CN104822522B - Hard coat film and transparent and electrically conductive film - Google Patents

Abstract

A kind of hard coat film, it is characterized in that, on at least one side of substrate film, be provided with the 1st hard coat layer containing particle, the protrusion that is formed by said particle exists in the density of 300～4000 per 100 μm ² On the surface of the hard coat layer, the centerline 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 properties and blocking resistance.

Description

Hard coat film and transparent conductive film

technical field

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

Background technique

A hard coat film (which is obtained by laminating a hard coat layer on a base film) is used as a base film for a display, a surface protection of a touch panel, or an electrode film for a touch panel (transparent conductive film used for a touch panel). The hard coat film used for the above-mentioned applications is required to have high transparency and good sliding properties and blocking resistance.

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

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 7-314628

Patent Document 2: Japanese Patent Laid-Open No. 2000-211082

Contents of the invention

However, the techniques disclosed in the above-mentioned patent documents have not been able to sufficiently satisfy the effects of transparency, sliding properties, and blocking resistance at the same time.

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

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

1) A hard coat film, characterized in that at least one side of the base film is provided with a first hard coat layer containing particles, and the protrusions formed by the particles are present at a density of 300 to 4000 per 100 ^μm The surface of the first hard coat layer has a centerline average roughness (Ra1) of less than 30 nm and a haze value of less than 1.5%.

2) The hard coat film according to 1), wherein the average particle diameter (r) of the particles is 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 protrusions is 0.03 to 0.3 μm, and the average height of the protrusions is 0.03 to 0.3 μm.

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

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 μm or more and less than 10 μm.

7) The hard coat film according to any one of 1) to 6), wherein there is a resin layer between the base film and the first hard coat layer, and the resin layer has a thickness of 0.005 to 0.3 μm and contains particles , the average particle size of the particles is more than 1.3 times the thickness of the resin layer.

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

9) The hard coat film according to any one of 1) to 8), wherein a resin layer having a wetting 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 μm.

11) The hard coat film according to any one of 1) to 10), wherein the particles contained in the first hard coat layer are selected from inorganic particles subjected to surface treatment for reducing the surface free energy of the particles , and at least one selected from the group consisting of inorganic particles whose surface has been hydrophobized.

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) using at least one selected from the group consisting of a fluorine atom-containing organosilane compound represented by the following general formula (1), a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate of the organosilane compound for surface treatment.

C _n F _2n+1 -(CH ₂ ) _m -Si(Q) ₃ General formula (1)

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

(II) Treatment is performed using a compound represented by the following general formula (2), and surface treatment is further performed using a fluorine compound represented by the following general formula (3).

BR ⁴ -SiR ⁵ _n (OR ⁶ ) _3-n General formula (2)

DR ⁷ -Rf ² ····General formula (3)

(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 with 1 to 3 carbon atoms, or an alkylene group derived from the alkylene The ester structure derived from the base, ^R5 and R6 each independently represent hydrogen or an alkyl group with 1 to ⁴ carbon atoms, ^Rf2 represents a fluoroalkyl group, and n represents an integer of 0 to 2.)

13) The hard coat film as described in 11), wherein the hydrophobic compound usable in the hydrophobizing treatment is selected from fluorine compounds having a reactive site and a fluoroalkyl group having 4 or more carbon atoms, having a reactive site and at least one compound selected from the group consisting of a long-chain hydrocarbon compound having a hydrocarbon group having 8 or more carbon atoms, and a siloxane compound having a siloxane group and a reactive site, wherein the hydrophobizing treatment is to obtain the Inorganic particles whose surface has undergone hydrophobization treatment are carried out.

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 hard coat film according to any one of 1) to 14), wherein a 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 second hard coat layer is 2. Substantially no protrusions formed of particles exist on the surface of the hard coat layer, and the centerline 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).

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

Description of drawings

FIG. 1 is an example of an observation diagram of the surface of the first hard coat layer observed with a scanning electron microscope.

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

Fig. 3 is a schematic view schematically showing the surface of the first hard coat layer in Fig. 1 .

FIG. 4 is a schematic diagram omitting a part of FIG. 3 .

detailed description

The hard coat film which concerns on one Embodiment of this invention has a 1st hard coat layer on at least one surface of a base film. The first hard coat layer contains particles, and has 300 to 4000 protrusions (hereinafter, sometimes simply referred to as "protrusions") caused by the particles per 100 μm ² on the surface of the first hard coat layer. The centerline average roughness (Ra1) of the surface of the first hard coat layer is less than 30 nm. The haze value of the hard coat film of this embodiment mentioned above is less than 1.5%.

The number of protrusions on the surface of the first hard coat layer is 300 to 4000 per unit area (100 μm ² ) of the surface of the first hard coat layer, thereby improving slipperiness and blocking resistance.

The range of the number density of the protrusions is preferably in the range of 400 to 3500 per 100 μm ² , more preferably in the range of 500 to 3000, still more preferably in the range of 600 to 3000, particularly preferably in the range of 700 to 2500.

When the number density of the particles is less than 300 particles per 100 μm ² , the slipperiness and blocking resistance will decrease. On the other hand, when the particle number density exceeds 4000 particles per 100 μm ² , the smoothness of the surface of the first hard coat layer decreases, the haze value increases, and the transparency of the hard coat film decreases.

One of the characteristics of the hard coat film of this embodiment is that the surface of the first hard coat film is relatively smooth despite having many protrusions on the surface of the first hard coat film as described above, and the haze value of the hard coat film is small. Specifically, it is important that the centerline average roughness (Ra1) of the surface of the first hard coat layer in this embodiment is less than 30 nm, and that the haze value of the hard coat film is less than 1.5%.

The centerline average roughness (Ra1) of the surface of the first hard coat layer is preferably 25 nm or less, more preferably 20 nm or less, particularly preferably 18 nm or less. From the viewpoint of securing slidability and blocking resistance, the lower limit of the centerline average roughness (Ra1) is preferably 5 nm or more, more preferably 7 nm or more, particularly preferably 9 nm or more.

When the centerline average roughness (Ra1) of the surface of the first hard coat layer is 30 nm or more, the smoothness falls, and the transparency of the hard coat film falls. 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 this embodiment is less than 1.5%. The haze value of the hard coat film of this embodiment is more preferably 1.1% or less, and more preferably 1.0% or less. The lower limit of the haze value is preferably as small as possible, but is actually about 0.01%.

In order to have 300 to 4000 protrusions per 100 μm ² on the surface of the first hard coat, and to make the centerline average roughness (Ra1) of the surface of the first hard coat less than 30 nm, and to make the haze value of the hard coat less than 1.5%, preferably, make the 1st hard coat layer contain the particle that average particle diameter (r) is 0.05～0.5 μm, and make this particle more exist near the surface of the 1st hard coat layer, thereby in the 1st hard coat layer Protrusions are formed on the surface of the hard coat.

Furthermore, the ratio (r/d) of the average particle diameter (r) (μm) of the particles contained in the first hard coat layer to the thickness (d) (μm) of the first hard coat layer is preferably 0.01 to 0.30. Thereby, the center line average roughness (Ra1) of the surface of a 1st hard-coat layer becomes small, and the haze value of a hard-coat film also becomes small.

Hereinafter, each component which comprises a hard coat film is demonstrated in detail.

[Substrate film]

As the base film, a plastic film can be preferably used. Examples of the material constituting the base film include polyesters 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, triacetylcellulose, and these A substance obtained by mixing and/or copolymerizing resins. The above-mentioned resin can be formed into a film in an unstretched state, or after uniaxial stretching or biaxial stretching, and this can be used as a base film.

Among the above-mentioned base films, polyester films are excellent in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, chemical resistance, etc., and polyethylene terephthalate films (PET membrane).

Regarding the thickness range of the substrate film, the appropriate range is 20 to 300 µm, preferably 30 to 200 µm, and more preferably 50 to 150 µm.

It is preferable to have the resin layer shown below on the surface which laminated|stacked the 1st hard-coat layer at least on the base film. That is, it is preferable to have the resin layer shown below between a base film and a 1st hard-coat layer.

[resin layer]

In order to reinforce the adhesiveness of a base film and a 1st hard-coat layer, it is preferable to provide a resin layer on the surface which laminated|stacked the 1st hard-coat layer at least on the base film.

The resin layer is a layer containing resin as a main component. Specifically, the resin layer is a layer containing 50% by mass or more of a 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 polyester resins, acrylic resins, polyurethane resins, polycarbonate resins, epoxy resins, alkyd resins, and urea resins. These resins may be used alone or in combination.

The resin layer exists between the base film and the first hard coat layer, and from the viewpoint of improving the adhesion between the base film and the first hard coat layer, the resin contains a resin selected from polyester resins, acrylic resins, and polyurethane resins. At least one of the group of is preferable. It is particularly preferable that the resin layer contains at least a polyester resin as the resin.

The content of the resin in the resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, based on 100% by mass of the total solid content of the resin layer. As for 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.

In addition, the resin layer may also be formed in a two-layer structure. In the case of a two-layer structure, it is preferable to comprise a first resin layer (containing a polyester resin as a main component) and a second resin layer (containing an acrylic resin as a main component) in order from the base film side. The two-layer structure will be described in detail below.

It is preferable that the resin layer contains particles from the viewpoint of ensuring moderate sliding properties and winding properties of the hard coat film in the production process.

The particles contained in the resin layer are not particularly limited, and include inorganic particles such as silica particles, titanium oxide, alumina, zirconia, calcium carbonate, and zeolite particles, acrylic particles, silicone particles, and polyimide particles. , Teflon (registered trademark) particles, cross-linked polyester particles, cross-linked polystyrene particles, cross-linked polymer particles, core-shell particles and other organic particles. Among them, silica particles are preferred, and colloidal silica is particularly preferred.

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

Slidability and blocking resistance are further improved by directly laminating the first hard coat layer on the resin layer containing particles having an average particle diameter larger than the thickness of the resin layer as described above.

The average particle diameter of the particles contained in the resin layer can be appropriately selected according to the thickness design of the resin layer. Specifically, the average particle diameter is preferably in the range of 0.02 to 1 μm, more preferably in the range of 0.05 to 0.7 μm, and particularly preferably in the range of The range of 0.1 ~ 0.5μm. When the average particle diameter is less than 0.02 μm, sliding properties and blocking resistance may decrease. When the average particle diameter is larger than 1 μm, the particles may fall off, the transparency may be lowered, or the appearance may be deteriorated.

The thickness of the resin layer is preferably in the range of 0.005 to 0.3 μm. When the thickness of a resin layer is less than 0.005 micrometer, the adhesiveness of a base film and a 1st hard-coat layer will fall. Moreover, when the thickness of a resin layer becomes larger than 0.3 micrometer, blocking resistance after laminating|stacking a 1st hard-coat layer may fall. The thickness of the resin layer is more preferably 0.01 μm or more, more preferably 0.015 μm or more, particularly preferably 0.02 μm or more. Regarding the upper limit, the thickness of the resin layer is preferably 0.25 μm or less, more preferably 0.2 μm or less, particularly preferably 0.15 μm or less. When there are plural resin layers, it is preferable that the value obtained by adding up the thicknesses of all the resin layers satisfies the above-mentioned thickness condition.

The content of the particles in the resin layer is preferably in the range of 0.05 to 10% by mass, more preferably in the range of 0.1 to 8% by mass, particularly preferably in the range of 0.5 to 5% by mass, based on 100% by mass of the total solid content of the resin layer. range. When the content of the particles in the resin layer is less than 0.05% by mass, good sliding properties and blocking resistance may not be obtained, and when the content of the particles exceeds 10% by mass, the transparency decreases, the coatability of the first hard coat layer deteriorates, Or when the adhesiveness of a base film and a 1st hard-coat layer falls.

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 a thermosetting layer as described above, the adhesion between the base film and the first hard coat layer can be further improved. Conditions (heating temperature and time) for thermosetting the resin layer are not particularly limited, but the heating temperature is preferably 70°C or higher, more preferably 100°C or higher, particularly preferably 150°C or higher, most preferably 200°C or higher. Regarding the upper limit, the heating temperature is preferably 300° C. or lower. The range of 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-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, isocyanate-based crosslinking agents, aziridine-based crosslinking agents, epoxy Cross-linking agent, methylolated or alkylated urea cross-linking agent, acrylamide cross-linking agent, polyamide resin, amide epoxy compound, various silane coupling agents, various titanates Class coupling agent, etc. Among them, melamine-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, isocyanate-based crosslinking agents, and aziridine-based crosslinking agents are preferred, and melamine-based crosslinking agents are particularly preferred.

Examples of the melamine-based crosslinking agent include imino-type methylated melamine resins, methylol-type melamine resins, methylol-type methylated melamine resins, and complete alkyl-type methylated melamine resins. Among these, imino-type melamine resins and methylolated melamine resins can be preferably used.

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

It is preferable that the reflection color of the hard coat film obtained by laminating|stacking a 1st hard coat layer on a base film via a resin layer is a neutral (neutral) colorless hue. From the above viewpoint, when a polyethylene terephthalate film (PET film) is used as the base film, the range of 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, Especially preferably, it is the range of 1.57-1.59.

The refractive index of a polyethylene terephthalate film (PET film) is usually about 1.62 to 1.70, and by setting the refractive index of the resin layer within the above range (1.55 to 1.61), the reflection color of the hard coat can be made close to neutral. Sexual colorless. 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 in the range of 0.03 to 0.09, and particularly preferably in the range of 0.04 to 0.09. within the range of 0.08.

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

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

As for the resin layer, it is preferable to apply it on the base film by a wet coating method, heat-cure it, and laminate it. More preferably, coating is performed by a so-called in-line coating method (a method of coating a resin layer by a wet coating method in a production process of a base film), thermally curing and laminating. As a wet coating method, a reverse roll coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method etc. are mentioned, for example.

As described above, the resin layer may be constituted by two layers. The above-mentioned two-layer resin layer is preferably formed by applying one coating liquid once and self-phase-separating during the drying process to form a two-layer resin layer. That is, it is preferable to adopt the following method: apply 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, and use the The first resin layer and the second resin layer are formed by self-phase separation.

When carrying out the above-mentioned phase separation method, it is preferable to increase the difference in surface energy 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 with high surface energy and an acrylic resin with low surface energy. In particular, in order to increase the surface energy of the polyester resin, it is preferable to use a polyester resin having a sulfonic acid group.

When the resin layer is composed of two layers, the thickness of the first resin layer is greater than The thickness of the second resin layer is preferable. The thickness of the first resin layer is preferably 1.5 times or more, more preferably 2.0 times or more, and particularly preferably 3.0 times or more the thickness of the second resin layer.

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

As for the resin layer provided between a base film and a 1st hard-coat layer, it is preferable that the wetting tension of the surface is 52 mN/m or less. That is, in the present invention, the wetting tension of the surface of the resin layer to which the first hard coat layer is applied is preferably 52 mN/m or less. By directly laminating the first hard coat layer on such a resin layer, it becomes easier to form protrusions due to particles on the surface of the first hard coat layer, and as a result, the sliding properties and blocking resistance are further improved. Here, the wetting tension is a physical property value specified in JIS-K-6768.

The above method of providing a resin layer having a wetting tension of 52 mN/m or less between the base film and the first hard coat layer is effective when the thickness of the first hard coat layer is small. As the thickness of the first hard coat layer decreases, the absolute amount of particles contained in the first hard coat layer also decreases. However, by laminating the first hard coat layer on the resin layer having a wetting tension of 52 mN/m or less, the particles contained in the first hard coat layer tend to be localized near the surface, and as a result, protrusions can be efficiently formed. . This method is effective when the thickness of the first hard coat layer is less than 2 μm, and is particularly effective when the thickness of the first hard coat layer is 1.7 μm or less.

From the above viewpoint, the wetting tension on the surface of the resin layer is more preferably 50 mN/m or less. On the other hand, from the viewpoint of ensuring the adhesion between the base film and the first hard coat layer, the lower limit of the wetting tension on the surface of the resin layer is preferably 35 mN/m or more, more preferably 37 mN/m or more, particularly preferably Above 40mN/m. When the wetting tension of the resin layer surface is less than 35 mN/m, the adhesiveness of a 1st hard-coat layer may fall.

From the viewpoint of controlling the wetting tension on 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, it is preferable to use a resin selected from polyester resins as the resin contained in the resin layer. At least one selected from the group consisting of , acrylic resin and polyurethane resin. Among the above-mentioned resins, it is more preferable to use polyester resin and/or acrylic resin, and it is particularly preferable to use at least polyester resin as the resin.

In addition, the wetting tension on the surface of the resin layer can also be controlled by adjusting the type and content of the above-mentioned crosslinking agent. For example, when the content of the crosslinking agent increases, the wetting tension on the surface of the resin layer tends to decrease, and conversely, when the content of the crosslinking agent decreases, the wetting tension on the surface of the resin layer tends to increase.

[the first hard coat]

The first hard coat layer contains particles, and protrusions caused by the particles are formed on the surface of the first hard coat layer. The number density of the protrusions on the surface of the first hard coat layer is 300 to 4000 per unit area (100 μm ² ) of the surface of the first hard coat layer. Furthermore, the range of the number density of the protrusions is preferably in the range of 400 to 3500 per 100 μm ² , more preferably in the range of 500 to 3000, still more preferably in the range of 600 to 3000, particularly preferably in the range of 700 to 2500 .

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 μm, more preferably in the range of 0.06 to 0.4 μm, and particularly preferably in the range of 0.07 to 0.3 μm.

When the average particle diameter (r) of the particles contained in the first hard coat layer is less than 0.05 μm, sufficiently large protrusions may not be formed on the surface of the first hard coat layer, and the sliding properties and blocking resistance may not be sufficiently improved. When the average particle diameter (r) is greater than 0.5 μm, the following disadvantages sometimes occur: the smoothness of the surface of the first hard coat layer is reduced, the centerline average roughness (Ra1) becomes 30 nm or more, or the haze value of the hard coat film becomes 1.5% or more, the transparency will decrease, etc.

The average particle diameter (r) of the particles contained in the first hard coat layer is preferably sufficiently small with respect to 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 to make many such particles exist near the surface of the first hard coat layer and to form many protrusions on the surface of the first hard coat layer as described above. Thereby, slidability and blocking resistance can be improved without reducing the smoothness of the surface of the first hard-coat layer.

The range of 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 more preferably in the range of 0.01 to 0.20, and more preferably in the range of 0.01 to 0.01. The range of 0.15, particularly preferably the range of 0.02 to 0.10, most preferably 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-mentioned particles is preferably in the range of 0.03 to 0.3 μm. Furthermore, the average diameter of the protrusions is preferably in the range of 0.04 to 0.25 μm, more preferably in the range of 0.05 to 0.2 μm. Thereby, slidability and blocking resistance can be improved without reducing transparency.

The range of the average height of the protrusions is preferably in the range of 0.03 to 0.3 μm. Further, the range of the average height of the protrusions is preferably in the range of 0.04 to 0.25 μm, more preferably in the range of 0.05 to 0.2 μm. Thereby, slidability and blocking resistance can be improved without reducing transparency.

The shape of the protrusions formed on the surface of the first hard coat layer is not particularly limited, but preferably has a circular or nearly circular planar shape. Here, the planar shape of a protrusion means the planar shape when the surface of a 1st hard-coat layer was observed with the scanning electron microscope (SEM).

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

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

The planar shape of the so-called protrusion is close to a circle, which means that in the schematic diagram shown in FIG. The ratio (Lmin/Lmax) of the maximum diameter (Lmax) is 0.65 or more.

The above ratio (Lmin/Lmax) is preferably 0.70 or more, more preferably 0.80 or more, 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 "nearly circular" as defined above.

In this specification, the diameter of a protrusion means the maximum diameter (Lmax) shown in FIG. 2 . The average diameter of the protrusions can be determined from a photograph of the surface of the first hard-coat layer obtained by a scanning electron microscope as shown in FIG. 1 .

In this specification, the height of a protrusion means the length from the apex of a protrusion to the surface of a 1st hard-coat layer. The average height of the protrusions can be measured from a cross-sectional photograph of the first hard coat layer taken with a transmission electron microscope (TEM).

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 μm, more preferably in the range of 0.15 to 0.50 μm, and particularly preferably in the range of 0.20 to 0.40 μm. Thereby, slidability and blocking resistance can be improved without reducing transparency.

The average interval of the protrusions can be obtained from a photograph of the surface of the first hard coat layer obtained by a scanning electron microscope. Fig. 3 is a patterned view of a photograph of the surface of the first hard coat layer obtained with a scanning electron microscope. Using Fig. 3, a method of measuring the average interval of protrusions will be described.

First, draw a straight line 20 along the horizontal direction, and then draw a vertical straight line 30 perpendicular to the horizontal straight line 20 . Next, for all the protrusions that fall on the transverse straight line 20 (ie, contact the straight line 20), the intervals between adjacent protrusions are measured. The same operation is performed for the vertical straight line 30 . The intervals (distances) of all the protrusions thus obtained were averaged.

A method of measuring the average interval of protrusions will be described in detail using FIG. 4 .

FIG. 4 only selects and edits the protrusions falling on the horizontal straight line 20 or the vertical straight line 30 in FIG. 3 . In FIG. 4 , the protrusions falling on the lateral straight line 20 are five protrusions denoted by reference numerals 1 to 5 . The interval between adjacent protrusions is, for example, the distance P between a protrusion 1 and a protrusion 2 adjacent to the protrusion 1 . Similarly, the intervals between protrusions 2 and 3 , the intervals between protrusions 3 and 4 , and the intervals between protrusions 4 and 5 are measured, and the intervals between adjacent protrusions are measured for all particles falling on the horizontal straight line 20 .

The same operation is performed, for all protrusions falling on the longitudinal straight line 30, the spacing between adjacent protrusions is measured.

The position of the horizontal straight line and the position of the vertical straight line were changed three times, and the above operation was carried out, and the average value of all the obtained protrusion intervals was taken, and the average value was taken as the average interval of the protrusions.

As shown in FIG. 1 , it is preferable that each protrusion on the surface of the first hard coat layer is formed from one particle. Thereby, it becomes easy to adjust the centerline average roughness (Ra1) of the surface of a 1st hard-coat layer to less than 30 nm, and it becomes easy to adjust the haze value of a hard-coat film to less than 1.5%. When a plurality of particles are aggregated to form protrusions, the centerline 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% by mass, more preferably in the range of 3 to 15% by mass, and particularly preferably It is the range of 4-12 mass %.

As mentioned above, it is preferable to make the first hard coat layer contain particles whose average particle diameter (r) is sufficiently small relative to the thickness (d) of the first hard coat layer, so that the particles are present in large numbers. In the vicinity of the surface of the first hard coat layer, many protrusions are formed on the surface of the first hard coat layer.

In order for the particles to exist in the vicinity of the surface of the first hard coat layer, it is necessary to move (float) the particles to the vicinity of the surface during the formation of the first hard coat layer. This can be achieved, for example, by using particles subjected to a surface treatment which serves to reduce the surface free energy of the particles, or particles which have undergone a hydrophobizing treatment which serves to hydrophobize the surface of the particles. As the particles to be treated, inorganic particles are preferable, and silica particles are particularly preferable.

Inorganic particles can be preferably used as the particles contained in the first hard coat layer. As the inorganic particles, inorganic particles containing an element selected from Si, Na, K, Ca, and Mg are preferably mentioned. Inorganic particles containing compounds selected from silica particles (SiO ₂ ), alkali metal fluorides (NaF, KF, etc.) and alkaline earth metal fluorides (CaF ₂ , MgF ₂ , etc.) In view of properties, etc., silica particles are particularly preferable.

As the above-mentioned surface treatment for reducing the surface free energy of the particles, the use of organosilane compounds selected from fluorine atom-containing compounds represented by the following general formula (1), the hydrolyzate of the organosilane, and the organosilane A method of surface-treating at least one compound of the group consisting of partial condensates of hydrolyzates.

C _n F _2n+1 -(CH ₂ ) _m -Si(Q) ₃

····General formula (1)

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

As a compound of general formula (1), the following compounds can be illustrated specifically.

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

In addition, as another surface treatment for reducing the surface free energy of inorganic particles, treatment with a compound represented by the following general formula (2) and further surface treatment with a fluorine compound represented by the following general formula (3) can be mentioned. The method of processing.

BR ⁴ -SiR ⁵ _n (OR ⁶ ) _3-n

····General formula (2)

DR ⁷ -Rf ²

····General formula (3)

(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 with 1 to 3 carbon atoms, or an alkylene group derived from the alkylene The ester structure derived from the base, ^R5 and R6 each independently represent hydrogen or an alkyl group with 1 to ⁴ carbon atoms, ^Rf2 represents a fluoroalkyl group, and n represents an integer of 0 to 2.)

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

Specific examples of the general formula (2) include acryloyloxyethyltrimethoxysilane, acryloyloxypropyltrimethoxysilane, acryloyloxybutyltrimethoxysilane, acryloyloxy Amyltrimethoxysilane, Acryloxyhexyltrimethoxysilane, Acryloxyheptyltrimethoxysilane, Methacryloxyethyltrimethoxysilane, Methacryloxypropyltrimethoxysilane Oxysilane, Methacryloxybutyltrimethoxysilane, Methacryloxyhexyltrimethoxysilane, Methacryloxyheptyltrimethoxysilane, Methacryloxypropyl Methyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, and compounds in which the methoxy group in the above compounds are substituted with other alkoxy groups or hydroxyl groups, and the like.

Specific examples of the general formula (3) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutyl acrylate Acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, perfluorooctylmethyl acrylate , 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutyl acrylate Acrylic acid-3-perfluoro-3-methoxybutyl-2-hydroxypropyl ester, acrylate-2-perfluoro-5-methylhexyl ethyl ester, acrylate-3-perfluoro-5-methyl Hexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, Hexafluorononyl, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, methacrylic acid-2 -Perfluorobutyl ethyl ester, 3-perfluorobutyl-2-hydroxypropyl methacrylate, perfluorooctyl methyl methacrylate, 2-perfluorooctyl ethyl methacrylate, methyl 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, methacrylic acid- 3-perfluoro-3-methylbutyl-2-hydroxypropyl ester, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl methacrylate- 2-hydroxypropyl ester, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, Octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, methyl Hexafluorobutyl acrylate, etc.

Examples of the hydrophobic compound used for hydrophobizing the particle surface include compounds having a hydrophobic group and a reactive site in the molecule. Generally, 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, for example, fluoroalkyl groups having 4 or more carbon atoms, fluoroalkyl groups having 8 carbon atoms, At least one functional group selected from the group consisting of the above hydrocarbon groups and siloxane groups.

The above-mentioned reactive site is a site that chemically reacts with free radicals (generated by receiving energy such as light or heat), etc., and as specific examples, vinyl, allyl, acryloyl, methacryl, etc. Acyl group, acryloyloxy group, methacryloyloxy group, epoxy group, carboxyl group, hydroxyl group and other reactive sites that receive energy such as light or heat to undergo chemical reactions.

That is, as the hydrophobic compound for performing hydrophobizing treatment on the particle surface, it is preferable to use a compound (fluorine compound) selected from a compound (fluorine compound) having a reactive site and a fluoroalkyl group having 4 or more carbon atoms, a reactive site and a carbon atom At least one compound selected from the group consisting of a compound having 8 or more hydrocarbon groups (long-chain hydrocarbon compound) and a compound having a siloxane group and a reactive site (siloxane compound).

The long-chain hydrocarbon compound means a compound having a reactive site and a hydrocarbon group having 8 or more carbon atoms as a hydrophobic group in the molecule. The carbon number of the hydrocarbon group having 8 or more carbon atoms is preferably 8 or more and 30 or less. In addition, as the hydrocarbon group having 8 or more carbon atoms, any of straight chain structure, branched chain structure and alicyclic structure can be selected. As the long-chain hydrocarbon compound, linear alkyl alcohols, alkylepoxides, alkyl acrylates, alkyl methacrylates, carboxylates, and alkyl methacrylates with a carbon number of 10 to 22 can be preferably used. Acid alkyl esters (including acid anhydrides and esters), etc.

Specific examples of long-chain hydrocarbon compounds include polyhydric alcohols such as octanol, octanediol, and stearyl alcohol, octyl acrylate, octyl methacrylate, 2-hydroxyoctyl acrylate, 2-methacrylate Acrylates (methacrylates) such as hydroxyoctyl esters, alkylalkoxysilanes such as octyltrimethoxysilane, and the like.

Examples of the siloxane compound include compounds having a reactive site and a siloxane group as a hydrophobic group in the molecule. As the reactive site of the siloxane compound, an acryloyloxy group or a methacryloyloxy group can be preferably used.

In addition, as the siloxane group, a polysiloxane group represented by the following general formula (4) can be preferably used.

-(Si(R ⁸ )(R ⁹ )-O) _m -

····General formula (4)

(In the general formula (4), R ⁸ and R ⁹ each independently represent an alkyl group with 1 to 6 carbon atoms, a phenyl group, a 3-acryloxy-2-hydroxypropyloxypropyl group, a 2- Acryloyloxy-3-hydroxypropyloxypropyl, polyethylene glycol propyl ether groups with acryloyloxy or methacryloyloxy groups at the end, or polyethylene glycol propyl ether groups with terminal hydroxyl groups, m represents an integer of 10 to 200.)

Specific examples of siloxane compounds having polysiloxane groups represented by general formula (4) as hydrophobic groups include dimethylsiloxane groups represented by general formula (5) below, and reactive site compounds. Specific examples of the dimethylsiloxane group having the general formula (5) and the siloxane compound at the reactive site include X-22-164B, X-22-164C, X-22-5002, X-22-174D, X-22-167B (the above are brand names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

(In the formula, R represents an alkyl group having 1 to 7 carbon atoms, k represents an integer of 0 or 1, and m represents an integer of 10 to 200.)

In addition, other specific examples of the siloxane compound having a reactive site and a polysiloxane group represented by the general formula (4) as a hydrophobic group include those having a 3-acryloyloxy group represented by the general formula (6). A compound having a 2-hydroxypropyloxypropyl group and a methyl group; a compound represented by general formula (7) having a 2-acryloyloxy-3-hydroxypropyloxypropyl group and a methyl group.

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

Furthermore, other specific examples of the siloxane compound having a reactive site and a polysiloxane group represented by the general formula (4) as a hydrophobic group include those represented by the general formula (8) having a methyl group and having a polysiloxane group at the end. Polyethylene glycol propyl ether group compound of acryloyloxy group or methacryloyloxy group; Polyethylene glycol propyl ether group compound represented by general formula (9) having a methyl group and a hydroxyl group at the end.

(In general formulas (8) and (9), R represents an alkyl group 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 10 to 200. )

A fluorine compound having a reactive site and a fluoroalkyl group having 4 or more carbon atoms will be described. Here, the fluoroalkyl group may have either a linear structure or a branched structure. In addition, the fluoroalkyl group preferably has 4 or more and 8 or less carbon atoms. As such fluorine compounds, fluoroalkyl alcohols, fluoroalkyl epoxides, fluoroalkyl halides, fluoroalkyl acrylates, fluoroalkyl methacrylates, fluoroalkyl carboxylates (including acid anhydrides and esters), etc. Among them, fluoroalkyl acrylate and fluoroalkyl methacrylate are preferable, and for example, a compound having a fluoroalkyl group having 4 or more carbon atoms selected from the compounds exemplified by the above general formula (3) can be used.

The number of fluoroalkyl groups in the fluorine compound does not have to be one, and the fluorine compound may have a plurality of fluoroalkyl groups.

The first hard coat layer preferably has high hardness in order to suppress damage to the surface of the hard coat film, and the pencil hardness defined in JIS K5600-5-4 (1999) is preferably H or higher. In addition, the upper limit of pencil hardness is about 9H.

The first hard coat layer preferably contains a thermosetting resin or an active energy ray-curable resin as the resin, and particularly preferably contains an active energy ray-curable resin. Here, the active energy ray-curable resin refers to a resin polymerized and cured by active energy rays such as ultraviolet rays and electron rays.

Examples of polymerizable compounds for obtaining active energy ray-curable resins include polymerizable functional groups such as acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, vinyl, and allyl. Compounds (monomers, oligomers).

The first hard coat layer is preferably formed by applying an active energy ray-curable composition containing the polymerizable compound by a wet coating method, drying if necessary, and then irradiating the active energy ray for curing.

Although the polymeric compound (monomer, oligomer) is illustrated below, it is not limited to these compounds. In addition, in the following description, the expression "... (meth)acrylate" includes both compounds of "... acrylate" and "... methacrylate".

Examples of monomers include methyl (meth)acrylate, lauryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, Phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) Monofunctional acrylates such as 2-hydroxypropyl acrylate and 2-hydroxy-3-phenoxy (meth)acrylate, 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, di Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol hexa(meth)triacrylate, Multifunctional acrylates such as trimethylolpropane (meth)acrylate benzoate, trimethylolpropane benzoate, glycerol di(meth)acrylate hexamethylene diisocyanate, pentaerythritol tri( Urethane acrylate such as meth)acrylate hexamethylene diisocyanate, etc.

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

Examples of oligomers include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyether (meth)acrylate, alkyd (meth)acrylate Acrylates, Melamine (meth)acrylates, Silicone (meth)acrylates, etc.

Among the above oligomers, a polyfunctional urethane (meth)acrylate oligomer having three or more polymerizable functional groups in one molecule can be preferably used. Commercially available products can be used for the polyfunctional urethane (meth)acrylate oligomer. Examples include urethane acrylate AH series, urethane acrylate AT series, and urethane acrylate UA series manufactured by Kyoeisha Chemical Co., Ltd., and UN- 3320 series, UN-900 series, NK ORIGO U series manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Ebecryl 1290 series manufactured by DAICEL UCB Co., Ltd., etc.

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 even more preferably 60% by mass relative to 100% by mass of the total solid content of the active energy ray-curable composition. % by mass or more, particularly preferably 70% by mass or more. The upper limit is preferably 97% by mass or less, more preferably 95% by mass or less.

When ultraviolet rays are used as the active energy rays, the active energy ray-curable composition preferably contains a photopolymerization initiator. As specific examples of the photopolymerization initiator, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone , 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzil, benzoin, benzoin Indium methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoylformate, p-isopropyl-α-hydroxyisobutyl benzophenone, α-hydroxyisobutyl benzophenone, Carbonyl compounds such as 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone , 2-chlorothioxanthone, 2-methylthioxanthone and other sulfur compounds. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, photoinitiators are usually commercially available, and those commercially available can be used. For example, IRGACURE (registered trademark) 184, IRGACURE 907, IRGACURE 379, IRGACURE 819, IRGACURE 127, IRGACURE 500, IRGACURE 754, IRGACURE 250, IRGACURE1800, IRGACURE 1870, IRGACURE OXE01, DAROCURE manufactured by Ciba Specialty Chemicals Co., Ltd. , DAROCUR 1173, etc., Speedcure MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Esacure ONE, Esacure KIP150, Esacure KTO46, etc. manufactured by Nihon Siber Hegner Co., Ltd., KAYACURE DETX-S, KAYACURE manufactured by Nippon Kayaku Co., Ltd. CTX, KAYACURE BMS, KAYACURE DMBI, etc.

The range of content of the said photoinitiator is suitably the range of 0.1-10 mass % with respect to 100 mass % of total solid content of an active energy ray-curable composition, Preferably it is the range of 0.5-8 mass %.

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 protrusions on the surface of the first hard-coat layer. As the particles, those subjected to surface treatment or hydrophobization treatment as described above can be preferably used. The content of the particles in the active energy ray-curable composition is preferably in the range of 2.5 to 17% by mass, more preferably 3 to 15% by mass, based on 100% by mass of the total solid content of the active energy ray-curable composition. The range is particularly preferably in the range of 4 to 12% by mass.

The range of the refractive index of a 1st hard-coat layer becomes like this. Preferably it is the range of 1.48-1.54, More preferably, it is the range of 1.50-1.54. The first hard coat layer having a refractive index in the range of 1.48 to 1.54 can be obtained by applying the above-mentioned active energy ray-curable composition by a wet coating method, drying if necessary, and then irradiating the active energy ray , to be cured to form a first hard coat layer.

Regarding the range of the thickness of the first hard coat layer, the range of 0.5 μm or more and less than 10 μm is suitable, but it is preferably the range of 0.8 μm or more and 7 μm or less, more preferably the range of 1 μm or more and 5 μm or less, particularly preferably 1 μm Above and below 3 μm.

When the thickness of the first hard coat layer is less than 0.5 μm, the hardness of the first hard coat layer is lowered, and scratches tend to be introduced. In addition, when the thickness of the first hard coat layer is 10 μm or more, disadvantages such as lowered sliding properties and blocking resistance, increased curl, lowered transmittance, etc. may occur.

[Hard Coating]

The hard coat film has a 1st hard coat layer on at least one surface of a base film. The hard coat film may have the first hard coat layer on only one side of the base film, or may have the first hard coat layer on both sides of the base film.

In addition, as another preferred embodiment of the hard coat film, there are provided a first hard coat layer on one side of the base film, and a first hard coat layer on the other side of the base film (that is, between the side of the base film and the first hard coat layer). The surface opposite to the coating layer) has a hard coat film of the second hard coat layer.

It should be noted that even when the second hard coat layer laminated on the other side of the base film adopts the same configuration as the first hard coat layer laminated on one side of the base film (that is, in When laminating a 1st hard-coat layer on both surfaces of a base film, respectively), it may also be called a 2nd hard-coat layer in order to distinguish it from the 1st hard-coat layer on one surface.

[the second hard coat]

Hereinafter, the 2nd hard-coat layer provided on the other surface of a base film is demonstrated.

The second hard coat layer preferably has high hardness in order to suppress damage to the surface of the hard coat film, and the pencil hardness defined in JIS K5600-5-4 (1999) is preferably H or higher, more preferably 2H or higher. In addition, 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 centerline 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 actually about 1 nm.

For the second hard coat layer, it is preferable that the second hard coat layer does not substantially contain particles having an average particle diameter larger than 0.5 μm in order to make the centerline average roughness (Ra2) of the surface of the second hard coat layer 25 nm or less. Here, the term that the second hard coat layer does not substantially contain particles having an average particle diameter larger than 0.5 μm means that particles that are not intentionally added to the coating liquid (for example, an active energy ray-curable composition) for forming the second hard coat layer ) to add particles with an average particle size greater than 0.5 μm.

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 does not substantially have protrusions due to particles. Here, the fact that the surface of the second hard coat layer does not substantially have protrusions due to particles means that the number of protrusions per unit area (100 μm ² ) of the surface of the second hard coat layer is 100 or less. The number of protrusions per unit area (100 μm ² ) of the surface of the second hard coat layer is preferably 50 or less, more preferably 30 or less, particularly preferably 0.

The second hard coat layer may contain particles having an average particle diameter of 0.5 μm 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 μm or less, more preferably 0.1 μm or less. Regarding the range of the content of the particles as described above, it is appropriate to be in the range of 0.1 to 15% by mass, more preferably in the range of 0.5 to 10% by mass, and particularly preferably It is the range of 1-8 mass %.

The second hard coat layer preferably contains a thermosetting resin or an active energy ray-curable resin as the resin, and particularly preferably contains an active energy ray-curable resin. Here, the active energy ray-curable resin refers to a resin polymerized and cured by active energy rays such as ultraviolet rays and electron rays.

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

Like the first hard coat layer, the second hard coat layer is preferably formed by applying an active energy ray-curable composition containing a polymerizable compound by a wet coating method, drying if necessary, and then irradiating an active energy ray for curing. Thus formed.

The range of the refractive index of a 2nd hard-coat layer becomes like this. Preferably it is the range of 1.48-1.54, More preferably, it is the range of 1.50-1.54. The second hard coat layer having a refractive index in the range of 1.48 to 1.54 can be obtained by applying the above-mentioned active energy ray-curable composition by a wet coating method, drying if necessary, and then irradiating the active energy ray , to be cured to form a second hard coat layer.

Regarding the range of the thickness of the second hard coat layer, the range of 0.5 μm or more and less than 10 μm is suitable, but it is preferably the range of 0.8 μm or more and 7 μm or less, more preferably the range of 1 μm or more and 5 μm or less, particularly preferably 1 μm Above and below 3 μm.

When the thickness of the second hard-coat layer is less than 0.5 μm, the hardness of the second hard-coat layer decreases, and scratches tend to be introduced. Moreover, when the thickness of a 2nd hard-coat layer becomes 10 micrometers or more, the following troubles, such as a slide property and anti-blocking property fall, curl becoming large, or a transmittance fall, etc. may generate|occur|produce.

In order to enhance the adhesiveness between the base film and the second hard coat layer, it is preferable that the resin layer is present between the base film and the second hard coat layer.

[Transparent conductive film]

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

The transparent conductive film may be laminated on only one surface of the hard coat film, or may be laminated on both surfaces.

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

i) 1st hard coat layer/resin layer/substrate film/resin layer/1st hard coat layer/transparent conductive film

ii) Transparent conductive film/1st hard coat layer/resin layer/substrate film/resin layer/1st hard coat layer/transparent conductive film

iii) 1st hard coat layer/resin layer/substrate film/resin layer/2nd hard coat layer/transparent conductive film

iv) Transparent conductive film/1st hard coat layer/resin layer/substrate film/resin layer/2nd hard coat layer

v) Transparent conductive film/1st hard coat layer/resin layer/substrate film/resin layer/2nd hard coat layer/transparent conductive film

Among the above configuration examples, i) or iii) is preferable. That is, from the viewpoint of ensuring the sliding properties and blocking resistance of the hard coat film in the lamination process of the transparent conductive film and the processing process, the transparent conductive film is not laminated on the first hard coat layer on one side, and the transparent conductive film is made in advance. It is preferable that the first hard coat layer is exposed.

Furthermore, it is more preferable that the hard coat layer on the surface where the transparent conductive film is laminated is relatively smooth and clear. Therefore, in the configuration example of iii), the centerline 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. By making the surface of the hard coat layer (for example, the second hard coat layer) on the surface where the transparent conductive film is laminated as described above relatively smooth and clear, the transparency of the transparent conductive film is improved, which is preferable.

[Transparent Conductive Film]

Examples of materials 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), metal nanowires (such as silver nano wires), carbon nanotubes. Among them, ITO can be preferably used.

From the viewpoint of ensuring good electrical conductivity with a surface resistance value of 10 ³ Ω/□ or less, the thickness of the transparent conductive film is preferably 10 nm or more, more preferably 15 nm or more, particularly preferably 20 nm or more. On the other hand, if the thickness of the transparent conductive film becomes too large, there may be disadvantages such as strong color feeling (coloring) and reduced transparency. Therefore, the upper limit of the thickness of the transparent conductive film is preferably 60 nm or less. It is preferably 50 nm or less, particularly preferably 40 nm or less.

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

The transparent conductive film formed as above can be patterned. Regarding patterning, various patterns can be formed according to the application to which the transparent conductive film is applied. In addition, a pattern part and a non-pattern part are formed by patterning a transparent conductive film, and as a shape of a pattern part, a stripe shape, a lattice shape, etc. are mentioned, for example.

Patterning of a transparent conductive film is usually performed by etching. For example, a patterned resist film is formed on a transparent conductive film by a photolithography method, a laser exposure method, or a printing method, and then an etching treatment is performed to pattern the transparent conductive film. After the transparent conductive film is patterned, the resist film can be stripped and removed with an alkaline aqueous solution.

As the etchant, conventionally known etchant can be used. For example, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and phosphoric acid, organic acids such as acetic acid, mixtures thereof, and aqueous solutions thereof can be used.

Examples of alkaline aqueous solutions that can be used for stripping and removing the resist film include 1 to 5% by mass sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, and the like.

[Refractive index adjustment layer]

In the configuration examples of the above-mentioned transparent conductive film, the transparent conductive film may be directly laminated on the first hard coat layer or the second hard coat layer, but it is preferable to laminate the transparent conductive film on the first hard coat layer or the second hard coat layer. There is a refractive index adjustment layer in between. Hereinafter, the refractive index adjustment layer will be described.

The refractive index adjustment layer may consist of only one layer, or may consist of a laminate of two or more layers. The refractive index adjustment layer is a layer having the function of adjusting the reflection color and transmission color of the transparent conductive film laminated thereon, or suppressing the so-called "pattern visibility (in Japanese: bone see え)" (which means that the pattern part of the patterned transparent conductive film can be visually recognized).

As the structure of the refractive index adjustment layer, for example, a single-layer structure of a high-refractive-index layer with a refractive index (n1) of 1.60 to 1.80, a single-layer structure of a low-refractive-index layer with a refractive index (n2) of 1.30 to 1.53, Or the lamination structure of the said high-refractive-index layer and the low-refractive-index layer (the low-refractive-index layer is arrange|positioned at the transparent conductive film side), etc.

The range of the refractive index (n1) of the said high refractive index layer is more preferably the range of 1.63-1.78, More preferably, it is the range of 1.65-1.75. The refractive index (n2) of the low refractive index layer is more preferably in the range of 1.30 to 1.50, more preferably in the range of 1.30 to 1.48, particularly preferably in the range of 1.33 to 1.46.

The thickness of the refractive index adjusting layer (total thickness in the case of a laminated structure of plural layers) is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 120 nm or less, most preferably 100 nm or less. The lower limit of the thickness 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 already patterned, it is preferable that the refractive index adjustment layer has a laminated structure of a high refractive index layer and a low refractive index layer from the viewpoint of suppressing "pattern visibility". In this case, the sum (nm) of the optical thickness of the high refractive index layer and the optical thickness of the low refractive index layer preferably satisfies (1/4)λ(nm). Here, the optical thickness (nm) is the product of the refractive index and the actual layer thickness (nm), and λ is the wavelength range of the visible light region, that is, 380 to 780 (nm).

In this specification, 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)λ(nm) and means that the following formula 1 is satisfied. It should be noted that, 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 ).

(380nm/4)≤(n1×d1)+(n2×d2)≤(780nm/4)

95nm≤(n1×d1)+(n2×d2)≤195nm (Formula 1)

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

Furthermore, the range of the sum 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, 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 with a refractive index of 1.65 or more by a wet coating method, drying if necessary, and then irradiating active energy rays to cure. This formation. Here, the active energy ray-curable composition is a composition containing a polymerizable compound and a photopolymerization initiator as described in the above-mentioned first hard coat layer.

Examples of metal oxide fine particles include metal oxide particles of titanium, zirconium, zinc, tin, antimony, cerium, iron, indium, and the like. Specific examples of metal oxide particles include titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonate, tin oxide-doped indium oxide (ITO), antimony-doped Doped tin oxide (ATO), phosphorus-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, fluorine-doped tin oxide, etc. These metal oxide fine particles may be used alone or in combination. Among the above-mentioned metal oxide fine particles, titanium oxide and zirconium oxide are particularly preferable since 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 at least 30% by mass, more preferably at least 40% by mass, particularly preferably at least 100% by mass of the solid content of the active energy ray-curable composition More than 50% by mass. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

The low-refractive-index layer can be formed, for example, by applying an active energy ray-curable composition containing low-refractive-index inorganic particles and/or a fluorine-containing compound as a low-refractive-index material by a wet coating method, drying if necessary, and irradiating active energy. rays, which solidify and thus form. Here, the active energy ray-curable composition is a composition containing a polymerizable compound and a photopolymerization initiator as described in the above-mentioned first hard coat layer.

As the low refractive index inorganic particles, inorganic particles such as silica and magnesium fluoride are preferable. Furthermore, these inorganic particles are preferably hollow or porous particles. The content of the aforementioned low-refractive-index inorganic particles is preferably 10% by mass or more, more preferably 20% by mass or more, 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% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less.

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

Examples of fluorine-containing monomers and fluorine-containing oligomers include 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-penta(meth)acrylate Fluoropropyl ester, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl)(meth)acrylate ) ethyl ester, (meth)acrylate-2-(perfluorodecyl)ethyl ester, (meth)acrylate-β-(perfluorooctyl)ethyl ester and other fluorine-containing (meth)acrylates, di( α-fluoroacrylic acid)-2,2,2-trifluoroethyl ethylene glycol ester, bis(α-fluoroacrylic acid)-2,2,3,3,3-pentafluoropropyl ethylene glycol ester, bis( α-fluoroacrylic acid)-2,2,3,3,4,4,4-heptafluorobutyl glycol ester, bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5 , 5,5-nonafluoropentyl glycol ester, bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,6-undecafluorohexylethylene di Alcohol ester, bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl glycol ester, bis(α -fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl glycol ester, di(α-fluoro Acrylic acid)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl glycol ester, bis(α-fluoroacrylic acid)-2,2 , 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 9-heptadecafluorononyl glycol ester and other di(α-fluoroacrylic acid) fluoroalkanes base esters.

As a fluorine-containing high molecular compound, the fluorine-containing copolymer which uses a fluorine-containing monomer and the monomer for imparting a crosslinkable group as a structural unit is mentioned, for example. Specific examples of fluorine-containing monomer units include, for example, fluoroolefins (such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -dioxole, etc.), partially or fully fluorinated alkyl ester derivatives of (meth)acrylic acid (such as Viscoat 6FM (manufactured by Osaka Organic Chemicals), M-2020 (manufactured by DAIKIN), etc.), completely or Partially fluorinated vinyl ethers, etc. As a monomer for imparting a crosslinkable group, in addition to a (meth)acrylate monomer having a crosslinkable functional group in the molecule such as glycidyl methacrylate, there are carboxyl, hydroxyl, , amino group, sulfonic acid group, etc. (meth)acrylate monomers (such as (meth)acrylic acid, hydroxymethyl (meth)acrylate, hydroxyalkyl (meth)acrylate, allyl acrylate, etc.).

The content of the fluorine-containing compound is preferably 30% by mass or more, more preferably 40% by mass or more, 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% by mass or less, more preferably 90% by mass or less, particularly preferably 80% by mass or less.

Among fluorine-containing compounds, fluorine-containing monomers and fluorine-containing oligomers can be preferably used. Since fluorine-containing monomers and fluorine-containing oligomers have polymerizable functional groups in their molecules, they contribute to the formation of a dense crosslinked structure of the low-refractive index layer, and can achieve a low refractive index.

[touch panel]

A transparent conductive film using the hard coat film of this embodiment as a base film can be preferably used as one of the constituent members of a touch panel.

Generally, a resistive touch panel has a structure in which upper electrodes and lower electrodes are arranged with a spacer plate interposed therebetween, and a transparent conductive film using the hard coat film of this embodiment as a base film can be used for the upper electrodes and lower electrodes. either or both of them.

In addition, capacitive touch panels are generally composed of patterned X electrodes and Y electrodes, and the transparent conductive film using the hard coat film of this embodiment as a base film can be used for either or both of the X electrodes and Y electrodes. square.

Transparent conductive films used in touch panels are required to have good transparency and processability (slidability, blocking resistance), and transparent conductive films using the hard coat film of this embodiment as a base film can fully satisfy the above characteristics .

Example

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples. In addition, the measurement method and evaluation method in this Example are as follows.

(1) Measurement of the refractive index of each layer

Each coating solution was coated on a silicon wafer using a spin coater to form a coating film (dry thickness of about 2 μm), and the resulting coating film was tested using a phase difference measuring device (Nikon Co., Ltd.) at a temperature of 25°C. ) system: NPDM-1000) to measure the refractive index at 589 nm.

In addition, the refractive index of the base film (PET film) was measured at 589 nm using an Abbe refractometer according to JIS K7105 (1981).

(2) Measurement of the thickness of the resin layer

Cut the cross _- section of the substrate film laminated with the resin layer into _ultrathin sections, and use TEM (transmission electron microscope) to observe the The cross-sectional structure was visually observed under the following conditions, and the thickness of the resin layer was measured from the cross-sectional photograph. In addition, the measurement site is a part where no particle exists. In addition, it measured about 5 places, and made the average value into the thickness of a resin layer.

・Measuring device: Transmission electron microscope (H-7100FA manufactured by Hitachi, Ltd.)

·Measurement conditions: accelerating voltage 100kV

·Specimen adjustment: Frozen ultrathin section method

Magnification: 300,000 times

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

The cross section of the hard coat film was cut into ultrathin sections, observed with an accelerating voltage of 100 kV using a TEM (transmission electron microscope) (observed at a magnification of 1 to 300,000 times), and the thickness was measured from the cross-sectional photograph. In addition, for the layer which has a protrusion on the surface like a 1st hard-coat layer, it is the thickness of the part which does not have a protrusion. The measurement of thickness was performed at 5 places, and the average value was made into thickness.

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

Use TEM (transmission electron microscope) to observe (approximately 10,000 to 100,000 times) the cross-section of the first hard coat layer, and measure the maximum length of each of 30 randomly selected particles from the cross-sectional photograph, average them, and obtain The value is taken as the average particle size.

(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 is observed at a magnification of 10,000 times using a SEM (scanning electron microscope), and the image of the particles (the depth of light brought by the particles) is connected to an image analyzer (such as CAMBRIDGE INSTRUMENT Co., Ltd. QTM900), change the observation site, read the data, and perform the following numerical processing when the total number of particles becomes 5000 or more, and use the number average particle diameter d obtained therefrom as the average particle diameter (diameter).

d=∑di/N

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

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

Based on JIS B0601 (1982), the measurement was performed using a stylus type surface roughness measuring instrument SE-3400 (manufactured by Kosaka Laboratories).

<Measurement conditions>

Transmission speed: 0.5mm/s

Evaluation length: 8mm

Cutoff value (cutoff value) λc: 0.08mm

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

Prepare a cut sample (20 cm × 15 cm) of the hard coat film, use a SEM (scanning electron microscope) to photograph (about 10,000 to 100,000 times) the first hard coat surface of the cut sample at 5 places, and make 5 images ( surface photo). Then, for each of the 5 images, the number of protrusions existing in the square with a side length of 1 μm (area 1 μm ² ) or a square with a side length of 2 μm (area 4 μm ² ) in the image was counted, and converted to an area of 100 μm ² The number of , take the average value. It should be noted that the area for measuring the number of protrusions can be appropriately changed according to the imaging magnification.

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

The surface of the 1st hard-coat layer of a hard-coat film is photographed (about 10,000 to 100,000 magnifications) using SEM (scanning electron microscope), and an image (surface photograph) is created. Then, the diameter (maximum length) of 30 protrusions randomly selected from the image was measured, and the average value was taken.

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

Prepare a cut sample (20cm×15cm) of the hard coat film, and use a SEM (scanning electron microscope) to photograph (approximately 10,000 to 100,000 times) the cross section of the first hard coat layer of the cut sample at 5 places, and make 5 cross-sectional photos . Then, the heights of all the protrusions present in the five cross-sectional photographs were measured and averaged.

(10) Average spacing of protrusions

The surface of the 1st hard-coat layer of a hard-coat film is photographed (about 10,000-100,000 times) using SEM (scanning electron microscope), and an image (surface photograph) is created. In this image, one perpendicular straight line is drawn horizontally and vertically. Then, the distance between adjacent protrusions was measured for all the protrusions falling on one straight line in the lateral direction (contacting the straight line). The same operation is performed on one straight line in the vertical direction. The position of the horizontal straight line and the position of the vertical straight line were changed three times, the above operation was performed, and all the obtained protrusion intervals were averaged.

(11) Determination of hard coating film

Based on JIS K 7136 (2000), it measured using the nephelometer "NDH-2000" by Nippon Denshoku Kogyo Co., Ltd.. At the time of measurement, it arrange|positions so that light may enter the surface of the hard-coat film opposite to the 1st hard-coat layer (namely, the surface on which the 2nd hard-coat layer was provided).

(12) Total light transmittance of hard coating film

Based on JIS-K7361 (1997), it measured using the nephelometer NDH2000 (made by Nippon Denshoku Industries Co., Ltd.).

(13) Visual evaluation of reflection color of hard coat film

Stick a black adhesive tape ("Vinyl Tape No.21 Special Black" manufactured by Nitto Denko) on the second hard coat surface of the hard coat film, and visually observe the first hard coat layer under a three-wavelength fluorescent lamp in a dark room The reflection color of the surface was evaluated according to the following criteria.

Similarly, a black adhesive tape ("Vinyl Tape No. 21 Special Black" manufactured by Nitto Denko) was attached to the first hard coat surface of the hard coat film, and the second hard coat was visually observed under a three-wavelength fluorescent lamp in a dark room. The reflection color of the coating surface was evaluated according to the following criteria.

A: The reflection color is neutral and almost colorless.

C: The reflection color exhibits coloration.

(14) Evaluation of sliding properties

The hard coat film was cut, and two sheet pieces (20 cm x 15 cm) were produced. Slightly stagger the two sheets in such a way that the first hard-coat surface of the two sheets is opposite to the second hard-coat surface, and place them on a smooth stage one by one. Fix it on the stage, slide the upper sheet by hand, and judge whether the sliding property is good or bad. The measurement environment was 23° C. and 55% RH.

A: Slidability of the upper sheet is good.

B: The slipperiness of the upper sheet sheet is poor, but still relatively good.

C: The upper sheet piece does not slide.

(15) Evaluation of blocking resistance

The hard coat film was cut, and two sheet pieces (20 cm x 15 cm) were produced. These two sheets were stacked so that the 1st hard-coat surface and the 2nd hard-coat surface faced. Then, the sample obtained by stacking two sheet pieces was sandwiched between glass plates, a weight of about 3 kg was placed, and it was left to stand in an atmosphere of 50° C. and 90% (RH) for 48 hours. Then, after confirming the state of occurrence of Newton rings by visually observing the overlapping surface, both were peeled off and evaluated according to the following criteria.

A: No Newton rings were generated before peeling, and peeling was performed lightly without generating a peeling sound.

B: Newton's rings were generated in the part before peeling, and a small peeling sound was generated during peeling, and peeled.

C: Newton's rings were generated on the entire surface before peeling, and a loud peeling sound was generated during peeling, resulting in peeling.

(16) Pencil hardness of the first and second hard coats

The surface of the 1st hard-coat layer and the surface of the 2nd hard-coat layer of a hard coat film were measured according to JISK5600-5-4 (1999), respectively. The load is 750g, and the speed is 30mm/min. As a measuring device, a surface hardness tester (HEIDON; model 14DR) manufactured by Shinto Scientific Co., Ltd. was used. The environment during the measurement is 23°C±2°C and the relative humidity is 55%±5%.

(17) Visual visibility of transparent conductive film pattern

The sample was placed on a black board, and whether the pattern part of a transparent conductive film can be visually recognized was evaluated by the following reference|standard.

A: The pattern part cannot be recognized visually.

C: The pattern part can be visually recognized.

(18) Determination of the wetting tension of the resin layer

The substrate film on which the resin layer was laminated was air-dried for 6 hours in a normal (23° C., 50% relative humidity) atmosphere, and measured in accordance with JIS-K-6768 (1999) in the same atmosphere.

<Coating solution for resin layer formation>

(Coating solution for resin layer formation a)

In terms of solid content mass ratio, 26% by mass of polyester resin a with a Tg (glass transition temperature) of 120°C, 54% by mass of polyester resin b with a Tg of 80°C, and 18% by mass of a melamine-based crosslinking agent , 2% by mass of the particles were mixed to prepare a water-dispersed coating solution.

・Polyester resin a: obtained by copolymerizing 43 mol% of 2,6-naphthalene dicarboxylic acid, 7 mol% of 5-sodium isophthalic acid, and 50 mol% of a diol component including ethylene glycol polyester resin

・Polyester resin b: Polyester resin obtained by copolymerizing 38 mol% of terephthalic acid, 12 mol% of trimellitic acid, and 50 mol% of a diol component including ethylene glycol

・Melamine-based crosslinking agent: "NIKALAC MW 12LF" manufactured by Sanwa Chemical Co., Ltd.

Particles: colloidal silica with an average particle size of 0.19 μm

(Coating liquid b for resin layer formation)

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

・Acrylic resin (acrylic resin formed from the following copolymer composition)

・Melamine-based crosslinking agent: "NIKALAC MW 12LF" manufactured by Sanwa Chemical Co., Ltd.

Particles: colloidal silica with an average particle size of 0.19 μm

<Surface-treated silica particle dispersion>

(Surface-treated silica particle dispersion A)

13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of colloidal silicon dioxide ("Organo Silica SolIPA-ST-ZL" manufactured by Nissan Chemical Industry Co., Ltd.) were mixed with 150 parts by mass of 10% by mass of formic acid aqueous solution was stirred at 70° C. for 1 hour. Then, after adding 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, it was heated and stirred at 90°C. After 60 minutes, a dispersion liquid was obtained.

(Surface-treated silica particle dispersion B)

13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of colloidal silicon dioxide ("Organo Silica SolIPA-ST-ZL" manufactured by Nissan Chemical Industry Co., Ltd.) were mixed with 150 parts by mass of 10% by mass of formic acid aqueous solution was stirred at 70° C. for 1 hour. Then, as a hydrophobic compound, 9 parts by mass of a fluorine compound (H ₂ C=CH-COO-CH ₂ -(CF ₂ ) ₈ F) and 4.8 parts by mass of a siloxane compound (Dainippon Ink Chemical Industry Co., Ltd. "PC-4131" manufactured by the manufacturer) and 0.57 parts by mass of 2,2-azobisisobutyronitrile, followed by heating and stirring at 90° C. for 60 minutes to obtain a dispersion liquid.

(Surface-treated silica particle dispersion C)

To 330 parts by mass of colloidal silicon dioxide ("Organo Silica SolIPA-ST-ZL" manufactured by Nissan Chemical Industry Co., Ltd.), 8 parts by mass of acryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. )), 2 parts by mass of tridecafluorooctyltrimethoxysilane (manufactured by GE Toshiba Silicone Co., Ltd.), and 1.5 parts by mass of diisopropoxy aluminum ethyl acetate were mixed , and then add 9 parts by mass of ion-exchanged water. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, and added 1.8 mass parts of acetylacetones. Then, adding cyclohexanone to the dispersion liquid, the solvent was replaced by vacuum distillation at a pressure of 20 kPa to obtain a dispersion liquid.

(Surface-treated silica particle dispersion D)

To 150 parts by mass of colloidal silica ("Organo Silica SolMEK-ST-2040" manufactured by Nissan Chemical Industry Co., Ltd.), 13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of 10% by mass of formic acid aqueous solution was stirred at 70° C. for 1 hour. Then, after adding 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, it was heated and stirred at 90°C. After 60 minutes, a dispersion was obtained.

(Surface-treated silica particle dispersion E)

13.7 parts by mass of methacryloxypropyltrimethoxysilane and 1.7 parts by mass of colloidal silica ("Organo Silica SolMEK-ST-L" manufactured by Nissan Chemical Industry Co., Ltd.) were mixed with 150 parts by mass of 10% by mass of formic acid aqueous solution was stirred at 70° C. for 1 hour. Then, after adding 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, it was heated and stirred at 90°C. After 60 minutes, a dispersion liquid was obtained.

[Example 1]

Prepare the hard coat film as follows.

<Production of resin layer laminated PET film>

On both surfaces of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 μm, resin layers were applied in-line in the production process of the PET film, respectively. That is, on both sides of the PET film uniaxially stretched in the longitudinal direction, the coating solution a for forming a resin layer was coated by a bar coating method, dried at 100° C., and then biaxially stretched in the width direction. It heat-processed at 230 degreeC for 20 second, it was made to heat-cure, and the PET film which laminated|stacked the resin layer on both surfaces was produced. The resin layers laminated on both surfaces of the PET film had a refractive index of 1.59 and a thickness of 0.09 μm.

<Lamination of 1st and 2nd hard coat layers>

On the resin layer of one side of the PET film laminated with the resin layer on both sides, the following active energy ray-curable composition a was coated by the gravure coating method, dried at 90°C, and then irradiated with ultraviolet rays at 400mJ/ ^cm2 for This is cured to form a first hard coat layer. The first hard coat layer had a thickness of 2.6 μm and a refractive index of 1.51.

Then, on the resin layer on the other side of the PET film (the side opposite to the side on which the first hard coat layer was laminated), the active energy ray-curable composition a was also used to form the second hard coat layer in the same manner as above. Coating, making hard coating film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.51.

<Active energy ray-curable composition a>

50 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), and a surface-treated silica particle dispersion having a solid content of 8 parts by mass A, 5 mass parts of photoinitiators ("IRGACURE 184" by Ciba Specialty Chemicals Co., Ltd.) were mixed with the organic solvent (methyl ethyl ketone), and it prepared.

[Example 2]

Except having changed the 2nd hard coat layer into the following active energy ray-curable composition b, it carried out similarly to Example 1, and produced the hard coat film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.52.

<Active Energy Ray Curable Composition b>

48 parts by mass of dipentaerythritol hexaacrylate, 47 parts by mass of urethane acrylate oligomer ("UN-901T" of Negami Industry Co., Ltd.; contains 9 polymerizable functional groups in the molecule), 5 parts by mass A photopolymerization initiator ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was dispersed and dissolved in an organic solvent (methyl ethyl ketone), and prepared.

[Example 3]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition c, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active energy ray curable composition c>

87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of surface-treated silica particle dispersion B in terms of solid content, and 5 parts by mass of a photopolymerization initiator ("IRGACURE" manufactured by Ciba Specialty Chemicals Co., Ltd.) 184") mixed in an organic solvent (methyl ethyl ketone) for preparation.

[Example 4]

Except having changed the 2nd hard coat layer into the said active energy ray curable composition b, it carried out similarly to Example 3, and produced the hard coat film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.52.

[Example 5]

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, a hard coat film was produced in the same manner as in Example 1. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active energy ray curable composition d>

87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of surface-treated silica particle dispersion C in terms of solid content, and 5 parts by mass of a photopolymerization initiator ("IRGACURE" manufactured by Ciba Specialty Chemicals Co., Ltd.) 184") by dispersing and dissolving in an organic solvent (a mixed solvent with a mass ratio of methyl ethyl ketone and cyclohexanone of 8:2) for preparation.

[Example 6]

Except having changed the 2nd hard coat layer into the said active energy ray curable composition b, it carried out similarly to Example 5, and produced the hard coat film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.52.

[Example 7]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition e, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active energy ray-curable composition e>

50 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), and a surface-treated silica particle dispersion having a solid content of 8 parts by mass D. 5 parts by mass of a photopolymerization initiator (“IRGACURE 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed with an organic solvent (methyl ethyl ketone), and prepared.

[Example 8]

Except having changed the 2nd hard coat layer into the said active energy ray curable composition b, it carried out similarly to Example 7, and produced the hard coat film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.52.

[Example 9]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition f, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active Energy Ray Curable Composition f>

50 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), and a surface-treated silica particle dispersion having a solid content of 8 parts by mass E. 5 parts by mass of a photopolymerization initiator (“IRGACURE 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed with an organic solvent (methyl ethyl ketone), and prepared.

[Example 10]

Except having changed the 2nd hard coat layer into the said active energy ray curable composition b, it carried out similarly to Example 9, and produced the hard coat film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.52.

[Comparative example 1]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition g, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active energy ray-curable composition g>

87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of silica particles ("Organo Silica Sol IPA-ST-ZL" manufactured by Nissan Chemical Industry Co., Ltd.) in terms of solid content, 5 parts by mass of photopolymerized An initiator ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was dispersed and dissolved in an organic solvent (a mixed solvent of methyl ethyl ketone and cyclohexanone in a mass ratio of 8:2), and prepared.

[Comparative example 2]

Except having changed the 2nd hard coat layer into the said active energy ray-curable composition b, it carried out similarly to the comparative example 1, and produced the hard coat film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.52.

[Comparative example 3]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition h, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.52.

<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 Co., Ltd.) in terms of solid content, 5 parts by mass of photopolymerization initiator An agent ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was dispersed and dissolved in an organic solvent (a mixed solvent with a mass ratio of methyl ethyl ketone and cyclohexanone of 8:2), and prepared.

[Comparative example 4]

Except having changed the 2nd hard coat layer into the said active energy ray curable composition b, it carried out similarly to the comparative example 3, and produced the hard coat film. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.52.

[Example 11]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition i, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active energy ray-curable composition i>

54 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), and a surface-treated silica particle dispersion having a solid content of 4 parts by mass A, 5 mass parts of photoinitiators ("IRGACURE 184" by Ciba Specialty Chemicals Co., Ltd.) were mixed with the organic solvent (methyl ethyl ketone), and it prepared.

[Example 12]

Except having changed the active energy ray-curable composition used for forming the 1st and 2nd hard coat layer into the following active energy ray-curable composition j, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active energy ray-curable composition j>

52 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), and a surface-treated silica particle dispersion of 6 parts by mass in terms of solid content A, 5 mass parts of photoinitiators ("IRGACURE 184" by Ciba Specialty Chemicals Co., Ltd.) were mixed with the organic solvent (methyl ethyl ketone), and it prepared.

[Example 13]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition k, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<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.), and 10 parts by mass of the surface-treated silica particle dispersion in terms of solid content A, 5 mass parts of photoinitiators ("IRGACURE 184" by Ciba Specialty Chemicals Co., Ltd.) were mixed with the organic solvent (methyl ethyl ketone), and it prepared.

[Example 14]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition 1, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active Energy Ray Curable Composition 1>

50 parts by mass of dipentaerythritol hexaacrylate, 33 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), and a surface-treated silica particle dispersion having a solid content of 12 parts by mass A. 5 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed with an organic solvent (methyl ethyl ketone), and prepared.

[Comparative Example 5]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard-coat layer into the following active-energy ray-curable composition m, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<Active energy ray-curable composition m>

56 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("ARONIX M111" manufactured by Toagosei Co., Ltd.), and a surface-treated silica particle dispersion of 2 parts by mass in terms of solid content A, 5 mass parts of photoinitiators ("IRGACURE 184" by Ciba Specialty Chemicals Co., Ltd.) were mixed with the organic solvent (methyl ethyl ketone), and it prepared.

[Comparative Example 6]

Except having changed the active energy ray-curable composition for forming a 1st and 2nd hard coat layer into the following active energy ray-curable composition n, it carried out similarly to Example 1, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

<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.), and a surface-treated silica particle dispersion liquid of 20 parts by mass in terms of solid content A, 5 mass parts of photoinitiators ("IRGACURE 184" by Ciba Specialty Chemicals Co., Ltd.) were mixed with the organic solvent (methyl ethyl ketone), and it prepared.

[Comparative Example 7]

In the production of the resin layer-laminated PET film of Example 1, except that the coating liquid for forming a resin layer was changed to the coating liquid b for forming a resin layer, it was performed in the same manner as in Example 1, and a PET film laminated with resin layers on both sides. Each of the resin layers laminated on both surfaces of the PET film had a refractive index of 1.52 and a thickness of 0.09 μm.

<Lamination of 1st and 2nd hard coat layers>

On the PET film laminated with the above-mentioned resin layer, it carried out similarly to the comparative example 5, laminated|stacked the 1st and 2nd hard coat layers, and produced the hard coat film. Both the first and second hard coat layers had a thickness of 2.6 μm, and both had a refractive index of 1.51.

[Evaluation of hard coat film]

Table 1 shows the configurations of the first and second hard coat films of the hard coat films of Examples and Comparative Examples obtained by the above operation, and Table 2 shows the evaluation results of these hard coat films.

Moreover, the average diameter, average height, and average interval of the protrusion on the surface of the 1st hard-coat layer were measured about the representative sample in the said Example and the comparative example. The results are shown in Table 3.

[table 3]

From the above results, it can be concluded that in Examples 1 to 14, 300 to 10,000 protrusions per unit area (100 μm ² ) were formed on the surface of the first hard coat layer, so the sliding properties and blocking resistance were good. . In addition, the following conclusions can be drawn: the centerline 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 becomes small (less than 1.5%), and the transparency is good. Therefore, the total light transmittance is high.

[Examples 15-24]

On the second hard coat surface of the hard coat films of Examples 1 to 10, an ITO film as a transparent conductive film was laminated by the sputtering method so that the thickness of the ITO film would be 25 nm to produce a transparent conductive film. Slidability and blocking resistance were evaluated for these transparent conductive films. The results are shown in Table 4.

[Table 4]

Hard coating sliding Blocking resistance Example 15 Example 1 A A Example 16 Example 2 A A Example 17 Example 3 A A Example 18 Example 4 A A Example 19 Example 5 A A Example 20 Example 6 A A Example 21 Example 7 A A Example 22 Example 8 A A Example 23 Example 9 B B Example 24 Example 10 B B

It should be noted that, regarding the evaluation of the sliding properties and blocking resistance of the transparent conductive film, in the above "(14) Evaluation of sliding properties" and "(15) Evaluation of blocking resistance", the first hard The evaluation was performed in the same manner except that the coating surface was overlapped so as to face the transparent conductive film surface.

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

[Example 25-29]

On the second hard coat surface of the hard coat films of Examples 2, 4, 6, 8 and 10, the following high refractive index layer and low refractive index layer are laminated in sequence, and then the following high refractive index layer is formed on the low refractive index layer. Transparent conductive film, a transparent conductive film used in capacitive touch panels.

<Lamination of High Refractive Index Layer>

The following active energy ray-curable composition for forming a high refractive index layer was applied by gravure coating, dried at 90°C, and cured by irradiating ultraviolet rays at 400mJ/ ^cm2 to form a high refractive index layer with a thickness of 50nm. Floor. The refractive index of this high refractive index layer was 1.68.

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

21 parts by mass of dipentaerythritol hexaacrylate, 21 parts by mass of urethane acrylate oligomer ("UN-901T" of Negami Industry Co., Ltd.; contains 9 polymerizable functional groups in the molecule), 55 parts by mass Zirconia and 3 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) were dispersed or dissolved in an organic solvent (propylene glycol monomethyl ether), and prepared.

<Lamination of Low Refractive Index Layer>

The following active energy ray-curable composition for forming a low-refractive index layer was applied by gravure coating, dried at 90°C, and then cured by irradiating ultraviolet light at 400mJ/ ^cm2 to form a low-refractive-index layer with a thickness of 40nm. Floor. The low refractive index layer had a refractive index of 1.40.

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

87 parts by mass of bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro Nonyl glycol ester, 10 parts by mass of dipentaerythritol hexaacrylate, and 3 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) were dispersed or dissolved in an organic solvent (methyl ethyl ketone) , for preparation.

<Lamination of transparent conductive film>

The ITO film was laminated by the sputtering method so that the thickness of the ITO film was 25 nm, patterned (etched) into a lattice pattern, and a transparent conductive film was formed.

[Evaluation]

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

[table 5]

It should be noted that, regarding the evaluation of the sliding properties and blocking resistance of the transparent conductive film, in the above-mentioned "(14) Evaluation of sliding properties" and "(15) Evaluation of blocking resistance", the first hard The evaluation was performed in the same manner except that the coating surface was overlapped so as to face the transparent conductive film surface.

The transparent conductive films of Examples 25 to 29 all showed good slidability, blocking resistance, and visibility of the transparent conductive film pattern.

[Examples 31-40]

Five types of coating solutions for forming a resin layer having different wetting tensions were prepared as shown below.

(Coating liquid c for resin layer formation; Wetting tension 42mN/m)

In terms of solid mass ratio, 27% by mass of the following polyester resin c, 54% by mass of polyester resin d, 18% by mass of a melamine-based crosslinking agent, and 1% by mass of particles were mixed to prepare an aqueous dispersion coating liquid.

・Polyester resin c: Polyester resin composed of 2,6-naphthalene dicarboxylic acid 43 mol%/isophthalic acid-5-sodium sulfonate 7 mol%/ethylene glycol 45 mol%/diethylene glycol 5 mol% .

· Polyester resin d: a polyester resin composed of 38 mol % of terephthalic acid/12 mol % of trimellitic acid/45 mol % of ethylene glycol/5 mol % of diethylene glycol.

・Melamine-based crosslinking agent: "NIKALAC MW12LF" manufactured by Sanwa Chemical Co., Ltd.

· Particles: colloidal silica having an average particle diameter of 0.19 μm.

(Coating liquid d for resin layer formation; Wetting tension 44mN/m)

In terms of solid mass ratio, 42% by mass of the following polyester resin e, 42% by mass of acrylic resin a, 6% by mass of epoxy crosslinking agent, 9% by mass of surfactant, 1% by mass of The particles are mixed to prepare a water-dispersed coating solution.

・Polyester resin e: 35 mol% of terephthalic acid/11 mol% of isophthalic acid/4 mol% of isophthalic acid-5-sodium sulfonate/45 mol% of ethylene glycol/4 mol% of diethylene glycol A polyester resin composed of 1 mol% polyethylene glycol (number of repeating units n = 23).

Acrylic resin a: 75 mol% of methyl methacrylate/18 mol% of ethyl acrylate/4 mol% of N-methylolacrylamide/methoxypolyethylene glycol (number of repeating units n=10) methyl An acrylic resin composed of 3 mol% of acrylate.

Epoxy crosslinking agent: 1,3-bis(N,N-diglycidylamine)cyclohexane

Surfactant: polyoxyethylene lauryl ether

· Particles: colloidal silica having an average particle diameter of 0.19 μm.

(Coating liquid e for resin layer formation; Wetting tension 48mN/m)

In terms of solid mass ratio, 40% by mass of the following polyester resin f, 40% by mass of acrylic resin b, 10% by mass of melamine crosslinking agent, 9% by mass of surfactant, 1% by mass of particles Mix to prepare a water-dispersed coating solution.

Polyester resin f: 30 mol% of terephthalic acid/15 mol% of isophthalic acid/5 mol% of isophthalic acid-5-sodium sulfonate/30 mol% of ethylene glycol/1,4-butanedi A polyester resin composed of 20 mol% alcohol.

・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-methylolacrylamide

・Melamine-based crosslinking agent: "NIKALAC MW12LF" manufactured by Sanwa Chemical Co., Ltd.

Surfactant: polyoxyethylene lauryl ether

· Particles: colloidal silica having an average particle diameter of 0.19 μm.

(Coating liquid f for resin layer formation; Wetting tension 51mN/m)

In terms of solid mass ratio, 45% by mass of the following polyester resin g, 45% by mass of acrylic resin c, 5% by mass of melamine crosslinking agent, 4% by mass of surfactant, 1% by mass of particles Mix to prepare a water-dispersed coating solution.

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

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

・Melamine-based crosslinking agent: "NIKALAC MW12LF" manufactured by Sanwa Chemical Co., Ltd.

Surfactant: polyoxyethylene lauryl ether

· Particles: colloidal silica having an average particle diameter of 0.19 μm.

(Coating solution for resin layer formation g; Wetting tension 53mN/m)

A coating liquid was prepared by mixing 85% by mass of polyurethane resin, 5% by mass of epoxy crosslinking agent, 9% by mass of surfactant, and 1% by mass of particles in terms of solid content mass ratio.

・Urethane resin: "HYDRAN AP-20" manufactured by Dainippon Ink Chemical Industry Co., Ltd.

· Epoxy crosslinking agent: triethylene glycol diglycidyl ether

Surfactant: polyoxyethylene lauryl ether

· Particles: colloidal silica having an average particle diameter of 0.19 μm.

[Example 31]

Prepare the hard coat film as follows.

<Production of resin layer laminated PET film>

On both surfaces of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 μm, resin layers were applied in-line in the production process of the PET film, respectively. That is, on both sides of the PET film uniaxially stretched in the longitudinal direction, the coating liquid c for forming a resin layer was coated by a bar coating method, dried at 100° C., and then biaxially stretched in the width direction, It heat-processed at 230 degreeC for 20 second, it was made to heat-cure, and the PET film which laminated|stacked the resin layer on both surfaces was produced. The resin layers laminated on both sides of the PET film had a thickness of 0.08 μm.

<Lamination of 1st and 2nd 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 with resin layers laminated on both sides by the gravure coating method, dried at 90°C, and then irradiated with ultraviolet rays at 400 mJ. /cm ² to make it solidify to form the first hard coat layer. The thickness of the first hard coat layer was 1.6 μm.

Then, on the resin layer on the other side of the PET film (the side opposite to the side on which the first hard coat layer was laminated), the same operation as above was performed using the active energy ray-curable composition b used in Example 2. , forming a second hard coat layer to make a hard coat film. The thickness of the second hard coat layer was 1.6 μm.

[Example 32-35]

Except having changed the coating liquid for resin layer formation as shown in Table 6, it carried out similarly to Example 31, and produced the hard coat film.

[Example 36-40]

Except having changed the thickness of the 1st hard-coat layer into 2.6 micrometers and the thickness of the 2nd hard-coat layer into 2.6 micrometers, it carried out similarly to Examples 31-35, and produced the hard coat film.

[Evaluation of hard coat film]

About the hard coat films of Examples 31-40 obtained by the above operation, the structure of the 1st and 2nd hard coat film is shown in Table 6, and the evaluation result of these hard coat films is shown in Table 7.

From the above results, it can be seen that by directly laminating the first hard coat layer on the resin layer having a wetting tension of 52 mN/m or less, protrusions caused by particles are easily formed on the surface of the first hard coat layer (it can be seen that the number of protrusions per unit area number increased). Furthermore, it turns out that when the thickness of a 1st hard-coat layer is less than 2 micrometers, the influence of the wetting tension of the surface of a resin layer becomes remarkable. That is, for the method of directly laminating the first hard coat layer on the resin layer having a wetting tension of 52 mN/m or less, when the thickness of the first hard coat layer is less than 2 μm, the first hard coat layer contains The particles tend to be localized near the surface, and as a result, protrusions caused by the particles can be efficiently formed. Moreover, when the thickness of a 1st hard-coat layer is less than 2 micrometers, a haze value will become smaller and transparency will improve.

Explanation of reference signs

1～5 protrusions

11 protrusions

20 horizontal lines

30 vertical lines

Claims (16)

1. a kind of hard coat film, it is characterised in that possess the 1st hard conating containing particle at least one side of base material film, by institute The projection of particle formation is stated with per 100 μm²It is present in the surface of the 1st hard conating for the density of 300～4000, the projection Average diameter is 0.03～0.3 μm, and the average height of the projection is 0.03～0.3 μm, and the center line of the 1st hard coating surface is put down All roughness Ra 1 is less than 30nm, and haze value is less than 1.5%, and the thickness (d) of the 1st hard conating is 0.5 μm less than 10 μm.

2. hard coat film as claimed in claim 1, wherein, the average grain diameter (r) of the particle is 0.05～0.5 μm.

3. hard coat film as claimed in claim 1 or 2, wherein, the average grain diameter (r) of the particle is with respect to the 1st hard conating The ratio (r/d) of thickness (d) is 0.01～0.30.

4. hard coat film as claimed in claim 1 or 2, wherein, the equispaced of the projection is 0.10～0.70 μm.

5. hard coat film as claimed in claim 1 or 2, wherein, the 1st hard conating is solid comprising thermosetting resin or active energy beam The property changed resin is used as resin, and the refractive index of the 1st hard conating is in the range of 1.48～1.54.

6. hard coat film as claimed in claim 1 or 2, wherein, possessing thickness between the base material film and the 1st hard conating is 0.005～0.3 μm of resin bed, the resin bed contain more than 1.3 times that average grain diameter is the resin layer thickness of particle.

7. hard coat film as claimed in claim 1 or 2, wherein, the base material film is formed by polyethylene terephthalate, institute State the resin bed for possessing between base material film and the 1st hard conating that refractive index is 1.55～1.61.

8. hard coat film as claimed in claim 1 or 2, wherein, possessing wetting tension between the base material film and the 1st hard conating is The resin bed of below 52mN/m.

9. hard coat film as claimed in claim 8, wherein, the thickness of the 1st hard conating is less than 2 μm.

10. hard coat film as claimed in claim 1 or 2, wherein, the particle contained in the 1st hard conating is comprising inorganic matter, right The surface of the particle implements process or the silicic acid anhydride for reducing surface free energy.

11. hard coat films as claimed in claim 10, wherein, for the surface of the particle contained in the 1st hard conating, use Formula 1 is C_nF_2n+1-(CH₂)_m-Si(Q)₃The organic silane compound of expression, the hydrolysate of the organic silane compound or institute The partial condensate of hydrolysate is stated, the process for reducing surface free energy is implemented,

Wherein, in formula 1, n represents 1～10 integer, and m represents 1～5 integer, and Q represents the alcoxyl that carbon number is 1～5 Base or halogen atom.

12. hard coat films as claimed in claim 10, wherein, for the surface of the particle contained in the 1st hard conating, make It is B-R with formula 2⁴-SiR⁵ _n(OR⁶)_3-nAfter the compound of expression is processed, the use of formula 3 is D-R⁷-Rf²The fluorine of expression Compound is processed, and has thus carried out hydrophobization,

Wherein, in formula 2 and 3, B and D represents reactive moieties, R independently of one another⁴And R⁷Represent carbon atom independently of one another Number is 1～3 alkylidene or the ester structure derived by the alkylidene, R⁵And R⁶Represent hydrogen or carbon number independently of one another For 1～4 alkyl, Rf²Represent fluoroalkyl, n represents 0～2 integer.

13. hard coat films as claimed in claim 10, wherein, for the surface of the particle contained in the 1st hard conating, use Fluorine compounds with the fluoroalkyl that reactive moieties and carbon number are more than 4, it is 8 with reactive moieties and carbon number The long-chain hydrocarbon compound of above alkyl or the silicone compounds with siloxy group and reactive moieties are processed, by This has carried out hydrophobization.

14. hard coat films as claimed in claim 1 or 2, wherein, the particle contained in the 1st hard conating is titanium dioxide silicon grain Son.

15. hard coat films as claimed in claim 1 or 2, wherein, in the base material film and the face phase for being provided with the 1st hard conating Possesses the 2nd hard conating on anti-face, the surface of the 2nd hard conating is created substantially absent the projection formed by particle, and the 2nd hard conating The center line average roughness Ra2 on surface is below 25nm.

A kind of 16. transparent and electrically conductive films, wherein, at least one side of the hard coat film any one of claim 1～15 Possesses nesa coating.