making the root-mean-square roughness Rq of the surface including the height difference of the interface between the auxiliary electrode layer and the transparent resin layer, which will be described later, within a specific range, it is possible to suppress a short circuit with the driving layer and the like inside the electronic device.
The transparent resin layer used in the present invention has a water vapor transmission rate of 20 (g/m) under a high humidity condition of × 90% RH at 40 ℃ and a film thickness of 100 μm2Day) below. The water vapor transmission rate is more than 20 (g/m)2Day), water vapor in the atmosphere permeates through the end of the transparent resin layer, so that the transparent conductive layer deteriorates to increase the surface resistivity, and an active layer and the like in the electronic device deteriorate with time, thereby shortening the lifetime of the device. The water vapor transmission rate is preferably 20 (g/m)2Day) or less, more preferably 10 (g/m)2Day) or less, more preferably 1 (g/m)2Day) below. When the water vapor transmission rate is within this range and the water vapor transmission rate of the transparent resin film substrate including the transparent gas barrier layer is within the range of the present invention, for example, when a transparent conductive layer is formed by laminating a transparent conductive layer on a composite layer of a film for laminating a transparent conductive layer, the surface resistivity can be maintained without deteriorating the transparent conductive layer. In addition, for example, when used as a light-transmissive electrode of an electronic device, deterioration with time of an active layer or the like in the device can be suppressed, and the device can have a long life.
As the transparent resin composition forming the transparent resin layer, any transparent resin composition may be used without particular limitation as long as the water vapor transmission rate is included within the scope of the present invention. Examples thereof include cured products of energy ray curable resins, thermoplastic resins, and the like. Here, the energy ray-curable resin refers to a polymerizable compound that is crosslinked and cured by irradiation with a radiation having an energy quantum among electromagnetic waves or charged particle rays, that is, ultraviolet rays or electron beams.
Among them, thermoplastic resins are preferred from the viewpoint of low water vapor permeability and ease of lamination.
Examples of the thermoplastic resin include: polyolefin resins such as polyethylene, polypropylene and polybutylene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, saponified ethylene-vinyl acetate copolymers, polyvinyl alcohol, polycarbonate resins, fluorine-containing resins, polyvinyl acetate resins, acetal resins, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polybutylene terephthalate (PBN), and polyamide resins such as nylon 6 and nylon 66. The resin may be used alone in 1 kind, or in combination with 2 or more kinds. Among these, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyvinylidene chloride are preferable, polyethylene, polypropylene, and polystyrene are more preferable, and polyethylene is particularly preferable from the viewpoint of low water vapor permeability and high transparency.
The thickness of the transparent resin layer is the same as the thickness of the auxiliary electrode layer, and is preferably 100nm to 100 μm, more preferably 100nm to 50 μm, and still more preferably 100nm to 20 μm.
The root mean square roughness Rq of the surface of the composite layer including the level difference between the auxiliary electrode layer and the transparent resin layer, as defined in JIS-B0601-1994, is preferably 200nm or less, more preferably 150nm or less, and still more preferably 100nm or less. When the root mean square roughness Rq is in this range, it is preferable that the transparent conductive layer is laminated to form a transparent conductive film, since transparency and surface resistivity can be maintained and short-circuiting with a driving layer of an electronic device can be suppressed.
[ transparent conductive film ]
The transparent conductive film of the present invention is obtained by laminating a transparent conductive layer on the composite layer in the film for laminating a transparent conductive layer of the present invention as described above. Therefore, the water vapor transmission rate can be suppressed, and thus the surface resistivity can be maintained without deteriorating the transparent conductive layer. In addition, since the auxiliary electrode layer is provided on the composite layer, the surface resistivity of the transparent conductive layer can be reduced at the same time.
(transparent conductive layer)
As the transparent conductive layer, a transparent conductive oxide can be preferably used. Specific examples thereof include: indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Aluminum Zinc Oxide (AZO), Gallium Zinc Oxide (GZO), Indium Gallium Zinc Oxide (IGZO), niobium oxide, titanium oxide, tin oxide, and the like, and these oxides may be used alone or in plural. Among them, Indium Tin Oxide (ITO) and Gallium Zinc Oxide (GZO) are preferable, and Indium Tin Oxide (ITO) is more preferable from the viewpoints of transmittance, surface resistivity, and stability.
In addition, as the transparent conductive layer, a conductive organic polymer is preferably used. Examples of the conductive organic polymer include: poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate) [ PEDOT: PSS ], polythiophene, polyaniline, polypyrrole, and the like. Among them, poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate) [ PEDOT: PSS ], and polythiophene are preferable from the viewpoint of conductivity and transparency, and poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate) [ PEDOT: PSS ] is more preferable from the viewpoint of conductivity and transparency.
The thickness of the transparent conductive layer is preferably 10 to 500nm, more preferably 20 to 200 nm. In this range, a film having both high transmittance and low surface resistivity can be obtained, and therefore, the film is preferable.
The total light transmittance of the transparent conductive layer is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, as measured in accordance with JIS K7361-1.
The surface resistivity of the transparent conductive layer single layer is preferably 1000(Ω/□) or less, and more preferably 100(Ω/□) or less.
The surface resistivity of the transparent conductive layer of the transparent conductive film having an auxiliary electrode layer of the present invention is preferably 5(Ω/□) or less, and more preferably 1(Ω/□) or less.
When the surface resistivity is 5(Ω/□) or less, even when the transparent conductive film is used for a light-transmitting electrode or the like of an electronic device requiring a large area such as an organic thin-film solar cell or organic EL lighting, it is possible to improve power loss (current density decreases due to the high resistivity of the transparent conductive layer and the conversion efficiency determining the battery performance decreases as the distance from the current-collecting electrode increases in the case of an electronic device for power generation such as a solar cell), and a characteristic distribution (current density decreases due to the high resistivity of the transparent conductive layer and the luminance distribution occurs as the distance from the voltage-applying electrode decreases in the case of an electronic device for light emission such as organic EL lighting).
(electronic devices)
The electronic device of the present invention is an electronic device in which at least one of the opposing electrodes is composed of the transparent conductive film of the present invention. Therefore, the water vapor permeability of the transparent conductive layer of the transparent conductive film can be suppressed, and therefore, when the transparent conductive film is incorporated into an electronic device, water vapor can be suppressed from permeating the inside of the device, and a long-life electronic device with little deterioration in the performance over time of an active layer or the like of the device can be obtained. At the same time, the surface resistivity of the transparent conductive layer can be reduced, and the transparent conductive layer has flexibility, and therefore, the transparent conductive layer can be preferably used for an organic thin film solar cell and an organic EL lighting which require a large area.
[ method for producing film for laminating transparent conductive layer ]
The method for producing a film for laminating a transparent conductive layer of the present invention is a method for producing a film for laminating a transparent conductive layer, in which a composite layer of at least a metal layer having an opening and a transparent resin layer provided in the opening is laminated on a transparent gas barrier layer on a transparent resin film substrate, and comprises the following steps (a) and (B).
(A) Forming a composite layer by forming the metal layer having the opening on the transfer substrate and forming the transparent resin layer on the opening
(B) A step of transferring the composite layer to the transparent gas barrier layer
A method for manufacturing a film for laminating a transparent conductive layer according to the present invention will be described with reference to the drawings.
Fig. 2 is a schematic view showing an example of the steps of the manufacturing method of the present invention in the order of steps, where (a) is a sectional view after forming the metal layer 5 on the transfer substrate 7, (b) is a sectional view after forming the transparent resin layer 6 in the opening of the metal layer 5 and forming the composite layer 4 composed of the metal layer 5 and the transparent resin layer 6, (c) is a sectional view showing a step of transferring the composite layer 4 to the transparent gas barrier layer 3 on the transparent resin film substrate 2, and (d) is a sectional view after transferring the composite layer 4, further peeling the transfer substrate 7 from the composite layer 4, and transferring the smoothness of the surface of the transfer substrate 7 to the composite layer 4.
< Process for Forming composite layer >
The composite layer forming step is a step of forming a composite layer of a metal layer having an opening and a transparent resin layer provided in the opening on a transfer substrate, and includes a metal layer forming step and a transparent resin layer forming step.
(Metal layer Forming Process)
The metal layer forming step is a step of forming a pattern (auxiliary electrode layer) made of a metal layer on the transfer substrate. In fig. 2(a), the auxiliary electrode layer 5 is formed on the transfer substrate 7.
The transfer substrate used in the present invention is preferably composed of a substrate film, and a cured layer obtained by curing the silicone resin composition is provided thereon.
The substrate film is not particularly limited, and examples thereof include: polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polypropylene and polymethylpentene, polycarbonate films, and polyvinyl acetate films, among which polyester films are preferred, and biaxially stretched polyethylene terephthalate films are particularly preferred. The thickness of the base film is preferably 10 to 500. mu.m, more preferably 20 to 300. mu.m, and still more preferably 30 to 100 μm, from the viewpoint of mechanical strength, durability, and transparency. The surface roughness of the base film is preferably 30nm or less, more preferably 20nm or less, and even more preferably 10nm or less in Rq from the viewpoint of the releasability of the transferred product and the surface roughness of the transferred product.
As a method for forming the cured layer, for example, a coating liquid including a silicone resin composition and various additive components used as needed may be applied to the substrate film by a gravure coating method, a bar coating method, a spray coating method, a spin coating method, or the like. In this case, an appropriate organic solvent may be added to adjust the viscosity of the coating liquid. The organic solvent is not particularly limited, and various solvents can be used. For example, as typified by hydrocarbon compounds such as toluene and ethane, ethyl acetate, methyl ethyl ketone, and mixtures thereof can be used.
Examples of the method for forming the auxiliary electrode layer include: a method of providing an unpatterned solid metal layer on a transfer substrate and then processing the solid metal layer into a predetermined pattern shape by a known physical treatment or chemical treatment mainly using a photolithography method, a method of combining various treatments, or the like, and a method of directly forming a pattern of an auxiliary electrode layer by an ink-jet method, a screen printing method, or the like.
Examples of the method for forming the unpatterned auxiliary electrode layer include: the auxiliary electrode layer may be appropriately selected depending on the material of the auxiliary electrode layer, for example, a dry process such as PVD (physical vapor deposition) such as vacuum deposition, sputtering, or ion plating, CVD (chemical vapor deposition) such as thermal CVD or Atomic Layer Deposition (ALD), various types of coating such as dip coating, spin coating, spray coating, gravure coating, die coating, or blade coating, a wet process such as electrodeposition, or a silver salt method.
In the case of forming a pattern of the auxiliary electrode layer by a method such as screen printing, a conductive paste containing conductive fine particles may be used. Of course, patterning may be performed by a method such as photolithography. From the viewpoint of simplicity of the process, cost, and reduction in the production pace, pattern printing using a conductive paste is preferable.
As the conductive paste, a conductive paste in which conductive fine particles such as metal fine particles, carbon fine particles, and ruthenium oxide fine particles are dispersed in a solvent containing a binder as described above can be used. The auxiliary electrode layer can be obtained by printing and curing the conductive paste.
The material of the fine metal particles is as described above.
(Process for Forming transparent resin layer)
The transparent resin layer forming step is a step of laminating a transparent resin layer on the opening of the metal layer, and for example, in fig. 2(b), is a step of forming a transparent resin layer 6 by forming a transparent resin composition containing a transparent resin on the opening of the metal layer 5 on the transfer substrate 7.
Examples of the method for forming the transparent resin layer include: thermal lamination, dip coating, spin coating, spray coating, gravure coating, die coating, blade coating, mayer rod coating, and the like. Among them, in the case of using a thermoplastic resin as the transparent resin layer, heat lamination is preferable from the viewpoint of enabling easy production. The thermal lamination can be carried out by a known method, and the lamination conditions are usually a heating temperature of 120 to 180 ℃ and a pressing amount of 0.1 to 25 MPa.
In the case of using an energy ray curable resin, examples of the method of irradiating with energy radiation include: ultraviolet rays, electron beams, and the like. The ultraviolet ray can be obtained by high pressure mercury lamp, FUSION H lamp, xenon lamp, etc., and the light amount is usually 100-500 mJ/cm2On the other hand, the electron beam can be obtained by an electron beam accelerator or the like, and the irradiation dose is usually 150 to 350 kV. Among these active energy rays, ultraviolet rays are particularly preferable. In the case of using an electron beam, a cured film can be obtained without adding a photopolymerization initiator.
< transfer Process of composite layer >
The composite layer transfer step is a step of transferring the composite layer on the transfer substrate obtained in the composite layer forming step to the transparent gas barrier layer surface side of the transparent film substrate, and for example, in fig. 2(c), is a step of laminating the composite layer 4 on the transparent gas barrier layer 3 by facing the transparent gas barrier layer 3 and the composite layer 4 to the transparent gas barrier layer 3 by transferring the composite layer 4 to the transparent gas barrier layer 3. This step also includes a step of peeling off the surface formed by the transfer substrate 7 and the composite layer 4. For example, after the laminated composite layer 4 is transferred, in fig. 2(d), the smoothness of the surface of the transfer substrate 7 can be transferred to the surface of the composite layer 4 by peeling off the interface between the transfer substrate 7 and the composite layer 4, thereby forming a surface formed of the auxiliary electrode layer and the transparent resin layer having small surface roughness and small level difference. The transfer method and the peeling method are not particularly limited, and can be performed by a known method.
< Process for Forming transparent conductive layer >
The transparent conductive layer forming step is a step of laminating a transparent conductive layer on the side of the composite layer formed of the auxiliary electrode layer and the transparent resin layer of the film for laminating a transparent conductive layer obtained in the above step.
Examples of the method for forming the transparent conductive layer include: PVD (physical vapor deposition) such as vacuum deposition, sputtering, and ion plating, CVD (chemical vapor deposition) such as thermal CVD and Atomic Layer Deposition (ALD), and the like. After the film formation by the above method, a transparent conductive layer having more excellent surface resistivity can be formed by applying heat treatment as needed within a range not affecting other laminated bodies.
As the transparent conductive layer, a coating liquid for forming a transparent conductive layer can be used. Examples of the method for forming the transparent conductive layer include: dip coating, spin coating, spray coating, gravure coating, die coating, blade coating, and the like. After coating and drying by the above-described method, if necessary, a transparent conductive layer having more excellent surface resistivity can be formed by applying curing treatment such as heat treatment or ultraviolet irradiation within a range not affecting other laminated bodies.
The coating liquid for forming a transparent conductive layer used in the present invention contains a solvent and conductive oxide fine particles dispersed in the solvent, and as the conductive oxide fine particles, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Aluminum Zinc Oxide (AZO), Gallium Zinc Oxide (GZO), Indium Gallium Zinc Oxide (IGZO), niobium oxide, titanium oxide, tin oxide, and the like, which have transparency and conductivity, which are exemplified as the material for a transparent conductive layer, can be used. The conductive oxide fine particles preferably have an average particle diameter of 10 to 100 nm. An average particle diameter within this range is preferable because high transparency and high conductivity can be secured.
In order to improve the film strength of the single layer, a binder may be added to the coating liquid for forming a transparent conductive layer. As the binder, both or either of an organic binder and an inorganic binder can be used, and it can be appropriately selected in consideration of the influence on the transparent resin layer and the auxiliary electrode layer which are to be formed surfaces.
The organic binder is not particularly limited, and may be appropriately selected from thermoplastic resins, thermosetting resins, Ultraviolet (UV) curable resins, electron beam curable resins, and the like. For example, the thermoplastic resin may be an acrylic resin, a polyolefin resin, a PET resin, a polyvinyl alcohol resin, or the like, the thermosetting resin may be an epoxy resin, or the like, the ultraviolet-curable resin may be a resin containing various oligomers, monomers, and a photopolymerization initiator, or the electron beam-curable resin may be a resin containing various oligomers and monomers.
The inorganic binder is not particularly limited, and examples thereof include a binder containing a silica sol as a main component. The inorganic binder may contain silica sol modified with organic functional groups, such as magnesium fluoride fine particles, alumina sol, zirconia sol, and titania sol.
According to the manufacturing method of the present invention, a film for laminating a transparent conductive layer in which a composite layer surface composed of an auxiliary electrode layer and a transparent resin layer is formed with small surface roughness and small difference in interface height and in which water vapor transmission rate is suppressed can be manufactured, and further, by laminating a transparent conductive layer on the composite layer surface, a transparent conductive film having an auxiliary electrode layer in which surface resistivity is low and electrical short-circuit with an electrode of a driving layer of an electronic device or the like is suppressed can be manufactured.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
The transparent resin used or produced in examples and comparative examples, the water vapor transmission rate of the transparent resin film substrate having a transparent gas barrier layer, the surface resistivity of the transparent conductive film, the surface roughness of the film for laminating a transparent conductive layer, and the calcium corrosion evaluation of the transparent conductive film were evaluated by the following methods.
(a) Evaluation of Water vapor Transmission Rate
The water vapor transmission rate was evaluated in accordance with JIS K7129.
(a-1) Water vapor Transmission Rate of transparent resin
The water vapor permeability of the transparent resin layer at 40 ℃ and 90% RH was measured using a water vapor permeability meter (Lyssy L80-5000, product of Systech Instruments Co., Ltd.), and the obtained value was converted to a value (g/m) at a film thickness of 100 μm2Day).
(a-2) Water vapor Transmission Rate of transparent resin film substrate having transparent gas Barrier layer
The water vapor transmission rate of the transparent resin film substrate having a transparent gas barrier layer at 40 ℃ and 90% RH was measured by using a water vapor transmission rate meter (manufactured by Mocon corporation, apparatus name: AQUATRAN).
(b) Surface resistivity of transparent conductive film
The surface resistivity (omega/□) of the surface of the transparent conductive layer was measured using a low resistivity meter (LorestaaX MCP-T370, manufactured by Mitsubishi Chemical Analyztech) at 25 ℃ and 50% RH.
(c) Height difference of interface and surface roughness
The surface roughness including the level difference of the interface portion was evaluated by measuring the root mean square roughness Rq specified in JIS-B0601-1994 on the surface of the interface portion of the transfer surface between the auxiliary electrode layer and the transparent resin layer in the composite layer of the film for laminating the transparent conductive layer using an optical interference surface roughness meter (model name: Wyko NT1100, manufactured by Veeco).
(d) Evaluation of calcium Corrosion of transparent conductive film
Fig. 3(a) is a cross-sectional view of a sample for evaluation of calcium corrosion test prepared in an example of the present invention and a comparative example. In fig. 3(a), a calcium corrosion test evaluation sample 11 has a structure in which a calcium layer 10 is disposed on a transparent conductive layer 1b via a sealing adhesive material layer 8 described below, and the transparent conductive layer 1b is laminated on a composite layer 4 used in the present invention. Specifically, a sample for evaluation of the calcium corrosion test was prepared in the following procedure.
100 parts by mass of an isobutylene-isoprene copolymer (Exxonbutyl 268, product name: manufactured by Japan Butyl Co., Ltd.) was added with a tackifier (manufactured by Nippon Ray Co., Ltd.; manufactured by Japan),The name of the product is: quintone R100) in toluene to prepare an adhesive resin composition having a solid content concentration of 20 mass%, and the adhesive resin composition was applied to a release film (product name: SP-PET38T103-1), dried at 120 ℃ for 2 minutes, to thereby form a sealing adhesive material layer 8 having a film thickness of 20 μm (water vapor transmission rate of 3.4 g/m)2Day).
On the other hand, 150nm calcium was deposited by a vapor deposition apparatus (apparatus name: E2000LL, manufactured by ALS Technology Co.) on a 45mm square (thickness: 0.685mm) glass substrate 9 (alkali-free glass substrate, manufactured by CORNING Co.) at a position 35mm square from the center of the surface thereof, thereby forming a calcium layer 10. Next, sample 11 for evaluation of calcium corrosion test was prepared by laminating the aforementioned sealing adhesive material layer 8 on the surface of the transparent conductive layer 1b of the transparent conductive film in a glove box, drying at 100 ℃ for 10 minutes, then peeling off the release film, and then laminating the release layer of the sealing adhesive material layer 8 on the side of the calcium layer 10 of the glass substrate 9.
The prepared evaluation sample was taken out of the glove box, left to stand at 60 ℃ under 95% RH for 100 hours, and the corrosion distance from the end of the calcium layer 10 was observed by using an optical microscope (model: VHX-1000, manufactured by KEYENCE).
Here, the erosion distance is defined as follows.
Fig. 3(b) is a plan view showing an image of the progress of corrosion of the calcium layer 10 of the sample 11 for evaluation of calcium corrosion test. The erosion distance 10d is defined as a distance in which erosion occurs in the direction from the left end (central portion) 10c of the calcium layer 10 toward the central portion of the calcium layer 10, i.e., from the left end (central portion) 10c of the calcium layer along the erosion proceeding direction 10p in the erosion region 10k, for example.
(example 1)
(1) Production of transparent gas barrier layer
The solution for forming an undercoat layer described below was applied to a transparent resin film substrate (Cosmoshine A4300, manufactured by Toyo Boseki K.K.) by a bar coating method, dried at 70 ℃ for 1 minute, and irradiated with UV rays (high pressure mercury lamp, manufactured by Fusion UVSystems JAPAN; cumulative light amount 100mJ @)cm2A liquid containing perhydropolysilazane (trade name: AZNL110A-20, manufactured by AZ Electronic Materials Co., Ltd.) was applied to the obtained primer layer by spin coating, and the obtained coating film was heated at 120 ℃ for 2 minutes to form a perhydropolysilazane layer having a thickness of 150nm, argon (Ar) was further plasma-ion-implanted into the obtained perhydropolysilazane layer under the following conditions to form a perhydropolysilazane layer after plasma ion-implantation (hereinafter, also referred to as "inorganic layer A"), and the water vapor transmission rate of the transparent resin film substrate having a transparent gas barrier layer (hereinafter, also referred to as "transparent resin film substrate having a transparent gas barrier layer A") was 8.0 × 10-3g/(m2Day).
Next, a perhydropolysilazane-containing liquid (AZNL 110A-20, manufactured by AZ Electronic Materials) was applied onto the inorganic layer a by a spin coating method, and the obtained coating film was heated at 120 ℃ for 2 minutes to form a perhydropolysilazane layer having a thickness of 150nm, and a silicon oxynitride layer (inorganic layer B) was formed on the inorganic layer a under the same film formation conditions as those for the inorganic layer a except that an applied voltage was set to-6 kV and the obtained perhydropolysilazane layer was subjected to plasma ion implantation, and a transparent resin film base material having a 2 nd layer transparent gas barrier layer and a 2-layer transparent gas barrier layer (hereinafter, also referred to as "transparent resin film base material B having a transparent gas barrier layer") was formed on the transparent resin film base material, and the water vapor permeability was 7.0 × 10-4g/(m2Day).
(solution for Forming undercoat layer)
20 parts by mass of dipentaerythritol hexaacrylate (product name: A-DPH, manufactured by Mitsumura chemical Co., Ltd.) was dissolved in 100 parts by mass of methyl isobutyl ketone, and then a photopolymerization initiator (product name: Irgacure127, manufactured by BASF) was added thereto in an amount of 3% by mass relative to the solid content to prepare a solution for forming an undercoat layer.
Plasma ion implantation was performed under the following implantation conditions using the following apparatus.
Plasma ion implantation apparatus
An RF power supply: model "RF 56000", manufactured by Nippon electronics Co., Ltd
High voltage pulse power supply: "PV-3-HSHV-0835", manufactured by Takayama Kabushiki Kaisha
Plasma ion implantation conditions
Plasma-generating gas: ar (Ar)
Gas flow rate: 100sccm
Duty ratio: 0.5 percent
Repetition frequency: 1000Hz
Applied voltage: -6kV
RF power supply: frequency 13.56MHz, applied power 1000W
Pressure in the chamber: 0.2Pa
Pulse width: 5 seconds
Processing time (ion implantation time): 200 seconds
Conveyance speed: 0.2 m/min
(2) Film for laminating transparent conductive layer and production of transparent conductive film
An auxiliary electrode layer comprising a grid-like fine metal wire pattern having a thickness of 6 μm, a line width of 50 μm and a pitch of 2000 μm was prepared by printing a conductive paste (EC-264, manufactured by Mitsuboshi Belting Co., Ltd.) on a transfer substrate (PLD 8030, manufactured by Lindcuke Co., Ltd.) using a screen printing apparatus (MT-320 TV, device name, manufactured by Micro Tech Co., Ltd.).
Next, a high-density Polyethylene resin film obtained by forming a high-density Polyethylene resin (manufactured by Keiyo Polyethylene corporation, brand name: F3001) as a transparent resin into a film was subjected to hot lamination at a heating temperature of 125 ℃ for 4 times at 0.3 m/min by using a hot laminator (manufactured by Royal Sovereign, device: RSL-382S), and the transparent resin was filled in the openings of the metal thin wires to provide a transparent resin layer, and a composite layer composed of an auxiliary electrode layer and the transparent resin layer was laminated. The obtained composite layer surface was opposed to the transparent gas barrier layer-side surface of the transparent resin film substrate B having the transparent gas barrier layer, and the composite layer was laminated on the transparent gas barrier layer, thereby performing transfer and lamination.
Next, the transfer substrate was peeled from the composite layer, thereby producing a film for laminating a transparent conductive layer, which had a transparent gas barrier layer and an auxiliary electrode layer on a transparent resin film substrate, the auxiliary electrode layer being composed of a thin metal wire layer with an opening filled with a transparent resin.
Further, 100nm Indium Tin Oxide (ITO) was laminated on the composite layer of the obtained film for laminating a transparent conductive layer by a sputtering apparatus (ISP-4000S-C, manufactured by ULVAC corporation), thereby producing a transparent conductive film. The evaluation results of the water vapor transmission rate of the transparent resin film substrate B having a transparent gas barrier layer and the transparent resin layer (in terms of a film thickness of 100 μm), the surface resistivity of the produced transparent conductive film, the root mean square roughness Rq of the film for laminating a transparent conductive layer, and the calcium corrosion distance of the transparent conductive film are shown in table 1.
(example 2)
A film for laminating a transparent conductive layer and a transparent conductive film were produced in the same manner as in example 1 except that the transparent resin was changed to a polystyrene resin film (product name: ALPHAN PK-002, manufactured by Oji F-Tex Co.) and the heating temperature at the time of thermal lamination was changed to 150 ℃. The evaluation results of the water vapor transmission rate of the transparent resin film substrate B having a transparent gas barrier layer and the transparent resin layer (in terms of a film thickness of 100 μm), the surface resistivity of the produced transparent conductive film, the root mean square roughness Rq of the film for laminating a transparent conductive layer, and the calcium corrosion distance of the transparent conductive film are shown in table 1.
Comparative example 1
An auxiliary electrode layer comprising a lattice-like fine metal wire pattern having a thickness of 6 μm, a wire width of 50 μm and a pitch of 2000 μm was produced in the same manner as in example 1.
Subsequently, an acrylic resin (product name: UVX-6125, manufactured by Toyo Synthesis Co., Ltd.) as a transparent resin was applied, and the openings of the metal thin wires were filled with the transparent resin to provide a transparent resin layer, and a composite layer composed of an auxiliary electrode layer and the transparent resin layer was laminated (the transparent resin layer was not cured). The obtained composite layer face was opposed to the transparent gas barrier layer-side face of the transparent resin film substrate B having a transparent gas barrier layer, the composite layer was laminated on the transparent gas barrier layer, UV irradiation was performed from the transparent resin film substrate side having a transparent gas barrier layer, and the transfer substrate was peeled from the composite layer, thereby producing a film for laminating a transparent conductive layer having a transparent gas barrier layer and an auxiliary electrode layer on the transparent resin film substrate, the auxiliary electrode layer being composed of a thin metal wire layer whose opening portion is filled with a transparent resin, and the transparent conductive film was produced by laminating a transparent conductive layer in the same manner as in example 1.
The evaluation results of the water vapor transmission rate of the transparent resin film substrate B having a transparent gas barrier layer and the transparent resin layer (in terms of a film thickness of 100 μm), the surface resistivity of the produced transparent conductive film, the root mean square roughness Rq of the film for laminating a transparent conductive layer, and the calcium corrosion distance of the transparent conductive film are shown in table 1.
Comparative example 2
An auxiliary electrode layer comprising a lattice-like fine metal wire pattern having a thickness of 6 μm, a wire width of 50 μm and a pitch of 2000 μm was produced in the same manner as in example 1.
Next, a silicone resin (product name: KER-2500, manufactured by shin-Etsu chemical Co., Ltd.) as a transparent resin was applied, and the openings of the metal thin wires were filled with the transparent resin to provide a transparent resin layer, and a composite layer composed of the auxiliary electrode layer and the transparent resin layer was laminated (the transparent resin layer was not cured). The obtained composite layer surface was opposed to the transparent gas barrier layer-side surface of the transparent resin film substrate B having a transparent gas barrier layer, the composite layer was laminated on the transparent gas barrier layer, and then heat cured, and the transfer substrate was peeled off from the composite layer, thereby producing a film for laminating a transparent conductive layer having a transparent gas barrier layer and an auxiliary electrode layer on the transparent resin film substrate, the auxiliary electrode layer being composed of a thin metal wire layer whose opening portion is filled with a transparent resin, and further producing a transparent conductive film by laminating a transparent conductive layer in the same manner as in example 1.
The evaluation results of the water vapor transmission rate of the transparent resin film substrate B having a transparent gas barrier layer and the transparent resin layer (in terms of a film thickness of 100 μm), the surface resistivity of the produced transparent conductive film, the root mean square roughness Rq of the film for laminating a transparent conductive layer, and the calcium corrosion distance of the transparent conductive film are shown in table 1.
Comparative example 3
In example 1, the transparent resin film substrate B having a transparent gas barrier layer was changed to a transparent resin film substrate having no transparent gas barrier layer (trade name: Cosmosine A4300, manufactured by Toyo Boseki K.K.; water vapor transmission rate > 1 (g/m)2Day)), a film for laminating a transparent conductive layer and a transparent conductive film were produced in the same manner as in example 1. The evaluation results of the water vapor transmission rate of the transparent resin film substrate and the transparent resin layer (converted to a film thickness of 100 μm) having no transparent gas barrier layer, the surface resistivity of the transparent conductive film produced, the root mean square roughness Rq of the film for laminating a transparent conductive layer, and the calcium corrosion distance of the transparent conductive film are shown in table 1.
Comparative example 4
A film for laminating a transparent conductive layer and a transparent conductive film were produced in the same manner as in example 1, except that in example 1, the transparent resin film substrate B having a transparent gas barrier layer was changed to the transparent resin film substrate a having a transparent gas barrier layer. The evaluation results of the water vapor transmission rate of the transparent resin film substrate a having a transparent gas barrier layer and the transparent resin layer (in terms of a film thickness of 100 μm), the surface resistivity of the produced transparent conductive film, the root mean square roughness Rq of the film for laminating a transparent conductive layer, and the calcium corrosion distance of the transparent conductive film are shown in table 1.
TABLE 1
As is clear from table 1, in examples 1 and 2, the calcium corrosion distance was significantly reduced and the corrosion resistance was high as compared with comparative example 1 in which the water vapor permeability of the transparent resin layer was high. In comparative example 2, deterioration of calcium was significantly increased, and the corrosion distance could not be accurately measured.
It is considered that the calcium corrosion distance could not be measured in comparative examples 3 and 4 because the transparent resin film substrate having no transparent gas barrier layer or the transparent resin film substrate a having a transparent gas barrier layer had a high water vapor transmission rate, and this determined the rate of progress of corrosion (i.e., the corrosion rate was high).
Industrial applicability
When the film for laminating a transparent conductive layer and the transparent conductive film of the present invention are used, the resistance of the transparent conductive layer can be lowered. Further, since the transparent resin film substrate and the transparent resin layer have low water vapor permeability, it is possible to suppress the transmission of water vapor from the composite layer composed of the transparent resin layer and the auxiliary electrode layer and the transparent conductive layer laminated on the composite layer, and for example, in an electronic device in which the transparent conductive film of at least one of the opposing electrodes is composed of the transparent conductive film of the present invention, the deterioration of the performance of the active layer and the like of the device is suppressed, and the life can be prolonged. This makes it possible to apply the organic thin film solar cell and the organic EL lighting to electronic devices.
Claims (10)
1. A film for laminating a transparent conductive layer, which is obtained by laminating a composite layer of at least a metal layer having an opening and a transparent resin layer provided in the opening on a transparent gas barrier layer provided on a transparent resin film base material,
the transparent resin film substrate having the transparent gas barrier layer has a water vapor transmission rate of 1.0 × 10 at 40 ℃ × 90% RH as defined in JIS K7129-3g/m2A water vapor transmission rate of 20g/m or less, and corresponding to 100 μm of the transparent resin layer and defined by JIS K7129, at 40 ℃ and × 90% RH2The number of days or less,
the composite layer has a root mean square roughness Rq of 200nm or less, which is defined by JIS-B0601-1994 and which includes a surface having a height difference between the metal layer and the transparent resin layer.
2. The film for laminating a transparent conductive layer according to claim 1, wherein the transparent resin layer is formed of polyethylene, polypropylene, polystyrene, polyvinyl chloride, or polyvinylidene chloride.
3. The film for laminating a transparent conductive layer according to claim 1, wherein the transparent gas barrier layer is formed of a silicon oxynitride layer, an inorganic oxide layer, or an inorganic nitride layer.
4. A transparent conductive film obtained by laminating a transparent conductive layer on the composite layer of the film for laminating a transparent conductive layer according to any one of claims 1 to 3.
5. The transparent conductive film according to claim 4, wherein the transparent conductive layer comprises a transparent conductive oxide or a conductive organic polymer.
6. The transparent conductive film according to claim 5, wherein the transparent conductive oxide is Indium Tin Oxide (ITO) or Gallium Zinc Oxide (GZO), and the conductive organic polymer is poly (3, 4-ethylenedioxythiophene: polystyrene sulfonate) [ PEDOT: PSS ].
7. The transparent conductive film according to any one of claims 4 to 6, wherein the surface resistivity of the transparent conductive layer of the transparent conductive film is 5 Ω/□ or less.
8. An electronic device comprising at least one of opposing electrodes formed of a transparent conductive film, wherein the transparent conductive film is the transparent conductive film according to any one of claims 4 to 7.
9. A method for producing a film for laminating a transparent conductive layer, which is a film for laminating a transparent conductive layer, comprising a transparent gas barrier layer on a transparent resin film base material and a composite layer of at least a metal layer having an opening and a transparent resin layer provided in the opening,
a water vapor transmission rate of 20g/m at 40 ℃ × 90% RH specified in JIS K7129 corresponding to 100 μm of the transparent resin layer2The number of days or less,
the composite layer has a root mean square roughness Rq of 200nm or less as defined in JIS-B0601-1994, which is a surface including a height difference between the metal layer and the transparent resin layer,
the production method comprises the following steps (A) and (B):
(A) forming a composite layer by forming the metal layer having the opening on the transfer substrate and forming the transparent resin layer in the opening;
(B) and transferring the composite layer to the transparent gas barrier layer.
10. The method for manufacturing a film for laminating a transparent conductive layer according to claim 9, comprising: and a step of further laminating a transparent conductive layer on the composite layer of the film for laminating a transparent conductive layer.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015066837 | 2015-03-27 | ||
| JP2015-066837 | 2015-03-27 | ||
| PCT/JP2016/052967 WO2016157987A1 (en) | 2015-03-27 | 2016-02-01 | Film for transparent conductive layer lamination, method for manufacturing same, and transparent conductive film |
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| CN107405880A CN107405880A (en) | 2017-11-28 |
| CN107405880B true CN107405880B (en) | 2020-06-30 |
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| JP (1) | JP6627863B2 (en) |
| KR (1) | KR102606932B1 (en) |
| CN (1) | CN107405880B (en) |
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| JP6816916B2 (en) * | 2016-11-16 | 2021-01-20 | リンテック株式会社 | Manufacturing method of transparent conductive laminate and transparent conductive laminate |
| CN110431008B (en) * | 2017-03-27 | 2022-05-06 | 凸版印刷株式会社 | Transparent conductive gas barrier laminate and device having the same |
| JP7082972B2 (en) * | 2017-03-30 | 2022-06-09 | リンテック株式会社 | A method for manufacturing a gas barrier laminated body, a sealed body, a conductive laminated body, and a conductive laminated body. |
| TW201840261A (en) * | 2017-03-31 | 2018-11-01 | 日商琳得科股份有限公司 | Transparent conductive laminate and production method therefor |
| JP6490262B2 (en) * | 2017-05-09 | 2019-03-27 | 日東電工株式会社 | Film with light transmissive conductive layer, light control film and light control device |
| JP6840251B2 (en) * | 2017-09-06 | 2021-03-10 | 富士フイルム株式会社 | Gas barrier film and manufacturing method of gas barrier film |
| CN108321239A (en) * | 2017-12-21 | 2018-07-24 | 君泰创新（北京）科技有限公司 | A kind of solar energy hetero-junction solar cell and preparation method thereof |
| CN109986599B (en) * | 2017-12-29 | 2020-10-02 | 北京纳米能源与系统研究所 | Triboelectric intelligent skin, manipulator and robot |
| WO2019205494A1 (en) * | 2018-04-27 | 2019-10-31 | 北京铂阳顶荣光伏科技有限公司 | Conductive electrode membrane layer and photovoltaic element |
| KR102294031B1 (en) * | 2018-10-26 | 2021-08-27 | 주식회사 엘지화학 | A barrier film |
| KR102294026B1 (en) * | 2018-10-26 | 2021-08-27 | 주식회사 엘지화학 | A barrier film |
| WO2020203109A1 (en) * | 2019-03-29 | 2020-10-08 | 東レ株式会社 | Metallized film and manufacturing method therefor |
| JP7230131B2 (en) * | 2020-09-04 | 2023-02-28 | デクセリアルズ株式会社 | Conductive laminate, optical device using same, method for manufacturing conductive laminate |
| US20230282387A1 (en) * | 2020-09-04 | 2023-09-07 | Dexerials Corporation | Conductive layered product, optical device using same, and manufacturing method for conductive layered product |
| WO2023238844A1 (en) * | 2022-06-06 | 2023-12-14 | 大日本印刷株式会社 | Resin film for current collector sheets, film for current collector sheets, current collector sheet, solar cell element with current collector sheet, and solar cell |
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| JP4615250B2 (en) | 2004-05-20 | 2011-01-19 | 藤森工業株式会社 | Transparent electrode substrate, method for producing the same, and dye-sensitized solar cell using the substrate |
| JP5245111B2 (en) * | 2007-12-06 | 2013-07-24 | コニカミノルタ株式会社 | Transparent conductive film |
| WO2011046011A1 (en) | 2009-10-14 | 2011-04-21 | コニカミノルタホールディングス株式会社 | Transparent conductor film with barrier properties, manufacturing method thereof, and organic electroluminescence element and organic solar cell using the transparent conductor film with barrier properties |
| JP2011155155A (en) * | 2010-01-27 | 2011-08-11 | Fujifilm Corp | Transparent conductive film and method of manufacturing the same, and organic thin-film solar cell |
| JP5343058B2 (en) * | 2010-10-15 | 2013-11-13 | リンテック株式会社 | Transparent conductive film, method for producing the same, member for electronic device, and electronic device |
| KR101530792B1 (en) * | 2010-11-19 | 2015-06-22 | 코니카 미놀타 가부시키가이샤 | Gas barrier film, method of producing a gas barrier film, and electronic device |
| JP2013016670A (en) * | 2011-07-05 | 2013-01-24 | Fujifilm Corp | Transparent conductive film, method for producing the same, and organic thin-film solar cell |
| JP2013211283A (en) * | 2012-02-29 | 2013-10-10 | Fujifilm Corp | Transparent conductive film and organic thin film solar cell including the same |
| JP5988867B2 (en) * | 2012-12-27 | 2016-09-07 | リンテック株式会社 | Transparent conductive film |
| JP2014216175A (en) * | 2013-04-25 | 2014-11-17 | リンテック株式会社 | Method of producing transparent conductive laminate and transparent conductive laminate |
| JP2015028857A (en) * | 2013-07-30 | 2015-02-12 | ペクセル・テクノロジーズ株式会社 | Dye-sensitized photo-electric conversion element and method for manufacturing dye-sensitized solar battery using the same |
| JP6209459B2 (en) * | 2014-02-07 | 2017-10-04 | リンテック株式会社 | Transparent conductive laminate, method for producing transparent conductive laminate, and electronic device using transparent conductive laminate |
| JP2015185440A (en) * | 2014-03-25 | 2015-10-22 | コニカミノルタ株式会社 | Transparent conductive film and method for producing the same |
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| CN107405880A (en) | 2017-11-28 |
| JPWO2016157987A1 (en) | 2018-01-18 |
| KR20170131440A (en) | 2017-11-29 |
| TW201638259A (en) | 2016-11-01 |
| JP6627863B2 (en) | 2020-01-08 |
| KR102606932B1 (en) | 2023-11-27 |
| WO2016157987A1 (en) | 2016-10-06 |
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