JP2017224115A - Transparent conductive film, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film that is characterized by excellent viewing prevention and a low resistance of a transparent conductive layer.SOLUTION: A transparent conductive film 1 has a substrate layer 2 containing a transparent base material 5, an intermediate layer 3, and a transparent conductive layer 4 in order. The intermediate layer 3 consists only of resin and has a refractive index of 1.59 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent conductive film and a touch panel, and particularly relates to a transparent conductive film and a touch panel including the transparent conductive film.

  Conventionally, it is known that a transparent conductive film is used as an electrode member such as a touch panel. For example, a transparent conductive film including a base film, an optical adjustment layer, and a transparent conductive layer in order has been proposed (see, for example, Patent Document 1 below).

  The optical adjustment layer of Patent Document 1 is made of an organic-inorganic composite material containing an organic component and an inorganic component, and has a refractive index of 1.60 or more and 1.90 or less.

JP 2010-27294 A

  However, in the transparent conductive film of Patent Document 1, the optical adjustment layer contains an inorganic component. Then, when the amorphous transparent conductive layer is crystallized, crystal growth of the transparent conductive layer is inhibited due to the inorganic component, and the specific resistance value of the transparent conductive layer is increased. Therefore, there is a problem that it cannot cope with the increase in the size of the touch panel.

  On the other hand, when the optical adjustment layer does not contain an inorganic component, since the inhibition of crystal growth caused by the inorganic component is suppressed, the specific resistance value of the transparent conductive layer can be lowered, while the refractive index of the optical adjustment layer Becomes lower. For this reason, when the transparent conductive layer is patterned, there is a problem that the difference between the pattern portion having the transparent conductive layer and the non-pattern portion not having the transparent conductive layer is clarified. That is, there is a problem that the visibility suppression is reduced.

  An object of the present invention is to provide a transparent conductive film that is excellent in visual suppression and has a low specific resistance value of a transparent conductive layer.

  The present invention (1) includes a base material layer including a transparent base material, an intermediate layer, and a transparent conductive layer in order, and the intermediate layer is made of only a resin and has a refractive index of 1.59 or more. It is a conductive film.

  In this transparent conductive film, since the intermediate layer has a high refractive index of 1.59 or more, it is excellent in visibility suppression when the transparent conductive layer is patterned.

  Moreover, since the intermediate layer is made only of resin, the specific resistance value of the transparent conductive layer can be lowered.

In the present invention (2), the intermediate layer is in contact with the base material layer, and the base material layer has a surface free energy of 60 mJ / m ² or more. Contains.

However, when the base material layer has a surface free energy of less than 60 mJ / m ^2, when the intermediate layer made only of the resin is formed on the base material layer, the repelling of the resin occurs and the intermediate layer is made uniform. There are cases where it cannot be formed.

  However, according to such a transparent conductive film, since the surface free energy of the base material layer is equal to or more than the lower limit described above, the intermediate layer made of only the resin is suppressed from repelling the resin and contacting the base material layer. Can be formed uniformly, and as a result, the specific resistance value of the transparent conductive layer can be lowered.

  In the present invention (3), the intermediate layer includes the transparent conductive film according to the above (1) or (2) having a thickness of 30 nm or more and 150 nm or less.

  According to such a transparent conductive film, since the thickness of the intermediate layer is within the above-described range, it is possible to reduce the thickness while maintaining the mechanical strength.

  In the present invention (4), the base material layer includes the transparent base material and a hard coat layer in order, and the hard coat layer is in contact with the intermediate layer. The transparent conductive film as described in any one of these is included.

  According to such a transparent conductive film, since the base material layer includes the hard coat layer, the scratch resistance can be improved.

  As for this invention (5), the said base material layer contains the transparent conductive film as described in any one of said (1)-(3) which consists only of the said transparent base material.

  Such a transparent conductive film can be manufactured at low cost because the base material layer is composed only of the transparent base material.

  This invention (6) contains the transparent conductive film as described in any one of said (1)-(5) whose said intermediate | middle layer is an optical adjustment layer.

  According to such a transparent conductive film, since the intermediate layer is an optical adjustment layer, the visibility is excellent when the transparent conductive layer is patterned.

  In the present invention (7), the transparent conductive layer is patterned, and includes the pattern portion having the transparent conductive layer and the non-pattern portion not having the transparent conductive layer. The transparent conductive film as described in any one of 6) is included.

  According to such a transparent conductive film, the visual recognition of the difference between the pattern portion and the non-pattern portion is suppressed, and the visual suppression property is excellent.

  Moreover, since the intermediate layer is made only of resin, the specific resistance value of the transparent conductive layer can be lowered.

  This invention (8) is the winding body wound up by roll shape, The transparent conductive film as described in any one of said (1)-(7) characterized by the above-mentioned is included.

  Since such a transparent conductive film is a wound body wound up in a roll shape, it is excellent in workability and transportability.

  This invention (9) contains the touchscreen provided with the transparent conductive film as described in said (7).

  Since such a touch panel includes the above-described transparent conductive film, the touch panel is excellent in visibility suppression and has a low specific resistance value, and thus can be enlarged.

  The transparent conductive film of this invention is excellent in visual suppression property, and can make the specific resistance value of a transparent conductive layer low.

  Since the touch panel of the present invention includes the transparent conductive film of the present invention, the touch panel is excellent in visibility suppression and has a low specific resistance value, and therefore can be enlarged.

FIG. 1: shows sectional drawing of 1st Embodiment (Aspect provided with a transparent base material, a hard-coat layer, an intermediate | middle layer, and a transparent conductive layer in order) of the transparent conductive film of this invention. FIG. 2 shows a cross-sectional view of an embodiment in which the transparent conductive layer of the transparent conductive film shown in FIG. 1 is patterned. FIG. 3 shows a cross-sectional view of a second embodiment of the transparent conductive film shown in FIG. 1 (an embodiment comprising a transparent substrate, an intermediate layer, and a transparent conductive layer in this order). FIG. 4 shows a cross-sectional view of a mode in which the transparent conductive layer of the transparent conductive film shown in FIG. 3 is patterned.

  1st Embodiment of the transparent conductive film of this invention is described with reference to FIG.

1. 1. Transparent conductive film As shown in FIG. 1, this transparent conductive film 1 has a film shape (including a sheet shape) having a predetermined thickness, extends in a direction (plane direction) perpendicular to the thickness direction, and is flat. It has an upper surface and a flat lower surface (two main surfaces).

  Specifically, the transparent conductive film 1 includes a transparent substrate 5, a hard coat layer 6, an intermediate layer 3, and a transparent conductive layer 4 in this order. That is, the transparent conductive film 1 is formed on the transparent substrate 5, the hard coat layer 6 provided on the transparent substrate 5, the intermediate layer 3 provided on the hard coat layer 6, and the intermediate layer 3. And a transparent conductive layer 4 to be provided. Preferably, the transparent conductive film 1 includes only the transparent base material 5, the hard coat layer 6, the intermediate layer 3, and the transparent conductive layer 4. Hereinafter, each layer will be described in detail.

2. Transparent substrate The transparent substrate 5 is a lower layer of the transparent conductive film 1. The transparent substrate 5 is a support layer (support material) that ensures the mechanical strength of the transparent conductive film 1. The transparent substrate 5 has a film shape extending in the surface direction, and has a flat plane and a flat lower surface (two main surfaces).

  The transparent substrate 5 is made of a polymer film. The polymer film has transparency.

  Examples of the material of the polymer film include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, for example, (meth) acrylic resins (acrylic resin and / or methacrylic resin) such as polymethacrylate, Polyolefin resins such as polyethylene, polypropylene, cycloolefin polymer (COP), for example, polycarbonate resins, for example, polyether sulfone resins, for example, polyarylate resins, for example, melamine resins, for example, polyamide resins, for example, polyimide resins, for example , Cellulose resin, for example, polystyrene resin, for example, synthetic resin of norbornene resin.

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

  From the viewpoints of transparency, mechanical properties, etc., polyester resins and polyolefin resins are preferable, and PET and COP are more preferable.

  The thickness of the transparent substrate 5 is, for example, 2 μm or more, preferably 20 μm or more, and for example, 300 μm or less, preferably 200 μm or less.

  The transparent base material 5 constitutes the base material layer 2 together with the hard coat layer 6 described later. The transparent substrate 5 is a lower layer in the substrate layer 2.

3. Hard Coat Layer The hard coat layer 6 is a layer that improves the scratch resistance of the transparent conductive film 1. The hard coat layer 6 has a film shape extending in the plane direction, and has a substantially flat upper surface and a flat lower surface (two main surfaces).

  The hard coat layer 6 has a film shape (including a sheet shape) and is in direct contact with the entire upper surface of the transparent substrate 5.

  The hard coat layer 6 is made of a resin composition containing a resin such as a thermosetting resin, a thermoplastic resin, or an ultraviolet curable resin. These resins can be used alone or in combination of two or more. From the viewpoint of workability, an ultraviolet curable resin is preferable.

  Examples of the ultraviolet curable resin include acrylic resins such as polyurethane acrylate, polyol acrylate, dipentaerythritol hexaacrylate, and epoxy resins. Moreover, the resin composition can contain an inorganic particle in a suitable ratio as needed.

  The surface (upper surface) of the hard coat layer 6 is subjected to surface treatment. Specific surface treatment will be described in detail later in the manufacturing method.

The surface free energy of the hard coat layer 6 is, for example, 60 mJ / m ² or more, preferably 70 mJ / m ² or more, more preferably 80 mJ / m ² or more, and for example, 95 mJ / m ² or less. .

  The method for measuring the surface free energy of the hard coat layer 6 will be described in detail in a later example.

  The thickness of the hard coat layer 6 is, for example, 0.1 μm or more, preferably 0.5 μm or more, and for example, 10 μm or less, preferably 5 μm or less.

  The hard coat layer 6 constitutes the base material layer 2 together with the transparent base material 5. That is, the base material layer 2 includes the transparent base material 5 and the hard coat layer 6. Preferably, the base material layer 2 consists only of the transparent base material 5 and the hard coat layer 6. The hard coat layer 6 is an upper layer in the base material layer 2.

4). Intermediate Layer The intermediate layer 3 is an intervening layer interposed between the base material layer 2 and the transparent conductive layer 4. The intermediate layer 3 is provided on the upper surface of the hard coat layer 6. The intermediate layer 3 is in direct contact with the entire upper surface of the hard coat layer 6. The intermediate layer 3 has a film shape extending in the surface direction, and has a flat plane and a flat lower surface (two main surfaces).

  Further, the intermediate layer 3 is configured so that the difference between the non-pattern part 8 and the pattern part 7 is not recognized after the transparent conductive layer 4 is arranged in a pattern in a later step (that is, to suppress the visual recognition of the pattern). ), An optical adjustment layer for adjusting the optical characteristics of the transparent conductive layer 4.

  The intermediate layer 3 is made of only resin. That is, the intermediate layer 3 does not substantially contain, for example, inorganic particles (for example, silica) for adjusting the refractive index of the intermediate layer 3. In other words, the intermediate layer 3 may contain inorganic particles at a minute ratio that does not impair the effects of the present invention, and specifically, 0.1% by mass or less with respect to 100 parts by mass of the resin. The inorganic particles having a content ratio of preferably 0.01% by mass or less, more preferably 0.001% by mass or less are allowed.

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

  Examples of the curable resin include an active energy ray-curable resin that is cured by irradiation with active energy rays (specifically, ultraviolet rays, electron beams, etc.), for example, a thermosetting resin that is cured by heating, and the like. Preferably, an active energy ray curable resin is used.

  Specific examples of the curable resin include acrylic resins, for example, urethane resins, for example, melamine resins, for example, alkyd resins, for example, siloxane-based polymers, for example, organosilane condensates, and the like. Preferably, acrylic resin is used.

  Examples of the acrylic resin include an acrylic resin having a fluorene skeleton, an acrylic resin having a phenyl skeleton, an acrylic resin having a urethane (meth) acrylate, and an acrylic resin having a polyisoprene skeleton. Preferably, an acrylic resin having a fluorene skeleton and an acrylic resin having a phenyl skeleton are used.

  As the curable resin, a commercially available product can be used. For example, as an acrylic resin having a fluorene skeleton, the OGSOL series (specifically, OGSOL EA-0200P, OGSOL EA-0250P, OGSOL GA-5000, OGSOL EA- F5710, manufactured by Osaka Gas Chemicals Co., Ltd.), for example, as an acrylic resin having a phenyl skeleton, KAYARAD series (specifically, KAYARAD-HRM-3000H, KAYARAD-BNP-1, manufactured by Nippon Kayaku Co., Ltd.) Can be mentioned.

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

  The refractive index of the resin is, for example, 1.58 or more, preferably 1.59 or more, more preferably 1.61 or more, and, for example, 2.0 or less.

  If the refractive index of the resin is equal to or greater than the above lower limit, the refractive index of the intermediate layer 3 can be adjusted to a range described later.

  The thickness of the intermediate layer 3 is, for example, 30 nm or more, preferably 50 nm or more, more preferably 70 nm or more. If the thickness of the intermediate layer 3 is equal to or greater than the above lower limit, the mechanical strength of the transparent conductive film 1 can be maintained.

  Moreover, the thickness of the intermediate | middle layer 3 is 150 nm or less, for example, Preferably, it is 100 nm or less. If the thickness of the intermediate layer 3 is not more than the above upper limit, the transparent conductive film 1 can be thinned.

  In addition, the measuring method of the thickness of the intermediate | middle layer 3 is explained in full detail in a subsequent Example.

  The refractive index of the intermediate layer 3 is the same as or higher than the refractive index of the resin, specifically, 1.59 or more, preferably 1.60 or more, more preferably 1.61 or more. Yes, and it is 2.0 or less.

  If the refractive index of the intermediate layer 3 is equal to or higher than the above lower limit, it is excellent in visibility suppression when the transparent conductive layer 4 is patterned. That is, if the refractive index of the intermediate layer 3 is less than the above lower limit, the visibility suppression when the transparent conductive layer 4 is patterned decreases.

  If the refractive index of the intermediate layer 3 is equal to or less than the above upper limit, the visibility suppression when the transparent conductive layer 4 is patterned is excellent.

  The intermediate layer 3 is usually a single layer, but it can also be formed in multiple layers.

5. Transparent conductive layer The transparent conductive layer 4 is an upper layer of the transparent conductive film 1. The transparent conductive layer 4 has a film shape (including a sheet shape) extending in the surface direction, and has a flat lower surface and a flat upper surface. The transparent conductive layer 4 is in direct contact with the entire upper surface of the intermediate layer 3. The transparent conductive layer 4 is a patterned electrode layer that can act as an electrode of a touch panel (described later).

  The material for forming the transparent conductive layer 4 is, for example, at least 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 containing one kind of metal can be given. If necessary, the metal oxide can be further doped with metal atoms shown in the above group.

  As a material, Preferably, indium tin complex oxide (ITO), antimony tin complex oxide (ATO), etc. are mentioned, More preferably, ITO is mentioned.

  The thickness of the transparent conductive layer 4 is, for example, 10 nm or more, preferably 20 nm or more, and for example, 35 nm or less, preferably 30 nm or less.

The specific resistance value of the transparent conductive layer 4 is, for example, 1.0 × 10 ⁻⁴ Ω · cm or more, for example, 3.00 × 10 ⁻⁴ Ω · cm or less, preferably 2.90 × 10 ^−4. Ω · cm or less, more preferably 2.80 × 10 ⁻⁴ Ω · cm or less, further preferably 2.70 × 10 ⁻⁴ Ω · cm or less, and particularly preferably 2.65 × 10 ⁻⁴ Ω · cm. cm or less.

If the specific resistance value of the transparent conductive layer 4 is not more than the above upper limit, a touch panel (described later) including the transparent conductive film 1 can be enlarged.
6). Manufacturing method of transparent conductive film This transparent conductive film 1 is obtained by disposing the hard coat layer 6, the intermediate layer 3, and the transparent conductive layer 4 in this order on the transparent substrate 5.

  In order to dispose the hard coat layer 6 on the surface of the transparent substrate 5, for example, the above-described resin composition is applied to the surface of the transparent substrate 5, and when the resin is an ultraviolet curable resin, it is irradiated with ultraviolet rays. And cure.

  Next, a surface treatment is performed on the surface (upper surface) of the hard coat layer 6.

  By this surface treatment, the surface free energy of the hard coat layer 6 is increased.

  Examples of the surface treatment include dry treatment such as sputtering, plasma treatment, corona treatment, ultraviolet irradiation, and electron beam irradiation, and wet treatment such as undercoating treatment.

  From the viewpoint of adhesion, preferably, dry treatment, more preferably corona treatment, plasma treatment, and still more preferably plasma treatment.

  In the plasma treatment, for example, the surface (upper surface) of the hard coat layer 6 is irradiated with plasma.

  Thereby, the hard coat layer 6 after the surface treatment has the surface free energy described above.

The surface free energy of the hard coat layer 6 before the surface treatment is, for example, less than 60 J / m ² , preferably 50 J / m ² or less, more preferably 40 J / m ² or less, and further preferably 30 J / m. ² or less.

  Percentage of surface free energy of hard coat layer 6 after surface treatment to surface free energy of hard coat layer 6 before surface treatment (surface free energy of hard coat layer 6 after surface treatment / hard coat layer 6 before surface treatment) The surface free energy × 100) is, for example, 120% or more, preferably 140% or more, more preferably 160% or more, further preferably 180% or more, and for example, 300% or less. is there.

  If the surface free energy of the hard coat layer 6 after the surface treatment is equal to or more than the lower limit described above, the repelling of the resin is suppressed, the hard coat layer 6 is contacted, and the intermediate layer 3 made of only the resin can be formed uniformly. As a result, the specific resistance value of the transparent conductive layer 4 can be lowered.

  Next, the intermediate layer 3 is disposed on the surface of the hard coat layer 6. In order to arrange the intermediate layer 3 on the surface of the hard coat layer 6, for example, the above-described resin is applied to the surface of the hard coat layer 6, and when the resin is an active energy ray curable resin, ultraviolet rays are irradiated. , Cure.

  Next, the transparent conductive layer 4 is disposed on the surface of the intermediate layer 3. In order to arrange the transparent conductive layer 4 on the surface of the intermediate layer 3, for example, sputtering is used. The transparent conductive layer 4 is amorphous, for example.

  Thereby, the transparent conductive film 1 is obtained.

  The transparent conductive film 1 can be obtained by laminating each layer by, for example, a roll-to-roll method. Thereby, the transparent conductive film 1 is obtained as a wound body wound up in a roll shape.

  The thickness of the transparent conductive film 1 is, for example, 20 μm or more, preferably 30 μm or more, and for example, 200 μm or less, preferably 150 μm or less.

  The transparent conductive film 1 is a part of a touch panel, that is, a part for producing a touch panel. Specifically, after the transparent conductive layer 4 of the transparent conductive film 1 is patterned by a method described later. This is a component mounted on the touch panel. In other words, the transparent conductive film 1 is a device that can be distributed industrially and used alone.

  As shown in FIG. 2, in the transparent conductive film 1, the transparent conductive layer 4 is patterned. In order to pattern the transparent conductive layer 4, for example, the transparent conductive layer 4 is etched. Accordingly, the transparent conductive film 1 has a pattern portion 7 having the transparent conductive layer 4 and a non-pattern portion 8 not having the transparent conductive layer 4.

  After patterning the transparent conductive layer 4, the transparent conductive layer 4 is crystallized, for example, by heating.

7). Use of transparent conductive film Such a transparent conductive film 1 is used as a touch panel in an image display device, for example.

  The touch panel is a touch sensor that operates a computer connected to the image display device by bringing a finger, a pen, or the like into contact with a menu displayed on the image display device.

  Examples of the touch panel include various methods such as an optical method, an ultrasonic method, a capacitance method, and a resistance film method. The transparent conductive film 1 is particularly suitably used for a capacitive touch panel.

8). Effect In this transparent conductive film 1, since the intermediate | middle layer 3 has a high refractive index of 1.59 or more, it is excellent in the visibility suppression in the case of patterning the transparent conductive layer 4. FIG.

  Further, the intermediate layer 3 is made only of a resin and does not substantially contain inorganic particles. Therefore, for example, when the transparent conductive layer 4 is crystallized, inhibition of crystal growth of the transparent conductive layer 4 due to inorganic particles can be suppressed. Therefore, the specific resistance value of the transparent conductive layer 4 can be lowered.

However, when the base material layer has a surface free energy of less than 60 mJ / m ^2, when the intermediate layer made only of the resin is formed on the base material layer, the repelling of the resin occurs and the intermediate layer is made uniform. There are cases where it cannot be formed.

  However, in the transparent conductive film 1, since the surface free energy of the hard coat layer 6 is equal to or higher than the lower limit described above, the intermediate layer 3 consisting only of the resin is suppressed by suppressing the repelling of the resin. It can be formed uniformly, and as a result, the specific resistance value of the transparent conductive layer 4 can be lowered.

  In the transparent conductive film 1, since the thickness of the intermediate layer 3 is in the above-described range, it is possible to reduce the thickness while maintaining the mechanical strength.

  In the transparent conductive film 1, since the base material layer 2 includes the hard coat layer 6, the scratch resistance can be improved.

  In the transparent conductive film 1, since the intermediate layer 3 is an optical adjustment layer, as shown in FIG. 2, it is excellent in visibility suppression when the transparent conductive layer 4 is patterned.

  In the transparent conductive film 1, the transparent conductive layer 4 is patterned, and includes the pattern portion 7 having the transparent conductive layer 4 and the non-pattern portion 8 not having the transparent conductive layer 4. And the non-pattern part 8 are suppressed from being visually recognized and excellent in visibility suppression.

  Since the transparent conductive film 1 is a wound body wound up in a roll shape, it is excellent in workability and transportability.

  If it is a touchscreen provided with the transparent conductive film 1, since it is excellent in visual recognition suppression and has a low specific resistance value, it can enlarge.

9. Second Embodiment In the following second embodiment, members and processes corresponding to the above-described parts are denoted by the same reference numerals, and detailed description thereof is omitted.

  In the first embodiment, as shown in FIG. 1, in the transparent conductive film 1, the base material layer 2 includes a hard coat layer 6. In the second embodiment, as shown in FIG. 3, the base material layer 2 may not be provided with the hard coat layer 6 and may be composed of only the transparent substrate 5.

  That is, in this 2nd Embodiment, the transparent conductive film 1 is equipped with the transparent base material 5, the intermediate | middle layer 3, and the transparent conductive layer 4 in order. The base material layer 2 consists only of the transparent base material 5. The intermediate layer 3 is in direct contact with the entire upper surface of the transparent substrate 5.

  The transparent conductive film 1 can be produced by sequentially arranging the intermediate layer 3 and the transparent conductive layer 4 on the transparent base material 5.

  In the method for producing the transparent conductive film 1 of the second embodiment, first, a surface treatment is performed on the surface (upper surface) of the transparent substrate 5.

  As the surface treatment, the same method as in the first embodiment can be mentioned.

  By the surface treatment described above, the surface free energy of the transparent substrate 5 is increased.

The surface free energy of the transparent substrate 5 after the surface treatment is, for example, 60 mJ / m ² or more, preferably 70 mJ / m ² or more, more preferably 80 mJ / m ² or more, and for example, 95 mJ / m. ² or less.

The surface free energy of the transparent substrate 5 before the surface treatment is, for example, less than 60 J / m ² , preferably 50 J / m ² or less, more preferably 40 J / m ² or less, and further preferably 30 J / m. ² or less.

  Percentage of the surface free energy of the surface free energy of the transparent substrate 5 after the surface treatment with respect to the surface free energy (the surface free energy of the surface of the transparent substrate 5 after the surface treatment / the surface of the transparent substrate 5 before the surface treatment) The surface free energy × 100) is, for example, 120% or more, preferably 140% or more, more preferably 160% or more, further preferably 180% or more, and for example, 300% or less. is there.

  If the surface free energy of the transparent substrate 5 after the surface treatment is equal to or more than the lower limit described above, the repelling of the resin is suppressed, the intermediate layer 3 made of only the resin can be uniformly formed by contacting the transparent substrate 5, As a result, the specific resistance value of the transparent conductive layer 4 can be lowered.

  The method for measuring the surface free energy of the transparent substrate 5 is the same as the method for measuring the surface free energy of the hard coat layer 6.

  Next, the intermediate layer 3 is disposed on the surface of the transparent substrate 5. In order to arrange the intermediate layer 3 on the surface of the transparent substrate 5, for example, the above-described resin is applied to the surface of the transparent substrate 5, and when the resin is an active energy ray curable resin, ultraviolet rays are irradiated. , Cure.

  Next, the transparent conductive layer 4 is disposed on the surface of the intermediate layer 3. In order to arrange the transparent conductive layer 4 on the surface of the intermediate layer 3, for example, sputtering is used. The transparent conductive layer 4 is amorphous, for example.

  Thereby, the transparent conductive film 1 is obtained.

  Next, as shown in FIG. 4, in the transparent conductive film 1, the transparent conductive layer 4 is patterned by etching.

  Next, the transparent conductive layer 4 is crystallized, for example, by heating.

  Also according to the second embodiment, the same effects as those of the first embodiment shown in FIG. 1 can be achieved.

  Moreover, since the base material layer 2 consists only of the transparent base material 5, compared with 1st Embodiment shown in FIG. Can be manufactured at low cost.

10. Modification In the first embodiment, the surface treatment (upper surface) of the hard coat layer 6 is subjected to the surface treatment, but for example, the surface treatment may not be performed.

  In 2nd Embodiment, although the surface treatment was given to the surface (upper surface) of the transparent base material 5, it is not necessary to give a surface treatment, for example.

In 1st Embodiment, although the resin composition was apply | coated to the surface of the transparent base material 5, and the hard-coat layer 6 was arrange | positioned on the surface of the transparent base material 5, for example, the sheet-like hard coat layer 6 surface-treated beforehand. Can be prepared and affixed to the surface of the transparent substrate 5.

  In 1st Embodiment and 2nd Embodiment, although the intermediate | middle layer 3 demonstrated as an optical adjustment layer, the functional layer which provides the functionality according to the objective may be sufficient, for example, in a roll-to-roll method, It may be a blocking layer for suppressing the overlapping transparent conductive films 1 from being in close contact with each other.

  In the first embodiment and the second embodiment, the amorphous transparent conductive layer 4 is etched and then crystallized. For example, the amorphous transparent conductive layer 4 is crystallized and then etched. You can also.

  In 1st Embodiment and 2nd Embodiment, although the transparent conductive film 1 is manufactured by the roll-to-roll method, for example, one part or all can also be manufactured by a batch system.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not limited to an Example and a comparative example at all. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to.

In addition, the symbol of each component used for a following example and a comparative example is shown below.
OGSOL EA-0250P: trade name, acrylic resin (active energy ray curable resin), refractive index 1.62, KAYARAD-HRM-3000H manufactured by Osaka Gas Chemicals Co., Ltd .: trade name, acrylic resin (active energy ray curable resin) ), Refractive index 1.62, KAYARAD-BNP-1 manufactured by Nippon Kayaku Co., Ltd .: trade name, acrylic resin (active energy ray curable resin), refractive index 1.62, Opstar Z7412 manufactured by Nippon Kayaku Co., Ltd .: trade name , Organic-inorganic composite materials (including ZrO ₂ as an inorganic material), refractive index 1.62, DPHA manufactured by JSR Corporation: trade name “M-400”, dipentaerythritol penta and hexaacrylate, refractive index 1.53, Toagosei Co., Ltd. 1. Production of transparent conductive film Example 1
100 parts by mass of dipentaerythritol hexaacrylate (trade name “A-DPH” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 5 parts by mass of hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator And then diluted with 100 parts by mass of methyl isobutyl ketone to prepare a hard coating agent.

Next, COP (thickness 100 μm, trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.) is prepared as a transparent substrate, and the resin composition is applied to the surface using a bar coater, dried, and irradiated with ultraviolet rays. Then, the resin composition was cured, and thereby a hard coat layer having a thickness of 5 μm was disposed on the surface of the transparent substrate. The surface free energy of the surface of the hard coat layer before the surface treatment was 30 mJ / m ² .

Subsequently, the surface of the hard coat layer was irradiated with plasma (frequency 20 kHz, processing power 150 V, processing time 20 seconds). The surface free energy of the surface of the hard coat layer after the surface treatment was 60 mJ / m ² .

  Next, OGSOL EA-0250P as a resin is applied to the surface of the hard coat layer using a spin coater, dried, and irradiated with ultraviolet rays to cure the resin. Layers were placed.

  The thickness of the obtained intermediate layer was 85 nm and the refractive index was 1.63.

  The thickness of the intermediate layer was calculated by measuring the reflection spectrum using U4100 manufactured by HITACHI and comparing the calculated value by the optical simulation with the spectrum shape.

  Then, the transparent conductive layer which consists of ITO with a thickness of 20 nm was arrange | positioned on the surface of the intermediate | middle layer using the winding-type sputtering device.

  Thereby, the transparent conductive film was manufactured.

  The surface free energy was measured using a “fully automatic contact angle meter DM700” manufactured by Kyowa Interface Science Co., Ltd., by measuring the contact angle of water and the contact angle of hexadecane with respect to the hard coat layer. The value was analyzed with analysis software FAMAS, and the surface free energy was calculated. As a calculation method, component analysis based on Kitazaki-Hat theory was used.

Examples 2 and 3, Comparative Examples 1 and 2
A transparent conductive film was produced in the same procedure as in Example 1 except that the change was made according to Table 1.

2. Evaluation 2-1. The surface resistance (Ω / cm) of the transparent conductive layer of each transparent conductive film was measured using a specific resistance four-terminal method (JIS K7194 (1994)). Next, the thickness of the transparent conductive layer was measured with a fluorescent X-ray analyzer (manufactured by Rigaku Corporation), and the specific resistance was calculated from the measured surface resistance and thickness.

  The results are shown in Table 1.

2-2. Visibility inhibition property The transparent conductive layer was etched to pattern the transparent conductive layer.

  Next, a black acrylic plate was bonded to the lower surface of the transparent substrate. Subsequently, visual recognition suppression of the pattern part was evaluated visually from the upper side of the transparent conductive layer. The case where the pattern portion was hardly visually recognized was evaluated as “◯”, and the case where the pattern portion was clearly recognized was evaluated as “x”.

  The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Transparent conductive film 2 Base material layer 3 Intermediate | middle layer 4 Transparent conductive layer 5 Transparent base material 6 Hard coat layer 7 Pattern part 8 Non-pattern part

Claims (9)

A substrate layer including a transparent substrate, an intermediate layer, and a transparent conductive layer are provided in this order.
The said intermediate | middle layer consists only of resin, and has a refractive index of 1.59 or more, The transparent conductive film characterized by the above-mentioned. The intermediate layer is in contact with the substrate layer;
The transparent conductive film according to claim 1, wherein the base material layer has a surface free energy of 60 mJ / m ² or more.   The transparent conductive film according to claim 1, wherein the intermediate layer has a thickness of 30 nm or more and 150 nm or less. The base material layer comprises the transparent base material and a hard coat layer in order,
The transparent conductive film according to claim 1, wherein the hard coat layer is in contact with the intermediate layer.   The transparent conductive film according to claim 1, wherein the base material layer is composed of only the transparent base material.   The said intermediate | middle layer is an optical adjustment layer, The transparent conductive film as described in any one of Claims 1-5 characterized by the above-mentioned. The transparent conductive layer is patterned,
A pattern portion having the transparent conductive layer;
The transparent conductive film according to claim 1, further comprising a non-pattern part not having the transparent conductive layer.   The transparent conductive film according to any one of claims 1 to 7, wherein the transparent conductive film is a wound body wound up in a roll shape.   A touch panel comprising the transparent conductive film according to claim 7.

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