TW201945763A - Hard coating film, transparent conductive film, transparent conductive film laminate, and image display device including a transparent substrate and a hard coat layer disposed on one side in a thickness direction of the transparent substrate - Google Patents

Abstract

A hard coating film of the present invention includes a transparent substrate and a hard coat layer disposed on one side in a thickness direction of the transparent substrate. The hard coat layer contains silicon dioxide particles, zirconia particles, and a resin. The content ratio of silicon dioxide particles in the hard coat layer is more than 0.5% or more by mass, and less than 3.0% by mass. The content ratio of the zirconia particles in the hard coat layer is 35.0% or more by mass, and less than 70.0% by mass.

Description

Hard coating film, transparent conductive film, transparent conductive film laminate, and image display device

The present invention relates to a hard coating film, a transparent conductive film, a transparent conductive film laminate, and an image display device.

Previously, a transparent conductive film in which a transparent conductive layer such as an indium tin composite oxide was formed on a transparent substrate so as to become a desired electrode pattern was used for optical applications such as a touch panel.

For example, Japanese Patent Laid-Open No. 2017-62609 discloses a transparent conductive film having a transparent resin film, a hard coat layer, an optical adjustment layer, and a transparent conductive layer in this order. In such a transparent conductive film, a hard coat layer is provided to impart scratch resistance to the transparent conductive film, and an optical adjustment layer is provided to prevent the electrode pattern from being recognized. Furthermore, in this transparent conductive film, a transparent conductive layer is laminated on a transparent substrate having good mechanical strength such as PET (polyethylene terephthalate).

However, in recent years, the difference between the amount of light passing through the electrode pattern (patterned portion) and the amount of light passing through portions other than the electrode pattern (non-patterned portion) can be reduced (halved), and it is easy to suppress the recognition of the electrode pattern. An image display device in which a transparent conductive film is arranged on the liquid crystal cell side (opposite to the viewing side) than the polarizing film is studied.

In such an image display device, since the polarized light passing through the polarizing film passes through the transparent conductive film, from the viewpoint of suppressing the elimination of polarized light, the transparent substrate must be a substrate with a low phase difference (for example, zero phase difference). membrane). Examples of such a base film having a low phase difference include a cycloolefin-based resin.

However, this cycloolefin-based resin is inferior in mechanical strength compared to PET and the like, so that it may cause a problem that it is easy to break when bent. Therefore, it is required to improve the cracking of the substrate.

On the other hand, if the formulation of the hard coat layer or the optical adjustment layer is changed in order to improve the cracking of the substrate, defects such as scratch resistance of the transparent conductive layer or visual suppression of the pattern may not reach the required level. In addition, the transparent conductive film also requires physical properties such as moist heat resistance, patterning property, and alkali resistance.

The present invention provides a hard coating film, a transparent conductive film, a transparent conductive film laminate, and an image display device that satisfy various physical properties required for optical applications while suppressing the cracking of the substrate.

The present invention [1] includes a hard coating film including a transparent substrate and a hard coating layer disposed on one side in the thickness direction of the transparent substrate, wherein the hard coating layer includes silica particles, zirconia particles, and a resin. The content ratio of the silicon dioxide particles in the hard coat layer is 0.5 mass% or more and less than 3.0 mass%, and the content ratio of the zirconia particles in the hard coat layer is 35.0 mass% or more and less than 70.0 mass. %.

The present invention [2] includes the hard coat film according to [1], wherein the transparent substrate is a cycloolefin-based substrate.

The present invention [3] includes the hard coating film according to [1] or [2], wherein the total content ratio of the silicon dioxide particles and the zirconia particles in the hard coating layer is 65.0% by mass or less.

The present invention [4] includes the hard coating film according to any one of [1] to [3], wherein the elastic modulus of the hard coating film is 4.2 GPa or more.

The present invention [5] includes the hard coating film according to any one of [1] to [4], wherein a thickness of the hard coating film is 0.7 μm or more and 2.0 μm or less.

The present invention [6] includes a transparent conductive film including the hard coating film according to any one of [1] to [4], and a transparent conductive layer disposed on one side in the thickness direction of the hard coating film.

The present invention [7] includes a transparent conductive film laminate including a polarizing element and the transparent conductive film according to [6].

The present invention [8] includes an image display device including an image display element and the transparent conductive film laminate according to claim 7, wherein the transparent conductive film is disposed on the polarizing element and the image display element. between.

The hard coating film, the transparent conductive film, the transparent conductive film laminate, and the image display device of the present invention include a transparent substrate and a hard coating layer, and the hard coating layer includes silicon dioxide particles, zirconia particles, and a resin. The content ratio of silicon dioxide particles in the hard coat layer is 0.5% by mass or more and less than 3.0% by mass, and the content ratio of zirconia particles in the hard coat layer is 35.0% by mass or more and less than 70.0% by mass. That is, in the hard coat film, the transparent conductive film, the transparent conductive film laminate, and the image display device of the present invention, the silica particles and zirconia particles in the hard coat layer exist at a specific content ratio. Therefore, while suppressing the cracking of the substrate, it satisfies various physical properties required for optical applications (when a laminated conductive layer has a transparent conductive layer, it is a visual suppression of a pattern, abrasion resistance, moist heat resistance, patterning resistance, and alkali resistance).

One embodiment of each of the hard coat film, the transparent conductive film, the transparent conductive film laminate, and the image display device of the present invention will be described with reference to FIGS. 1 to 4.

In FIG. 1, the upper and lower directions on the paper surface are the up and down directions (thickness direction, first direction), the upper side of the paper surface is the upper side (thickness side, first direction side), and the lower side of the paper surface is the lower side (the other side in the thickness direction, 1st direction on the other side). The left-right direction and the depth direction of the paper surface are plane directions orthogonal to the up-down direction. Specifically, according to the direction arrow of each figure.

1. Hard Coating Film As shown in FIG. 1, the hard coating film 1 has a film shape (including a sheet shape) having a specific thickness, extends in a specific direction (plane direction) orthogonal to the thickness direction, and has a flat upper surface. And flat undersurface.

The hard coating film 1 is a film with a hard-coat layer provided with the transparent base material 2 and the hard-coat layer 3 arrange | positioned on the upper surface (one side of thickness direction) of the transparent base material 2. Preferably, the hard coating film 1 includes a transparent substrate 2 and a hard coating layer 3.

(Transparent substrate)
The transparent substrate 2 is a transparent substrate for ensuring the mechanical strength of the hard coating film 1 (and the transparent conductive film 4). That is, the transparent base material 2 supports the hard coat layer 3, and the following transparent conductive film 4 supports the following transparent conductive layer 5 and the hard coat layer 3 together.

The transparent substrate 2 is the lowermost layer of the hard coating film 1 and has a film shape. The transparent substrate 2 is arranged on the entire lower surface of the hard coating layer 3 so as to be in contact with the lower surface of the hard coating layer 3.

The transparent substrate 2 is, for example, a polymer film having transparency. Examples of the material of the transparent substrate 2 include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; for example, polymethacrylic acid (Meth) acrylic resins such as esters (acrylic resins and / or methacrylic resins); for example, olefin resins such as polyethylene, polypropylene, and cycloolefin polymers (such as norbornene and cyclopentadiene); For example, polycarbonate resin, polyether resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, cellulose resin, polystyrene resin, and the like. The transparent base material 2 can be used individually or in combination of 2 or more types.

The transparent substrate 2 is preferably a cycloolefin-based substrate (COP substrate) formed of a cycloolefin polymer. When a COP substrate is used as the transparent substrate 2, the transparency is excellent. In addition, since the COP substrate has a low in-plane birefringence and a phase difference of substantially zero, the transparent conductive film laminate 8 described below can suppress the elimination of polarized light from passing through the polarizing element 10, and can reliably pass the polarized light. .

The total light transmittance (JIS K 7375-2008) of the transparent substrate 2 is, for example, 80% or more, and preferably 85% or more.

The in-plane birefringence of the transparent substrate 2 is, for example, 10 nm or less, and preferably 5 nm or less. The in-plane birefringence can be measured, for example, by a birefringence measurement system (manufactured by Axometrics, trade name "AxoScan").

From the viewpoints of mechanical strength and dot characteristics when the transparent conductive film 4 is used as a film for a touch panel, the thickness of the transparent substrate 2 is, for example, 2 μm or more, preferably 20 μm or more, and, for example, 300 μm Hereinafter, it is preferably 150 μm or less. The thickness of the transparent substrate 2 can be measured using, for example, a micrometer-type thickness meter.

(Hard coating)
The hard coat layer 3 is a layer for suppressing breakage of the transparent substrate 2. The hard coat layer 3 is also a layer for suppressing damage to the transparent conductive layer 5 when the transparent conductive layer 5 is arranged.

The hard coat layer 3 is the uppermost layer of the hard coat film 1 and has a film shape. The hard coat layer 3 is arranged 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.

The hard coat layer 3 is a hardened resin layer and is formed of a hard coat composition. The hard coating composition contains a resin and inorganic particles.

Examples of the resin include a curable resin, a thermoplastic resin (for example, a polyolefin resin), and the like, preferably a curable resin.

Examples of the curable resin include active energy ray-curable resins that are cured by irradiation with active energy rays (specifically, ultraviolet rays, electron beams, and the like), and thermosetting resins that are cured by heating. Preferred examples include active energy ray-curable resins.

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 vinyl, (meth) acrylfluorenyl (methacrylfluorenyl and / or acrylfluorenyl), and the like.

Specific examples of the active energy ray-curable resin include (meth) acrylic UV-curable resins such as acrylic urethane and epoxy acrylate.

Examples of the curable resin other than the active energy ray curable resin include a urethane resin, a melamine resin, an alkyd resin, a siloxane polymer, and an organic silane condensate.

These resins can be used alone or in combination of two or more.

The content ratio of the resin is, for example, 30.0 mass% or more, preferably 35.0 mass% or more, and, for example, 60.0 mass% or less, and preferably 50.0 mass% or less with respect to the hard coating composition (that is, the hard coat layer 3). It is more preferably 38.0% by mass or less. When the said ratio is more than the said minimum, the flexibility of the hard-coat film 1 is excellent. Moreover, if the said ratio is below the said upper limit, since deterioration of the resin (hard coat layer 2) under high temperature and high humidity can be reduced, it is excellent in the wet heat resistance in the transparent conductive film 4.

Examples of the inorganic particles include silicon dioxide (SiO ₂ ) particles and zirconia (ZrO ₂ ) particles. By having both the silicon dioxide particles and the zirconia particles in the hard coat layer 3, cracking of the transparent substrate 2 can be suppressed. Further, in the transparent conductive film 4 in which the transparent conductive layer 5 is laminated on the hard coat layer 3, the visibility of the pattern portion 6 (described below) can be suppressed or scratch resistance, moist heat resistance, patterning properties, and the like can be improved. Moreover, since the optical adjustment function can be provided to the hard-coat layer 3, it is not necessary to provide an optical adjustment layer separately, and thin film formation and productivity improvement can be achieved.

The average particle diameter of the silicon dioxide particles is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 50 nm or less, preferably 20 nm or less, and more preferably 15 nm or less.

The average particle diameter of the inorganic particles (silicon dioxide particles, zirconia particles, etc.) refers to the average particle diameter (D ₅₀ ) of the particle size distribution based on the volume basis. For example, light scattering and scattering methods can be used for particles dispersed in water. The solution was measured.

The content ratio of the silicon dioxide particles is 0.5% by mass or more and less than 3.0% by mass based on the hard coating composition. It is preferably 1.0% by mass or more and 2.8% by mass or less. When the content ratio of the silicon dioxide particles is at least the above lower limit, the transparent conductive layer 5 can be more closely adhered to the hard coat layer 3. Therefore, in the transparent conductive film 4, the transparent conductive layer 5 is excellent in abrasion resistance, moist heat resistance, and patterning property. On the other hand, if the content ratio of the silicon dioxide particles is below the above upper limit, when the silicon dioxide particles are brought into contact with chemicals such as an alkali solution and an acid solution, excessive damage (dissolution, etc.) of the silicon dioxide particles can be suppressed, and hard coating can be suppressed. Layer 3 is cracked. Therefore, the hard coat layer 3 is excellent in chemical resistance such as alkali resistance. In addition, during patterning, the hard coat layer 3 on the lower side of the pattern portion 6 can be reliably held, and the patternability is excellent.

The average particle diameter of the zirconia particles is, for example, 5 nm or more, preferably 10 nm or more, and, for example, 100 nm or less, preferably 50 nm or less, and more preferably 40 nm or less.

The content ratio of the zirconia particles is 35.0% by mass or more and less than 70.0% by mass based on the hard coating composition. It is preferably 39.5 mass% or more, more preferably 45.0 mass% or more, still more preferably 55.0 mass% or more, still more preferably 68.0 mass% or less, even more preferably 65.0 mass% or less, and still more preferably 63.0 mass%. the following. When the content ratio of the zirconia particles is greater than or equal to the above lower limit, the refractive index of the hard coat layer 3 can be increased, and the transparent conductive film 4 can reduce the hue difference (ΔE) and suppress the visibility of the pattern portion 6. In addition, if the content ratio of the zirconia particles is equal to or less than the above upper limit, the hard coating film 1 has moderate strength and toughness in the transparent substrate 2 in which the hard coating layer 3 containing silicon dioxide particles is laminated, so that it can be suppressed rupture. In addition, the phenomenon of coagulation and precipitation of zirconia particles on the surface of the hard coat layer 3 (bleeding out) can be suppressed, and the transmittance of the hard coat film 1 can be made good.

The mass ratio of zirconia particles to silica particles (mass of zirconia / mass of silica) is, for example, 10.0 times or more, preferably 18.0 times or more, more preferably 22.0 times or more, and, for example, 40.0 times. Hereinafter, it is preferably 30.0 times or less, and more preferably 25.0 times or less. When the said ratio is the said range, it will be excellent in the cracking of the transparent base material 2, the visual inspection of a pattern (non-visualization), abrasion resistance, and moist heat resistance.

Examples of the inorganic particles include metal oxide particles including titanium oxide, zinc oxide, tin oxide, and the like, and carbonate particles such as calcium carbonate. As an inorganic particle, it is preferable to consist only of a silica particle and a zirconia particle.

The total content ratio of the silica particles and zirconia particles is, for example, 70.0% by mass or less, preferably 65.0% by mass or less, and, for example, 40.0% by mass or more, and preferably 50.0% by mass relative to the hard coating composition. % Or more, more preferably 62.0% by mass or more. When the total content ratio is equal to or less than the above upper limit, cracking can be suppressed in the transparent substrate 2 in which the hard coat layer 3 containing silicon dioxide particles is laminated. In addition, on the surface of the hard coat layer 3, bleeding of the silicon dioxide particles or zirconia particles can be more surely suppressed, and the transmittance of the hard coat film 1 can be improved.

The content ratio of the inorganic particles is, for example, 70.0% by mass or less, preferably 65.0% by mass or less, and also, for example, 40.0% by mass or more, preferably 50.0% by mass or more, and more preferably 62.0% with respect to the hard coating composition. Above mass%. When the total content ratio is equal to or less than the above-mentioned upper limit, cracking of the transparent base material 2 and bleeding of the inorganic particles can be more surely suppressed.

The content of the inorganic particles (especially the total of silica particles and zirconia particles) with respect to 100 parts by mass of the resin is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, and, for example, 300 parts by mass or less, preferably It is 200 parts by mass or less.

The hard coating composition may further contain known additives such as a leveling agent, a thixotropic agent, and an antistatic agent.

The refractive index of the hard coat layer 3 is, for example, 1.55 or more, preferably 1.58 or more, more preferably 1.60 or more, and, for example, 1.80 or less, preferably 1.75 or less, and more preferably 1.70 or less. When the refractive index of the hard-coat layer 3 is in the said range, the visibility of the pattern part 6 of the transparent conductive layer 5 can be suppressed. The refractive index can be measured by, for example, an Abbe refractometer.

The elastic modulus of the hard coat layer 3 is, for example, 4.0 GPa or more, preferably 4.2 GPa or more, more preferably 4.4 GPa or more, and, for example, 10 GPa or less, preferably 5.8 GPa or less, and more preferably 4.7 GPa or less. If the elastic modulus is above the lower limit described above, in the transparent conductive layer 5 laminated on the hard coating layer 3 containing silicon dioxide particles, the adhesion between the hard coating layer 3 and the transparent conductive layer 5 can be improved, and a moderate elasticity can be imparted. . Therefore, even if the transparent conductive layer 5 is subjected to an impact (scratch) from the outside, the transparent conductive layer 5 is less likely to be damaged, and the transparent conductive layer 5 is not easily peeled from the surface of the hard coat layer 3. As a result, an excessive increase in the resistance value of the transparent conductive layer 5 due to abrasion can be further suppressed, and abrasion resistance is more excellent.

The plastic deformation amount of the hard coat layer 3 is, for example, 50 nm or more, preferably 60 nm or more, and, for example, 100 nm or less, and preferably 80 nm or less. When the amount of plastic deformation is within the above range, cracking of the transparent base material 2 can be more reliably suppressed.

The elastic modulus and the amount of plastic deformation are obtained, for example, by measuring the surface (upper surface) of the hard coat layer 3 using a nanoindenter under the condition of an indentation depth of 200 nm.

From the viewpoint of abrasion resistance, the thickness of the hard coat layer 3 is, for example, 0.5 μm or more, preferably 0.7 μm or more, and, for example, 10 μm or less, and preferably 2.0 μm or less. The thickness of the hard coat layer 3 can be calculated based on the wavelength of the interference spectrum observed using an Intensified Multichannel Photodetector, for example.

(Manufacturing method of hard coating film)
Next, the manufacturing method of the hard-coat film 1 is demonstrated.

First, a known or commercially available transparent substrate 2 is prepared.

From the viewpoint of adhesion between the transparent substrate 2 and the hard coat layer 3, if necessary, the upper surface of the transparent substrate 2 may be subjected to, for example, sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical treatment, and oxidation. Wait for etching treatment or primer treatment. In addition, the transparent substrate 2 can be dust-removed and purified by solvent washing, ultrasonic washing, and the like.

Then, a hard coat layer 3 is provided on the upper surface of the transparent substrate 2. For example, the hard coat composition 3 is formed on the upper surface of the transparent substrate 2 by wet-coating the hard coating composition on the upper surface of the transparent substrate 2.

Specifically, for example, a solution (varnish) obtained by diluting the hard coating composition with a solvent is prepared, and then the prepared hard coating composition solution is applied to the upper surface of the transparent substrate 2 and dried.

Examples of the solvent include organic solvents, water-based solvents (specifically, water), and the like, and organic solvents are preferred. 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; and ester compounds such as ethyl acetate and butyl acetate; Ether compounds such as propylene glycol monomethyl ether; for example, aromatic compounds such as toluene and xylene. These solvents can be used alone or in combination of two or more.

The solid content component concentration in the hard coating composition solution is, for example, 1% by mass or more, preferably 10% by mass or more, and, for example, 30% by mass or less, and preferably 20% by mass or less.

Furthermore, in the preparation of the hard coating composition solution, a silicon dioxide particle dispersion (silica dioxide sol) in which silica particles are dispersed in a solvent, and zirconia particles in which zirconia particles are dispersed in a solvent are prepared. The dispersion is mixed with the resin, and then further diluted with a solvent.

The coating method can be appropriately selected depending on the hard coating composition solution and the transparent substrate 2. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a bar coating method, a gravure coating method, and an extrusion coating method.

The drying temperature is, for example, 50 ° C or higher, preferably 70 ° C or higher, for example, 200 ° C or lower, and preferably 100 ° C or lower.

The drying time is, for example, 0.5 minutes or more, preferably 1 minute or more, and, for example, 60 minutes or less, and preferably 20 minutes or less.

Thereafter, when the hard coating composition contains an active energy ray-curable resin, the active energy ray-curable resin is hardened by irradiating the active energy ray after drying the hard coating composition solution.

When the hard coating composition contains a thermosetting resin, the drying step allows the thermosetting resin to be thermally cured while drying the solvent.

Thereby, the hard-coat film 1 is obtained.

Furthermore, if necessary, a functional layer such as an anti-blocking layer may be provided on the lower surface of the transparent substrate 2 of the hard coating film 1.

The thickness of the obtained hard coating film 1 is, for example, 2 μm or more, preferably 20 μm or more, and, for example, 300 μm or less, and preferably 150 μm or less.

(use)
The hard coating film 1 is used for the transparent conductive film 4, for example. Specifically, the hard coat film 1 is used as a support film for supporting the transparent conductive layer 5 in the transparent conductive film 4. The hard coating film 1 is a component for producing, for example, the following transparent conductive film 4, a transparent conductive film laminate 8, an image display device 11, and the like. That is, the hard coat film 1 is a device which does not include the following transparent conductive layer 5, the polarizing element 10, and the image display element 14 (a liquid crystal cell, etc.), but is a single part and is commercially available.

In addition, the hard coating film 1 can suppress cracking of the transparent substrate 2 (especially a cycloolefin-based substrate as a flexible substrate) when it is bent. In addition, it satisfies various physical properties required for optical applications (especially touch panel applications) with good balance. Specifically, when the transparent conductive layer 5 is formed on the hard coat layer 3 of the hard coating film 1, the non-recognizability of the pattern portion 6 (described below), the scratch resistance of the transparent conductive layer 5, and the transparent conductive layer 5 Moisture and heat resistance, patterning properties of the transparent conductive layer 5, and alkali resistance of the hard coat layer 3 are good.

2. Transparent conductive film As shown in FIG. 2A, the transparent conductive film 4 has a film shape having a specific thickness, extends in the plane direction, and has a flat upper surface and a flat lower surface.

The transparent conductive film 4 includes a hard coat film 1 and a transparent conductive layer 5 disposed on the upper surface thereof. That is, the transparent conductive film 4 includes a transparent base material 2, a hard coat layer 3 disposed on the upper surface of the transparent base material 2, and a transparent conductive layer 5 disposed on the upper surface of the hard coating layer 3. Preferably, the transparent conductive film 4 includes a transparent substrate 2, a hard coat layer 3, and a transparent conductive layer 5.

(Transparent conductive layer)
The transparent conductive layer 5 is used to crystallize as needed, and is formed into a desired pattern in the subsequent steps to form transparent conductive portions of the patterned portion 6 (see FIG. 2B) and the non-patterned portion 7.

The transparent conductive layer 5 is the uppermost layer of the transparent conductive film 4 and has a film shape. The transparent conductive layer 5 is disposed on the entire upper surface of the hard coating layer 3 so as to be in contact with the upper surface of the hard coating layer 3.

Examples of the material of the transparent conductive layer 5 include at least one selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. A metal oxide of 1 metal. If necessary, the metal oxides may be further doped in the metal oxides.

Specific examples of the transparent conductive layer 5 include indium-containing oxides such as indium tin composite oxide (ITO), and antimony-containing oxides such as antimony tin composite oxide (ATO), and preferably include indium-containing oxides. The oxide is more preferably ITO.

When the transparent conductive layer 5 is an indium tin composite oxide layer such as an ITO layer, the content ratio of tin oxide (SnO ₂ ) is 0.5% by mass or more based on the total amount of tin oxide and indium oxide (In ₂ O ₃ ). It is preferably 5 mass% or more, and for example, 30 mass% or less, and more preferably 25 mass% or less. When the content ratio of tin oxide is at least the above lower limit, the durability of the transparent conductive layer 5 can be further improved. In addition, if the content ratio of tin oxide is equal to or less than the above-mentioned upper limit, the crystal conversion of the transparent conductive layer 5 can be facilitated, and the transparency and the stability of the surface resistance can be improved.

The "ITO" in this specification may be a composite oxide containing at least indium (In) and tin (Sn), and may include additional components other than these. Examples of the additional component include metal elements other than In and Sn, and specifically, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, and Pb , Ni, Nb, Cr, Ga and so on.

The surface resistance of the transparent conductive layer 5 is, for example, 20 Ω / □ or more and 70 Ω / □ or less. The surface resistance can be measured by a four-terminal method.

The thickness of the transparent conductive layer 5 is, for example, 10 nm or more, preferably 30 nm or more, and, for example, 50 nm or less, and preferably 40 nm or less. The thickness of the transparent conductive layer 5 can be measured using, for example, an Intensified Multichannel Photodetector.

The transparent conductive layer 5 may be either amorphous or crystalline.

Whether the transparent conductive layer 5 is amorphous or crystalline can be determined, for example, by the following method. When the transparent conductive layer 5 is an ITO layer, it is immersed in hydrochloric acid (concentration: 5 mass%) at 20 ° C for 15 minutes and then washed. , Dry, measure the resistance between the terminals about 15 mm. In this specification, when the ITO layer is made amorphous when immersed in hydrochloric acid (20 ° C, concentration: 5% by mass), washed with water, and dried, and the resistance between the terminals between 15 mm exceeds 10 kΩ, When the inter-terminal resistance between 15 mm is 10 kΩ or less, the ITO layer is made crystalline.

(Manufacturing method of transparent conductive film)
Next, a method for manufacturing the transparent conductive film 4 will be described.

When manufacturing the transparent conductive film 4, a hard coating film 1 is prepared, and a transparent conductive layer 5 is formed on the upper surface of the hard coating layer 3 by, for example, a dry method.

Examples of the dry method include a vacuum deposition method, a sputtering method, and an ion plating method. Preferably, a sputtering method is mentioned. A transparent conductive layer 5 of a thin film can be formed by this method.

When a sputtering method is used, examples of the target include the above-mentioned inorganic substances constituting the transparent conductive layer 5, and preferably ITO. From the viewpoints of durability and crystallization of the ITO layer, the tin oxide concentration of ITO is, for example, 0.5% by mass or more, preferably 3% by mass or more, and, for example, 15% by mass or less, and preferably 13% by mass or less. .

Examples of the sputtering gas include an inert gas such as Ar. If necessary, a reactive gas such as oxygen may be used in combination. When the reactive gas is used in combination, the flow rate ratio of the reactive gas is not particularly limited, and it is, for example, 0.1 flow% or more and 5 flow% or less with respect to the total flow ratio of the sputtering gas and the reactive gas.

The sputtering method is performed under vacuum. Specifically, from the viewpoints of suppression of reduction in sputtering rate, discharge stability, and the like, the air pressure during sputtering is, for example, 1 Pa or less, and preferably 0.7 Pa or less.

The power source used in the sputtering method may be any of a DC (Direct Current) power source, an AC (Alternating Current) power source, an MF (Medium Frequency) power source, and an RF (Radio Frequency) power source. Also, it can be a combination of these.

In addition, in order to form the transparent conductive layer 5 with a desired thickness, it is also possible to appropriately set a target, sputtering conditions, and the like, and to perform multiple sputterings.

Thereby, as shown in FIG. 2A, a transparent conductive film 4 including a transparent substrate 2, a hard coat layer 3, and a transparent conductive layer 5 in this order is obtained. The transparent conductive film 4 is a non-patterned transparent conductive film that has not been patterned.

The thickness of the transparent conductive film 4 is, for example, 2 μm or more, preferably 20 μm or more, and, for example, 100 μm or less, and preferably 50 μm or less.

Then, if necessary, as shown in FIG. 2B, the transparent conductive film 5 is patterned by a known etching process.

The pattern of the transparent conductive layer 5 is appropriately determined depending on the application to which the transparent conductive film 4 is applied, and examples thereof include an electrode pattern such as a stripe pattern or a wiring pattern.

Etching, for example, arranges a covered portion (masking tape, etc.) on the transparent conductive layer 5 so as to correspond to the pattern portion 6 and the non-patterned portion 7, and uses an etchant to expose the transparent conductive layer 5 (non-patterned) exposed from the covered portion Section 7) Etching. Examples of the etching solution include acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, phosphoric acid, and mixed acids thereof. After that, the covered portion is removed from the upper surface of the transparent conductive layer 5 by, for example, peeling.

Thereby, a patterned transparent conductive film 4 of the transparent conductive layer 5 as shown in FIG. 2B is obtained. That is, a patterned transparent conductive film 4 including a pattern portion 6 and a non-pattern portion 7 is obtained.

Furthermore, if necessary, a crystal conversion treatment is performed on the transparent conductive layer 5 of the transparent conductive film 4 before or after the etching.

Specifically, the transparent conductive film 4 is heat-treated in the atmosphere.

The heat treatment can be performed using, for example, an infrared heater or an oven.

The heating temperature is, for example, 100 ° C or higher, preferably 120 ° C or higher, and, for example, 200 ° C or lower, and preferably 160 ° C or lower. When the heating temperature is within the above range, thermal damage to the transparent substrate 2 and impurities generated from the transparent substrate 2 can be suppressed, and crystal conversion can be surely performed.

The heating time is appropriately determined depending on the heating temperature, and is, for example, 10 minutes or more, preferably 30 minutes or more, and, for example, 5 hours or less, and preferably 3 hours or less.

Thereby, the transparent conductive film 4 in which the transparent conductive layer 5 was crystallized was obtained.

The transmittance difference ΔE (color difference) between the pattern portion 6 and the non-pattern portion 7 in the transparent conductive film 4 is, for example, 4.0 or less, and preferably 3.0 or less. When the transmittance difference ΔE is within the above range, the visibility of the pattern portion 6 such as an electrode pattern can be suppressed.

The transmittance difference ΔE can be calculated by measuring L ₁ , a * ₁ , b * ₁ in the pattern portion 6, and L ₂ , a * ₂ , and b * ₂ in the non-pattern portion 7 and calculating the following formula.

ΔE = {(L _2- L ₁ ) ² + (a * _2-a * ₁ ) ² + (b * _2- b * ₁ ) ² } ^1/2
The transmittance difference ΔE is obtained, for example, by measuring in a wavelength range from 380 nm to 800 nm using an ultraviolet-visible near-infrared spectrophotometer ("U4100" manufactured by Hitachi High-Tech Science Corporation).

(use)
The transparent conductive film 4 can be used, for example, as a substrate for a touch panel included in an optical device such as the image display device 11 (described below). Examples of the form of the touch panel include various methods such as an optical method, an ultrasonic method, an electrostatic capacitance method, and a resistive film method, and are particularly suitable for a touch panel of an electrostatic capacitance method.

The transparent conductive film 4 is a component for producing a transparent conductive film laminate 8, an image display device 11, and the like. That is, the transparent conductive film 4 is a device which does not include the polarizing element 10 and the image display element 14 but is circulated as a single component and is industrially usable.

In addition, the transparent conductive film 4 can suppress cracking of the transparent substrate 2 (especially a cycloolefin-based substrate as a flexible substrate) when it is bent. In addition, the balance satisfies various physical properties required for optical applications. Specifically, in the transparent conductive film 4, the visibility of the pattern portion 6, scratch resistance, moist heat resistance, patterning property, alkali resistance, and the like are good.

3. Transparent conductive film laminate As shown in FIG. 3, the transparent conductive film laminate 8 has a film shape having a specific thickness, extends in the plane direction, and has a flat upper surface and a flat lower surface.

The transparent conductive film laminate 8 includes a transparent conductive film 4, and a first adhesive layer 9 and a polarizing element 10 arranged on the upper surface thereof. That is, the transparent conductive film laminate 8 includes a transparent substrate 2, a hard coating layer 3 disposed on the upper surface of the transparent substrate 2, a transparent conductive layer 5 disposed on the upper surface of the hard coating layer 3, and a transparent conductive layer. 5 The first adhesive layer 9 on the upper surface and the polarizing element 10 disposed on the upper surface of the first adhesive layer 9. Preferably, the transparent conductive film laminate 8 includes a transparent substrate 2, a hard coat layer 3, a transparent conductive layer 5, a first adhesive layer 9, and a polarizer 10. In the transparent conductive film laminate 8, the transparent conductive layer 5 is preferably patterned and has a pattern portion 6 and a non-pattern portion 7.

(1st adhesive layer)
The first adhesive layer 9 is a layer for adhering the transparent conductive film 4 and the polarizing element 10.

The first adhesive layer 9 has a film shape. The first adhesive layer 9 is disposed on the entire upper surface of the transparent conductive layer 5 (pattern portion 6) and the hard coat layer 3 (non-pattern portion 7) exposed from the first conductive layer 5 so as to contact the upper surface of the transparent conductive layer 5. The first adhesive layer 9 is disposed on the entire lower surface of the polarizing element 10 so as to be in contact with the lower surface of the polarizing element 10.

Examples of the material of the first adhesive layer 9 include an acrylic adhesive, a butyl rubber adhesive, a silicone adhesive, a polyester adhesive, a polyurethane adhesive, and a polymer. Amine-based adhesives, epoxy-based adhesives, vinyl alkyl ether-based adhesives, fluororesin-based adhesives, and the like.

The thickness of the first adhesive layer 9 is, for example, 1 μm or more, preferably 10 μm or more, and, for example, 300 μm or less, and preferably 150 μm or less.

(Polarizing element)
The polarizing element 10 is a layer for converting light into linearly polarized light.

The polarizing element 10 is the uppermost layer of the transparent conductive film laminate 8 and has a film shape. The polarizing element 10 is disposed on the upper surface of the first adhesive layer 9 so as to be in contact with the upper surface of the first adhesive layer 9.

Examples of the polarizing element 10 include a polyvinyl alcohol-based film containing iodine.

Examples of the material of the polyvinyl alcohol-based film include polyvinyl alcohol and derivatives thereof. Examples of the derivative include polyvinyl formal and polyvinyl acetal. Examples of the derivative include modified bodies obtained by modifying polyvinyl alcohol with olefins (for example, ethylene and propylene), unsaturated carboxylic acids (such as acrylic acid and methacrylic acid), and acrylamide.

The polarizing element 10 is obtained by adding iodine to a film containing vinyl alcohol or a derivative thereof, followed by stretching.

Such a polarizing element is described in, for example, Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, Japanese Patent No. 4691205, and Japanese Patent No. 4751481. in.

The polarizing element 10 may be provided with a protective film on the upper surface and the lower surface of the polyvinyl alcohol-based film, respectively. That is, the polarizing element 10 may be a laminated body including a polyvinyl alcohol-based film and protective films disposed on both surfaces thereof. As a material of a protective film, the material of the said transparent base material 2 is mentioned, for example.

The thickness of the polarizing element 10 is, for example, 1 μm or more, preferably 5 μm or more, and, for example, 200 μm or less, and preferably 100 μm or less.

The transparent conductive film laminated body 8 can be formed by, for example, applying a liquid adhesive or disposing an adhesive tape on the upper surface of the transparent conductive film 4 to form a first adhesive layer 9, and then disposing the polarizing element 10 on the first adhesive. It is manufactured on the upper surface of the agent layer 9.

(use)
The transparent conductive film laminate 8 is used, for example, as a substrate for a touch panel included in an optical device such as the image display device 11.

The transparent conductive film laminated body 8 is a component for producing an image display device 11 and the like. That is, the transparent conductive film 4 is a device which does not include the image display element 14 but is circulated as a single component and is industrially usable.

In addition, the transparent conductive film laminate 8 can suppress cracking of the transparent substrate 2 (especially, a cycloolefin-based substrate as a flexible substrate) when it is bent. In addition, the balance satisfies various physical properties required for optical applications. Specifically, in the transparent conductive film laminated body 8, the non-recognizability of the pattern part 6, abrasion resistance, moist heat resistance, patterning property, alkali resistance, etc. are favorable.

4. Image display device As shown in FIG. 4, the image display device 11 includes a transparent conductive film laminate 8, a second adhesive layer 12 and a transparent protective plate 13 disposed on the upper surface thereof, and an oppositely disposed transparent device. The image display element 14 on the lower surface of the conductive film laminate 8. That is, the image display device 11 includes an image display element 14, a transparent substrate 2, a hard coat layer 3, a transparent conductive layer 5, a first adhesive layer 9, a polarizer 10, and a second adhesive in this order in the thickness direction. Layer 12, and transparent protective plate 13. Furthermore, in FIG. 4, the upper side is the visual recognition side, and the lower side is the image display element side.

(Second Adhesive Layer)
The second adhesive layer 12 is a layer for adhering the transparent conductive film laminate 8 and the transparent protective plate 13.

The second adhesive layer 12 has a film shape. The second adhesive layer 12 is disposed on the entire upper surface of the polarizing element 10 and the entire lower surface of the transparent protective plate 13 so as to be in contact with the upper surface of the polarizing element 10 and the lower surface of the transparent protective plate 13.

The material of the second adhesive layer 12 may be the same as the material described in the first adhesive layer 9.

The thickness of the second adhesive layer 12 is, for example, 1 μm or more, preferably 5 μm or more, and, for example, 300 μm or less, and preferably 150 μm or less.

(Transparent protective plate)
The transparent protective plate 13 is a layer for protecting internal components of the image display device such as the image display element 14 from impacts or stains from the outside.

The transparent protective plate 13 has a substantially flat plate shape in a plan view, and is disposed on the entire upper surface of the second adhesive layer 12 so as to be in contact with the upper surface of the second adhesive layer 12.

The transparent protective plate 13 has transparency, and has a moderate thickness and mechanical strength.

Examples of the transparent protective plate 13 include a resin plate containing a hard resin such as an acrylic resin and a polycarbonate resin, such as a glass plate.

The thickness of the transparent protective plate 13 is, for example, 10 μm or more, preferably 500 μm or more, and, for example, 10 mm or less, and preferably 5 mm or less.

(Image display element)
The image display element 14 is disposed to face the hard coating film 1 with a gap therebetween.

Examples of the image display element 14 include a liquid crystal cell. Although not shown, the liquid crystal cell includes a liquid crystal layer, a polarizing element disposed below the liquid crystal layer, and a color filter.

Since the image display device 11 includes the transparent conductive film 4, the visual recognition of the pattern portion 6 of the transparent conductive layer 5 is suppressed, and it exhibits good durability.

[Example]

Examples and comparative examples are shown below to further specifically describe the present invention. The present invention is not limited to any Examples and Comparative Examples. In addition, specific numerical values such as the blending ratio (containment ratio), physical property values, and parameters used in the following description may be substituted for the corresponding blending ratio (containment ratio), physical property values, and parameters described in the above-mentioned "Embodiment". Corresponds to the record upper limit (values defined as "below" and "not reached") or the lower limit value (values defined as "above" and "exceed").

(Hard coating film)
Example 1
A cycloolefin resin film (thickness: 40 μm, manufactured by Japan Zeon Corporation, “ZEONOR ZF-16”, in-plane birefringence: 5 nm) was prepared as a transparent substrate.

Ultraviolet-curable acrylic urethane ("UA-160TM" manufactured by Shin Nakamura Chemical Industry Co., Ltd.), a silica dispersion (silica dioxide, average particle diameter 10 nm, methyl ethyl ketone solvent) , Manufactured by Nissan Chemical Industries, "MEK-ST-40"), and zirconia dispersion (average particle size 15-40 nm, manufactured by Nissan Chemical Industries, "OZ-S30K") are based on acrylic urethane, The silicon dioxide particles and zirconia were mixed in such a manner that the mass ratio was 58.0% by mass, 2.5% by mass, and 39.5% by mass, and then butyl acetate was added to the mixture to prepare a hard coating composition having a solid content of 16% by mass物 溶液。 The solution.

The hard coating composition solution was applied to the upper surface of a transparent substrate using a wire bar coater, and dried at 80 ° C. for 1 minute, and then the coating film was irradiated with ultraviolet rays using an air-cooled mercury lamp to harden the hard coating composition. . Thereby, a hard coat layer having a thickness of 1.0 μm was formed on the upper surface of the transparent substrate to produce a hard coat film.

Examples 2 to 6
A hard coat film was produced in the same manner as in Example 1 except that the ratio of the acrylic urethane, the silica particles, and the zirconia was changed to the ratio described in Table 1 in the hard coat composition.

Comparative Example 1
A hard coating film was produced in the same manner as in Example 1 except that only an acrylic urethane ("ELS888" manufactured by DIC Corporation) was used as the hard coating composition.

Comparative Example 2
A hard coat film was produced in the same manner as in Example 1 except that the ratio of the acrylic urethane, the silica particles, and the zirconia was changed to the ratio described in Table 1 in the hard coat composition.

Comparative Example 3
A "KZ6506" (containing 60% by mass of acrylic urethane and 40% by mass of silica particles) manufactured by JSR was used as a hard coating composition, and a hard coating film was produced in the same manner as in Example 1. .

Comparative Example 4
A "KZ6519" (containing 40% by mass of acrylic urethane and 60% by mass of silica particles) manufactured by JSR was used as a hard coating composition, and a hard coating film was produced in the same manner as in Example 1. .

Comparative Example 5
The same procedure as in Example 1 was used on the upper surface of a transparent substrate except that a diluent of an ultraviolet-curable acrylic resin ("Z-850-6L" manufactured by AICA Industries Co., Ltd.) was used as the hard coating composition solution. A hard coat layer having a thickness of 1.0 μm was formed to produce a hard coat film.

Next, a diluted solution of a mixture of "KZ7412" and "KZ7416" (containing 40% by mass of acrylic urethane and 60% by mass of zirconia particles) manufactured by JSR was adjusted as a composition solution for an optical adjustment layer. The composition adjustment solution for an optical adjustment layer was applied to the upper surface of the hard coat layer and dried, and then irradiated with ultraviolet rays to form an optical adjustment layer having a thickness of 0.1 μm.

Thereby, a hard coating film with an optical adjustment layer sequentially provided with a transparent substrate, a hard coat layer, and an optical adjustment layer was manufactured.

(Transparent conductive film)
In the hard coating films of Examples and Comparative Examples, an amorphous ITO layer (transparent conductive layer) having a thickness of 40 nm was formed on the upper surface of the hard coating layer by DC sputtering. Specifically, an ITO target containing a sintered body of 90% by mass of indium oxide and 10% by mass of tin oxide was sputtered in a vacuum environment in which a pressure of 0.4% Pa of argon gas and 2% oxygen gas was introduced. In Comparative Examples 5 to 6, an ITO layer was provided on the upper surface of the optical adjustment layer.

Thereby, a transparent conductive film is manufactured.

(Measurement of refractive index)
With respect to the hard coat layers of the hard coat films of the respective examples and comparative examples, the refractive index of the hard coat layer was measured using an Abbe refractometer. In Comparative Example 5, the refractive index of the optical adjustment layer was measured. The results are shown in Table 1.

(Measurement of elastic modulus and plastic deformation)
Regarding the hard coat layers of the hard coat films of each example and each comparative example, the elastic modulus at a depth of 200 nm was measured using a nanoindenter under the following conditions. In Comparative Example 5, the elastic modulus was measured for the optical adjustment layer. The results are shown in Table 1.

Nano indenter: "Triboindeter" manufactured by Hysitoron
Indenter: Berkobich (triangular cone type)
Measurement mode: single pressure measurement temperature: room temperature (25 ° C)
Indentation depth: 200 nm
(Substrate cracked)
For the hard coating films of each example and each comparative example, a 180 ° bending test was performed with the transparent substrate side as the inner side. The surface of the transparent base material after the test was observed, and the case where the fracture of the transparent base material was not visually recognized was evaluated as ○, and the case where the edge of the transparent base material was recognized as a small crack was evaluated as △, and the case was confirmed as transparent The state of fracture of the substrate was evaluated as ×. The results are shown in Table 1.

(Measurement of patternability, non-recognizability of patterns, and transmittance difference ΔE)
The transparent conductive films of Examples and Comparative Examples were heated at 130 ° C. for 90 minutes to crystallize the transparent conductive layer. Next, the adhesive tape (1 cm wide) was attached to the surface of the transparent conductive layer of the crystallized transparent conductive film in a stripe pattern at intervals of 1 cm, and the transparent conductive layer was etched using 50 ° C, 10% by mass of hydrochloric acid. , Peel off the adhesive tape. Thereby, a pattern portion having a width of 1 cm and a non-pattern portion having a width of 1 cm are formed (see FIG. 2B).

Patternability: The surface of the pattern portion of the transparent conductive layer was observed with a microscope (magnification 20 times), and the occurrence of cracks was evaluated as ○, and the occurrence of cracks was evaluated as ×.

Non-visibility of the pattern: The fluorescent film is irradiated from the transparent conductive layer side with a fluorescent lamp, and the transparent substrate side is observed visually. A case where the difference between the patterned portion and the non-patterned portion was not recognized was evaluated as ○, a case where the patterned portion and the non-patterned portion were slightly confirmed was evaluated as △, and a case where the patterned portion and the non-patterned portion were definitely confirmed as ×.

Transmittance difference ΔE: L ₁ , a * ₁ , b in the pattern portion were measured using a UV-Vis near-infrared spectrophotometer (manufactured by Hitachi High-Tech Science Corporation, “U4100”) in a wavelength range of 380 nm to 800 nm * ₁ and L ₂ , a * ₂ , and b * ₂ in the non-patterned portion are calculated by the following formula.

ΔE = {(L _2- L ₁ ) ² + (a * _2-a * ₁ ) ² + (b * _2- b * ₁ ) ² } ^1/2
These results are shown in Table 1.

(Scratch resistance)
The transparent conductive films of Examples and Comparative Examples were heated at 130 ° C. for 90 minutes to crystallize the transparent conductive layer. Then, an industrial wiper ("Anticon, Gold Sorb" manufactured by CONTEC Corporation) was pressed against the transparent conductive layer of the crystallized transparent conductive film within a range of 11 mm in diameter so as to be a load of 400 g. Surface, slide the wiper 5 times within a range of 10 cm in length. Thereafter, a 4-probe type probe was arranged on the surface of the transparent conductive layer so as to measure across the orthogonal direction orthogonal to the sliding direction, and the surface resistance value R ₁₀ of the transparent conductive film after sliding was measured. In addition, the surface resistance value at the same position of the transparent conductive film before sliding was set to R ₀ .

A case where the change rate (R ₁₀ / R ₀ ) of the surface resistance value was less than 2 was evaluated as ○, a case where it was 2 or more and less than 5 was evaluated as Δ, and a case where it was 5 or more was evaluated as ×. The results are shown in Table 1.

(Damp heat resistance)
The transparent conductive films of Examples and Comparative Examples were heated at 130 ° C. for 90 minutes to crystallize the transparent conductive layer. Then, the crystallized transparent conductive film was left under the condition of 85 ° C. and 85% RH for 240 hours, and a 100 grid cross-cut test was performed.

A case where the number of meshes after the transparent conductive layer was less than 20 was evaluated as ○, a case where 20 or more and less than 50 was evaluated as Δ, and a case where 50 or more was evaluated as ×. The results are shown in Table 1.

(Alkali resistance)
The transparent conductive films of Examples and Comparative Examples were heated at 130 ° C. for 90 minutes to crystallize the transparent conductive layer. Then, a 1 cm incision was cut into the crystallized transparent conductive film with a cutter, and immersed in a 3% by mass aqueous solution of KOH (temperature: 30 ° C.) for 20 minutes. The incision portion was observed with a microscope (magnification: 20 times), and a case where cracks were not recognized in the hard coat layer was evaluated as ○, and a case where cracks were confirmed as being x was evaluated. The results are shown in Table 1.

[Table 1]

The above invention is provided as an exemplified embodiment of the present invention, which is merely an example and should not be interpreted in a limited manner. Variations of the present invention that are clear to those skilled in the art are included in the scope of patent applications described below.

1‧‧‧hard coating

2‧‧‧ transparent substrate

3‧‧‧hard coating

4‧‧‧ transparent conductive film

5‧‧‧ transparent conductive layer

6‧‧‧ Pattern Department

7‧‧‧ non-patterned department

8‧‧‧ transparent conductive film laminate

9‧‧‧ the first adhesive layer

10‧‧‧ polarizing element

11‧‧‧Image display device

12‧‧‧ 2nd adhesive layer

13‧‧‧Transparent protection board

14‧‧‧Image display element

FIG. 1 is a cross-sectional view showing an embodiment of a hard coating film according to the present invention. 2A to 2B are cross-sectional views of a transparent conductive film provided with the hard coating film shown in FIG. 1, FIG. 2A is a cross-sectional view of an unpatterned transparent conductive film, and FIG. 2B is a cross-sectional view of a patterned transparent conductive film. Sectional view. 3 is a cross-sectional view of a transparent conductive film laminate including the transparent conductive film shown in FIG. 2B. FIG. 4 is a cross-sectional view of an image display device including the transparent conductive film laminate shown in FIG. 3.

Claims (8)

A hard coating film, comprising: Transparent substrate; and A hard coating layer disposed on one side in the thickness direction of the transparent substrate; and The hard coat layer contains silica particles, zirconia particles, and a resin, The content ratio of the silicon dioxide particles in the hard coat layer is 0.5% by mass or more and less than 3.0% by mass. The content ratio of the zirconia particles in the hard coat layer is 35.0% by mass or more and less than 70.0% by mass. The hard coating film according to claim 1, wherein the transparent substrate is a cycloolefin-based substrate. The hard coating film according to claim 1 or 2, wherein the total content ratio of the silicon dioxide particles and the zirconia particles in the hard coating layer is 65.0% by mass or less. For example, the hard coating film of item 1 or 2, wherein the elastic modulus of the hard coating film is 4.2 GPa or more. The hard coating film of claim 1 or 2, wherein the thickness of the hard coating film is 0.7 μm or more and 2.0 μm or less. A transparent conductive film, comprising: If hard coating of item 1 or 2 is requested; and The transparent conductive layer is disposed on one side in the thickness direction of the hard coating film. A transparent conductive film laminate is characterized in that: Polarizing elements; and A transparent conductive film as claimed in item 6. An image display device, comprising: Image display elements; and The transparent conductive film laminate as claimed in item 7; and The transparent conductive film is disposed between the polarizing element and the image display element.