KR20150048927A - Hard coat film and transparent conducting film - Google Patents

Abstract

Wherein at least one surface of the base film is provided with a first hard coat layer containing particles and the surface of the first hard coat layer is present at a density of 300 to 4,000 densities per 100 m ² of the particle, Wherein the center line average roughness Ra1 of the surface of the first hard coat layer is less than 30 nm and the haze value is less than 1.5%.
The present invention provides a hard coat film having high transparency and good sliding property and blocking resistance.

Description

[0001] Hard Coat Film and Transparent Conductive Film [0002]

The present invention relates to a hard coat film having high transparency and good sliding property and blocking resistance, and specifically relates to a hard coat film suitable for a transparent conductive film.

A hard coat film in which a hard coat layer is laminated on a base film is used as a surface protection of a display or a touch panel, and also as a base film of an electrode film for a touch panel (a transparent conductive film for a touch panel). The hard coat film used in these applications is required to have high transparency and good sliding property and blocking resistance.

In order to improve the sliding property and blocking resistance of a hard coat film or a polyester film, it has been proposed to provide projections on the surface (Patent Documents 1 and 2)

Japanese Patent Application Laid-Open No. 7-314628 Japanese Patent Application Laid-Open No. 2000-211082

However, in the technique disclosed in the above patent documents, the transparency, the sliding property and the blocking resistance were not sufficiently satisfied at the same time.

Accordingly, an object of the present invention is to provide a hard coat film having high transparency and good sliding and blocking properties in view of the problems of the prior art. Another object of the present invention is to provide a hard coat film preferable for a transparent conductive film.

The above object of the present invention can be achieved by any one of the following constitutions 1) to 15).

1) A first hard coat layer containing particles is provided on at least one surface of a base film, protrusions comprising the particles are present on the surface of the first hard coat layer at a density of 300 to 4,000 per 100 μm ² , The center line average roughness (Ra1) of the surface of the first hard coat layer is less than 30 nm, and the haze value is less than 1.5%.

2) The hard coat film according to 1), wherein the particles have an average particle diameter (r) of 0.05 to 0.5 μm.

3) The hard coat film according to 1) or 2), wherein the ratio (r / d) of the average particle diameter r of the particles to the thickness d of the first hard coat layer is 0.01 to 0.30. .

4) The hard coat film according to any one of 1) to 3), wherein the average diameter of the projections is 0.03 to 0.3 탆 and the average height of the projections is 0.03 to 0.3 탆.

5) The hard coat film according to any one of 1) to 4), wherein the average interval of the projections is 0.10 to 0.70 탆.

6) The hard coat film according to any one of 1) to 5), wherein the thickness (d) of the first hard coat layer is 0.5 탆 or more and less than 10 탆.

7) The resin composition according to any one of 1) to 6), further comprising a resin layer between the base film and the first hard coat layer, wherein the resin layer has a thickness of 0.005 to 0.3 mu m, Of the hard coat film.

(8) The hard coat film according to any one of (1) to (7), wherein the base film is a polyethylene terephthalate film and a resin layer having a refractive index of 1.55 to 1.61 is provided between the base film and the first hard coat layer.

(9) The hard coat film according to any one of (1) to (8), wherein a resin layer having a wet tension of 52 mN / m or less is provided between the base film and the first hard coat layer.

10) The hard coat film according to 9), wherein the thickness of the first hard coat layer is less than 2 탆.

11) The method according to any one of 1) to 10), wherein the surface treatment is performed on the inorganic particles to reduce the surface free energy of the particles contained in the first hard coat layer, and the inorganic particles Wherein the hard coat film is at least one selected from the group consisting of a hard coat film and a hard coat film.

12) The hard coat film according to 11), wherein the surface treatment for obtaining the inorganic particles subjected to the surface treatment for reducing the surface free energy of the particles is the following (I) or (II).

(I) at least one organosilane compound selected from the group consisting of an organosilane compound having a fluorine atom represented by the following general formula (1), a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate of the organosilane Surface treatment with compound.

C _n F _{2n +1} - (CH ₂ ) _m -Si (Q) ₃ ????? (1)

[In the general formula (1), n represents an integer of 1 to 10, and m represents an integer of 1 to 5. Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom]

(II) is treated with a compound represented by the following general formula (2), and further treated with a fluorine compound represented by the following general formula (3).

BR ⁴ -SiR ⁵ _n (OR ⁶ ) _3-n ????? (2)

DR ⁷ -Rf ² ????? (3)

[In formulas (2) and (3), B and D each independently represent a reactive moiety, and R ⁴ and R ⁷ each independently represents an alkylene group having 1 to 3 carbon atoms or an ester derived from the alkylene group , R ⁵ and R ⁶ each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, Rf ² represents a fluoroalkyl group, and n represents an integer of 0 to ² ,

13) The hydrophobic compound used in the hydrophobic treatment for obtaining the inorganic particles having the surface of the particle hydrophobized in the process 11) is a fluoroalkyl group having 4 or more carbon atoms and a fluorine compound having a reactive site, A long-chain hydrocarbon compound having a siloxane group and a silicone compound having a reactive site, and a silicone compound having a siloxane group and a reactive site.

(14) The hard coat film according to any one of (1) to (13), wherein the particles contained in the first hard coat layer are silica particles.

15) The method of any one of 1) to 14), wherein a second hard coat layer is provided on a surface of the base film opposite to a surface on which the first hard coat layer is provided, and the surface of the second hard coat layer And the center line average roughness (Ra2) of the surface of the second hard coat layer is 25 nm or less.

16) A transparent conductive film comprising a transparent conductive film on at least one surface of the hard coat film according to any one of 1) to 15) above.

(Effects of the Invention)

According to the present invention, it is possible to provide a hard coat film having high transparency and good sliding property and blocking resistance. The hard coat film of the present invention is preferable for the base film of the transparent conductive film.

1 is an example of an observation view of the surface of the first hard coat layer observed with a scanning electron microscope.
2 is a diagram schematically showing a planar shape of a projection on the surface of the first hard coat layer.
FIG. 3 is a schematic diagram schematically showing the surface of the first hard coat layer of FIG. 1; FIG.
Fig. 4 is a schematic view showing a part of Fig. 3 is omitted.

The hard coat film according to one embodiment of the present invention has a first hard coat layer on at least one side of the base film. A first hard coat layer containing particles, and has a first (that is sometimes referred to hereinafter simply referred to as "projections") 300-4000 per 100㎛ ² protrusions by the particles on the surface of the hard coat layer. The center line average roughness Ra1 of the surface of the first hard coat layer is less than 30 nm. The hard coat film of this embodiment has a haze value of less than 1.5%.

By providing the surface of the first hard coat layer with protrusions of 300 to 4000 per unit area (100 탆 ² ) of the surface of the first hard coat layer, the sliding properties and the blocking resistance are improved.

The number density of protrusions is preferably in the range of 400 to 3,500, more preferably in the range of 500 to 3,000, more preferably in the range of 600 to 3,000, and particularly preferably in the range of 700 to 2,500 per 100 μm ² .

When the number density of particles is less than 300 per 100 mu m < ^{2 &} gt ;, the sliding property and anti-blocking property are deteriorated. On the other hand, when the number density of particles exceeds 4000 per 100 μm ² , the smoothness of the surface of the first hard coat layer is lowered, the haze value is increased, and the transparency of the hard coat film is lowered.

As described above, the hard coat film of this embodiment has a relatively large number of protrusions on the surface of the first hard coat layer, and is characterized in that the surface of the first hard coat layer is relatively smooth or the haze value of the hard coat film is small. Specifically, it is important that the center line average roughness Ra1 of the surface of the first hard coat layer in this embodiment is less than 30 nm, and the haze value of the hard coat film is less than 1.5%.

The center line average roughness Ra1 of the surface of the first hard coat layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 18 nm or less. The center line average roughness Ra1 of the lower limit is preferably not less than 5 nm, more preferably not less than 7 nm, and particularly preferably not less than 9 nm from the viewpoint of ensuring sliding property and blocking resistance.

When the center line average roughness Ra1 of the surface of the first hard coat layer is 30 nm or more, the smoothness is lowered and the transparency of the hard coat film is lowered. That is, the haze value of the hard coat film becomes large.

From the viewpoint of realizing high transparency, it is important that the haze value of the hard coat film of the present embodiment is less than 1.5%. The haze value of the hard coat film of the present embodiment is preferably 1.1% or less, more preferably 1.0% or less. The haze value of the lower limit is preferably as small as possible, but is practically about 0.01%.

A first hard coat layer has a protrusion piece 300-4000 100㎛ per ^second on the surface, and a first center line average roughness (Ra1) of the hard coat layer surface is less than 30nm, and further less than 1.5% the haze value of the hard coat film , Particles having an average particle diameter (r) of 0.05 to 0.5 占 퐉 are contained in the first hard coat layer and the particles are relatively present in the vicinity of the surface of the first hard coat layer, .

The ratio (r / d) of the average particle diameter (r) (mu m) of the particles contained in the first hard coat layer to the thickness d (mu m) of the first hard coat layer is preferably 0.01 to 0.30 . As a result, the centerline average roughness Ra1 of the surface of the first hard coat layer is reduced, and the haze value of the hard coat film is also reduced.

Hereinafter, each component constituting the hard coat film will be described in detail.

[Base film]

A plastic film is preferably used for the base film. Examples of the material constituting the base film include polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride , Polycarbonate, polymethyl methacrylate, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose, and resins obtained by mixing and / or copolymerizing these resins. These resins can be applied as a base film in the form of unstretched or uniaxially or biaxially stretched film.

Among the above base films, the polyester film is excellent in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, chemical resistance and the like, and in particular, a polyethylene terephthalate film (PET film) is preferably used.

The thickness of the base film is suitably in the range of 20 to 300 占 퐉, preferably in the range of 30 to 200 占 퐉, and more preferably in the range of 50 to 150 占 퐉.

It is preferable that the base film has a resin layer as shown below on the side where at least the first hard coat layer is laminated. That is, it is preferable that a resin layer shown below is provided between the base film and the first hard coat layer.

[Resin Layer]

In order to enhance adhesion between the base film and the first hard coat layer, it is preferable that a resin layer is provided on a surface of the base film on which at least the first hard coat layer is laminated.

The resin layer is a layer containing a resin as a main component. Specifically, the resin layer is a layer containing 50% by mass or more of the resin with respect to 100% by mass of the total solid content of the resin layer. Examples of the resin forming the resin layer include a polyester resin, an acrylic resin, a urethane resin, a polycarbonate resin, an epoxy resin, an alkyd resin and a urea resin. These resins may be used singly or in combination.

From the viewpoint that the resin layer is interposed between the base film and the first hard coat layer and improves the adhesion between the base film and the first hard coat layer, it is preferable to use at least a resin selected from the group consisting of polyester resin, acrylic resin and polyurethane resin It is preferable to contain one species. In particular, it is preferable that the resin layer contains at least a polyester resin as a resin.

The content of the resin in the resin layer is preferably 60 mass% or less, more preferably 70 mass% or more, and particularly preferably 80 mass% or more, based on 100 mass% of the total solid content of the resin layer. Regarding the upper limit, the content of the resin in the resin layer is preferably 95% by mass or less, more preferably 90% by mass or less.

The resin layer may be formed in a two-layer structure. In the case of the two-layer structure, the first resin layer mainly composed of a polyester resin and the second resin layer mainly composed of an acrylic resin are preferably formed in this order from the base film side. Details of the two-layer structure will be described later.

The resin layer preferably contains particles from the viewpoint of ensuring adequate sliding property and winding property in the production process of the hard coat film.

Examples of the particles contained in the resin layer include, but are not limited to, inorganic particles such as silica particles, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate and zeolite particles, acrylic particles, silicone particles, polyimide particles, Teflon (registered trademark) , Crosslinked polyester particles, crosslinked polystyrene particles, crosslinked polymer particles, core shell particles and the like. Among these, silica particles are preferable, and colloidal silica is particularly preferable.

It is preferable that the average particle size of the particles contained in the resin layer is larger than the thickness of the resin layer. Specifically, the average particle diameter is preferably 1.3 times or more of the thickness of the resin layer, more preferably 1.5 times or more, and particularly preferably 2.0 times or more. The upper limit is preferably 20 times or less, more preferably 15 times or less, and particularly preferably 10 times or less.

Sliding property and anti-blocking property are further improved by directly laminating the first hard coat layer on a resin layer containing particles having an average particle diameter larger than the thickness of the resin layer.

The average particle diameter of the particles contained in the resin layer is appropriately selected according to the design of the thickness of the resin layer. Specifically, the average particle diameter is preferably in the range of 0.02 to 1 mu m, more preferably in the range of 0.05 to 0.7 mu m And particularly preferably in the range of 0.1 to 0.5 mu m. If the average particle diameter is less than 0.02 탆, the sliding property and blocking resistance may be lowered. If the average particle diameter exceeds 1 占 퐉, the particles may fall off, the transparency may deteriorate, or the appearance may be deteriorated.

The range of the thickness of the resin layer is preferably in the range of 0.005 to 0.3 mu m. When the thickness of the resin layer is less than 0.005 탆, the adhesion between the base film and the first hard coat layer deteriorates. If the thickness of the resin layer is larger than 0.3 mu m, the anti-blocking property may decrease after the first hard coat layer is laminated. The thickness of the resin layer is also preferably 0.01 占 퐉 or more, more preferably 0.015 占 퐉 or more, and particularly preferably 0.02 占 퐉 or more. Regarding the upper limit, the thickness of the resin layer is preferably 0.25 占 퐉 or less, more preferably 0.2 占 퐉 or less, particularly preferably 0.15 占 퐉 or less. When there are a plurality of resin layers, it is preferable that the sum of the thicknesses of all the resin layers satisfies the condition of the thickness.

The content of the particles in the resin layer is preferably in the range of 0.05 to 10 mass%, more preferably in the range of 0.1 to 8 mass%, particularly preferably in the range of 0.5 to 5 mass%, based on 100 mass% of the total solid content of the resin layer. Is preferable. When the content of the particles in the resin layer is less than 0.05 mass%, good sliding property and blocking resistance may not be obtained. When the content of the particles exceeds 10 mass%, the transparency decreases or the coating of the first hard coat layer The adhesion between the base film and the first hard coat layer may deteriorate.

The resin layer preferably further contains a crosslinking agent. The resin layer is preferably a thermosetting layer containing the above-mentioned resin and a crosslinking agent. By making the resin layer into such a thermosetting layer, the adhesion between the base film and the first hard coat layer can be further improved. The heating temperature, the heating temperature, the heating temperature, the heating temperature, the heating temperature, the heating temperature, the heating temperature, the heating temperature and the heating temperature are preferably 100 ° C or more, more preferably 150 ° C or more, Is most preferable. Regarding the upper limit, the heating temperature is preferably 300 DEG C or less. The heating time is preferably in the range of 5 to 300 seconds, more preferably in the range of 10 to 200 seconds.

Examples of the crosslinking agent include melamine crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, epoxy crosslinking agents, methylol or alkylol urea crosslinking agents, acrylamide crosslinking agents, poly Amide-based resins, amide epoxy compounds, various silane coupling agents, and various titanate-based coupling agents. Among them, a lamin-based crosslinking agent, an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, an isocyanate-based crosslinking agent and an aziridine-based crosslinking agent are preferable, and a melamine crosslinking agent is particularly preferable.

Examples of the melamine-based cross-linking agent include imino group-type methylated melamine resin, methylol group type melamine resin, methylol group type methylated melamine resin and fully alkyl type methylated melamine resin. Of these, an imino type melamine resin and a methylol melamine resin are preferably used.

The content of the crosslinking agent in the resin layer is preferably in the range of 0.5 to 40 mass%, more preferably in the range of 1 to 30 mass%, particularly preferably in the range of 2 to 20 mass%, based on 100 mass% of the total solid content of the resin layer. Is preferable.

The color of the hard coat film obtained by laminating the first hard coat layer on the base film through the resin layer is preferably a neutral colorless hue. From this viewpoint, when a polyethylene terephthalate film (PET film) is used as the base film, the refractive index of the resin layer is preferably in the range of 1.55 to 1.61, more preferably in the range of 1.56 to 1.60, Range is particularly preferred.

The refractive index of the polyethylene terephthalate film (PET film) is generally about 1.62 to 1.70, and the refractive index of the resin layer is in the above range (1.55 to 1.61), so that the reflection color of the hard coat film can be brought close to the neutral colorlessness. That is, the difference (np-nr) between the refractive index np of the PET film and the refractive index nr of the resin layer is preferably in the range of 0.02 to 0.1, more preferably 0.03 to 0.09, and most preferably 0.04 to 0.08 Is particularly preferable.

In order to set the refractive index of the resin layer to 1.55 to 1.61, it is preferable to use a polyester resin containing a naphthalene ring in the molecule as a resin. The naphthalene ring-containing polyester resin can be synthesized by using, for example, a polycarboxylic acid such as 1,4-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid as a copolymerization component.

The content of the polyester resin containing naphthalene rings in the molecule in the resin layer is preferably in the range of 5 to 70 mass%, more preferably in the range of 10 to 60 mass%, based on 100 mass% of the total resin .

It is preferable that the resin layer is laminated on the base film by a wet coating method and thermally cured. It is also preferred that the resin layer is applied by a wet coating method in a production process of a base film, applied by the so-called in-line coating method, and thermally cured. Examples of the wet coating method include a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method and a die coating method.

As described above, the resin layer having a two-layer structure can be employed. It is preferable that the resin layer of the two-layer structure is formed by applying one coating liquid once and causing magnetic phase separation in the drying process. That is, a coating liquid containing the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer is applied, and by using the magnetic phase separation of each component in the drying process, It is preferable to employ a method of forming a second layer and a second resin layer.

In carrying out this phase separation method, it is preferable to increase the surface energy difference between the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer. That is, it is preferable to use a polyester resin having a high surface energy and an acrylic resin having a low surface energy. Particularly, in order to increase the surface energy of the polyester resin, it is preferable to use a polyester resin having a sulfonic acid group.

From the viewpoint that the adhesion between the base film and the first hard coat layer is enhanced and the reflection color of the hard coat film is close to neutral colorless when the resin layer has a two-layer structure, the thickness of the first resin layer Is preferably larger than the thickness. The thickness of the first resin layer is preferably 1.5 times or more of the thickness of the second resin layer, more preferably 2.0 times or more, particularly 3.0 times or more.

The thickness of the first resin layer is preferably in the range of 0.02 to 0.2 mu m, more preferably in the range of 0.03 to 0.15 mu m, and particularly preferably in the range of 0.05 to 0.12 mu m. The thickness of the second resin layer is preferably in the range of 0.005 to 0.1 mu m, more preferably in the range of 0.01 to 0.07 mu m, and particularly preferably in the range of 0.01 to 0.05 mu m.

The resin layer provided between the base film and the first hard coat layer preferably has a wettability tension of 52 mN / m or less. That is, in the present invention, it is preferable that the wet tension of the surface of the resin layer to which the first hard coat layer is applied is 52 mN / m or less. By directly laminating the first hard coat layer on the resin layer, protrusions due to particles are easily formed on the surface of the first hard coat layer, and as a result, the sliding property and blocking resistance are further improved. Here, the wet tensile strength is a physical property value stipulated in JIS-K-6768.

An embodiment in which a resin layer having a wet tension of 52 mN / m or less is provided between the base film and the first hard coat layer is effective when the thickness of the first hard coat layer is relatively small. As the thickness of the first hard coat layer becomes smaller, the absolute amount of the particles contained in the first hard coat layer also becomes smaller. However, by laminating the first hard coat layer on the resin layer having a wet tension of 52 mN / m or less, the particles contained in the first hard coat layer are likely to be localized near the surface, and as a result, do. This embodiment is effective when the thickness of the first hard coat layer is less than 2 mu m, and is particularly effective when the thickness of the first hard coat layer is 1.7 mu m or less.

From the above viewpoint, it is more preferable that the wettability of the surface of the resin layer is 50 mN / m or less. On the other hand, from the viewpoint of ensuring adhesion between the base film and the first hard coat layer, the lower limit of the wetting tension of the surface of the resin layer is preferably 35 mN / m or more, more preferably 37 mN / m or more, desirable. If the wettability of the surface of the resin layer is less than 35 mN / m, the adhesion of the first hard coat layer may decrease.

From the viewpoint of controlling the wettability of the surface of the resin layer to 52 mN / m or less and improving the adhesion between the base film and the first hard coat layer, the resin to be contained in the resin layer includes polyester resin, acrylic resin and polyurethane resin At least one selected from the group consisting of Among these resins, it is more preferable to use a polyester resin and / or an acrylic resin, and it is particularly preferable to use at least a polyester resin as the resin.

The wetting tension on the surface of the resin layer can also be controlled by adjusting the kind or content of the cross-linking agent. For example, when the content of the crosslinking agent is large, the wet tension of the surface of the resin layer tends to be small. On the contrary, if the content of the crosslinking agent is small, the wet tension of the surface of the resin layer tends to become large.

[First hard coat layer]

The first hard coat layer contains particles, and protrusions formed by the particles are formed on the surface of the first hard coat layer. The number density of protrusions on the surface of the first hard coat layer is 300 to 4000 per unit area (100 탆 ² ) of the surface of the first hard coat layer. In addition, the range of the number density of protrusions is preferably preferably in the range of 400-3500 per 100㎛ ^2, and the range of 500-3000, and more preferably, to a range of more preferably 600-3000, in particular 700-2500 of range Do.

The range of the average particle diameter (r) of the particles contained in the first hard coat layer is preferably in the range of 0.05 to 0.5 mu m, more preferably in the range of 0.06 to 0.4 mu m, and particularly preferably in the range of 0.07 to 0.3 mu m .

When the average particle diameter (r) of the particles contained in the first hard coat layer is less than 0.05 탆, protrusions of sufficient size are not formed on the surface of the first hard coat layer, and the sliding property and blocking resistance are not sufficiently improved have. When the average particle diameter (r) exceeds 0.5 mu m, the smoothness of the surface of the first hard coat layer decreases, the center line average roughness Ra1 becomes 30 nm or more, or the haze value of the hard coat film becomes 1.5% There is a possibility that a problem such as occurrence of a problem may occur.

The average particle diameter (r) of the particles contained in the first hard coat layer is preferably sufficiently smaller than the thickness (d) of the first hard coat layer. That is, the ratio of the average particle diameter (r) of the particles to the thickness (d) of the first hard coat layer is preferably in the range of 0.01 to 0.30. It is preferable that relatively large protrusions are formed on the surface of the first hard coat layer as described above by relatively presenting such particles in the vicinity of the surface of the first hard coat layer. This makes it possible to improve the sliding property and blocking resistance without lowering the smoothness of the surface of the first hard coat layer.

The ratio (r / d) of the average particle diameter (r) of the particles contained in the first hard coat layer to the thickness (d) of the first hard coat layer is also preferably in the range of 0.01 to 0.20, more preferably in the range of 0.01 to 0.15 More preferably in the range of 0.02 to 0.10, and most preferably in the range of 0.02 to 0.08.

The average diameter of the protrusions formed on the surface of the first hard coat layer by the above-described particles is preferably in the range of 0.03 to 0.3 mu m. The average diameter of the projections is preferably in the range of 0.04 to 0.25 탆, and more preferably in the range of 0.05 to 0.2 탆. This makes it possible to improve the sliding property and the blocking resistance without lowering the transparency.

The average height of the projections is preferably in the range of 0.03 to 0.3 mu m. The average height of the projections is preferably in the range of 0.04 to 0.25 탆, and more preferably in the range of 0.05 to 0.2 탆. This makes it possible to improve the sliding property and the blocking resistance without lowering the transparency.

The shape of the protrusions formed on the surface of the first hard coat layer is not particularly limited, but it is preferable that the protrusions have a circular or circular planar shape. Here, the plane shape of the projections indicates a planar shape when the surface of the first hard coat layer is observed with a scanning electron microscope (SEM).

1 is an example of a surface photograph of a first hard coat layer by a scanning electron microscope. On the surface of the first hard coat layer, protrusions 11 made of particles are formed.

2 is a diagram schematically showing a planar shape of a projection on the surface of the first hard coat layer.

The planar shape of the projection is close to a circle. In the schematic view shown in Fig. 2, the line segment indicating the maximum diameter Lmax of the projection 11, the diameter Lmin of the projection 11 perpendicular to the center Lc, (Lmin / Lmax) of the maximum diameter Lmax of the honeycomb structure 11 is 0.65 or more.

The ratio (Lmin / Lmax) is preferably 0.70 or more, more preferably 0.80 or more, and particularly preferably 0.85 or more. The upper limit is 1.0.

The planar shapes of the protrusions in the surface photograph of Fig. 1 are all circular, or a " close to circular shape "

In the present specification, the diameter of the protrusion means the maximum diameter Lmax shown in Fig. The average diameter of the protrusions can be obtained from a photograph of the surface of the first hard coat layer as shown in Fig. 1 by a scanning electron microscope.

In the present specification, the height of the projection means the length from the apex of the projection to the surface of the first hard coat layer. The average height of the protrusions can be measured from a cross-sectional photograph taken with a transmission electron microscope (TEM) of the first hard coat layer.

The average interval of the protrusions on the surface of the first hard coat layer is preferably in the range of 0.10 to 0.70 탆, more preferably in the range of 0.15 to 0.50 탆, and particularly preferably in the range of 0.20 to 0.40 탆. This makes it possible to improve the sliding property and the blocking resistance without lowering the transparency.

The average interval of the projections can be obtained from a photograph of the surface of the first hard coat layer by a scanning electron microscope. 3 is a schematic view of a surface photograph of a first hard coat layer by a scanning electron microscope. A method of measuring the average interval of the projections will be described with reference to Fig.

First, one straight line 20 is drawn in the transverse direction, and a straight line 30 perpendicular to the transverse straight line 20 is drawn. Then, for all of the projections on the straight line 20 in the transverse direction (that is, in contact with the straight line 20), the distance between adjacent projections is measured. The same operation is also performed on the straight line 30 in the vertical direction. The intervals (distances) of all the projections thus obtained are averaged.

A method of measuring the average interval of the projections will be described in detail with reference to Fig.

FIG. 4 shows only the protrusions on the straight line 20 in the horizontal direction or the straight line 30 in the vertical direction in FIG. In Fig. 4, the protrusions on the straight line 20 in the transverse direction are five, denoted by reference numerals (1 to 5). The distance between the adjacent projections is the distance P between the projections 1 and the projections 2 adjacent to the projections 1, for example. Similarly, the distance between the protrusions 2 and 3, the distance between the protrusions 3 and 4, and the distance between the protrusions 4 and 5 are measured, The intervals of adjacent stone periods are measured for all the particles.

Similarly, with respect to all the protrusions on the straight line 30 in the longitudinal direction, the interval of the adjacent stone period is measured.

The above operation is performed by changing the position of the straight line in the transverse direction and the position of the straight line in the vertical direction three times, and the average of all the obtained protrusion intervals is referred to as the average interval of the protrusions.

As shown in Fig. 1, it is preferable that the individual projections on the surface of the first hard coat layer are each formed by one particle. This makes it easy to adjust the centerline average roughness Ra1 of the surface of the first hard coat layer to less than 30 nm and adjust the haze value of the hard coat film to less than 1.5%. If the projections are formed in a state in which a plurality of particles are aggregated, the center line average roughness Ra1 of the surface of the first hard coat layer and the haze value of the hard coat film tend to increase, which is not preferable.

The content of the particles in the first hard coat layer is preferably in the range of 2.5 to 17 mass%, more preferably in the range of 3 to 15 mass% with respect to 100 mass% of the total solid content of the first hard coat layer, Particularly preferably from 4 to 12 mass%.

As described above, the first hard coat layer contains particles sufficiently small in average particle diameter (r) with respect to the thickness (d) of the first hard coat layer, and the particles are relatively large in the vicinity of the surface of the first hard coat layer So that relatively large projections are formed on the surface of the first hard coat layer.

In order to allow the particles to exist near the surface of the first hard coat layer, it is necessary to move (float) the particles near the surface in the process of forming the first hard coat layer. This can be achieved, for example, by using surface-treated particles for reducing the surface free energy of the particles, or particles subjected to hydrophobic treatment for hydrophobizing the surface of the particles. As the particles to be subjected to these treatments, inorganic particles are preferable, and silica particles are particularly preferable.

As the particles contained in the first hard coat layer, inorganic particles are preferably used. As the inorganic particles, inorganic particles containing an element selected from Si, Na, K, Ca and Mg are preferably used. More preferably, inorganic particles containing a compound selected from silica particles (SiO ₂ ), alkali metal fluorides (NaF, KF, etc.) and alkaline earth metal fluorides (CaF ₂ , MgF ₂ and the like) Particularly preferred are silica particles.

As the surface treatment for reducing the surface free energy of the particles, an organosilane compound having a fluorine atom represented by the following general formula (1), a hydrolyzate of the organosilane, and a partial condensation of the hydrolyzate of the organosilane Water and at least one compound selected from the group consisting of water and the like.

C _n F _{2n +1} - (CH ₂ ) _m -Si (Q) ₃ ????? (1)

[In the general formula (1), n represents an integer of 1 to 10, and m represents an integer of 1 to 5. Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom]

Specific examples of the compound represented by the general formula (1) include the following compounds.

C ₄ F ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃

C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃

C ₈ F ₁₇ CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃

C ₆ F ₁₃ CH ₂ CH ₂ SiCl ₃

C ₆ F ₁₃ CH ₂ CH ₂ SiBr ₃

C ₆ F ₁₃ CH ₂ CH ₂ CH ₂ SiCl ₃

C ₆ F ₁₃ CH ₂ CH ₂ Si (OCH ₃ ) Cl ₂

Further, a surface treatment other than the one for reducing the surface free energy of the inorganic particles, a treatment with a compound represented by the following general formula (2), and a surface treatment with a fluorine compound represented by the following general formula (3) .

BR ⁴ -SiR ⁵ _n (OR ⁶ ) _3-n ????? (2)

DR ⁷ -Rf ² ????? (3)

[In formulas (2) and (3), B and D each independently represent a reactive moiety, and R ⁴ and R ⁷ each independently represents an alkylene group having 1 to 3 carbon atoms or an ester derived from the alkylene group Wherein R ⁵ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, Rf ² is a fluoroalkyl group, and n is an integer of 0 to ² ,

Examples of the reactive moiety represented by B and D include vinyl, allyl, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, epoxy, carboxyl and hydroxyl.

Specific examples of the general formula (2) include acryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane, acryloxybutyltrimethoxysilane, acryloxypentyltrimethoxysilane, acryloxyhexyltrimethoxysilane, acryloxy Methacryloxypropyltrimethoxysilane, heptyltrimethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxyhexyltrimethoxysilane, methacryloxyheptyltrimethoxysilane , Methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, and compounds containing a compound in which an alkoxyl group or a hydroxyl group is substituted with methoxy group among these compounds.

Specific examples of the general formula (3) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutyl ethyl acrylate, 3- 2-hydroxypropyl acrylate, 2-perfluorohexyl ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, perfluorooctyl methyl acrylate, 2- Perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluoro decyl ethyl acrylate, 2-perfluoro-3-methyl butyl ethyl acrylate, 3-perfluoro 2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexyl ethyl acrylate, 3-perfluoro-5-methylhexyl- Perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoro Pentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3 Perfluorobutyl methyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, perfluorooctyl methyl methacrylate, 2-perfluoro Perfluorohexyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3- Perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl- 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctyl Ethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-tri Fluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, and the like.

Examples of the hydrophobic compound for carrying out the hydrophobic treatment on the above-mentioned particle surface include a compound having a hydrophobic group and a reactive site in the molecule. The hydrophobic group of the hydrophobic compound is not particularly limited as long as it has a hydrophobic function. Specific examples of the hydrophobic group include at least a fluoroalkyl group having at least 4 carbon atoms, a hydrocarbon group having at least 8 carbon atoms, and a siloxane group One functional group is exemplified.

The reactive site is a site chemically reacted with radicals generated by energy such as light or heat. Specific examples thereof include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, More preferably a reactive site that undergoes chemical reaction by receiving energy such as light or heat such as an epoxy group, a carboxyl group or a hydroxyl group.

That is, as the hydrophobic compound for carrying out the hydrophobic treatment on the particle surface, a compound (fluorine compound) having a fluoroalkyl group having 4 or more carbon atoms and a reactive site, a compound having a reactive site with a carbon number of 8 or more (long chain hydrocarbon compound) It is preferable to use at least one member selected from the group consisting of a siloxane group and a compound having a reactive site (silicone compound).

The long-chain hydrocarbon compound represents a compound having a hydrocarbon group and a reactive site having at least 8 carbon atoms, which is a hydrophobic group in the molecule. The hydrocarbon group having 8 or more carbon atoms preferably has 8 or more and 30 or less carbon atoms. The hydrocarbon group having 8 or more carbon atoms may be selected without regard to a straight chain structure, a branched structure and an alicyclic structure. More preferably, the long-chain hydrocarbon compound is a linear alkyl alcohol, alkyl epoxide, alkyl acrylate, alkyl methacrylate, alkyl carboxylate (including acid anhydrides and esters) having 10 to 22 carbon atoms Can be used.

Specific examples of the long chain hydrocarbon compound include polyhydric alcohols such as octanol, hexanediol, heptanediol, octanediol, and stearyl alcohol, octyl acrylate, octyl methacrylate, 2-hydroxyoctyl methacrylate, Acrylate such as acrylate (methacrylate) and octyltrimethoxysilane, and the like.

As the silicone compound, a compound having a siloxane group and a reactive site, which are hydrophobic groups in the molecule, can be mentioned. The reactive site of the silicone compound is preferably an acryloyloxy group or a methacryloyloxy group.

As the siloxane group, a polysiloxane group represented by the following general formula (4) is preferably used.

- (Si (R ⁸ ) (R ⁹ ) -O) _m - ????? (4)

[In the formula (4), R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3-acryloxy-2-hydroxypropyl-oxypropyl group, a 2-acryloxy- A polyethylene glycol propyl ether group having an acryloyloxy group or a methacryloyloxy group at the terminal, or a polyethylene glycol propyl ether group having a terminal hydroxy group, and m represents an integer of 10 to 200,

Specific examples of the silicone compound having a polysiloxane group represented by the general formula (4) as a hydrophobic group include a compound having a dimethylsiloxane group represented by the following general formula (5) and a reactive site. Specific examples of the silicone compound having a dimethylsiloxane group and a reactive site of the general formula (5) and X-22-164B, X-22-164C, X-22-5002, X-22-174D, X-22-167B (All trade names, produced by Shin-Etsu Chemical Co., Ltd.).

... (5)

Wherein R represents alkyl having 1 to 7 carbon atoms, k represents an integer of 0 or 1, and m represents an integer of 10 to 200,

Another example of the silicone compound having a polysiloxane group and a reactive site represented by the general formula (4) as a hydrophobic group is a 3-acryloxy-2-hydroxypropyl-oxypropyl group represented by the general formula (6) A compound having a methyl group and a 2-acryloxy-3-hydroxypropyl-oxypropyl group represented by the general formula (7).

(6)

... (7)

Wherein R represents an alkyl of 1 to 7 carbon atoms, k represents an integer of 0 or 1, and m represents any integer of 10 to 200). [In the general formulas (6) and (7)

Another example of the silicone compound having a reactive site with the polysiloxane group represented by the general formula (4) as a hydrophobic group is a polyethylene glycol propyl ester having an acryloyloxy group or a methacryloyloxy group at the end represented by the general formula (8) A compound having an ether group and a methyl group, and a compound having a methyl group and a polyethylene glycol propyl ether group having a hydroxy group at the terminal represented by the general formula (9).

... (8)

... (9)

Wherein R represents an alkyl having 1 to 7 carbon atoms, k represents an integer of 0 or 1, x represents an integer of 1 to 10, and m represents an integer of from 10 to 10 (in the general formulas (8) and (9) ≪ / RTI >

A fluoroalkyl group having at least four carbon atoms and a fluorine compound having a reactive site will be described. Here, the fluoroalkyl group may be either a straight-chain structure or a branched structure. The fluoroalkyl group preferably has 4 or more and 8 or less carbon atoms. Examples of such fluorine compounds include fluoroalkyl alcohols, fluoroalkyl epoxides, fluoroalkyl halides, fluoroalkyl acrylates, fluoroalkyl methacrylates, fluoroalkyl carboxylates (including acid anhydrides and esters) Can be used. Among these, fluoroalkyl acrylates and fluoroalkyl methacrylates are preferable, and among the compounds exemplified by the above-mentioned general formula (3), compounds having fluoroalkyl groups having 4 or more carbon atoms can be used.

The number of fluoroalkyl groups in the fluorine compound is not necessarily one, and the fluorine compound may have plural fluoroalkyl groups.

The first hard coat layer preferably has a high hardness in order to inhibit the occurrence of scratches on the surface of the hard coat film, and preferably has a pencil hardness of at least H defined in JIS K5600-5-4 (1999). The upper limit of pencil hardness is about 9H.

The first hard coat layer preferably comprises a thermosetting resin or an active energy ray-curable resin as the resin, and particularly preferably contains an active energy ray-curable resin. Herein, the active energy ray-curable resin means a resin which is polymerized and cured by an active energy ray such as ultraviolet ray or electron ray.

Examples of the polymerizable compound for obtaining an active energy ray-curable resin include a compound (monomer or oligomer) having a polymerizable functional group such as an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, .

The first hard coat layer is preferably formed by coating the active energy ray-curable composition containing the polymerizable compound by a wet coating method, drying it if necessary, and irradiating it with an active energy ray to cure it.

Polymerizable compounds (monomers and oligomers) are exemplified below, but are not limited to these compounds. In the following description, the expression "(meth) acrylate" includes two compounds of "... acrylate" and "... methacrylate".

Examples of the monomer include monomers such as methyl (meth) acrylate, lauryl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, (Meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate such as neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol hexa (meta) triacrylate, trimethylol propane (meth) acrylic acid benzoic acid ester, trimethylolpropane benzoic acid ester And urethane acrylates such as glycidyl (meth) acrylate hexamethylene diisocyanate, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate, and the like.

Among the above-mentioned monomers, a multifunctional monomer having three or more polymerizable functional groups in one molecule is preferably used.

Examples of the oligomer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, alkyd , And silicone (meth) acrylate.

Among these oligomers, polyfunctional urethane (meth) acrylate oligomers having three or more polymerizable functional groups in one molecule are preferably used. Such polyfunctional urethane (meth) acrylate oligomer may be commercially available. For example, Kyoeisha Chemical Co., Ltd. Urethane acrylate AH series, Urethane acrylate AT series, Urethane acrylate UA series, Negami Chemical Industrial Co., Ltd. UN-3320 series, UN-900 series, Shin-Nakamura Chemical Co., Ltd. Manufactured by NK Oligo U series, Daicel · Huls Ltd. And the Ebecryl 1290 series manufactured by Toshiba Corporation.

The content of the polymerizable compound in the active energy ray-curable composition is preferably 50% by mass or more, more preferably 55% by mass or more, and more preferably 60% by mass or more based on 100% by mass of the total solid content of the active energy ray- , And particularly preferably 70 mass% or more. The upper limit is preferably 97 mass% or less, more preferably 95 mass% or less.

When ultraviolet rays are used as an active energy ray, the active energy ray curable composition preferably contains a photopolymerization initiator. Specific examples of such photopolymerization initiators include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoyl formate, p-isopropyl myristate, methyl isobutyl ketone, methyl isobutyl ketone, carbonyl compounds such as? -hydroxyisobutylphenone,? -hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexylphenylketone, And sulfur compounds such as tetramethylthiomal disulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, photopolymerization initiators are generally commercially available, and they can be used. For example, Irgacure (registered trademark) 184, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure OXE01, DAROCUR TPO , DAROCUR 1173, etc., Nihon SiberHegner KK Speedcure MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Esacure ONE, Esacure KIP150, Esacure KTO46, etc., Nippon Kayaku Co., Ltd. KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE DMBI and so on.

The content of the photopolymerization initiator is suitably in the range of 0.1 to 10 mass%, preferably in the range of 0.5 to 8 mass%, based on 100 mass% of the total solid content of the active energy ray curable composition.

The active energy ray curable composition may further contain various additives such as antioxidants, ultraviolet absorbers, leveling agents, particle dispersants, organic antistatic agents, lubricants, colorants, pigments and the like.

The active energy ray curable composition contains particles for forming projections on the surface of the first hard coat layer. As such particles, particles subjected to the surface treatment or hydrophobic treatment described above are preferably used. The content of the particles in the active energy ray-curable composition is preferably in the range of 2.5 to 17 mass%, more preferably in the range of 3 to 15 mass% with respect to 100 mass% of the total solid content of the active energy ray curable composition, Particularly preferably from 4 to 12 mass%.

The refractive index of the first hard coat layer is preferably in the range of 1.48 to 1.54, more preferably in the range of 1.50 to 1.54. The above active energy ray curable composition is applied by a wet coating method, dried if necessary, and then irradiated with active energy rays to be cured to form a first hard coat layer, whereby a first hard coat layer having a refractive index of 1.48 to 1.54 Layer can be obtained.

The range of the thickness of the first hard coat layer is suitably in the range of 0.5 탆 to less than 10 탆, but is preferably in the range of 0.8 탆 to 7 탆, more preferably in the range of 1 탆 to 5 탆, Or more and 3 mu m or less.

When the thickness of the first hard coat layer is less than 0.5 탆, the hardness of the first hard coat layer is lowered and the scratches are likely to enter. If the thickness of the first hard coat layer is 10 占 퐉 or more, the sliding property and anti-blocking property may deteriorate, the curl may increase, and the transmittance may decrease.

[Hard Coat Film]

The hard coat film has a first hard coat layer on at least one side of the base film. The hard coat film may have the first hard coat layer only on one side of the base film or may have the first hard coat layer on both sides of the base film.

In another preferred embodiment of the hard coat film, the first hard coat layer is provided on one surface of the base film, and the second hard coat layer is provided on the other surface of the base film A hard coat film having a second hard coat layer may be mentioned.

When the second hard coat layer laminated on the other surface of the base film is completely identical to the first hard coat layer laminated on one surface of the base film (that is, The case where the first hard coat layer is laminated on the first hard coat layer) may be referred to as a second hard coat layer in order to distinguish it from the first hard coat layer on one side.

[Second hard coat layer]

Hereinafter, the second hard coat layer provided on the other surface of the base film will be described.

The second hard coat layer preferably has a high hardness in order to inhibit the occurrence of scratches on the surface of the hard coat film. The pencil hardness defined by JIS K5600-5-4 (1999) is preferably at least H, more preferably at least 2H Is more preferable. The upper limit of pencil hardness is about 9H.

The surface of the second hard coat layer is preferably relatively smooth and clear. For example, the center line average roughness Ra2 of the surface of the second hard coat layer is preferably 25 nm or less, more preferably 20 nm or less, particularly preferably 15 nm or less. The lower limit is not particularly limited, but is practically about 1 nm.

The second hard coat layer preferably contains substantially no particles having an average particle diameter larger than 0.5 탆 in order to make the center line average roughness Ra2 of the surface of the second hard coat layer 25 nm or less . If the second hard coat layer does not substantially contain particles having an average particle diameter larger than 0.5 탆, a coating liquid (for example, an active energy ray curable composition) for forming the second hard coat layer has a mean particle diameter Means that particles larger than 0.5 mu m are not intentionally added.

The surface of the second hard coat layer is preferably relatively smooth and clear. Therefore, it is preferable that the surface of the second hard coat layer is substantially free of protrusions due to particles. Here, when the protrusions due to particles are not substantially present on the surface of the second hard coat layer, it means that the number of protrusions per unit area (100 탆 ² ) of the surface of the second hard coat layer is 100 or less. Preferably, the number of projections per unit area (100 탆 ² ) of the surface of the second hard coat layer is 50 or less, more preferably 30 or less, particularly preferably 0 or less.

The second hard coat layer may contain particles having an average particle diameter of 0.5 탆 or less, but from the above viewpoint, it is preferable to adjust the average particle diameter of the particles contained in the second hard coat layer.

When particles are contained in the second hard coat layer, the average particle diameter of the particles is preferably 0.2 탆 or less, more preferably 0.1 탆 or less. The content of such particles is suitably in the range of 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, particularly preferably 1 to 8 mass%, based on 100 mass% of the total solid content of the second hard coat layer Range is preferred.

The second hard coat layer preferably comprises a thermosetting resin or an active energy ray-curable resin as the resin, particularly preferably an active energy ray-curable resin. Herein, the active energy ray-curable resin means a resin which is polymerized and cured by an active energy ray such as ultraviolet rays or electron rays.

As the polymerizable compound for obtaining the active energy ray-curable resin, the same ones as described in the first hard coat layer described above can be used.

The second hard coat layer is preferably formed by coating the active energy ray curable composition containing a polymerizable compound by a wet coating method, drying it if necessary, and irradiating with an active energy ray to harden the same, like the first hard coat layer Do.

The refractive index of the second hard coat layer is preferably in the range of 1.48 to 1.54, more preferably in the range of 1.50 to 1.54. The second hard coat layer is formed by applying the above active energy ray curable composition by a wet coating method, drying it if necessary, and then irradiating an active energy ray to form the second hard coat layer, thereby forming a second hard coat layer having a refractive index of 1.48 to 1.54 Layer can be obtained.

The range of the thickness of the second hard coat layer is preferably in the range of 0.5 탆 to less than 10 탆, but is preferably in the range of 0.8 탆 to 7 탆, more preferably in the range of 1 탆 to 5 탆, Or more and 3 mu m or less.

When the thickness of the second hard coat layer is less than 0.5 占 퐉, the hardness of the second hard coat layer is lowered and scratches are likely to enter. When the thickness of the second hard coat layer is 10 占 퐉 or more, the sliding property and anti-blocking property may deteriorate, the curl may become large, and the transmittance may decrease.

It is preferable to interpose the above-mentioned resin layer between the base film and the second hard coat layer in order to enhance the adhesion between the base film and the second hard coat layer.

[Transparent conductive film]

The hard coat film of this embodiment is preferable as the base film of the transparent conductive film. That is, the transparent conductive film using the hard coat film of this embodiment as a base film is a transparent conductive film laminated on at least one surface of the hard coat film of the present embodiment.

The transparent conductive film may be laminated only on one side of the hard coat film or on both sides of the hard coat film.

Some examples of the constitution of the transparent conductive film using the hard coat film of the present invention as a base film are illustrated below, but the present invention is not limited thereto.

i) First hard coat layer / resin layer / base film / resin layer / first hard coat layer / transparent conductive film

ii) Transparent conductive film / first hard coat layer / resin layer / base film / resin layer / first hard coat layer / transparent conductive film

iii) First hard coat layer / resin layer / base film / resin layer / second hard coat layer / transparent conductive film

iv) a transparent conductive film / a first hard coat layer / a resin layer / a base film / a resin layer / a second hard coat layer

v) transparent conductive film / first hard coat layer / resin layer / base film / resin layer / second hard coat layer / transparent conductive film

Among the above examples, i) or iii) is preferable. That is, from the viewpoint of securing the sliding property and anti-blocking property of the hard coat film in the process of laminating and processing the transparent conductive film, it is preferable to expose the transparent conductive film to one of the first hard coat layers without being laminated.

It is preferable that the hard coat layer on the side where the transparent conductive film is laminated is relatively smooth and clear. Therefore, in the constitution example of iii), the center line average roughness Ra2 of the surface of the second hard coat layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 15 nm or less. As described above, the surface of the hard coat layer (for example, the second hard coat layer) on the surface of the transparent conductive film to be laminated is relatively smooth and clear, so that the transparency of the transparent conductive film is improved.

[Transparent conductive film]

Examples of the material for forming the transparent conductive layer include metal oxides such as tin oxide, indium oxide, antimony oxide, zinc oxide, ITO (indium tin oxide), ATO (antimony tin oxide) Silver nanowires), and carbon nanotubes. Of these, ITO is preferably used.

The thickness of the transparent conductive film is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more from the viewpoint of ensuring a good electrical conductivity of 10 ³ Ω / square or less. On the other hand, if the thickness of the transparent conductive film is excessively large, there is a problem that the color (coloring) becomes strong or the transparency deteriorates. In this case, the upper limit of the thickness of the transparent conductive film is preferably 60 nm or less, more preferably 50 nm or less, Or less.

The method for forming the transparent conductive film is not particularly limited, and conventionally known methods can be used. Specifically, a dry film forming method (vapor phase film forming method) such as a vacuum vapor deposition method, a sputtering method and an ion plating method, or a wet coating method can be mentioned.

The transparent conductive film thus formed may be patterned. The patterning can form various patterns according to the application to which the transparent conductive film is applied. Further, the pattern portion and the non-pattern portion are formed by patterning the transparent conductive film, but the shape of the pattern portion includes, for example, a stripe shape and a lattice shape.

The patterning of the transparent conductive film is generally performed by etching. For example, a patterned etching resist film is formed on a transparent conductive film by a photolithography method, a laser exposure method, or a printing method, and is subjected to an etching treatment to pattern the transparent conductive film. After the transparent conductive film is patterned, the etching resist film is stripped off with an aqueous alkaline solution.

Conventionally known etchants may be used as the etchant. For example, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, and phosphoric acid, organic acids such as acetic acid, and mixtures thereof, and aqueous solutions thereof can be used.

Examples of the aqueous alkaline solution used for peeling and removing the etching resist film include an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide in an amount of 1 to 5 mass%.

[Refractive index adjusting layer]

In the structural example of the transparent conductive film, the transparent conductive film may be directly laminated on the first hard coat layer or the second hard coat layer, but the refractive index may be adjusted between the transparent conductive film and the first hard coat layer or the second hard coat layer Layer. Hereinafter, the refractive index adjustment layer will be described.

The refractive index adjustment layer may be composed of only one layer, or may have a laminated structure of two or more layers. The refractive index adjustment layer is a layer having a function for adjusting the reflection color or transmittance color of the transparent conductive film to be laminated thereon or a function for suppressing the so-called " pattern appearance " in which the patterned transparent conductive film is observed.

As the structure of the refractive index adjusting layer, for example, a single layer structure of a high refractive index layer having a refractive index (n1) of 1.60 to 1.80 and a single layer structure of a low refractive index layer having a refractive index (n2) of 1.30 to 1.53, And a lamination structure of the low refractive index layer (the low refractive index layer is disposed on the transparent conductive film side).

The refractive index n1 of the high refractive index layer is also preferably in the range of 1.63 to 1.78, more preferably in the range of 1.65 to 1.75. The refractive index n2 of the low refractive index layer is also preferably in a range of 1.30 to 1.50, more preferably in a range of 1.30 to 1.48, and particularly preferably in a range of 1.33 to 1.46.

The thickness of the refractive index adjustment layer (in the case of a laminated structure of plural layers, the total thickness) is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 120 nm or less, and most preferably 100 nm or less. The thickness of the lower limit is preferably 30 nm or more, more preferably 40 nm or more, particularly preferably 50 nm or more, and most preferably 60 nm or more.

When the transparent conductive film is patterned, it is preferable that the refractive index adjustment layer is a laminated structure of a high refractive index layer and a low refractive index layer from the viewpoint of suppressing " pattern appearance ". In this case, it is preferable that the sum (nm) of the optical thickness of the high refractive index layer and the optical thickness of the low refractive index layer satisfies (1/4)? (Nm). Here, the optical thickness (nm) is the product of the refractive index and the thickness (nm) of the actual layer, and? Is 380 to 780 (nm), which is the wavelength range of the visible light region.

In the present specification, when the sum of the optical thickness (nm) of the high refractive index layer and the optical thickness (nm) of the low refractive index layer satisfies (1/4)? (Nm) In the formula, n1 represents the refractive index of the high refractive index layer, d1 represents the thickness (nm) of the high refractive index layer, n2 represents the refractive index of the low refractive index layer, and d2 represents the thickness (nm) of the low refractive index layer.

(380 nm / 4)? (N1 x d1) + (n2 x d2)? (780 nm / 4)

95 nm? (N1 x d1) + (n2 x d2)? 95 nm (1)

That is, the sum of the optical thickness (n1 x d1) of the high refractive index layer and the optical thickness (n2 x d2) of the low refractive index layer is preferably 95 nm or more and 195 nm or less.

The total of the optical thickness of the high refractive index layer and the optical thickness of the low refractive index layer is more preferably in the range of 95 to 163 nm, particularly preferably in the range of 95 to 150 nm, and most preferably in the range of 100 to 140 nm .

The high refractive index layer can be formed, for example, by applying an active energy ray curable composition containing metal oxide fine particles having a refractive index of 1.65 or more by a wet coating method, drying it if necessary, and irradiating an active energy ray to cure. Here, the active energy ray-curable composition is a composition containing the polymerizable compound and the photopolymerization initiator described in the first hard coat layer.

Examples of the metal oxide fine particles include metal oxide particles such as titanium, zirconium, zinc, tin, antimony, cerium, iron and indium. Specific examples of the metal oxide fine particles include titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonate, indium tin oxide (ITO), antimony doped tin oxide , Indoped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and fluorine-doped tin oxide. These metal oxide fine particles may be used singly or in combination. Among the above-mentioned metal oxide fine particles, titanium oxide and zirconium oxide are particularly preferred because they can increase the refractive index without lowering the transparency.

The content of the metal oxide fine particles in the active energy ray-curable composition is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more based on 100% by mass of the total solid content of the active energy ray- desirable. The upper limit is preferably 70 mass% or less, and more preferably 60 mass% or less.

The low refractive index layer can be obtained by coating an active energy ray curable composition containing a low refractive index inorganic particle and / or a fluorine compound as a low refractive index material by a wet coating method, drying it if necessary, Followed by curing. Here, the active energy ray-curable composition is a composition containing the polymerizable compound and the photopolymerization initiator described in the first hard coat layer.

As the low refractive index inorganic particles, inorganic particles such as silica and magnesium fluoride are preferable. These inorganic particles are preferably hollow or porous. The content of such low refractive index inorganic particles is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more based on 100% by mass of the total solid content of the active energy ray curable composition. The upper limit is preferably 70 mass% or less, more preferably 60 mass% or less, particularly preferably 50 mass% or less.

Examples of fluorinated compounds include fluorinated monomers, fluorinated oligomers, and fluorinated polymer compounds. Here, the fluorine-containing monomer or fluorine-containing oligomer is a monomer or oligomer having a polymerizable functional group (a functional group containing a carbon-carbon double bond group) and a fluorine atom in the molecule.

Examples of fluorinated monomers and fluorinated oligomers include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (Perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- Fluorine-containing (meth) acrylic acid esters such as ethyl (meth) acrylate and? - (perfluorooctyl) ethyl (meth) acrylate, di- Fluoroethyl ethylene glycol, di- (? -Fluoroacrylic acid) -2,2,3,3,3-pentafluoropropylethylene glycol, di- (? -Fluoroacrylic acid) -2,2,3,3 , 4,4,4-heptafluorobutyl ethylene glycol, di- (? - fluoroacrylic acid) -2,2,3,3,4,4,5,5,5-nonafluoropentyl ethylene glycol, di - (? -fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl ethylene Glycol, di- (? - fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptylethylene glycol, di- (? -Fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctylethylene glycol, di- (? - fluoro (Acrylic acid) -3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylethylene glycol, di- (? - fluoroacrylic acid) -2, Di- (? -Fluoroacrylic acid) such as 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl ethylene glycol, And fluoroalkyl esters.

Examples of the fluorinated polymer compound include fluorinated monomers and fluorinated copolymers containing a monomer for imparting a crosslinkable group as a constitutional unit. Specific examples of fluorinated monomer units include fluoroolefins (e.g., fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2 -Dimethyl-1,3-dioxol), partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Viscot 6FM (manufactured by Osaka Organic Chemical Industry Ltd.) or M- 2020 (manufactured by Daikin Industries, Ltd.), fully or partially fluorinated vinyl ethers, and the like. Examples of the monomer for imparting a crosslinkable group include (meth) acrylate monomers having a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group and the like, as well as (meth) acrylate monomers having a crosslinkable functional group in advance in the molecule such as glycidyl methacrylate (Meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allylacrylate and the like).

The content of the fluorine compound is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, based on 100% by mass of the total solid content of the active energy ray curable composition. The upper limit is preferably 95 mass% or less, more preferably 90 mass% or less, and particularly preferably 80 mass% or less.

Of the fluorinated compounds, fluorinated monomers and fluorinated oligomers are preferably used. Since the fluorinated monomer and fluorinated oligomer have a polymerizable functional group in the molecule, they contribute to the formation of a dense crosslinked structure of the low refractive index layer and can lower the refractive index.

[Touch Panel]

The transparent conductive film using the hard coat film of the present embodiment as the base film is preferably used as one of constituent members of the touch panel.

The resistance film type touch panel generally has a structure in which the upper electrode and the lower electrode are arranged through a spacer. However, the transparent conductive film using the hard coat film of the present embodiment as a base film is not limited to the one of the upper electrode and the lower electrode Can be used.

The capacitive touch panel generally comprises a patterned X electrode and a Y electrode. However, the transparent conductive film using the hard coat film of the present embodiment as a base film may be used for either or both of the X electrode and the Y electrode .

The transparent conductive film used in the touch panel is required to have good transparency and workability (slidability and blocking resistance), but the transparent conductive film using the hard coat film of the present embodiment as the base film can sufficiently satisfy the above characteristics .

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measurement method and the evaluation method in this embodiment are shown below.

(1) Measurement of refractive index of each layer

The refractive index of 589 nm was measured with a phase difference measuring apparatus (Nikon Corporation: NPDM-1000) under a temperature condition of 25 캜 with respect to a coating film (dry thickness of about 2 탆) formed by coating each coating liquid on a silicon wafer with a spin coater did.

The refractive index of the base film (PET film) was measured at 589 nm in the Abbe's refractive index meter based on JIS K7105 (1981).

(2) Measurement of the thickness of the resin layer

The cross section of the substrate film on which the resin layer is laminated is cut into ultra slim pieces and the cross-sectional structure can be observed with a TEM (transmission electron microscope) by staining with RuO ₄ dye, OsO ₄ dye, The thickness of the resin layer was measured from the cross-sectional photographs. In addition, the measurement portion was a portion where no particles existed. In addition, five points were measured and the average value was referred to as the thickness of the resin layer.

· Measuring device: transmission electron microscope (H-7100FA type manufactured by Hitachi, Ltd.)

Measurement conditions: acceleration voltage 100 kV

· Sample adjustment:

· Magnification: 300,000 times

(3) Measurement of the thicknesses of the first and second hard coat layers, the high refractive index layer and the low refractive index layer

The cross section of the hard-coated film was cut into ultra-thin slices and observed with a TEM (transmission electron microscope) at an acceleration voltage of 100 kV (at a magnification of 1 to 3000000). In the case of the layer having the protrusion on the surface like the first hard coat layer, it is the thickness in the portion where the protrusion is not present. The thickness was measured at five places, and the average value was referred to as thickness.

(4) Measurement of average particle diameter of particles contained in the first hard coat layer

The cross section of the first hard coat layer was observed with a TEM (transmission electron microscope) (about 10,000 to 100,000 times), and the maximum length of each of the 30 randomly selected particles from the cross-sectional photograph was measured, Called particle diameter.

(5) Measurement of the average particle diameter of the particles contained in the resin layer

The surface of the resin layer laminated on the base film was observed at a magnification of 10,000 times using an SEM (scanning electron microscope), and the image of the particle (the density of light that can be made by the particle) was measured with an image analyzer QTM900), the data was taken by changing the observation place, and the following numerical processing was performed where the total number of particles became 5,000 or more, and the number average diameter d obtained thereby was referred to as an average particle diameter (diameter) .

d =? di / N

Where di is the equivalent circle diameter of the particle (the diameter of the circle having the same area as the cross-sectional area of the particle), and N is the number.

(6) Measurement of center line average roughness (Ra1, Ra2) of the surfaces of the first and second hard coat layers

Was measured using a stylus type surface roughness meter SE-3400 (manufactured by Kosaka Laboratory Ltd.) based on JIS B0601 (1982).

<Measurement Conditions>

Feed rate; 0.5mm / s

Evaluation length; 8mm

Cutoff value? C; 0.08mm

(7) Measurement of the number of projections on the surface of the first hard coat layer

A cut sample (20 cm x 15 cm) of a hard coat film was prepared and the surface of the first hard coat layer of this cut sample was photographed at five positions (about 10,000 to 100,000 times) by SEM (scanning electron microscope) (Surface photograph). Then, for each of the five images 1㎛ × 1㎛ of the image (area 1㎛ ²⁾ or 2㎛ × 2㎛ measuring the number of protrusions existing in a range (area 4㎛ ^2), and area per 100㎛ ² And the number was converted and averaged. The area for measuring the number of projections is appropriately changed according to the imaging magnification.

(8) Measurement of average diameter of projections on the surface of the first hard coat layer

The surface of the first hard coat layer of the hard coat film was photographed (about 10,000 to 100,000 times) with an SEM (scanning electron microscope) to prepare an image (surface photograph). Then, the diameter (maximum length) of 30 protrusions randomly selected from the image was measured and averaged.

(9) Measurement of average height of projections on the surface of the first hard coat layer

A cut sample (20 cm x 15 cm) of a hard coat film was prepared, and the cross section of the first hard coat layer of this cut sample was photographed at five locations (about 10,000 to 100,000 times) by SEM (scanning electron microscope) I made a photo. Then, the heights of all the projections existing in the five sectional photographs were measured and averaged.

(10) Average spacing of protrusions

The surface of the first hard coat layer of the hard coat film was photographed (about 10,000 to 100,000 times) with an SEM (scanning electron microscope) to produce an image (surface photograph). One straight line orthogonal to the horizontal and vertical directions was drawn on the image. Subsequently, the distance between adjacent projections was measured with respect to all of the projections (in contact with the straight line) on one straight line in the transverse direction. The same operation was performed on one straight line in the vertical direction. This operation was performed by changing the position of the straight line in the transverse direction and the position of the straight line in the vertical direction three times, and the obtained interval of all the projections was averaged.

(11) Measurement of hard coat film

Based on JIS K 7136 (2000), Nippon Denshoku Industries Co., Ltd. NDH-2000 &quot; manufactured by Toshiba Corporation. During the measurement, the light was placed on the surface of the hard coat film opposite to the first hard coat layer (that is, the surface on which the second hard coat layer was provided).

(12) Total light transmittance of hard coat film

Was measured using a turbidimeter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS-K7361 (1997).

(13) Evaluation of the reflection color of the hard coat film

A black adhesive tape ("Vinyl Tape No. 21 EXTRA WIDE BLACK", manufactured by Nitto Denko Corporation) was applied to the surface of the second hard coat layer of the hard coat film and the reflection color of the surface of the first hard coat layer was observed under a dark three- And the measurement was carried out based on the following criteria.

Similarly, a black adhesive tape ("Vinyl Tape No. 21 EXTRA WIDE BLACK" manufactured by Nitto Denko Corporation) was attached to the surface of the first hard coat layer of the hard coat film and the reflection color of the surface of the second hard coat layer was changed to a dark room tri- Under the following criteria.

A: The reflection color is neutral and almost colorless.

C: The reflection color is showing coloration.

(14) Evaluation of sliding property

The hard coat film was cut to produce two sheet pieces (20 cm x 15 cm). Two sheets of sheet pieces are slightly shifted and placed on a smooth target so that the surface of the first hard coat layer and the surface of the second hard coat layer face each other and the lower sheet sheet is fixed with a finger And the upper and lower sheet pieces were slid by hand. The measurement environment was 23 ° C and 55% RH.

A: Sliding property of the upper sheet member is good.

B: Sliding property of the upper sheet member is poor but relatively good.

C: The upper sheet piece does not slip.

(15) Evaluation of blocking resistance

The hard coat film was cut to produce two sheet pieces (20 cm x 15 cm). The first hard coat layer surface of the two sheets and the second hard coat layer surface are opposed to each other. Subsequently, a sample containing two sheet pieces was placed on a glass plate, and a weight of about 3 kg was put thereon and left for 48 hours in an atmosphere of 50 DEG C and 90% (RH). Subsequently, the overlapping surface was observed with a naked eye to confirm the occurrence of Newton's ring, and the both were peeled off and evaluated according to the following criteria.

A: Newton ring does not occur before peeling, and peeling is lightly peeled off without peeling.

B: Some Newton rings occur before peeling, and peeling occurs when peeling, with a small peeling.

C: A Newton ring is formed on the front surface before peeling, and peeled off while giving a large peeling sound when peeling.

(16) Pencil hardness of the first and second hard coat layers

The surface of the first hard coat layer and the surface of the first hard coat layer of the hard coat film were measured according to JIS K5600-5-4 (1999). The load was 750 g and the speed was 30 mm / min. The measuring device was Shinto Scientific Co., Ltd. A surface hardness tester (HEIDON type 14DR) was used. The environment at the time of measurement was 23 캜 2 캜 and relative humidity 55% 5%.

(17) Visibility of the transparent conductive film pattern

A sample was placed on a black plate, and whether or not the pattern portion of the transparent conductive film could be visually inspected was evaluated based on the following criteria.

A: The pattern part can not be recognized.

C: The pattern part can be recognized.

(18) Measurement of wetting tension of resin layer

The substrate film on which the resin layer was laminated was seasoned for 6 hours in an atmosphere of a state (23 DEG C, relative humidity 50%) and measured under a copper atmosphere according to JIS-K-6768 (1999).

&Lt; Coating liquid for resin layer formation >

(Coating liquid a for forming a resin layer)

, A polyester resin (b) having a Tg (glass transition temperature) of 120 deg. C at a solid content of 26 mass%, a polyester resin (b) having a Tg of 80 deg. C at 54 mass%, a melamine crosslinking agent at 18 mass% To prepare a water dispersion coating liquid.

Polyester resin a; 43 mol% of 2,6-naphthalene dicarboxylic acid, 7 mol% of 5-sodium sulfoisophthalic acid, and 50 mol% of a diol component containing ethylene glycol

Polyester resin b; A polyester resin obtained by copolymerizing 38 mol% of terephthalic acid, 12 mol% of trimellitic acid and 50 mol% of a diol component containing ethylene glycol

Melamine-based crosslinking agents; Sanwa Chemical Co., Ltd. Production "NIKALAC MW12LF"

·particle; Colloidal silica having an average particle diameter of 0.19 mu m

(Coating liquid for forming a resin layer b)

80% by mass of the following acrylic resin, 18% by mass of a melamine crosslinking agent, and 2% by mass of particles were mixed in a solid content ratio by mass to prepare a water dispersion coating liquid.

· Acrylic resin (acrylic resin having the following copolymerization composition)

Methyl methacrylate 63 wt%

35% by weight of ethyl acrylate

1% by weight of acrylic acid

N-methylol acrylamide 1 wt%

Melamine-based crosslinking agents; Sanwa Chemical Co., Ltd. Production "NIKALAC MW12LF"

·particle; Colloidal silica having an average particle diameter of 0.19 mu m

<Surface-treated silica particle dispersion>

(Surface-treated silica particle dispersion A)

To 150 parts by mass of colloidal silica ("Organosilica solzol IPA-ST-ZL" manufactured by Nissan Chemical Industries, Ltd.), 13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of a 10 mass% Followed by stirring at 70 占 폚 for 1 hour. Subsequently, 13.8 parts by mass of a fluorine compound (H ₂ C = CH-COO-CH ₂ - (CF ₂ ) ₈ F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C for 60 minutes To obtain a dispersion.

(Surface-treated silica particle dispersion B)

To 150 parts by mass of colloidal silica ("Organosilica solzol IPA-ST-ZL" manufactured by Nissan Chemical Industries, Ltd.), 13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of a 10 mass% Followed by stirring at 70 占 폚 for 1 hour. Subsequently, 9 parts by mass of a fluorine compound (H ₂ C═CH-COO-CH ₂ - (CF ₂ ) ₈ F) as a hydrophobic compound and 4.8 parts by mass of a silicone compound ("PC-4131" And 0.57 parts by mass of 2,2-azobisisobutyronitrile was added, followed by heating and stirring at 90 DEG C for 60 minutes to obtain a dispersion.

(Surface-treated silica particle dispersion C)

Acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 8 (trade name) was added to 330 parts by mass of colloidal silica ("Organosilica solzol IPA-ST- , 2 parts by mass of tridecafluorooctyltrimethoxysilane (manufactured by GE Toshiba Silicone Co., Ltd.), and 1.5 parts by mass of diisopropoxyaluminum ethyl acetate were mixed and then mixed with 9 parts by mass of ion-exchanged water Was added. After reacting at 60 DEG C for 8 hours, the reaction mixture was cooled to room temperature, and 1.8 parts by mass of acetylacetone was added. Subsequently, cyclohexanone was added to the dispersion, and the solvent was replaced by distillation under reduced pressure at a pressure of 20 kPa to obtain a dispersion.

(Surface-treated silica particle dispersion D)

13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of a 10 mass% formic acid aqueous solution were mixed with 150 parts by mass of colloidal silica ("Organosilica sol Mez-ST-2040" manufactured by Nissan Chemical Industries, Ltd.) Followed by stirring at 70 占 폚 for 1 hour. Subsequently, 13.8 parts by mass of a fluorine compound (H ₂ C = CH-COO-CH ₂ - (CF ₂ ) ₈ F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C for 60 minutes To obtain a dispersion.

(Surface-treated silica particle dispersion E)

To 150 parts by mass of colloidal silica ("Organosilica sol MES-ST-L" manufactured by Nissan Chemical Industries, Ltd.), 13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of a 10 mass% Followed by stirring at 70 占 폚 for 1 hour. Subsequently, 13.8 parts by mass of a fluorine compound (H ₂ C = CH-COO-CH ₂ - (CF ₂ ) ₈ F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C for 60 minutes To obtain a dispersion.

[Example 1]

A hard coat film was produced by the following procedure.

&Lt; Fabrication of resin layer laminated PET film >

On both sides of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 占 퐉, a resin layer was in-line coated in the production process of a PET film. That is, a coating liquid a for forming a resin layer was applied to both surfaces of a uniaxially stretched PET film in the longitudinal direction by a bar coating method and dried at 100 DEG C, followed by biaxial stretching in the width direction and heated at 230 DEG C for 20 seconds Treated and thermally cured to prepare a PET film laminated with a resin layer on both sides. The resin layers laminated on both sides of the PET film had a refractive index of 1.59 and a thickness of 0.09 mu m, respectively.

<Lamination of first and second hard coat layers>

The following active energy ray curable composition (a) was applied on a resin layer on one side of a PET film having a resin layer laminated on both surfaces thereof by gravure coating method, dried at 90 DEG C, and cured by irradiating ultraviolet rays at 400 mJ / Thereby forming a coat layer. The first hard coat layer had a thickness of 2.6 탆 and a refractive index of 1.51.

Subsequently, a second hard coat layer was formed on the resin layer on the other surface (the surface opposite to the surface on which the first hard coat layer was laminated) of the PET film by using the actinic energy ray curable composition a in the same manner as described above , And a hard coat film was produced. The second hard coat layer had a thickness of 2.6 탆 and a refractive index of 1.51.

&Lt; Active Energy ray curable composition a >

, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), 8 parts by mass of a surface-treated silica particle dispersion A in terms of solid content, 10 parts by mass of a photopolymerization initiator (Ciba Irgacure 184 &quot; manufactured by Specialty Chemicals) were mixed in an organic solvent (methyl ethyl ketone).

[Example 2]

A hard coat film was produced in the same manner as in Example 1 except that the second hard coat layer was changed to the following active energy ray curable composition b. The thickness of the second hard coat layer was 2.6 mu m, and the refractive index was 1.52.

&Lt; Active energy ray curable composition b >

48 parts by mass of dipentaerythritol hexaacrylate, 47 parts by mass of a urethane acrylate oligomer ("UN-901T" manufactured by Negami Chemical Industrial Co., Ltd., containing 9 polymerizable functional groups in the molecule), a photopolymerization initiator (Ciba Irgacure 184 &quot; manufactured by Specialty &amp; Chemicals) were dispersed and dissolved in an organic solvent (methyl ethyl ketone).

[Example 3]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition c. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition c >

87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of the surface-treated silica particle dispersion B in terms of solid content, and 5 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were dissolved in an organic solvent (methyl ethyl ketone) And mixed.

[Example 4]

A hard coat film was produced in the same manner as in Example 3 except that the second hard coat layer was changed to the active energy ray curable composition b. The thickness of the second hard coat layer was 2.6 mu m, and the refractive index was 1.52.

[Example 5]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition d. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition d >

87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of the surface-treated silica particle dispersion C in terms of solid content, and 5 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were dissolved in an organic solvent (methyl ethyl ketone and cyclo Hexanone in a mass ratio of 8: 2).

[Example 6]

A hard coat film was produced in the same manner as in Example 5 except that the second hard coat layer was changed to the active energy ray curable composition b. The thickness of the second hard coat layer was 2.6 mu m, and the refractive index was 1.52.

[Example 7]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition e. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition e >

, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), 8 parts by mass of a surface-treated silica particle dispersion D in terms of solid content, a photopolymerization initiator (Ciba Irgacure 184 &quot; manufactured by Specialty Chemicals) were mixed in an organic solvent (methyl ethyl ketone).

[Example 8]

A hard coat film was produced in the same manner as in Example 7 except that the second hard coat layer was changed to the active energy ray curable composition b. The thickness of the second hard coat layer was 2.6 mu m, and the refractive index was 1.52.

[Example 9]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition f. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition f >

, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), 8 parts by mass of a surface-treated silica particle dispersion E in terms of solid content, a photopolymerization initiator (Ciba Irgacure 184 &quot; manufactured by Specialty Chemicals) were mixed in an organic solvent (methyl ethyl ketone).

[Example 10]

A hard coat film was produced in the same manner as in Example 9 except that the second hard coat layer was changed to the active energy ray curable composition b. The thickness of the second hard coat layer was 2.6 mu m, and the refractive index was 1.52.

[Comparative Example 1]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition g. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition g >

87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of silica particles ("Organosilica sol IPA-ST-ZL", manufactured by Nissan Chemical Industries, Ltd.) in terms of solid content, 8 parts by mass of a photopolymerization initiator (produced by Ciba Specialty Chemicals Irgacure 184 &quot;) were dispersed and dissolved in an organic solvent (a mixed solvent of methyl ethyl ketone and cyclohexanone in a mass ratio of 8: 2).

[Comparative Example 2]

A hard coat film was produced in the same manner as in Comparative Example 1 except that the second hard coat layer was changed to the active energy ray curable composition b. The thickness of the second hard coat layer was 2.6 mu m, and the refractive index was 1.52.

[Comparative Example 3]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition h. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and the refractive indexes were 1.52, respectively.

&Lt; Active energy ray curable composition h >

87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of polymethylmethacrylate particles ("MX-150H" manufactured by Soken Chemical &amp; Engineering Co., Ltd.) in terms of solid content, 8 parts by mass of a photopolymerization initiator (Ciba Specialty Chemicals Irgacure 184 &quot;) were dispersed and dissolved in an organic solvent (a mixed solvent of methyl ethyl ketone and cyclohexanone in a mass ratio of 8: 2).

[Comparative Example 4]

A hard coat film was produced in the same manner as in Comparative Example 3 except that the second hard coat layer was changed to the active energy ray curable composition b. The thickness of the second hard coat layer was 2.6 mu m, and the refractive index was 1.52.

[Example 11]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition i. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition i >

, 59 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), 4 parts by mass of the surface-treated silica particle dispersion A in terms of solid content, Irgacure 184 &quot; manufactured by Specialty Chemicals) were mixed in an organic solvent (methyl ethyl ketone).

[Example 12]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition j. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition j >

, 37 parts by mass of an acrylate compound (&quot; ARONIX M111 &quot; produced by Toagosei Co., Ltd.), 6 parts by mass of a surface-treated silica particle dispersion A in terms of solid content, a photopolymerization initiator (Ciba Irgacure 184 &quot; manufactured by Specialty Chemicals) were mixed in an organic solvent (methyl ethyl ketone).

[Example 13]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition k. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition k >

50 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), 10 parts by mass of the surface-treated silica particle dispersion A in terms of solid content, Irgacure 184 &quot; manufactured by Specialty &amp; Chemicals) in an organic solvent (methyl ethyl ketone).

[Example 14]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition 1. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition 1 >

, 33 parts by mass of an acrylate compound (&quot; ARONIX M111 &quot; produced by Toagosei Co., Ltd.), 12 parts by mass of a surface-treated silica particle dispersion A in terms of solid content, a photopolymerization initiator (Ciba Irgacure 184 &quot; manufactured by Specialty &amp; Chemicals) in an organic solvent (methyl ethyl ketone).

[Comparative Example 5]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition m. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

&Lt; Active energy ray curable composition m >

, 57 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), 2 parts by mass of the surface-treated silica particle dispersion A in terms of solid content, Irgacure 184 &quot; manufactured by Specialty &amp; Chemicals) in an organic solvent (methyl ethyl ketone).

[Comparative Example 6]

A hard coat film was produced in the same manner as in Example 1 except that the active energy ray curable composition for forming the first and second hard coat layers was changed to the following active energy ray curable composition n. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

<Active Energy ray-curable composition n>

45 parts by mass of dipentaerythritol hexaacrylate, 30 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), 20 parts by mass of the surface-treated silica particle dispersion A in terms of solid content, Irgacure 184 &quot; manufactured by Specialty &amp; Chemicals) in an organic solvent (methyl ethyl ketone).

[Comparative Example 7]

A resin layer laminated PET film of Example 1 was produced in the same manner as in Example 1 except that the coating liquid for forming a resin layer was changed to a coating liquid for forming a resin layer b, . The resin layers laminated on both sides of the PET film had a refractive index of 1.52 and a thickness of 0.09 mu m, respectively.

<Lamination of first and second hard coat layers>

The first and second hard coat layers were laminated on the resin layer laminated PET film in the same manner as in Comparative Example 5 to produce a hard coat film. The thicknesses of the first and second hard coat layers were respectively 2.6 占 퐉 and 1.51, respectively.

[Evaluation of hard coat film]

Table 1 shows the structures of the first and second hard coat layers of the hard coat films obtained in the above-mentioned Examples and Comparative Examples. Table 2 shows the evaluation results of these hard coat films.

The average diameter, the average height, and the average interval of the projections on the surface of the first hard coat layer were measured for representative samples of the examples and the comparative examples. The results are shown in Table 3.

From the above results, in Examples 1 to 14, since 300 to 10000 protrusions were formed per unit area (100 탆 ² ) on the surface of the first hard coat layer, the sliding property and the blocking resistance were good. Further, the center line average roughness Ra1, Ra2 of the first and second hard coat layers is less than 30 nm, the haze value of the hard coat film is less than 1.5%, and the transparency is good, so that the total light transmittance is high .

[Examples 15 to 24]

On the surfaces of the second hard coat layer of the hard coat films of Examples 1 to 10, an ITO film as a transparent conductive film was laminated by a sputtering method so as to have a thickness of 25 nm to prepare a transparent conductive film. These transparent conductive films were evaluated for sliding property and blocking resistance. The results are shown in Table 4.

The sliding property and the blocking resistance of the transparent conductive film were evaluated in the same manner as in the evaluation of (14) Sliding property and (15) Evaluation of blocking resistance, The evaluation was carried out in the same manner except that the change was made such that it was opposed to face each other.

All of the transparent conductive films of Examples 15 to 24 had good sliding properties and blocking resistance.

[Examples 25 to 29]

The following high refractive index layer and a low refractive index layer were laminated in this order on the surface of the second hard coat layer of the hard coat film of Examples 2, 4, 6, 8, and 10, and then the following transparent conductive film To produce a transparent conductive film for a capacitive touch panel.

&Lt; Lamination of high refractive index layer &

The active energy ray curable composition for forming the following high refractive index layer was coated by a gravure coating method, dried at 90 占 폚 and irradiated with ultraviolet rays of 400 mJ / cm2 to form a high refractive index layer having a thickness of 50 nm. The refractive index of this high refractive index layer was 1.68.

(Active energy ray curable composition for forming a high refractive index layer)

21 parts by mass of dipentaerythritol hexaacrylate, 21 parts by mass of a urethane acrylate oligomer ("UN-901T" manufactured by Negami Chemical Industrial Co., Ltd., containing 9 polymerizable functional groups in the molecule), 55 parts by mass of zirconium oxide , And 3 parts by mass of a photopolymerization initiator ("Irgacure 184" manufactured by Ciba Specialty Chemicals) were dispersed or dissolved in an organic solvent (propylene glycol monomethyl ether).

&Lt; Lamination of low refractive index layer &

The active energy ray-curable composition for forming the following low refractive index layer was coated by a gravure coating method, dried at 90 占 폚, and cured by irradiation with ultraviolet rays of 400 mJ / cm2 to form a low refractive index layer having a thickness of 40 nm. The refractive index of this low refractive index layer was 1.40.

(Active energy ray curable composition for forming a low refractive index layer)

Di- (? -Fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene , 87 parts by mass of glycol, 10 parts by mass of dipentaerythritol hexaacrylate, and 3 parts by mass of a photopolymerization initiator (&quot; Irgacure 184 &quot; manufactured by Ciba Specialty Chemicals) were dispersed or dissolved in an organic solvent (methyl ethyl ketone).

<Lamination of Transparent Conductive Film>

The ITO film was laminated by sputtering to a thickness of 25 nm and patterned (etched) in a lattice pattern to form a transparent conductive film.

[evaluation]

Sliding properties, blocking resistance, and visibility of transparent conductive film patterns of the transparent conductive films of Examples 25 to 29 were evaluated. The results are shown in Table 5.

The sliding property and the blocking resistance of the transparent conductive film were evaluated in the same manner as in the evaluation of (14) Sliding property and (15) Evaluation of blocking resistance, The evaluation was carried out in the same manner except that the change was made such that it was opposed to face each other.

All of the transparent conductive films of Examples 25 to 29 exhibited good sliding properties, blocking resistance, and visibility of the transparent conductive film pattern.

[Examples 31 to 40]

As shown below, five kinds of coating liquids for forming a resin layer having different wetting pressures were prepared.

(Coating liquid c for forming a resin layer (wet tension 42 mN / m)

A water dispersion coating liquid was prepared by mixing 27 mass% of the polyester resin c, 54 mass% of the polyester resin d, 18 mass% of the melamine crosslinking agent, and 1 mass% of the particles in solid content by mass ratio.

Polyester resin c; 43 mol% of 2,6-naphthalene dicarboxylic acid / 7 mol% of 5-sodium sulfoisophthalic acid / 45 mol% of ethylene glycol / 5 mol% of diethylene glycol.

Polyester resin d; 38 mol% of terephthalic acid / 12 mol% of trimellitic acid / 45 mol% of ethylene glycol / 5 mol% of diethylene glycol.

Melamine-based crosslinking agents; Sanwa Chemical Co., Ltd. Production "NIKALAC MW12LF"

·particle; Colloidal silica having an average particle diameter of 0.19 mu m.

(Coating liquid d for forming a resin layer; wetting tension: 44 mN / m)

The water-dispersed coating liquid was prepared by mixing 42 mass% of the polyester resin e, 42 mass% of the acrylic resin a, 6 mass% of the epoxy crosslinking agent, 9 mass% of the surfactant, and 1 mass% did.

Polyester resin e; (Composed of 35 mol% of terephthalic acid / 11 mol% of isophthalic acid / 5 mol% of sodium sulfoisophthalic acid / 45 mol% of ethylene glycol / 4 mol% of diethylene glycol / 1 mol% of polyethylene glycol Polyester resin.

Acrylic resin a; An acrylic resin consisting of 75 mole% of methyl methacrylate / 18 mole% of ethyl acrylate / 4 mole% of N-methylol acrylamide / 3 mole% of methoxypolyethylene glycol (n = 10 repeating units) methacrylate.

Epoxy crosslinking agents; 1,3-bis (N, N-diglycidylamine) cyclohexane

·Surfactants; Polyoxyethylene lauryl ether

·particle; Colloidal silica having an average particle diameter of 0.19 mu m.

(Coating liquid e for forming a resin layer (wet tension: 48 mN / m)

The aqueous dispersion liquid was prepared by mixing 40% by mass of the polyester resin f, 40% by mass of the acrylic resin b, 10% by mass of the melamine crosslinking agent, 9% by mass of the surfactant and 1% did.

Polyester resin f; A polyester resin composed of 30 mol% of terephthalic acid / 15 mol% of isophthalic acid / 5 mol% of sodium sulfoisophthalic acid / 30 mol% of ethylene glycol / 20 mol% of 1,4-butanediol.

Acrylic resin b; An acrylic resin composed of 75 mol% of methyl methacrylate / 22 mol% of ethyl acrylate / 1 mol% of acrylic acid / 2 mol% of N-methylol acrylamide

Melamine-based crosslinking agents; Sanwa Chemical Co., Ltd. Production "NIKALAC MW12LF"

·Surfactants; Polyoxyethylene lauryl ether

·particle; Colloidal silica having an average particle diameter of 0.19 mu m.

(Coating liquid f for forming a resin layer (wet tension: 51 mN / m)

A water-dispersion coating liquid was prepared by mixing 45% by mass of the polyester resin g, 45% by mass of the acrylic resin c, 5% by mass of the melamine crosslinking agent, 4% by mass of the surfactant and 1% did.

Polyester copolymer g: polyester copolymer composed of 32 mol% terephthalic acid / 12 mol% isophthalic acid / 6 mol% 5-sodium sulfoisophthalic acid / 46 mol% ethylene glycol / 4 mol% diethylene glycol.

Acrylic resin c: an acrylic copolymer composed of 70 mol% of methyl methacrylate / 22 mol% of ethyl acrylate / 4 mol% of N-methylol acrylamide / 4 mol% of N, N-dimethylacrylamide.

Melamine-based crosslinking agents; Sanwa Chemical Co., Ltd. Production "NIKALAC MW12LF"

·Surfactants; Polyoxyethylene lauryl ether

·particle; Colloidal silica having an average particle diameter of 0.19 mu m.

(Coating liquid g for forming a resin layer; wet tension: 53 mN / m)

The coating liquid was prepared by mixing 85% by mass of a urethane resin, 5% by mass of an epoxy crosslinking agent, 9% by mass of a surfactant, and 1% by mass of particles by solid content ratio by mass.

Urethane resins; Dainippon Ink & Chamicals, Inc. Production "HYDRAN AP-20"

Epoxy crosslinking agents; Triethylene glycol diglycidyl ether

·Surfactants; Polyoxyethylene lauryl ether

·particle; Colloidal silica having an average particle diameter of 0.19 mu m.

[Example 31]

A hard coat film was produced by the following procedure.

&Lt; Fabrication of resin layer laminated PET film >

On both sides of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 占 퐉, a resin layer was in-line coated in the production process of a PET film. That is, a coating liquid c for forming a resin layer was applied to both surfaces of a uniaxially stretched PET film in the longitudinal direction by a bar coating method, followed by drying at 100 DEG C, followed by biaxial stretching in the width direction and heating at 230 DEG C for 20 seconds Treated and thermally cured to prepare a PET film laminated with a resin layer on both sides. The thicknesses of the resin layers laminated on both sides of the PET film were 0.08 탆.

<Lamination of first and second hard coat layers>

The active energy ray curable composition a used in Example 1 was coated on the resin layer on one side of the PET film having the resin layers laminated on both sides thereof by gravure coating method and dried at 90 DEG C and then irradiated with ultraviolet rays at 400 mJ / To form a first hard coat layer. The thickness of the first hard coat layer was 1.6 mu m.

Subsequently, the active energy ray curable composition b used in Example 2 was coated on the resin layer on the other surface (the surface opposite to the surface on which the first hard coat layer was laminated) of the PET film, To form a hard coat film. The thickness of the second hard coat layer was 1.6 탆.

[Examples 32 to 35]

A hard coat film was produced in the same manner as in Example 31 except that the coating liquid for forming the resin layer was changed as shown in Table 6. [

[Examples 36 to 40]

A hard coat film was produced in the same manner as in Examples 31 to 35 except that the thickness of the first hard coat layer was changed to 2.6 占 퐉 and the thickness of the second hard coat layer was changed to 2.6 占 퐉.

[Evaluation of hard coat film]

The compositions of the first and second hard coat layers obtained in the above-mentioned Examples 31 to 40 are shown in Table 6, and the evaluation results of these hard coat films are shown in Table 7.

From the above results, it was found that the projections due to particles were liable to be formed on the surface of the first hard coat layer by directly laminating the first hard coat layer on the resin layer having a wet tension of 52 mN / m or less (the number of projections per unit area . It has been found that the influence of the wet tension on the surface of the resin layer becomes significant when the thickness of the first hard coat layer is less than 2 mu m. That is, in the embodiment in which the first hard coat layer is directly laminated on the resin layer having a wet tension of 52 mN / m or less, when the thickness of the first hard coat layer is less than 2 탆, And as a result, protrusions due to particles are efficiently formed. Further, by setting the thickness of the first hard coat layer to less than 2 mu m, the haze value becomes smaller and the transparency improves.

1 to 5 projections 11 projections
20 Straight line in the horizontal direction 30 Straight line in the vertical direction

Claims (17)

Wherein at least one surface of the base film is provided with a first hard coat layer containing particles, and the surface of the first hard coat layer has protrusions of the above-mentioned particles at a density of 300 to 4,000 per 100 μm ² , Wherein the center line average roughness Ra1 of the surface of the first hard coat layer is less than 30 nm and the haze value is less than 1.5%. The method according to claim 1,
Wherein the average particle diameter (r) of the particles is 0.05 to 0.5 占 퐉. 3. The method according to claim 1 or 2,
Wherein the ratio (r / d) of the average particle diameter (r) of the particles to the thickness (d) of the first hard coat layer is 0.01 to 0.30. 4. The method according to any one of claims 1 to 3,
Wherein the average diameter of the protrusions is 0.03 to 0.3 占 퐉 and the average height of the protrusions is 0.03 to 0.3 占 퐉. 5. The method according to any one of claims 1 to 4,
Wherein the average interval of the protrusions is 0.10 to 0.70 占 퐉. 6. The method according to any one of claims 1 to 5,
And the thickness (d) of the first hard coat layer is 0.5 占 퐉 or more and less than 10 占 퐉. 7. The method according to any one of claims 1 to 6,
Wherein a resin layer having a thickness of 0.005 to 0.3 mu m is provided between the base film and the first hard coat layer, and the resin layer contains particles having an average particle diameter of 1.3 times or more in thickness. 8. The method according to any one of claims 1 to 7,
Wherein the base film is made of polyethylene terephthalate and a resin layer having a refractive index of 1.55 to 1.61 is provided between the base film and the first hard coat layer. 9. The method according to any one of claims 1 to 8,
And a resin layer having a wet tension of 52 mN / m or less between the base film and the first hard coat layer. 10. The method of claim 9,
Wherein the thickness of the first hard coat layer is less than 2 占 퐉. 11. The method according to any one of claims 1 to 10,
Wherein the particles contained in the first hard coat layer are made of an inorganic material and subjected to treatment for reducing surface free energy or hydrophobic treatment for the surface of the particles. 12. The method of claim 11,
An organosilane compound represented by the general formula 1 (C _n F _{2n + 1} - (CH ₂ ) _m -Si (Q) ₃ ) with respect to the surface of the particles contained in the first hard coat layer, Wherein the hydrolyzate of the compound or the partial condensate of the hydrolyzate is used to reduce the surface free energy.
(In the general formula (1), n represents an integer of 1 to 10, and m represents an integer of 1 to 5. Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom] 12. The method of claim 11,
The surface of the particles contained in the first hard coat layer is treated with a compound represented by the general formula 2 (BR ⁴ -SiR ⁵ _n (OR ⁶ ) _{3 -n} ), and then the compound represented by the general formula 3 (DR ⁷ -Rf ² ). &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
In the general formulas (2) and (3), B and D each independently represent a reactive site, R ⁴ and R ⁷ each independently represent an alkylene group having 1 to 3 carbon atoms, , R ⁵ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, Rf ² is a fluoroalkyl group, and n is an integer of 0 to ² , 12. The method of claim 11,
The surface of the particles contained in the first hard coat layer may be a fluorine compound having a fluoroalkyl group having 4 or more carbon atoms and a reactive site, a long-chain hydrocarbon compound having a reactive site with a hydrocarbon group having 8 or more carbon atoms, or a silicon compound having a reactive site with a siloxane group Lt; RTI ID = 0.0 &gt; hydrophobic &lt; / RTI &gt; 15. The method according to any one of claims 1 to 14,
Wherein the particles contained in the first hard coat layer are silica particles. 16. The method according to any one of claims 1 to 15,
The second hard coat layer is provided on the surface of the base film opposite to the surface on which the first hard coat layer is provided and the surface of the second hard coat layer is substantially free of protrusions made of particles, Wherein the center line average roughness (Ra2) of the surface of the layer is 25 nm or less. A transparent conductive film comprising a transparent conductive film on at least one surface of the hard coat film according to any one of claims 1 to 16.

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