TWI724281B - Hard coat film with optical adjustment layer for transparent conductive film, and transparent conductive film - Google Patents

Abstract

[Problem] To provide a hard coat film with an optical adjustment layer for a transparent conductive film. Even in a transparent conductive film provided with a transparent conductive layer, sufficient adhesion resistance can be obtained and the decrease in visibility can be suppressed. [Solution] A hard coat film with an optical adjustment layer (1), comprising: a transparent base film (2) formed of an amorphous polymer, and a layer sequentially laminated on one side of the transparent base film (2) The hard coat layer (3) and the optical adjustment layer (4) on the hard coat layer (3). The optical adjustment layer (4) contains a plurality of particles (4a, 4a). The average particle diameter of the particles (4a, 4a) is larger than the average film thickness of the optical adjustment layer (4), and the average particle diameter (r1 ), and its average film thickness (d1) is: 50nm≦(r1-d1)≦1900nm. On the surface of the optical adjustment layer (4), the arithmetic average roughness (Ra) of the specific part other than the convex part formed by the particles (4a) is in the range of 0.3 nm to 20 nm.

Description

Hard coat film with optical adjustment layer for transparent conductive film, and transparent conductive film

The present invention relates to a hard coat film with an optical adjustment layer for a transparent conductive film using a transparent film as a base material, and a transparent conductive film.

In the past, for example, smart phones or tablet terminals, as devices that input information by touching a display screen, capacitive touch panels, etc., have been widely used. Among them, as a transparent conductive film for touch panels, it is generally a transparent conductive layer that is laminated with indium tin oxide (ITO: Indium Tin Oxide) by evaporation or sputtering on a base film. (For example, refer to Patent Document 1).

Next, as the substrate of the transparent conductive film, although a crystalline polymer film with high birefringence, that is, polyethylene terephthalate film, is used, for example, when operating a mobile terminal through sunglasses, the use of polarized sunglasses may cause problems. There is a problem of uneven interference, and it has been proposed to use an amorphous polymer film with low birefringence as a substrate.

However, the use of a transparent conductive film using an amorphous polymer film as a base material can eliminate the occurrence of the above-mentioned interference fringes, but it is amorphous. Compared with a crystalline polymer film, a polymer film has the disadvantage of being easily damaged on the surface of the film. In addition, compared with crystalline polymer films, amorphous polymer films also have the disadvantage of being easy to break. When the film is transported, it adheres to a smooth surface such as a transport roller to cause wrinkles and cracks. Here, consider a hard coat film for a transparent conductive film in which a hard coat layer is provided on one or both sides of an amorphous polymer film. However, in this case, after the hard-coated film is wound in a roller shape, there may be a problem of adhesion between the inner surface of the substrate of the superimposed hard-coated film and the hard coat, or the hard coats adhere to each other. Here, it is proposed to provide a hard coat layer containing particles of 1 to 5 μm on an amorphous polymer film, and form irregularities on the hard coat layer and the surface of the ITO layer (transparent conductive layer) on the hard coat layer to improve Anti-blocking (for example, refer to Patent Documents 2 and 3).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 7-68690 A

[Patent Document 2] JP 2013-107349 A

[Patent Document 3] JP 2013-243115 A

However, in order to form irregularities on the surface of the ITO layer (transparent conductive layer), etc., when a hard coat layer containing particles of 1 to 5 μm is provided on an amorphous polymer film used as a base material, the hard coat layer or The hard coat The thickness of the upper ITO layer (transparent conductive layer), etc., when the particle size is 1~2μm, there is a concern that the adhesion resistance is insufficient, and when the particle size is greater than 2μm, there is a concern that the visibility will be reduced.

The present invention provides a hard coat film with an optical adjustment layer for a transparent conductive film, and a transparent conductive film using the hard coat film with an optical adjustment layer, even if the transparent conductive film is installed by vapor deposition or sputtering. Also in the transparent conductive film of the conductive layer, sufficient blocking resistance can be obtained, and the decrease in visibility can be suppressed.

The hard coat film with an optical adjustment layer for the transparent conductive film of the present invention and the transparent conductive film are formed by the following structure in order to achieve the aforementioned object. That is, the hard coat film with an optical adjustment layer for a transparent conductive film of the present invention includes: a transparent base film formed of an amorphous polymer, and a transparent base film sequentially laminated on at least one side of the transparent base film The hard coat layer and the optical adjustment layer on the hard coat layer. Wherein, the optical adjustment layer contains a plurality of particles, the average particle diameter of the particles is larger than the average film thickness of the optical adjustment layer, and the average particle diameter r1 and the average film thickness d1 are: 50nm≦(r1- d1) The relationship of ≦1900nm. Next, the arithmetic average roughness Ra of the specific part of the surface of the optical adjustment layer except for the convex part formed by the particle is in the range of 0.3 nm to 20 nm. Among them, when the optical adjustment layer is formed of multiple layers (high refractive index layer + low refractive index layer), the average particle size r1 is the filled particles (flat Particles whose average particle size is larger than the average film thickness d1) The average particle size of the whole, but the average film thickness d1 is the average film thickness of the whole when the particles are filled in both layers and when the particles are filled only in the high refractive index layer , Only when the low refractive index layer is filled with particles, is the average film thickness of the low refractive index layer (the same below).

According to this hard coat film with an optical adjustment layer for a transparent conductive film, the optical adjustment layer laminated on the hard coat layer contains plural particles. Next, the average particle diameter r1 of the particles contained in the optical adjustment layer is larger than the average film thickness d1 of the optical adjustment layer, and the difference is in the range of 50 nm to 1900 nm. In addition, the arithmetic average roughness Ra of the specific part of the surface of the optical adjustment layer excluding the convex part formed by the particles is in the range of 0.3 nm to 20 nm. In this case, by setting the difference between the average particle diameter of the particles contained in the optical adjustment layer and the average film thickness of the optical adjustment layer to 50 nm or more, and setting the arithmetic average roughness Ra of the aforementioned specific portion of the surface of the optical adjustment layer to If the thickness is 0.3 nm or more, even in a transparent conductive film in which a transparent conductive layer is formed on the optical adjustment layer by vapor deposition or sputtering, sufficient adhesion resistance can be obtained. In addition, the difference between the average particle diameter of the particles contained in the optical adjustment layer and the average film thickness of the optical adjustment layer is 1900 nm or less, and the arithmetic average roughness Ra of the aforementioned specific part of the surface of the optical adjustment layer is set to 20nm or less, even in the subsequent transparent conductive film, it is possible to suppress the decrease in visibility.

In addition, the average particle diameter r1 of the particles contained in the optical adjustment layer is in the range of 100 nm to 2000 nm, and the average particle diameter r1 (nm) and the number of particles N (pieces/mm ² ) are: 199.03exp(- 0.002r1)≦N≦3676.4exp(-0.002r1). Here, the number of particles N refers to the number of particles present at a height of 50 nm or more from the surface of the optical adjustment layer (when the optical adjustment layer is a plurality of layers, the outermost surface) (the same applies hereinafter).

In addition, the average film thickness d1 of the optical adjustment layer and the average particle diameter r1 of the particles contained in the optical adjustment layer have a relationship of (d1/r1)<0.5.

In addition, the hard coat layer contains a plurality of particles, and the average particle diameter of the particles is smaller than the average film thickness of the hard coat layer, and the particles are unevenly distributed on the surface of the hard coat layer.

In addition, the average film thickness d2 of the hard coat layer and the average particle diameter r2 of the particle diameter contained in the hard coat layer have a relationship of (d2/r2)>2.

Further, the surface area of the valley side of the optical adjustment layer is ² or less per 661780μm ² 200000μm. Here, the valley side area of the surface of the optical adjustment layer refers to the area of the surface of the optical adjustment layer on the valley side of 3 nm or more from the average height of the optical adjustment layer in the part where particles do not exist in the optical adjustment layer. (The same below)

In addition, the hard coat layer and the optical adjustment layer may be provided on one side of the transparent base film, and a protective film may be bonded to the other side of the transparent base film to form the outermost layer.

In addition, the hard coat layer and the optical adjustment layer are provided on both sides of the transparent base film, and are bonded to the other side of the transparent base film It is also possible to protect the film to form the outermost layer.

In addition, the transparent conductive film of the present invention is formed by forming a transparent conductive layer on the surface of the optical adjustment layer in the aforementioned hard coat film with an optical adjustment layer.

According to the hard coat film with an optical adjustment layer for a transparent conductive film of the present invention, the optical adjustment layer contains particles, and the average particle size of the particles is larger than the average film thickness of the optical adjustment layer and is between 50 nm and 1900 nm The arithmetic average roughness Ra of the specific part of the surface of the optical adjustment layer except for the convex part formed by the particles is 0.3nm~20nm, even in the transparent conductive film provided with the transparent conductive layer later, It is also possible to obtain sufficient adhesion resistance, and it is possible to suppress the decrease in visibility.

1: With optical adjustment layer hard coating film

2: Transparent substrate film

3: Hard coating

3a: particles

4: Optical adjustment layer

4a: particles

6: Protective film

[Fig. 1] A schematic cross-sectional view of a hard coat film with an optical adjustment layer according to the first embodiment of the present invention.

[Fig. 2] A graph showing the relationship between the average particle size and the number of particles in the same optical adjustment layer.

[Fig. 3] A schematic cross-sectional view of a hard coat film with an optical adjustment layer according to a second embodiment of the present invention.

[Fig. 4] The third embodiment of the present invention is a hard-coated thin film with an optical adjustment layer A schematic cross-sectional view of the membrane.

[Fig. 5] A schematic cross-sectional view of a hard coat film with an optical adjustment layer according to another embodiment of the present invention.

[Fig. 6] A schematic cross-sectional view of a hard coat film with an optical adjustment layer according to another embodiment of the present invention.

Hereinafter, the form of the hard coat film with an optical adjustment layer and the transparent conductive film for implementing the transparent conductive film of the present invention will be described based on the drawings.

Figures 1 to 2 show the first embodiment of the present invention. The symbol 1 in the figure represents a hard coat film with an optical adjustment layer used for a transparent conductive film. 2 represents a transparent substrate film. 3 means hard coat. 4 represents the optical adjustment layer.

The hard coat film 1 with an optical adjustment layer includes: a transparent base film 2, and a hard coat layer 3 sequentially laminated on at least one side of the transparent base film 2 (one side in the embodiment shown in the figure) and the hard The optical adjustment layer 4 on the coating 3.

Among them, the optical adjustment layer 4 contains a plurality of particles 4a, 4a, the average particle diameter of the particles 4a, 4a is larger than the average film thickness of the optical adjustment layer 4, and the average particle diameter r1 and the average film thickness d1 are: 50nm≦(r1-d1)≦1900nm. In other words, the average particle diameter r1 is larger than the average film thickness d1 by 50 nm to 1900 nm. Next, the surface of the optical adjustment layer 4, in addition to the light contained in the The arithmetic average roughness Ra of the specific part other than the convex part formed by the aforementioned particles 4a of the science adjustment layer 4 is in the range of 0.3 nm to 20 nm (preferably 0.3 nm to 10 nm).

Among them, the transparent conductive film (not shown) is formed by forming a conductive layer on the surface of the optical adjustment layer 4 in the hard coat film 1 with an optical adjustment layer.

According to this hard coat film 1 with an optical adjustment layer, the optical adjustment layer 4 laminated on the hard coat layer 3 contains plural particles 4a and 4a. Next, the average particle diameter r1 of the particles 4a contained in the optical adjustment layer 4 is larger than the average film thickness d1 of the optical adjustment layer 4, and the difference is in the range of 50 nm to 1900 nm. In addition, the arithmetic average roughness Ra of the specific part of the surface of the optical adjustment layer 4 excluding the convex part formed by the particles 4a is in the range of 0.3 nm to 20 nm. By setting the difference between the average particle diameter r1 of the particles 4a contained in the optical adjustment layer 4 and the average film thickness d1 of the optical adjustment layer 4 to 50 nm or more, and the arithmetic average roughness of the aforementioned specific part of the surface of the optical adjustment layer 4 When the degree Ra is set to 0.3 nm or more, even in a transparent conductive film in which a transparent conductive layer is provided on the optical adjustment layer 4 by vapor deposition, sputtering, or the like, sufficient adhesion resistance can be obtained. In other words, two types of protrusions, including the protrusions formed by the particles 4a and the protrusions 4b that form the arithmetic average roughness of the specific part, are not only the hard coat film with optical adjustment layer 1, but also the subsequent ones. In the transparent conductive film, adhesion resistance is also found. In addition, by setting the difference between the average particle size r1 of the particles 4a contained in the optical adjustment layer 4 and the average film thickness d1 of the optical adjustment layer 4 to 1900 nm or less, the arithmetic calculation of the aforementioned specific part of the surface of the optical adjustment layer 4 The average roughness Ra is set to 20nm or less, even in In the subsequent transparent conductive film, the reduction in visibility can also be suppressed.

In this way, by making the optical adjustment layer 4 contain the particles 4a, and the average particle size of the particles 4a is larger than the average film thickness of the optical adjustment layer 4 and in the range of 50nm~1900nm, and the surface of the optical adjustment layer 4 The arithmetic average roughness Ra of the specific part is 0.3nm~20nm. Even in the transparent conductive film where the transparent conductive layer is provided later, sufficient adhesion resistance can be obtained and the decrease in visibility can be suppressed.

In addition, although the hard coat film 1 with an optical adjustment layer for a transparent conductive film of the present invention is more suitable for use as a capacitive touch panel, it is not limited to the aforementioned touch panel use.

Specifically, the transparent base film 2 is formed of an amorphous polymer. As the amorphous polymer, an amorphous olefin having an alicyclic structure is preferred, but it is not limited to this. Examples of amorphous olefins include cycloolefin polymers and cycloolefin copolymers. In addition, the material of the transparent base film 2 may be polycarbonate, cellulose triacetate, polyimide, or the like. The thickness of the transparent substrate film 2 is preferably 10 μm to 500 μm, more preferably 10 μm to 200 μm, and still more preferably 20 μm to 100 μm. In addition, by applying pretreatments such as coating of an easy-adhesion layer or physical treatment such as corona discharge treatment on the surface of the transparent base film 2, it is possible to make the layered hard coat layer 3 dense Significant improvement.

The average film thickness of the hard coat layer 3 is preferably in the range of 0.5 μm to 10.0 μm, and more preferably in the range of 0.75 μm to 5.0 μm in order to obtain hard coat properties. If the film thickness is less than 0.5 μm, the hardness of the hard coat layer 3 may be insufficient. If the thickness exceeds 10.0 μm, the hard coat layer 3 or the layer on it may crack. There is not only the difficulty of winding, but also the deterioration of optical properties such as transparency.

Furthermore, in order to obtain the convex part 4b of the aforementioned specific part of the optical adjustment layer (that is, the aforementioned value of the arithmetic mean roughness Ra of the specific part), the surface of the hard coat layer 3 (that is, the surface opposite to the transparent substrate film 2)的面), the arithmetic average roughness Ra is preferably in the range of 2nm~20nm, more preferably 3nm~10nm. If the arithmetic average roughness Ra of the surface of the hard coat layer 3 is less than 2 nm, the arithmetic average roughness Ra of the aforementioned specific part of the subsequent optical adjustment layer 4 may be less than 0.3 nm, and the adhesion resistance may decrease. In addition, if the arithmetic average roughness Ra of the surface of the hard coat layer 3 is greater than 20 nm, there is a concern that optical properties such as transparency may be reduced.

In the illustrated embodiment, the hard coat layer 3 contains plural particles 3 a and 3 a, and the average particle diameter of the particles 3 a and 3 a is smaller than the average film thickness of the hard coat layer 3. Next, the particles 3a and 3a are unevenly distributed on the surface of the hard coat layer 3 (that is, the surface opposite to the side where the transparent base film 2 exists). Among them, as the surface protrusions formed by the particles 3a, 3a that are unevenly distributed on the surface of the hard coat layer 3, protrusions 4b, 4b, 3a are formed on the surface of the optical adjustment layer 4 on the hard coat layer 3, 4b, the convex portions 4b and 4b reflect the value of the arithmetic average roughness Ra of the specific part of the surface of the optical adjustment layer 4.

Specifically, the hard coat coating liquid for forming the hard coat layer 3 includes a binder, plural particles 3 a and 3 a having an average particle diameter smaller than the average film thickness of the hard coat layer 3, and a solvent. Next, the hard coat coating liquid is applied to the transparent substrate film 2 and dried, and during UV exposure (especially in the drying process), the particles 3 a are unevenly distributed on the surface of the hard coat 3. By using With this method, the suitable surface roughness of the surface of the hard coat layer 3 can be obtained uniformly and efficiently.

Specifically, the hard coat coating liquid is a curable composition that forms the hard coat 3, and contains particles 3a and a binder, and is preferably cured by ultraviolet light. Although the binder contained in the hard coat coating liquid is not particularly limited, in order to ensure scratch resistance and impart flexibility, urethane acrylic can be used. The average particle diameter of the particles 3a contained in the hard coat coating liquid is preferably in the range of 50 nm to 500 nm, more preferably in the range of 80 nm to 400 nm, and still more preferably in the range of 120 nm to 400 nm. Among them, although these particles 3a, 3a form convex parts on the surface, if the average particle size is less than 50nm, there is a concern that sufficient convex parts cannot be formed on the surface. If the average particle size exceeds 500nm, there will be haze (haze ) Rising doubts. In addition, the average film thickness d2 of the hard coat layer 3 and the average particle diameter r2 of the particles 3a contained in the hard coat layer 3 preferably have a relationship of (d2/r2)>2. By making it within this range, The increase in haze can be suppressed.

Although there are no particular limitations on the particles 3a, various inorganic and organic particles can be used. As the particles 3a, for example, there are silicon dioxide, aluminum oxide, titanium dioxide, acrylic resin, styrene-acrylic copolymer resin, styrene resin, polyurethane resin, epoxy resin, silicone resin, polyethylene resin, and phenol resin. However, it is not limited to particles and the like as materials, and two or more types may be combined.

When organic particles are used as the particles 3a, in order to obtain particles with a desired average particle diameter, it is preferable to use acrylic particles and synthesize by an emulsion polymerization method.

In addition, when inorganic particles are used for the particles 3a, the surface Silicon dioxide particles whose surface free energy is reduced by treatment and surfactants are preferred. By reducing the surface free energy in this way, the particles 3a are likely to be unevenly distributed on the surface of the hard coat layer 3.

In addition, in the hard coat coating liquid, if necessary, dispersing agents, leveling agents, defoaming agents, thixotropic agents, antifouling agents, antibacterial agents, flame retardants, damage prevention agents, etc. are contained within a range that does not affect performance. Additives such as slip agents may also be used.

In addition, from the viewpoint of adjustment of the film thickness, etc., the hard coat coating liquid may be diluted with an organic solvent. For example, alcohol-based organic solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGM), and diethylene glycol monobutyl ether, or methyl ethyl ketone (MEK), methyl isopropyl ether can be used. Ketone organic solvents such as butyl ketone (MIBK), cyclohexanone (anone), and acetone, or ester systems such as butyl acetate, ethyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate Organic solvents, aromatic organic solvents such as toluene and xylene, or amine-based organic solvents such as N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. Next, the exemplified organic solvents may be used alone or in combination of two or more, but the solubility parameter δ is preferably in the range of 8-11, and the solubility parameter δ is more preferably in the range of 8-10.

For coating, for example, reverse gravure coating method, direct gravure coating method, wafer coating method, die coating method, wire bar coating method, roller coating method, spin coating method, dip coating method can be used , Spraying method, blade coating method, contact pressure coating method and other coating methods, or various printing methods, but not limited to these methods.

Regarding the drying process, if the drying process is too fast, the aggregation/uneven distribution to the surface will become insufficient. Drying is preferably carried out at a temperature of 50°C to 120°C for 10 seconds to 180 seconds, especially the drying temperature is 50 ℃~80℃ is better. The longer the drying time is, the better, but in consideration of productivity, it is better to set it to 10 seconds to 120 seconds.

Regarding the UV exposure process, after drying, by irradiating the hard coat layer 3 with ultraviolet light to harden it, it is possible to fix the aggregates of the particles 3 a on the surface side of the hard coat layer 3. Ultraviolet light can be irradiated with high-pressure mercury lamp, electrodeless (microwave method) lamp, xenon lamp, metal halide lamp, and any other ultraviolet light irradiation device. If necessary, it can also be irradiated with inert gas atmosphere such as nitrogen. can. In addition, the irradiation amount of ultraviolet light is ^{preferably in the range of 50 to 800 mJ/cm 2 and} more preferably in the range of 100 to 300 mJ/cm ² .

The optical adjustment layer 4 is based on the difference in reflectance between the part where the patterned transparent conductive layer of the transparent conductive film and the part where the transparent conductive layer does not exist. In order to alleviate the phenomenon that the pattern can be seen visually (that is, the pattern visibility phenomenon), it is hard-coated Layer 3 is stacked on top. In order to alleviate the visible phenomenon of the figure, the refractive index of the optical adjustment layer 4 can be set between the refractive index of the transparent conductive layer and the refractive index of the hard coat layer 3. Therefore, the refractive index of the optical adjustment layer 4 is in the range of 1.55 to 1.80 Better. In addition, the average film thickness of the optical adjustment layer 4 varies depending on the refractive index of the transparent base film 2, the hard coat layer 3, and the optical adjustment layer 4, but it is adjusted to a transparent conductive layer in the range of 5 nm to 500 nm The thickness of the difference in reflectance between the existing part and the non-existing part is made as small as possible. If the film thickness of the optical adjustment layer 4 is less than 5nm, there is a concern that the particles 4a will fall off. When the film thickness is greater than 500nm, the transparent conductive layer There is a concern that sufficient adhesion resistance cannot be obtained after film formation, such as the metal layer.

The average particle diameter of the particles 4a contained in the optical adjustment layer 4 is preferably in the range of 100 nm to 2000 nm, more preferably 200 nm to 1500 nm, and even more preferably 400 nm to 1000 nm. By making the average particle size of the particles 4a within this range, the transparent conductive layer or the metal layer can be formed by vapor deposition or sputtering to maintain sufficient adhesion resistance, and it is possible to suppress the decrease in visibility . If the average particle size of the particles 4a is less than 100nm, there is a concern that sufficient adhesion resistance cannot be obtained after the transparent conductive layer and the metal layer are formed by vapor deposition or sputtering. The average particle size of the particles 4a is more than 2000nm When it is still old, there will be doubts about reduced identifiability.

In addition, the relationship between the average film thickness d1 of the optical adjustment layer 4 and the average particle diameter r1 of the particles 4a contained in the optical adjustment layer 4 is preferably (d1/r1)<0.5. By setting it as this range, even if the average particle diameter r1 of the particle 4a is reduced, the convex part with sufficient height can be produced. Next, the film thickness of the optical adjustment layer 4, the film thickness of the transparent conductive layer, and the average particle diameter of the film thickness adjustment particles 4a of the metal layer can be adjusted.

However, if (d1/r1)<0.5, more than half of the particles 4a become convex portions. Although there is a concern that the particles 4a may fall off due to friction or the like, it is because there are convex portions 4b in the aforementioned specific portion of the optical adjustment layer 4 , The slipperiness is increased, and the particles 4a can be prevented from falling off due to friction or the like.

The amount of particles 4a added varies according to the average particle size of the particles 4a. The average particle size r1 (nm) and the number of particles 4a N (pieces/mm ² ) are: 199.03exp(-0.002) The relationship of r1)≦N≦3676.4exp(-0.002r1) is preferable (the range of N is represented by the diagonal line rising to the right in FIG. 2). Next, it is more preferable to have a relationship of 480.48exp(-0.002r1)≦N≦2277exp(-0.002r1) (the range of N is represented by a diagonal line descending to the right in FIG. 2).

Moreover, when the surface of the optical adjustment layer 4 in the portion where the particles 4a contained in the optical adjustment layer 4 does not exist has large undulations, it may be difficult to conduct conduction when a conductive film such as ITO is provided. Here, the area of the surface of the optical adjustment layer 4 (the area of the valley side of the surface of the optical adjustment layer 4) on the valley side of 3 nm or more from the average height of the optical adjustment layer 4 in the non-existent part of the particle 4a is preferably per 661780μm ² is 200000μm ² or less, more preferably 150000μm ² or less. That is, the surface of the optical adjustment layer 4 of the non-existing part of the particle 4a is completely flat. Although it is better for the conduction of the transparent conductive film, it has the problem of adhesion resistance. The opposite can be solved by the aforementioned convex portion 4b. problem.

The optical adjustment layer 4 is obtained by applying the optical adjustment layer coating liquid on the surface of the hard coat layer 3, drying, and UV exposure. As the coating liquid for the optical adjustment layer, a conventional coating material for adjusting refractive index (for example, "(AICAAITRON) Z-816-3L (product name)" manufactured by Aica Kogyo Co., Ltd.) can be used. "(LIODURAS)TYZ-A15-S (product name)" manufactured by Toyochem Co., Ltd.). In order to obtain a high refractive index of 1.55 to 1.80, metal oxide particles may be included. Examples of the metal oxide particles include oxides of titanium, zirconium, tin, zinc, silicon, niobium, aluminum, chromium, magnesium, germanium, gallium, antimony, platinum, etc., but zirconium oxide and titanium oxide are particularly preferred. Also, make these oxides Multiple combinations are also possible.

As the material of the particles 4a contained in the optical adjustment layer 4, inorganic or organic polydispersed or monodispersed conventional particles (for example, manufactured by Soken Chemical & Engineering Co., Ltd.) can be used. "MX-80H3wT (product name)").

In addition, if necessary, a dispersant, leveling agent, defoaming agent, thixotropic agent, antifouling agent, antibacterial agent, flame retardant, damage prevention agent, and enhancement agent are included in the optical adjustment layer coating liquid within the range that does not affect the performance. Additives such as slip agents may also be used. In particular, the leveling agent has the purpose of reducing the valley side area of the surface of the optical adjustment layer 4, and has a better ability to adjust the surface tension reduction.

In addition, from the viewpoint of adjustment of the film thickness, etc., the optical adjustment layer coating liquid may be diluted with an organic solvent. For example, it is possible to use alcohol-based organic solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGM), and diethylene glycol monobutyl ether, or methyl ethyl ketone (MEK) and methyl isopropyl ether. Ketone organic solvents such as butyl ketone (MIBK), cyclohexanone (anone), and acetone, or ester systems such as butyl acetate, ethyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate Organic solvents, aromatic organic solvents such as toluene and xylene, or amine-based organic solvents such as N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. Next, these exemplified organic solvents may be used alone or in combination of two or more, but the solubility parameter δ is preferably in the range of 8-11, and δ is more preferably in the range of 8-10. The surface tension of the organic solvent used is 20 ~ 40dyne / cm ² and preferably, in order to reduce the area of the valley-side surface of the optical adjustment layer 4 for the purpose of drying the coating concentration increases due to engineering in order to reduce the concentration of each It is better to select the organic solvent type of the coating liquid for the optical adjustment layer as the method of the difference in surface tension.

For coating, for example, reverse gravure coating method, direct gravure coating method, wafer coating method, die coating method, wire bar coating method, roller coating method, spin coating method, dip coating method can be used , Spraying method, blade coating method, contact pressure coating method and other coating methods, or various printing methods, but not limited to these methods.

Regarding the drying process, it is preferable to perform the drying process at a temperature of 50°C to 150°C for about 10 seconds to 180 seconds from the viewpoint of productivity. If the temperature is within the range that does not affect the performance, if it is high, the viscosity of the hardened coating film surface will decrease, and the surface area of the valley side of the optical adjustment layer 4 will decrease due to rapid flattening (smoothing), so set it to 80°C~150 ℃ is better.

Regarding the UV exposure process, after drying, the optical adjustment layer 4 is irradiated with ultraviolet light to harden the film to fix the film. Ultraviolet light can be irradiated with high-pressure mercury lamp, electrodeless (microwave method) lamp, xenon lamp, metal halide lamp, and any other ultraviolet light irradiation device. If necessary, it can also be irradiated with inert gas atmosphere such as nitrogen. can. In addition, the irradiation amount of ultraviolet light is ^{preferably in the range of 50 to 800 mJ/cm 2 and} more preferably in the range of 100 to 300 mJ/cm ² .

Fig. 3 shows the second embodiment of the present invention. Compared with the first embodiment, this embodiment is different in that a hard coat layer is also provided on the other side of the transparent base film 2, but everything else is the same. In the following, the same symbols are attached to the same parts, and the differences are mainly explained. section.

The hard coat film 1 with an optical adjustment layer is on the other side of the transparent substrate film 2 (that is, the opposite side of the hard coat layer 3 and the optical adjustment layer 4). 的面) has a second hard coat layer 5. The second hard coat layer 5 contains a plurality of particles 5a, 5a, and the particles 5a, 5a are unevenly distributed on the surface of the second hard coat layer 5 (that is, the surface opposite to the side where the transparent base film 2 exists). Thereby, it is possible to provide scratch resistance and adhesion resistance not only on one side of the hard coat film 1 with an optical adjustment layer, but also on the other side. Therefore, even if an amorphous polymer film having the disadvantage of easily causing damage to the easily broken surface is used for the transparent base film 2, an optical adjustment layer with sufficient hard coat properties and sufficient adhesion resistance can be obtained. Hard coating film. Here, in order not to reduce the visibility, it is better to set the average particle size of the plural particles 5a, 5a to be smaller than the average film thickness of the second hard coat layer 5, but in order to provide more slipperiness or thin film placement For the purpose of performance, it is better to set the average particle size of the particles 5a to be larger than the average film thickness of the second hard coat layer 5 if necessary.

Fig. 4 shows the third embodiment of the present invention. Compared with the second embodiment, this embodiment is different in that a protective film is provided, but everything else is the same. Hereinafter, the same symbols are attached to the same parts, and the different parts are mainly described.

In the hard coat film 1 with an optical adjustment layer, the hard coat layer 3 and the optical adjustment layer 4 are provided on one side of the transparent base film 2, and the other side of the transparent base film 2 is pasted to form the outermost layer.合保护膜6。 Protection film 6. In detail, the hard coat film with an optical adjustment layer 1 uses the hard coat film with an optical adjustment layer 1 of the second embodiment as a main body 1a of the hard coat film with an optical adjustment layer, and the hard coat film with an optical adjustment layer 1a On the other side of the transparent base film 2 in the second hard coat layer 5, the protective film 6 formed of the transparent base film 6a for the protective film and the adhesive layer 6b is attached by the adhesive layer 6b. Together.

In this way, by providing the protective film 6 on the hard coat film 1 with an optical adjustment layer, even when the transparent base film 2 is very thin, the workability can be optimized and contamination can be prevented.

Although the material for forming the protective film 6 is not particularly limited, from the viewpoint of control of curling during and after the heat treatment process, the heat shrinkage rate and linear expansion coefficient are close to those of the hard coat film body 1a with an optical adjustment layer. The material is better.

In addition, the present invention is not limited to the above-mentioned embodiment, and various other modifications are possible. For example, the plural particles 4a and 4a contained in the optical adjustment layer 4 may be different as shown in FIG. 5 even if the particle diameters are different. The same applies to the particles 3a and 3a contained in the hard coat layer 3.

In addition, the optical adjustment layer 4 is not one layer, but may be formed of two or more layers such as a high refractive index layer and a low refractive index layer. At this time, by setting the refractive index of the optical adjustment layer on the side of the hard coat layer 3 to a high refractive index of 1.55 to 1.80, the refractive index of the optical adjustment layer on the side of the laminated transparent conductive layer is set to a low refractive index of 1.50 or less , Can alleviate the visual phenomenon of graphics. Next, the particles 4a contained in the optical adjustment layer may be contained in any layer, and may be contained in a plurality of layers, but they are preferably contained in the optical adjustment layer on the side farthest from the transparent base film 2.

In addition, in order to set the arithmetic average roughness Ra of a specific part of the surface of the optical adjustment layer 4 within a predetermined range, although the hard coat layer 3 contains plural particles 3a, 3a, the surface of the hard coat layer 3 (and There is a transparent base film 2 on the opposite side) to set the convex part to reflect the convex part to the optical adjustment However, as a method of providing protrusions on the surface of the hard coat layer 3, particles 3a are not used, and a method of forming protrusions by phase separation of two or more types of materials, or by pressing A method of forming a convex portion by patterning may be used (refer to the convex portion 3b shown in FIG. 6).

In addition, the hard coat film 1 with an optical adjustment layer is provided with a hard coat layer 3 and an optical adjustment layer 4 on one side of the transparent base film 2, but a hard coat layer 3 and an optical adjustment layer are provided on both sides of the transparent base film 2 4 is fine too. Next, at this time, a protective film may be attached to any surface side of the transparent base film 2 (that is, the surface of any optical adjustment layer 4) so as to form the outermost layer.

In addition, in the second and third illustrated embodiments, the second hard coat layer 5 contains plural particles 5a, but these particles 5a may not be included.

[Example]

Hereinafter, the present invention will be explained in more detail using examples.

<Example 1>

The transparent base film 2 used "ZeonorFilm ZF16-100 (product name)" manufactured by Zeon Corporation. After corona treatment is applied to one side of the transparent base film 2, a hard coat layer 3 is laminated on this side to produce a hard coat film. Next, the optical adjustment layer 4 was laminated on the surface of the hard coat layer 3 in the hard coat film to produce a hard coat film with an optical adjustment layer.

(Preparation of Hard Coating Liquid (1a))

In a disposable cup, "PC16-2291 (product name)" manufactured by DIC Corporation, butyl acetate and methyl ethyl ketone (MEK) are mixed in the next mixing ratio to prepare a hard coat coating.液(1a).

(Production of Hard Coated Film (1A))

The aforementioned hard coat coating liquid (1a) was coated on the corona-treated surface of the transparent substrate film 2 using a #5 wire rod, and then dried at 80°C for 1.0 minute, and then a high-pressure mercury lamp was used , Irradiate ultraviolet light with a light quantity of 200mJ/cm ² to produce a hard coat film (1A).

(Preparation of optical adjustment layer coating liquid (1b))

Among the disposable cups are "(AICAAITRON) Z-816-3L (product name)" made by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. ) "(CHEMISNOW) MX-80H3wT (product name)" and methyl ethyl ketone (MEK) were mixed at the next mixing ratio to prepare an optical adjustment layer coating liquid (1b).

(Production of hard coat film with optical adjustment layer (1B))

Coating the optical adjustment layer coating liquid (1b) on the surface of the hard coating layer 3 of the hard coating film (1A) with a #3 wire rod, and then drying it at 80°C for 1.0 minute, and then passing ultraviolet light The window is set in the upper container, and the film is put into it, and the container is placed in a nitrogen environment for 3 minutes. Then, a high-pressure mercury lamp was used to ^{irradiate ultraviolet light with a light quantity of 200 mJ/cm 2} to produce a hard coat film with an optical adjustment layer (1B).

<Example 2>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed to produce a hard coat film with an optical adjustment layer.

(Preparation of optical adjustment layer coating liquid (2b))

Among the disposable cups are "(AICAAITRON) Z-816-3L (product name)" made by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. ) Manufactured "(CHEMISNOW) MX-40 (product name)" and methyl ethyl ketone (MEK) were mixed in the next mixing ratio to prepare an optical adjustment layer coating liquid (2b).

(Production of hard coat film with optical adjustment layer (2B))

The optical adjustment layer coating liquid (2b) was used, and the others were completely the same as in Example 1, to produce a hard coat film with an optical adjustment layer (2B).

<Example 3>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed to produce a hard coat film with an optical adjustment layer.

(Preparation of optical adjustment layer coating liquid (3b))

Among the disposable cups are "(AICAAITRON) Z-816-3L (product name)" made by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. ) "(CHEMISNOW) MX-150 (product name)" and methyl ethyl ketone (MEK) were mixed in the next mixing ratio to prepare an optical adjustment layer coating liquid (3b).

(Production of hard coat film with optical adjustment layer (3B))

The optical adjustment layer coating liquid (3b) was used, and other things were completely the same as in Example 1, to produce a hard coat film with an optical adjustment layer (3B).

<Example 4>

The coating liquid of the hard coat layer 3 of Example 1 was changed to produce a hard coat film. Next, the same optical adjustment layer 4 as in Example 1 was laminated on the surface of the hard coat layer 3 in the hard coat film to produce a hard coat film with an optical adjustment layer.

(Preparation of Hard Coating Liquid (4a))

Put DIC Corporation (DIC Corporation) hard coat agents "PC16-2291 (product name)" and "PC16-9081 (product name)", butyl acetate and methyl ethyl ketone (MEK) in a disposable cup The mixture was mixed at the next mixing ratio to prepare a hard coat coating liquid (4a).

(Production of hard coat film (4A))

Using the hard-coating coating liquid (4a), and other things being completely the same as the production of the hard-coating hard-coating film (1A) of Example 1, a hard-coating film (4A) was produced.

(Production of hard coat film with optical adjustment layer (4B))

Using the hard-coated film (4A), the optical adjustment layer 4 was laminated in the same manner as in Example 1, and a hard-coated film with an optical adjustment layer (4B) was produced.

<Example 5>

The coating liquid of the optical adjustment layer 4 of Example 4 was changed to produce a hard coat film with an optical adjustment layer.

(Production of hard coat film with optical adjustment layer (5B))

Using the optical adjustment layer coating liquid (2b), and the rest were completely the same as in Example 4, a hard coat film with an optical adjustment layer (5B) was produced.

<Example 6>

The coating liquid of the optical adjustment layer 4 of Example 4 was changed to produce a hard coat film with an optical adjustment layer.

(Production of hard coat film with optical adjustment layer (6B))

Using the optical adjustment layer coating liquid 3b, and other things were completely the same as in Example 4, a hard coat film with an optical adjustment layer (6B) was produced.

<Example 7>

The coating liquid of the hard coat layer 3 of Example 1 was changed to produce a hard coat film. Next, the same optical adjustment layer 4 as in Example 1 was laminated on the surface of the hard coat layer 3 in the hard coat film to produce a hard coat film with an optical adjustment layer.

(Preparation of Hard Coating Liquid (7a))

Among the disposable cups are "(AICAAITRON) Z-739L (product name)" made by Aica Kogyo Co., Ltd. and Dow Corning Toray Co., Ltd. "8019 ADDITIVE (product name)" and methyl isobutyl ketone (MIBK) were mixed in the next mixing ratio to prepare an optical adjustment layer coating liquid (7a).

(Production of hard coating film (7A))

Using the hard-coating coating liquid (7a), and other things being completely the same as the production of the hard-coating film (1A) of Example 1, a hard-coating film (7A) was produced.

(Production of hard coat film with optical adjustment layer (7B))

Using the hard coat film (7A), the optical adjustment layer 4 was laminated in the same manner as in Example 1, and a hard coat film with an optical adjustment layer (7B) was produced.

<Example 8>

The hard coat layer 3 and the optical adjustment layer 4 were formed on the side (the other side) of the transparent substrate film 2 of the hard coat film with an optical adjustment layer (1B) of Example 1 in the same order as in Example 1, to produce a double-sided optical Adjustment layer hard coating film (8B).

<Example 9>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed to produce a hard coat film with an optical adjustment layer.

(Preparation of optical adjustment layer coating liquid (9b))

Among the disposable cups are "(AICAAITRON) Z-816-3L (product name)" made by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. ) Manufactured "(CHEMISNOW) MX-80H3wT (product name)" and methyl ethyl ketone (MEK) were mixed at the next mixing ratio to prepare an optical adjustment layer coating liquid (9b).

(Production of hard coat film with optical adjustment layer (9B))

The optical adjustment layer coating liquid (9b) was used, and other things were completely the same as in Example 1, to produce a hard coat film with an optical adjustment layer (9B).

<Example 10>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed to produce a hard coat film with an optical adjustment layer.

(Preparation of optical adjustment layer coating liquid (10b))

Among the disposable cups are "(AICAAITRON) Z-816-3L (product name)" made by Aica Kogyo Co., Ltd. and Soken Chemical & Engineering Co., Ltd. ) Manufactured "(CHEMISNOW) MX-80H3wT (product name)" and methyl ethyl ketone (MEK) were mixed at the next mixing ratio to prepare an optical adjustment layer coating liquid (10b).

(Production of hard coat film with optical adjustment layer (10B))

The optical adjustment layer coating liquid (10b) was used, and other things were completely the same as in Example 1, to produce a hard coat film with an optical adjustment layer (10B).

<Example 11>

The order of the coating liquid and the wire bar of the hard coat layer 3 of Example 1 was changed to produce a hard coat film. Next, the same optical adjustment layer 4 as in Example 1 was laminated on the surface of the hard coat layer 3 in the hard coat film to produce a hard coat film with an optical adjustment layer.

(Preparation of Hard Coating Liquid (11a))

In a disposable cup, Nippon Paint Automotive Coatings (Nippon Paint Automotive Coatings Co., Ltd.) manufactured "UT-1147/P55 (products) Name)", butyl acetate and methyl isobutyl ketone (MIBK) are mixed in the next mixing ratio to prepare a hard coat coating liquid (11a).

(Production of hard coat film (11A))

The hard-coated coating liquid (11a) was used, and a #7 wire rod was used for the coating of the coating liquid, and the other things were completely the same as the production of the hard-coated film (1A) of Example 1, to produce a hard-coated film (11A).

(Production of hard coat film with optical adjustment layer (11B))

Using the hard-coated film (11A), the optical adjustment layer 4 was laminated in the same manner as in Example 1, and a hard-coated film with an optical adjustment layer (11B) was produced.

<Example 12>

The coating liquid of the hard coat layer 3 and the coating liquid of the optical adjustment layer 4 of Example 1 were changed to produce a hard coat film with an optical adjustment layer.

(Preparation of Hard Coating Liquid (12a))

In a disposable cup, Aica Kogyo Co., Ltd. made "(AICAAITRON) Z-735L-35 (product name)" and propylene glycol monomethyl ether (PGM) in the following blending ratio Mix and hard coat the coating liquid (12a).

(Production of hard coating film (12A))

Using the hard-coating coating liquid (12a), and other things being completely the same as the production of the hard-coating film (1A) of Example 1, a hard-coating film (12A) was produced.

(Preparation of optical adjustment layer coating liquid (12b))

In the disposable cup, "(AICAAITRON) Z-816-3L made by Aica Kogyo Co., Ltd. is changed to (product name)", and Soken Chemical & Engineering Co., Ltd. Ltd.) "(CHEMISNOW) MX-80H3wT (product name)", propylene glycol monomethyl ether (PGM), and BYK Japan KK "BYK-UV3570 (product name)" The following mixing ratio is mixed to prepare an optical adjustment layer coating liquid (12b).

(Production of hard coat film with optical adjustment layer (12B))

Use the optical adjustment layer coating solution (12b), and the others are completely the same as in Example 1. At the same time, a hard coat film with an optical adjustment layer (12B) was produced.

<Example 13>

The coating liquid of the optical adjustment layer 4 of Example 12 was changed to produce a hard coat film with an optical adjustment layer.

(Preparation of optical adjustment layer coating liquid (13b))

In the disposable cup, Toyochem Co., Ltd. (LIODURAS) TYZ-A15-S (product name), and Soken Chemical & Engineering Co., Ltd. .) "(CHEMISNOW) MX-80H3wT (product name)" and propylene glycol monomethyl ether (PGM) were mixed at the next mixing ratio to prepare an optical adjustment layer coating liquid (13b).

(Production of hard coat film with optical adjustment layer (13B))

The optical adjustment layer coating liquid (13b) was used, and other things were completely the same as in Example 12, to produce a hard coat film with an optical adjustment layer (13B).

<Example 14>

The drying conditions of the optical adjustment layer 4 of Example 13 were changed to produce an attached light Learn to adjust the hard-coated film.

(Production of hard coat film with optical adjustment layer (14B))

Except that the drying temperature after application of the optical adjustment layer was set to 100°C, it was completely the same as in Example 13, and a hard coat film with an optical adjustment layer (14B) was produced.

<Example 15>

The drying conditions of the optical adjustment layer 4 of Example 14 were changed to produce a hard coat film with an optical adjustment layer.

(Production of hard coat film with optical adjustment layer (15B))

Except that the drying temperature after application of the optical adjustment layer was set to 130°C, it was completely the same as in Example 14, and a hard coat film with an optical adjustment layer (15B) was produced.

<Example 16>

The coating liquid of the optical adjustment layer 4 of Example 15 was changed to produce a hard coat film with an optical adjustment layer.

(Preparation of optical adjustment layer coating liquid (16b))

In the disposable cup, Toyochem Co., Ltd. (LIODURAS) TYZ-A15-S (product name), and Soken Chemical & Engineering Co., Ltd. .)system "(CHEMISNOW) MX-80H3wT (product name)" and propylene glycol monomethyl ether (PGM) were mixed in the next mixing ratio to prepare an optical adjustment layer coating liquid (16b).

(Production of hard coat film with optical adjustment layer (16B))

The optical adjustment layer coating liquid (16b) was used, and other things were completely the same as in Example 15, to produce a hard coat film with an optical adjustment layer (16B).

<Comparative Example 1>

The coating liquid of the optical adjustment layer 4 of Example 1 was changed to produce a hard coat film with an optical adjustment layer.

(Preparation of optical adjustment layer coating liquid (Xb))

In a disposable cup, "(AICAAITRON) Z-816-3L (product name)" manufactured by Aica Kogyo Co., Ltd. and methyl ethyl ketone (MEK) are blended in the following ratio Mix and prepare an optical adjustment layer coating liquid (Xb).

(Production of hard coat film (XB) with optical adjustment layer)

The optical adjustment layer coating liquid (Xb) was used, and other things were completely the same as in Example 1, to produce a hard coat film with an optical adjustment layer (XB).

<Example 17>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (1B) of Example 1, sputtering and vapor deposition of 21 nm was performed to produce a transparent conductive film (17).

<Example 18>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (2B) of Example 2, sputtering and vapor deposition of 21 nm was performed to produce a transparent conductive film (18).

<Example 19>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (3B) of Example 3, a 21 nm sputtering vapor deposition was performed to produce a transparent conductive film (19).

<Example 20>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (4B) of Example 4, a 21 nm sputtering vapor deposition was performed to produce a transparent conductive film (20).

<Example 21>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (5B) of Example 5, sputtering and vapor deposition of 21 nm was performed to produce a transparent conductive film (21).

<Example 22>

Using an ITO target on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (6B) of Example 6, sputtering and vapor deposition of 21 nm was performed to produce a transparent conductive film (22).

<Example 23>

An ITO target was used on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (13B) of Example 13, sputtering and vapor deposition of 21nm was carried out, and annealing (annealing) was carried out in an oven at 145°C for 1 hour to produce a transparent conductive性膜(23).

<Example 24>

An ITO target was used on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (14B) of Example 14, sputtering and vapor deposition of 21nm was carried out, and annealing (annealing) was carried out at 145°C for 1 hour to produce a transparent conductive Sex film (twenty four).

<Example 25>

An ITO target was used on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (15B) of Example 15, sputtering and vapor deposition of 21nm was carried out, and annealing was carried out for 1 hour in an oven at 145°C to produce a transparent conductive性膜(25).

<Example 26>

An ITO target was used on the optical adjustment layer 4 side of the hard coat film with an optical adjustment layer (16B) of Example 16, sputtering and vapor deposition of 21 nm was performed, and annealing was performed for 1 hour in an oven at 145°C to produce a transparent conductive性膜(26).

<Example 27>

On the ITO layer side of the transparent conductive film (23) of Example 23, sputtering and vapor deposition of 200 nm was performed using a copper target to produce a transparent conductive film with a metal layer (27).

<Example 28>

On the ITO layer side of the transparent conductive film (26) of Example 26, a copper target was used for sputtering and vapor deposition of 200 nm to produce a transparent conductive film with a metal layer (28).

<Evaluation results of hard coat film with optical adjustment layer>

The evaluation results of the hard coat film with an optical adjustment layer are shown in Table 15 and Table 16 below.

It is obvious from Table 15 and Table 16 that the hard coat films with optical adjustment layers in Examples 1 to 16 contained particles 4a having an average particle diameter larger than the average film thickness of the optical adjustment layer 4 in the optical adjustment layer 4. The arithmetic average roughness Ra of the specific part of the optical adjustment layer 4 is 0.3 nm to 10 nm, the Hz (haze) is low, the static friction coefficient is also lower than 1, and no particles fall off. The hard-coated film with optical adjustment layer has good recognizability, and the surface of the optical adjustment layer is transparent. Adequate adhesion resistance can also be obtained when the conductive layer is used.

In addition, although the hard coat film with an optical adjustment layer of Comparative Example 1 also had good visibility, no particles were added to the optical adjustment layer 4, and the static friction coefficient exceeded 1. Therefore, when a transparent conductive layer is provided on the surface of the optical adjustment layer, sufficient adhesion resistance cannot be obtained.

<Evaluation Results of Transparent Conductive Film>

The evaluation results of the transparent conductive film are shown in Table 17 and Table 18 below.

In Table 17 and Table 18, although the transparent conductive films in Examples 17 to 26 used the hard coat films with optical adjustment layers of Examples 1 to 6 and Examples 13 to 16, the Hz (haze) was low. The coefficient of static friction is low. The transparent conductive film has good recognizability, and has sufficient adhesion resistance even with a transparent conductive layer. Further, in Example 26 of the transparent conductive film 23 to the valley area of the side surface of the optical adjustment layer in each 661780μm ² is 200000μm ² or less, the resistance value is low.

<Evaluation results of transparent conductive film with metal layer>

The evaluation results of the transparent conductive film with a metal layer are shown in Table 19 below.

In Table 19, the transparent conductive films with a metal layer of Examples 27 to 28, although the transparent conductive films of Example 23 and Example 26 were used, the metal layer added as an electrode also had sufficient adhesion resistance.

<Evaluation method> (Hz)

It is measured by the method of JIS-K7136 using "Haze Meter NDH2000 (product name)" manufactured by Nippon Denshoku Industries Co., Ltd..

(Identifiable)

By visually observing the transmitted light of a 3-wavelength fluorescent lamp, the case where almost no particles are seen is regarded as ○, the case where the particles can be seen but cannot be separated is regarded as △, and the case where the particles can be clearly seen is regarded as ×.

(Adhesion resistance)

Using "(AUTOGRAPH) AG-IS MS (AG-1kNIS) (product name)" manufactured by Shimadzu Corporation, a vertical load of 4.4 kg was applied to an area of 60 mm × 50 mm in the rubbing direction to measure the measurement surface of the sample The coefficient of static friction between each other. When the static friction coefficient is 1 or more, it is regarded as ×, and when it is less than 1, it is regarded as ○.

(Particle shedding)

Using "AB-301 COLOR FASTNESS RUBBING TESTER (product name)" manufactured by Tester Sangyo Co., Ltd., the French blue flannel (No. 16 double-thread blue fleece WKF2254) was repeated with a load of 500g The surface of the optical adjustment layer was rubbed 500 times, and then the surface was used "(Microscope) VHX- 1000 (product name)" Check whether the particles 4a have fallen off. The particles 4a that did not fall off were regarded as ○, and the particles 4a that had fallen off were regarded as ×.

(Average thickness of hard coat layer)

The average film thickness of the hard coat layer 3 was measured using the "Filmetrics F20 film thickness measurement system (product name)" manufactured by Filmetrics Co., Ltd.

(Average film thickness of optical adjustment layer)

The film thickness of the optical adjustment layer 4 was measured in the following procedure.

(1) Using "UV3600 (product name)" manufactured by Shimadzu Corporation, the reflectance at a wavelength of 380 to 800 nm was measured to obtain a waveform.

(2) Using the optical simulation software, input the information of the laminated film other than the thickness of the optical adjustment layer 4 [composition, the refractive index of the transparent base film 2 (set to 1.52) and thickness, and the refractive index of the hard coat layer 3 ( Set to 1.50), the average film thickness (the measured value of the average film thickness of the hard coat layer 3 described above), and the refractive index of the optical adjustment layer (Examples 13 to 16 are set to 1.60. Other examples are set to 1.62)].

(3) The waveform obtained by inputting an arbitrary film thickness to the optical adjustment layer of the optical simulation, and the film thickness value when the waveform obtained in (1) coincides with the waveform obtained in (1) are used as the average film thickness of the optical adjustment layer.

That is, after the interference waveform is obtained by "UV3600 (product name)" manufactured by Shimadzu Corporation, the measured interference waveform and the calculated waveform obtained by simulation are used as the average film thickness of the optical adjustment layer. thick.

(Average particle size of particles contained in the hard coat layer)

The arithmetic average of the volume-based particle size distribution obtained by the laser diffraction and scattering method in accordance with the Japanese Industrial Standards JIS Z8825 in accordance with the ISO 13320 standard of the International Organization for Standardization is regarded as the average particle size of the particles.

(Average particle size of particles contained in the optical adjustment layer)

The arithmetic average of the volume-based particle size distribution obtained by the laser diffraction and scattering method in accordance with the Japanese Industrial Standards JIS Z8825 in accordance with the ISO 13320 standard of the International Organization for Standardization is regarded as the average particle size of the particles.

(Arithmetic average roughness Ra of a specific part of the optical adjustment layer)

Using Mitsubishi Chemical Systems, Inc. (former company name: Ryoka Systems Inc.) "Non-contact surface and layer profile measurement system VertScan2.0 (type: R5300GL-L) -A100-AC) (product name)", put a sample cut out with a size of 50mm×50mm on a stage, and measure the surface shape with a 10x lens. After that, the measurement data was observed, and the arithmetic average roughness Ra in the range of 50 μm×50 μm in the specific part other than the convex part formed by the particles 4 a contained in the optical adjustment layer 4 was calculated.

(The number of particles contained in the optical adjustment layer N)

Using Mitsubishi Chemical Systems, Inc. (former company name: Ryoka Systems Co., Ltd.) Inc.)) "Non-contact surface ‧ layer cross-sectional shape measurement system VertScan2.0 (model: R5300GL-L-A100-AC) (product name)", the sample cut out with a size of 50mm×50mm is placed on the stage, and The 10x lens measures the surface shape. After that, particle analysis of the measurement data is performed, and the number of particles existing from the surface of the optical adjustment layer 4 to a height of 50 nm or more in 1 mm×1 mm is calculated.

(The area of the valley side of the surface of the optical adjustment layer)

Using Mitsubishi Chemical Systems, Inc. (former company name: Ryoka Systems Inc.) "Non-contact surface and layer profile measurement system VertScan2.0 (type: R5300GL-L) -A100-AC) (product name)", place a sample cut out with a size of 50mm×50mm on a stage, and measure the surface shape with a 5x lens. After that, the positioning analysis of the measurement data is performed, from the average height of the optical adjustment layer 4 in the non-existent part of the particle 4a to the valley side area of 3 nm or more (the valley side area of the surface of the optical adjustment layer) per 661780 μm ² value.

(Resistance value of transparent conductive film)

The measurement was performed using Mitsubishi Chemical Analytech Co., Ltd. (former company name: "Loresta-GP (model: MCP-T610) (product name)" manufactured by Mitsubishi Analytech Co., Ltd.).

[Industrial Utilization Possibility]

The above-mentioned hard coat film with optical adjustment layer and transparent conductive film are suitable for capacitive touch panels and the like.

1‧‧‧Hard-coated film with optical adjustment layer

2‧‧‧Transparent substrate film

3‧‧‧Hard coating

3a‧‧‧Particle

4‧‧‧Optical adjustment layer

4a‧‧‧Particle

4b‧‧‧Protrusion

Claims (10)

A hard coat film with an optical adjustment layer for a transparent conductive film, comprising: a transparent base film formed of an amorphous polymer, and a hard coat layer laminated on at least one surface of the transparent base film; The optical adjustment layer laminated on the coating layer, wherein the optical adjustment layer contains a plurality of particles forming convex portions on the surface of the optical adjustment layer, and the average particle diameter of the particles is larger than the average film thickness of the optical adjustment layer , And its average particle size r1 and its average film thickness d1 are: 50nm≦(r1-d1)≦1900nm; the arithmetic average of the specific part of the surface of the optical adjustment layer except for the convex part formed by the particles The roughness Ra is in the range of 0.3 nm to 20 nm; and the average particle diameter r1 of the particles contained in the optical adjustment layer is in the range of 100 nm to 2000 nm. The hard coat film with an optical adjustment layer for a transparent conductive film as described in claim 1, wherein the average particle diameter r1 (nm) of the particles contained in the optical adjustment layer and the number of particles N (pieces) /mm ² ) is: 199.03exp(-0.002r1)≦N≦3676.4exp(-0.002r1). As described in claim 1 or 2 for the transparent conductive film with optical adjustment The whole-layer hard coating film, wherein the average film thickness d1 of the optical adjustment layer and the average particle diameter r1 of the particles contained in the optical adjustment layer have a relationship of (d1/r1)<0.5. The hard coat film with an optical adjustment layer for a transparent conductive film according to claim 1 or 2, wherein the hard coat layer contains a plurality of particles, and the average particle diameter of the particles is higher than that of the hard coat layer. The film thickness is still small, and the particles are unevenly distributed on the surface of the aforementioned hard coat layer. The hard coat film with an optical adjustment layer for a transparent conductive film according to claim 4, wherein the average film thickness d2 of the hard coat layer and the average particle diameter r2 of the particle diameter contained in the hard coat layer are : The relationship of (d2/r2)>2. The optical adjustment layer attached to the transparent conductive film request item 1 or 2 described with hard coat film, wherein the surface area of the valley side of the optical adjustment layer in each 661780μm ² is 200000μm ² or less. The hard coat film with an optical adjustment layer for a transparent conductive film according to claim 1 or 2, wherein the hard coat layer and the optical adjustment layer are provided on one side of the transparent base film, and the transparent base film A protective film is attached to the other side to form the outermost layer. The hard coat film with an optical adjustment layer for a transparent conductive film according to claim 7, wherein a hard coat layer is provided on the other surface of the transparent base film, and the protective film is bonded to the surface of the hard coat layer. The hard coat film with an optical adjustment layer for a transparent conductive film according to claim 1 or 2, wherein the hard coat layer and the optical adjustment layer are provided on both sides of the transparent base film, and the transparent base film A protective film is attached to either side of the film to form the outermost layer. A transparent conductive film formed by forming a transparent conductive layer on the surface of the optical adjustment layer in the hard coat film with an optical adjustment layer as described in any one of claims 1 to 9.

Images