TWI770141B - Antiglare hard coat film and method for producing the same - Google Patents

Abstract

The provided is an antiglare hard coat film and a method for producing the same having a preventing whitening property and the like.

The present invention relates to an antiglare hard coat film, wherein an antiglare hard coat layer having a thickness of 8 μm or less, is derived from a formulation comprising (A) 100 pbw of an active energy ray curable resin, (B1) 5 to 25 pbw of silica particles, and (B2) 3 to 30 pbw of high refractive index particles, and the silica particles protrude from the film surface.

Description

Anti-glare hard coating film and method for producing anti-glare hard coating film

The present invention relates to an anti-glare hard-coat film and a method for producing the anti-glare hard-coat film.

In particular, it relates to an anti-glare hard-coat film which can effectively prevent discoloration and the like, and an effective method for producing the anti-glare hard-coat film.

In the past, in displays such as tablet terminals and satellite navigation devices, external light was reflected on the screen display surface, making it difficult to visually recognize the displayed image.

On the other hand, when these displays are displayed in black, fading is observed on the display surface of the screen (hereinafter referred to as fading). With the enlargement of displays in recent years, the importance of solving this problem is increasing.

Therefore, as a means to solve the problem of the reflection of external light, a technique of using an anti-glare hard coating material having an anti-glare hard coating layer has been proposed.

That is, in the anti-glare hard coat layer, when forming the hard coat layer, there is a method of roughening the surface of the hard coat layer by physical means, and it is used in the formation of the hard coat layer. A method of mixing a filler in a hard coating agent, a method of using the phase separation by mixing two incompatible components in a hard coating agent for hard coating formation, and the like.

All of these measures take the surface of the hard coat layer, that is, the surface on the opposite side of the hard coat layer to the plastic substrate, as the surface of the hard coat layer (the same applies hereinafter), and by forming fine irregularities on the surface, suppressing the effect of external light Specular reflection, which prevents the reflection of external light such as fluorescent lamps.

For example, an anti-glare film is proposed in which an anti-glare layer is laminated on a transparent base film, and the anti-glare layer contains a mixture of large-diameter fine particles and small-diameter fine particles having a larger specific gravity than the large-diameter fine particles and a smaller particle size. In the anti-glare layer of a specific thickness, the volume ratio of large particle size fine particles is 0.5% to 40%, and the volume ratio of small particle size fine particles is 15% to 65% (refer to Patent Document 1).

Here, as the large particle size particles, resin particles such as acrylic resin having an average particle diameter of 0.1 to 5 μm are disclosed, and as the small particle diameter particles, zirconia and silicon oxide particles having an average particle diameter of 0.01 to 0.1 μm are disclosed. inorganic particles.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2016-133722 (Patent Application Scope)

However, the anti-glare film disclosed in Patent Document 1 uses A plurality of fillers are used to suppress the flicker of the screen (hereinafter sometimes referred to as "sparkle"), and although an anti-glare film that can ensure the visibility of the image is disclosed, there is no intention to suppress the fading.

Not only that, but also because the large particle size particles are organic particles and their average particle size is relatively large, it is impossible to obtain an anti-glare film with a thin anti-glare layer. When the thickness of the anti-glare layer is thick, an anti-glare film can be seen. Curl problem.

In addition, the organic fine particles are easily peeled off from the surface of the hard coat layer, and sufficient scratch resistance cannot be obtained. Furthermore, there is a problem that the anti-glare property tends to further decrease with time.

Therefore, the inventors of the present invention have made active studies in view of the above situation, and mixed at least three kinds of particles in a specific ratio in a material for forming an anti-glare hard coat layer, and limited the thickness of the anti-glare hard coat layer to a specific value or less, thus completing the present invention.

That is, the object of the present invention is to provide a combination of a plurality of particles in a specific ratio, which can effectively prevent discoloration, have excellent anti-glare properties, and provide high surface hardness even if the thickness of the anti-glare hard coat layer is relatively thin. An anti-glare hard-coat film with less occurrence of curl, and an effective method for producing the anti-glare hard-coat film.

According to the present invention, the following problems can be solved by providing the following anti-glare hard coating film. The anti-glare hard coating film is characterized by having an anti-glare hard coating film on the surface of a plastic substrate. , the anti-glare hard coat layer is derived from the anti-glare hard coat layer forming material, and the thickness is less than 8 μm An anti-glare hard coat layer containing 5 to 25 parts by mass of silicon oxide particles as a component (B1) relative to 100 parts by mass of an active energy ray-curable resin as a component (A) , 3-30 parts by mass of high-refractive-index particles as component (B2), and 4-25 parts by mass of resin particles as component (B3), and silicon oxide particles from the anti-glare hard coat layer opposite to the plastic substrate The side surfaces are protruding.

That is, according to the anti-glare hard coating film of the present invention, the anti-glare hard coating contains at least three kinds of particles (B1 to B3) in a specific ratio, and the thickness thereof is limited to a specific value or less, so that the silicon oxide particles can be reliably formed. And stably protrude from the surface of the anti-glare hard coat layer (the other surface of the anti-glare hard coat layer located on the opposite side of the plastic substrate on which the anti-glare hard coat layer is provided, the same below).

Therefore, it is possible to obtain an anti-glare hard-coat film which can effectively prevent discoloration, has excellent anti-glare property, and has high surface hardness and little curl even if the thickness of the anti-glare hard-coat layer is relatively thin.

In addition, when constituting the anti-glare hard coat film of the present invention, the silicon oxide particles are preferably pulverized silicon oxide particles.

This is because the particle size distribution of the pulverized silica particles tends to be wider than that of the spherical silica particles, and there is a tendency to effectively improve the mutual adhesion with other materials.

Therefore, pulverized silicon oxide particles having a relatively large average particle size are more likely to exist, part of the pulverized silicon oxide particles can be stably protruded from the surface of the anti-glare hard coat layer, and the surface hardness is higher and curling is less likely to occur. Less anti-glare hard coat film.

In addition, when forming the anti-glare hard coat film of the present invention, the average particle diameter of the silicon oxide particles is preferably a value within the range of 2.1 to 10 μm.

By using silicon oxide particles whose average particle size is controlled, the discoloration property can be further effectively prevented, and the more excellent anti-glare property and the like can be obtained.

In addition, when constituting the anti-glare hard coat film of the present invention, the average particle diameter of the high refractive index particles is preferably a value within the range of 1 to 1000 nm.

By using high-refractive-index particles controlled to this average particle size in combination with specific silicon oxide particles and resin particles, it is possible to more effectively prevent discoloration and obtain better anti-glare properties.

In addition, when constituting the anti-glare hard coat film of the present invention, the average particle diameter of the resin particles is preferably a value within the range of 0.5 to 2 μm.

By using resin particles controlled to this average particle size, in addition to specific silicon oxide particles and resin particles, it is possible to more effectively prevent discoloration, and to obtain better anti-glare properties.

In addition, when forming the anti-glare hard coating film of the present invention, the overall haze value of the anti-glare hard coating film measured in accordance with JIS K 7136 (2000) is preferably a value within the range of 15 to 40%, and the internal haze is preferably within the range of 15 to 40%. The value is within the range of 5~38%, and the external turbidity value is less than 40%.

By controlling not only the overall haze value of the anti-glare hard coat layer, but also the external haze value, the fading property can be prevented more effectively, and better anti-glare property, image visibility, glare suppression property, etc. can be obtained. .

In addition, when constituting the anti-glare hard coat film of the present invention, the surface hardness of the anti-glare hard coat layer is preferably 2H or more.

By controlling this surface hardness, even if the thickness of the anti-glare hard coat layer is relatively thin, an anti-glare hard coat film which can stably have an anti-glare hard coat layer having a higher surface hardness can be obtained.

In addition, another aspect of the present invention is a method for producing an anti-glare hard coating film, which is characterized in that the anti-glare hard coating film is provided with an anti-glare hard coating on the surface (especially one side) of a plastic substrate. A manufacturing method, and at least comprises the following steps (1)～(3), (1) With respect to 100 parts by mass of the active energy ray-curable resin as the component (A), 5 to 25 parts by mass of the silicon oxide particles as the component (B1) and 3 to 30 parts by mass of the high refractive index particles as the component (B2) The steps of blending 4 to 25 parts by mass of resin particles as the component (B3) to prepare a material for forming an anti-glare hard coat layer, (2) the step of coating the anti-glare hard coat layer forming material on the substrate to form a coating film, (3) The coating film on the base material is irradiated with active energy rays to form an anti-glare hard coat layer with a thickness of 8 μm or less protruding from the surface of the anti-glare hard coat layer on the opposite side of the plastic base material. step.

By forming an anti-glare hard coat film containing such at least three kinds of particles (B1 to B3) in a specific ratio, the silicon oxide particles can be reliably and stably self-contained from the anti-glare hard coat (film-like cured product). ) of a particular surface protruding state.

Therefore, it is possible to effectively obtain an anti-glare hard coat film that can effectively prevent discoloration and has excellent anti-glare properties, and has high surface hardness and less curl even if the thickness of the anti-glare hard coat layer is relatively thin.

10: Anti-glare hard coating film

12: Plastic substrate

14: Specific complex particles

14a: Silicon oxide particles

14b: High refractive index particles (zirconia particles)

14c: resin particles

15: Active energy ray curable resin

16: Anti-glare hard coating

110: Anti-glare hard coating film

111: Polarizer

112a: Plastic substrate (1st TAC film)

112b: Plastic substrate (2nd TAC film)

115a: Adhesive layer (first adhesive layer)

115b: Adhesive layer (second adhesive layer)

116: Anti-glare hard coating

118: Adhesive layer

119: Peel off the sheet

120: polarizer

FIGS. 1( a ) to ( b ) are diagrams for comparatively explaining the aspect of the anti-glare hard coat film of the present invention and the aspect of the conventional anti-glare hard coat film.

Fig. 2(a) is a diagram for explaining the particle size distribution chart of the silicon oxide particles used in Example 1 and the like, and Fig. 2(b) is a diagram for explaining the particle size distribution chart of other silicon oxide particles. 2(c) is a graph for illustrating the particle size distribution chart of the resin particles used in Example 1 and the like.

FIG. 3 is a diagram for explaining the state of a polarizing plate using the anti-glare hard coat film of the present invention.

FIGS. 4( a ) to ( b ) are diagrams for explaining the image visibility of Example 1 and Comparative Example 1, respectively.

[1st Embodiment]

The first embodiment is an anti-glare hard coating film, which is characterized by an anti-glare hard coating film having an anti-glare hard coating on the surface of a plastic substrate, and the anti-glare hard coating is derived from the anti-glare hard coating A layer forming material having an anti-glare hard coat layer having a thickness of 8 μm or less, the anti-glare hard coat layer forming material containing (B1) 5~25 parts by mass of silicon oxide particles, 3 to 30 parts by mass of high refractive index particles as the component (B2), and 4 to 25 parts by mass of the resin particles as the component (B3), and the silicon oxide particles are from the anti-glare hard coat layer on the opposite side of the plastic substrate The surface stands out.

Hereinafter, the anti-glare hard coat film according to the first embodiment of the present invention will be specifically described with reference to the drawings as appropriate. For example, FIG. 1( a ) is a diagram for explaining the cross section of the anti-glare hard coat film 10 according to the first embodiment, and FIG. 1( b ) is for explaining the conventional anti-glare hard coat film 10 ' of the cross section.

1. Anti-glare hard coating

(1) Anti-glare hard coat layer forming material

As shown in FIG. 1( a ), the anti-glare hard coating film 10 of the present invention includes an anti-glare hard coating layer (sometimes) containing specific plural particles 14 ( 14 a , 14 b , 14 c ) on the plastic substrate 12 It is called a film-like hardened product) 16.

That is, as shown in the cross section of FIG. 1( a ), the anti-glare hard coat layer 16 is typically composed of a film-like cured product of the anti-glare hard coat layer-forming material. The active energy ray-curable resin 15 as the component (A), the silicon oxide particles 14a as the component (B1), the high refractive index particles 14b as the component (B2), the resin particles 14c as the component (B3), and the (C) The photopolymerization initiator of the component.

On the other hand, as shown in the cross section of FIG. 1( b ), a typical conventional anti-glare hard coat film 10 ′ has anti-glare properties including spherical resin particles 14 ′ on a plastic substrate 12 ′ Hard coat 16'.

That is, only a relatively large spherical shape is used for the anti-glare hard coat layer 16'. The resin particles 14' are particles for imparting anti-glare properties based on light scattering or the like, and correspond to the configurations shown in Comparative Examples 13 to 17 of the present invention.

(1)-1(A) component: Active energy ray curable resin

The type of active energy ray-curable resin (including ultraviolet curable resin) as the component (A) is not particularly limited, and can be selected from those known in the art, but energy ray-curable monomers, oligomers, and resins are exemplified. or a mixture of these.

More specifically, polyfunctional (meth)acrylic monomers and (meth)acrylate-based prepolymers are preferably used.

In addition, as a polyfunctional (meth)acrylic monomer, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyldiol are exemplified. Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, Caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate Acid ester di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate Meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acrylooxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta(methyl) Polyfunctional (meth)acrylates such as acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc.

Moreover, these monomers may be used by 1 type, and may be used in combination of 2 or more types.

Moreover, as a (meth)acrylate type prepolymer, for example, polyester acrylate type, epoxy acrylate type, urethane acrylate type, polyol acrylate type, etc. are mentioned, for example.

Here, as a polyester acrylate-based prepolymer, for example, the hydroxyl groups of the polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol can be esterified with (meth)acrylic acid, Or the terminal hydroxyl group of the oligomer obtained by adding an alkylene oxide to a polycarboxylic acid is esterified by (meth)acrylic acid.

In addition, the epoxy acrylate-based prepolymer can be obtained by, for example, reacting and esterifying ethylene oxide of a relatively low molecular weight bisphenol-type epoxy resin or a novolak-type epoxy resin with (meth)acrylic acid.

Also, urethane acrylic prepolymers can be (meth)acrylated by (meth)acrylated polyurethane oligomers obtained, for example, by reacting polyether polyols or polyester polyols with polyisocyanates and obtained.

In addition, the polyol acrylate-based prepolymer can be obtained by (meth)acrylate esterification of the hydroxyl group of the polyether polyol. These prepolymers may be used individually by 1 type, or may be used in combination of 2 or more types, and the said polyfunctional (meth)acrylate type monomer may be used together.

(1)-2(B) Components: Plural kinds of particles

(i) (B1) Component (Silicon Oxide Particles)

(type)

2)與作為(B3)成分之樹脂粒子之平均粒徑(

3)更大的平均粒徑(

1)，且其粒徑分佈中，分佈有比防眩性硬塗層之膜厚(t)更大粒徑之粒子，而且相當硬(例如維氏(Vickers)硬度為1200MPa以上)。 The silicon oxide particles as the component (B1) are characterized in that they have an average particle diameter (

2) and the average particle size of the resin particles as the component (B3) (

3) Larger average particle size (

1), and in the particle size distribution, particles with a larger particle size than the film thickness (t) of the anti-glare hard coat layer are distributed, and they are quite hard (for example, Vickers hardness is 1200 MPa or more).

Therefore, since the silicon oxide particles are located on the surface side of the anti-glare hard coat layer opposite to the plastic base material, and a part of the silicon oxide particles protrudes, it is possible to effectively prevent discoloration and exhibit excellent anti-glare properties. The anti-glare hard coat layer has a relatively thin thickness, and also has a high surface hardness and an anti-glare hard coat film with less occurrence of curling.

Here, examples of the type of silicon oxide particles as the component (B1) are, for example, spherical silicon oxide, amorphous pulverized silicon oxide, and the like, alone or in combination of two or more.

Moreover, as the silicon oxide particles, pulverized silicon oxide particles are more preferable.

The reason for this is that when the silica particles are pulverized, the particle size distribution tends to be wider than that of the spherical silica particles, and the particles with a larger average particle size and The reason why the existence ratio of the smaller particles is increased, respectively.

When there are many particles with a larger average particle diameter, a part of the particles tends to protrude stably from the surface of the anti-glare hard coat layer, which can effectively prevent discoloration and exhibit excellent anti-glare properties.

On the other hand, when the presence ratio of particles having a smaller average particle diameter is high, the presence ratio of the silicon oxide particles in the anti-glare hard coat layer is increased, and an anti-glare hard coat layer having a high surface hardness can be obtained.

Furthermore, since there are many fine irregularities (corners or protrusions) on the surface of the pulverized silica particles, the surface area of the pulverized silica particles is larger than that of the spherical silica particles, so the contact area with other materials becomes larger. .

As a result, the mutual adhesion between the pulverized silica particles and other materials is effectively improved, and an anti-glare hard coat layer having a high surface hardness can be obtained even if the thickness of the anti-glare hard coat layer is relatively thin.

Therefore, by using pulverized silicon oxide particles, as described above, by virtue of the particle size distribution and other characteristics of the particles, it is possible to obtain anti-glare properties that can effectively prevent discoloration and exhibit excellent anti-glare properties, and have high surface hardness. Hard coat film.

In addition, the so-called pulverized silicon oxide particles refer to silicon oxide particles obtained by pulverizing spherical silicon oxide such as molten silicon oxide or crystalline silicon oxide by a specific method. Usually, the surface has sharp corners or irregularities such as protrusions. particle.

(The average particle size)

1：體積平均粒徑)通常較好為2.1~10μm之範圍內之值。 The average particle diameter of the silicon oxide particles (B1) contained in the anti-glare hard coat layer

1: The volume average particle diameter) is usually preferably a value within a range of 2.1 to 10 μm.

If the average particle size of the silicon oxide particles is within this range, the external haze value can be easily adjusted, and the fading property can be effectively prevented, and the excellent anti-glare property can be exhibited, and the image visibility can be maintained. Occurrence can also be effectively suppressed. Furthermore, by setting the average particle diameter of the silicon oxide particles to be within this range, it is possible to obtain anti-glare properties with a relatively thin anti-glare hard coat layer, high surface hardness and less occurrence of curling. Anti-glare properties of hard coat Hard coat film.

More specifically, when the average particle diameter of the silicon oxide particles is less than 2.1 μm, the silicon oxide particles are not likely to protrude from the surface of the anti-glare hard coat layer, and it is difficult to adjust the value such as the external haze value, and it is difficult to maintain a sufficient value. Anti-glare and glare suppression.

On the other hand, when the average particle diameter of the silicon oxide particles exceeds 10 μm, it may be difficult to prevent discoloration or ensure image visibility, and further surface hardness may be easily reduced or curling may occur, especially when applied to a high-definition display.

Therefore, the average particle diameter of the silicon oxide particles is more preferably a value within a range of 2.5 to 8 μm, and more preferably a value within a range of 3 to 6 μm.

1)較好考慮硬塗層之膜厚(t)而決定，進而，較好該氧化矽粒子之平均粒徑與硬塗層之膜厚大致相等。 The average particle size of silicon oxide particles (

1) It is preferably determined in consideration of the film thickness (t) of the hard coat layer. Furthermore, the average particle diameter of the silicon oxide particles is preferably approximately equal to the film thickness of the hard coat layer.

The reason for this is that if the average particle diameter of the silicon oxide particles is approximately equal to the film thickness of the hard coat layer, a part of the silicon oxide particles can protrude uniformly and stably from the surface of the anti-glare hard coat layer.

1≦2.0×t之關係式，更好滿足0.9×t≦

1≦1.8×t之關係式，氧化矽粒子容易自防眩性硬塗層之與塑膠基材相反側之表面側使氧化矽粒子之一部分突出，而容易有效地調整外部濁度值等。 For example, by satisfying 0.8×t≦

The relational expression of 1≦2.0×t is better to satisfy 0.9×t≦

The relational expression of 1≦1.8×t means that the silicon oxide particles tend to protrude part of the silicon oxide particles from the surface side of the anti-glare hard coat layer opposite to the plastic substrate, so that the external haze value can be easily adjusted effectively.

As a result, it is possible to obtain a hard coat layer capable of effectively preventing discoloration, exhibiting excellent anti-glare properties, ensuring image visibility, and suppressing the occurrence of glare.

Furthermore, when referring to the silicon oxide particles as the component (B1), The particle size distribution preferably has a particle size distribution diagram as shown in Fig. 2(a) or Fig. 2(b).

That is, the particle size distribution diagram of the silicon oxide particles shown in FIG. 2(a) corresponds to the silicon oxide particles used in Example 1, etc., and has two peaks on the particle size distribution diagram, which is understood to be composed of two or more particle sizes. A mixture of silicon oxide particles with different distributions.

That is, it is a silicon oxide particle (average particle size: 3.2 μm) which is a combination of first silicon oxide particles having an average particle size of about 8 μm and second silicon oxide particles having an average particle size of about 0.7 μm.

On the other hand, the particle size distribution diagram of the silicon oxide particles shown in FIG. 2(b) is characterized by having a peak on the particle size distribution diagram. That is, it can be understood as single silicon oxide particles (average particle diameter: 3.2 μm) having an average particle diameter of about 3 μm.

Furthermore, in the case of Example 1 and the like of the present invention, although the silicon oxide particles having the particle size distribution combination shown in FIG. 2(a) are used, when the single silicon oxide particles having the particle size distribution shown in FIG. In addition, it was confirmed that the same discoloration prevention properties and anti-glare properties were exhibited.

(mixing amount)

In addition, the blending amount of the silicon oxide particles as the component (B1) contained in the anti-glare hard coat layer forming material is preferably within a range of 5 to 25 parts by mass with respect to 100 parts by mass of the component (A) value.

If the content of the silicon oxide particles is within this range, the external haze value, etc. can be easily adjusted, the fading property can be effectively prevented, and the Excellent anti-glare properties, thus maintaining image visibility, and effectively suppressing the occurrence of glare.

More specifically, when the blending amount of the silicon oxide particles is less than 5 parts by mass, a part of the silicon oxide particles does not easily protrude from the surface of the anti-glare hard coat layer, and it is difficult to adjust values such as the external haze value. Therefore, there are cases where it is difficult to exhibit sufficient anti-glare properties, or there are cases where it is difficult to suppress the occurrence of glare.

On the other hand, when the compounding amount of the silicon oxide particles exceeds 25 parts by mass, it may be difficult to prevent discoloration or ensure image visibility, or the surface hardness may be lowered, especially when applied to a high-definition display.

Therefore, the blending amount of the silicon oxide particles is preferably a value within a range of 7 to 20 parts by mass, more preferably a value within a range of 10 to 15 parts by mass, relative to 100 parts by mass of the component (A).

(ii) (B2) component: high refractive index particles

(type)

The high-refractive-index particles as the component (B2) correspond to, for example, inorganic fine particles having a refractive index (n _d ) of 1.8 or more, more preferably inorganic fine particles having a refractive index (n _d ) of 1.9 or more, and more preferably a refractive index ( n _d ) is an inorganic fine particle of 2.0 or more.

Specifically, zirconia particles (n _d : 2.1), titanium oxide particles (n _d : 2.5 to 2.7), chromium oxide (trivalent) (n _d : 2.5), copper oxide (n _d : 2.7), At least one of zinc oxide (n _d : 2.0), platinum (n _d : 2.95), tungsten ( _nd : 2.76), and the like, and zirconia particles are particularly preferred.

The reason for this is that if the high refractive index particles are zirconia particles, the The specific gravity of the components of the anti-glare hard coat layer is relatively large, and since the average particle size is small, it tends to exist at the bottom, that is, on the plastic substrate side of the anti-glare hard coat layer, together with the component (B3) described later, mainly to effectively utilize the internal The adjustment function of turbidity value, etc.

In addition, the zirconia particles tend to be concentrated around the relatively large silicon oxide particles as the component (B1), so by blending the zirconia particles, not only the fixability and surface hardness of the silicon oxide particles can be improved, but also the cause The surface hardness of silicon oxide particles is more effective.

Here, the type of zirconia particles as the component (B2) preferably corresponds to, for example, a compound represented by ZrO ₂ and has a monoclinic crystal structure as a main component at room temperature.

Therefore, stabilized zirconia particles obtained by blending zirconium with rare earth oxides such as calcium oxide, magnesia, or yttria, or quasi-stabilized zirconia particles based on these can also be used as zirconia particles.

In addition, in order to agglomerate the zirconia particles, prevent excessive bias, and firmly fix them in the anti-glare hard coat layer, it is preferable to mix and coat the surface of the zirconia particles with a monomer or oligomer having a radical reactive group. Reactive zirconia particles made of materials, etc.

Therefore, according to these reactive zirconia particles, the surface hardness of the anti-glare hard coat layer can be exerted more effectively because they are further concentrated around the relatively large silicon oxide particles to form a strong inorganic region.

(The average particle size)

：體積平均粒徑)較好為1~1000nm之範圍內之值。 In the present invention, the average particle diameter (

: volume average particle diameter) is preferably a value within the range of 1 to 1000 nm.

The reason for this is that if the average particle diameter of the high refractive index particles is within this range, the internal haze value can be easily adjusted, excellent anti-glare properties and image visibility can be maintained, and the occurrence of glare can be effectively suppressed. .

When the average particle diameter of the high-refractive-index particles is less than a value of 1 nm, it may be difficult to maintain sufficient anti-glare properties.

On the other hand, when the average particle diameter of the high-refractive-index particles exceeds 1000 nm, it may be difficult to effectively suppress the occurrence of flare when especially applied to a high-definition display.

Therefore, the average particle diameter of the high refractive index particles is more preferably a value within a range of 5 to 500 nm, and more preferably a value within a range of 10 to 100 nm.

In addition, the average particle diameter (volume average particle diameter) of the high refractive index particles can be measured as D50 of the median diameter based on a volume-based particle size distribution chart prepared using, for example, a laser diffraction scattering particle size distribution analyzer. .

(mixing amount)

The blending amount of the high refractive index particles as the component (B2) is preferably a value within a range of 3 to 30 parts by mass relative to 100 parts by mass of the component (A).

The reason for this is that if the blending amount of the high refractive index particles is within this range, the internal haze value and the like can be easily adjusted, so that excellent anti-glare properties and image visibility can be maintained, and it is also effective against the occurrence of glare. Because of inhibition.

That is, when the blending amount of the high-refractive index particles is less than 3 parts by mass, it may be difficult to adjust values such as the internal haze value, and it may be difficult to exhibit sufficient anti-glare properties.

On the other hand, when the blending amount of the high refractive index particles exceeds 30 parts by mass, In particular, when applied to a high-definition display, it may be difficult to suppress the occurrence of glare or ensure image visibility.

Therefore, the blending amount of the high-refractive-index particles is preferably set within a range of 5 to 28 parts by mass, more preferably within a range of 8 to 25 parts by mass, more preferably within a range of 10 to 20 parts by mass value within.

(iii) (B3) component: resin particle

The resin particles as the component (B3) are relatively small with respect to the film thickness (t) of the anti-glare hard coat layer, so they are not present on the surface of the anti-glare hard coat layer, but are mostly present in the interior, which is the same as the component (B2) With the high refractive index particles, the internal haze value of the anti-glare hard coat layer of the present invention can be adjusted more easily.

The reason for this is that the anti-glare hard coat layer tends to have a structure with different refractive indices due to the presence of the resin particles as the component (B3) and the presence of the high-refractive-index particles as the (B2) component. , the adjustment of the internal turbidity value, etc. is easy.

Here, as the type of resin particles of the component (B3), for example, silicone resin particles, modified silicone resin particles, melamine resin particles, and acrylic polymer resin particles (for example, polymethyl methacrylate) are preferred. resin microparticles, etc.), acrylic-styrene copolymer resin microparticles, polycarbonate resin microparticles, polyethylene resin microparticles, styrene polymer resin microparticles, benzoguanamine resin microparticles, etc. singly or in combination of two or more.

Among them, free acrylic polymer resin fine particles, acrylic-styrene copolymer resin fine particles, styrene polymer resin fine particles and At least one selected from the group of polysiloxane microparticles.

The reason for this is that the resin fine particles are relatively inexpensive, and on the other hand, they contribute to the dispersibility of the silicon oxide particles of the component (B1) and the high-refractive index particles of the component (B2), and contribute to the improvement of anti-glare properties. The surface of the coating layer is stably formed due to the fine irregularities of the component (B1), and is complemented by the component (B2), and it is easy to obtain a desired internal haze value and the like.

Furthermore, in terms of the relationship with the component (B1), when the anti-glare hard coat layer forming material is coated on the surface of the plastic substrate, it can effectively suppress the self-prevention of silicon oxide as the component (B1) in the coating film. The prominent defects on the surface of the glare hard coat layer can more stably form the fine irregularities on the surface of the anti-glare hard coat layer.

As a result, it is possible to obtain an anti-glare hard coat that can effectively prevent discoloration and exhibit excellent anti-glare properties, and can ensure image visibility and suppress glare in combination with the ease of adjustment of the internal haze value as described above. Floor.

(The average particle size)

The average particle diameter (volume average particle diameter) of the resin particles as the component (B3) is preferably a value within a range of 0.5 to 2 μm.

The reason for this is that when the average particle diameter of the resin particles is within this range, the internal haze can be easily adjusted mainly, excellent anti-glare properties and image visibility can be maintained, and the occurrence of glare can be effectively suppressed.

When the average particle diameter of the resin particles is less than 0.5 μm, it may be difficult to effectively suppress the occurrence of glare.

On the other hand, when the average particle diameter of the resin particles exceeds 2 μm, it may be difficult to ensure image visibility when especially applied to a high-definition display.

Therefore, the average particle diameter of the resin particles is more preferably a value within a range of 0.8 to 1.8 μm, and more preferably a value within a range of 1.0 to 1.6 μm.

The average particle diameter of the resin particles can be calculated as D50 of the median diameter by obtaining a volume-based particle size distribution chart as shown in FIG.

(mixing amount)

The compounding quantity of the resin particle which is (B3) component is preferable to be the value within the range of 4-25 mass parts with respect to 100 mass parts of (A) components.

The reason for this is that there are relatively small resin particles inside the anti-glare hard coat layer to exhibit a specific internal haze value, thereby ensuring image visibility, and by stably forming oxidation caused by the component (B1) Because of the fine irregularities of the silicon particles, excellent anti-glare properties are obtained.

More specifically, when the blending amount of the resin particles is less than 4 parts by mass, fine unevenness may not be sufficiently formed on the surface of the anti-glare hard coat layer, and it may be difficult to obtain desired anti-glare properties.

On the other hand, when the compounding amount of resin particles exceeds 25 parts by mass, the haze value becomes too large, and the image visibility of the displayed image of the display may decrease.

Therefore, the compounding amount of the resin particles is preferably set to a value within the range of 8 to 23 parts by mass, and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin as the component (A). The value within the range is more preferably a value within the range of 12 to 18 parts by mass.

(1)-4(C) Component: Photopolymerization Initiator

(i) Kind

The anti-glare hard coat layer forming material preferably further contains a photopolymerization initiator as the component (C) in order to easily react and cure the active energy ray-curable resin as the component (A) in a short time.

Examples of the types of these photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzene Ethanone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane- 1-ketone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethyl Aminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthene Ketone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylacetal, acetophenone Dimethyl acetal, p-dimethylaminobenzoate, etc. singly or in combination of two or more.

(ii) Blending amount

The blending amount of the photopolymerization initiator as the component (C) is usually preferably a value within a range of 0.2 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin as the component (A).

The reason for this is that when the blending amount of the photopolymerization initiator is less than 0.2 parts by mass, it may be difficult to obtain sufficient curability.

On the other hand, when the blending amount of the photopolymerization initiator exceeds 10 parts by mass, the scratch resistance may decrease.

Therefore, the blending amount of the photopolymerization initiator is preferably set to a value within the range of 0.5 to 7 parts by mass, and more preferably 1 to 100 parts by mass of the active energy ray-curable resin as the component (A). Values within the range of 5 parts by mass.

(1)-5 Additives, etc.

The anti-glare hard coat layer forming material can be prepared by appropriately adding the above-mentioned (A) to (C) components to an appropriate solvent, and uniformly dissolving or dispersing them as necessary.

In this case, in addition to the components (A) to (C), it is also preferable to further blend additives such as antioxidants, ultraviolet absorbers, silane-based coupling agents, light stabilizers, leveling agents, antifoaming agents, and dispersing agents. At least one of , lubricant, etc.

In addition, examples of the solvent to be used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and vinyl chloride, methanol, ethanol, propanol, and butyl alcohol. Alcohols such as alcohols, acetone, methyl ethyl ketone, 2-pentanone, isophorone, ketones such as cyclohexanone, ethyl acetate, esters such as butyl acetate, cellulose-based solvents such as ethyl cellulose, etc. .

In addition, the concentration and viscosity of the anti-glare hard coat layer-forming material thus prepared may be within the range of values that can be coated on the surface of the plastic substrate, and can be appropriately selected according to the situation.

(2) Thickness

The thickness (t) of the anti-glare hard coat layer is characterized by a value of 8 μm or less.

The reason for this is that if the thickness of the anti-glare hard coat layer exceeds 8 μm, In some cases, the desired structure of the anti-glare hard coat layer cannot be obtained, or it may be difficult to suppress curling accompanying the hardening and shrinkage of the active energy ray-curable resin, or it may be difficult to suppress the occurrence of bending of the anti-glare hard coat film. When the anti-glare hard coat is cracked.

However, when the thickness of the anti-glare hard coat layer is too thin, it may be difficult to obtain the surface hardness necessary for practical use.

Therefore, the thickness of the anti-glare hard coat layer is preferably set to a value within a range of 1 to 7 μm, more preferably set to a value within a range of 2 to 6 μm, more preferably set to a value within a range of 3 to 5 μm .

2. Plastic substrate

As the type of the plastic substrate, it can be appropriately selected and used from those known as transparent substrates for optical hard coat films.

Thus, for example, polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., polyethylene films, polypropylene films, cellulphene, diethyl Acetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, Polymethylpentene, polyamide, polyether ether ketone, polyether ash, polyetherimide, polyimide, fluororesin, polyamide, acrylic resin, norbornene-based resin, cycloolefin-based resin, etc. .

In particular, the plastic base material is preferably triacetoxycellulose (TAC).

The reason for this is that according to TAC, in addition to less optical anisotropy, the transparency is high, the possibility of blurring of image display is less, and the cost is relatively cheap, And for economic reasons.

Also, from the viewpoint of good handling properties, the film thickness of the plastic base material is preferably within a range of 15 to 300 nm, more preferably within a range of 30 to 200 nm, and still more preferably within a range of 50 to 100 nm value within the range.

Moreover, as shown in FIG. 3 , the anti-glare hard coat film 110 of the present invention can also be attached to the polarizer 111 to form a polarizer 120 .

That is, as the plastic base material, a film with less optical anisotropy such as a triacetate cellulose (TAC) film (the first TAC film) 112a is used, and an anti-glare hard coat layer 116 is formed on one side thereof, Then, an anti-glare hard coat film 110 is prepared.

Next, the first TAC film 112a having the anti-glare hard coat layer 116 is laminated on one side of the polarizer 111, such as a polyvinyl alcohol-based polarizer, via the first adhesive layer 115a.

On the other hand, on the other opposite surface of the polarizer 111, that is, on the side where the anti-glare hard coat layer 116 is not formed, the second TAC film 112b is laminated via the second adhesive layer 115b.

Thereby, the polarizing plate 120 which has excellent anti-glare property and can effectively suppress the occurrence of glare even when applied to a high-definition display can be obtained.

Furthermore, as shown in FIG. 3 , the polarizing plate 120 is also preferably provided with an adhesive layer 118 or a peeling sheet 119 for adhering to optical components such as a liquid crystal cell.

3. Characteristics of anti-glare hard coating film

(1) Turbidity value

(Total turbidity value)

Moreover, it is preferable that the whole haze value of the anti-glare hard coat film measured based on JIS K 7136 (2000) (it may be abbreviated as haze value) is a value within the range of 15 to 40%.

The reason for this is that when the overall haze value is less than 15%, it may be difficult to obtain excellent glare suppression properties.

On the other hand, when the total haze value exceeds 40%, the discoloration of the display remarkably occurs, and the image visibility may be remarkably lowered.

Therefore, the overall haze value of the anti-glare hard coat film is more preferably a value within a range of 18 to 35%, and more preferably a value within a range of 20 to 33%.

(internal turbidity value)

The internal haze value of the anti-glare hard coat film is preferably a value within the range of 5 to 38%.

When the internal haze value is less than 5%, discoloration, glare, and anti-glare properties may decrease.

On the other hand, when the internal haze value exceeds 38%, the image visibility may be remarkably lowered.

Therefore, the internal haze value of the anti-glare hard coat film is more preferably a value within a range of 6 to 30%, and more preferably a value within a range of 8 to 25%.

(External turbidity value)

The external haze value of the anti-glare hard coat film is preferably a value of less than 40%.

When the external haze value is 40% or more, the discoloration of the display may occur remarkably.

However, when the external haze value is too low, glare and anti-glare properties may decrease.

Therefore, the external haze value of the anti-glare hard coat film is more preferably a value within a range of 6 to 35%, and more preferably a value within a range of 8 to 25%.

(2) Surface hardness

The anti-glare hard coat film preferably has a specific surface hardness as pencil hardness, and has no change in appearance in the evaluation of scratch resistance using steel wool.

The reason for this is that when the surface hardness is too low, a change in appearance is seen in the evaluation of the scratch resistance, and it may be difficult to obtain sufficient scratch resistance as a hard coat film.

Therefore, the surface hardness (pencil hardness) of the anti-glare hard coat film is preferably a value of 1H or more, more preferably a value of 2H or more.

The reason for this is that by restricting the surface hardness of the anti-glare hard coat layer in this way, an anti-glare hard coat film having an anti-glare hard coat layer with more excellent scratch resistance can be obtained even if it is relatively thin.

(3) Surface roughness 1

Furthermore, the arithmetic mean roughness (Ra), which is one of the indexes of the surface roughness of the anti-glare hard coat film measured in accordance with JIS B 0601 (2001), is preferably a value within the range of 0.1 to 0.3 nm.

The reason for this is that when the Ra is less than 0.1 nm, it may be difficult to obtain excellent anti-glare properties.

On the other hand, when this Ra is a value exceeding 0.3 nm, the fading property is remarkable reduced situation.

Therefore, the Ra is preferably set to a value within a range of 0.15 to 0.28, and is further preferably set to a value within a range of 0.2 to 0.25.

(4) Surface roughness 2

Furthermore, the maximum cross-sectional height (Rt), which is one of the indexes of the surface roughness of the anti-glare hard coat film measured in accordance with JIS B 0601 (2001), is preferably a value within the range of 1 to 4.5 nm.

The reason for this is that when the Rt is a value of less than 1 nm, it may be difficult to obtain excellent anti-glare properties.

On the other hand, when this Ra is a value exceeding 4.5 nm, the discoloration property may fall remarkably.

Therefore, the surface roughness (Rt) of the anti-glare hard coat film is preferably set to a value within a range of 1.5 to 4 nm, and more preferably set to a value within a range of 2 to 3 nm.

[Second Embodiment]

In addition, the second embodiment is a method for producing an anti-glare hard coating film, which is characterized in that the method for producing an anti-glare hard coating film having an anti-glare hard coating on the surface of a plastic substrate comprises at least the following steps: 1) to (3).

(1) With respect to 100 parts by mass of the active energy ray-curable resin as the component (A), 5 to 25 parts by mass of the silicon oxide particles as the component (B1) and 3 to 30 parts by mass of the high refractive index particles as the component (B2) parts, and 4 to 25 parts by mass of the resin particles as the component (B3) are blended to form an anti-glare hard coat layer. material steps, (2) the step of coating the anti-glare hard coat layer forming material on the substrate to form a coating film, (3) The coating film on the substrate is irradiated with active energy rays to form silicon oxide particles as an anti-glare hard coat layer protruding from the surface of the anti-glare hard coat layer on the opposite side to the plastic substrate and having a thickness of 8 μm The following steps for the anti-glare hard coat.

1. Manufacturing steps of the anti-glare hard coat layer forming material

To 100 parts by mass of the active energy ray-curable resin as the component (A), 5 to 25 parts by mass of the silicon oxide particles as the component (B1), 3 to 30 parts by mass of the high refractive index particles as the component (B2), And the ratio of 4-25 mass parts of resin particles as a component (B3) is blended, and the manufacturing process of the anti-glare hard-coat layer forming material is made.

That is, it is a step of uniformly mixing specific amounts of (A) component, (B1) component, (B2) component, and (B3) component, respectively, using a conventional mixing apparatus to prepare an anti-glare hard coat layer forming material.

Further, in order to uniformly mix and stir the blended components in a short time, as conventional mixing devices, propeller mixers, ball mills, bead mills, V-blenders, three-roll mixers, kneaders, planetary mixers, At least one of jet mill and the like.

2. The step of forming the coating film from the anti-glare hard coat layer forming material

Next, a coating film is formed from an anti-glare hard coat layer forming material.

That is, as the coating film forming step, conventionally known lamination methods such as bar coating method, blade coating method, roll coating method, blade coating method, die coating method, gravure coating method, etc. are used. , the step of coating the anti-glare hard coating forming material on the surface of the plastic substrate to form the coating film.

3. Hardening step of coating film

Next, a hardening step of the coating film is carried out.

That is, after drying the coating film, the coating film is irradiated with active energy rays to harden the coating film, and an anti-glare hard coating film can be obtained by making the coating film an anti-glare hard coating layer of a specific thickness.

Here, the active energy rays at the time of curing the coating film are, for example, ultraviolet rays, and the ultraviolet rays can be irradiated by a high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, or the like.

The irradiation amount of ultraviolet rays is usually a value within the range of 100 to 500 mJ/cm ² , and more preferably a value within the range of 150 to 400 mJ/cm ² .

[Example]

Hereinafter, the anti-glare hard coat film of the present invention will be described in more detail with reference to Examples.

[Example 1]

1. Manufacture of anti-glare hard coating film

(1) Preparation steps of the anti-glare hard coat layer forming material

For the ultraviolet curable resin (multifunctional acrylic type) as the component (A) A mixture of 50 parts by mass of the monomer and 50 parts by mass of the urethane acrylate oligomer) 100 parts by mass, as the component (B1), pulverized silica particles (average particle size: 3.2 μm, refractive index: 1.5) were mixed ) 7 parts by mass as the component (B2) reactive zirconia particles (manufactured by SOLAR Co., Ltd., ZR-020, average particle diameter: 50 nm, refractive index: 2.1) 10 parts by mass as the component (B3) acrylic resin Particles (manufactured by Sekisui Chemical Industry Co., Ltd., XX-27LA, average particle size: 1.5 μm, refractive index: 1.5) 15 parts by mass, (C) Component photopolymerization initiator (manufactured by BASF, OMNIRAD184) 2 mass part, and diluted with propylene glycol monomethyl ether at the same time to manufacture an anti-glare hard coat layer forming material with a solid content of 30% by weight.

In addition, the mass parts of (B1)-(B3) components in Table 1 are the blending ratios with respect to 100 mass parts of (A) components.

(2) Coating step

Next, using a wire bar #14, the obtained anti-glare hard coat layer forming material was applied to triacetin-based cellulose as an easily adhesive layer of a plastic substrate so that the film thickness after curing was 3.5 μm. A specific coating film was formed on the easy-adhesive layer of the thin film (TACBRIGHT Co., Ltd., TECPHAN P980RO, film thickness: 80 μm).

(3) Drying step

Next, the obtained coating film was dried at 70° C. for 1 minute using a hot air drying apparatus.

(4) Hardening step

Next, the dried coating film was irradiated with ultraviolet rays using an ultraviolet irradiation device (manufactured by JS Corporation, light source: high-pressure mercury lamp) under the following conditions to harden the coating film and form an anti-glare hard coat layer as a film-like cured product , to obtain the final anti-glare hard coating film.

Illuminance: 100mW/cm ²

Light quantity: 240mJ/cm ²

2. Evaluation of anti-glare hard coating films

(1) Evaluation 1 (Surface Roughness)

In accordance with JIS B 0601 (2001), the surface roughness (Ra and Rt) of the obtained anti-glare hard coat film was measured using a surface roughness meter (manufactured by Mitutoyo, SV-3000).

(2) Evaluation 2 (turbidity value)

According to JIS K 7136 (2000), the haze value (%) of the obtained anti-glare hard coating film was measured using a haze meter (manufactured by Nippon Denshoku Industries, Ltd., NDH 5000), and this was taken as the total haze value (%).

Next, peel off the single-sided release film of the optically transparent adhesive material (manufactured by LINTEC Co., Ltd., OPTERIANO-T015) of the double-sided adhesive material, and apply the anti-glare hard coating layer of the anti-glare hard coating film to the exposed surface. After aligning in the opposite way, the anti-glare hard coating film is attached.

The haze value was measured in a state where the release film on the other side of the optical adhesive was peeled off, and this was taken as the internal haze value (%) of the anti-glare hard coat film.

In addition, the internal haze value (%) was subtracted from the total haze value (%), and it was set as the external haze value (%) of the anti-glare hard coat film.

(3) Evaluation 3 (Fading Property)

On the display screen of a 264ppi (pixels/inch) display device (made by APPLE (stock), New iPad (registered trademark)), the resulting anti-glare hard-coat film was placed with the anti-glare hard coating facing upward.

Next, the display device was driven to display a specific image (black) on the entire surface, and the fading property of the obtained anti-glare hard coat film was evaluated according to the following criteria.

◯: No discoloration was observed, and no reduction in visibility was observed.

Δ: Discoloration was slightly observed, and a decrease in visibility was slightly observed.

×: Discoloration was observed, and a decrease in visibility accompanying this was remarkably observed.

(4) Evaluation 4 (anti-glare property)

The opposite side of the anti-glare hard coat layer of the obtained anti-glare hard coating film and the black plate were bonded together using a transparent adhesive material for optics (manufactured by LINTEC Co., Ltd., OPTERIA NO-T015) using a double-sided tape.

Next, a 3-wavelength fluorescent lamp was lit on the top of the anti-glare hard coating film, and the anti-glare property was evaluated according to the following criteria based on the visual state of the fluorescent lamp that was visually recognized by the reflection of the anti-glare hard coating film. .

○: The outline of the visible fluorescent lamp is blurred.

△: The outline of the fluorescent lamp is slightly blurred.

×: The outline of the fluorescent lamp is not blurred as seen.

(5) Evaluation 5 (Sparkle)

The resulting anti-glare hard coating film was placed 10 cm away from the display screen of a 264ppi (pixels/inch) display device (made by APPLE (stock), New iPad (registered trademark)) so that the anti-glare hard coating was facing upward.

Next, the display device was driven to display green on the entire display screen, and the glare suppression property of the obtained anti-glare hard coat film was evaluated according to the following criteria.

○: No flare was observed.

△: Sparkling is slightly observed.

×: Sparkling was observed remarkably.

(6) Evaluation 6 (image visibility)

The resulting anti-glare hard coating film was placed 10 cm away from the display screen of a 264ppi (pixels/inch) display device (made by APPLE (stock), New iPad (registered trademark)) so that the anti-glare hard coating was facing upward.

Next, the display device was driven to display a specific image (●▲■) as shown in FIG. 4( a ), and the image visibility of the obtained anti-glare hard coat film was evaluated according to the following criteria.

○: The outline of the specific image is clearly seen and can be sufficiently recognized.

△: Although the outline of the specific image is blurred, it is slightly recognizable.

×: The outline of the specific image is blurred and cannot be sufficiently recognized.

(7) Evaluation 7 (surface hardness/scratch resistance)

Evaluation of the surface hardness (scratch resistance) of the obtained anti-glare hard coat film was performed.

First, the obtained anti-glare hard coat film was cut out to prepare test pieces (5 pieces) of 10 cm×10 cm.

Five test pieces were placed on a flat portion so that each of the anti-glare hard coat layers faced upward, and the surface hardness of the anti-glare hard coat layer was evaluated according to the pencil hardness test (JIS K 5600-5-4).

In addition, the anti-glare hard coating layer of the obtained anti-glare hard coating film was subjected to a reciprocating rubbing test 10 times with a load of 250 g/cm ² and a sliding distance of 10 cm using a steel wool of #0000.

Next, the appearance change (number of scratches) of the anti-glare hard coat layer was visually confirmed under a 3-wavelength fluorescent lamp, and evaluated according to the following criteria.

○: The average value of the obtained surface hardness is 2H or more, and less than 3 scratches have occurred.

△: The average value of the obtained surface hardness was less than 2H, and 1H or more, and 4 to 10 scratches occurred.

×: The average value of the obtained surface hardness was less than 1H, and 11 or more flaws occurred.

(8) Evaluation 8 (curlability)

First, the obtained anti-glare hard coat film was cut out to prepare test pieces (5 pieces) of 10 cm×10 cm.

Five test pieces were placed on a flat part with the anti-glare hard coat layer facing upward, and the maximum heights of the four corners were measured, and the curling property of the obtained anti-glare hard coat film was evaluated according to the following criteria. .

The evaluation of curling property of the obtained anti-glare hard coat film was performed.

○: The average value of the maximum height is 10 mm or less.

△: The average value of the maximum height exceeds 10 mm and is 15 mm or less.

×: The average value of the maximum height exceeds 15 mm and is 16 mm or less.

[Example 2]

In Example 2, except having increased the blending amount of the component (B1) in the antiglare hard coat layer forming material to 10 parts by mass, an antiglare hard coat film was produced and evaluated in the same manner as in Example 1.

[Example 3]

In Example 3, except that the blending amount of the (B1) component in the anti-glare hard coat layer forming material was increased to 10 parts by mass, and the blending amount of the (B3) component was reduced to 10 parts by mass, the same as the Example 1 An anti-glare hard coat film was produced and evaluated in the same manner.

[Example 4]

In Example 4, except that the blending amount of the (B1) component in the anti-glare hard coat layer forming material was increased to 16 parts by mass, the blending amount of the (B2) component was reduced to 20 mass parts, and the (B3) component The blending amount was reduced to 8 parts by mass, and the film thickness of the anti-glare hard coat layer was set to other than 5 μm, and an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Example 5]

In Example 5, except (B3) in the anti-glare hard coat layer forming material Except that the blending amount of the components was slightly reduced to 10 parts by mass, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Comparative Example 1]

In Comparative Example 1, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1, except that the component (B1) in the anti-glare hard coat layer-forming material was increased to 30 parts by mass.

Furthermore, in the evaluation of image visibility, the display device was driven to display a specific image (●▲■), but as shown in FIG. 4( b ), the outline of the specific image was blurred and could not be sufficiently recognized.

[Comparative Example 2]

In Comparative Example 2, an anti-glare hard coat film was produced in the same manner as in Example 1, except that the (B2) component in the anti-glare hard coat layer forming material was increased to 20 parts by mass and the (B3) component was increased to 30 parts by mass and evaluate.

[Comparative Example 3]

In Comparative Example 3, anti-glare properties were produced in the same manner as in Example 1, except that the component (B1) was increased to 10 parts by mass, the component (B2) was increased to 20 parts by mass, and the component (B3) was greatly increased to 30 parts by mass. Hard coat films and evaluate.

[Comparative Example 4]

In Comparative Example 4, except that the component (B1) in the anti-glare hard coat layer-forming material was greatly increased to 30 parts by mass, the component (B2) was increased to 20 parts by mass, and Moreover, except that the component (B3) was significantly increased to 30 parts by mass, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Comparative Example 5]

In Comparative Example 5, it was produced in the same manner as in Example 1, except that the blending amount of the component (B1) in the anti-glare hard coat layer-forming material was greatly increased to 30 parts by mass, and the component (B3) was reduced to 10 parts by mass. Anti-glare hard coat film and evaluation.

[Comparative Example 6]

In Comparative Example 6, except that the blending amount of the component (B1) in the anti-glare hard coat layer forming material was increased to 20 parts by mass, the component (B2) was reduced to 5 parts by mass, and the component (B3) was reduced to 6 parts by mass The thickness of the anti-glare hard coat layer was set to 10 μm, and an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Comparative Example 7]

In Comparative Example 7, except that the blending amount of the component (B1) in the anti-glare hard coat layer forming material was increased to 24 parts by mass, the component (B2) was reduced to 3 parts by mass, and the component (B3) was reduced to 4 parts by mass The thickness of the anti-glare hard coat layer was set to 15 μm, and an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Comparative Example 8]

In Comparative Example 8, except that the average particle diameter of the component (B1) in the anti-glare hard coat layer forming material was set to 1.5 μm, it was blended at a ratio of 30 parts by mass, and the component (B3) was reduced to 10 mass parts. Except for the parts, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Comparative Example 9]

In Comparative Example 9, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1, except that the component (B2) in the anti-glare hard coat layer forming material was not blended and the component (B3) was reduced to 2 parts by mass. .

[Comparative Example 10]

In Comparative Example 10, except that the blending amount of the (B1) component in the anti-glare hard coat layer forming material was increased to 10 parts by mass, the (B2) component was not blended, and the (B3) component was greatly reduced to 2 mass parts Except for the parts, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Comparative Example 11]

In Comparative Example 11, except that the blending amount of the component (B1) in the anti-glare hard coat layer forming material was increased to 30 parts by mass, the component (B2) was not blended, and the component (B3) was reduced to 4 parts by mass Other than that, it carried out similarly to Example 1, produced and evaluated the anti-glare hard coat film.

[Comparative Example 12]

In Comparative Example 12, except for (B1) in the anti-glare hard coat layer forming material The blending amount of the components was reduced to 3 parts by mass, and except that the components (B2) and (B3) were not blended, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1.

[Comparative Example 13]

In Comparative Example 13, an anti-glare hard coat film was produced and evaluated in the same manner as in Example 1, except that the components (B2) and (B3) in the anti-glare hard coat layer forming material were not blended.

[Comparative Example 14]

In Comparative Example 14, except that the blending amount of the (B1) component in the anti-glare hard coat layer forming material was increased to 10 parts by mass, and the (B2) component and the (B3) component were not blended, the same as Example 1. An anti-glare hard coat film was produced and evaluated in the same manner.

[Comparative Example 15]

In Comparative Example 15, except that the blending amount of the (B1) component in the anti-glare hard coat layer forming material was increased to 15 parts by mass, and the (B2) component and the (B3) component were not blended, the same as Example 1. An anti-glare hard coat film was produced and evaluated in the same manner.

[Comparative Example 16]

In Comparative Example 16, except that the blending amount of the (B1) component in the anti-glare hard coat layer forming material was greatly increased to 30 parts by mass, and the (B2) component and the (B3) component were not blended, the same as the Example. 1 An anti-glare hard coat film was produced and evaluated in the same manner.

[Industrial Availability]

As described in detail above, according to the present invention, at least three kinds of particles are blended in a specific ratio with respect to the anti-glare hard coat layer forming material for forming the anti-glare hard coat layer, while the thickness is limited to a specific value or less , which can effectively prevent discoloration, and can obtain an anti-glare hard-coat film exhibiting excellent anti-glare property, and even if the anti-glare hard coat layer is relatively thin, it has high surface hardness and less occurrence of curling.

Furthermore, according to the present invention, even when applied to a high-definition display such as a satellite navigation, it is possible to obtain an anti-glare hard coat film that can improve image visibility and effectively suppress the occurrence of glare.

Further, according to the present invention, since the entire anti-glare hard coat film is easily thinned, the production steps can be simplified and the production cost can be reduced.

Therefore, according to the present invention, even when applied to a high-definition display such as a satellite navigation, it is possible to obtain an anti-glare hard coat film that can improve image visibility and effectively suppress the occurrence of glare.

In addition, according to the anti-glare hard coating film of the present invention, even if the anti-glare hard coating is not formed on both sides of the plastic substrate, but only on one side, it can exhibit specific anti-glare properties, etc. Prevents curling.

Therefore, since the entire anti-glare hard coat film is easily thinned, the production steps can be simplified and the production cost can be reduced.

10: Anti-glare hard coating film

10': Anti-glare hard coating film

12: Plastic substrate

12': plastic substrate

14: Specific complex particles

14': spherical resin particles

14a: Silicon oxide particles

14b: High refractive index particles (zirconia particles)

14c: resin particles

15: Active energy ray curable resin

16: Anti-glare hard coating

16': Anti-glare hard coat

Claims (5)

An anti-glare hard coating film, characterized in that the surface of a plastic substrate is provided with an anti-glare hard coating, and the anti-glare hard coating system comprises an active energy ray curable resin as component (A), and an active energy ray curable resin as (B1) ), the high-refractive index particles as the component (B2) are inorganic fine particles with a refractive index of 1.8 or more, and the resin particles as the (B3) component are derived from an anti-glare hard coat layer forming material, and have a thickness of An anti-glare hard coating film with an anti-glare hard coating of 8 μm or less, the average particle size of the silicon oxide particles as the component (B1) is in the range of 2.1 to 10 μm, and the above-mentioned as the component (B2) The higher The average particle diameter of the refractive index particles is in the range of 1 to 500 nm, and the average particle diameter of the resin particles as the component (B3) is in the range of 0.5 to 2 μm, relative to the activity of the component (A) described above. 100 parts by mass of the energy ray curable resin, the blending amount of the silicon oxide particles as the component (B1) is 5-25 mass parts, and the blending amount of the high-refractive-index particles as the component (B2) is 3-30 Parts by mass and the blending amount of the resin particles as the component (B3) is 4 to 25 parts by mass, and the silicon oxide particles are obtained from the anti-glare hard coat layer and the plastic substrate. The surface on the opposite side protrudes. The anti-glare hard coat film according to claim 1, wherein the silicon oxide particles are pulverized silicon oxide particles. The anti-glare hard coating film as claimed in claim 1, wherein the overall haze value of the anti-glare hard coating film measured according to JIS K 7136 is in the range of 15~40%, and the internal haze value is 5~38% The value within the range, and the external turbidity value does not reach the value of 40%. The anti-glare hard coating film according to claim 1, wherein the surface hardness of the anti-glare hard coating is 2H or more. A method for producing an anti-glare hard coating film, characterized in that the surface of a plastic substrate is provided with an anti-glare hard coating, and the anti-glare hard coating system comprises an active energy ray curable resin as component (A), Silicon oxide particles as the component (B1), high-refractive index particles as the component (B2) are inorganic fine particles having a refractive index of 1.8 or more, and resin particles as the component (B3) derived from an anti-glare hard coat layer forming material , The production method of the anti-glare hard coating film of the anti-glare hard coating, the average particle size of the silicon oxide particles as the component (B1) is a value in the range of 2.1 to 10 μm, and the above-mentioned as the component (B2) High The average particle size of the refractive index particles is in the range of 1 to 500 nm, The average particle size of the resin particles as the component (B3) is in the range of 0.5 to 2 μm, and at least the following steps (1) to (3) are included, (1) to the active energy of the component (A) described above. 100 parts by mass of linear curable resin, 5 to 25 parts by mass of silicon oxide particles as component (B1), 3 to 30 parts by mass of high refractive index particles as component (B2), and 4 resin particles as component (B3) The steps of mixing ~25 parts by mass to prepare the anti-glare hard coat layer forming material, (2) the step of coating the aforementioned anti-glare hard coat layer forming material on the substrate to form a coating film, (3) The coating film on the substrate is irradiated with active energy rays to form an anti-glare hard coat layer with a thickness of 8 μm or less protruding from the surface of the anti-glare hard coat layer on the opposite side of the plastic substrate by the silicon oxide particles. step.

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