TWI494225B - A hard coat substrate and a transparent conductive film using the same - Google Patents

Description

Hard coat substrate and transparent conductive film using the same

According to the present invention, the pattern trace between the pattern portion and the non-pattern portion of the patterned transparent conductive film can be made unrecognizable, and the interference fringe can be reduced, and the transparent conductive property having a good appearance can be recognized for the touch panel use. film.

The touch panel has a resistive film method, an electrostatic capacity method, an optical type, an ultrasonic method, and the like depending on the difference in the detection method. Among them, in recent years, the market for multi-touch, such as smart phones or tablet PCs, which is a possible electrostatic capacity type touch panel, has gradually increased. The electrostatic capacitance method, in particular, the projection type touch panel is configured by pairing patterned transparent conductive films, and detecting position information by detecting a change in electrostatic capacitance of the touch portion. In the transparent conductive film used in the electrostatic capacitance method, the pattern portion and the non-pattern portion having the transparent conductive layer are present. Therefore, the pattern difference between the pattern portion and the non-pattern portion is different, and the pattern mark cannot be visually recognized. There is a problem that the display element of the touch panel has a poor appearance when viewed.

In view of the above problems, Patent Document 1 discloses that it is transparent. The conductive layer is provided with at least two types of undercoat layers, and the transparent conductive film of which the refractive index and the thickness of the base coating layers are each set to a specific value to improve the appearance of the display element.

Further, Patent Document 2 discloses that a transparent coating layer is provided with a hard coating layer and an intermediate layer having a specific refractive index and thickness, and a transparent conductive film which is an appearance of a display element is similarly improved.

Further, Patent Document 3 discloses that by adjusting the refractive index of the hard coating constituting the transparent conductive film, the patterned transparent conductive film does not have a striking transparent conductive film.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Patent No. 4647741

[Patent Document 2] JP-A-2012-25066

[Patent Document 3] JP-A-2010-208169

However, in Patent Document 1, the refractive index of the first layer of the base coating layer is from 1.5 to 1.7 from the transparent base film, and the color difference between the pattern portion and the non-pattern portion is obtained when the transparent conductive layer is patterned in the refractive index range ( △ E) The improvement is insufficient. Further, in claim 1 of Patent Document 1, it is described that the base coating layer farthest from the transparent film substrate is also the same as the transparent conductive layer. The sample was patterned. This is because at least two projects are required for the patterning process, and the possibility of complicated engineering or increased cost is high, and the base coating layer is not patterned and remains, resulting in that the chromatic aberration between the pattern portion and the non-pattern portion is not sufficiently improved. Further, when the entire optical thickness of the transparent conductive layer including the undercoat layer is 208 to 554 nm, and the functional layer such as hard coating is formed on the opposite surface of the transparent conductive layer, the thickness balance of both surfaces is liable to become uneven, and is transparent. When the conductive film is selectively annealed, a curl of a film is generated, which may cause a problem in film processing.

On the other hand, Patent Document 2 laminates a hard coat layer, an intermediate layer, and a tin-doped indium oxide layer (ITO layer) on a transparent base film to improve the appearance, but it is required to include a hard coat layer, an intermediate layer, and a back surface. A coating process of at least three layers of the coating layer may be problematic in terms of cost. Further, in the formation of the transparent conductive layer starting from the ITO layer, a low refractive index layer such as ruthenium oxide is often formed under the ITO layer for the purpose of improving the adhesion and the improvement of the visibility, and it is difficult to sufficiently improve the pattern portion in the above configuration. The color difference between the non-pattern parts.

Further, the transparent planar body disclosed in Patent Document 3 includes a transparent conductive film laminated in the order of a transparent conductive film, a base coating layer, a hard coat layer, and a transparent substrate, and a surface of the base coating layer. A cover layer to be covered in which the pattern shape of the transparent conductive film is not conspicuous by optimizing the refractive index of the hard coat layer. Specifically, the refractive index of the hard coat layer is set to 1.60 or more and 1.80 or less to improve the visibility of the pattern shape. However, when the refractive index on the substrate is set to be high refractive index, the refractive index difference between the substrates is obtained. Become bigger The interference fringes caused by the light interference between the coating film and the substrate tend to become conspicuous. Therefore, when a transparent substrate having an easy-adhesion layer having a general refractive index as used in the examples of Patent Document 3 is used, when the transparent planar body is used as a member of a display element, appearance defects may occur.

The present invention has been made to solve the above problems of the prior art, and an object of the present invention is to provide a transparent conductive film which has a very good appearance as a display element because the patterned shape of the transparent conductive layer is not conspicuous at a low cost.

The Hard Coat substrate of the present invention comprises a transparent substrate, an easy adhesion layer, and a refractive index adjusting layer, wherein the refractive index adjusting layer is at a wavelength of 550 nm. The refractive index is 1.60 to 1.90, the thickness of the refractive index adjusting layer is 0.3 to 5 μm, and the refractive index of the above-mentioned easy-adhesion layer at a wavelength of 550 nm is 1.56 to 1.70.

Further, the transparent conductive film of the present invention is a transparent conductive film comprising a transparent conductive layer and a hard coated substrate, wherein the hard coated substrate comprises a transparent substrate, an easy-to-attach layer, and In the refractive index adjusting layer, the refractive index adjusting layer has a refractive index of 1.60 to 1.90 at a wavelength of 550 nm, the refractive index adjusting layer has a thickness of 0.3 to 5 μm, and the refractive index of the easy-adhesion layer at a wavelength of 550 nm is 1.56. 1.70, wherein the transparent conductive layer is disposed on the refractive index adjusting layer, wherein the transparent conductive layer has a refractive index of 1.8 to 2.3 at a wavelength of 550 nm, and the transparent conductive layer has a thickness of 10 to 30 nm.

According to the present invention, it is possible to provide a transparent conductive film which is inconspicuous in the patterned shape of the transparent conductive layer and which has an excellent appearance as a display element at a low cost.

10,20‧‧‧Transparent conductive film

11,21‧‧‧ Transparent substrate

12,22‧‧‧Easy layer

13,23‧‧‧index adjustment layer

14,24‧‧‧low refractive index layer

15,25‧‧‧Transparent conductive layer

15a, 25a‧‧‧ Pattern Department

15b, 25b‧‧‧Non-pattern department

26‧‧‧ functional layer

Fig. 1 is a schematic cross-sectional view showing an example of a transparent conductive film of the present invention.

Fig. 2 is a schematic cross-sectional view showing another example of the transparent conductive film of the present invention.

The hard coated substrate of the present invention is provided with a transparent substrate, an easy-adhesion layer, and a refractive index adjusting layer, wherein the refractive index adjusting layer has a refractive index of 1.60 to 1.90 at a wavelength of 550 nm, and the above refraction The thickness of the rate adjusting layer is 0.3 to 5 μm, and the refractive index of the above-mentioned easy-adhesion layer at a wavelength of 550 nm is 1.56 to 1.70.

Moreover, the transparent conductive film of the present invention includes a transparent conductive layer and a hard coated substrate, and the hard coated substrate includes a transparent substrate, an easy-adhesion layer, and a refractive index adjusting layer. The refractive index adjusting layer has a refractive index of 1.60 to 1.90 at a wavelength of 550 nm, a thickness of the refractive index adjusting layer of 0.3 to 5 μm, and a refractive index of the easily-adhesive layer at a wavelength of 550 nm of 1.56 to 1.70. layer, The transparent conductive layer has a refractive index of 1.8 to 2.3 at a wavelength of 550 nm and a thickness of the transparent conductive layer of 10 to 30 nm.

In the above-mentioned transparent conductive film using the above-mentioned hard-coated substrate, the patterned shape of the transparent conductive layer is not conspicuous, and it has a very good appearance as a display element.

Hereinafter, the present invention will be described in detail based on the drawings.

Fig. 1 is a schematic cross-sectional view showing an example of a transparent conductive film according to a first embodiment of the present invention. In Fig. 1, a transparent conductive film 10 of the present invention is formed by sequentially laminating a transparent substrate 11, an easy-contact layer 12, a refractive index adjusting layer 13, a low refractive index layer 14, and a transparent conductive layer 15. Further, the transparent conductive layer 15 is patterned by the pattern portion 15a composed of the transparent conductive layer 15 and the non-pattern portion 15b from which the transparent conductive layer 15 is removed. In Fig. 1, the transparent substrate 11, the easy-adhesion layer 12, and the refractive index adjusting layer 13 correspond to the hard coated substrate of the present invention.

2 is a schematic cross-sectional view showing another example of the transparent conductive film of the second embodiment of the present invention. In FIG. 2, the transparent conductive film 20 of the present invention is formed by sequentially laminating a transparent substrate 21, an easy-adhesion layer 22, a refractive index adjusting layer 23, a low refractive index layer 24, and a transparent conductive layer 25. The organic energy supply layer 26 is disposed on the side opposite to the side on which the refractive index adjustment layer 23 of the transparent substrate 21 is formed. Further, the transparent conductive layer 25 is patterned by the pattern portion 25a composed of the transparent conductive layer 25 and the non-pattern portion 25b from which the transparent conductive layer 25 is removed. 2, the transparent substrate 21, the easy adhesion layer 22 and the refractive index adjustment layer 23 It corresponds to the hard coated substrate of the present invention. The difference between FIG. 1 and FIG. 2 differs only in the presence or absence of the function providing layer 26, and the other components are the same.

<Transparent substrate>

The type of the transparent substrate is not particularly limited, and a resin film having transparency is usually used. Further, the resin used for the resin film is, for example, a polyester resin, a polycarbonate resin, a polymethyl methacrylate (PMMA) resin, a cellulose triacetate (TAC) resin, a polyolefin (PO) resin, or the like. The polyester resin, in which polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferred, from the viewpoint of cost surface or refractive index adjustment. The thickness of the transparent substrate is not particularly limited, and is preferably from 10 to 250 μm, more preferably from 20 to 188 μm, in consideration of balance between light transmittance and strength.

<easy layer>

An easy-adhesion layer is formed on the surface of the transparent substrate in order to impart adhesion to the upper coating film. The refractive index of the above-mentioned easy-adhesion layer for the wavelength of 550 nm needs to be in the range of 1.56 to 1.70, more preferably 1.60 to 1.68. In the transparent conductive film of the present invention, in order to make the pattern of the transparent conductive layer unrecognizable, it is necessary to apply a refractive index adjusting layer having a high refractive index to the transparent substrate, but the refractive index of the easily-adhesive layer of the transparent substrate is less than 1.56. The difference in refractive index between the layer and the coated refractive index adjusting layer is increased, and the interference fringe is likely to become conspicuous. When the refractive index is greater than 1.70, the difference in refractive index between the transparent substrate and the transparent substrate is increased, which is not preferable.

The above-mentioned easy-adhesion layer may be formed by a person who has been previously processed at the time of film formation of a transparent substrate, or may be formed by applying an easy-adhesion layer by a method such as wet coating. When the above-mentioned easy-adhesion layer is separately formed on the transparent substrate, a material for the easy-adhesion layer is usually used, for example, a polyester resin, a polymethyl methacrylate resin, a urethane resin, an epoxy resin, a polycarbonate resin, or the like. . Further, in the case of the high refractive index of the above-mentioned easy-adhesion layer, a material having a high refractive index such as titanium oxide may be dispersed in the easy-adhesion layer, and the aqueous polyester resin and the water-soluble inorganic chelating compound may be dispersed in the easily-adhesive layer ( Inorganic chelate compound) Alternatively, a polyester resin having a high refractive index fluorene backbone may be applied to a transparent substrate to form an easy-adhesion layer.

The thickness of the above-mentioned easy-adhesion layer is not particularly limited, but is usually about 50 to 150 nm.

<refractive index adjustment layer>

A refractive index adjusting layer is formed on the above-mentioned easy-adhesion layer. The refractive index adjusting layer needs to have a refractive index of 550 nm of 1.60 to 1.90, more preferably 1.65 to 1.80. By setting the refractive index of the refractive index adjusting layer to the above range, the transparent conductive film of the present invention can reduce the chromatic aberration caused by the presence or absence of the patterned pattern portion of the transparent conductive layer. When the refractive index is less than 1.60, the chromatic aberration of the pattern portion ‧ non-pattern portion cannot be sufficiently reduced, and when it is higher than 1.90, the difference in refractive index between the transparent substrate and the easy-to-adhere layer becomes large, and the interference fringe of the refractive index adjusting layer becomes conspicuous. There is a problem in appearance when it is a transparent conductive film.

Further, the thickness of the refractive index adjusting layer needs to be 0.3 to 5 μm, more preferably 0.5 to 3 μm. When the thickness is less than 0.3 μm, the function of the hard coating layer is not sufficiently exhibited, and the annealing treatment is performed at 150 ° C for 30 minutes for the purpose of crystallization and stabilization of the transparent conductive layer. The elution of the low molecular weight component of the substrate does not allow the refractive index adjusting layer to be blocked, resulting in deterioration of the optical characteristics (especially, an increase in haze, etc.) of the transparent conductive film of the present invention. Further, when the thickness is more than 5 μm, the light transmittance is lowered or the haze is increased, which is disadvantageous for workability or cost.

Since the refractive index adjusting layer is required to have a high refractive index, it is preferably a metal oxide such as titanium oxide or zirconium oxide containing a high refractive index filler. In addition, after the coating liquid in which the metal oxide and the ultraviolet curable resin are combined is applied onto the easy-adhesion layer, ultraviolet irradiation is performed by a high-pressure mercury lamp or a metal halide lamp to cure the coating film to form a refractive index adjusting layer. Better. That is, in order to improve the efficiency of the manufacturing process, the above refractive index adjusting layer is preferably formed by a wet coating method. The method of the above wet coating is not particularly limited, and it can be applied by a known method such as roll coating, die coating, air knife coating, blade coating, reverse coating, gravure coating, or micro gravure coating.

The material of the above ultraviolet curable resin is usually a material using a compound having a double bond which is possible by radical polymerization. For example, a monomer, a prepolymer or a polymer having an unsaturated polymerizable functional group such as a (meth)acryloyl group, a vinyl group, a styryl group or an allyl group can be used. They can be used alone or in combination Two or more kinds are used, and among them, a monomer having a (meth)acryloyl group and a prepolymer are preferably used. In addition, it is preferable to use a polyfunctional resin having two or more unsaturated groups (double bond) which may be radically polymerized from the viewpoint of both productivity and hardness.

<low refractive index layer>

Preferably, a low refractive index layer is disposed between the refractive index adjusting layer and the transparent conductive layer. By the arrangement of the low refractive index layer described above, the function of the optical refractive index adjusting layer can be solved, and the effect of improving the adhesion between the transparent conductive layers laminated thereon can be obtained. The low refractive index layer has a refractive index of 135 nm and a refractive index of 1.35 to 1.45, and the thickness thereof is 5 to 30 nm.

As a constituent material of the low refractive index layer, for example, cerium oxide, aluminum fluoride, lithium fluoride, magnesium fluoride, calcium fluoride, cesium fluoride, sodium fluoride or the like can be used. Further, the low refractive index layer can be formed by a sputtering method, a vacuum deposition method, an ion plating method, a CVD method, or the like, and the film formation by the sputtering method has the advantage of productivity because of the high film formation speed.

<Transparent Conductive Layer>

The transparent conductive layer is formed on the low refractive index layer. When the low refractive index layer is not disposed, the transparent conductive layer is directly formed on the refractive index adjusting layer. The constituent material of the transparent conductive layer is not particularly limited as long as it has good transparency and high conductivity, and for example, tin oxide, indium-doped tin oxide (ITO), antimony-doped tin oxide (ATO), and fluorine can be used. Doped with tin oxide (FTO), zinc oxide, aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO) and other metal oxides, especially ITO with high transparency and conductivity. Further, the transparent conductive layer can be formed by a sputtering method, a vacuum deposition method, an ion plating method, a CVD method, or the like, and the film formation by the sputtering method has the advantage of productivity because of the high film formation speed.

Further, as described above, the transparent conductive layer can be annealed at 150 ° C for 30 minutes for the purpose of crystallization and stabilization of the transparent conductive layer.

The refractive index of the transparent conductive layer is determined according to the material of the transparent conductive layer, and the refractive index of the transparent conductive layer at a wavelength of 550 nm is in the range of 1.8 to 2.3, in order to adjust the refractive index of the layer by the set refractive index. The color difference suppression effect of the pattern portion and the non-pattern portion is preferably 1.9 to 2.2 in the refractive index of the transparent conductive layer at a wavelength of 550 nm.

Further, the thickness of the transparent conductive layer is preferably from 10 to 30 nm, more preferably from 12 to 25 nm. When the thickness is thinner than 10 nm, the desired specific resistance cannot be obtained, and the desired electrode characteristics cannot be obtained. When the thickness is 30 nm, the light transmittance is lowered, and the optical characteristics may not be satisfied.

As shown in FIGS. 1 and 2, the transparent conductive layer may be patterned into a desired pattern for the purpose thereof. The patterning method can be, for example, a photolithography method in which a photoresist is applied to a transparent conductive layer to form a photoresist, and etching is performed. In FIG. 1 and FIG. 2, the state in which the transparent conductive layer is patterned is a state in which the low refractive index layer remains, and the low refractive index layer can be removed during patterning.

The color difference (ΔE) between the reflection chromaticity of the pattern portion formed of the transparent conductive layer and the reflection chromaticity of the non-pattern portion from which the transparent conductive layer is removed is preferably 5 or less, more preferably 3 or less. When ΔE is larger than 5, the pattern portion and the non-pattern portion can be clearly recognized, and when the transparent conductive film of the present invention is incorporated into the display element, the appearance is impaired.

Here, the color difference (ΔE) can be calculated by the following formula in accordance with the L ^* a ^* b ^* chromaticity diagram.

△E=(△L ^*2 +Δa ^*2 +△b ^*2 ) ^1/2

<function layer>

On the side opposite to the side of the above-mentioned transparent substrate on which the refractive index adjusting layer is formed, a function providing layer can be further disposed as shown in Fig. 2 . The above functional providing layer may be, for example, a hard coat layer, an AN (Anti-Newton's rings layer, an AFP (anti-fingerprint) layer, an antireflection layer, or the like.

Further, when the transparent conductive film of the present invention is produced, in order to simplify the process without using a protective layer film, it is preferred to wind the film without adhesion (adhesion). Therefore, the functional providing layer is preferably resistant to adhesion.

For example, when a smooth coating film of a hard coating layer is applied to both surfaces of a transparent substrate, adhesion (adhesion) occurs during winding of the film, which may cause difficulty in winding. Therefore, the protective layer film is usually adhered to the coated side of the sheet side so that it can be taken up. However, when the protective layer film is pasted, it is transparent conductive The manufacturing and processing of thin films will result in an extra project, which may increase the cost. Therefore, the above-mentioned function is provided with a function called layer anti-adhesive property, that is, a function of having a minute uneven shape on the surface of the coating film, which can suppress adhesion between the coating films, and it is not necessary to protect the layered film during winding. Winding in the case of adhesion.

The method for providing the anti-adhesive property of the above-mentioned function providing layer is not particularly limited. For example, a coating material containing a filler of a specific size may be applied, and drying may be performed to cause a filler exudation function to provide a surface of the layer to form a fine uneven structure. Provides a method of anti-adhesion. In addition, a plurality of resin components having different physical properties and lacking in compatibility are mixed, and phase separation occurs during drying, and the resin is analyzed to form a surface of the coating film, and the function providing layer has irregularities to form an anti-adhesion property. .

The above-mentioned function providing layer also has a dissolution function for suppressing a low molecular weight component derived from a transparent substrate during annealing of the transparent conductive layer. Further, in the above-described function providing layer, the effect of suppressing the curl of the transparent conductive film during annealing treatment is also obtained. Therefore, when the thickness of the refractive index adjusting layer on the side of the transparent conductive layer is a, and the thickness of the functional providing layer on the opposite side is b, the thickness is preferably in the range of 2a > b > 0.5a. When the thickness outside the above range is set, the balance of heat shrinkage of the two coating films is largely collapsed, which may cause curling of the film.

The above-described function providing layer is preferably formed by the aforementioned wet coating method for the efficiency of the manufacturing process.

[Examples] <Production of refractive index adjustment coating>

The refractive index adjusting coatings 1 to 4 were produced as follows.

(refractive index adjustment coating 1)

A dispersion of zirconia having an average particle diameter of 5 nm "SZR-K" (solid content concentration: 30% by mass) of 100 parts by mass, pentaerythritol hexaacrylate "KAYARAD DPHA" (Japanese chemical) The 10 parts by mass of the ultraviolet curable resin of the company and the photopolymerization initiator "IRGACURE 184" (manufactured by BASF Corporation) were mixed in a mass portion of 0.3 to prepare a refractive index adjusting coating material 1. The refractive index of the cured product of the refractive index adjusting coating material 1 produced at 550 nm was measured and found to be 1.71.

(refractive index adjustment coating 2)

The refractive index adjusting coating material 2 was produced in the same manner as the refractive index adjusting coating material 1 except that the amount of use of "KAYARAD DPHA" was changed to 7.5 parts by mass, and the amount of use of "IRGACURE 184" was changed to 0.2 parts by mass. The refractive index of the cured product of the produced refractive index adjusting coating material 2 at 550 nm was measured and found to be 1.75.

(refractive index adjustment coating 3)

30 parts by mass of ultrafine titanium oxide "TTO-V-3" (manufactured by Ishihara Sangyo Co., Ltd.), "SOLSPERSE 36000" (manufactured by Lubrizol Corp., Japan), and 5 parts of propylene glycol monomethyl ether. In the plastic container, zirconia beads having a diameter of 0.1 mm were added, and the average particle diameter of the titanium oxide was 30 nm. The dispersion was carried out by a paint shaker (manufactured by Toyo Seiki Co., Ltd.), and finally oxidized zirconium beads were removed by filtration to prepare an oxidation. Titanium slurry.

The produced titanium oxide slurry 100 mass portion, "KAYARAD DPHA" 7 mass portion, and "IRGACURE 184" 0.3 mass portion were mixed by a dispenser to prepare a refractive index adjusting coating material 3. The refractive index of the cured product of the refractive index adjusting coating material 3 produced at 550 nm was measured and found to be 1.92.

(refractive index adjustment coating 4)

The "KAYARAD DPHA" 30 mass part, "IRGACURE 184" 0.9 mass part, and methyl ethyl ketone (MEK) 70 mass parts were mixed by a dispenser to prepare a refractive index adjusting coating material 4. The refractive index of the cured product of the produced refractive index adjusting coating material 4 at 550 nm was measured and found to be 1.53.

Next, using the refractive index adjusting coating materials 1 to 4 described above, a transparent conductive film was produced as follows.

(Example 1)

Low refractive index easy-to-layer layer of the PET film "lumirror QT-D0" (thickness: 125 μm) made of Toray Industries, Inc., a transparent substrate which is easily processed on both sides, which is easy to handle on both sides (refractive index of the adhesion layer: 1.58) The coating was applied by a micro gravure coater to a thickness of 300 mJ/cm ² by a high pressure mercury lamp so that the thickness of the anti-adhesive hard coating agent "Z-739" (manufactured by Aica Kogyo Co., Ltd., manufactured by Limited) was 2 μm. The amount of light is irradiated with ultraviolet rays to harden, and an anti-adhesive hard coating layer as a function providing layer is formed to form an anti-adhesive hard coating film.

In the above-mentioned anti-adhesive hard coating film, a high refractive index on the opposite side of the anti-adhesive hard coating layer is formed on the opposite layer (refractive index of the adhesion layer: 1.65) so that the refractive index adjusting coating 1 is dried. The coating was applied so as to have a thickness of 2 μm, and the refractive index adjusting layer was formed by irradiating ultraviolet rays with a light amount of 300 mJ/cm ² by a high pressure mercury lamp to form a refractive index adjusting hard coating film A.

(Example 2)

A refractive index-adjusted hard coat film B was produced in the same manner as in Example 1 except that the refractive index adjusting coating material 1 was replaced with the refractive index adjusting coating material 2.

(Example 3)

On the refractive index adjusting layer of the refractive index-adjusting hard coat film A produced in Example 1, a ruthenium oxide layer was laminated by magnetron sputtering to form a low refractive index layer (refractive index: 1.40, thickness: 10 nm). Thereafter, a layer of indium doped tin oxide (ITO) is deposited on the low refractive index layer by magnetron sputtering to form a transparent conductive layer (refractive index: 2.0, thickness: 15 nm), and photolithography is performed. The transparent conductive layer is patterned to form a transparent conductive film A having a pattern portion and a non-pattern portion.

(Example 4)

A transparent conductive film B was produced in the same manner as in Example 3 except that instead of the refractive index-adjusting hard-coated film A and the refractive index-adjusting hard-coated film B.

(Example 5)

In addition to the use of the PET film "KEB-03W" (thickness: 125 μm, refractive index of the two-sided easy-adhesive layer: 1.60) manufactured by Teijin DuPont Film Co., Ltd. as the transparent substrate which was easily treated on both sides, and Example 1 and 3 A transparent conductive film C was produced in the same manner.

(Example 6)

A transparent conductive film D was produced in the same manner as in Example 3 except that the thickness of the transparent conductive layer was changed to 20 nm.

(Comparative Example 1)

A refractive index-adjusted hard coat film C was produced in the same manner as in Example 1 except that the refractive index adjusting coating material 1 was used instead of the refractive index adjusting coating material 3.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that a PET film "lumirror U34" (thickness: 125 μm, refractive index of the two-sided easy-adhesion layer: 1.51) manufactured by Toray Industries, Inc. was used as a transparent substrate which was easily treated on both sides. A refractive index-adjusted hard coat film D was produced.

(Comparative Example 3)

A transparent conductive film E was produced in the same manner as in Example 3 except that instead of the refractive index-adjusting hard-coated film A and the refractive index-adjusted hard-coated film C.

(Comparative Example 4)

In place of the refractive index adjusting coating 1, the refractive index adjusting coating 4 was used, and the PET film "U48" (thickness: 125 μm, refractive index of the two-sided easy-adhesive layer: 1.58) manufactured by Toray Industries, Inc. was used as the two sides. A transparent conductive film F was produced in the same manner as in Examples 1 and 3 except for the transparent substrate to be processed.

(Comparative Example 5)

A transparent conductive film G was produced in the same manner as in Example 3 except that instead of the refractive index-adjusting hard-coated film A and the refractive index-adjusted hard-coated film D.

(Comparative Example 6)

A transparent conductive film H was produced in the same manner as in Examples 1 and 3 except that the thickness of the refractive index adjusting layer was changed to 0.1 μm.

(Comparative Example 7)

Replace the anti-adhesive hard coating agent "Z-739", use refractive index adjustment coating 4 A functionally provided layer was formed, and a transparent conductive film was produced in the same manner as in Examples 1 and 3. However, when the coating of the refractive index adjusting layer was taken up, film adhesion occurred, and subsequent film production could not be performed.

The refractive indices of the respective layers of the films of Examples 1 to 6 and Comparative Examples 1 to 6 were measured as follows.

<Measurement of refractive index>

The refractive index adjustment layer was applied to a 100 μm PET film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) using a bar coater (Bar Coater) so that the film thickness after drying was 500 nm. The film was easily subjected to an untreated surface, and after drying, the coating film was cured by irradiating ultraviolet rays with a high-pressure mercury lamp at a light amount of 300 mJ/cm ² . Then, the black tape of the film surface on the opposite side to the side of the coating film was formed, and the absolute reflectance of the coating film side was measured using a reflection spectroscopic film thickness meter ("FE-3000" manufactured by Otsuka Electronics Co., Ltd.). The reflectance spectrum was measured for refractive index.

Further, the refractive index of the easy-adhesion layer of the transparent substrate was measured by a total adhesion of the black film to the film surface on the side opposite to the side on which the easy-to-adhere layer was formed, and the measurement was carried out in the same manner as described above using the above-described reflection spectroscopic film thickness meter. When an easy-adhesion layer was formed on both surfaces of the transparent substrate, the black tape was adhered to one of the film faces, and the refractive index of the easily-adherent layer was measured in the same manner as above.

Further, the refractive index of the transparent conductive layer and the low refractive index layer is formed by forming the respective layers so that the thickness of the PET film is 20 nm by magnetron sputtering, and then performing the same method as described above. The refractive index of the layer is determined.

Next, each of the films formed in the above Examples 1 to 6 and Comparative Examples 1 to 6 was evaluated as follows.

<Measurement of reflection chromaticity>

A black strip was adhered to the opposite surface of each of the produced transparent conductive films on which the transparent conductive layer was formed, and a pattern of the transparent conductive layer was used using a multi-channel spectrophotometer ("MCPD-3700" manufactured by Otsuka Electronics Co., Ltd.). The reflection spectrum of the portion and the non-pattern portion is measured, and the color calculation mode (light source: D65, field of view: 2 degrees) is used to analyze the L ^* a ^* b ^* of the reflection color, and the transparency is calculated by the following formula. The color difference ΔE between the pattern portion and the non-pattern portion of the conductive layer.

△E=(△L ^*2 +Δa ^*2 +△b ^*2 ) ^1/2

<Appearance of film>

Each of the produced films was placed on a test stand having a three-wavelength fluorescent lamp (light quantity: 3000 LUX), and the appearance of the film was visually observed, and the interference fringes of the hard-coated film unit and the refractive index adjusting layer were brought to the transparent conductive layer. The influence of the interference fringes was evaluated according to the following criteria.

When the color fringes caused by interference fringes are very thin: good

When the color fringes caused by interference fringes are roughly recognizable: insufficient

When the color fringes caused by interference fringes can be clearly identified:

<Curling after heating>

The prepared film was cut into a size of 100 mm × 100 mm, and the slice was heated to 150 ° C and placed in a thermostatic bath for 30 minutes, and then taken out, and the height of the film curl after 2 hours after the take-out was measured at the four corners. The highest value is taken as the size of the curl. Further, in the transparent conductive films of Examples 3 to 6 and Comparative Examples 3 to 6, when the transparent conductive layer was convexly curled toward the upper side, the curl was expressed by a negative (-).

<Film processability>

In the production of each film, the coating property of the refractive index adjusting coating by the micro gravure coater and the processability at the time of film winding were evaluated. Specifically, the following evaluation was performed in accordance with the following criteria.

No bad situation, coating ‧ coiling possible: good

Part of the coating ‧ when there is a problem with the coiling: insufficient

When coating ‧ coiling is impossible: not

The above evaluation results are shown in Tables 1 to 4. Further, the constitution of each film is also shown in Tables 1 to 4.

As is apparent from Table 1, in Examples 1 and 2, by optimizing the refractive index of the easily-adhesive layer and the refractive index of the refractive index adjusting layer, a refractive index-adjusting hard coat film having less interference fringes in appearance can be obtained.

Further, as is clear from Table 2, in Examples 3 to 6, the reflection chromatic aberration between the pattern portion and the non-pattern portion of the transparent conductive layer can be suppressed. As a result, it was confirmed that the pattern marks of the transparent conductive films of Examples 3 to 6 were unrecognizable. Further, as is apparent from Examples 3 to 6, the interference fringe can be suppressed by optimizing the refractive index of the easy-adhesion layer and the refractive index adjusting layer. Further, in Examples 3 to 6, a transparent conductive film in which curling after heating was suppressed and film processability was not problematic was obtained.

On the other hand, as is clear from Table 3, in Comparative Examples 1 and 2, the refractive index of the easy-adhesion layer and the refractive index of the refractive index adjusting layer were not optimal, and as a result of appearance confirmation, color fringes caused by interference fringes can be clearly recognized, and interference The stripes are getting worse.

In Comparative Example 3, since the refractive index of the refractive index adjusting layer was too high, the refractive index difference between the transparent substrate and the easily-adherent layer became large, and the color fringes caused by the interference fringes when the transparent conductive layer was laminated could be clearly recognized.

In Comparative Example 4, the refractive index of the refractive index adjusting layer was too low, and the reflected color difference between the pattern portion and the non-pattern portion was more than 5, and the pattern marks were sufficiently recognized.

In Comparative Example 5, the refractive index of the easy-adhesion layer was too low, the refractive index difference between the refractive index adjusting layers became large, and the color fringes caused by the interference fringes in the transparent conductive layer were clearly recognized.

In Comparative Example 6, the thickness of the refractive index adjusting layer was too thin, so that the function on the opposite side provided thickness balance between the layers, and the film was greatly curled after the heat treatment. Further, the hard coatability is also insufficient, and a slight scratch is generated when the film travels, and the film processability is also insufficient.

In Comparative Example 7, the function providing layer was made of a material having no anti-adhesion property, and the production of the film could not be completed as described above, and Comparative Example 7 is not shown in Table 4.

10‧‧‧Transparent conductive film

11‧‧‧Transparent substrate

12‧‧‧Easy layer

13‧‧‧Refractive index adjustment layer

14‧‧‧Low refractive index layer

15‧‧‧Transparent conductive layer

15a‧‧‧The Department of Patterns

15b‧‧‧Non-pattern department

Claims (12)

A hard coated substrate comprising a transparent substrate, an easy adhesion layer, and a coating type refractive index adjusting layer, wherein the coating type refractive index adjusting layer is refracted at a wavelength of 550 nm The ratio is 1.60 to 1.90, the thickness of the coating type refractive index adjusting layer is 0.3 to 5 μm, and the refractive index of the above-mentioned easy-adhesion layer at a wavelength of 550 nm is 1.56 to 1.70. The hard coated substrate according to claim 1, wherein the coating type refractive index adjusting layer is composed of a metal oxide and an ultraviolet curable resin, and the metal oxide is zirconium oxide or titanium oxide. The hard-coated substrate according to claim 1 or 2, wherein the organic energy-providing layer is additionally disposed on the side opposite to the side of the transparent substrate on which the coating-type refractive index adjusting layer is formed. A hard coated substrate according to claim 3, wherein the above-mentioned function provides a layer having anti-adhesion properties. The hard coat substrate according to claim 1 or 2, wherein the coating type refractive index adjusting layer is formed by a wet coating method. A transparent conductive film comprising a transparent conductive layer and a hard coated substrate, wherein the hard coated substrate comprises a transparent substrate, an easy-to-adhere layer, and a coated refractive index. Adjusting the hard coated substrate of the layer, wherein the coating type refractive index adjusting layer has a refractive index of 1.60 to 1.90 at a wavelength of 550 nm, The coated refractive index adjusting layer has a thickness of 0.3 to 5 μm, and the refractive index of the easy-adhesion layer at a wavelength of 550 nm is 1.56 to 1.70, and the transparent conductive layer is disposed on the coating-type refractive index adjusting layer. The refractive index of the transparent conductive layer at a wavelength of 550 nm is 1.8 to 2.3, and the thickness of the transparent conductive layer is 10 to 30 nm. The transparent conductive film of claim 6, wherein a coating type low refractive index layer is additionally disposed between the coating type refractive index adjusting layer and the transparent conductive layer, and the coating type low refractive index layer is at a wavelength The refractive index at 550 nm is 1.35 to 1.45, and the thickness of the coated low refractive index layer is 5 to 30 nm. The transparent conductive film of claim 6 or 7, wherein the transparent conductive layer is patterned, the reflection chromaticity of the pattern portion formed of the transparent conductive layer, and the non-pattern of the transparent conductive layer removed The color difference (ΔE) between the reflection chromaticities of the portions is 5 or less. The transparent conductive film according to claim 6 or 7, wherein the coating-type refractive index adjusting layer is composed of a metal oxide and an ultraviolet curable resin, and the metal oxide is zirconium oxide or titanium oxide. The transparent conductive film of claim 6 or 7, wherein the organic energy supply layer is additionally disposed on the side opposite to the side of the transparent substrate on which the coating-type refractive index adjusting layer is formed. The transparent conductive film of claim 10, wherein the above-mentioned function provides a layer having anti-adhesion properties. The transparent conductive film of claim 6 or 7, wherein the coating type refractive index adjusting layer is formed by a wet coating method.