KR102453732B1 - Anti-glare hard coat film and method of producing anti-glare hard coat film - Google Patents

Abstract

This invention makes it a subject to provide the anti-glare hard-coat film etc. which can prevent color fading.
As a means for solving such a subject, as an anti-glare hard coat film etc., with respect to 100 mass parts of active energy ray-curable resin as (A) component, 5-25 mass parts of silica particles as (B1) component, (B2) ) An anti-glare hard coat layer with a thickness of 8 µm or less derived from an anti-glare hard coat layer forming material containing 3 to 30 parts by mass of high refractive index particles as a component and 4 to 25 parts by mass of resin particles as component (B3) In addition, it is characterized in that the silica particles protrude from the film surface.

Description

The manufacturing method of an anti-glare hard-coat film and an anti-glare hard-coat film TECHNICAL FIELD

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

In particular, it relates to an anti-glare hard coat film capable of effectively preventing color fading and the like, and an efficient manufacturing method of such an anti-glare hard coat film.

BACKGROUND ART Conventionally, in displays such as tablet-type terminals and car navigation systems, there has been a problem that external light is reflected on a screen display surface, and the displayed image becomes difficult to visually recognize.

On the other hand, when these displays are displayed in black, a phenomenon in which the screen display surface appears faded (hereinafter referred to as color fading) is seen, and with the recent enlargement of the display, the importance of solving this problem increases, have.

Then, as a means to solve the problem of such external light reflection, the technique of using the anti-glare hard-coat material which has an anti-glare hard-coat layer is proposed.

That is, in such an anti-glare hard coat layer, when forming the hard coat layer, a method of roughening the surface of the hard coat layer by a physical method, a filler in the hard coat agent for forming the hard coat layer There is a method of mixing incompatible two components into a hard coat agent for forming a hard coat layer, and a method of utilizing their phase separation.

All of these countermeasures are by making the surface of the hard coat layer, that is, the surface opposite to the plastic substrate of the hard coat layer, the surface of the hard coat layer (hereinafter the same), and forming fine irregularities on the surface. , which suppresses the specular reflection of external light and prevents reflection of external light such as a fluorescent lamp.

For example, as an anti-glare layer of a predetermined thickness comprising large-diameter fine particles and small-diameter fine particles having a specific gravity larger than that of the large-diameter fine particles and having a smaller particle diameter in a transparent base film, the volume ratio of the large-diameter fine particles is 0.5% or more and 40% Below, the anti-glare film formed by laminating|stacking the glare-proof layer whose volume ratio of 15 % or more and 65 % or less of small-diameter microparticles|fine-particles is proposed (refer patent document 1).

Here, as large-diameter fine particles, resin particles such as acrylic resin having an average particle diameter of 0.1 to 5 µm are disclosed, and as small-diameter fine particles, inorganic particles such as zirconium oxide or silica having an average particle diameter of 0.01 to 0.1 µm are disclosed. .

Japanese Patent Application Laid-Open No. 2016-133722 (Scope of Claims)

However, the anti-glare film disclosed in Patent Document 1 uses a plurality of types of fillers to ensure image visibility while suppressing the glare feeling on the screen (hereinafter, simply referred to as “glare”). Although the anti-glare film which can be made is disclosed, it did not intend at all about suppressing color fading.

In addition, the large-diameter fine particles are organic fine particles, and due to the fact that the average particle diameter is relatively large, an anti-glare film with a thin thickness of the anti-glare layer cannot be obtained, or when the thickness of the anti-glare layer is thick, the anti-glare film is The problem of curling appeared.

Moreover, organic microparticles|fine-particles fall off easily from the surface of a hard-coat layer, sufficient abrasion resistance cannot be acquired, and also the problem that anti-glare property falls more easily by time-lapse appeared.

Then, in view of the above circumstances, the present inventors made earnest efforts, In the forming material of an anti-glare hard-coat layer WHEREIN: While mix|blending at least 3 types of particle|grains in a predetermined ratio, the anti-glare hard-coat layer By limiting the thickness to a predetermined value or less, the present invention has been completed.

That is, an object of the present invention is to be able to effectively prevent color fading by using a plurality of types of particles together in a predetermined ratio, etc., and to have excellent anti-glare properties and the like, and the thickness of the anti-glare hard coat layer It is to provide the anti-glare hard-coat film with little generation|occurrence|production of curl, and the efficient manufacturing method of such an anti-glare hard-coat film which has high surface hardness even if it is comparatively thin.

According to the present invention, an anti-glare hard coat film having an anti-glare hard coat layer on the surface of a plastic substrate, the anti-glare hard coat layer comprising:

(A) With respect to 100 mass parts of active energy ray-curable resins as a component,

(B1) 5-25 mass parts of silica particles as a component,

(B2) 3-30 mass parts of high refractive index particle|grains as a component,

(B3) 4-25 mass parts of resin particles as a component

It is an anti-glare hard coat layer with a thickness of 8 μm or less, derived from an anti-glare hard coat layer forming material containing An anti-glare hard coat film is provided, characterized in that there is, it is possible to solve the above-mentioned problems.

That is, according to the anti-glare hard coat film of the present invention, the anti-glare hard coat layer contains at least three kinds of particles (B1 to B3) in a predetermined ratio and limits the thickness to a predetermined value or less. , from the surface of the anti-glare hard coat layer (meaning the other surface of the anti-glare hard coat layer on the opposite side to the plastic substrate provided with the anti-glare hard coat layer. Hereinafter, the same applies), silica particles are certain Moreover, it can be set as the state which protruded stably.

Therefore, while being able to prevent color fading effectively, it has the excellent anti-glare property, and even if the thickness of an anti-glare hard-coat layer is comparatively thin, it has high surface hardness, and a room with little generation|occurrence|production of curl. An express hard coat film can be obtained.

Moreover, in constituting the anti-glare hard coat film of the present invention, it is preferable that the silica particles are pulverized silica particles.

This is because, compared with the spherical silica particles, the pulverized silica particles tend to have a wide particle size distribution, and the mutual adhesion with other materials tends to increase effectively.

Therefore, the pulverized silica particles having a relatively large average particle size are likely to exist, and a part of the pulverized silica particles are likely to stably protrude from the surface of the anti-glare hard coat layer, and have higher surface hardness, and also have higher surface hardness. It is because the anti-glare hard-coat film with little generation|occurrence|production of can be obtained.

Moreover, in comprising the anti-glare hard coat film of this invention, it is preferable to make the average particle diameter of a silica particle into the value within the range of 2.1-10 micrometers.

Thus, by using the silica particle which controlled the average particle diameter, while being able to prevent color fading more effectively, more excellent anti-glare property etc. can be acquired.

Moreover, in comprising the anti-glare hard coat film of this invention, it is preferable to make the average particle diameter of high refractive index particle|grains into the value within the range of 1-1000 nm.

Thus, by using the high refractive index particle|grains whose average particle diameter is controlled, it mixes with predetermined silica particle and resin particle, and while being able to prevent color fading more effectively, more excellent anti-glare property etc. can be acquired.

Moreover, in comprising the anti-glare hard coat film of this invention, it is preferable to make the average particle diameter of a resin particle into the value within the range of 0.5-2 micrometers.

Thus, by using the resin particle which controlled the average particle diameter, while being able to mix with predetermined silica particle and resin particle, color fading property can be prevented more effectively, more excellent anti-glare property etc. can be acquired.

Moreover, in constituting the anti-glare hard coat film of the present invention, the total haze value of the anti-glare hard coat film measured in accordance with JIS K 7136 (2000) is set to a value within the range of 15 to 40%, and internal haze value It is preferable to set the value within the range of 5 to 38%, and to set the external haze value to a value less than 40%.

In this way, by controlling not only the overall haze value of the anti-glare hard coat layer, but also the external haze value, etc., color fading can be more effectively prevented, and more excellent anti-glare properties, image visibility, glare suppression, etc. can be obtained

Moreover, in comprising the anti-glare hard-coat film of this invention, it is preferable that the surface hardness of an anti-glare hard-coat layer is 2H or more.

Thus, by controlling surface hardness, even if the thickness of an anti-glare hard-coat layer is comparatively thin, the anti-glare hard-coat film provided with the anti-glare hard-coat layer which has higher surface hardness stably can be obtained.

Further, another aspect of the present invention is a method for producing an anti-glare hard coat film having an anti-glare hard coat layer on the surface (especially one side) of a plastic substrate, comprising at least steps (1) to (3) It is a manufacturing method of the anti-glare hard coat film, characterized in that.

(1) With respect to 100 mass parts of active energy ray-curable resin as (A) component, 5-25 mass parts of silica particles as (B1) component, 3-30 mass parts of high refractive index particle|grains as (B2) component, (B3) The process of mix|blending the resin particle as a component in the ratio of 4-25 mass parts, and setting it as an anti-glare hard-coat layer forming material.

(2) The process of coating an anti-glare hard-coat layer forming material on a base material, and forming 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 in which silica particles protrude from the surface of the anti-glare hard coat layer on the opposite side to the plastic substrate. forming process.

Thus, by forming the anti-glare hard coat film comprising at least three kinds of particles (B1 to B3) in a predetermined ratio, the silica particles are reliably formed from the predetermined surface of the anti-glare hard coat layer (film-like cured product). Moreover, it can be set as the state which protruded stably.

Therefore, while being able to prevent color fading effectively, it is equipped with the outstanding anti-glare property, and even if the thickness of an anti-glare hard-coat layer is comparatively thin, it has high surface hardness, and there is little generation|occurrence|production of curl. An anti-glare hard coat film can be obtained efficiently.

1(a)-(b) is a figure provided in order to compare and demonstrate the aspect of the anti-glare hard-coat film of this invention, and the aspect of the conventional anti-glare hard-coat film.
Fig. 2 (a) is a diagram provided to explain a particle size distribution chart of silica particles used in Example 1, etc., and Fig. 2 (b) is a diagram provided to explain a particle size distribution chart of other silica particles. and FIG. 2C is a diagram provided to explain a particle size distribution chart of resin particles used in Example 1 and the like.
It is a figure provided in order to demonstrate the aspect of the polarizing plate formed using the anti-glare hard-coat film of this invention.
4A to 4B are diagrams provided to explain the image visibility in Example 1 and Comparative Example 1, respectively.

[First embodiment]

A first embodiment is an anti-glare hard coat film having an anti-glare hard coat layer on the surface of a plastic substrate, the anti-glare hard coat layer comprising:

(A) With respect to 100 mass parts of active energy ray-curable resins as a component,

(B1) 5-25 mass parts of silica particles as a component,

(B2) 3-30 mass parts of high refractive index particle|grains as a component,

(B3) 4-25 mass parts of resin particles as a component

It is an anti-glare hard coat layer with a thickness of 8 μm or less, derived from an anti-glare hard coat layer forming material containing It is an anti-glare hard coat film characterized in that there is.

EMBODIMENT OF THE INVENTION Hereinafter, 1st Embodiment of this invention is specifically demonstrated with reference to drawings suitably. For example, FIG. 1(a) is a figure provided in order to demonstrate the cross section of the anti-glare hard-coat film 10 of 1st Embodiment, FIG. It is a view provided to explain the cross-section of the film 10'.

1. Anti-glare hard coat layer

(1) Anti-glare hard coat layer forming material

As shown to Fig.1 (a), the anti-glare hard coat film 10 of this invention contains the predetermined plurality of particle|grains 14 (14a, 14b, 14c) on the plastic base material 12, The room which consists of It includes an expressive hard coat layer (sometimes set as a film-like cured product) 16 .

That is, as the cross section is shown to Fig.1 (a), the anti-glare hard-coat layer 16 is typically active energy ray-curable resin 15 as (A) component, and (B1) component An anti-glare hard coat layer forming material comprising silica particles 14a, high refractive index particles 14b as a component (B2), a resin particle 14c as a component (B3), and a photopolymerization initiator as a component (C) It is comprised from film-form hardened|cured material.

On the other hand, as the cross section is shown in FIG.1(b), typical conventional anti-glare hard-coat film 10' contains spherical resin particle 14' on plastic base material 12'. An anti-glare hard coat layer 16' is provided.

That is, as particles for imparting anti-glare properties based on light scattering or the like to the anti-glare hard coat layer 16', for example, only relatively large spherical resin particles 14' are used, and Comparative Example 13 of the present invention It corresponds to the structure shown in -17.

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

The kind of active energy ray-curable resin (including ultraviolet-ray-curable resin) as component (A) is not particularly limited and can be selected from conventionally known ones, but energy ray-curable monomers, oligomers, resins, or mixtures thereof can be heard

More specifically, it is preferable to use a polyfunctional (meth)acrylic-based monomer or a (meth)acrylate-based prepolymer.

Further, as the polyfunctional (meth)acrylic monomer, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid Di(meth)acrylate, allylated cyclohexyldi(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, Propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid modified di Polyfunctional (meth)acrylates, such as pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, are mentioned.

In addition, these monomers may be used 1 type, and may be used in combination of 2 or more type.

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

Here, as the polyester acrylate-based prepolymer, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both terminals obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol with (meth)acrylic acid, or It can obtain by esterifying the hydroxyl group of the terminal of the oligomer obtained by adding alkylene oxide to carboxylic acid with (meth)acrylic acid.

Further, the epoxy acrylate-based prepolymer can be obtained by, for example, esterifying (meth)acrylic acid by reacting (meth)acrylic acid with an oxylan ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin.

In addition, a urethane acrylate type prepolymer can be obtained by esterifying with (meth)acrylic acid the polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol, and polyisocyanate, for example.

Moreover, a polyol acrylate type prepolymer can be obtained by esterifying the hydroxyl group of polyether polyol with (meth)acrylic acid. These prepolymers may be used individually by 1 type, may be used in combination of 2 or more type, and may be used together with the polyfunctional (meth)acrylate type monomer mentioned above.

(1)-2 (B) component: multiple types of particles

(i) (B1) component (silica particles)

(type)

The silica particles as component (B1) have a larger average particle diameter (φ1) than the average particle diameter (φ2) of the high refractive index particles as the component (B2) or the average particle diameter (φ3) of the resin particles as the component (B3), In addition, in the particle size distribution, particles having a larger particle size than the film thickness t of the anti-glare hard coat layer are distributed, and furthermore, there is a characteristic of being quite hard (eg, Vickers hardness of 1200 MPa or more).

Therefore, since a part of the silica particle protrudes on the surface side of the anti-glare hard-coat layer opposite to the plastic base material, color fading can be effectively prevented and excellent anti-glare property of these silica particles. It expresses, and even if an anti-glare hard-coat layer is comparatively thin, while having high surface hardness, it can be set as the anti-glare hard-coat film with little generation|occurrence|production of curl.

Here, as a kind of silica particle as (B1) component, 1 type, such as spherical silica and amorphous pulverized silica, or a combination of 2 or more types is mentioned, for example.

And as such a silica particle, it is more preferable that it is a pulverized silica particle.

The reason for this is that, in the case of pulverized silica particles, the particle size distribution tends to be wider than that of spherical silica particles, and the abundance ratio of particles larger and smaller than the average particle size of the pulverized silica particles is higher than that of the spherical silica particles, respectively. because it rises

When the abundance ratio of particles larger than the average particle diameter increases, some of the particles tend to protrude stably from the surface of the anti-glare hard coat layer, effectively preventing color fading and exhibiting excellent anti-glare properties. have.

On the other hand, when the abundance ratio of the particle|grains smaller than an average particle diameter increases, the abundance ratio of the silica particle in an anti-glare hard-coat layer will become high, and the anti-glare hard-coat layer which has high surface hardness can be obtained.

Further, since the surface of the pulverized silica particle has many fine irregularities (corners and protrusions), the surface area of the pulverized silica particle is larger than that of the spherical silica particle or the like, and thus the contact area with other materials is large.

As a result, the mutual adhesiveness of a pulverized silica particle and another material becomes high effectively, and even if the thickness of an anti-glare hard-coat layer is comparatively thin, the anti-glare hard-coat layer which has a higher surface hardness can be obtained.

Therefore, by using the pulverized silica particles, as described above, the characteristics such as the particle size distribution of the particles effectively prevent color fading, exhibit excellent anti-glare properties, and have high surface hardness. An anti-glare hard coat film having

The pulverized silica particles are silica particles formed by pulverizing spherical silica such as fused silica or crystalline silica by a predetermined means, and usually mean silica particles having irregularities such as sharp corners and protrusions on the surface.

(average particle size)

It is preferable that the average particle diameter (phi 1: volume average particle diameter) of the silica particle as (B1) component contained in the anti-glare hard-coat layer forming material sets it as the value within the range of 2.1-10 micrometers normally.

When the average particle diameter of the silica particles is a value within this range, adjustment of the external haze value and the like becomes easy mainly, effectively preventing color fading, and exhibiting excellent anti-glare properties, improving image visibility While maintaining it, it can suppress effectively also about generation|occurrence|production of glare. In addition, when the average particle diameter of the silica particles is a value within this range, it becomes possible to make the thickness of the anti-glare hard coat layer relatively thin, and an anti-glare hard coat layer with high surface hardness and little occurrence of curls. The anti-glare hard-coat film which has can be obtained.

More specifically, when the average particle diameter of the silica particles is a value of less than 2.1 μm, the silica particles are less likely to protrude from the surface of the anti-glare hard coat layer, and it becomes difficult to adjust the values such as the external haze value. It may become difficult to maintain the suppression of glare or glare.

On the other hand, when the average particle diameter of the silica particles exceeds 10 µm, it becomes difficult to prevent color fading or ensure image visibility, particularly when applied to a high-definition display, or decrease in surface hardness or curl. etc. are likely to occur or may occur.

Therefore, it is more preferable to make the average particle diameter of a silica particle into the value within the range of 2.5-8 micrometers, and it is more preferable to set it as the value within the range of 3-6 micrometers.

It is preferable to determine the average particle diameter (phi 1) of a silica particle in consideration of the film thickness t of a hard-coat layer, and it is also preferable that the average particle diameter of such a silica particle and the film thickness of a hard-coat layer are substantially equal.

This is because if the average particle diameter of these silica particles and the film thickness of a hard-coat layer are substantially equal, a part of a silica particle can protrude uniformly and stably from the surface of an anti-glare hard-coat layer.

For example, by satisfying the relational expression of 0.8 x t ≤ φ 1 ≤ 2.0 x t, more preferably by satisfying the relation of 0.9 x t ≤ φ 1 ≤ 1.8 x t, the silica particles form an anti-glare hard coat layer A part of silica particles protrude easily on the surface side opposite to the plastic base material, and it becomes easy to adjust an external haze value etc. effectively.

As a result, while effectively preventing color fading, the excellent anti-glare property can be expressed and the hard-coat layer which suppressed generation|occurrence|production of glare can be obtained, ensuring image visibility.

Moreover, when referring to the particle size distribution of the silica particle as (B1) component, it is preferable to have the particle size distribution chart shown to FIG.2(a) or FIG.2(b).

That is, the particle size distribution chart of silica particles shown in Fig. 2 (a) corresponds to the silica particles used in Example 1 and the like, but on the particle size distribution chart, it has two peaks, so two or more types of silica particles having different particle size distributions It is understood that the particles are mixed.

That is, it is a combination silica particle (average particle diameter: 3.2 μm) of the first silica particles having an average particle diameter of about 8 μm and the second silica particles having an average particle diameter of about 0.7 μm.

On the other hand, the particle size distribution chart of the silica particle shown in FIG.2(b) has one peak on the said particle size distribution chart, It is characterized by the above-mentioned. That is, it is understood as single silica particles (average particle diameter: 3.2 μm) having an average particle diameter of about 3 μm.

And, in the case of Example 1 of the present invention, although the combined silica particles of the particle size distribution shown in Fig. 2 (a) are used, even when single silica particles of the particle size distribution shown in Fig. 2 (b) are used, It has been confirmed separately that it exhibits the same anti-fading properties, anti-glare properties, and the like.

(Amount)

Moreover, it is preferable to make the compounding quantity of the silica particle as (B1) component contained in the anti-glare hard-coat layer forming material into the value within the range of 5-25 mass parts with respect to 100 mass parts of (A) component.

When the blending amount of the silica particles is a value within this range, it is mainly possible to easily adjust the external haze value, etc., effectively preventing color fading, and exhibiting excellent anti-glare properties, The occurrence of glare can be effectively suppressed while maintaining image visibility.

More specifically, when the compounding amount of such silica particles is less than 5 parts by mass, it becomes difficult for a part of the silica particles to protrude from the surface of the anti-glare hard coat layer, and it becomes difficult to adjust values such as external haze value. . Therefore, when sufficient anti-glare property expression becomes difficult, it may become difficult to suppress generation|occurrence|production of glare.

On the other hand, when the compounding quantity of such silica particles exceeds 25 parts by mass, especially when applied to a high-definition display, it may become difficult to prevent color fading and ensure image visibility, or surface hardness may decrease. .

Therefore, it is more preferable to make the compounding quantity of a silica particle into the value within the range of 7-20 mass parts with respect to 100 mass parts of (A) component, and it is still more preferable to set it as the value within the range of 10-15 mass parts.

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

(type)

(B2) The high refractive index particles as the component, for example, the refractive index (n _d ) corresponds to inorganic fine particles of 1.8 or more, more preferably, the refractive index (n _d ) of 1.9 or more inorganic fine particles, more preferably, It is an inorganic fine particle whose refractive index (n _d ) is 2.0 or more.

Specifically, zirconium oxide 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), zinc oxide (n _d : 2.0), platinum (n _d : 2.95), tungsten (n _d : 2.76), etc. are mentioned at least 1 sort(s), Especially, it is preferable that they are zirconium oxide particle|grains.

The reason for this is that if the high refractive index particles are zirconium oxide particles, they are relatively large with respect to the component specific gravity of the anti-glare hard coat layer, and since the average particle size is small, together with the component (B3) described later, the bottom portion, namely , it is unevenly distributed on the plastic base material side of the anti-glare hard coat layer, and mainly, it is possible to effectively exert an adjustment function such as an internal haze value.

In addition, if it is a zirconium oxide particle, since it is easy to gather around the comparatively large silica particle as (B1) component, by mix|blending these zirconium oxide particle|grains, not only the fixability and surface hardness of a silica particle are improved, but also One surface hardness can be exhibited more effectively.

Here, as a kind of zirconium oxide particle|grains as (B2) component, for example, as a main component, _the compound represented by ZrO2 corresponds, and it is preferable to have a monoclinic crystal structure at room temperature.

In addition, as the zirconium oxide particles, a stabilized zirconium oxide particle formed by blending zirconium with a rare earth oxide such as calcium oxide, magnesium oxide, or yttrium oxide, and metastabilized zirconium oxide particles corresponding thereto can also be used.

In addition, in order to prevent aggregation of zirconium oxide particles and excessive localization, and to be firmly fixed inside the anti-glare hard coat layer, a monomer or oligomer having a radical reactive group is mixed on the surface of the zirconium oxide particles. It is preferable to use the reactive zirconium oxide particle|grains formed by coating.

Therefore, if it is such a reactive zirconium oxide particle, since it further gathers around the periphery of a comparatively large silica particle and forms a strong inorganic area|region, the effect of further raising the surface hardness of an anti-glare hard-coat layer can also be exhibited.

(average particle size)

In this invention, it is preferable to make the average particle diameter (phi 2: volume average particle diameter) of high refractive index particle|grains as (B2) into a value within the range of 1-1000 nm.

The reason for this is that if the average particle diameter of these high refractive index particles is within this range, it is easy to adjust the internal haze value, etc., and while maintaining excellent anti-glare properties and image visibility, the occurrence of glare can also be effectively suppressed. Because.

When the average particle diameter of high refractive index particle|grains becomes a value less than 1 nm, it may become difficult to maintain sufficient anti-glare property.

On the other hand, when the average particle diameter of high refractive index particle|grains exceeds 1000 nm, especially when it applies to a high-definition display, it may become difficult to suppress generation|occurrence|production of glare effectively.

Therefore, it is more preferable to make the average particle diameter of high refractive index particle|grains into the value within the range of 5-500 nm, and it is more preferable to set it as the value within the range of 10-100 nm.

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

(Amount)

(B2) It is preferable to make the compounding quantity of the high refractive index particle|grains as a component into the value within the range of 3-30 mass parts with respect to 100 mass parts of (A) component.

The reason for this is that when the blending amount of the high refractive index particles falls within this range, adjustment of the internal haze value and the like becomes easy. because it can

That is, when the compounding quantity of high refractive index particle|grains becomes a value less than 3 mass parts, adjustment of an internal haze value etc. becomes difficult, and it may become difficult to exhibit sufficient anti-glare property.

On the other hand, when the compounding quantity of high refractive index particle|grains exceeds 30 mass parts and it applies especially to a high-definition display, generation|occurrence|production suppression of glare and ensuring of image visibility may become difficult.

Accordingly, the blending amount of the high refractive index particles is more preferably within the range of 5 to 28 parts by mass, more preferably within the range of 8 to 25 parts by mass, and most preferably within the range of 10 to 20 parts by mass. desirable.

(iii) (B3) component: resin particles

(B3) Since the resin particle as a component is comparatively small with respect to the film thickness (t) of an anti-glare hard-coat layer, it exists not in the surface of an anti-glare hard-coat layer, but exists inside, and high refractive index which is (B2) component. In combination with the particles, it is possible to further facilitate adjustment of the internal haze value of the anti-glare hard coat layer of the present invention.

The reason for this is due to the presence of a portion in which the resin particles as component (B3) and a portion in which high refractive index particles as component (B2) exist, in the anti-glare hard coat layer, a structure having a different refractive index is formed. This is because, as a result, adjustment of the internal haze value and the like becomes easy.

Here, as a kind of resin particle as (B3) component, for example, silicone resin microparticles|fine-particles, modified silicone resin microparticles|fine-particles, melamine resin microparticles|fine-particles, acrylic polymer resin microparticles|fine-particles (For example, polymethylmethacrylate resin microparticles|fine-particles, etc. are mentioned ), acrylic-styrene copolymer resin microparticles, polycarbonate resin microparticles, polyethylene resin microparticles, styrene polymer resin microparticles, benzoguanamine resin microparticles, etc. alone, or a mixture of two or more thereof is preferable.

Especially, it is preferable that it is at least 1 sort(s) selected from the group which consists of acrylic polymer resin microparticles|fine-particles, acryl- styrene copolymer resin microparticles|fine-particles, styrene polymer resin microparticles|fine-particles, and silicone resin microparticles|fine-particles.

The reason for this is that these resin fine particles contribute to the dispersibility of the silica particles as the component (B1) and the high refractive index particles as the component (B2), on the other hand, on the surface of the anti-glare hard coat layer, on the surface of the anti-glare hard coat layer, while being relatively inexpensive. It is because it contributes to stably forming the fine unevenness|corrugation resulting from this, and it becomes easy to obtain a desired internal haze value etc. in harmony with (B2) component.

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, the silica particles as the component (B1) in the coating film protrude from the surface of the anti-glare hard coat layer. The precision can be controlled effectively, and the fine unevenness|corrugation of the surface of an anti-glare hard-coat layer can be formed more stably.

As a result, while effectively preventing color fading, excellent anti-glare properties can be expressed, and furthermore, in harmony with the ease of adjustment such as the above-described internal haze value, image visibility is ensured, while generation of glare is suppressed. An overt hard coat layer can be obtained.

(average particle size)

(B3) It is preferable to make the average particle diameter (volume average particle diameter) of the resin particle as a component into the value within the range of 0.5-2 micrometers.

The reason for this is that when the average particle diameter of the resin particles falls within this range, it is mainly possible to easily adjust the internal haze and effectively suppress the occurrence of glare while maintaining excellent anti-glare properties and image visibility. to be.

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

On the other hand, when the average particle diameter of a resin particle exceeds 2 micrometers and it applies to a high definition display especially, it may become difficult to ensure image visibility.

Therefore, it is more preferable to make the average particle diameter of a resin particle into the value within the range of 0.8-1.8 micrometers, and it is more preferable to set it as the value within the range of 1.0-1.6 micrometers.

In addition, the average particle diameter of the resin particles is, for example, using a laser diffraction scattering type particle size distribution analyzer to obtain a volume-based particle size distribution chart as shown in Fig. 2(c), from which D50 as the median diameter. As, it can be calculated.

(mixture)

(B3) It is preferable to make the compounding quantity of the resin particle as a component into the value within the range of 4-25 mass parts with respect to 100 mass parts of (A) component.

This reason is in order to ensure image visibility by making a comparatively small resin particle exist inside an anti-glare hard-coat layer, and expressing a predetermined internal haze value, and also originating in the silica particle which is (B1) component. This is because the excellent anti-glare property is obtained by stably forming the unevenness.

More specifically, when the compounding quantity of a resin particle becomes a value of less than 4 mass parts, fine unevenness|corrugation cannot fully be formed in the surface of an anti-glare hard-coat layer, but it may become difficult to obtain desired anti-glare property.

On the other hand, when the compounding quantity of a resin particle will be a value exceeding 25 mass parts, a haze value may become large excessively and the image visibility of the display image of a display may fall.

Therefore, it is more preferable to make the compounding quantity of resin microparticles|fine-particles into the value within the range of 8-23 mass parts with respect to 100 mass parts of active energy ray-curable resin as (A) component, It is to set it as the value within the range of 10-20 mass parts It is more preferable, and it is still more preferable to set it as the value within the range of 12-18 mass parts.

(1)-4 (C) Component: Photoinitiator

(i) kind

In order for the anti-glare hard-coat layer forming material to make the active energy ray-curable resin as (A) component react easily and in a short time, and to harden|cure, it is preferable to contain the photoinitiator as (C)component further.

As a kind of such a photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydro Roxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy -2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone , 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal , p-dimethylaminobenzoic acid ester, etc. 1 type individually or 2 or more types of combinations are mentioned.

(ii) compounding amount

(C) It is preferable to make the compounding quantity of the photoinitiator as a component into the value within the range of 0.2-10 mass parts normally with respect to 100 mass parts of active energy ray-curable resins as (A) component.

This reason is because it may become difficult to obtain sufficient sclerosis|hardenability when the compounding quantity of a photoinitiator will be a value less than 0.2 mass part.

On the other hand, when the compounding quantity of a photoinitiator becomes a value exceeding 10 mass parts, abrasion resistance may fall.

Therefore, it is more preferable to make the compounding quantity of a photoinitiator into the value within the range of 0.5-7 mass parts with respect to 100 mass parts of active energy ray-curable resin as (A) component, It is to set it as a value within the range of 1-5 mass parts more preferably.

(1)-5 additives, etc.

The anti-glare hard-coat layer forming material can be prepared by adding the above-mentioned (A)-(C) component suitably in a suitable solvent as needed, and melt|dissolving or disperse|distributing uniformly.

At this time, in addition to the components (A) to (C), as an additive, for example, at least one of antioxidants, ultraviolet absorbers, silane coupling agents, light stabilizers, leveling agents, defoamers, dispersants, slip agents, etc. is further blended. It is also preferable to

Examples of the solvent used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, alcohols such as methanol, ethanol, propanol, butanol, and acetone. and ketones such as methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolve solvents such as ethyl cellosolve.

Moreover, as a density|concentration and viscosity of the anti-glare hard-coat layer forming material prepared in this way, what is necessary is just a numerical range which can be coated on the surface of a plastic base material, According to a situation, it can select suitably.

(2) thickness

The thickness t of the anti-glare hard coat layer is set to a value of 8 µm or less.

The reason for this is that when the thickness of such an anti-glare hard coat layer becomes a value exceeding 8 μm, the desired structure in the anti-glare hard coat layer cannot be obtained, or curls accompanying curing shrinkage of the active energy ray-curable resin. It is because it may become difficult to suppress the crack in the anti-glare hard-coat layer which arises when suppression becomes difficult or when bending an anti-glare hard-coat film.

However, when the thickness of such an anti-glare hard-coat layer becomes thin too much, it may become difficult to obtain the surface hardness required for practical use.

Accordingly, the thickness of the anti-glare hard coat layer is more preferably within the range of 1 to 7 µm, more preferably within the range of 2 to 6 µm, and more preferably within the range of 3 to 5 µm. it is most preferable

2. Plastic substrate

As a kind of plastic base material, it can select suitably from among well-known plastic base materials as a transparent base material of the hard-coat film for optics conventionally, and can be used.

Therefore, for example, polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, Polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, polyamide, Acrylic resin, norbornene-type resin, cycloolefin resin, etc. are mentioned.

In particular, it is preferable that the plastic base material is triacetyl cellulose (TAC).

The reason for this is that, in the case of TAC, optical anisotropy is small, transparency is high, and there is little possibility of blurring of image display, and the cost is relatively low and economical.

Further, from the viewpoint of good handleability and the like, the film thickness of the plastic substrate is preferably set to a value within the range of 15 to 300 µm, more preferably within the range of 30 to 200 µm, and preferably from 50 to 100 µm. It is more preferable to set it as a value within the range.

Moreover, as shown in FIG. 3, the anti-glare hard-coat film 110 of this invention can also be bonded together to the polarizer 111, and it can also be set as the polarizing plate 120.

That is, as a plastic substrate, for example, a film with little optical anisotropy, such as a triacetyl cellulose (TAC) film (first TAC film) 112a, is used, and on one surface, the anti-glare hard coat layer 116 is used. ) to form an anti-glare hard coat film 110 .

Next, the first TAC film 112a in which the anti-glare hard coat layer 116 is formed on one side of the polarizer 111, for example, a polyvinyl alcohol-based polarizer is applied through the first adhesive layer 115a. stack up

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

Thereby, while having the outstanding anti-glare property, even if it is a case where it applies to a high-definition display, the polarizing plate 120 which can suppress generation|occurrence|production of glare effectively can be obtained.

Moreover, as shown in FIG. 3, it is also preferable to provide the adhesive layer 118 and the peeling sheet 119 for bonding to optical components, such as a liquid crystal cell, in such a polarizing plate 120.

3. Characteristics of anti-glare hard coat film

(1) Haze value

(Total haze value)

Moreover, it is preferable to make into the value within the range of 15 to 40% of the total haze value (it may simply set it as a haze value) of the anti-glare hard-coat film measured based on JISK7136 (2000).

This is because it may become difficult to obtain the outstanding glare suppression property when this total haze value will be less than 15 %.

On the other hand, when such a total haze value exceeds 40 %, it is because the color fading of a display may generate|occur|produce remarkably or image visibility may fall remarkably.

Therefore, it is more preferable to make all the haze values of an anti-glare hard-coat film into the value within the range of 18 to 35 %, and it is more preferable to set it as the value within the range of 20 to 33 %.

(Internal haze value)

It is preferable to make the internal haze value of an anti-glare hard-coat layer into the value within the range of 5 % - 38 %.

When this internal haze value becomes a value less than 5 %, color fading property, glare, and anti-glare property may fall.

On the other hand, when such an internal haze value exceeds 38 %, image visibility may fall remarkably.

Therefore, it is more preferable to make the internal haze value of an anti-glare hard-coat film into the value within the range of 6 to 30 %, and it is more preferable to set it as the value within the range of 8 to 25 %.

(External haze value)

It is preferable to make the external haze value of an anti-glare hard-coat layer into a value less than 40 %.

When this external haze value becomes a value of 40% or more, the color fading property of a display may generate|occur|produce remarkably.

However, when such an external haze value becomes low excessively, glare or anti-glare property may fall.

Therefore, it is more preferable to make the external haze value of an anti-glare hard-coat film into the value within the range of 6 to 35 %, and it is more preferable to set it as the value within the range of 8 to 25 %.

(2) surface hardness

It is preferable that the anti-glare hard coat film has a predetermined surface hardness as pencil hardness, and there is no change in appearance in evaluation of abrasion resistance using steel wool.

This reason is because, when surface hardness is too low, an external appearance change will be confirmed in such evaluation of abrasion resistance, Furthermore, it is because it may become difficult to obtain sufficient scratch resistance as a hard-coat film.

Therefore, as for surface hardness (pencil hardness), it is preferable to set it as 1H or more, and, as for an anti-glare hard-coat film, it is more preferable to set it as 2H or more.

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

(3) Surface roughness 1

Moreover, it is preferable to make arithmetic mean roughness Ra which is one of the parameter|index of the surface roughness of the anti-glare hard-coat film measured based on JISB0601 (2001) into the value within the range of 0.1-0.3 nm.

This is because it may become difficult to obtain the excellent anti-glare property when such Ra becomes a value less than 0.1 nm.

On the other hand, when such Ra becomes a value exceeding 0.3 nm, color fading property may fall remarkably.

Therefore, it is more preferable to set this Ra to a value within the range of 0.15 to 0.28, and it is still more preferable to set it as a value within the range of 0.2 to 0.25.

(4) surface roughness 2

Moreover, it is preferable to make the maximum cross-sectional height Rt which is one of the parameter|index of the surface roughness of the anti-glare hard-coat film measured based on JISB0601 (2001) into the value within the range of 1-4.5 nm.

This reason is because it may become difficult to obtain the outstanding anti-glare property when this Rt becomes a value of less than 1 nm.

On the other hand, when such Ra becomes a value exceeding 4.5 nm, color fading property may fall remarkably.

Therefore, it is more preferable to make the surface roughness Rt of an anti-glare hard-coat film into the value within the range of 1.5-4 nm, and it is more preferable to set it as the value within the range of 2-3 nm.

[Second embodiment]

Moreover, 2nd Embodiment is a manufacturing method of the anti-glare hard-coat film provided with the anti-glare hard-coat layer on the surface of a plastic base material, Comprising: The anti-glare property characterized by including the process (1)-(3) at least. It is a manufacturing method of a hard-coat film.

(1) With respect to 100 mass parts of active energy ray-curable resin as (A) component, 5-25 mass parts of silica particles as (B1) component, 3-30 mass parts of high refractive index particle|grains as (B2) component, (B3) The process of mix|blending the resin particle as a component in the ratio of 4-25 mass parts, and setting it as an anti-glare hard-coat layer forming material.

(2) The process of coating an anti-glare hard-coat layer forming material on a base material, and forming a coating film.

(3) The coating film on the substrate is irradiated with an active energy ray, and as an anti-glare hard coat layer, silica particles protrude from the surface of the anti-glare hard coat layer on the opposite side to the plastic substrate, and have a thickness of 8 µm. The process of forming the following anti-glare hard-coat layers.

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

(A) With respect to 100 mass parts of active energy ray-curable resin as a component, 5-25 mass parts of silica particles as (B1) component, 3-30 mass parts of high refractive index particle|grains as (B2) component, (B3) It is a manufacturing process which mix|blends the resin particle as a component in the ratio of 4-25 mass parts, and uses it as an anti-glare hard-coat layer forming material.

That is, using a well-known mixing apparatus, predetermined amounts of component (A), component (B1), component (B2), component (B3) are mixed uniformly, respectively, the process of making an anti-glare hard-coat layer forming material to be.

In addition, in order to uniformly mix and stir the blended components in a short time, as a known mixing device, at least one of a propeller mixer, a ball mill, a bead mill, a V blender, three rolls, a kneader, a planetary mixer, a jet mill, etc. It is preferred to use the species.

2. Formation process of coating film by anti-glare hard-coat layer forming material

Next, the coating film by the anti-glare hard-coat layer forming material is formed.

That is, as a process for forming a coating film, an anti-glare hard coat layer forming material is applied to the surface of a plastic substrate by a conventionally known lamination method, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, and a die. It is a process of forming a coating film by coating using a coating method, a gravure coating method, etc.

3. Coating film curing process

Next, the hardening process of a coating film is implemented.

That is, after drying a coating film, an active energy ray is irradiated, a coating film is hardened, and an anti-glare hard-coat film can be obtained by making a coating film into an anti-glare hard-coat layer of predetermined thickness.

Here, an ultraviolet-ray is mentioned as an active energy ray when a coating film is hardened, and this ultraviolet-ray can be irradiated by a high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, etc.

Moreover, as an irradiation amount of an ultraviolet-ray, it is preferable to set it as the value within the range of 100-500 mJ/cm<2> normally, and it is more preferable to set it as the value within the range of 150-400 mJ/cm<2>.

(Example)

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

[Example 1]

1. Preparation of anti-glare hard coat film

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

(A) With respect to 100 parts by mass of the ultraviolet curable resin (a mixture of 50 parts by mass of polyfunctional acrylate-based monomer and 50 parts by mass of urethane acrylate oligomer) as component (B1), pulverized silica particles (average particle size: 3.2 µm, refractive index) : 1.5) with 7 parts by mass, (B2) reactive zirconium oxide particles (manufactured by Solar Co., Ltd., ZR-020, average particle diameter: 50 nm, refractive index: 2.1) with 10 parts by mass, (B3) as component 15 parts by mass of acrylic resin particles (manufactured by Sekisuigasehin Kogyo Co., Ltd., XX-27LA, average particle diameter: 1.5 µm, refractive index: 1.5) and 2 parts by mass of a photopolymerization initiator (manufactured by BASF, OMNIRAD184) as component (C) It diluted with propylene glycol monomethyl ether while sub-mixing, and the anti-glare hard-coat layer forming material of 30 weight% of solid content was manufactured.

In addition, in Table 1, the mass part of (B1)-(B3) component is a compounding ratio with respect to 100 mass parts of (A) component.

(2) Coating process

Next, the obtained anti-glare hard coat layer-forming material was applied to the easily adhesive layer of a triacetyl cellulose film (manufactured by TACBRIGHT, TECPHANP980RO, film thickness: 80 µm) with an easily adhesive layer as a plastic substrate, wire bar #14 was used so that the film thickness after curing was 3.5 µm to form a predetermined coating film.

(3) drying process

Next, the obtained coating film was dried on 70 degreeC and conditions for 1 minute using the hot air drying apparatus.

(4) curing process

Next, the dried coating film is irradiated with ultraviolet rays under the following conditions using an ultraviolet irradiation device (manufactured by GS Yuasa Corporation, light source: high-pressure mercury lamp) to cure the coating film, thereby preventing glare as a film-like cured product. The hard-coat layer was formed and the final anti-glare hard-coat film was obtained.

Illuminance: 100mW/cm2

Light quantity: 240mJ/㎠

2. Evaluation of anti-glare hard coat film

(1) Evaluation 1 (surface roughness)

Based on JISB0601 (2001), the surface roughness (Ra and Rt) of the obtained anti-glare hard-coat film was measured using the surface roughness meter (made by Mitutoyo, SV-3000).

(2) Evaluation 2 (haze value)

Based on JIS K 7136 (2000), using a haze meter (Nippon Denshoku Kogyo Co., Ltd. make, NDH5000), the haze value (%) of the obtained anti-glare hard coat film is measured, and it is the total haze value (%) ) was made.

Next, the peeling film of one side of the optically transparent adhesive material (Lintech Co., Ltd. product, OPTERIA NO-T015) which is a double-sided adhesive material is peeled, and with respect to the exposed surface, the anti-glare hard coat layer of the anti-glare hard coat film After positioning so as to oppose, the anti-glare hard coat film was affixed.

The haze value was measured in the state which peeled the peeling film of the other side of the transparent adhesive material for optics, and it was made into 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 made into the external haze value (%) of the anti-glare hard-coat film.

(3) Evaluation 3 (color fading)

On the display screen of the 264 ppi (pixel/inch) display device (Apple Co., Ltd. product, New iPad (trademark)), the obtained anti-glare hard-coat film was installed so that the anti-glare hard-coat layer might face upward.

Next, the display device was driven, a predetermined image (black) was displayed over the entire area, and the color fading property of the obtained anti-glare hard coat film was evaluated based on the following reference|standard.

○: No color fading was observed, and no decrease in visibility accompanying it was observed.

(triangle|delta): color fading property was slightly observed, and the fall of visibility accompanying it was observed slightly.

x: color fading was observed, and a decrease in visibility accompanying it was remarkably observed

(4) Evaluation 4 (anti-glare)

The opposite surface of the anti-glare hard-coat layer in the obtained anti-glare hard-coat film, and the black plate were bonded together using the transparent adhesive material for optics (Lintec Co., Ltd. product, OPTERIA NO-T015) which is a double-sided tape.

Next, from the upper side of the anti-glare hard coat film, a 3-wavelength fluorescent lamp was turned on, and according to the visibility state of the fluorescent lamp visually recognized by reflection of the anti-glare hard-coat film, according to the following reference|standard, anti-glare property was evaluated.

○: The outline of the visible fluorescent lamp is blurred

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

×: The outline of the fluorescent lamp visually recognized is not blurred

(5) Rating 5 (glare)

10 cm apart from the display screen of a 264 ppi (pixel/inch) display device (Apple Co., Ltd., New iPad (registered trademark)) installed

Next, the display device was driven, the display screen was displayed in full green, and the glare suppression property of the obtained anti-glare hard-coat film was evaluated based on the following reference|standard.

○: No glare was observed.

△: Slight glare was observed.

×: Glare was observed remarkably

(6) Evaluation 6 (image visibility)

10 cm apart from the display screen of a 264 ppi (pixel/inch) display device (Apple Co., Ltd., New iPad (registered trademark)) installed

Next, the display apparatus was driven, as shown to Fig.4 (a), a predetermined image (-▲■) was displayed, and the image visibility of the obtained anti-glare hard-coat film was evaluated based on the following reference|standard.

○: The outline of a predetermined image is clearly visible and can be recognized sufficiently

△: The outline of a predetermined image is blurred, but it is almost recognizable

×: The outline of a predetermined image is blurred and cannot be sufficiently recognized

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

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

First, the obtained anti-glare hard coat film was cut out, and it was set as the test piece (5 sheets) of 10 cm x 10 cm.

Five test pieces were placed in a flat place with the anti-glare hard coat layer facing upward, respectively, and the surface hardness of the anti-glare hard coat layer was measured according to the pencil hardness test (JIS K 5600-5-4). evaluated.

Moreover, using the steel wool of #0000, the anti-glare hard-coat layer of the obtained anti-glare hard coat film was subjected to 10 reciprocal friction tests at a sliding distance of 10 cm under a load of 250 g/cm 2 .

And the appearance change (the number of occurrences of a flaw) in the anti-glare hard-coat layer was visually confirmed under a 3-wavelength fluorescent lamp, and the following reference|standard evaluated it.

(circle): The average value of the obtained surface hardness is 2H or more, and generation|occurrence|production of a flaw is less than 3

(triangle|delta): The average value of the obtained surface hardness is less than 2H and 1H or more, and generation|occurrence|production of a flaw is less than 4-10.

x: The average value of the obtained surface hardness is less than 1H, and generation|occurrence|production of a flaw is 11 or more.

(8) Evaluation 8 (curl property)

The obtained anti-glare hard coat film was cut out and it was set as the test piece (5 sheets) of 10 cm x 10 cm.

Five test pieces were placed in a flat place with the anti-glare hard coat layer facing upward, respectively, the maximum height of the lifting of the four corners was measured, and the curling properties of the obtained anti-glare hard coat film were based on the following standards. evaluated.

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

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

△: The average value of the maximum height exceeds 10 mm and less than or equal to 15 mm

×: The average value of the maximum height exceeds 15 mm and less than or equal to 16 mm

[Example 2]

In Example 2, the anti-glare hard coat film was manufactured and evaluated similarly to Example 1 except having increased the compounding quantity of (B1) component in the anti-glare hard-coat layer forming material to 10 mass parts.

[Example 3]

In Example 3, while increasing the compounding quantity of (B1) component in an anti-glare hard-coat layer forming material to 10 mass parts, Example 1 and except having reduced the compounding quantity of (B3) component to 10 mass parts. Similarly, an anti-glare hard coat film was produced and evaluated.

[Example 4]

In Example 4, while increasing the compounding quantity of (B1) component in an anti-glare hard-coat layer forming material to 16 mass parts, the compounding quantity of (B3) component is reduced to 8 mass parts, Furthermore, an anti-glare hard coat An anti-glare hard coat film was produced and evaluated in the same manner as in Example 1, except that the film thickness of the layer was 5 µm.

[Example 5]

In Example 5, the anti-glare hard coat film was manufactured and evaluated similarly to Example 1 except having reduced the compounding quantity of the (B3) component in an anti-glare hard-coat layer forming material slightly to 10 mass parts.

[Comparative Example 1]

In the comparative example 1, the anti-glare hard-coat film was manufactured and evaluated similarly to Example 1 except having increased the (B1) component in the anti-glare hard-coat layer forming material to 30 mass parts.

Moreover, in the evaluation of image visibility, the display device was driven and a predetermined image (●▲■) was displayed, but as shown in Fig. 4(b), the outline of the predetermined image was blurred and could not be sufficiently recognized.

[Comparative Example 2]

In the comparative example 2, the anti-glare hard-coat film was manufactured and evaluated similarly to Example 1 except having increased the (B3) component in the anti-glare hard-coat layer forming material to 30 mass parts.

[Comparative Example 3]

In Comparative Example 3, the component (B1) was increased to 10 parts by mass and the component (B2) was increased to 20 parts by mass, and the component (B3) was also significantly increased to 30 parts by mass, as in Example 1 An anti-glare hard coat film was produced and evaluated.

[Comparative Example 4]

In Comparative Example 4, the component (B1) in the anti-glare hard-coat layer forming material was significantly increased to 30 parts by mass, and the component (B2) was increased to 20 parts by mass, and the component (B3) was also increased to 30 parts by mass. An anti-glare hard coat film was manufactured and evaluated similarly to Example 1 except having increased significantly.

[Comparative Example 5]

In Comparative Example 5, while significantly increasing the compounding quantity of (B1) component in the anti-glare hard-coat layer forming material to 30 mass parts, (B3) component was reduced to 10 mass parts similarly to Example 1 An anti-glare hard coat film was produced and evaluated.

[Comparative Example 6]

In the comparative example 6, while increasing the compounding quantity of (B1) component in the anti-glare hard-coat layer forming material to 20 mass parts, (B2) component is reduced to 5 mass parts, and (B3) component is 6 mass parts. An anti-glare hard coat film was produced and evaluated in the same manner as in Example 1 except that the thickness of the anti-glare hard coat layer was increased to 10 µm.

[Comparative Example 7]

In the comparative example 7, while increasing the compounding quantity of (B1) component in the anti-glare hard-coat layer forming material to 24 mass parts, and reducing (B2) component to 3 mass parts, also about (B3) component to 4 mass parts. An anti-glare hard coat film was produced and evaluated in the same manner as in Example 1 except that the thickness of the anti-glare hard coat layer was increased to 15 µm.

[Comparative Example 8]

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

[Comparative Example 9]

In Comparative Example 9, the anti-glare hard coat film 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. manufactured and evaluated.

[Comparative Example 10]

In the comparative example 10, while increasing the compounding quantity of (B1) component in an anti-glare hard-coat layer forming material to 10 mass parts, (B2) component is not mix|blended, and (B3) component is largely 2 mass parts. An anti-glare hard coat film was produced and evaluated in the same manner as in Example 1, except that it was reduced to

[Comparative Example 11]

In the comparative example 11, while increasing the compounding quantity of (B1) component in an anti-glare hard-coat layer forming material to 30 mass parts, (B2) component is not mix|blended, and (B3) component is reduced to 4 mass parts. In the same manner as in Example 1, an anti-glare hard coat film was produced and evaluated.

[Comparative Example 12]

In the comparative example 12, while reducing the compounding quantity of (B1) component in the anti-glare hard-coat layer forming material to 3 mass parts, except having not mix|blended component (B2) and (B3) component, Example 1 and Similarly, an anti-glare hard coat film was produced and evaluated.

[Comparative Example 13]

In the comparative example 13, the anti-glare hard-coat film was manufactured and evaluated similarly to Example 1 except not having mix|blended the (B2) component and (B3) component in the anti-glare hard-coat layer forming material.

[Comparative Example 14]

In the comparative example 14, while increasing the compounding quantity of (B1) component in the anti-glare hard-coat layer forming material to 10 mass parts, Example 1 except having not mix|blended the (B2) component and the (B3) component. Similarly, an anti-glare hard coat film was produced and evaluated.

[Comparative Example 15]

In the comparative example 15, while increasing the compounding quantity of (B1) component in the anti-glare hard-coat layer forming material to 15 mass parts, Example 1 except having not mix|blended the (B2) component and the (B3) component. Similarly, an anti-glare hard coat film was produced and evaluated.

[Comparative Example 16]

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

[Table 1]

As mentioned above, according to this invention, while mix|blending at least 3 types of particle|grains in a predetermined ratio with respect to the anti-glare hard-coat layer forming material for forming an anti-glare hard-coat layer, thickness is below a predetermined value. By limiting to , color fading can be effectively prevented, excellent anti-glare properties are expressed, and even if the anti-glare hard coat layer is relatively thin, it has high surface hardness and less curls. It became possible to obtain an anti-glare hard coat film.

Moreover, according to this invention, even if it is a case where it applies to high definition displays like a car navigation system, the anti-glare hard-coat film which can suppress generation|occurrence|production of glare effectively was obtained, improving image visibility.

Moreover, according to this invention, since thin film formation becomes easy as the whole anti-glare hard-coat film, while being able to simplify a manufacturing process, manufacturing cost reduction became possible.

Therefore, according to this invention, even if it is a case where it applies to high definition displays like a car navigation system, the anti-glare hard-coat film which can suppress generation|occurrence|production of glare effectively was obtained, improving image visibility.

Further, according to the anti-glare hard coat film of the present invention, the anti-glare hard coat layer is not formed on both sides of the plastic substrate, but is formed on one side only, while exhibiting predetermined anti-glare properties, etc., and also preventing the occurrence of curls There are things that can be done.

Therefore, thin film formation becomes easy as the whole anti-glare hard coat film, Therefore, while being able to simplify a manufacturing process, it became possible to reduce manufacturing cost remarkably.

10: anti-glare hard coat film 12: plastic substrate
14: predetermined plurality of particles 14a: silica particles
14b: high refractive index particles (zirconium oxide particles)
14c: resin particle 15: active energy ray-curable resin
16: anti-glare hard coat layer 110: anti-glare hard coat film
112a: plastic substrate (first TAC film)
112b: plastic substrate (second TAC film)
115a: adhesive layer (first adhesive layer) 115b: adhesive layer (second adhesive layer)
116: anti-glare hard coat layer 118: adhesive layer
119 release sheet 120 polarizing plate

Claims (8)

An anti-glare hard coat film having an anti-glare hard coat layer on the surface of a plastic substrate,
The anti-glare hard coat layer,
(A) With respect to 100 mass parts of active energy ray-curable resins as a component,
(B1) 5-25 mass parts of silica particles as a component,
(B2) 3 to 30 parts by mass of high refractive index particles having an average particle diameter within the range of 1 to 500 nm as a component;
(B3) 4-25 mass parts of resin particles as a component
It is an anti-glare hard coat layer with a thickness of 8 µm or less, derived from an anti-glare hard coat layer forming material comprising:
The anti-glare hard coat film, characterized in that the silica particles protrude from the surface of the anti-glare hard coat layer opposite to the plastic substrate. The method of claim 1,
The said silica particle is a pulverized silica particle, The anti-glare hard coat film characterized by the above-mentioned. The method of claim 1,
The anti-glare hard coat film characterized by making the average particle diameter of the said silica particle into the value within the range of 2.1-10 micrometers. The method of claim 1,
The said high refractive index particle|grains are inorganic fine particles which have a refractive index of 1.8 or more, The anti-glare hard coat film characterized by the above-mentioned. The method of claim 1,
The average particle diameter of the said resin particle is made into the value within the range of 0.5-2 micrometers, The anti-glare hard-coat film characterized by the above-mentioned. The method of claim 1,
Let the total haze value of the anti-glare hard coat film measured based on JISK7136 be the value within the range of 15 to 40%, let the internal haze value be the value within the range of 5 to 38%, and the external haze value An anti-glare hard coat film, characterized in that the value is less than 40%. The method of claim 1,
The anti-glare hard coat film, characterized in that the surface hardness of the anti-glare hard coat layer is 2H or more. A method for producing an anti-glare hard coat film having an anti-glare hard coat layer on the surface of a plastic substrate,
The manufacturing method of the anti-glare hard-coat film characterized by including the process (1)-(3) at least.
(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 silica particles as the component (B1) and the average particle size as the component (B2) is a value within the range of 1 to 500 nm. A step of mixing 3 to 30 parts by mass of high refractive index particles and 4 to 25 parts by mass of resin particles as component (B3) to obtain an anti-glare hard coat layer forming material.
(2) The process of coating the said anti-glare hard-coat layer forming material on a base material, and forming a coating film
(3) The coating film on the substrate is irradiated with active energy rays, and the silica particles protrude from the surface of the anti-glare hard coat layer on the opposite side to the plastic substrate. A process of forming a coat layer.

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