CN111145938A - Conductive film and touch panel - Google Patents

Conductive film and touch panel Download PDF

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Publication number
CN111145938A
CN111145938A CN201911060487.1A CN201911060487A CN111145938A CN 111145938 A CN111145938 A CN 111145938A CN 201911060487 A CN201911060487 A CN 201911060487A CN 111145938 A CN111145938 A CN 111145938A
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China
Prior art keywords
layer
optical adjustment
adjustment layer
particles
less
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Pending
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CN201911060487.1A
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Chinese (zh)
Inventor
中岛宽伦
猪饲和宏
桥本尚树
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN111145938A publication Critical patent/CN111145938A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

Provided are a conductive film and a touch panel, wherein the peeling of a metal layer can be suppressed while suppressing the reduction of the optical properties of an optical adjustment layer. The conductive film (1) comprises a transparent base material (2), an optical adjustment layer (4), a transparent conductive layer (5) and a metal layer (6) in this order on the upper side, and the optical adjustment layer (4) contains SiO2Particles, ZrO2Particles and a resin, wherein the Si element existing ratio is 20% or more when the total element existing ratio of Si and Zr is 100% in the range from the upper surface to the lower side 10nm of the optical adjustment layer (4), and the optical adjustment layer (4) is divided into 3 layers uniformly in the vertical directionThe difference between the Si element existing ratio of the layer having the highest Si element existing ratio and the Si element existing ratio of the layer having the lowest Si element existing ratio is 15% or less.

Description

Conductive film and touch panel
Technical Field
The present invention relates to a conductive thin film and a touch panel provided with the same.
Background
Conventionally, an image display device is known which includes a transparent conductive film in which a transparent conductive layer such as an indium tin composite oxide (ITO) layer is disposed on a transparent base material as a film for a touch panel. In recent years, in order to form routing lines at the outer edge of the touch input region and to achieve a narrower frame, a conductive film in which a copper layer is further disposed on the upper surface of an ITO layer has been proposed as such a transparent conductive film (see, for example, patent document 1).
Such a conductive film is produced by, for example, sequentially forming a transparent conductive layer and a copper layer on one surface of a transparent base material by a sputtering method, and winding the conductive film into a roll.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-161282
Disclosure of Invention
Problems to be solved by the invention
However, when a metal layer is formed on a transparent conductive layer and wound in a roll shape, the strain of the metal layer becomes strong. As a result, the metal layer is peeled off together with the transparent conductive layer from the transparent base material. Therefore, improvement in adhesion between the transparent conductive layer and the transparent substrate is required.
On the other hand, when the transparent conductive layer is formed with a predetermined wiring pattern, the optical adjustment layer is usually disposed between the transparent conductive layer and the transparent base material in the conductive film so that the wiring pattern is not recognized.
In this way, it has been studied to impart a high adhesion function to the optical adjustment layer to improve the adhesion between the transparent conductive layer and the transparent base material. Specifically, compounding of SiO into the optical adjustment layer was investigated2And (3) granules.
However, if SiO is blended in the optical adjustment layer2The particles may cause a problem that the optical characteristics of the optical adjustment layer are degraded. Specifically, for example, the following disadvantages occur: the reflection spectrum of the desired optical adjustment layer is greatly changed to generate color tone in the optical adjustment layerAnd the like.
The invention provides a conductive film and a touch panel, which can inhibit the reduction of the optical property of an optical adjusting layer and inhibit the stripping of a metal layer.
Means for solving the problems
The invention [1]Comprises a conductive thin film having a transparent substrate, an optical adjustment layer, a transparent conductive layer and a metal layer in this order in one direction of the thickness direction, wherein the optical adjustment layer contains SiO2Particles, ZrO2The particles and the resin component have an Si element existing ratio of 20% or more when the total element existing ratio of Si and Zr is 100% in a range from one surface in the thickness direction of the optical adjustment layer to the other side 10nm in the thickness direction, and when the optical adjustment layer is divided into 3 layers uniformly in the thickness direction, the difference between the Si element existing ratio of the layer having the highest Si element existing ratio and the Si element existing ratio of the layer having the lowest Si element existing ratio is 15% or less.
The invention [2] comprises the conductive thin film according to [1], wherein the optical adjustment layer has a thickness of 30nm to 150 nm.
The invention [3] comprises the conductive thin film according to [1] or [2], and further comprises a hard coat layer disposed between the transparent base material and the optical adjustment layer.
The present invention [4] includes a touch panel including the conductive thin film according to any one of [1] to [3 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the conductive film and the touch panel of the present invention, the transparent substrate, the optical adjustment layer, the transparent conductive layer, and the metal layer are provided in this order in one direction in the thickness direction, and the Si element presence ratio is 20% or more when the total Si and Zr element presence ratio is 100% in the range from one surface in the thickness direction of the optical adjustment layer to the other side in the thickness direction by 10 nm. Therefore, the adhesion between the transparent conductive layer and the optical adjustment layer is improved, and the peeling of the metal layer can be suppressed.
When the optical adjustment layer is divided into 3 layers uniformly in the thickness direction, the highest Si element is presentThe difference between the Si element existing ratio of the existing ratio layer and the Si element existing ratio of the layer having the lowest Si element existing ratio is 15% or less. Therefore, SiO can be inhibited from being compounded2The change in the reflection spectrum of the optical adjustment layer due to the particles can suppress the degradation of the optical characteristics.
Drawings
Fig. 1 is a side sectional view showing an embodiment of the conductive thin film of the present invention.
Fig. 2 illustrates a side cross-sectional view of a patterned conductive film formed from the conductive film illustrated in fig. 1.
Fig. 3 is a side sectional view showing another embodiment (mode without a hard coat layer) of the conductive thin film of the present invention.
Fig. 4 is a side cross-sectional view of another embodiment (mode without a hard coat layer) of the patterned conductive thin film of the present invention.
Fig. 5 shows an image obtained by Element mapping (Element mapping) in a TEM cross-sectional view of the optical adjustment layer in the conductive thin film of example 1.
Fig. 6 shows an image obtained by element mapping in a TEM cross-sectional view of the optical adjustment layer in the conductive thin film of comparative example 2.
Fig. 7 shows an image obtained by element mapping in a TEM cross-sectional view of the optical adjustment layer in the conductive thin film of comparative example 3.
Description of the reference numerals
1 conductive thin film
2 transparent substrate
3 hard coating
4 optical adjustment layer
5 transparent conductive layer
6 Metal layer
Detailed Description
Embodiments of the present invention will be described with reference to the drawings. In fig. 1, the vertical direction on the paper surface is the vertical direction (thickness direction), the upper side on the paper surface is the upper side (thickness direction side), and the lower side on the paper surface is the lower side (thickness direction side). The horizontal direction and the depth direction of the paper surface are the plane directions orthogonal to the vertical direction. Specifically, directional arrows in the drawings are used as references.
< embodiment 1 >
1. Conductive thin film
As shown in fig. 1, for example, the conductive thin film 1 as embodiment 1 of the conductive thin film of the present invention has a thin film shape (including a sheet shape) extending in a planar direction and having a predetermined thickness. The film shape is defined as a thin plate shape having a flat upper surface (one surface in the thickness direction) and a flat lower surface (the other surface in the thickness direction) (hereinafter, the same applies).
The conductive film 1 is not an image display device, but is a member such as a touch panel substrate provided in an image display device. That is, the conductive film 1 is a member used for manufacturing an image display device or the like, does not include an image display element such as an LCD module, includes a transparent substrate 2, a hard coat layer 3, an optical adjustment layer 4, a transparent conductive layer 5, and a metal layer 6, which will be described later, and is a device that can be used in producing a product by circulating the members alone.
Specifically, as shown in fig. 1, the conductive thin film 1 includes, in order from the top (one direction in the thickness direction): a transparent substrate 2, a hard coat layer 3, an optical adjustment layer 4, a transparent conductive layer 5, and a metal layer 6. More specifically, the conductive thin film 1 includes: a transparent substrate 2, a hard coat layer 3 disposed on the upper surface of the transparent substrate 2, an optical adjustment layer 4 disposed on the upper surface of the hard coat layer 3, a transparent conductive layer 5 disposed on the upper surface of the optical adjustment layer 4, and a metal layer 6 disposed on the upper surface of the transparent conductive layer 5. The conductive film 1 preferably includes a transparent substrate 2, a hard coat layer 3, an optical adjustment layer 4, a transparent conductive layer 5, and a metal layer 6.
Each layer is described in detail below.
2. Transparent substrate
The transparent substrate 2 is a substrate for securing the mechanical strength of the conductive thin film 1. The transparent substrate 2 supports the transparent conductive layer 5 and the metal layer 6 together with the hard coat layer 3 and the optical adjustment layer 4.
The transparent substrate 2 is, for example, a transparent polymer film. Examples of the material of the polymer film include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, (meth) acrylic resins such as polymethacrylate (acrylic resins and/or methacrylic resins), olefin resins such as polyethylene, polypropylene, and cycloolefin polymer (COP), polycarbonate resins, polyether sulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins. The polymer film may be used alone or in combination of 2 or more.
From the viewpoint of transparency, heat resistance, mechanical strength, and the like, polyester resins and olefin resins are preferably used, and PET and COP are more preferably used.
The thickness of the transparent substrate 2 is, for example, 2 μm or more, preferably 20 μm or more, and, for example, 300 μm or less, preferably 150 μm or less, from the viewpoints of mechanical strength, scratch resistance, dot characteristics when the conductive film 1 is formed into a film for a touch panel, and the like.
The thickness of the transparent substrate 2 can be measured, for example, using a film thickness meter (digital dial gauge).
If necessary, an easy-adhesion layer, an adhesive layer, a spacer, or the like may be provided on the upper surface and/or the lower surface of the transparent base material 2.
3. Hard coating
The hard coat layer 3 is a scratch protective layer for preventing scratches from being generated on the surface of the conductive thin film 1 (i.e., the upper surface of the metal layer 6) when a plurality of conductive thin films 1 are stacked. In addition, it can also be used as the conductive film 1 to provide anti-blocking layer.
The hard coat layer 3 has a thin film shape, and is disposed on the entire upper surface of the transparent substrate 2 so as to be in contact with the upper surface of the transparent substrate 2, for example. More specifically, the hard coat layer 3 is disposed between the transparent substrate 2 and the optical adjustment layer 4 so as to be in contact with the upper surface of the transparent substrate 2 and the lower surface of the optical adjustment layer 4.
The hard coat layer 3 is formed of, for example, a hard coat composition. The hard coat composition contains, preferably consists of, a resin component.
Examples of the resin component include a curable resin, a thermoplastic resin (for example, a polyolefin resin), and the like, and a curable resin is preferably used.
Examples of the curable resin include, for example, an active energy ray-curable resin which is cured by irradiation with an active energy ray (specifically, ultraviolet ray, electron beam, or the like), a thermosetting resin which is cured by heating, and the like, and preferably an active energy ray-curable resin.
Examples of the active energy ray-curable resin include polymers having a functional group having a polymerizable carbon-carbon double bond in the molecule. Examples of such a functional group include a vinyl group, a (meth) acryloyl group (a methacryloyl group and/or an acryloyl group), and the like.
Specific examples of the active energy ray-curable resin include (meth) acrylic ultraviolet-curable resins such as urethane acrylate and epoxy acrylate.
Examples of the curable resin other than the active energy ray-curable resin include urethane resins, melamine resins, alkyd resins, siloxane polymers, and organosilane condensates.
These resin components may be used alone or in combination of 2 or more.
The resin component may contain a resin additive such as a polymerization initiator.
Examples of the polymerization initiator include radical polymerization initiators such as photopolymerization initiators and thermal polymerization initiators. These polymerization initiators may be used alone or in combination of 2 or more.
Examples of the photopolymerization initiator include benzoin ether compounds, acetophenone compounds, α -ketol compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzoin compounds, benzil compounds, benzophenone compounds, thioxanthone compounds, α -aminoketone compounds, and the like.
Examples of the thermal polymerization initiator include organic peroxides and azo compounds.
The hardcoat composition may contain particles.
Examples of the particles include inorganic particles and organic particles. Examples of the inorganic particles include Silica (SiO)2) Particles, e.g. comprising zirconium oxide (ZrO)2) Metal oxide particles such as titanium oxide, zinc oxide, and tin oxide, and carbonate particles such as calcium carbonate. Examples of the organic particles include crosslinked acrylic resin particles. The particles may be used singly or in combination of 2 or more.
The hard coat composition may further contain known additives such as a leveling agent, a thixotropic agent, and an antistatic agent.
The thickness of the hard coat layer 3 is, for example, 0.5 μm or more, preferably 1 μm or more, and is, for example, 10 μm or less, preferably 3 μm or less, and more preferably 2 μm or less. The thickness of the hard coat layer 3 can be measured, for example, using a film thickness meter (digital dial gauge).
4. Optical adjustment layer
The optical adjustment layer 4 is a layer for adjusting the refractive index of the conductive film 1 in order to suppress the pattern of the transparent conductive layer 5 from being recognized and to ensure excellent transparency of the conductive film 1. The optical adjustment layer 4 is also an adhesion layer for improving adhesion between the metal layer 6 side (particularly, the transparent conductive layer 5) of the conductive film 1 and the transparent substrate 2 side (particularly, the hard coat layer 3) and suppressing interlayer peeling inside the conductive film 1.
The optical adjustment layer 4 has a thin film shape, and is disposed on the entire upper surface of the hard coat layer 3 so as to be in contact with the upper surface of the hard coat layer 3, for example. More specifically, the optical adjustment layer 4 is disposed between the hard coat layer 3 and the transparent conductive layer 5 so as to be in contact with the upper surface of the hard coat layer 3 and the lower surface of the transparent conductive layer 5.
The optical adjustment layer 4 is formed of an optical adjustment composition. The optical adjustment composition contains an inorganic particle component and a resin component, and is preferably formed of an inorganic particle component and a resin component. That is, the optical adjustment layer 4 is a resin layer containing an inorganic particle component, and is preferably a resin layer formed of an inorganic particle component and a resin component.
Examples of the resin component include the same resin components as those used in the hard coat composition. The curable resin is preferably used, and the actinic radiation curable resin is more preferably used.
The content of the resin component is, for example, 34.0% by mass or more, preferably 40.0% by mass or more, and is, for example, 60.0% by mass or less, preferably 50.0% by mass or less, and more preferably 45.0% by mass or less with respect to the optical adjustment composition.
The inorganic particle component contains SiO2(silica) particles and ZrO2(zirconia) particles, preferably made of SiO2Particles and ZrO2And (4) forming particles.
SiO2Particles and ZrO2The particles are preferably all surface treated. Thus, SiO can be more reliably formed2Particles and ZrO2The particles are uniformly dispersed in the optical adjustment layer 4.
As SiO2Examples of the surface treatment agent used for the surface treatment of the particles include silane-based coupling agents, zirconium-based coupling agents, titanium-based coupling agents, phosphorus-based coupling agents, and combinations thereof.
In the present invention, SiO2The surface treatment of the particles is designed in such a way that they are uniformly dispersed in the optical adjustment layer 4. This can suppress SiO in the optical adjustment layer 42The unevenness of the particles is present to suppress the generation of the color tone of the optical adjustment layer 4.
As ZrO2Examples of the surface treatment agent used for the surface treatment of the particles include silane-based coupling agents, zirconium-based coupling agents, titanium-based coupling agents, phosphorus-based coupling agents, and combinations thereof.
SiO in the inorganic particle component2The content ratio of the particles is, for example, 1.0% by mass or more, preferably 5.0% by mass or more, more preferably 10.0% by mass or more, and is, for example, 50.0% by mass or less, preferably 40.0% by mass or less, more preferably 30.0% by mass or less. SiO 22When the content ratio of the particles is within the above range, the adhesion is excellent.
ZrO in the inorganic particle component2The content ratio of the particles is, for example, 50.0% by mass or more, preferably 60.0% by mass or more, more preferably 70.0% by mass or more, and is, for example, 99.0% by mass or less, preferably 95.0% by mass or less, more preferably 90.0% by mass or less. ZrO (ZrO)2When the content ratio of the particles is within the above range, the refractive index of the optical adjustment layer 4 can be increased, and the pattern of the transparent conductive layer 5 can be prevented from being recognized.
SiO2The average particle diameter of the particles is, for example, 1nm or more, preferably 5nm or more, and is, for example, 100nm or less, preferably 50nm or less.
ZrO2The average particle diameter of the particles is, for example, 10nm or more, preferably 20nm or more, and is, for example, 100nm or less, preferably 50nm or less.
The average particle diameter of the particles means the average particle diameter (D) of the particle size distribution on a volume basis50) For example, a solution in which particles are dispersed in water can be measured by a light diffraction/scattering method.
The content ratio of the inorganic particle component is, for example, 40.0 mass% or more, preferably 50.0 mass% or more, more preferably 55.0 mass% or more, and is, for example, 66.0 mass% or less, preferably 60.0 mass% or less with respect to the optical adjustment composition (further, the optical adjustment layer 4). When the content ratio of the inorganic particle component is not more than the upper limit, the adhesiveness is excellent. When the content ratio of the inorganic particle component is not less than the lower limit, the pattern of the transparent conductive layer 5 can be further inhibited from being recognized.
The Si element is present in a proportion of 20% or more, preferably 30% or more, for example 50% or less, preferably 40% or less, and more preferably 35% or less, in a range of 10nm from the upper surface (one surface in the thickness direction) 4a to the lower side (the other side in the thickness direction) of the optical adjustment layer 4, that is, in a range of 10nm from the upper surface of the optical adjustment layer 4 to the depth of 10 nm.
When the Si element is present in a ratio of at least the lower limit, adhesion between the transparent conductive layer 5 and the optical adjustment layer 4 can be improved, and peeling of the metal layer 6 can be suppressed.
In addition, the optical adjustment layer 4 is equally divided into 3 layers in the thickness direction. That is, the optical adjustment layer 4 is divided into an upper layer, an intermediate layer, and a lower layer uniformly in the vertical direction in a cross-sectional view. In this case, the difference between the Si element existing ratio of the layer having the highest Si element existing ratio (the maximum Si layer) and the Si element existing ratio of the layer having the lowest Si element existing ratio (the minimum Si layer) is 15% or less, preferably 10% or less, and more preferably 5% or less.
When the difference is not more than the upper limit, SiO can be used in the optical adjustment layer 42The particles are uniformly arranged in the thickness direction, and SiO can be inhibited2Variation in the reflectance spectrum caused by the non-uniform presence of particles. As a result, the occurrence of color tone of the optical adjustment layer 4 can be suppressed.
The Si element is present at a ratio (Si/Si + Zr) where the total element presence ratio of Si and Zr is 100%. That is, the Si element presence ratio is a ratio of the Si element presence amount when the total of the Si element presence amount and the Zr element presence amount is 100, and is calculated by (Si element presence/(Si element presence amount + Zr element presence amount) × 100).
The amounts of Si and Zr elements present (or the ratios of the elements present) were determined as follows: elemental analysis was performed using an energy-dispersive X-ray analysis system, and the elements (Si and Zr) were mapped to calculate the mapped areas.
The refractive index of the optical adjustment layer 4 is, for example, 1.60 or more, preferably 1.62 or more, and is, for example, 1.70 or less, preferably 1.68 or less. When the refractive index of the optical adjustment layer 4 is within the above range, the pattern of the transparent conductive layer 5 can be prevented from being recognized.
The refractive index can be measured, for example, by an Abbe refractometer at a wavelength of 589 nm.
The thickness of the optical adjustment layer 4 is, for example, 10nm or more, preferably 30nm or more, and is, for example, 300nm or less, preferably 150nm or less. When the thickness of the optical adjustment layer 4 is within the above range, the pattern of the transparent conductive layer 5 can be further inhibited from being recognized.
The thickness of the optical adjustment layer 4 can be measured by observing the cross section of the conductive thin film 1 using a transmission electron microscope, for example.
5. Transparent conductive layer
The transparent conductive layer 5 is a transparent conductive layer for forming a wiring pattern (patterned transparent conductive layer 5A described later) in a later step, for example, a wiring pattern (for example, electrode wiring) in a touch input region of a touch panel.
The transparent conductive layer 5 has a thin film shape, and is disposed on the entire upper surface of the optical adjustment layer 4 so as to be in contact with the upper surface of the optical adjustment layer 4, for example. More specifically, the transparent conductive layer 5 is disposed between the optical adjustment layer 4 and the metal layer 6 so as to be in contact with the upper surface of the optical adjustment layer 4 and the lower surface of the metal layer 6.
Examples of the material of the transparent conductive layer 5 include metal oxides containing at least 1 metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. The metal oxide may be further doped with a metal atom shown in the above group as necessary.
Examples of the material of the transparent conductive layer 5 include an indium-containing oxide such as Indium Tin Oxide (ITO) and an antimony-containing oxide such as Antimony Tin Oxide (ATO), and preferably an indium-containing oxide, and more preferably ITO.
When ITO is used as the material of the transparent conductive layer 5, tin oxide (SnO)2) The content of tin oxide and indium oxide (In)2O3) The total amount of (b) is, for example, 0.5% by mass or more, preferably 3% by mass or more, and is, for example, 15% by mass or less, preferably 13% by mass or less. When the content of tin oxide is not less than the lower limit, the durability of the ITO layer can be further improved. When the content of the tin oxide is not more than the upper limit, the crystal transformation of the ITO layer can be facilitated, and the stability of the transparency and the resistivity can be improved.
The "ITO" In the present specification may contain an additional component other than the compound oxide containing at least indium (In) and tin (Sn). Examples of the additional component include metal elements other than In and Sn, and specifically include Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, Cr, Ga, and the like.
The thickness of the transparent conductive layer 5 is, for example, 10nm or more, preferably 20nm or more, and is, for example, 50nm or less, preferably 30nm or less.
The thickness of the transparent conductive layer 5 can be measured by observing the cross section of the conductive thin film 1 using a transmission electron microscope, for example.
The transparent conductive layer 5 may be either crystalline or amorphous, or may be a mixture of crystalline and amorphous. The transparent conductive layer 5 is preferably formed of a crystalline material, more specifically, a crystalline ITO layer. This can improve the transparency of the transparent conductive layer 5 and further reduce the surface resistance value of the transparent conductive layer 5.
The transparent conductive layer 5 is crystalline, for example, as follows: when the transparent conductive layer 5 is an ITO layer, it is immersed in hydrochloric acid (concentration 5 mass%) at 20 ℃ for 15 minutes, washed with water and dried, and the inter-terminal resistance between about 15mm is measured. In the present specification, the ITO layer was judged to be crystalline when the resistance between the terminals between 15mm was 10 kOmega or less after immersion, washing with water and drying in hydrochloric acid (20 ℃ C., concentration: 5% by mass).
The surface resistance value of the transparent conductive layer 5 (particularly, crystalline ITO layer) is, for example, less than 100 Ω/□, preferably 80 Ω/□ or less, and, for example, 10 Ω/□ or more. The surface resistance value can be measured by a 4-terminal method in accordance with JIS K7194 (1994), for example.
6. Metal layer
The metal layer 6 is a conductive metal layer for forming a wiring pattern (patterned metal layer 6A described later) in a later process, for example, a wiring pattern (for example, routing wiring) forming an outer edge portion (outer peripheral edge portion) of an outer side (outer periphery) of a touch input region of the touch panel.
The metal layer 6 is the uppermost layer of the conductive thin film 1, has a thin film shape, and is disposed on the entire upper surface of the transparent conductive layer 5 so as to be in contact with the upper surface of the transparent conductive layer 5.
Examples of the material of the metal layer 6 include metals such as copper, nickel, chromium, iron, titanium, and alloys thereof. From the viewpoint of conductivity, copper is preferably used.
When the metal layer 6 is made of a material that is easily oxidized, such as copper, the surface of the metal layer 6 may be oxidized. Specifically, when the metal layer 6 is a copper layer, the metal layer 6 may be a copper layer having a copper oxide on a part or the whole of the surface.
The thickness of the metal layer 6 is, for example, 100nm or more, preferably 150nm or more, and is, for example, 400nm or less, preferably 300nm or less. When the thickness of the metal layer 6 is not less than the lower limit, the surface resistance value of the metal layer 6 can be reduced, and the conductivity is excellent. Therefore, a narrow and long wiring pattern (a routed wiring line of the frame portion) can be formed in response to an increase in size of the touch panel. When the thickness of the metal layer 6 is not more than the upper limit, the frame portion can be made thin.
The thickness of the metal layer 6 can be measured by observing the cross section of the conductive thin film 1 using a transmission electron microscope, for example.
7. Method for producing conductive thin film
In order to produce the conductive film 1, for example, in a roll-to-roll process, the hard coat layer 3, the optical adjustment layer 4, the transparent conductive layer 5, and the metal layer 6 are provided in this order on one surface of the transparent base material 2. Specifically, while the transparent substrate 2 long in the longitudinal direction is fed by a feed roller and conveyed to the downstream side in the conveying direction, the hard coat layer 3 is provided on the upper surface of the transparent substrate 2, the optical adjustment layer 4 is provided on the upper surface of the hard coat layer 3, the transparent conductive layer 5 is provided on the upper surface of the optical adjustment layer 4, the metal layer 6 is provided on the upper surface of the transparent conductive layer 5, and the conductive film 1 is wound by a winding roller.
The details will be described below.
First, a long transparent substrate 2 wound around a feed roller is prepared, and the transparent substrate 2 is conveyed so as to be wound around a take-up roller.
Thereafter, from the viewpoint of adhesion between the transparent base material 2 and the hard coat layer 3, the surface of the transparent base material 2 may be subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, or oxidation, or undercoating treatment, as necessary. The transparent base material 2 may be cleaned or dedusted by solvent cleaning, ultrasonic cleaning, or the like.
Next, the hard coat layer 3 is provided on the upper surface of the transparent base material 2. For example, the hard coating composition is wet-coated on the upper surface of the transparent substrate 2, thereby forming the hard coating layer 3 on the upper surface of the transparent substrate 2.
Specifically, for example, a hard coat composition coating liquid is prepared by diluting a hard coat composition with a solvent, and then the coating liquid is applied to the upper surface of the transparent substrate 2 and dried.
Examples of the solvent include an organic solvent and an aqueous solvent (specifically, water), and preferably an organic solvent. Examples of the organic solvent include alcohol compounds such as methanol, ethanol, and isopropanol, ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester compounds such as ethyl acetate and butyl acetate, ether compounds such as propylene glycol monomethyl ether, and aromatic compounds such as toluene and xylene. These solvents may be used alone or in combination of 2 or more. Preferred examples thereof include ester compounds and ether compounds.
The solid content concentration in the coating liquid is, for example, 1 mass% or more, preferably 10 mass% or more, and is, for example, 30 mass% or less, preferably 20 mass% or less.
The coating method can be appropriately selected depending on the coating liquid and the transparent substrate 2. Examples thereof include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire bar coating method, a gravure coating method, and an ink jet method.
The drying temperature is, for example, 50 ℃ or higher, preferably 60 ℃ or higher, for example 200 ℃ or lower, preferably 150 ℃ or lower.
The drying time is, for example, 0.5 minutes or more, preferably 1 minute or more, for example 60 minutes or less, preferably 20 minutes or less.
Thereafter, when the hard coat composition contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating active energy rays after the coating liquid is dried.
When the hard coating composition contains a thermosetting resin, the drying step can dry the solvent and thermally cure the thermosetting resin.
Next, the optical adjustment layer 4 is provided on the upper surface of the hard coat layer 3. For example, the optical adjustment composition is wet-coated on the upper surface of the hard coat layer 3, whereby the optical adjustment layer 4 is formed on the upper surface of the hard coat layer 3.
Specifically, for example, an optical adjustment composition coating liquid prepared by diluting an optical adjustment composition with a solvent is prepared as necessary, and then the coating liquid is applied to the upper surface of the hard coat layer 3 and dried.
Examples of conditions for preparing, coating, and drying the optical adjustment composition include the same conditions for preparing, coating, and drying as exemplified for the hard coat composition.
Then, when the optical adjustment composition contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating active energy rays after the coating liquid is dried.
In addition, when the optical adjustment composition contains a thermosetting resin, the thermosetting resin can be thermally cured simultaneously with drying of the solvent in the drying step.
In particular, in the present invention, the following optical conditioning compositions are used as the optical conditioning composition: when the optical adjustment layer is equally divided into 3 layers in the thickness direction, the difference between the proportion of Si element present in the layer having the highest proportion of Si element present and the proportion of Si element present in the layer having the lowest proportion of Si element present is 15% or less. Such optical conditioning composition is prepared by mixing SiO2Particles, ZrO2The particles and the resin component may be appropriately selected from known or commercially available functional coating materials for optical use. As such optical functionSpecific examples of the coating material include "RA 026" and "RA 043" manufactured by seikagawa chemical corporation.
Next, the transparent conductive layer 5 is provided on the upper surface of the optical adjustment layer 4. The transparent conductive layer 5 is formed on the upper surface of the optical adjustment layer 4 by, for example, a dry method.
Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method. A sputtering method is preferably used. By this method, the transparent conductive layer 5 can be formed to be thin and uniform in thickness.
In the sputtering method, a target and an adherend (transparent base material 2 on which an optical adjustment layer 4 and a hard coat layer 3 are laminated) are placed in opposition to each other in a vacuum chamber, and a gas is supplied and a voltage is applied from a power source, whereby gas ions are accelerated and irradiated onto the target, and a target material is ejected from the target surface and laminated on the adherend surface.
Examples of the sputtering method include a diode sputtering method, an ECR (electron cyclotron resonance) sputtering method, a magnetron sputtering method, and an ion beam sputtering method. A magnetron sputtering method is preferably used.
In the case of the sputtering method, the target material may be the metal oxide constituting the transparent conductive layer 5, and ITO is preferably used. The tin oxide concentration of the ITO is, for example, 0.5 mass% or more, preferably 3 mass% or more, and, for example, 15 mass% or less, preferably 13 mass% or less, from the viewpoint of durability, crystallization, and the like of the ITO layer.
Examples of the gas include inert gases such as Ar. Further, reactive gases such as oxygen may be used in combination as necessary. When the reactive gases are used in combination, the flow rate (sccm) of the reactive gas is not particularly limited, and is, for example, 0.1 to 5% by flow rate based on the total flow rate of the sputtering gas and the reactive gas.
The gas pressure during sputtering is, for example, 1Pa or less, preferably 0.1Pa or more and 0.7Pa or less, from the viewpoints of suppressing a decrease in sputtering rate, discharge stability, and the like.
The power source may be any of a DC power source, an AC power source, an MF power source, and an RF power source, for example, or a combination thereof.
Next, a metal layer 6 is provided on the upper surface of the transparent conductive layer 5. The metal layer 6 is formed on the upper surface of the transparent conductive layer 5 by, for example, a dry method.
The dry method may be the same as the method described above for forming the transparent conductive layer 5, and preferably a sputtering method. By this method, the metal layer 6 having a uniform thickness even if it is thick can be formed.
The conditions of the sputtering method for the metal layer 6 may be the same as those exemplified for the formation of the transparent conductive layer 5.
The target material may be the metal constituting the metal layer 6, and preferably copper.
Thus, as shown in fig. 1, a conductive film 1 including a transparent base 2, a hard coat layer 3, an optical adjustment layer 4, a transparent conductive layer 5, and a metal layer 6 was obtained.
If necessary, the transparent conductive layer 5 of the conductive thin film 1 may be subjected to crystal conversion treatment. The crystal conversion treatment may be performed on the obtained conductive thin film 1, or may be performed on the conductive thin film 1 (intermediate laminate, that is, laminate of the transparent substrate 2, the hard coat layer 3, the optical adjustment layer 4, and the transparent conductive layer 5) before the metal layer 6 is laminated.
Specifically, the conductive thin film 1 or the intermediate laminate is subjected to heat treatment in the air.
The heat treatment can be performed using, for example, an infrared heater, an oven, or the like.
The heating temperature is, for example, 100 ℃ or higher, preferably 120 ℃ or higher, and is, for example, 200 ℃ or lower, preferably 160 ℃ or lower. When the heating temperature is within the above range, the crystal transformation can be reliably performed while suppressing thermal damage to the transparent substrate 2 and impurities generated from the transparent substrate 2.
The heating time is suitably determined depending on the heating temperature, and is, for example, 10 minutes or more, preferably 30 minutes or more, and is, for example, 5 hours or less, preferably 3 hours or less.
This can provide the conductive film 1 having the crystallized transparent conductive layer 5.
In the above step, the sheet may be wound around a take-up roll for each layer to be formed. Further, the process may be continuously performed without winding until the hard coat layer 3, the optical adjustment layer 4, the transparent conductive layer 5, and the metal layer 6 are formed, and may be wound around a winding roll after the metal layer 6 is formed.
If necessary, the transparent conductive layer 5 and/or the metal layer 6 may be patterned into a wiring pattern such as a stripe pattern by a known etching method before or after the crystal conversion treatment.
When the transparent conductive layer 5 and the metal layer 6 are etched, they may be etched at the same time, or may be etched separately, and it is preferable that they are etched separately from the viewpoint that the transparent conductive layer 5 and the metal layer 6 can be reliably patterned separately.
For example, first, the metal layer 6 (particularly, the central portion in a plan view) is removed by etching so that a desired wiring pattern (for example, lead wiring) is formed on the peripheral end portion (for example, the region corresponding to the lead wiring) in a plan view of the metal layer 6. Next, the transparent conductive layer 5 exposed from the metal layer 6 (particularly, the central portion in a plan view) is removed by etching so as to form a desired wiring pattern (for example, a wiring pattern in the touch input region).
As a result, as shown in fig. 2, a patterned conductive film 1A including a transparent substrate 2, a hard coat layer 3, an optical adjustment layer 4, a patterned transparent conductive layer 5A, and a patterned metal layer 6A was obtained as an embodiment of the conductive film 1.
The patterned metal layer 6A forms a frame portion having a frame shape in plan view, and the patterned transparent conductive layer 5A forms a predetermined wiring pattern in the patterned metal layer 6A.
8. Touch panel
The conductive film 1 is used, for example, as a base material for a touch panel provided in an image display device. Examples of the form of the touch panel include various forms such as a capacitance type and a resistance film type, and the touch panel is particularly preferably used for a capacitance type touch panel. Specifically, the patterned conductive thin film 1A is disposed on a protective base material such as a protective glass, and used as a touch panel.
The conductive thin film 1 can be suitably used for flexible display elements such as an electrophoretic display device, a twist ball display device, a thermal rewritable display device, an optical writing liquid crystal display device, a polymer dispersed liquid crystal display device, a guest host liquid crystal display device, a toner display device, a color changing device, and an electric field deposition device.
9. Effect of action
The conductive film 1 includes a transparent substrate 2, an optical adjustment layer 4, a transparent conductive layer 5, and a metal layer 6 in this order toward the upper side. Further, the optical adjustment layer 4 contains SiO2Particles, ZrO2Granules and a resin component. Therefore, it is possible to suppress recognition of a wiring pattern (e.g., a pattern in a touch input region of a touch panel; the transparent conductive layer 5A is patterned) when the transparent conductive layer 5 is formed into the wiring pattern.
In the range from the upper surface 4a of the optical adjustment layer 4 to the lower side 10nm, the Si element presence ratio is 20% or more when the total element presence ratio of Si and Zr is 100%.
Therefore, the adhesion at the interface between the transparent conductive layer 5 (inorganic layer) and the optical adjustment layer 4 (organic layer) is improved. Therefore, the metal layer 6 can be prevented from peeling off from the transparent substrate 2 together with the optical adjustment layer 4.
When the optical adjustment layer 4 is divided into 3 layers evenly in the thickness direction, the difference between the Si element existing ratio of the layer having the highest Si element existing ratio and the Si element existing ratio of the layer having the lowest Si element existing ratio is 15% or less. Thus, in the optical adjustment layer 4, SiO2The particles are uniformly present in the thickness direction, and SiO can be inhibited2The change in the optical characteristics of the optical adjustment layer 4 due to the presence of the unevenness of the particles can suppress the occurrence of color tones in particular.
It is noted that, in order to adjust the layer to the optical system4 to impart an adhesion function, the inventors of the present invention have studied to provide ZrO with2SiO is blended in the optical adjustment layer 4 of the particles2Grains, as a result, it was newly found that2Particles and SiO2Relationship of particles, SiO2The particles are present unevenly in the thickness direction, and thus influence the optical characteristics of the optical adjustment layer 4. Specifically, it was found that only ZrO was present2Particles as inorganic particles the peak position of the reflection spectrum of the optical adjustment layer 4 is formed by compounding SiO2The particles change greatly, and the color tone of the optical adjustment layer 4 is affected. Based on this finding, the present inventors have focused on the presence ratio of the Si element in the optical adjustment layer 4, and have adopted the above-described configuration, thereby suppressing the reduction in the optical characteristics of the optical adjustment layer 4 and the peeling of the metal layer 6.
< modification example >
In the embodiment shown in fig. 1, the conductive thin film 1 is provided with the hard coat layer 3, and for example, as shown in fig. 3, the conductive thin film 1 may not be provided with the hard coat layer 3.
That is, the conductive film 1 shown in fig. 3 includes a transparent substrate 2, an optical adjustment layer 4, a transparent conductive layer 5, and a metal layer 6.
In the embodiment shown in fig. 2, the patterned conductive thin film 1 includes the hard coat layer 3, but for example, as shown in fig. 4, the conductive thin film 1 may not include the hard coat layer 3. That is, the conductive film 1 shown in fig. 4 includes a transparent base 2, an optical adjustment layer 4, a patterned transparent conductive layer 5A, and a patterned metal layer 6A.
This embodiment also exhibits the same operational advantages as the embodiment shown in fig. 1 and 2. From the viewpoint of scratch resistance, the embodiments shown in fig. 1 and 3 are preferable.
In the embodiment shown in fig. 1 and 2, the lower surface of the transparent base material 2 is exposed, but for example, although not shown, all or a part of the hard coat layer 3, the optical adjustment layer 4, the transparent conductive layer 5, and the metal layer 6 may be further provided on the lower surface of the transparent base material 2.
This embodiment also exhibits the same operational advantages as the embodiment shown in fig. 1 and 2.
[ examples ]
The present invention will be described more specifically below with reference to examples and comparative examples. The present invention is not limited to the examples and comparative examples. Specific numerical values such as the blending ratio (content ratio), the physical property value, and the parameter used in the following description may be replaced with upper limit values (numerical values defined as "lower" or "lower") or lower limit values (numerical values defined as "upper" or "lower" or "upper" of the above-mentioned description such as the blending ratio (content ratio), the physical property value, and the parameter described in the above-mentioned "specific embodiment" in correspondence with them.
(example 1)
As a long transparent substrate, a cycloolefin polymer film (COP film, manufactured by Nippon Zeon corporation, "ZEONOR ZF 16") having a thickness of 55 μm was prepared.
A hard coat composition coating solution was prepared by mixing 100 parts by mass of an ultraviolet-curable acrylic resin (ELS 888, available from DIC Co., Ltd.), 2 parts by mass of a photopolymerization initiator (Irgacure 184, available from BASF Co., Ltd.) and 160 parts by mass of ethyl acetate. The hard coat composition coating liquid was applied to the upper surface of the COP film, dried at 80 ℃ for 1 minute, and irradiated with ultraviolet rays. Thereby, a hard coat layer having a thickness of 2 degrees was formed on the upper surface of the COP film.
An optical adjustment composition coating solution was prepared by mixing 700 parts by mass of propylene glycol monomethyl ether with 100 parts by mass of an optical adjustment composition (RA 026, manufactured by Mitsugawa chemical industries, Ltd.). The optical control composition coating liquid was applied on the upper surface of the hard coat layer, dried at 60 ℃ for 1 minute, and irradiated with ultraviolet rays. Thus, an optical adjustment layer having a thickness of 80nm was formed on the upper surface of the hard coat layer.
The solid content of the optical control composition (manufactured by mitaka chemical industry co., "RA 026") was 59.5 mass% of the inorganic particle component and 40.5 mass% of the resin component (acrylic ultraviolet-curable resin). Further, the ratio of the inorganic particle component is SiO214.25% by mass of particles (average particle diameter 10nm) and ZrO2Particles (average particle diameter 25nm) 85.75% by mass.
Next, the laminate of COP film/hard coat layer/optical adjustment layer was put into a roll-to-roll sputtering apparatus, and an ITO layer (amorphous) having a thickness of 30nm was formed on the upper surface of the optical adjustment layer. Specifically, the optical adjustment layer was sputtered under a vacuum atmosphere of 0.4Pa in which 98% argon gas and 2% oxygen gas were introduced, using an ITO target formed of a sintered body of 97% by mass of indium oxide and 3% by mass of tin oxide.
Next, the laminate of COP film/hard coat layer/optical adjustment layer/ITO layer (amorphous) was put into a take-up sputtering apparatus, and a copper layer having a thickness of 200nm was formed on the upper surface of the ITO layer. Specifically, the ITO layer was sputtered in a vacuum atmosphere of 0.4Pa of pressure into which argon gas was introduced, using a Cu target made of oxygen-free copper.
Thus, the conductive thin film of example 1 was produced.
(example 2)
A conductive thin film was produced in the same manner as in example 1, except that "RA 043" manufactured by seikagawa chemical industries, co.
The solid content of "RA 043" manufactured by seikagawa chemical industries co., ltd.is 53.5 mass% of the inorganic particle component and 46.5 mass% of the resin component (acrylic ultraviolet curable resin). Further, the ratio of the inorganic particle component is SiO226.63% by mass of particles (average particle diameter 10nm) and ZrO273.37% by mass of particles (average particle diameter 25 nm). SiO 22Particles and ZrO2The particles were subjected to the same surface treatment as in example 1.
Comparative example 1
A conductive film was produced in the same manner as in example 1, except that "OPSTAR KZ 6961" manufactured by mithrawa chemical industries, ltd.c. was used as the optical adjustment composition for forming the optical adjustment layer.
The solid content of "OPSTAR KZ 6961" manufactured by Mitsuwa chemical industries, Ltd., was 59.5 mass% of the inorganic particle component and the resin component (acrylic ultraviolet-curable resin)) 40.5% by mass. Further, the ratio of the inorganic particle component is SiO2(average particle diameter 10nm) 14.25% by mass and ZrO2Particles (average particle diameter 25nm) 85.75% by mass.
Comparative example 2
A conductive film was produced in the same manner as in example 1, except that "TYZ 64-a 03" manufactured by tyo INK co.
Comparative example 3
A conductive thin film was produced in the same manner as in example 1, except that "RA 001" manufactured by seikagawa chemical industries, co.
The solid content of "RA 001" manufactured by seikagawa chemical industries co., ltd.is 53.5 mass% of the inorganic particle component and 46.5 mass% of the resin component (acrylic ultraviolet curable resin). Further, the ratio of the inorganic particle component is SiO226.63% by mass of particles (average particle diameter 10nm) and ZrO273.37% by mass of particles (average particle diameter 25 nm).
Comparative example 4
A conductive film was produced in the same manner as in example 1, except that "OPSTAR KZ 6956" manufactured by seikagawa chemical co.
The solid content of "opsar KZ 6956" manufactured by seikagawa chemical industries co., ltd "was 51.7 mass% of the inorganic particle component and 48.3 mass% of the resin component (acrylic ultraviolet curable resin). In addition, the proportion of the inorganic particle component is ZrO2100% by mass of particles (average particle diameter 25 nm).
(thickness of each layer)
The thickness of the layer less than 1.0 μm was measured by observing the cross section of the conductive film using a transmission electron microscope (manufactured by Hitachi, Ltd. "H-7650"). The thickness of the layer having a thickness of 1.0 μm or more was measured by using a film thickness meter (digital dial gauge DG-205 manufactured by Peacock).
(refractive index of optical adjustment layer)
The refractive index of the optical adjustment layer at a wavelength of 589nm was measured using an abbe refractometer (ATAGO co., ltd.). The results are shown in Table 1.
(elemental analysis of optical adjustment layer)
Ultrathin-sliced samples were prepared from the conductive films obtained in the examples and comparative examples by means of a microtome (UC 7, manufactured by Leica microorganisms). Elemental analysis of Si and Zr was performed on the optical adjustment layer portion of the sample by using an energy dispersive X-ray analysis System ("NORAN System 7", manufactured by Thermo Fisher scientific Co., Ltd.). Then, element mapping is performed by software installed in the X-ray analysis system, and the element existence ratio of Si is calculated.
In this case, the Si element and the Zr element in the optical adjustment layer are colored green and red, respectively, and the green area and the red area are defined as the Si element existing amount and the Zr element existing amount, respectively. Then, the total of the amount of Si element and the amount of Zr element was set to 100, and the ratio of the amount of Si element was calculated. That is, the Si element existence ratio is calculated by the formula "Si element existence amount/(Si element existence amount and Zr element existence amount) × 100".
The presence ratio of the Si element was calculated for each of the 3 layers by dividing each optical adjustment layer into 3 parts of the upper layer, the intermediate layer, and the lower layer uniformly in the vertical direction.
The Si content was calculated in the same manner for the range from the upper surface of the optical adjustment layer to the depth of 10 nm.
The results are shown in Table 1. Fig. 5 to 7 show images obtained by element mapping TEM cross-sectional views of the optical adjustment layers of example 1, comparative example 2, and comparative example 3.
(adhesion; non-peeling property of copper layer)
The surfaces of the copper layers of the conductive films obtained in the examples and comparative examples were cut into a checkered pattern by a dicing blade so that 100 pieces of 1mm square checkered patterns (10 rows × 10 columns) were formed. Subsequently, the following procedure was repeated 2 times: an adhesive tape (manufactured by waterlogging chemical industries, Ltd. "Cellotape (registered trademark) No. 252") was attached to the surface of the copper layer from which the slit was cut, and then peeled off. The surface of the copper layer at this time was visually observed, and adhesion was evaluated as follows. The results are shown in Table 1.
5: peeling of the copper layer was not observed at all (peeling area less than 1%).
4: the degree of defect (peeling area of 1% or more and less than 10%) was observed around the cut of the checkerboard.
3: the copper layer has a peeling area of 10% or more and less than 40%.
2: the copper layer has a peeling area of 40% or more and less than 60%.
1: the copper layer has a peeling area of 60% or more and less than 80%.
0: the copper layer has a peeling area of 80% or more.
(optical characteristics of optical adjustment layer: change in Peak reflectance)
In each of examples and comparative examples, a film (a laminate of COP film/hard coat layer/optical adjustment layer) before forming a copper layer and an ITO layer was prepared. A reflectance spectrum of each film at a wavelength of 200nm to 800nm was obtained by a spectrophotometer ("U4100", manufactured by Hitachihigh-Technologies Corporation). The reflectance spectra of the examples and comparative examples were superimposed such that the bottom positions of the reflectance spectra were coincident with each other. Next, the reflectance spectrum (ZrO) of comparative example 4 was calculated2Spectrum of 100 mass% of particles) and reflectance at the maximum peak position of the reflectance spectrum of each example and each comparative example.
The evaluation results are shown in table 1, with the difference in the maximum peak reflectance being less than 1.0%, △ when the difference is 1.0% or more and less than 5.0%, and x when the difference is 5.0% or more.
The larger the difference in the maximum peak reflectance of the reflectance spectrum, the larger the difference from the conventional optical adjustment layer (containing 100 mass% of ZrO as inorganic particles)2Particles) have more different optical characteristics, and therefore, more color tones (cyan and yellow colors) are generated. Therefore, it is required to be preferably less than 1.0%.
(suppression of Pattern recognition)
The conductive films obtained in the examples and comparative examples were cut into pieces of 10cm × 10cm, a dry film resist of a predetermined pattern was disposed on the metal layer of the conductive film, only the metal layer was etched, and then the resist was removed. Thus, the metal layer corresponding to the lead wiring of the frame is patterned only at the peripheral edge.
Next, a dry film resist of a predetermined pattern is disposed on the ITO layer of the conductive thin film except for the frame in the center in a plan view, and after etching only the ITO layer, the resist is removed. Thereby, the ITO layer corresponding to the wiring pattern is patterned at the center in a plan view (see fig. 2).
The wiring pattern of the resulting patterned conductive film was visually observed from a direction inclined at 45 degrees under an LED light source.
The results are shown in table 1, in which ○ represents the case where no wiring pattern was confirmed, △ represents the case where a wiring pattern was slightly confirmed, and x represents the case where a wiring pattern was clearly confirmed.
[ Table 1]
Figure BDA0002257804790000251

Claims (4)

1. A conductive film comprising a transparent substrate, an optical adjustment layer, a transparent conductive layer and a metal layer in this order in one direction of the thickness direction,
the optical adjustment layer contains SiO2Particles, ZrO2A particulate and a resin component, wherein the resin component,
the Si element existing proportion is more than 20% when the total element existing proportion of Si and Zr is 100% in the range from one surface of the optical adjustment layer in the thickness direction to the other side of the optical adjustment layer in the thickness direction by 10nm,
when the optical adjustment layer is divided into 3 layers evenly in the thickness direction, the difference between the Si element existing ratio of the layer having the highest Si element existing ratio and the Si element existing ratio of the layer having the lowest Si element existing ratio is 15% or less.
2. The conductive film according to claim 1, wherein the thickness of the optical adjustment layer is 30nm or more and 150nm or less.
3. The conductive film according to claim 1 or 2, further comprising a hard coat layer disposed between the transparent substrate and the optical adjustment layer.
4. A touch panel comprising the conductive thin film according to any one of claims 1 to 3.
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Application publication date: 20200512