JP6571488B2 - Hard coat film and transparent conductive film - Google Patents

Description

  The present invention relates to a hard coat film and a transparent conductive film, and more particularly to a hard coat film and a transparent conductive film including the hard coat film.

  Conventionally, a laminated film in which a hard coat layer is laminated on a base sheet is known.

  For example, a base sheet and a hard coat layer laminated on the surface thereof are provided, and the hard coat layer is a laminated film containing two or three kinds of particles having different primary particle diameters of 500 nm or less. It has been proposed (see, for example, Patent Document 1).

  The laminated film described in Patent Document 1 prevents blocking by a combination of particle diameters.

JP 2012-66477 A

  In recent years, more excellent blocking resistance has been required for laminated films. However, the laminated film of Patent Document 1 has a problem that it cannot satisfy the above requirements.

  On the other hand, the laminated film is also required to have an excellent appearance.

  An object of the present invention is to provide a hard coat film excellent in blocking resistance and appearance and a transparent conductive film including the same.

  The present invention is as follows.

[1] A transparent substrate and a hard coat layer disposed on one surface in the thickness direction of the transparent substrate, wherein the hard coat layer is composed of a composition containing a resin and particles, and the particles are 40 nm or more 1st inorganic particle which has an average particle diameter of 100 nm or less, and 2nd inorganic particle which has an average particle diameter of 10 nm or more and 20 nm or less, and the mixture ratio of the said particle | grain is 65 with respect to the said composition. Exceeding mass% and less than 80 mass%, the blending ratio of the first inorganic particles is 10 mass% or more and 65 mass% or less with respect to the composition, and the blending ratio of the second inorganic particles is A hard coat film characterized by being over 0% by mass and 60% by mass or less with respect to the composition,
[2] The hard coat film according to the above [1], wherein the particles are silica particles,
[3] The hard coat film according to [1] or [2] above, wherein the thickness of the hard coat layer is 0.5 μm or more,
[4] A transparent conductive film comprising the hard coat film according to any one of [1] to [3] above, an optical adjustment layer, and a transparent conductive layer in this order,
[5] The transparent conductive film according to [4], wherein the transparent conductive layer is made of ITO.

  The hard coat film of the present invention can have excellent blocking resistance and excellent appearance.

  Since the transparent conductive film of the present invention includes the hard coat film described above, it can have excellent blocking resistance and excellent appearance.

FIG. 1 shows a cross-sectional view of one embodiment of the hard coat film of the present invention. FIG. 2 shows a cross-sectional view of a transparent conductive film comprising the hard coat film shown in FIG.

  In FIG. 1, the vertical direction of the paper is the vertical direction (thickness direction, first direction), the upper side of the paper is the upper side (one side in the thickness direction, the first direction), and the lower side of the paper is the lower side (thickness direction). The other side, the other side in the first direction). In FIG. 1, the left-right direction on the paper surface is the left-right direction (width direction, second direction orthogonal to the first direction), the left side on the paper surface is the left side (second side in the second direction), and the right side on the paper surface is the right side (the other side in the second direction). ). In FIG. 1, the paper thickness direction is the front-rear direction (a third direction orthogonal to the first direction and the second direction), the front side of the paper is the front side (the third direction one side), and the back side of the paper surface is the rear side (the third direction). The other side). Specifically, it conforms to the direction arrow in each figure.

1. As shown in FIG. 1, the hard coat film 1 which is one embodiment of the present invention has a film shape (including a sheet shape) having a predetermined thickness, and a predetermined direction (front-rear direction) perpendicular to the thickness direction. And it extends in the left-right direction, that is, the surface direction, and has a flat upper surface and a flat lower surface (two main surfaces).

  The hard coat film 1 is, for example, one component provided in the transparent conductive film 6 (see FIG. 2) described later, that is, not the transparent conductive film 6. That is, the hard coat film 1 is a component for producing the transparent conductive film 6, does not include functional layers such as the optical adjustment layer 4 and the transparent conductive layer 5, is distributed alone and is industrially usable. It is a device.

  Specifically, the hard coat film 1 includes a transparent substrate 2 and a hard coat layer 3. That is, the hard coat film 1 includes a transparent substrate 2 and a hard coat layer 3 disposed on the upper surface of the transparent substrate 2. Further, preferably, the hard coat film 1 is composed of only the transparent substrate 2 and the hard coat layer 3. Hereinafter, each layer will be described in detail.

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

  The transparent substrate 2 is made of a polymer film. The polymer film has transparency. Examples of the material of the polymer film include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, for example, (meth) acrylic resins (acrylic resin and / or methacrylic resin) such as polymethacrylate, for example, polyethylene, Olefin resin such as polypropylene and cycloolefin polymer (COP), for example, polycarbonate resin, eg, polyether sulfone resin, eg, polyarylate resin, eg, melamine resin, eg, polyamide resin, eg, polyimide resin, eg, cellulose resin Examples thereof include polystyrene resins such as norbornene resins. These polymer films can be used alone or in combination of two or more. From the viewpoint of transparency and mechanical properties, preferably, an olefin resin is used, and more preferably, COP is used.

  The surface roughness of the transparent substrate 2 is, for example, 1 nm or less, preferably 0.3 nm or less, and, for example, 0.1 nm or more.

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

3. Hard Coat Layer The hard coat layer 3 is an upper layer of the hard coat film 1 and is an anti-blocking layer for imparting blocking resistance to the hard coat film 1. The hard coat layer 3 has a film shape extending in the surface direction, and has a flat upper surface and a flat lower surface (two main surfaces).

  The hard coat layer 3 has a film shape (including a sheet shape) and is disposed so as to contact the entire upper surface of the transparent substrate 2.

  The hard coat layer 3 is made of (prepared from) a resin composition. The resin composition contains a resin and particles. Preferably, a resin composition consists only of resin and particle | grains.

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

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

  Specifically, as the active energy ray curable resin, for example, (meth) acrylic ultraviolet curable resins such as urethane acrylate and epoxy acrylate, for example, urethane resin, for example, melamine resin, for example, alkyd resin, for example, Examples thereof include siloxane-based polymers such as organosilane condensates. Preferably, (meth) acrylic ultraviolet curable resin, more preferably, urethane acrylate is used.

  The compounding ratio of the resin is, for example, less than 35% by mass, preferably 30% by mass or less, and, for example, 25% by mass or more with respect to the composition.

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

  Examples of the particles include inorganic particles and organic particles. Examples of the inorganic particles include silica particles, for example, metal oxide particles composed of zirconium oxide, titanium oxide, zinc oxide, tin oxide, and the like, for example, carbonate particles such as calcium carbonate. Examples of the organic particles include crosslinked acrylic resin particles. One kind of particles can be used alone, or a plurality of kinds can be used in combination. The particles are preferably inorganic particles, more preferably silica particles. Since the silica particles are inexpensive and excellent in physical properties, the high quality hard coat film 1 can be obtained while reducing the production cost of the hard coat film 1.

  The particles have, for example, a substantially spherical shape, a substantially needle shape, a substantially plate shape, and an indefinite shape, and preferably have a substantially spherical shape.

  And a particle | grain contains the 1st inorganic particle which has an average particle diameter of 40 nm or more and 100 nm or less, and the 2nd inorganic particle which has an average particle diameter of 10 nm or more and 20 nm or less. Preferably, the particles are composed only of the first inorganic particles and the second inorganic particles.

  The first inorganic particles are large particles having a large average particle diameter among the particles, and are anti-blocking particles (anti-blocking agent) that impart excellent blocking resistance to the hard coat film 1.

  The first inorganic particles have an average particle diameter of 40 nm or more and 100 nm or less, preferably more than 40 nm, more preferably 45 nm or more, and preferably 90 nm or less, more preferably 80 nm or less, Preferably, it has an average particle size of 70 nm or less, particularly preferably 60 nm or less. When the average particle diameter of the first inorganic particles exceeds the lower limit described above, the hard coat film 1 can have excellent blocking resistance. When the average particle diameter of the first inorganic particles is less than the above upper limit, the hard coat film 1 can have an excellent appearance.

  The average particle diameter is a volume average particle diameter measured by the BET method.

  The average particle size of the first inorganic particles is the average particle size of the primary particles of the first inorganic particles. Preferably, the first inorganic particles are monodisperse particles having a standard deviation of particle size distribution within 10%.

  The blending ratio of the first inorganic particles is 10% by mass or more, preferably more than 10% by mass, more preferably 15% by mass or more, still more preferably 20% by mass or more, particularly preferably. Is 25% by mass or more. Moreover, the blending ratio of the first inorganic particles is, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more with respect to the total amount of particles. The blending ratio of the first inorganic particles is, for example, 25 parts by mass or more, preferably 50 parts by mass or more, and more preferably 75 parts by mass or more with respect to 100 parts by mass of the resin.

  Further, the blending ratio of the first inorganic particles is 65% by mass or less, preferably less than 65% by mass, more preferably 60% by mass or less, and further preferably 55% by mass or less, Especially preferably, it is 50 mass% or less. Moreover, the mixture ratio of the 1st inorganic particle is 95 mass% or less with respect to the total amount of particle | grains, Preferably, it is 90 mass% or less. Moreover, the mixture ratio of the 1st inorganic particle is 250 mass parts or less with respect to 100 mass parts of resin, Preferably, it is 200 mass parts or less.

  If the blending ratio of the first inorganic particles exceeds the above lower limit, the hard coat film 1 can have excellent blocking resistance and can have an excellent appearance. If the blending ratio of the first inorganic particles is lower than the upper limit described above, the hard coat film 1 can reduce haze and can ensure excellent transparency, and thus has an excellent appearance. it can.

  The second inorganic particles are small particles having a small average particle size among the particles. The second inorganic particles are anti-blocking auxiliary agents that assist the blocking resistance of the first inorganic particles, and are also extenders that increase the bulk of the hard coat layer 3.

  The second inorganic particles have an average particle size of 10 nm or more and 20 nm or less, preferably less than 20 nm, more preferably 15 nm or less.

  If the average particle diameter of the second inorganic particles is below the upper limit described above, the hard coat film 1 can have an excellent appearance.

  The average particle size of the second inorganic particles is the average particle size of the primary particles of the second inorganic particles. Preferably, the second inorganic particles are monodisperse particles having a standard deviation of particle size distribution within 10%.

  The blending ratio of the second inorganic particles exceeds 0% by mass with respect to the composition, preferably 5% by mass or more, and preferably exceeds 5% by mass. Moreover, the mixture ratio of the 2nd inorganic particle is 5 mass% or more with respect to the total amount of particle | grains, Preferably, it is 10 mass% or more. Moreover, the mixture ratio of the 2nd inorganic particle is 10 mass parts or more with respect to 100 mass parts of resin, Preferably, it is 25 mass parts or more.

  Further, the blending ratio of the second inorganic particles is 60% by mass or less, preferably less than 60% by mass, more preferably 55% by mass or less, and still more preferably 50% by mass or less. Especially preferably, it is less than 50 mass%, Most preferably, it is 45 mass% or less, Furthermore, it is 40 mass% or less. The blending ratio of the second inorganic particles is, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% by mass or less, with respect to the total amount of particles. It is. The blending ratio of the second inorganic particles is, for example, 200 parts by mass or less, preferably 175 parts by mass or less, and more preferably 150 parts by mass or less with respect to 100 parts by mass of the resin.

  If the blending ratio of the second inorganic particles exceeds the lower limit described above, an excellent appearance can be obtained. If the blending ratio of the second inorganic particles is below the upper limit described above, the hard coat film 1 can have an excellent appearance.

  Further, the ratio R of the first inorganic particles to the second inorganic particles (number of blended parts of the first inorganic particles / number of blended parts of the second inorganic particles) is, for example, 0.1 or more, preferably 0.3 or more, more preferably. Is 0.5 or more, and is, for example, 20 or less, preferably 10 or less, and more preferably 3.0 or less. If above-mentioned ratio R is more than an above-described minimum, the blocking resistance of the hard coat film 1 can be improved. If above-mentioned ratio R is below the above-mentioned upper limit, the hard coat film 1 can have the outstanding external appearance.

  The blending ratio of the particles is more than 65% by mass, preferably 70% by mass or more, and less than 80% by mass, preferably 75% by mass or less based on the composition. The mixing ratio of the particles is, for example, 200 parts by mass or more, preferably 230 parts by mass or more, and less than 400 parts by mass, preferably 300 parts by mass or less, more preferably 100 parts by mass of the resin. Is 250 parts by mass or less.

  When the mixing ratio of the particles is below the above lower limit, the hard coat film 1 cannot be provided with sufficient blocking resistance. On the other hand, when the mixing ratio of the particles exceeds the above upper limit, excellent transparency cannot be ensured, and therefore, an excellent appearance cannot be obtained.

  The thickness of the hard coat layer 3 is, for example, 0.1 μm or more, preferably 0.5 μm or more, and for example, 10 μm or less, preferably 5.0 μm or less.

  If the thickness of the hard coat layer 3 is equal to or more than the lower limit described above, sufficient blocking resistance can be imparted to the hard coat layer 3. When the thickness of the hard coat layer 3 is equal to or less than the above-described upper limit, the hard coat layer 3 can be provided with sufficient blocking resistance.

  The thickness of the hard coat layer 3 is measured using an instantaneous multi-photometry system “MCPD2000” (trade name) manufactured by Otsuka Electronics. Specifically, it is measured according to the method described in JP-A-2015-141684.

4). Next, a method for manufacturing the hard coat film 1 will be described.

  The hard coat film 1 is manufactured by the roll-to-roll method, for example, with the following layers.

  In this method, first, a hard coat film 1 is prepared.

  Thereafter, the transparent substrate 2 is disposed on the upper surface of the hard coat film 1. Specifically, the composition is disposed on the upper surface of the hard coat film 1 by, for example, a wet method.

  More specifically, first, a coating solution (varnish) obtained by diluting the composition with a solvent is prepared.

  The concentration of the solvent in the coating solution of the composition (solid content concentration) is, for example, 1% by mass or more, preferably 10% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less. Thus, it mix | blends with respect to a composition.

  Moreover, resin, 1st inorganic particle, and 2nd inorganic particle are mix | blended, and a composition is prepared. Alternatively, a particle resin mixture in which a resin and any one of the first inorganic particles and the second inorganic particles are mixed in advance may be prepared, and the particle resin mixture and the other particles may be mixed.

  Preferably, a particle resin mixture in which a resin and second inorganic particles are mixed in advance is prepared, and the particle resin mixture and the first inorganic particles are mixed. In this case, the slurry can be prepared as a slurry in which the first inorganic particles are dispersed in an organic solvent (organosilica sol when the first inorganic particles are silica particles), and the slurry can be blended into the particle resin mixture. The organic solvent is not particularly limited, for example, alcohol solvents such as methanol, isopropyl alcohol, butanol, ethylene glycol, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Examples thereof include ester solvents such as ethyl acetate and butyl acetate, and aromatic solvents such as xylene and toluene. In the organic solvent, the blending ratio of the first inorganic particles is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 50% by mass or less, preferably 40% by mass or less, with respect to the slurry. It mix | blends so that it may become.

  Preferably, a particle resin mixture is first prepared, and then the particle resin mixture and the slurry are mixed. In addition, as a particle resin mixture, a commercial item (Opstar series, manufactured by JSR Corporation) can be used. As the slurry, commercially available products (organosilica sol series, manufactured by Nissan Chemical Industries, Ltd.) can be used. According to this method, a particle resin mixture is prepared in which the second inorganic particles that are difficult to uniformly mix due to the small average particle diameter are uniformly mixed in advance with the resin. Subsequently, the first inorganic particles that are easy to uniformly mix due to the large average particle diameter are blended into the particle resin mixture. Therefore, both the first inorganic particles and the second inorganic particles can be uniformly dispersed in the resin in a short time.

  The mixing ratio of the second inorganic particles and the resin in the particle resin mixture and the mixing ratio of the particle resin mixture and the first inorganic particles in the composition are the above-described mixing ratios of the resin, the first inorganic particles, and the second inorganic particles. Thus, it is adjusted as appropriate.

  Thereafter, the composition is diluted with a solvent so that the solid content concentration falls within the above range, thereby preparing a coating solution (varnish).

  Subsequently, a coating solution (varnish) is applied to the entire upper surface of the hard coat film 1.

  Thereafter, the solvent is removed by heating. The heating temperature is, for example, 50 ° C. or more, preferably 60 ° C. or more, and for example, 100 ° C. or less, preferably 80 ° C. or less. The heating time is, for example, 10 seconds or more, preferably 30 seconds or more, and for example, 5 minutes or less, preferably 3 minutes or less.

  Thereby, the coating film which consists of a composition is formed.

  Thereafter, when the resin is an active energy ray curable resin, the coating film is irradiated with active energy rays. Thereby, the resin is cured.

  Thereby, the hard coat layer 3 is formed on the upper surface of the transparent substrate 2.

  Thereby, the hard coat film 1 provided with the transparent base material 2 and the hard coat layer 3 is manufactured.

  The particles contained in the hard coat layer 3 in the hard coat film 1 are qualitatively analyzed (identified) by, for example, burning the hard coat film 1 and then elementally analyzing the obtained ash. The first inorganic particles and the second inorganic particles are quantitatively analyzed by measuring the particle size of the particles with a laser diffraction particle size distribution measuring device or the like. In the quantitative analysis described above, a particle size distribution curve having two peaks based on two average particle diameters (median diameters) of the first inorganic particles and the second inorganic particles is obtained, and from these peaks, the first inorganic particles and The average particle diameter and the mixing ratio of the second inorganic particles are obtained.

  And this hard coat film 1 is used for each industrial use, for example, optical uses, such as a transparent conductive film and a light control film, Furthermore, an electromagnetic shield use etc. are used. Preferably, it is used for optical applications, more preferably for transparent conductive films.

5. Transparent conductive film Next, the transparent conductive film 6 provided with the hard coat film 1 is demonstrated with reference to FIG.

  The transparent conductive film 6 has a film shape (including a sheet shape) having a predetermined thickness, extends in the surface direction, and has a flat upper surface and a flat lower surface (two main surfaces). The transparent conductive film 6 is a component such as a base material for a touch panel or a light control panel provided in an optical device (for example, an image display device or a light control device), that is, not an optical device. That is, the transparent conductive film 6 is a component for producing an optical device or the like, does not include an image display element such as an LCD module, and a light source such as an LED, and is a device that can be distributed and used industrially. It is.

  And this transparent conductive film 6 is equipped with the hard-coat film 1, the optical adjustment layer 4, and the transparent conductive layer 5 in order. Specifically, the transparent conductive film 6 includes a transparent substrate 2, a hard coat layer 3, an optical adjustment layer 4, and a transparent conductive layer 5 in this order. Preferably, the transparent conductive film 6 includes only the transparent substrate 2, the hard coat layer 3, the optical adjustment layer 4, and the transparent conductive layer 5.

  The optical adjustment layer 4 is configured so that the difference between the non-pattern part and the pattern part is not recognized after the transparent conductive layer 5 is formed in the wiring pattern in a later step (that is, the visual recognition of the wiring pattern is suppressed). It is a layer for adjusting the optical properties of the transparent conductive film 6.

  The optical adjustment layer 4 is disposed on the entire upper surface of the hard coat layer 3. The optical adjustment layer 4 has a film shape extending in the surface direction, and has a flat plane and an uneven lower surface (not shown) (two main surfaces).

  The optical adjustment layer 4 is prepared from a resin composition. The resin composition contains, for example, a resin and particles. The resin composition preferably contains only a resin, and more preferably consists only of a resin. Examples of the resin include the above-described resins.

  The thickness of the optical adjustment layer 4 is, for example, 30 nm or more, preferably 80 nm or more, and for example, 150 nm or less, preferably 130 nm or less.

  The transparent conductive layer 5 is a conductive layer that is formed in a wiring pattern in a later step to form a pattern portion. The transparent conductive layer 5 is the uppermost layer of the transparent conductive film 6 and has a film shape (including a sheet shape) extending in the surface direction, and has a flat lower surface and a flat upper surface.

  The material for forming the transparent conductive layer 5 is, for example, at least selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. A metal oxide containing one kind of metal can be given. If necessary, the metal oxide can be further doped with a metal atom shown in the above group.

  As a material, Preferably, indium tin complex oxide (ITO), antimony tin complex oxide (ATO), etc. are mentioned, More preferably, ITO is mentioned. With ITO, excellent transparency and low specific resistance can be ensured with ITO.

  The thickness of the transparent conductive layer 5 is, for example, 10 nm or more, preferably 20 nm or more, and for example, 35 nm or less, preferably 30 nm or less.

  The transparent conductive film 6 is obtained by sequentially arranging the optical adjustment layer 4 and the transparent conductive layer 5 on the hard coat film 1.

6). Effect The hard coat film 1 can have excellent blocking resistance and excellent appearance.

  In addition, if the particles are silica particles, the silica particles are excellent in physical properties while being inexpensive, so that the high-quality hard coat film 1 can be obtained while reducing the production cost of the hard coat film 1.

  Furthermore, if the thickness of the hard coat layer 3 is equal to or greater than the above-described lower limit, the hard coat layer 3 can be provided with sufficient blocking resistance.

  Moreover, since the transparent conductive film 6 is equipped with the hard coat film 1, the optical adjustment layer 4, and the transparent conductive layer 5 in order, the transparent conductive layer 5 is reliably supported by the hard coat film 1, and optical adjustment is carried out. With the layer 4, excellent conductivity can be ensured by the transparent conductive layer 5 while suppressing the visibility of the transparent conductive layer 5 patterned in a later step.

  Moreover, if the transparent conductive layer 5 consists of ITO, the transparent conductive layer 5 can ensure the outstanding transparency and low specific resistance.

7). In an embodiment shown in FIG. 1, the hard coat film 1 includes a hard coat layer 3 arranged only on the upper surface of the transparent substrate 2. However, arrangement | positioning of the hard-coat layer 3 is not limited above, For example, although not shown in figure, the hard-coat layer 3 arrange | positioned at the upper surface and lower surface (both surfaces) of the transparent base material 2 can also be provided.

  The same effect as the hard coat film 1 of one embodiment can be obtained by the hard coat film 1 of this modification.

  In one embodiment shown in FIG. 2, the transparent conductive film 6 includes a hard coat layer 3, an optical adjustment layer 4, and a transparent conductive layer 5 disposed only on the upper side of the transparent substrate 2. The arrangement of the optical adjustment layer 4 and the transparent conductive layer 5 is not limited to the above. For example, the hard adjustment layer 4, the optical adjustment layer 4, and the transparent conductive layer 5 are sequentially arranged on both sides of the transparent substrate 2. You can also.

  The same effect as the transparent conductive film 6 of one embodiment can be obtained also by the transparent conductive film 6 of this modification.

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

  “Parts” and “%” are based on mass unless otherwise specified.

(Preparation of coating solution)
Preparation Example 1
Particle resin mixture in which urethane acrylate as an ultraviolet curable resin and silica particles having an average particle diameter of 10 nm as a second inorganic particle are preliminarily blended (manufactured by JSR, product name “OPSTAR KZ6507”, content ratio of second inorganic particles: 40 mass %)), And an organosilica sol (product name “MEK-ST-L”, manufactured by Nissan Chemical Co., Ltd.) in which silica particles having an average particle diameter of 50 nm as first inorganic particles are dispersed in methyl ether. The solid content was 190 parts by mass as the solid content, and organosilica sol (product name “MEK-ST”, manufactured by Nissan Chemical Co., Ltd.) in which silica particles having an average particle size of 10 nm as the second inorganic particles were dispersed in methyl ether. Next, the composition is diluted with butyl acetate so as to have a solid content of 16% by mass and coated. Liquid (the hard coating agent) was prepared.

Preparation Examples 2-9 and Comparative Preparation Examples 1-13
A coating solution was prepared in the same manner as in Preparation Example 1 except that the formulation was changed according to the descriptions in Tables 1 and 2.

(Preparation of hard coat film)
Example 1
First, a COP film (ZEONOR ZF-16, surface roughness 0.2 nm, manufactured by Nippon Zeon Co., Ltd.) having a thickness of 100 μm was prepared as the transparent substrate 2.

Subsequently, the coating liquid of Preparation Example 1 was applied to the surface of the transparent substrate 2 using the wire bar # 6, and then dried in an oven at 80 ° C. for 1 minute in a drying oven to remove butyl acetate. Volatilized to form a coating film composed of the composition. Subsequently, a coating film, using an oxygen concentration 2500ppm atmosphere at 160 W / cm ² of air-cooled mercury lamp (manufactured by Eye Graphics Co., Ltd.), illuminance 60 mW / cm ² and an irradiation dose of 280 mJ / cm ² The coating was cured.

  Thereby, a hard coat layer 3 having a thickness of 1 μm was formed on the surface of the transparent substrate 2. That is, the hard coat film 1 provided with the transparent base material 2 and the hard coat layer 3 laminated | stacked on the surface was manufactured.

Examples 2-9 and Comparative Examples 1-13
A hard coat film 1 having a hard coat layer 3 was produced in the same manner as in Example 1 except that the formulation was changed according to the description in Table 3.

  In addition, about Examples 2-9 and Comparative Examples 1-13, the coating liquid of Preparation Examples 2-9 and Comparative Preparation Examples 1-13 was used, respectively.

Evaluation The following items are evaluated and the results are shown in Table 3.

[Thickness of hard coat layer]
The thickness of the hard coat layer 3 of each example and each comparative example was measured using MCPD2000 (manufactured by Otsuka Electronics Co., Ltd.).

[Blocking resistance]
Another transparent substrate 2 (ZEONOR ZF-16, manufactured by Nippon Zeon Co., Ltd.) is pressure-bonded to the surface of the hard coat layer 3 of each Example and each Comparative Example, and the hard coat layer 3 of the other transparent substrate 2 is pressed. The sticking (blocking resistance) to was evaluated as follows.
A: Sticking of the other transparent substrate 2 to the hard coat layer 3 did not occur.
Δ: Another transparent substrate 2 was once stuck to the hard coat layer 3, but separated from the hard coat layer 3 after 10 seconds.
X: Another transparent base material 2 stuck to the hard coat layer 3, and did not leave the hard coat layer 3 even after 10 seconds.

[appearance]
The following items were evaluated for the hard coat film 1 of each example and each comparative example.

(1) Transparency The hard coat film 1 of each example and each comparative example was visually observed, and transparency was evaluated according to the following criteria.
○: Almost transparent.
Δ: Light turbidity was observed.
X: Dark turbidity was observed.

(2) Haze The haze of the hard coat film 1 of each Example and each Comparative Example was measured with a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.), and the degree of cloudiness was evaluated according to the following criteria.
○: Haze was less than 0.5%.
Δ: Haze was 0.5% or more and less than 1.0%.
X: Haze was 1.0% or more.

DESCRIPTION OF SYMBOLS 1 Hard coat film 2 Transparent base material 3 Hard coat layer 4 Optical adjustment layer 5 Transparent conductive layer 6 Transparent conductive film

Claims (5)

A transparent base material and a hard coat layer are provided in order,
The hard coat layer is composed of a composition containing a resin and particles,
The particles are
First inorganic particles having an average particle diameter of 40 nm or more and 100 nm or less;
Containing second inorganic particles having an average particle diameter of 10 nm or more and 20 nm or less,
The blending ratio of the particles is more than 65% by mass and less than 80% by mass with respect to the composition.
The blending ratio of the first inorganic particles is 10% by mass or more and 65% by mass or less with respect to the composition,
The hard coat film, wherein the blending ratio of the second inorganic particles is 0% by mass and 60% by mass or less with respect to the composition.   The hard coat film according to claim 1, wherein the particles are silica particles.   The hard coat film according to claim 1, wherein the hard coat layer has a thickness of 0.5 μm or more.   A transparent conductive film comprising the hard coat film according to claim 1, an optical adjustment layer, and a transparent conductive layer in this order.   The transparent conductive film according to claim 4, wherein the transparent conductive layer is made of ITO.

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