TWI628457B - Anti-glare film, polarizing plate, liquid crystal panel, and image display device - Google Patents

Abstract

Provided is an anti-glare film, a polarizing plate, a liquid crystal panel, and an image display device, which can obtain anti-glare properties to the extent that reflection is not taken into consideration, and at the same time can obtain good anti-glare properties and good black color.

According to one aspect of the present invention, an anti-glare film (10) is provided, which comprises a light-transmitting substrate (11) and an anti-glare layer (12) provided on the light-transmitting substrate (11) to prevent glare. The surface of the layer (12) becomes a concave-convex surface (12A), and the anti-glare layer (12) includes a binder resin (16) and a plurality of agglomerated inorganic particles present in the binder resin (16). The first inorganic fine particle aggregates (13) and the first inorganic fine particle aggregates (13) are formed by including the aforementioned inorganic fine particles as a connection and having a flexure (13A) of an inner region (13B) buried with an adhesive resin (16). ).

Description

Anti-glare film, polarizing plate, liquid crystal panel, and image display device

The invention relates to an anti-glare film, a polarizing plate, a liquid crystal panel, and an image display device.

The image display surface of an image display device such as a liquid crystal display (LCD), a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), etc., is usually An anti-glare film having unevenness on the surface or an anti-reflection film having anti-reflection on the outermost surface is provided in order to suppress reflection of the observer and the background of the observer (for example, refer to Japanese Patent Application Laid-Open No. 2011-215515 ).

The anti-glare film mainly includes a light-transmitting substrate and an anti-glare layer having an uneven surface provided on the light-transmitting substrate. The anti-glare film is a person who scatters external light on the concave-convex surface of the anti-glare layer and suppresses the reflection of the observer and the background of the observer.

The anti-glare film has anti-glare properties to such an extent that reflection is not taken into consideration. However, not only an anti-glare film having almost no reflection, but also an anti-glare film having anti-glare properties to such an extent that reflection is not noticed. In the case of the surface of a display device, there is a concern that the image light is scattered by the uneven surface of the anti-glare layer, and so-called glare occurs. In order to prevent the occurrence of glare, it has been proposed to increase the haze. However, when the haze is increased, the occurrence of the glare can be prevented, but the contrast may be reduced.

In addition, at present, in terms of anti-glare films, it is required to have both excellent contrast and dynamic performance when displaying animations (for example, the scene of a young man under a blue sky is taken as an example. (Smooth black, pupils are moist black, skin has youthful luster and looks vibrant, etc.).

The present invention was created by the author to solve the above-mentioned problems. That is, the object is to provide an anti-glare film, a polarizing plate, a liquid crystal panel, and an image display device, which can obtain anti-glare properties to the extent that reflection is not noticed, and at the same time can obtain good anti-glare properties and good black color. .

According to one aspect of the present invention, there is provided an anti-glare film including a light-transmitting substrate and an anti-glare layer provided on the light-transmitting substrate. The surface of the anti-glare layer becomes a concave-convex surface, and the anti-glare The layer includes a binder resin, and a plurality of first inorganic fine particle aggregates aggregated by three or more inorganic fine particles existing in the binder resin, and the first inorganic fine particle aggregation system includes the inorganic fine particles as a link to form and With The buckled portion of the inner region where the adhesive resin is buried.

According to another aspect of the present invention, an anti-glare film is provided, which includes a light-transmitting substrate and an anti-glare layer provided on the light-transmitting substrate and having an uneven surface. The anti-glare layer includes a plurality of organic fine particles. Arithmetic of the clarity of the penetrating image of the anti-glare film, a plurality of inorganic fine particles, and a binder resin measured using a light comb of 0.125 mm width, 0.25 mm width, 0.5 mm width, 1.0 mm width, and 2.0 mm width The average value is 70% or more and 95% or less, and the absolute value of the difference between the arithmetic mean value and the clarity of the transmitted image measured using the optical combs is within 10%.

According to another aspect of the present invention, an anti-glare film is provided, which includes a light-transmitting substrate and an anti-glare layer provided on the light-transmitting substrate and having an uneven surface. The anti-glare layer includes a plurality of organic fine particles. , A plurality of inorganic fine particles, and a binder resin, when the frequency distribution of the inclination angle of the surface of the anti-glare film with respect to the surface of the light-transmitting substrate is determined at 0.01 degree, the cumulative percentage of the frequency of the inclination angle The ratio of the 99th percentile to the 3rd quartile is 3.0 or more and 5.0 or less.

According to another aspect of the present invention, there is provided a polarizing plate characterized by comprising: the anti-glare film described above, and the opposite side of the anti-glare layer formed on the light-transmitting substrate formed on the anti-glare film. Polarizing element on the side surface.

According to another aspect of the present invention, there is provided a liquid crystal display panel including the above-mentioned anti-glare film or the above-mentioned polarizing plate.

According to another aspect of the present invention, there is provided an image display device including the above-mentioned anti-glare film or the above-mentioned polarizing plate.

According to one aspect of the present invention, an anti-glare film, and other aspects of a polarizing plate, a liquid crystal panel, and an image display device, the anti-glare layer includes an adhesive resin, and three or more inorganic resins present in the foregoing adhesive resin. The microparticles are aggregated as a plurality of first inorganic fine particle aggregates. The first inorganic fine particle aggregation system includes the inorganic fine particles connected to form a bending portion having an inner region buried with the binder resin, so that reflection is not obtained. The degree of anti-glare will be taken into consideration, and at the same time, good anti-glare properties and good black color feeling can be obtained.

According to other aspects of the anti-glare film, and other aspects of the polarizing plate, the liquid crystal panel, and the image display device, light of 0.125 mm width, 0.25 mm width, 0.5 mm width, 1.0 mm width, and 2.0 mm width are used. The arithmetic mean value of the transmitted image sharpness of the anti-glare film measured by combing is 70% or more and 95% or less, and the arithmetic mean value and The absolute value of the difference is within 10%, so anti-glare properties to the extent that reflection is not taken into consideration can be obtained, and at the same time good anti-glare properties and good black color feeling can be obtained.

According to other aspects of the anti-glare film of the present invention, and other aspects of the polarizing plate, liquid crystal panel, and image display device, the inclination of the surface of the anti-glare film with respect to the surface of the light-transmitting substrate is determined at 0.01 degrees In the frequency distribution of angles, the ratio of the cumulative percentage of the frequency of the aforementioned inclination angles to the 99th percentile of the 3rd quartile is 3.0 or more and 5.0 or less, so that reflections can be obtained to such an extent that Anti-glare properties Good anti-glare and good black color.

10, 50, 60, 100‧‧‧ Anti-glare film

10A, 60A, 100A‧‧‧ surface

11, 51, 61, 101‧‧‧ transparent substrate

12, 52, 62, 102‧‧‧Anti-glare layer

12A, 52A, 62A, 102A

13, 53, 64A, 104A‧‧‧ the first inorganic fine particle aggregate

14, 54, 64D, 104D ‧‧‧ 2nd inorganic fine particle aggregate

15, 63A, 103A‧‧‧Organic particulate aggregates

16, 56, 65, 105‧‧‧ binder resin

20, 70, 110‧‧‧ polarizing plates

21‧‧‧polarizing element

30, 80, 120‧‧‧ LCD panel

40, 90, 130‧‧‧ video display devices

55‧‧‧organic particles

[Fig. 1] A schematic configuration diagram of an anti-glare film according to a first embodiment.

[Fig. 2] A part of Fig. 1 is enlarged.

[Fig. 3] A schematic configuration diagram of a polarizing plate according to the first embodiment.

4 is a schematic configuration diagram of a liquid crystal panel according to a first embodiment.

[FIG. 5] A schematic configuration diagram of a liquid crystal display as an example of an image display device according to the first embodiment.

6 is a schematic configuration diagram of another anti-glare film according to the second embodiment.

[Fig. 7] An enlarged view of a part of Fig. 6. [Fig.

8 is a schematic configuration diagram of an anti-glare film according to a third embodiment.

[FIG. 9] A part of FIG. 8 is enlarged.

[FIG. 10] A part of FIG. 9 is enlarged.

[Fig. 11] A schematic diagram showing a state where the penetration image clarity of the anti-glare film according to the third embodiment is measured by a penetration image sharpness measuring device.

12 is a schematic configuration diagram of a polarizing plate according to a third embodiment.

13 is a schematic configuration diagram of a liquid crystal panel according to a third embodiment.

14 is a schematic configuration diagram of a liquid crystal display as an example of an image display device according to a third embodiment.

15 is a schematic configuration diagram of an anti-glare film according to a fourth embodiment.

[FIG. 16] A part of FIG. 15 is enlarged.

[Fig. 17] An enlarged view of a part of Fig. 16. [Fig.

18 is a schematic configuration diagram of a polarizing plate according to a fourth embodiment.

19 is a schematic configuration diagram of a liquid crystal panel according to a fourth embodiment.

[FIG. 20] A schematic configuration diagram of a liquid crystal display as an example of an image display device according to a fourth embodiment.

21 A photograph of a cross-section of an anti-glare film according to Example A1, which was photographed using a scanning electron microscope function of a scanning electron microscope.

[Fig. 22] A photograph of a cross-section of an anti-glare film according to Example A1, which was photographed with a scanning electron microscope function of a scanning electron microscope and having a higher magnification than that of Fig. 21. [Fig.

[Fig. 23] A cross-sectional photograph of an anti-glare film according to Example A2, which was photographed using a scanning electron microscope function of a scanning electron microscope.

[Fig. 24] A cross-sectional photograph of an anti-glare film according to Example A2, which was photographed using a scanning electron microscope function of a scanning electron microscope and having a higher magnification than that of Fig. 23.

[First Embodiment]

Hereinafter, an anti-glare film and the like according to the first embodiment of the present invention will be described with reference to the drawings. First, in this specification, The terms "membrane", "sheet", "board" and so on are based on differences in terms of names, not differences. Therefore, for example, "film" includes the concept of a material such as a sheet or a plate. As a specific example, the "anti-glare film" includes a material called "anti-glare sheet" or "anti-glare plate". In addition, in this specification, "weight average molecular weight" is the value obtained by styrene conversion using the conventionally well-known gel permeation chromatography (GPC) method which melt | dissolved in the solvent, such as tetrahydrofuran (THF).

<<< Anti-glare film >>>

FIG. 1 is a schematic configuration diagram of an anti-glare film according to this embodiment, and FIG. 2 is an enlarged view of a part of FIG. 1. As shown in FIG. 1, the anti-glare film 10 includes at least a light-transmitting substrate 11 and an anti-glare layer 12 provided on the light-transmitting substrate 11.

<< Transparent substrate >>

The light-transmitting substrate 11 is not particularly limited as long as it has light-transmitting properties. Examples include a cellulose halide substrate, a cycloolefin polymer substrate, a polycarbonate substrate, an acrylate polymer substrate, Polyester substrate or glass substrate.

In the case of cellulose halide substrates, examples are cellulose triacetate substrates and cellulose diacetate substrates. In the case of cyclic olefin polymer substrates, examples are: substrates made of polymers of norbornene-based monomers and monocyclic cyclic olefin monomers.

In the case of polycarbonate substrates, examples are: aromatic polycarbonate substrates based on bisphenols (bisphenol A, etc.), aliphatic polycarbonate groups such as diethylene glycol diallyl carbonate, etc.材 等。 Materials and so on.

In the case of acrylate polymer substrates, examples are: poly (meth) acrylate substrate, poly (meth) acrylate substrate, methyl (meth) acrylate-butyl (meth) acrylate Copolymer substrates and the like.

In the case of polyester substrates, examples include at least one of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Substrates and the like as constituent components.

In terms of glass substrates, examples are glass substrates such as soda-lime-silica glass, borosilicate glass, and alkali-free glass.

Among these, a cellulose halide base is preferable from the point which is excellent in retardation and it is easy to adhere to a polarizing element, and a triethyl cellulose is preferable among a cellulose halide base. Substrate (TAC substrate). Triethyl cellulose base material is a light-transmitting base material with an average light transmittance of 50% or more in the visible light region of 380 ~ 780nm. The average light transmittance of the triethylammonium cellulose substrate is preferably 70% or more, and more preferably 85% or more.

In addition, in the aspect of triethyl cellulose, in addition to pure triethyl cellulose, cellulose such as cellulose acetate propionate and cellulose acetate butyrate can be used in combination. Esters of fatty acids other than acetic acid. In addition, in these triethyl cellulose, it can be added as needed: other cellulose lower fatty acid esters such as diethyl cellulose, or plasticizers, ultraviolet absorbers, slip aids, etc. Various additives.

Cyclic olefin polymer substrates are preferred from the viewpoint of excellent retardation and heat resistance, and polyester substrates are preferred from the viewpoint of mechanical properties and heat resistance.

The thickness of the light-transmitting base material 11 is not particularly limited, but may be 5 μm or more and 1000 μm or less. The lower limit of the thickness of the light-transmitting base material 11 is preferably 15 μm or more and 25 μm from the viewpoint of processing capacity and the like. The above is better. The upper limit of the thickness of the translucent base material 11 is preferably 80 μm or less from the viewpoint of thinning.

<< Anti-glare layer >>

The anti-glare layer 12 is a layer exhibiting anti-glare properties. The anti-glare layer 12 may be one that exhibits anti-glare properties while performing other functions. Specifically, the anti-glare layer 12 may be a layer that exhibits anti-glare properties and functions such as hard coat properties, anti-reflection properties, anti-static properties, or anti-fouling properties.

In the case where the anti-glare layer 12 is a layer exhibiting hard coating properties in addition to anti-glare properties, the anti-glare layer 12 has a "H" in the pencil hardness test (4.9N load) specified in JIS K5600-5-4 (1999). ”Above hardness.

The surface of the anti-glare layer 12 is an uneven surface 12A. In this specification, the "surface of the anti-glare layer" means the following: the surface on the opposite side of the surface (the back surface of the anti-glare layer) on the light-transmitting substrate side of the anti-glare layer. In the present embodiment, no functional layer such as a low-refractive index layer is provided on the anti-glare layer 12, so that the uneven surface 12A of the anti-glare layer 12 becomes the surface 10A of the anti-glare film 10 as shown in FIG. 1. In this manual, "functional layer" is intended to The anti-glare film has a layer that performs some functions, and specifically includes, for example, a layer that provides functions such as antireflection, antistatic, or antifouling properties. The functional layer is not only a single layer, but also a layer of two or more layers.

The anti-glare layer 12 shown in FIG. 1 is composed of a plurality of first inorganic fine particle aggregates 13 in which three or more inorganic fine particles are aggregated, and a plurality of second inorganic fine particles in which two or more inorganic fine particles are aggregated. The body 14, two or more organic fine particles are aggregated into a plurality of organic fine particle aggregates 15, and a binder resin 16. The anti-glare layer 12 may not include the second inorganic fine particle aggregates 14 and the organic fine particle aggregates 15.

The anti-glare layer 12 corresponds to the first inorganic surface of the uneven surface 12A of the anti-glare layer 12 in a cross section along the thickness direction of the anti-glare layer 12 (the normal direction of the light-transmitting substrate 11). The ratio of the length of the regions other than the regions of the fine particle aggregates 13, the second inorganic fine particle aggregates 14, and the organic fine particle aggregates 15 is preferably 15% or more and 70% or less. This ratio is more than 15%, so that the anti-glare film can produce a moderate positive transmission (orthogonal reflection) component, which can guarantee the gloss, brightness, and contrast of the image. In addition, the ratio is less than 70%, so that excessive positive reflection will not occur Therefore, anti-glare properties can be guaranteed. The lower limit of this ratio is preferably 20% or more, and the upper limit of this ratio is preferably 60% or less.

The above "length corresponding to a region other than the region of the first inorganic fine particle aggregate, the second inorganic fine particle aggregate, and the organic fine particle aggregate" means that, in a section along the thickness direction of the anti-glare layer, the anti-glare When viewed in the thickness direction of the layer, the length (linear distance) of a region other than the region of the uneven surface overlapping the first inorganic fine particle aggregate, the second inorganic fine particle aggregate, and the organic fine particle aggregate. Areas corresponding to areas other than the first inorganic fine particle aggregates, the second inorganic fine particle aggregates, and the organic fine particle aggregates are areas in which diffusion elements contributing to internal diffusion and / or surface diffusion do not exist, and a reflection of this area is transmitted The light system is composed only of the components in the normal transmission direction, and the external light is also composed of only the regular reflection components. Conversely, a region corresponding to a region of the first inorganic fine particle aggregate, the second inorganic fine particle aggregate, and the organic fine particle aggregate is a region having a diffusion element that contributes to internal diffusion and / or surface diffusion, and transmits a reflection of this region The light system is made of a diffusive component, and also has a diffuse reflection component in the external light. For example, in the case of FIG. 2, the lengths of the regions corresponding to regions other than the first inorganic fine particle aggregates 13, the second inorganic fine particle aggregates 14, and the organic fine particle aggregates 15 are L ₁ to L ₄ . The length ratio is a value measured from an image of a cross-section electron microscope (TEM, STEM) using image processing software.

In the anti-glare layer 12, it is preferable to measure the inclination angle of the concave-convex surface 12A with respect to the surface of the light-transmitting substrate 11 in a section along the thickness direction of the anti-glare layer 12 by 0.1 degrees. The ratio of the cumulative percentage of the frequency of the tilt angle to the 99th percentile of the 3rd quartile (99th percentile / 3rd quartile) is 4.0 or more and less than 5.0. This ratio is 4.0 or more, so that the rate of change of the inclination angle is not excessively increased to prevent glare. In addition, the ratio is less than 5.0, so that the proportion of the portion of the uneven surface 12A having an excessive inclination angle will be It is controlled so that the decrease in contrast can be suppressed.

When the anti-glare layer 12 has a hard-coating property, the thickness of the anti-glare layer 12 is preferably 2.0 μm or more and 7.0 μm or less. As long as the thickness of the anti-glare layer 12 is within this range, a desired hardness can be obtained. In addition, it is possible to reduce the thickness of the anti-glare layer, and on the other hand, it is possible to suppress cracking and curling of the anti-glare layer. The thickness of the anti-glare layer is a value measured from an image of a cross-section electron microscope (TEM, STEM) using image processing software. Here, since the surface of the anti-glare layer is a concave-convex surface, the thickness varies depending on the location. However, the "thickness of the anti-glare layer" is an average value of the thickness of the anti-glare layer. The lower limit of the thickness of the anti-glare layer is more preferably 2.5 μm or more, and the upper limit is more preferably 5 μm or less.

In terms of the uneven surface 12A of the anti-glare layer 12, the average interval Sm of the unevenness constituting the uneven surface 12A is preferably 0.1 mm or more and 0.6 mm or less, and more preferably 0.2 mm or more and 0.4 mm or less. In terms of the uneven surface 12A of the anti-glare layer 12, the average inclination angle θa of the unevenness constituting the uneven surface 12A is preferably 0.05 ° or more and 0.30 °, and more preferably 0.15 ° or more and 0.25 ° or less.

As for the uneven surface 12A of the anti-glare layer 12, the arithmetic mean roughness Ra of the unevenness constituting the uneven surface 12A is preferably 0.02 μm or more and 0.20 μm or less, and more preferably 0.04 μm or more and 0.10 μm or less.

The definitions of "Sm" and "Ra" above are based on JIS B0601-1994. The definition of "θa" is based on a surface roughness measuring instrument: SE-3400 / Osaka Research Institute (Instruction) (1995.07.20 revised). Specifically, θa represents the following formula (1).

θa = tan ^-1 △ a ... (1)

In the formula, Δa represents an inclined person in an aspect ratio, which is a value obtained by dividing the total of the difference between the minimum and maximum portions (corresponding to the height of each convex portion) of each uneven portion by the reference length.

Sm, θa, and Ra can be measured, for example, using a surface roughness measuring device (model: SE-3400 / Kosaka Research Institute, Ltd.) under the following measurement conditions.

1) Stylus of surface roughness detection unit (trade name SE2555N (2μ standard), manufactured by Kosaka Research Institute, Ltd.)

． Tip curvature radius 2μm, apex angle 90 °, diamond material

2) Measurement conditions of surface roughness measuring device

． Reference length (cutoff value of roughness curve λc): 2.5mm

． Evaluation length (reference length (cut-off value λc) × 5): 12.5mm

． Stylus travel speed: 0.5mm / s

． Preliminary length: (cut value λc) × 2

． Vertical magnification: 2000 times

． Horizontal magnification: 10 times

<First inorganic fine particle aggregate>

The first inorganic fine particle aggregate 13 exists in the binder resin 16 and is composed of three or more inorganic fine particles as described above. In the present invention, as shown in FIG. 2, the first inorganic fine particle aggregate 13 has The buckling portion 13A formed by joining the inorganic fine particles. Here, in this specification, "buckling part" also includes the concept of a bending part. Examples of the shape having the bent portion 13A include a V shape, a U shape, an arc shape, a C shape, a curl shape, and a cage shape. Both ends of the flexure 13A may be closed. For example, the first inorganic fine particle aggregate 13 may have a ring structure having the flexure 13A.

The buckling portion 13A can also be formed by connecting inorganic fine particles, and is composed of an aggregate of inorganic fine particles that is buckled. It can also be a dry portion formed by connecting inorganic fine particles, and the inorganic portion can be connected from the dry portion. It can be constituted by the branch portions formed therefrom, or it can be constituted by two branch portions which are branched from the stem portion and connected to the stem portion. The "cadre" in this specification refers to the longest part of the first inorganic fine particle aggregate.

The flexion portion 13A has an inner region 13B as shown in FIG. 2. In this specification, the "inside area" refers to the area sandwiched by the flexion. This inner region 13B is buried with the adhesive resin 16. The bent portion 13A is preferably present so as to sandwich the inner region 13B from the thickness direction of the anti-glare layer 12.

Inorganic fine particles aggregate into agglomerated inorganic fine particle aggregates, which act as a single solid when curing and shrinking (polymerizing shrinkage) of the photopolymerizable compound of the binder resin 16 after curing, so the uneven surface of the anti-glare layer corresponds. Depending on the shape of the aggregate of inorganic fine particles. In this regard, the first inorganic fine particle aggregate 13 has a buckled portion 13A having an inner region 13B, and therefore acts as a solid having a buffering effect when it is hardened and contracted. because Therefore, when the first inorganic fine particle aggregate 13 is hardened and contracted, it is easily crushed with uniformity. Thereby, the shape of the uneven surface 12A becomes slower than the shape before the curing shrinkage.

In the first inorganic fine particle aggregate 13, the ratio of the inorganic fine particles connected to one or more and three or less inorganic fine particles below one inorganic fine particle is preferably 95% or more. When the proportion of inorganic fine particles connected to one or more inorganic fine particles below one inorganic fine particle is 95%, the inorganic fine particles are connected to four or more inorganic fine particles below one inorganic fine particle. Since the proportion of the inorganic fine particles is extremely small, the overall shape of the first inorganic fine particle aggregate 13 does not become massive. The proportion of the inorganic fine particles is more than 97%, and more preferably more than 99%.

The proportion of the first inorganic fine particle aggregates 13 in the anti-glare layer 12 is preferably higher on the light-transmitting substrate 11 side of the anti-glare layer 12 than on the uneven surface 12A side of the anti-glare layer 12. Here, the first inorganic fine particle aggregate exists on the light-transmitting substrate side of the anti-glare layer or on the uneven surface side, which is the following: a half of the thickness of the anti-glare layer is taken as a boundary, and the following It is judged that the boundary exists on the translucent base material side or the boundary exists on the uneven surface side. In addition, it can be confirmed from a cross-section electron microscope (TEM, STEM) image that the existence ratio of the first inorganic fine particle aggregate is higher on the light-transmitting substrate side of the anti-glare layer than on the uneven surface side of the anti-glare layer. The existence ratio of the first inorganic fine particle agglomerates 13 is that the light-transmitting substrate 11 side of the anti-glare layer 12 is higher than the uneven surface 12A side of the anti-glare layer 12, so that the uneven surface 12A is smoother without a steep slope. With very close to regular reflection and / or normal transmission Diffusion performance. With this, even if the anti-glare layer 12 has anti-glare properties, it is not only excellent in contrast in a bright room, but also suppresses the generation of stray light of the image light. Therefore, it is also excellent in contrast in a dark room, and can have a very high level. Anti-glare film 10 with high contrast and black color.

Specifically, in a cross section along the thickness direction of the anti-glare layer 12, the first inorganic fine-particle aggregates 13 existing on the light-transmitting substrate 11 side of the anti-glare layer 12 among the first inorganic fine-particle aggregates 13 are made. When the number of Nb is Nb and the number of the first inorganic fine particle aggregates 13 existing on the uneven surface 12A side of the anti-glare layer 12 is Nf, the Nb / Nf system preferably satisfies the following formula (2).

1.5 <Nb / Nf ... (2)

Nb / Nf satisfies the above formula (2), so that the above-mentioned anti-glare property and excellent black color feeling can be obtained more surely.

The first inorganic fine particle aggregates 13 are preferably located at least on the surface of the organic fine particle aggregates 15 and at positions separated from the organic fine particle aggregates 15 and between the organic fine particle aggregates 15. In the uneven surface 12A, the position corresponding to the organic fine particle aggregates 15 becomes a convex portion. The first inorganic fine particle aggregates 13 exist on the surface of the organic fine particle aggregates 15 so that the specific gravity of the organic fine particle aggregates 15 becomes large. The floating surface is suppressed and the buffering effect against the hardening shrinkage of the adhesive resin 16 is exhibited, so that the lower end of the convex portion of the uneven surface 12A changes smoothly, whereby the uneven surface 12A becomes a smoother. Furthermore, the convex-concave surface 12A is a convex portion at a position corresponding to the organic fine particle aggregates 15. Therefore, the organic fine particle aggregates 15 are recessed portions. The particle agglomerates 15 are separated, and the first inorganic fine particle agglomerates 13 are present between the organic fine particle agglomerates 15 to increase the position of the concave portion of the uneven surface 12A. Since it is reduced, the uneven surface 12A becomes smoother, and as described above, extremely gentle unevenness is formed between the uneven surface 12A, so that the anti-glare property can be confirmed without deteriorating the contrast.

The average aggregation diameter of the first inorganic fine particle aggregates 13 is preferably 100 nm or more and 2.0 μm or less. When the average aggregation diameter of the first inorganic fine particle aggregates 13 is 100 nm or more, a smooth uneven surface 12A can be easily formed, and when the average aggregation diameter of the first inorganic fine particle aggregates 13 is 2.0 μm or less, the first inorganic fine particles aggregate can be suppressed. The diffusion of light from the aggregates 13 can obtain the anti-glare film 10 excellent in contrast. The average aggregation diameter of the first inorganic fine particle aggregates 13 is preferably 200 nm or more, and the upper limit is preferably 1.5 μm or less.

The average agglomeration diameter of the first inorganic fine particle aggregates is as follows: Based on the observation (approximately 10,000 to 20,000 times) with a cross-section electron microscope, a 5 μm square area containing a large number of the first inorganic fine particle aggregates is selected. The aggregation diameters of the first inorganic fine particle aggregates in this region were measured, and the aggregation diameters of the first ten inorganic fine particle aggregates were averaged. In addition, the "average agglomeration diameter of the first inorganic fine particle aggregates" refers to a case where the cross section of the first inorganic fine particle aggregates is sandwiched by two parallel lines that are arbitrarily parallel, and the distance between the two straight lines becomes the largest two. The combination of two straight lines is measured in the form of the distance between the straight lines. In addition, the average agglomeration diameter of the first inorganic fine particle agglomerates can also use image analysis software And figure it out.

The first inorganic fine particle aggregate 13 preferably has a larger aggregate diameter in a direction orthogonal to the thickness direction than the aggregate diameter in the thickness direction of the anti-glare layer 12. The "aggregation diameter in the thickness direction" refers to the distance between two straight lines when the cross section of the first inorganic fine particle aggregate is sandwiched by two parallel straight lines perpendicular to the thickness direction of the anti-glare layer. For determination. The "aggregation diameter in the direction orthogonal to the thickness direction" refers to two straight lines when the cross section of the first inorganic fine particle aggregate is sandwiched by two parallel straight lines parallel to the thickness direction of the anti-glare layer. The distance is measured. These condensation diameters can also be calculated using image analysis software.

The first inorganic fine particle agglomerates 13 are formed by, for example, hydrophobizing treatment of the inorganic fine particles constituting the first inorganic fine particle aggregates 13 and the second inorganic fine particle aggregates 14, and the hydrophilicizing treatment of the organic fine particles constituting the organic fine particle aggregates 15. And obtained by controlling the presence ratio of the hydroxyl groups of the binder resin 16. There are hydroxyl groups on the surface of the inorganic fine particles. However, when the hydrophobic treatment is performed on the aggregates of the inorganic fine particles, the number of hydroxyl groups existing on the surfaces of the inorganic fine particles is reduced, and the excessive aggregation of the inorganic fine particles is suppressed. In addition, the surface of the inorganic fine particles can be hydrophobized to improve the chemical resistance and alkali resistance of the inorganic fine particles themselves.

Such a hydrophobic treatment can be performed using a surface treatment agent such as a silane or silazane. In terms of specific surface treatment agents, examples are: dimethyldichlorosilane or polysiloxane, hexamethyldisiloxane, Octylsilane, cetylsilane, aminosilane, methacrylfluorenylsilane, octamethylcyclotetrasiloxane, polydimethylsiloxane, etc.

In addition, the first inorganic fine particle aggregate 13 can also be obtained by a method other than the above-mentioned method. Therefore, the method of obtaining the first inorganic fine particle aggregate 13 is not limited to the above-mentioned method. For example, the reactive groups can be spread on the surface of the inorganic fine particles, and the aggregation state of the inorganic fine particles can be controlled to obtain the first inorganic fine particle aggregates 13. In addition, the affinity and volatility of the inorganic fine particles and the binder resin can also be used. Different solvents can control the aggregation by changing the affinity during the drying, and the first inorganic fine particle aggregate 13 is obtained.

The inorganic fine particles constituting the first inorganic fine particle aggregate 13 are not particularly limited, but examples include silicon dioxide (SiO ₂ ) fine particles, aluminum oxide fine particles, titanium oxide fine particles, tin oxide fine particles, and antimony-doped tin oxide. (Abbreviation: ATO) Inorganic oxide fine particles such as fine particles, zinc oxide fine particles.

When silicon dioxide particles are used for the inorganic fine particles, fuming silicon dioxide particles are preferable from the viewpoint that an anti-glare layer having a smooth uneven surface can be easily formed among the silicon dioxide particles. Fuming silicon dioxide is an amorphous silicon dioxide having a particle size of 200 nm or less produced by a dry method, and can be obtained by reacting a silicon-containing volatile compound in a gas phase. Specifically, for example, a silicon compound such as silicon tetrachloride (SiCl ₄ ) is produced by hydrolysis in a flame of oxygen and hydrogen. Examples of display products of fumed silica particles are: AEROSIL R805 manufactured by NIPPON AEROSIL Co., Ltd. and the like.

When inorganic oxide particles are used for the inorganic fine particles, the inorganic oxide fine particles are preferably amorphous. The reason for this is that when the inorganic oxide particles are crystalline, due to the lattice defects contained in the crystal structure, the Lewis acid-base of the inorganic oxide fine particles becomes strong, and it becomes impossible to excessively control the inorganic oxide particles. The cohesion of control.

In addition, when fuming silica particles are used for the inorganic fine particles, among the fuming silica particles, there are those exhibiting hydrophilicity and those exhibiting hydrophobicity, but among these, the amount of absorption from moisture becomes small and easy. From the viewpoint of scattering in the composition for an anti-glare layer, those exhibiting hydrophobicity are preferred. Hydrophobic fumed silica can be obtained by chemically reacting the surface treating agent with the silanol group existing on the surface of the fumed silica fine particles.

The inorganic fine particles are preferably spherical in the shape of a single particle. The single particle of the inorganic fine particles has such a spherical shape that when the anti-glare film is arranged on the image display surface of the image display device, an image having better contrast can be obtained. Here, "spherical" means, for example, that it includes true spheres, ellipsoids, etc., but does not include so-called amorphous ones.

The average primary particle diameter of the inorganic fine particles is preferably from 1 nm to 100 nm. The inorganic primary particles have an average primary particle diameter of 1 nm or more, so that it is easier to form an anti-glare layer having a smooth uneven surface. In addition, the average primary particle diameter is 100 nm or less. Therefore, it is possible to suppress the diffusion of light due to the particles and obtain excellent results. Of contrast. The lower limit of the average primary particle diameter of the inorganic fine particles is more preferably 10 nm or more. The average primary particle diameter of the inorganic fine particles is more preferable. The upper limit of the diameter is more preferably 50 nm or less.

The average primary particle size of the inorganic fine particles is a value measured using an image processing software from an image of a cross-section electron microscope (preferably a magnification of 50,000 times or more under a transmission type such as TEM or STEM).

<Second inorganic fine particle aggregate>

The second inorganic fine particle aggregates 14 are present on or near the uneven surface 12A. In addition, in the second inorganic fine particle aggregate 14, the ratio of the inorganic fine particles connected to the inorganic fine particles of one or more and three or less of the inorganic fine particles is preferably 95% or more. In addition, it is preferable that the second inorganic fine particle agglomerate 14 has a larger agglomerate diameter in a direction orthogonal to the thickness direction than the agglomerate diameter in the thickness direction of the anti-glare layer 12, and is more preferably two-dimensionally agglomerated. In addition, the second inorganic fine particle agglomerate 14 is located closer to the uneven surface 12A or in the vicinity of the first inorganic fine particle agglomerate 13 compared with the first inorganic fine particle agglomerate 13, and therefore has a lower thickness than the first inorganic fine particle agglomerate 13. The condensed diameter in the direction becomes smaller, so that the uneven surface 12A can be made smoother.

The presence of the second inorganic fine particle agglomerates 14 on or near the uneven surface 12A makes it possible to increase the hardness of the surface of the anti-glare layer 12. Therefore, a softer binder resin can be used for the binder resin 16, thereby obtaining the flexibility in flexion. An anti-glare film 10 having excellent properties.

The average aggregation diameter of the second inorganic fine particle aggregates 14 is preferably 100 nm or more and 2.0 μm or less for the same reason as that of the first inorganic fine particle aggregates 13. Second inorganic fine particles The average aggregation diameter of the polymer 14 is more preferably a lower limit of 200 nm or more, and an upper limit of 1.5 μm or less.

The inorganic fine particles constituting the second inorganic fine particle aggregate 14 are the following: the same as the inorganic fine particles constituting the first inorganic fine particle aggregate 13 may be used. Therefore, the description is omitted here. The second inorganic fine particle agglomerates 14 are similar to the first inorganic fine particle agglomerates 13. For example, the second inorganic fine particle agglomerates 14 can be made organic by hydrophobicizing the inorganic fine particles constituting the first inorganic fine particle agglomerates 13 and the second inorganic fine particle agglomerates 14. Hydrophilization treatment of the organic fine particles of the microparticle aggregates 15 and the presence ratio of the hydroxyl groups of the binder resin 16 are controlled. However, in order to make the aggregation state of the second inorganic microparticle agglomerate 14 different from the aggregation state of the first inorganic microparticle agglomerate 13, for example, the second inorganic microparticle agglomerate 14 may be used in combination with the first inorganic microparticle agglomerate 13. Different surface treatment agents and different surface treatment agent concentrations from the first inorganic fine particle aggregate 13.

<Organic fine particle aggregates>

The organic fine particle aggregate 15 is composed of two or more organic fine particles as described above. As for the anti-glare layer 12, it is preferable that the maximum height of the organic fine particle aggregates 15 in the thickness direction of the anti-glare layer 12 is less than the thickness of the anti-glare layer 12. The maximum height of the organic fine particle aggregate 15 is less than the thickness of the anti-glare layer 12, so that steep uneven surfaces are not generated, and it is possible to suppress the decrease in contrast and black color while exhibiting anti-glare properties.

In the case of organic microparticles, the system may include, for example, plastic particles. In terms of plastic granules, as specific examples, examples are: styrene granules, melamine resin granules, acrylic granules, acrylic-styrene granules, polysilica granules, benzoguanamine granules, and benzoguanamine granules. Formaldehyde condensation particles, polycarbonate particles, polyethylene particles, etc. It is also preferable to hydrophilize the surface of the organic fine particles. The surface of the organic fine particles is subjected to a hydrophilization treatment, so that the aggregation state with the inorganic fine particles can be controlled.

The average primary particle diameter of the organic fine particles is preferably 1 μm or more and 5 μm or less. The average primary particle size of the organic fine particles is as follows: In the observation of an electron microscope (TEM, STEM, and other transmission types are preferred) through a section near the center of the organic fine particles, any of the same kind is regarded as approximately the same position. Thirty organic fine particles were observed, and the maximum particle diameter of the cross section was measured and calculated as the average value. It can also be calculated using image analysis software. The average primary particle diameter of the organic fine particles is 1 μm or more, so that the anti-glare property can be more ensured. In addition, the average primary particle diameter of the organic fine particles is 5 μm or less, so that a decrease in contrast can be suppressed. The lower limit of the average primary particle diameter of the organic fine particles is more preferably 1.5 μm or more, and the upper limit of the average primary particle diameter of the organic fine particles is more preferably 4.0 μm or less.

When the thickness of the anti-glare layer 12 is T and the average primary particle diameter of the organic fine particles is R, it is preferable that the R / T system satisfies the relationship of the following formula (3).

0.2 <R / T <0.7 ... (3)

R / T satisfies the above formula (3), so that the combination of anti-glare property and black color feeling can be made more reliable.

The number of the organic fine particles constituting the organic fine particle aggregate 15 is preferably two or more and three or less. The number of organic fine particles constituting the organic fine particle agglomerate 15 is two or more, so that in terms of the uneven surface 12A, the area of the peak of the sloped convex portion increases, and the area of the rising portion of the steeply inclined convex portion decreases, so it can be suppressed. Deterioration of contrast. In addition, the number of the organic fine particles constituting the organic fine particle aggregate 15 is three or less, so that it is possible to prevent the formation of organic fine particle aggregates having a thickness greater than the thickness T of the anti-glare layer 12 and to prevent the formation of steep convex portions.

The organic microparticle agglomerate 15 can be used, for example, to allow reactive groups to spread on the surface of the organic microparticles, and control the aggregation state of the organic microparticles to obtain the organic microparticle agglomerates 15. In addition, the affinity between the organic microparticles and the binder resin Solvents with different properties and volatility can control the agglomeration by changing the affinity during the drying process to obtain the organic fine particle agglomerate 15, and can also agglomerate the first inorganic fine particle agglomerate 13 and the second inorganic fine particle agglomerate. It is obtained by controlling the hydrophobic treatment of the inorganic fine particles of the body 14, the hydrophilic treatment of the organic fine particles constituting the organic fine particle aggregate 15, and the presence ratio of the hydroxyl groups of the binder resin 16.

<Binder Resin>

The binder resin 16 is a polymer (crosslinked product) containing a photopolymerizable compound. The binder resin may include a solvent-drying resin and a thermosetting resin in addition to the polymer (crosslinked product) of the photopolymerizable compound. Photopolymerizable compound having at least one photopolymerizable functional group By. The "photopolymerizable functional group" in this specification is a functional group which can perform a polymerization reaction by light irradiation. In terms of photopolymerizable functional groups, examples are: (meth) acrylfluorenyl, vinyl, allyl, and other ethylenic double bonds. In addition, "(meth) acrylfluorenyl" means including both "acrylfluorenyl" and "methacrylfluorenyl". Examples of the light irradiated when the photopolymerizable compound is polymerized include visible light, and free radiation such as ultraviolet rays, X-rays, electron beams, alpha rays, beta rays, and gamma rays.

The photopolymerizable compound is exemplified by a photopolymerizable monomer, a photopolymerizable oligomer, or a photopolymerizable prepolymer, and these can be appropriately adjusted and used. The photopolymerizable compound is preferably a combination of a photopolymerizable monomer, a photopolymerizable oligomer, or a photopolymerizable prepolymer.

The hydrophilicity of the binder resin 16 is preferably controlled. For example, an anti-glare film is prepared by using an adhesive resin in which the degree of hydrophilicity is controlled by changing the mixing ratio of the photopolymerizable compound having a hydroxyl group and the photopolymerizable compound having no hydroxyl group in advance, and it is confirmed that An anti-glare film in which the degree of aggregation and unevenness of organic fine particles and inorganic fine particles is controlled.

(Photopolymerizable monomer)

Photopolymerizable monomers are those having a weight average molecular weight of 1,000 or less. In addition, as for the photopolymerizable monomer, not only one type but also plural types may be used.

As the photopolymerizable monomer, a polyfunctional monomer having two or more photopolymerizable functional groups (that is, bifunctional) is preferred.

In the case of monomers with more than two functions, examples are: trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and dipropylene glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Tripentaerythritol octa (meth) acrylate, tetrapentaerythritol dec (meth) acrylate, isocyanurate tri (meth) acrylate, isocyanurate di (meth) acrylate, polyester tri (meth) acrylate Ester, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerol tetra (meth) acrylate, adamantyl di (meth) acrylate, isobornyl di ( (Meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, di-trimethylolpropane tetra (Meth) acrylates, or those modified with PO, EO, etc.

Among these, from the viewpoint of obtaining an antiglare layer with high hardness, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), and dipentaerythritol pentaacrylate (DPPA) ) And so on are preferred.

(Photopolymerizable oligomer)

Photopolymerizable oligomers are those having a weight average molecular weight of more than 1,000 and less than 10,000.

The photopolymerizable oligomer is preferably a polyfunctional oligomer having three (trifunctional) or more photopolymerizable functional groups. As for a photopolymerizable oligomer, a bifunctional or more polyfunctional oligomer is preferable. In the case of polyfunctional oligomers, examples are: polyester (meth) acrylates, urethane (meth) acrylates, polyester-urethane (meth) acrylates, polyethers ( (Meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, isocyanurate (meth) acrylate, epoxy (meth) acrylate, and the like.

(Photopolymerizable prepolymer)

The photopolymerizable prepolymer has a weight average molecular weight of more than 10,000, and is preferably 10,000 or more and 80,000 or less in terms of weight average molecular weight, and more preferably 10,000 or more and 40,000 or less. When the weight-average molecular weight exceeds 80,000, there is a concern that the viscosity is high, the coating suitability is reduced, and the appearance of the obtained optical laminated body is deteriorated. In the above-mentioned multifunctional polymer, examples are: urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester-urethane (meth) acrylate, Epoxy (meth) acrylate and the like.

Solvent-drying resins are resins that become a film only by drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin. When solvent-drying resin is added, antiglare is formed When the layer 12 is used, it is possible to effectively prevent film defects on the coating surface of the coating liquid. The solvent-drying resin is not particularly limited, and in general, a thermoplastic resin can be used.

Examples of thermoplastic resins include styrene resins, (meth) acrylic resins, vinyl acetate resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, Polyester-based resins, polyamide-based resins, cellulose derivatives, silicone resins, rubbers, and elastomers.

The thermoplastic resin is amorphous and preferably soluble in organic solvents (especially a common solvent capable of dissolving a plurality of polymers or hardening compounds). In particular, from the viewpoint of transparency or weather resistance, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (such as cellulose esters), and the like Better.

The thermosetting resin is not particularly limited, and examples thereof include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, Amino alkyd resin, melamine-urea co-condensation resin, silicone resin, polysiloxane resin, etc.

<< Physical properties of anti-glare film >>

The anti-glare film 10 preferably has a total light transmittance of 85% or more. When the total light transmittance is 85% or more, when the anti-glare film 10 is mounted on the surface of an image display device, color reproducibility and visibility can be further improved. The total light transmittance is better than 90%. The total light transmittance in this specification is to make The measurement was performed by a haze meter (manufactured by Murakami Color Technology Research Institute, product number; HM-150) by a method according to JIS K7361.

The haze value (overall haze value) of the entire anti-glare film 10 is preferably 2% or less. When the overall haze value is 2% or less, desired optical characteristics can be obtained, and the visibility when the anti-glare film 10 is disposed on the image display surface is further improved. The overall haze value is better than 1%. The overall haze value in this specification can be measured by a haze meter (manufactured by Murakami Color Technology Research Institute, product number; HM-150) by a method according to JIS K7136.

The internal haze value of the anti-glare film 10 is preferably 0% or more and 2.0% or less. Here, in this specification, "internal haze value is 0%" means that it is not limited to the case where the internal haze value is completely 0%, and includes: even if the internal haze value exceeds 0%, it is Within the range of the measurement error, the internal haze value is regarded as a range of approximately 0% (for example, an internal haze value of 0.3% or less).

The surface haze value of the anti-glare film 10 is preferably 0% or more and 0.3% or less. The surface haze value is based on the uneven shape on the uneven surface of the anti-glare layer, and can be obtained in the following manner. First, the entire haze value of the anti-glare film was measured using a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) in accordance with JIS K7136. After that, on the surface of the anti-glare layer, a light-transmitting resin substrate is pasted through an adhesive layer, an adhesive tape, or the like. Thereby, the uneven shape on the uneven surface of the anti-glare layer is crushed, and the surface of the anti-glare film becomes flat. Then, in this state, a haze meter is used to measure the haze value in accordance with JIS K7136, and the above-mentioned adhesive layer or tape itself is further measured. The haze is subtracted to obtain the internal haze value. This internal haze value is not included in the uneven shape on the uneven surface of the anti-glare layer. Therefore, the internal haze value is subtracted from the overall haze value, so that the irregular shape on the surface of the anti-glare layer can be obtained. The surface haze value.

For the anti-glare film 10, the average value of the transmitted image sharpness measured using a light comb of 0.125 mm width, 0.5 mm width, 1.0 mm width, and 2.0 mm width, and the wear resistance measured using each light comb The difference in the sharpness of the transparent image is preferably within 10%. This difference is within 10%, making it possible to more reliably suppress glare.

The above-mentioned transmission image sharpness can be measured by a transmission sharpness measuring device based on a transmission method of image sharpness according to JIS K7105. Examples of such a measuring device include an image sharpness measuring device ICM-1T manufactured by SUGA TEST INSTRUMENTS.

The average value of the transmitted image clarity of the anti-glare film 10 measured using the above-mentioned four types of optical combs is preferably 80% or more. The transmitted image clarity of the anti-glare film 10 measured using a 0.125 mm wide optical comb is preferably 80% or more, and the transmitted image clarity of the anti-glare film 10 measured using a 0.5 mm wide optical comb It is preferably 80% or more, and the anti-glare film 10 of the anti-glare film 10 measured by using a 1.0 mm wide optical comb is preferably 80% or more of the anti-glare film measured by using a 2.0 mm wide optical comb. A transmission image clarity of 10 is preferably 90% or more.

According to this embodiment, the first inorganic fine particle aggregate 13 has a buckling portion 13A having an inner region 13B. Therefore, as described above, the first inorganic fine particle aggregate 13 is easily and uniformly worn when it is hardened and contracted. Sexually crushed. Thereby, although the first inorganic fine particle aggregate 13 has the function of forming the uneven surface 12A, the shape of the uneven surface 12A becomes slower than the amount of hardening shrinkage, and the uneven surface 12A has an observer (observer) and an observer The degree of anti-glare of the background reflection is not taken into consideration, and it is possible to effectively prevent the sudden change of the inclination angle change rate that causes a sudden change in brightness, so good anti-glare can be obtained. In addition, the degree of anti-glare to the extent that the reflection of the observer (observer) and the background of the observer is not taken into consideration is the anti-glare property as follows: the presence of the observer is confirmed, but only its outline becomes unclear blur The state and the existence of objects in the background of the observer are also confirmed, but the outline and boundary become unclear. In this way, only the outline of the observer is blurred, and the observer is in a state in which reflection is not noticed.

In addition, the inclination angle of the unevenness constituting the uneven surface 12A does not increase, so that excessive diffusion of external light does not occur. This can suppress a decrease in the contrast of the bright room. In addition, since the image light can be prevented from becoming stray light, a good dark room contrast can also be obtained. In addition, it has a moderate specular reflection component, so when playing an animation image, the gloss and brightness of the image will increase, and a dynamic feeling can be obtained. Thereby, a black color feeling having both excellent contrast and dynamic feeling can be obtained.

<<< Manufacturing method of anti-glare film >>>

The anti-glare film 10 can be formed in the following manner, for example. First, a composition for an anti-glare layer is applied on the light-transmitting substrate 11. In terms of the method of applying the composition for the anti-glare layer, examples are: spin coating method, dipping method, spray coating Well-known coating methods such as a coating method, a swash plate coating method, a bar coating method, a roll coating method, a gravure coating method, and a film nozzle coating method.

The composition for an anti-glare layer includes at least a first inorganic fine particle aggregate 13, a second inorganic fine particle aggregate 14, an organic fine particle aggregate 15, and the photopolymerizable compound. Moreover, you may add the said thermoplastic resin, the said thermosetting resin, a solvent, and a polymerization initiator to the composition for anti-glare layers as needed. Furthermore, for the composition for the anti-glare layer, conventionally known dispersants, surfactants, antistatic agents, etc. may be added for the purpose of increasing the hardness of the anti-glare layer, suppressing hardening shrinkage, and controlling the refractive index. Silane coupling agent, tackifier, anti-colorant, colorant (pigment, dye), defoamer, leveling agent, flame retardant, UV absorber, adhesion promoter, polymerization inhibitor, antioxidant, surface modification Agents, slip agents, etc.

<Solvent>

Examples of solvents include alcohol (e.g., methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), and ketones. (Acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl isobutyl ketone, diacetone alcohol, cyclobutanone, diethyl ketone, etc.), ethers (1,4-dioxane, two (Oxane, diisopropyl ether dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene) Etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, etc.), esters (methyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, etc.), fibrinolysin class (Methyl lysinolysin, ethyl lysinolysin, butyl lysinolysin, etc.), cellolysin acetates, fluorenes (dimethyl fluorene, etc.), amines (dimethylformamide, Methylacetamide, etc.) and the like may also be a mixture thereof.

<Polymerization initiator>

The polymerization initiator is a component that is decomposed by light irradiation and generates radicals to start or proceed the polymerization (crosslinking) of the photopolymerizable compound.

The polymerization initiator is not particularly limited as long as it is a substance that can release radical polymerization by light irradiation. In terms of the polymerization initiator, it is not particularly limited, and known ones can be used. In the specific examples, the examples are: acetophenones, benzophenones, Miebenzyl benzoate, α -Amyl oxime esters, thioxanthones, propanylbenzenes, benzyls, benzoin, fluorenylphosphine oxides. In addition, a photosensitizer is preferably used in combination, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

In the polymerization initiator, when the binder resin is a resin system having a radical polymerizable unsaturated group, the acetophenones, benzophenones, thioxanthone, benzoin, Benzoin methyl ether and the like are preferably used alone or in combination.

The content of the polymerization initiator in the composition for the anti-glare layer is preferably 0.5 parts by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the photopolymerizable compound. When the content of the polymerization initiator is within this range, the performance of the hard coat layer can be sufficiently ensured, and the hardening resistance can be suppressed.

The content ratio of the raw materials in the composition for the anti-glare layer (solid The content is not particularly limited, but it is usually preferably 5 mass% or more and 70 mass% or less, and more preferably 25 mass% or more and 60 mass% or less.

The method for preparing the composition for the anti-glare layer is not particularly limited as long as the components can be uniformly mixed. For example, it can be performed using a known device such as a paint shaker, a bead mill, a kneader, and a kneader.

After applying the composition for the anti-glare layer on the light-transmitting substrate 11, the composition for the anti-glare layer in the form of a coating film is dried and then transported to a heated area, and is transferred by various known methods. The composition for the anti-glare layer is dried to evaporate the solvent. Here, the affinity between the solvent and the solid content, the relative evaporation speed of the solvent, the solid content concentration, the temperature of the coating solution, the drying temperature, the wind speed of the drying wind, the drying time, and the concentration of the solvent environment in the drying area are selected, so that the first The distribution states of the 1 inorganic fine particle aggregates 13, the second inorganic fine particle aggregates 14, and the organic fine particle aggregates 15 are adjusted.

In particular, the method of adjusting the distribution state of the aggregates of the fine particles according to the selection of the drying conditions is simple and preferable. In terms of specific drying temperature, 30 ~ 120 ° C is preferred, and in terms of drying wind speed, 0.2 ~ 50m / s is preferred. One or more times of drying treatment with appropriate adjustment within this range is performed, so that the fine particles can be dried. The distribution state of the aggregates is adjusted to a desired state.

Thereafter, the coating film-like composition for the anti-glare layer is irradiated with light such as ultraviolet rays, and the photopolymerizable compound is polymerized (crosslinked) to harden the composition for the anti-glare layer to form the anti-glare layer 12 . Here, as described above, the first inorganic fine particle aggregate 13 has The buckled portion 13A of the inner region 13B acts as a solid having a cushioning effect when it is hardened and contracted. Therefore, when the first inorganic fine particle aggregate 13 is hardened and contracted, it is easily crushed with uniformity.

When ultraviolet rays are used for curing the composition for the anti-glare layer, ultraviolet rays emitted from ultra-high-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, xenon arcs, and metal halide lamps can be used. In addition, in terms of the wavelength of ultraviolet rays, a wavelength band of 190 to 380 nm can be used. In terms of specific examples of the electron beam source, there are various types of electrons such as Kirklauf Wolten type, Vander Graff type, resonant transformer type, insulated core transformer type, or linear type, DYNAMITRON type, high frequency type, etc. Beam accelerator.

<<< Polarizer >>>

The anti-glare film 10 can be used by being incorporated in a polarizing plate, for example. FIG. 3 is a schematic configuration diagram of a polarizing plate incorporating an anti-glare film according to this embodiment. As shown in FIG. 3, the polarizing plate 20 includes an anti-glare film 10, a polarizing element 21, and a protective film 22. The polarizing element 21 is formed on the surface of the translucent base material 11 opposite to the surface on which the anti-glare layer 12 is formed. The protective film 22 is provided on the surface of the polarizing element 21 opposite to the surface on which the anti-glare film 10 is provided. The protective film 22 may be a retardation film.

Examples of the polarizing element 21 include polyvinyl alcohol-based films dyed and extended with iodine, polyvinyl formal films, polyvinyl acetal films, and ethylene-vinyl acetate copolymer-based saponified films. When the anti-glare film 10 and the polarizing element 21 are laminated, the transparent substrate is prepared in advance. 11 It is better to implement alkali treatment. An antistatic effect can be obtained by performing an alkali treatment so that the adhesiveness is good.

<<< LCD Panel >>>

The anti-glare film 10 and the polarizing plate 20 can be incorporated into a liquid crystal panel and used. FIG. 4 is a schematic configuration diagram of a liquid crystal panel incorporating an anti-glare film according to this embodiment.

The liquid crystal panel shown in FIG. 4 has the following structure: from the light source side (backlight unit side) to the observer side, a protective film 31 such as a triethyl cellulose film (TAC film), a polarizing element 32, and a phase difference The film 33, the adhesive layer 34, the liquid crystal cell 35, the adhesive layer 36, the retardation film 37, the polarizing element 21, and the anti-glare film 10 are laminated in this order. The liquid crystal cell 35 is arranged between two glass substrates, and includes a liquid crystal layer, an alignment film, an electrode layer, and a color filter.

For the retardation films 33 and 37, examples are triacetam cellulose films and cycloolefin polymer films. The retardation film 37 may be the same as the protective film 22. An example of the adhesive constituting the adhesive layers 34 and 36 is a pressure sensitive adhesive (PSA).

<<< Image display device >>>

The anti-glare film 10, the polarizing plate 20, and the liquid crystal panel 30 can be incorporated into an image display device and used. In terms of image display devices, examples are: liquid crystal display (LCD), cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD), field emission display (FED), touch panel, tablet PC, electronic paper, etc. FIG. 5 is a schematic configuration diagram of a liquid crystal display as an example of an image display device incorporating an anti-glare film according to this embodiment.

The image display device 40 shown in FIG. 5 is a liquid crystal display. The image display device 40 is composed of a backlight unit 41 and a liquid crystal panel 30 provided with an anti-glare film 10 which is disposed closer to the observer side than the backlight unit 41. As the backlight unit 41, a known backlight unit can be used.

[Second Embodiment]

Hereinafter, an anti-glare film according to a second embodiment of the present invention will be described with reference to the drawings. In addition, the content overlapping with the first embodiment is the following: unless otherwise specified, it is omitted. FIG. 6 is a schematic configuration diagram of another anti-glare film according to this embodiment, and FIG. 7 is an enlarged view of a part of FIG. 6.

<<< Anti-glare film >>>

As shown in FIG. 6, the anti-glare film 50 includes at least a light-transmitting substrate 51 and an anti-glare layer 52 provided on the light-transmitting substrate 51. The light-transmitting substrate 51 is the same as the light-transmitting substrate 11 described in the first embodiment, so the following is adopted: The description is omitted in this embodiment.

<< Anti-glare layer >>

The anti-glare layer 52 is composed of three or more inorganic fine particles The first inorganic fine particle aggregates 53 and two or more inorganic fine particles are agglomerated second inorganic fine particle aggregates 54, unorganized single-particle organic fine particles 55, and a binder resin 56. The anti-glare layer 52 may not include the second inorganic fine particle aggregates 54 and the organic fine particles 55.

In the anti-glare layer 52, the organic fine particles 55 are unevenly present on the light-transmitting substrate 51 side. Organic particles are unevenly present on the side of the light-transmitting substrate, and can be confirmed by a cross-section electron microscope (TEM, STEM) image.

Here, for example, the average value of the thickness of the adhesive resin 56 between the light-transmitting substrate 51 and the organic fine particles 55 and the average value of the thickness of the adhesive resin 56 between the uneven surface 52A and the organic fine particles 55 are compared. This makes it possible to show the extent to which the organic fine particles 55 are unevenly present.

Specifically, in the anti-glare layer 52, the average value of the thickness of the adhesive resin 56 between the light-transmitting substrate 51 and the organic fine particles 55 is Tb, and the adhesive between the uneven surface 52A and the organic fine particles 55 is set to Tb. When the average value of the thickness of the resin 56 is Tf, it is preferable that Tf / Tb satisfy the following formula (4).

2.5 <Tf / Tb ... (4)

Tf / Tb satisfies the above-mentioned formula (4), makes the uneven surface 52A smooth, and prevents the occurrence of a large inclination angle that deteriorates contrast and glare.

The uneven surface 52A of the anti-glare layer 52 is composed of unevenness The average interval Sm of the unevenness of the surface 52A is preferably 0.1 mm or more and 0.6 mm or less, and more preferably 0.2 mm or more and 0.4 mm or less. As for the uneven surface 52A of the anti-glare layer 52, the average inclination angle θa of the unevenness constituting the uneven surface 52A is preferably 0.05 ° or more and 0.30 ° or less, and more preferably 0.15 ° or more and 0.25 ° or less.

As for the uneven surface 52A of the anti-glare layer 52, the arithmetic mean roughness Ra of the unevenness constituting the uneven surface 52A is preferably 0.02 μm or more and 0.20 μm or less, and more preferably 0.04 μm or more and 0.10 μm or less. The definitions and measurement methods of "Sm", "Ra", and "θa" are the same as those in the first embodiment.

<First inorganic fine particle aggregate>

In this embodiment, as in the first embodiment, in the first inorganic fine particle aggregate 53, the ratio of the inorganic fine particles connected to one or more inorganic fine particles below one inorganic fine particle is 95. %. In addition, as shown in FIG. 7, the first inorganic fine particle aggregates 53 have a buckling portion 53A formed by connecting the inorganic fine particles. The flexion 53A has an inner region 53B as shown in FIG. 7.

In addition, other than the following, it is the first inorganic fine particle aggregate 13 as described in the first embodiment, so the description is omitted.

The first inorganic fine particle aggregates 53 are located at least on the surface of the organic fine particles 55 and are separated from the organic fine particles 55 between the organic fine particles 55 for the same reason as in the first embodiment. good.

<Second inorganic fine particle aggregate>

The second inorganic fine particle aggregates 54 are present on or near the uneven surface 52A. Except for this, the second inorganic fine particle aggregates 14 described in the first embodiment will be omitted.

<Organic fine particles>

The organic fine particles 55 have the same material and the same average primary particle diameter as those of the organic fine particles described in the first embodiment. Here, for example, a solvent having a different affinity and volatility between the organic fine particles and the binder resin is used, and the agglomeration of the organic fine particles 55 is controlled during the drying by changing the affinity, so it can be used in the antiglare layer 52 Existing as the organic fine particles 55 in a single particle state, the organic fine particles 55 can be unevenly present on the light-transmitting substrate 51 side.

<Binder Resin>

Since the binder resin 56 is the same as the binder resin 16 described in the first embodiment, the description is omitted.

<<< Manufacturing method of anti-glare film >>>

The anti-glare film 50 can be formed by the same method as that of the first embodiment, so the description is omitted.

In this embodiment, also in the anti-glare layer 52, Since the first inorganic fine particle aggregate 53 including the flexed portion 53A having the inner region 53B is included, for the same reason as in the first embodiment, the observer (observer) and the background reflection of the observer are not taken into consideration. Anti-glare properties, and at the same time can obtain good anti-glare properties and good black color.

[Third Embodiment]

Hereinafter, an anti-glare film according to a third embodiment of the present invention will be described with reference to the drawings.

<<< Anti-glare film >>>

FIG. 8 is a schematic configuration diagram of an anti-glare film according to this embodiment, FIG. 9 is an enlarged view of a part of FIG. 8, FIG. 10 is an enlarged view of a part of FIG. 9, and FIG. The image sharpness measuring device is a schematic diagram for measuring the sharpness of the penetration image of the anti-glare film according to the embodiment.

As shown in FIG. 8, the anti-glare film 60 includes a light-transmitting substrate 61 and an anti-glare layer 62 provided on the light-transmitting substrate 61 and having an uneven surface 62A.

The surface 60A of the anti-glare film 60 is an uneven surface. In this embodiment, since the functional layer such as a low refractive index layer is not provided on the anti-glare layer 62, the uneven surface 62A of the anti-glare layer 62 becomes the surface 60A of the anti-glare film 60.

As for the anti-glare film 60, it was measured using a light comb of 0.125mm width, 0.25mm width, 0.5mm width, 1.0mm width, and 2.0mm width. The absolute value of the difference between the arithmetic mean value of the definition of the transmitted image sharpness and the transmitted image sharpness measured using each optical comb is within 10%.

In the present specification, the "transparent image clarity of the anti-glare film" refers to the clarity of the transmission image measured over the entire anti-glare film. In this embodiment, the anti-glare layer 62 is not provided with a functional layer such as a low-refractive index layer. Therefore, the transparent image of the anti-glare film 60 is clear. The transmitted image sharpness measured by the anti-glare film 60 formed of the layer 62. In addition, when a functional layer such as a low-refractive index layer is provided on the anti-glare layer, the clarity of the anti-glare film through the image is formed by using a light-transmitting substrate, an anti-glare layer, and a functional layer. The anti-glare film was used to determine the transmitted image clarity.

The above-mentioned transmission image sharpness can be measured by a transmission sharpness measuring device based on a transmission method of image sharpness according to JIS K7374. Examples of such a measuring device include an image sharpness measuring device ICM-1T manufactured by SUGA TEST INSTRUMENTS.

As shown in FIG. 11, the transmission image sharpness measuring device 200 includes a light source 201, a slit 202, a lens 203, a lens 204, an optical comb 205, and a light receiver 206. The transmission sharpness measuring device 200 is configured to make the light emitted from the light source 201 and pass through the slit 202 become parallel light by the lens 203, and illuminate the parallel light on the back surface of the anti-glare film 60 (prevention of the transparent substrate 61) The surface opposite to the surface on the side of the glare layer 62) condenses the light transmitted from the uneven surface 62A of the anti-glare layer 62 of the anti-glare film 60 by the lens 204, and the light passing through the light comb 205 is a light receiver 206 as a light receiver, based on the amount of light received by this light receiver 206, borrowed Formula (5) calculates the clarity C of the transmitted image.

C (n) = {(M-m) / (M + m)} × 100 (%) ... (5)

In formula (5), C (n) is the sharpness (%) of the transmitted image when the width of the comb is n (mm), M is the highest light amount when the width of the comb is n (mm), and m is the comb The minimum light quantity at the width n (mm).

The optical comb 205 is movable along the longitudinal direction of the optical comb 205 and includes a light shielding portion and a transmitting portion. The ratio of the width of the light-shielding portion and the transmission portion of the optical comb 205 is 1: 1. Here, in JIS K7374, five types of optical combs with a width of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm are defined in terms of optical combs. The anti-glare film 60 is arranged such that light that is made parallel by the lens 203 is incident on the back surface of the anti-glare film 60 perpendicularly to the anti-glare film 60.

The arithmetic mean value of the transmitted image clarity of the anti-glare film 60 measured using the above-mentioned five types of optical combs is 70% or more and 95% or less. The lower limit of the arithmetic mean of the clarity of the penetration image of the anti-glare film 60 is preferably more than 80%. good. The transmitted image clarity of the anti-glare film 60 measured using a 0.125 mm wide optical comb is preferably at least 70%, and the transmitted image clarity of the anti-glare film 60 measured using a 0.25 mm wide optical comb It is better to be 70% or more, and the anti-glare film 60 of the anti-glare film 60 measured by using a 0.5mm wide optical comb is preferably 80% or more, and the anti-glare film is measured using a 1.0mm wide optical comb. The penetration image clarity of 60 is preferably 80% or more, and the penetration image clarity of the anti-glare film 60 measured using a 2.0 mm wide optical comb is 90% or more. Better.

In the surface 60A of the anti-glare film 60, the average interval Sm of the irregularities constituting the surface 60A is preferably 0.1 mm or more and 0.6 mm or less, and more preferably 0.2 mm or more and 0.4 mm or less. In the surface 60A of the anti-glare film 60, the average inclination angle θa of the unevenness constituting the surface 60A is preferably 0.05 ° or more and 0.30 ° or less, and more preferably 0.15 ° or more and 0.25 ° or less.

In the surface 60A of the anti-glare film 60, the arithmetic average roughness Ra of the unevenness constituting the surface 60A is preferably 0.02 μm or more and 0.20 μm or less, and more preferably 0.04 μm or more and 0.10 μm or less.

The definitions and measurement methods of "Sm", "Ra", and "θa" are the same as those in the first embodiment.

The anti-glare film 60 has a total light transmittance of 85% or more, and more preferably 90% or more, for the same reason as in the first embodiment. The total light transmittance can be measured by the same method as in the first embodiment.

The haze value (full haze value) of the entire anti-glare film 60 is based on the same reason as the first embodiment, and is preferably 2% or less, and more preferably 1% or less. The total haze value can be measured by the same method as in the first embodiment.

The internal haze value of the anti-glare film 60 is preferably 0% or more and 2.0% or less. The surface haze value of the anti-glare film 60 is preferably 0% or more and 0.3% or less. The internal haze and surface haze values can be obtained by the same method as in the first embodiment.

In the anti-glare film 60, it is preferable that the surface 60A of the anti-glare film 10 with respect to the surface 61A of the light-transmitting substrate 61 in a cross section along the thickness direction of the anti-glare layer 60 be 0.1 degrees. When measuring the tilt angle, the ratio of the cumulative percentage of the frequency of the tilt angle to the 99th percentile of the 3rd quartile (99th percentile / 3rd quartile) is 4.0 or more , Less than 5.0. This ratio is 4.0 or more, so that the rate of change of the inclination angle is not excessively increased to prevent glare. In addition, the ratio is less than 5.0, so that the proportion of the portion of the surface 60A of the anti-glare film 60 having an excessive inclination angle is controlled. Therefore, the decrease in contrast can be suppressed.

<< Transparent substrate >>

The light-transmitting base material 61 is the same as the light-transmitting base material 11 described in the first embodiment. Therefore, descriptions thereof will be omitted.

<< Anti-glare layer >>

The anti-glare layer 62 is a layer exhibiting anti-glare properties, and as shown in FIG. 9, it includes a plurality of organic fine particles 63, a plurality of inorganic fine particles 64, and an adhesive resin 65. The surface of the anti-glare layer 62 is an uneven surface 62A. The anti-glare layer 62 may be one that exhibits anti-glare properties while performing other functions. Specifically, the anti-glare layer 62 may be a layer that exhibits anti-glare properties and functions such as hard coat properties, anti-reflection properties, anti-static properties, or anti-fouling properties.

The anti-glare layer 62 exhibits hard coat properties in addition to anti-glare properties. In the case of a layer, the anti-glare layer 62 has a hardness of “H” or higher in a pencil hardness test (4.9N load) specified in JIS K5600-5-4 (1999).

When the anti-glare layer 62 has a hard coat property, the thickness of the anti-glare layer 62 is preferably 2.0 μm or more and 7.0 μm or less for the same reason as in the first embodiment. The lower limit of the thickness of the anti-glare layer is more preferably 2.5 μm or more, and the upper limit is more preferably 5 μm or less. The thickness of the anti-glare layer was measured by the same method as in the first embodiment.

<Organic fine particles>

It is preferable that at least a part of the plurality of organic fine particles 63 is in the form of an aggregate of organic fine particles 63A in which two or more organic fine particles 63 are aggregated. The number of organic microparticles 63 constituting the organic microparticle agglomerate 63A is two or more, so that in terms of the uneven surface 62A, the area of the peak of the gently inclined convex portion increases, and the area of the rising surface of the steeply inclined convex portion decreases. Suppresses deterioration of contrast.

For the anti-glare layer 62, for the same reason as in the first embodiment, it is preferable that the maximum height of the organic fine particle aggregate 63A in the thickness direction of the anti-glare layer 62 is less than the thickness of the anti-glare layer 62.

The organic fine particles 63 are exemplified by the plastic particles exemplified in the first embodiment. For the same reason as in the first embodiment, it is also preferable to hydrophilize the surface of the organic fine particles 63.

The average primary particle diameter of the organic fine particles 63 is preferably 1 μm or more and 5 μm or less for the same reason as in the first embodiment. The average primary particle diameter of the organic fine particles can be obtained by the same method as in the first embodiment. And figure it out. The lower limit of the average primary particle diameter of the organic fine particles 63 is more preferably 1.5 μm or more, and the upper limit of the average primary particle diameter of the organic fine particles 63 is more preferably 4.0 μm or less.

When the thickness of the anti-glare layer 62 is set to T and the average primary particle size of the organic fine particles 63 is set to R, for the same reason as in the first embodiment, the R / T system preferably satisfies the relationship of the above formula (3).

The number of organic fine particles 63 constituting the organic fine particle aggregate 63A is preferably two or more and three or less for the same reasons as in the first embodiment. The organic microparticle agglomerate 63A can also be obtained, for example, by controlling the agglomerated state similarly to the first embodiment.

<Inorganic fine particles>

The inorganic fine particles 64 are not particularly limited, but examples include the same inorganic acid fine particles as the inorganic acid fine particles exemplified in the first embodiment. When silica particles are used for the inorganic fine particles 64, fuming silica particles are preferable from the viewpoint that an anti-glare layer having a smooth uneven surface can be easily formed among the silica particles.

When inorganic oxide particles are used for the inorganic fine particles 64, the inorganic oxide fine particles are preferably amorphous for the same reasons as in the first embodiment.

When the fumed silica particles are used for the inorganic fine particles 64, fumed silica particles exhibiting hydrophobicity are preferred for the same reason as in the first embodiment. Hydrophobic fuming silica is a silanol that can be used on the surface of fine particles of fuming silica. It is obtained by chemically reacting the surface treatment agent as described above.

For the same reason as the first embodiment, the inorganic fine particles 64 have a spherical shape in a single particle state.

The average primary particle diameter of the inorganic fine particles 64 is preferably 1 nm or more and 100 nm or less for the same reason as in the first embodiment. The lower limit of the average primary particle diameter of the inorganic fine particles 64 is more preferably 10 nm or more, and the upper limit of the average primary particle diameter of the inorganic fine particles 64 is more preferably 50 nm or less. The average primary particle diameter of the inorganic fine particles 64 is a value measured by the same method as in the first embodiment.

It is preferable that at least a part of the plurality of inorganic fine particles 64 is the first inorganic fine particle aggregate 64A in which three or more inorganic fine particles 64 are aggregated.

The first inorganic fine particle aggregate 64A is present in the binder resin 65 and is composed of three or more inorganic fine particles 64 as described above. The first inorganic fine particle aggregate 64A is shown in FIG. 10, and it is preferable that the inorganic fine particles 64 have a buckled portion 64B formed by connecting the inorganic fine particles 64. The shape of the flexion portion 64B is exemplified by the same shape as the flexion portion 13A.

The buckling portion 64B can also be formed by connecting inorganic fine particles, and is composed of an aggregate of inorganic fine particles that is buckled. It can also be a dry portion formed by connecting inorganic fine particles, and the dry portion can be connected by inorganic particles. The formed branch portion may be formed by two branch portions which are branched from the stem portion and connected to the stem portion.

The flexion portion 64B has an inner region as shown in FIG. 10 64C. This inner region 64C is buried with the adhesive resin 65. The buckling portion 64C preferably exists so as to sandwich the inner region 64C from the thickness direction of the anti-glare layer 62.

Inorganic fine particles aggregate into agglomerated inorganic fine particle aggregates, which act as a single solid when curing and shrinking (polymerizing shrinkage) of a photopolymerizable compound that becomes a binder resin after hardening. Therefore, the uneven surface of the anti-glare layer corresponds to Shape of aggregate of inorganic fine particles. In this regard, since the first inorganic fine particle aggregate 64A has a flexure 64B having an inner region 64C, it acts as a solid having a buffering effect when it is hardened and contracted. Therefore, when the first inorganic fine particle aggregate 64A is hardened and contracted, it is easily crushed with uniformity. Thereby, the shape of the uneven surface 62A becomes slower than the shape before the curing shrinkage.

In the first inorganic fine particle aggregate 64A, for the same reason as in the first embodiment, the ratio of the inorganic fine particles connected to one or more and three or less inorganic fine particles below one inorganic fine particle is 95% or more. good. The proportion of the inorganic fine particles is more than 97%, and more preferably more than 99%.

The existence ratio of the first inorganic fine particle aggregates 64A in the anti-glare layer 62 is the same as that of the first embodiment. The light-transmitting substrate 61 side of the anti-glare layer 62 is higher than the uneven surface 62A of the anti-glare layer 62. The side is better. Here, the first inorganic fine particle aggregate is present on the light-transmitting substrate side of the anti-glare layer or on the uneven surface side, which is the following: judged by the same method as the method described in the first embodiment .

Specifically, the section along the thickness direction of the anti-glare layer 62 In the surface, among the first inorganic fine particle aggregates 64A, the number of the first inorganic fine particle aggregates 64A existing on the light-transmitting substrate 61 side of the anti-glare layer 62 is Nb, and the unevenness of the anti-glare layers 62 is present. When the number of the first inorganic fine particle aggregates 64A on the surface 62A side is Nf, it is preferable that the Nb / Nf system satisfies the above formula (2) for the same reason as in the first embodiment.

The first inorganic microparticle agglomerates 64A are located at least on the surface of the organic microparticle agglomerates 63A, and are separated from the organic microparticle agglomerates 63A and the positions between the organic microparticle agglomerates 63A for the same reasons as in the first embodiment. good.

The average agglomeration diameter of the first inorganic fine particle aggregate 64A is preferably 100 nm or more and 2.0 μm or less for the same reason as in the first embodiment. The average aggregation diameter of the first inorganic fine particle agglomerates 64A is preferably 200 nm or more, and more preferably 1.5 μm or less. The average aggregation diameter of the first inorganic fine particle aggregate can be obtained by the same method as in the first embodiment.

It is preferable that the first inorganic fine particle aggregate 64A has a larger aggregate diameter in a direction orthogonal to the thickness direction than the aggregate diameter in the thickness direction of the anti-glare layer 62. The "agglomeration diameter in the thickness direction" and "agglomeration diameter in a direction orthogonal to the thickness direction" are measured by the same method as in the first embodiment.

The first inorganic fine particle aggregate 64A can be obtained by controlling, for example, the hydrophilic treatment of the organic fine particles 63, the hydrophobic treatment of the inorganic fine particles 64, and the presence ratio of the hydroxyl groups of the binder resin 65. There are hydroxyl groups on the surface of the inorganic fine particles 64, but there is no When the organic fine particles 64 are hydrophobized, the number of hydroxyl groups existing on the surface of the inorganic fine particles 64 is reduced, and excessive aggregation of the inorganic fine particles can be suppressed. In addition, the surface of the inorganic fine particles 64 may be subjected to a hydrophobizing treatment, so as to improve the chemical resistance and alkali resistance of the inorganic fine particles themselves.

Such a hydrophobic treatment can be performed using a surface treatment agent such as a silane or silazane. Specific surface treatment agents include, for example, dimethyldichlorosilane and the like as exemplified in the first embodiment.

The first inorganic fine particle aggregate 64A can also be obtained by a method other than the above-mentioned method, or by a method described in the first embodiment.

As for the inorganic fine particles 64 in the anti-glare layer 62, as shown in FIG. 9 and FIG. 10, together with the first inorganic fine particle aggregate 64A, there are two or more inorganic fine particles 64 aggregated as the second inorganic fine particle aggregate 64D. Yes. The second inorganic fine particle aggregate 64D is present on or near the uneven surface 62A. In addition, in the second inorganic fine particle aggregate 64D, the ratio of the inorganic fine particles connected to the inorganic fine particles of one or more and three or less of the inorganic fine particles is preferably 95% or more. The second inorganic fine particle agglomerate 64D preferably has a larger agglomerate diameter in a direction orthogonal to the thickness direction than the agglomerate diameter in the thickness direction of the anti-glare layer 62, and is more preferably two-dimensionally agglomerated. In addition, the second inorganic fine particle agglomerate 64 is located closer to the uneven surface 62A or in the vicinity of the first inorganic fine particle agglomerate 64A than the first inorganic fine particle agglomerate 64A. Therefore, the thickness of the lower anti-glare layer 62 is smaller than the first inorganic fine particle agglomerate 64A. Condensing path It becomes small, making the uneven surface 62A smoother.

When the second inorganic fine particle aggregate 64D is present on or near the uneven surface 62A, for the same reason as in the first embodiment, an anti-glare film 60 having excellent flexibility is obtained.

The average aggregation diameter of the second inorganic fine particle aggregate 64D is preferably 100 nm or more and 2.0 μm or less for the same reason as that of the first inorganic fine particle aggregate 64A. The average aggregation diameter of the second inorganic fine particle agglomerates 64D is more preferably 200 nm or more, and more preferably 1.5 μm or less.

As the inorganic fine particles 64 constituting the second inorganic fine particle aggregate 64D, the same ones as the inorganic fine particles 64 constituting the first inorganic fine particle aggregate 64A may be used, so the following is adopted: the description is omitted here. The second inorganic microparticle agglomerate 64D is similar to the first inorganic microparticle agglomerate 64A. For example, the hydrophilic ratio of the organic microparticles 63, the hydrophobic treatment of the inorganic microparticles 64, and the ratio of the hydroxyl groups of the binder resin 65 can be obtained. Gain control. However, in order to make the aggregation state of the second inorganic fine particle aggregate 64D different from the aggregation state of the first inorganic fine particle aggregate 64A, for example, the second inorganic fine particle aggregate 64D may be used in combination with the first inorganic fine particle aggregate 64A. Different surface treatment agents and different surface treatment agent concentrations from the first inorganic fine particle aggregate 64A.

The anti-glare layer 62 corresponds to the organic fine particles 63 in the uneven surface 62A of the anti-glare layer 62 in a cross section along the thickness direction of the anti-glare layer 62 (the normal direction of the light-transmitting substrate 61). And inorganic particles The ratio of the length of the area other than the area of the sub-64 is preferably 15% or more and 70% or less. This ratio is more than 15%, so that the anti-glare film generates a moderately positive transmission (orthogonal reflection) component, which can guarantee the gloss, brightness and contrast of the image. In addition, the ratio is less than 70%, so that excessive positive reflection will not occur. Guaranteed anti-glare properties. The lower limit of this ratio is preferably 20% or more, and the upper limit of this ratio is preferably 60% or less.

In this specification, "the length of a region other than the region corresponding to the organic fine particles and the inorganic fine particles" means that when viewed from the thickness direction of the anti-glare layer in a cross section along the thickness direction of the anti-glare layer, and The length (linear distance) of a region other than the area of the uneven surface where the organic fine particles (organic fine particle aggregates) and inorganic fine particles (first inorganic fine particle aggregates and second inorganic fine particle aggregates) overlap. The area other than the area corresponding to the organic fine particles and the inorganic fine particles is an area where diffusion elements contributing to internal diffusion and / or surface diffusion do not exist. The image light transmitted through this area is only composed of the components in the normal transmission direction, and the outside The light side is also made only by the specular reflection component. Conversely, the areas corresponding to the organic fine particles and the inorganic fine particles are areas having a diffusion element that contributes to internal diffusion and / or surface diffusion. The image light transmitted through this area is made of a diffusing component, and it also has diffusion in external light. Reflection component. For example, in the case of FIG. 10, the lengths of the regions other than the regions corresponding to the organic fine particles 63 and the inorganic fine particles 64 are L ₁ to L ₄ . The length ratio is a value measured from an image of a cross-section electron microscope (TEM, STEM) using image processing software.

<Binder Resin>

The binder resin 65 is the same as the binder resin 16 described in the first embodiment. Therefore, in this embodiment, the description is omitted.

According to this embodiment, the anti-glare film 60 uses a light comb of 0.125 mm width, 0.25 mm width, 0.5 mm width, 1.0 mm width, and 2.0 mm width to measure the sharpness of the transmitted image, and the arithmetic average is 70% or more. Moreover, the absolute value of the difference between the arithmetic mean and the sharpness of the transmitted image measured using each optical comb is within 10%, so that anti-glare properties to which reflection is not taken into consideration can be obtained, and good anti-glare properties can be obtained at the same time. Glare and good black color. That is, since the absolute value of the difference between the above-mentioned arithmetic average value and the transmitted image sharpness measured using each optical comb is within 10%, the difference between the transmitted image sharpness of each optical comb is small. This means that the transmitted light diffuses only on the convex portions on the surface of the anti-glare film, and does not diffuse on the flat portions of the surface of the anti-glare film. That is, it shows that there is almost no tilt in the flat portion. In this way, there is almost no inclination in the flat portion, so that the occurrence of glare can be suppressed, so good anti-glare properties can be obtained. In addition, there is almost no tilt in the flat part, so that it can have a moderate specular reflection component. Therefore, when animated images are displayed, the gloss and brightness of the images will increase, and a sense of excitement can be obtained. Furthermore, since the arithmetic average of the clarity of the transmitted image becomes 70% or more, the convex portion on the surface of the anti-glare film is not excessively large. For this reason, in addition to the above-mentioned effects, excessive diffusion of external light does not occur, it is possible to suppress a decrease in the contrast of the bright room, and at the same time prevent the image light from becoming stray light, so a good dark room contrast can also be obtained. In addition, the arithmetic average value of the clarity of the penetrating image becomes 95% or less, so that the flat portion is not excessive, and The surface of the glare film has moderately formed convex portions, and the reflected light is appropriately diffused, so that anti-glare properties to the extent that reflection is not taken into consideration can be obtained. Thereby, it is possible to obtain anti-glare to such an extent that reflection is not taken into consideration, and at the same time to obtain a good black color feeling having both good anti-glare properties and excellent contrast and dynamism. In addition, the degree of anti-glare to the extent that the reflection of the observer (observer) and the background of the observer is not taken into consideration is the anti-glare property as follows: the presence of the observer is confirmed, but only its outline becomes unclear blur The state and the existence of objects in the background of the observer are also confirmed, but the outline and boundary become unclear. In this way, only the observer's outline and the like become blurred, and the observer becomes more in a state where reflection is not noticed.

According to this embodiment, the first inorganic fine particle aggregate 64A has a flexure portion 64B having an inner region 64C. Therefore, for the same reason as the first embodiment, good anti-glare properties can be obtained, and further, excellent contrast can be obtained. And the black color sense of dynamism.

<<< Manufacturing method of anti-glare film >>>

The anti-glare film 60 can be formed in the following manner, for example. First, the composition for an anti-glare layer is applied to the light-transmitting substrate 61 by the same method as in the first embodiment.

<< Composition for antiglare layer >>

The composition for the anti-glare layer contains at least the organic fine particles 63, the inorganic fine particles 64, and the photopolymerizable compound, and preferably contains the organic fine particle aggregates 63A, the first inorganic fine particle aggregates 64A, and the second inorganic Microparticle aggregates 64D. Moreover, you may add the said thermoplastic resin, the said thermosetting resin, a solvent, and a polymerization initiator to the composition for anti-glare layers as needed. The composition for the anti-glare layer may be added with a conventionally known dispersant and the like exemplified in the first embodiment.

<Solvent, polymerization initiator>

The solvent and the polymerization initiator are the same as the solvent and the polymerization initiator described in the first embodiment, and thus the description is omitted.

After applying the composition for the anti-glare layer on the light-transmitting substrate 61, the composition for the anti-glare layer in the form of a coating film is dried and then transported to a heated area, and is transferred by various known methods. The composition for the anti-glare layer is dried to evaporate the solvent. Here, the affinity between the solvent and the solid content, the relative evaporation speed of the solvent, the solid content concentration, the temperature of the coating solution, the drying temperature, the wind speed of the drying wind, the drying time, and the concentration of the solvent environment in the drying area are selected, so that it can be used for organic The distribution states of the fine particle aggregates 63A, the first inorganic fine particle aggregates 64A, and the second inorganic fine particle aggregates 64D are adjusted.

Thereafter, the coating film-like composition for the anti-glare layer is irradiated with light such as ultraviolet rays, and the photopolymerizable compound is polymerized (crosslinked) to harden the composition for the anti-glare layer to form the anti-glare layer 62. . Here, as described above, the first inorganic fine particle aggregate 64A has a buckled portion 64B having an inner region 64C, and therefore acts as a solid having a buffering effect when it is hardened and contracted. Therefore, when the first inorganic fine particle aggregate 64A is hardened and contracted, it is easily crushed with uniformity.

Regarding the method for preparing the composition for the anti-glare layer, the drying conditions, and the light when the composition for the anti-glare layer is hardened, it is the same as that of the first embodiment, and descriptions thereof will be omitted.

<< Polarizer, LCD panel, image display device >>

As shown in FIGS. 12 to 14, the anti-glare film 60 is the same as the first embodiment, and can be used by being incorporated in, for example, a polarizing plate 70, a liquid crystal panel 80, and an image display device 90. In Figs. 12 to 14, components having the same reference numerals as those in Figs. 3 to 5 indicate the same components as those described in the first embodiment.

[Fourth Embodiment]

Hereinafter, an anti-glare film according to a fourth embodiment of the present invention will be described with reference to the drawings.

<<< Anti-glare film >>>

FIG. 15 is a schematic configuration diagram of an anti-glare film according to this embodiment, FIG. 16 is an enlarged view of a part of FIG. 15, and FIG. 17 is an enlarged view of a part of FIG. 16.

As shown in FIG. 15, the anti-glare film 100 includes a light-transmitting substrate 101 and an anti-glare layer 102 provided on the light-transmitting substrate 101 and having an uneven surface 102A.

The surface 100A of the anti-glare film 100 is an uneven surface. In this embodiment, the anti-glare layer 102 is not provided with a low refractive index layer or the like. The functional layer, therefore, the uneven surface 102A of the anti-glare layer 102 becomes the surface 100A of the anti-glare film 100.

For the anti-glare film 100, when the frequency distribution of the inclination angle with respect to the surface 100A of the anti-glare film 100 on the surface 101A of the light-transmitting substrate 101 is determined at 0.01 degree, the cumulative percentage of the frequency of the inclination angle is relative The ratio of the 99th percentile at the 3rd quartile (99th percentile / 3rd quartile) is 3.0 or more and 5.0 or less. The lower limit of the 99th percentile / 3rd quartile is preferably 4.0 or higher, and the upper limit of the 99th percentile / 3rd quartile is preferably 4.5 or lower.

"Tilt angle" refers to the tilt angle of the surface of the anti-glare film. That is, as in this embodiment, when a functional layer such as a low refractive index layer is not provided on the anti-glare layer, the "tilt angle" measured is the inclination angle of the uneven surface of the anti-glare layer. In addition, when a functional layer such as a low refractive index layer is provided on the anti-glare layer, the "tilt angle" is not the inclination angle of the uneven surface of the anti-glare layer, but the inclination angle of the surface of the functional layer. The "tilt angle" is an absolute value.

The inclination angle is obtained by measuring the surface shape of the surface of the anti-glare film. As an apparatus for measuring the surface shape, examples are: a contact surface roughness meter and a non-contact surface roughness meter (for example, an interference microscope, a confocal microscope, an atomic force microscope, etc.). Among these, an interference microscope is preferable in terms of simplicity of measurement. An example of such an interference microscope is the "New View" series made by Zygo.

To calculate the inclination angle using an interference microscope, for example, the inclination St at each point across the entire surface of the surface of the anti-glare film is obtained, and the inclination St is converted into the inclination angle θ _i by the following formula (6).

θ _i = tan ^-1 St ... (6)

The inclination St can be obtained from the following formula (7).

Here, when one of the two orthogonal directions on the measurement surface is the x-axis and the other is the y-axis, Sx is the inclination of the x-axis direction with respect to the x-axis, and Sy is the y-axis direction with respect to the y-axis. The inclination is calculated from the following formulae (8) and (9).

Sx = (Z _{i + 1, j} -Z _{i-1, j} ) / 2⊿ ... (8)

Sy = (Z _{i, j + 1} -Z _{i, j-1} ) / 2⊿ ... (9)

In formulas (8) and (9), Z _{i, j} is the height of the i-th in the x-axis direction and the j-th in the y-axis direction, and is the sampling interval.

For the measurement of the surface shape of the surface 100A, it is preferable to calculate the tilt angle from the concave-convex shape that excludes the meandering component by a high-pass filter with a cutoff value of 300 μm.

It is known that the inclination angle is greatly affected by the sampling interval. In the present invention, the sampling interval is preferably 0.2 μm or more and 2 μm or less. The reason is that if the sampling interval is too small, the high-frequency components of the unevenness on the noise will be picked up, and the tilt angle may be overestimated. If the sampling interval is too large, the surface angle may not be accurately estimated. It is preferable that the measurement area is wide, at least 200 μm × 200 μm or more, and more preferably, the area is 500 μm × 500 μm or more.

For the anti-glare film 100, the arithmetic mean of the transmitted image clarity measured using a light comb of 0.125 mm width, 0.25 mm width, 0.5 mm width, 1.0 mm width, and 2.0 mm width, and the use of each light comb It is more preferable that the absolute value of the difference in sharpness of the transmitted image is within 10%. This difference is within 10%, making it possible to more reliably suppress glare. The above-mentioned transmission image sharpness can be measured using the same device as the third embodiment.

The average value of the transmitted image clarity of the anti-glare film 100 measured using the above-mentioned five types of optical combs is preferably 80% or more. The transmitted image clarity of the anti-glare film 100 measured using a 0.125 mm wide optical comb is preferably at least 70%, and the transmitted image clarity of the anti-glare film 100 measured using a 0.25 mm wide optical comb It is better to be 70% or more, and the anti-glare film 100 of the anti-glare film 100 measured using a 0.5mm wide optical comb is more than 80%, and it is better to use an anti-glare film measured using a 1.0mm wide optical comb. The transmission image clarity of 100 is preferably 80% or more, and the transmission image clarity of the anti-glare film 100 measured using a 2.0 mm wide light comb is preferably 90% or more.

In the surface 100A of the anti-glare film 100, the average interval Sm of the irregularities constituting the surface 100A is preferably 0.1 mm or more and 0.6 mm or less, and more preferably 0.2 mm or more and 0.4 mm or less. On the surface 100A of the anti-glare film 100, the average inclination angle θa of the unevenness constituting the surface 100A is preferably 0.05 ° or more and 0.30 ° or less, and more preferably 0.15 ° or more and 0.25 ° or less.

In the surface 100A of the anti-glare film 100, the arithmetic mean roughness Ra of the unevenness constituting the surface 100A is 0.02 μm or more, It is preferably 0.20 μm or less, and more preferably 0.04 μm or more and 0.10 μm or less.

The definitions and measurement methods of "Sm", "Ra", and "θa" are the same as those in the first embodiment.

The anti-glare film 100 has a total light transmittance of 85% or more, and more preferably 90% or more, for the same reason as in the first embodiment. The total light transmittance can be measured by the same method as in the first embodiment.

The haze value (full haze value) of the entire anti-glare film 100 is based on the same reason as the first embodiment, and is preferably 2% or less, and more preferably 1% or less. The total haze value can be measured by the same method as in the first embodiment.

When the anti-glare film has an internal haze value, the anti-glare property is improved. On the other hand, when the internal haze value is too large, stray light may be generated, and the black color may be deteriorated. Therefore, the anti-glare property and the black color may be deteriorated. From the viewpoint of improvement, the internal haze value of the anti-glare film 100 is preferably 0.1% or more and 2.0% or less. The internal haze value of the anti-glare film 100 is more preferably 0.5% or more and 1.5% or less. The internal haze value can be measured by the same method as in the first embodiment.

The surface haze value of the anti-glare film 100 is preferably 0% or more and 0.3% or less. The surface haze value can be obtained by the same method as in the first embodiment.

<< Transparent substrate >>

The transparent substrate 101 is transparent as explained in the first embodiment. Since the optical base material 11 is omitted, description is omitted.

<< Anti-glare layer >>

The anti-glare layer 102 is a layer exhibiting anti-glare properties. As shown in FIG. 16, the anti-glare layer 102 includes a plurality of organic fine particles 103, a plurality of inorganic fine particles 104, and an adhesive resin 105. The anti-glare layer 102 may be one that exhibits anti-glare properties while performing other functions. Specifically, the anti-glare layer 102 may be a layer that exhibits anti-glare properties and functions such as hard coat properties, anti-reflection properties, anti-static properties, or anti-fouling properties.

When the anti-glare layer 102 is a layer exhibiting hard coating properties in addition to anti-glare properties, the anti-glare layer 102 has a "H" in the pencil hardness test (4.9N load) specified in JIS K5600-5-4 (1999). ”Above hardness.

The surface of the anti-glare layer 102 is an uneven surface 102A. In this embodiment, since the uneven surface 102A of the anti-glare layer 102 is the surface 100A of the anti-glare film 100, the uneven surface of the anti-glare layer 102 with respect to the surface 101A of the light-transmitting substrate 101 is determined at 0.01 degrees. In the frequency distribution of the tilt angle of 102A, the ratio of the cumulative percentage of the frequency of the tilt angle to the 99th percentile of the 3rd quartile (99th percentile / 3rd quartile) becomes 3.0 or more and 5.0 or less.

When the anti-glare layer 102 has a hard coat property, the thickness of the anti-glare layer 102 is preferably 2.0 μm or more and 7.0 μm or less for the same reason as in the first embodiment. The lower limit of the thickness of the anti-glare layer is more preferably 2.5 μm or more, and the upper limit is more preferably 5 μm or less.

<Organic fine particles>

It is preferable that at least a part of the organic microparticles in the plurality of organic microparticles 103 have an organic microparticle agglomerate 103A in which two or more organic microparticles 103 are aggregated for the same reason as in the third embodiment.

For the anti-glare layer 102, for the same reason as in the first embodiment, it is preferable that the maximum height of the organic fine particle aggregate 103A in the thickness direction of the anti-glare layer 102 is less than the thickness of the anti-glare layer 12.

The organic fine particles 103 are exemplified by the plastic particles exemplified in the first embodiment. For the same reason as in the first embodiment, it is also preferable that the surface of the organic fine particles 103 be subjected to a hydrophilization treatment.

The average primary particle diameter of the organic fine particles 103 is preferably 1 μm or more and 5 μm or less for the same reason as in the first embodiment. The average primary particle diameter of the organic fine particles can be calculated by the same method as in the first embodiment. The lower limit of the average primary particle diameter of the organic fine particles 103 is more preferably 1.5 μm or more, and the upper limit of the average primary particle diameter of the organic fine particles 103 is more preferably 4.0 μm or less.

In addition, when the thickness of the anti-glare layer 102 is T and the average primary particle diameter of the organic fine particles 103 is R, for the same reason as in the first embodiment, it is preferable that the R / T system satisfies the relationship of the above formula (3).

The number of organic fine particles 103 constituting the organic fine particle aggregate 103A is preferably two or more and three or less for the same reasons as in the first embodiment. Organic fine particle agglomerates 103A, for example It can be obtained by controlling the aggregation state similarly to the first embodiment.

<Inorganic fine particles>

The inorganic fine particles 104 are not particularly limited, but examples include the same inorganic acid fine particles as the inorganic acid fine particles exemplified in the first embodiment. When the silica particles are used for the inorganic fine particles 104, the fumed silica particles are preferable from the viewpoint that an anti-glare layer having a smooth uneven surface can be easily formed among the silica particles.

When inorganic oxide particles are used for the inorganic fine particles 104, the inorganic oxide fine particles are preferably amorphous for the same reasons as in the first embodiment. When fuming silica particles are used for the inorganic fine particles 104, fuming silica particles exhibiting hydrophobicity are preferred for the same reason as in the first embodiment. Hydrophobic fumed silica can be obtained by chemically reacting the surface treating agent with the silanol group existing on the surface of the fumed silica fine particles.

The inorganic fine particles 104 are spherical in the single particle state for the same reason as in the first embodiment.

The average primary particle diameter of the inorganic fine particles 104 is preferably 1 nm or more and 100 nm or less for the same reason as in the first embodiment. The lower limit of the average primary particle diameter of the inorganic fine particles 104 is more preferably 10 nm or more, and the upper limit of the average primary particle diameter of the inorganic fine particles 104 is more preferably 50 nm or less. The average primary particle diameter of the inorganic fine particles 104 is a value measured by the same method as in the first embodiment.

None of the plurality of inorganic fine particles 104 The organic fine particles 104 are preferably in the form of the first inorganic fine particle aggregate 104A in which three or more inorganic fine particles 104 are aggregated.

The first inorganic fine particle aggregate 104A is present in the binder resin 105 and is composed of three or more inorganic fine particles 104 as described above. As shown in FIG. 17, the first inorganic fine particle aggregated body 104A preferably has a buckled portion 104B formed by connecting the inorganic fine particles 104. The shape of the buckling portion 104B is exemplified by the same shape as the buckling portion 13A.

The buckling portion 104B can also be formed by connecting inorganic fine particles, and is composed of an aggregate of inorganic fine particles that is buckled. It can also be a dry portion formed by connecting inorganic fine particles, and the dry portion can be connected by inorganic particles. The formed branch portion may be formed by two branch portions which are branched from the stem portion and connected to the stem portion.

The buckling portion 104B has an inner region 104C as shown in FIG. 17. This inner region 104C is buried with the adhesive resin 105. It is preferable that the buckling portion 104B exists so as to sandwich the inner region 104C from the thickness direction of the anti-glare layer 102.

Inorganic fine particles aggregate into agglomerated inorganic fine particle aggregates, which act as a single solid when curing and shrinking (polymerizing shrinkage) of a photopolymerizable compound that becomes a binder resin after hardening. Therefore, the uneven surface of the anti-glare layer corresponds to Shape of aggregate of inorganic fine particles. In this regard, the first inorganic fine particle aggregate 104A has a buckled portion 104B having an inner region 104C, and therefore acts as a solid having a buffering effect when it is hardened and contracted. Therefore, the first inorganic fine particle aggregate 104A is easy to be hardened and contracted. And crushed with uniformity. Thereby, the shape of the uneven surface 102A becomes slower than the shape before the curing shrinkage.

Regarding the first inorganic fine particle aggregate 104A, for the same reason as in the first embodiment, the ratio of the inorganic fine particles connected to one or more inorganic fine particles under one inorganic fine particle is 95% or more. good. The proportion of the inorganic fine particles is more than 97%, and more preferably more than 99%.

The existence ratio of the first inorganic fine particle aggregates 104A in the anti-glare layer 102 is the same as in the first embodiment. The light-transmitting substrate 101 side of the anti-glare layer 102 is higher than the uneven surface 102A of the anti-glare layer 102. The side is better. Here, the first inorganic fine particle aggregate is present on the light-transmitting substrate side of the anti-glare layer or on the uneven surface side, which is the following: judged by the same method as the method described in the first embodiment .

Specifically, in a cross section along the thickness direction of the anti-glare layer 102, among the first inorganic fine particle aggregates 104A, the first inorganic fine particle aggregates existing on the light-transmitting substrate 101 side of the anti-glare layer 102 are made. When the number Nb of 104A is Nf, the number of the first inorganic fine particle aggregates 104A existing on the uneven surface 102A side of the anti-glare layer 102 is Nf. For the same reason as in the first embodiment, the Nb / Nf system satisfies the above formula. (2) Better.

The first inorganic microparticle agglomerates 104A are located at least on the surface of the organic microparticle agglomerates 103A for the same reason as in the first embodiment, and the positions are separated from the organic microparticle agglomerates 103A and between the organic microparticle agglomerates 103A. good.

The average agglomeration diameter of the first inorganic fine particle aggregate 104A, For the same reason as in the first embodiment, it is preferably 100 nm or more and 2.0 μm or less. The average aggregation diameter of the first inorganic fine particle aggregates 104A is preferably 200 nm or more, and more preferably 1.5 μm or less. The average aggregation diameter of the first inorganic fine particle aggregate can be obtained by the same method as in the first embodiment.

The first inorganic fine particle aggregate 104A preferably has a larger aggregate diameter in a direction orthogonal to the thickness direction than the aggregate diameter in the thickness direction of the anti-glare layer 102. The "agglomeration diameter in the thickness direction" and "agglomeration diameter in a direction orthogonal to the thickness direction" are measured by the same method as in the first embodiment.

The first inorganic fine particle aggregate 104A can be obtained by controlling, for example, the hydrophilic treatment of the organic fine particles 103, the hydrophobic treatment of the inorganic fine particles 104, and the presence ratio of the hydroxyl groups of the binder resin 105. A hydroxyl group is present on the surface of the inorganic fine particles 104. However, when the first inorganic fine particles 104 are hydrophobized, the number of the hydroxyl groups present on the surface of the inorganic fine particles 104 is reduced, and excessive aggregation of the inorganic fine particles can be suppressed. In addition, the surface of the inorganic fine particles 104 may be subjected to a hydrophobizing treatment, so as to improve the chemical resistance and alkali resistance of the inorganic fine particles themselves.

Such a hydrophobic treatment can be performed using a surface treatment agent such as a silane or silazane. The specific surface treatment agent is exemplified by dimethyl dichlorosilane and the like described in the first embodiment.

The first inorganic fine particle aggregate 104A can be obtained by a method other than the above-mentioned method, and can also be obtained by a method described in the first embodiment.

As for the inorganic fine particles 104 in the anti-glare layer 102, as shown in FIGS. 16 and 17, together with the first inorganic fine particle aggregates 104A, there are two or more inorganic fine particles 104 aggregated as the second inorganic fine particle aggregates 104D. Yes. The second inorganic fine particle aggregate 104D is present on or near the uneven surface 102A. In addition, in the second inorganic fine particle aggregate 104D, the ratio of the inorganic fine particles connected to the inorganic fine particles of one or more and three or less of the inorganic fine particles is preferably 95% or more. In addition, it is preferable that the second inorganic fine particle agglomerate 104D has a larger agglomerate diameter in a direction orthogonal to the thickness direction than the agglomerate diameter in the thickness direction of the anti-glare layer 102, and is more preferably two-dimensionally agglomerated. In addition, since the second inorganic fine particle aggregate 104 is located closer to the uneven surface 102A or near the first inorganic fine particle aggregate 104A, the thickness of the lower anti-glare layer 12 is smaller than that of the first inorganic fine particle aggregate 104A. The condensed diameter in the direction becomes smaller, so that the uneven surface 102A can be made smoother.

The existence of the second inorganic fine particle aggregate 104D on or near the uneven surface 102A makes it possible to increase the hardness of the surface of the anti-glare layer 102. Therefore, a softer adhesive resin can be used for the adhesive resin 105, thereby achieving the effect of buckling. Anti-glare film 100 having excellent properties.

The average aggregation diameter of the second inorganic fine particle aggregates 104D is preferably 100 nm or more and 2.0 μm or less for the same reason as that of the first inorganic fine particle aggregates 104A. The average aggregation diameter of the second inorganic fine particle aggregates 104D is more preferably 200 nm or more, and more preferably 1.5 μm or less.

The inorganic fine particles 104 constituting the second inorganic fine particle aggregate 104D can be the same as the inorganic fine particles 104 constituting the first inorganic fine particle aggregate 104A, so the following is adopted: The description is omitted here. In addition, the second inorganic fine particle aggregate 104D is similar to the first inorganic fine particle aggregate 104A, and can be subjected to, for example, a hydrophilic treatment of the organic fine particles 103, a hydrophobic treatment of the inorganic fine particles 104, and a ratio of the hydroxyl groups of the binder resin 105. Gain control. However, in order to make the aggregation state of the second inorganic microparticle agglomerate 104D different from the aggregation state of the first inorganic microparticle agglomerate 104A, for example, the second inorganic microparticle agglomerate 104D may be used in combination with the first inorganic microparticle agglomerate 104A. Different surface treatment agents and different surface treatment agent concentrations from the first inorganic fine particle aggregate 104A.

The anti-glare layer 102 has the same unevenness as the third embodiment in the cross-section along the thickness direction of the anti-glare layer 102 (the normal direction of the transparent substrate 101). In the surface 102A, the ratio of the length of the region other than the region corresponding to the organic fine particles 103 and the inorganic fine particles 104 is preferably 15% or more and 70% or less. The lower limit of this ratio is preferably 20% or more, and the upper limit of this ratio is preferably 60% or less.

<Binder Resin>

The binder resin 105 is the same as the binder resin 16 described in the first embodiment. Therefore, in this embodiment, the description is omitted.

In this embodiment, when the frequency distribution of the inclination angle with respect to the surface 100A of the anti-glare film 100 on the surface 101A of the light-transmitting substrate 101 is determined at 0.01 degree, the cumulative percentage of the frequency of the inclination angle relative to The ratio of the 99th percentile of the 3rd quartile (99th percentile / 3rd quartile) is 3.0 or more and 5.0 or less, so that anti-glare to the extent that reflection is not noticed can be obtained Properties, at the same time can obtain good anti-glare properties and good black color. That is, the 99th percentile shows the maximum value of the tilt angle, and the 3rd quartile is the representative value of the main tilt angle in the tilt angle distribution, so the 99th percentile / 3rd quartile The large number indicates that the main part of the uneven shape on the surface of the anti-glare film is inclined to a small inclination angle, that is, there are many flat portions on the surface of the anti-glare film. In this embodiment, the 99th percentile / third quartile is greater than 3.0, so the 99th percentile / third quartile is large, and there are many on the surface 100A of the anti-glare film 100. Flat part. There are many flat portions on the surface 100A of the anti-glare film 100, so that the occurrence of glare can be suppressed, and good anti-glare properties can be obtained. In addition, since there are many flat portions on the surface 100A of the anti-glare film 100, a moderate specular reflection component can be provided. Therefore, when an animated image is displayed, the gloss and brightness of the image will increase, and a sense of excitement can be obtained. In addition, there is no excessive diffusion of external light, which can suppress the decrease in the contrast of the bright room, and also prevent the image light from becoming stray light, so a good dark room contrast can also be obtained. On the other hand, if the 99th percentile / third quartile is too large, there will be too many flat portions on the surface of the anti-glare film, and thus the anti-glare property will be deteriorated. In this embodiment, the 99th percentile / third quartile is 5.0 or less, so There is no excessive flat portion on the surface 100A of the anti-glare film 100, and anti-glare properties to such an extent that reflection is not taken into consideration can be obtained. Thereby, it is possible to obtain anti-glare to such an extent that reflection is not taken into consideration, and at the same time to obtain good anti-glare properties and good black color feeling. In addition, the degree of anti-glare to the extent that the reflection of the observer (observer) and the background of the observer is not taken into consideration is the following anti-glare property: the presence of an observer is confirmed, but only the outline is blurred. In addition, the existence of objects in the background of the observer is also confirmed, but the outline and boundary become unclear. In this way, only the observer's outline and the like become blurred, and the observer becomes more in a state where reflection is not noticed.

According to this embodiment, the first inorganic fine particle aggregate 104A has a buckling portion 104B having an inner region 104C. Therefore, for the same reason as the first embodiment, good anti-glare properties can be obtained, and excellent contrast can be obtained. And the black color sense of dynamism.

<<< Manufacturing method of anti-glare film >>>

The anti-glare film 100 can be formed in the following manner, for example. First, a composition for an anti-glare layer is coated on the light-transmitting substrate 101 by the same method as in the first embodiment.

<< Composition for antiglare layer >>

The composition for the anti-glare layer contains at least the organic fine particles 103, the inorganic fine particles 104, and the photopolymerizable compound, and preferably contains the organic fine particle aggregates 103A, the first inorganic fine particle aggregates 104A, and the second inorganic fine particle aggregates 104D . In addition, the anti-glare layer can also be used as required. Added with the composition: the above-mentioned thermoplastic resin, the above-mentioned thermosetting resin, a solvent, and a polymerization initiator. The composition for the anti-glare layer may be added with a conventionally known dispersant and the like exemplified in the first embodiment.

<Solvent and polymerization initiator>

The solvent and the polymerization initiator are the same as the solvent and the polymerization initiator described in the first embodiment, and thus the description is omitted.

After applying the composition for the anti-glare layer on the light-transmitting substrate 101, the composition for the anti-glare layer in the form of a coating film is dried and then transported to a heated area. The composition for the anti-glare layer is dried to evaporate the solvent. Here, the affinity between the solvent and the solid content, the relative evaporation speed of the solvent, the solid content concentration, the temperature of the coating solution, the drying temperature, the wind speed of the drying wind, the drying time, and the concentration of the solvent environment in the drying area are selected so that the The distribution states of the fine particle aggregates 103A, the first inorganic fine particle aggregates 104A, and the second inorganic fine particle aggregates 104D are adjusted.

Thereafter, the composition for the antiglare layer of the coating film is irradiated with light such as ultraviolet rays, and the photopolymerizable compound is polymerized (crosslinked) to harden the composition for the antiglare layer to form the antiglare layer 102. . Here, as described above, the first inorganic fine particle aggregate 104A has a buckling portion 104B having an inner region 104C, and therefore functions as a solid having a buffering effect when it is hardened and contracted. Therefore, the first inorganic fine particle aggregate 104A is easily and uniformly crushed when it is cured and contracted.

Method for preparing composition for anti-glare layer and drying strip The light when the composition for the anti-glare layer is hardened is the same as that of the first embodiment, so the description is omitted.

<< Polarizer, LCD panel, image display device >>

As shown in FIGS. 18 to 20, the anti-glare film 100 is the same as the first embodiment, and can be used by being incorporated in, for example, a polarizing plate 110, a liquid crystal panel 120, and an image display device 130. In Figs. 18 to 20, components having the same reference numerals as those in Figs. 3 to 5 indicate the same components as those described in the first embodiment.

[Example]

In order to explain the present invention in detail, the examples are described below, but the present invention is not limited to these descriptions.

<< Example A >> <Preparation of composition for anti-glare layer>

First, each component was formulated so that it might become a composition shown below, and the composition for anti-glare layers was obtained.

(Composition A1 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 3 parts by mass

． Fuming silica (inorganic fine particles, hexamethyldisilazane treatment, flat 50nm average primary particle size (manufactured by NIPPON AEROSIL): 1 part by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Isocyanurate ethoxy modified diacrylate (product name "M-215", manufactured by Toa Kosei Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Methyl isobutyl ketone (MIBK): 30 parts by mass

(Composition A2 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 4 parts by mass

． Fuming silica (inorganic fine particles, hexamethyldisilazane treatment, average primary particle size 50 nm, manufactured by NIPPON AEROSIL): 1 part by mass

． Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Urethane acrylate (product name "UV1700B", manufactured by Nippon Synthetic Chemical Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Cyclohexanone: 30 parts by mass

(Composition A3 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 1 part by mass

． Fuming silica (inorganic fine particles, octyl silane treatment, average primary particle size 12 nm, manufactured by NIPPON AEROSIL): 1 part by mass

． Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Urethane acrylate (product name "UV1700B", manufactured by Nippon Synthetic Chemical Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 105 parts by mass

． Isopropanol: 30 parts by mass

． Cyclohexanone: 15 parts by mass

(Composition A4 for anti-glare layer)

． Fuming silica (inorganic fine particles, octyl silane treatment, average particle size 12 nm, manufactured by NIPPON AEROSIL) 2.5 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 70 parts by mass

． Urethane acrylate (product name "V-4000BA", manufactured by DIC Corporation): 30 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 105 parts by mass

． Isopropanol: 35 parts by mass

． Cyclohexanone: 10 parts by mass

(Composition A5 for anti-glare layer)

． Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle size (laser diffraction scattering method) 4.1 μm, manufactured by Fuji Silia Chemical Co., Ltd.): 4 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 100 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 150 parts by mass

． Methyl isobutyl ketone (MIBK): 35 parts by mass

The above-mentioned amorphous silicon dioxide particles were produced by a gel method.

(Composition A6 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 3.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 7 parts by mass

． Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle size (laser diffraction scattering method) 2.7 μm, manufactured by Fuji Silia Chemical Co., Ltd.): 2 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 100 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Cyclohexanone: 30 parts by mass

The above-mentioned amorphous silicon dioxide particles were produced by a gel method.

<Example A1>

A 60 μm-thick triethyl cellulose base material (manufactured by Fujifilm Corporation, TD60UL) was prepared as a light-transmitting base material, and one side of the triethyl cellulose base material was coated with a composition A1 for an anti-glare layer to form Coating film. Next, the formed coating film was dried at 70 ° C for 15 seconds at a flow rate of 0.2 m / s, and then dried at 70 ° C for 30 seconds at a flow rate of 10 m / s to dry the coating. The solvent in the film was evaporated, and the coating film was hardened by irradiating ultraviolet rays under a nitrogen environment (oxygen concentration of 200 ppm or less) so that the accumulated light amount became 100 mJ / cm ² to form an anti-glare layer having a thickness of 4 μm at the time of hardening. An anti-glare film related to Example A1 was provided.

<Example A2>

In Example A2, an anti-glare layer composition A2 was used in place of the anti-glare layer composition A1, and the thickness of the anti-glare layer at the time of curing was 3 μm. Glare film.

<Example A3>

In Example A3, an anti-glare film was produced in the same manner as in Example A1, except that the anti-glare layer composition A3 was used instead of the anti-glare layer composition A1.

<Example A4>

In Example A4, except that the composition A4 for an anti-glare layer was used instead of the composition A1 for an anti-glare layer, an anti-glare film was produced in the same manner as in Example A1.

<Comparative example A1>

In Comparative Example A1, an anti-glare layer composition A5 was used instead of the anti-glare layer composition A1, and the thickness of the anti-glare layer at the time of curing was set to 2 μm. Glare film.

<Comparative example A2>

In Comparative Example A2, an anti-glare layer composition A6 was used instead of the anti-glare layer composition A1, and the thickness of the anti-glare layer at the time of curing was set to 3 μm. Glare film.

<Cross section observation of anti-glare film>

The cross sections of the anti-glare films obtained in the above-mentioned Examples A1 and A2 were photographed using a scanning transmission electron microscope (STEM) function of a scanning electron microscope (SEM) (S-4800, manufactured by Hitachi Advanced Technologies). The obtained STEM profile photograph was observed. 21 is a cross-sectional photograph of an anti-glare film according to Example A1, which was photographed using a scanning electron microscope function of a scanning electron microscope, and FIG. 22 is an enlarged photograph thereof. FIG. 23 is a cross-sectional photograph of the anti-glare film according to Example A2, which was photographed using a scanning electron microscope function of a scanning electron microscope, and FIG. 24 is an enlarged photograph thereof.

From the photo in FIG. 21, it was confirmed that: organic fine particle aggregates exist; inorganic fine particle aggregates exist; and the inorganic fine particle aggregates exist at least on or near the uneven surface of the anti-glare layer, the position of the surface of the organic fine particle aggregates, And the position separated from the organic microparticle agglomerates and between the organic microparticle agglomerates; and the inorganic microparticle agglomerates existing on or near the uneven surface of the anti-glare layer, the diameter of the agglomerates in a direction orthogonal to the thickness direction It is larger than the condensing diameter in the thickness direction of the anti-glare layer.

In addition, as a result of image analysis of the photograph in FIG. 22, it was confirmed that the inorganic fine particle aggregates existing on the surface of the organic fine particle aggregates and the positions separated from the organic fine particle aggregates and between the organic fine particle aggregates had The flexion in the inner region buried with the adhesive resin.

Similarly, from the photograph of FIG. 23, it was confirmed that individual organic fine particles are unevenly present on the triethyl cellulose base material side; inorganic fine particle aggregates are present, and the inorganic fine particle aggregates are present at least on the uneven surface of the antiglare layer or Nearby positions, positions on the surface of the organic fine particles, and positions separated from the organic fine particles and between the organic fine particles; and the inorganic fine particle aggregates existing on or near the uneven surface of the anti-glare layer are in the aforementioned thickness direction The agglomeration diameter in the orthogonal direction is larger than the agglomeration diameter in the thickness direction of the anti-glare layer.

In addition, as a result of image analysis of the photograph in FIG. 24, it was confirmed that the inorganic fine particle aggregates existing on the surface of the organic fine particle aggregates and the positions separated from the organic fine particle aggregates and between the organic fine particle aggregates include the Inner area buried with adhesive resin The flexion of the field.

<Anti-glare properties>

On the side opposite to the surface on which the anti-glare layer of the triacetam cellulose substrate of each of the anti-glare films obtained in Examples A1 to A4 and Comparative Examples A1 and A2 was formed, a transparent adhesive was used for adhesion to prevent A black acrylic plate with back reflection was used as a sample. This sample was evaluated visually in a bright room environment using 15 subjects, and the anti-glare properties were evaluated to such an extent that the reflection of the observer and the background of the observer was not taken into consideration according to the following criteria.

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Glare>

For each anti-glare film obtained in Examples A1 to A4 and Comparative Examples A1 and A2, the following methods were used to evaluate the glare. The light box (white surface light source) with a brightness of 1500cd / m ² , a black matrix glass of 140ppi, and an anti-glare film are stacked in the order from the bottom, and a distance of about 30cm is selected from various angles from top to bottom and left and right. Fifteen subjects underwent a visual assessment. Whether or not to care about glare was evaluated based on the following criteria.

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Black look>

Regarding each anti-glare film obtained in Examples A1 to A4 and Comparative Examples A1 and A2, the black color feeling was evaluated in the following manner. The polarizing plate on the outermost surface of the LCD TV "KDL-40X2500" manufactured by Sony Corporation was peeled off, and a polarizing plate without surface coating was attached. Next, the obtained anti-glare films related to Examples A1 to A4 and Comparative Examples A1 and A2 were made on the side of the anti-glare layer so as to be the outermost surface by using a transparent adhesive film for optical film (total transmittance of 91%) Above, products with a haze of 0.3% or less and a film thickness of 20 to 50 μm, such as MHM series: manufactured by NICHIEI, etc.). This LCD TV was set up in a room where the illuminance was about 1000Lx, and the DVD "Opera Phantom of the Opera" was played by Media Factory. The LCD TV was separated from the LCD TV by a distance of 1.5 ~ 2.0m. The black color feeling was evaluated by the functional evaluation. The black color feeling is determined based on whether the contrast is high when the animation image is played, whether the image is shiny and bright, and whether it feels a sense of dynamism. The evaluation criteria are as follows.

◎: 10 or more people answered well

○: 5-9 people answered well

×: The number of people who answered well was less than 04

<Measurement of overall haze, internal haze, and surface haze>

For the anti-glare films obtained in the above-mentioned Examples A1 to A4 and Comparative Examples A1 and A2, the overall haze, internal haze, and surface haze were measured in the following manner. First, a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) was used to calculate the overall haze value of the anti-glare film in accordance with JIS K7136. The determination was performed. Then, on the surface of the anti-glare layer, a triethyl cellulose base material (manufactured by Fujifilm, TD60UL) was applied through a transparent optical adhesive layer. Thereby, the uneven shape on the uneven surface of the anti-glare layer is crushed, and the surface of the anti-glare film becomes flat. In this state, a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) was used to measure the haze value in accordance with JIS K7136, and the haze of the adhesive layer itself was further subtracted to determine the interior. Haze value. Then, the internal haze value is subtracted from the overall haze value to obtain the surface haze value.

<Penetration image clarity>

For each anti-glare film obtained in Examples A1 to A4 and Comparative Examples A1 and A2, an image sharpness measuring device (model: ICM-1T, SUGA) was set according to the image sharpness measuring method using the transmission method of JIS K7105. Test Machine Co., Ltd.), the triethyl cellulose base material side was set to face the light source, and the clarity of the transmitted image was measured. As for the optical comb, the clarity of the transmitted image was measured by using 0.125 mm, 0.5 mm width, 1.0 mm width, and 2.0 mm width, respectively. In addition, the clearness of the transmitted images measured separately is totaled, and the average value is calculated.

<Measurement of Sm, θa, and Ra>

The surface of each anti-glare film obtained in Examples A1 to A4 and Comparative Examples A1 and A2 was measured for Sm, θa, and Ra. The definitions of Sm and Ra are based on JIS B0601-1994, and θa is based on a surface roughness tester: SE-3400 / (Kosaka) Manufacturing Co., Ltd. The written certificate (revised 1995.07.20).

Sm, θa, and Ra were specifically measured using a surface roughness measuring device (model: SE-3400 / Kosaka Research Institute, Ltd.) under the following measurement conditions.

1) Stylus of surface roughness detection unit (trade name SE2555N (2μ standard), manufactured by Kosaka Research Institute, Ltd.)

． Tip curvature radius 2μm, apex angle 90 °, diamond material

2) Measurement conditions of surface roughness measuring device

． Reference length (cutoff value of roughness curve λc): 2.5mm

． Evaluation length (reference length (cut-off value λc) × 5): 12.5mm

． Stylus travel speed: 0.5mm / s

． Preliminary length: (cut value λc) × 2

． Vertical magnification: 2000 times

． Horizontal magnification: 10 times

<Buckling resistance test>

For each anti-glare film obtained in Examples A1 to A4 and Comparative Examples A1 and A2, a buckling resistance test was performed using a buckling tester having a mandrel, and the minimum diameter of the mandrel without cracks is described in Table 2. The buckling resistance test was performed in accordance with JIS K5600-5-1 (1999).

<Scratch resistance>

For each of the anti-glare films obtained in Examples A1 to A4 and Comparative Examples A1 and A2, steel wool # 0000 (product name: BONSTAR, manufactured by NIPPON STEEL WOOL Co., Ltd.) was used, and a load of 700 g / cm ^{2 was} applied while loading. After rubbing back and forth 10 times at a speed of 100 mm / sec, a black tape was pasted on the opposite side of the anti-glare layer on the triethyl cellulose substrate, and the presence or absence of abrasion was visualized under a 3-wavelength fluorescent lamp. And an assessment was made. The evaluation criteria of the abrasion resistance evaluation are as follows.

(Circle): The grade which abrasion was not confirmed or a little abrasion was confirmed, but there was no problem practically.

×: Most scratches were confirmed.

The results are shown in Tables 1 and 2 below.

As shown in Table 1, in Comparative Example A1, good anti-glare properties were obtained, but glare was deteriorated. The reason for this is conceivable: In Comparative Example A1, the unevenness of the surface of the anti-glare layer was formed by using amorphous silicon dioxide, but the amorphous silicon dioxide became agglomerates, and a sharp change in the tilt angle occurred. In Comparative Example A2, the antiglare property was good, and glare was not noticed, but the black color feeling was low. The reason for this is thought to be that, in Comparative Example A2, the unevenness on the surface of the anti-glare layer was formed by using acrylic-styrene copolymer particles as organic fine particles and amorphous silicon dioxide, and the haze was suppressed because of high haze. However, the amorphous silicon dioxide becomes massive, so it has an excessively large tilt angle in terms of unevenness. In contrast, in Examples A1 to A4, the anti-glare property was good, the glare was not noticed, and the black color feeling was good.

<< Example B >> <Preparation of composition for anti-glare layer>

First, each component was formulated so that it might become a composition shown below, and the composition for anti-glare layers was obtained.

(Composition B1 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 3 parts by mass

． Fuming silica (inorganic fine particles, hexamethyldisilazane treatment, average primary particle size 50 nm, manufactured by NIPPON AEROSIL): 1 part by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Isocyanurate ethoxy modified diacrylate (product name "M-215", manufactured by Toa Kosei Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Methyl isobutyl ketone (MIBK): 30 parts by mass

(Composition B2 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 4 parts by mass

． Fuming silica (inorganic fine particles, hexamethyldisilazane treatment, average primary particle size 50 nm, manufactured by NIPPON AEROSIL): 1 part by mass

． Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Urethane acrylate (product name "UV1700B", manufactured by Nippon Synthetic Chemical Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Cyclohexanone: 30 parts by mass

(Composition B3 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 2 parts by mass

． Fuming silica (inorganic fine particles, octyl silane treatment, average primary particle size 12 nm, manufactured by NIPPON AEROSIL): 2 parts by mass

． Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Urethane acrylate (product name "UV1700B", manufactured by Nippon Synthetic Chemical Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 105 parts by mass

． Isopropanol: 30 parts by mass

． Cyclohexanone: 15 parts by mass

(Composition B4 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 3.5 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 4.5 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 65 parts by mass

． Isocyanuric acid modified triacrylate (product name "M-313", manufactured by Toa Kosei Co., Ltd.): 35 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 110 parts by mass

． Cyclohexanone: 50 parts by mass

(Composition B5 for anti-glare layer)

． Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle size (laser diffraction scattering method) 2.3 μm, manufactured by Fuji Silia Chemical Co., Ltd.): 2 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 100 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 150 parts by mass

． Methyl isobutyl ketone (MIBK): 35 parts by mass

The above-mentioned amorphous silicon dioxide particles were produced by a gel method.

(Composition B6 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 3.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 7 parts by mass

． Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle size (laser diffraction scattering method) 2.7 μm, manufactured by Fuji Silia Chemical Co., Ltd.): 2 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 100 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Cyclohexanone: 30 parts by mass

The above-mentioned amorphous silicon dioxide particles were produced by a gel method.

<Example B1>

A 60 μm-thick triethyl cellulose base material (manufactured by Fujifilm Corporation, TD60UL) was prepared as a light-transmitting base material, and one side of the triethyl cellulose base material was coated with a composition B1 for an anti-glare layer to form Coating film. Next, the formed coating film was dried at 70 ° C for 15 seconds at a flow rate of 0.2 m / s, and then dried at 70 ° C for 30 seconds at a flow rate of 10 m / s to dry the coating. The solvent in the film was evaporated, and the coating film was hardened by irradiating ultraviolet rays under a nitrogen environment (oxygen concentration of 200 ppm or less) so that the accumulated light amount became 100 mJ / cm ² to form an anti-glare layer having a thickness of 4 μm at the time of hardening. An anti-glare film related to Example B1 was provided.

<Example B2>

Example B2 was produced in the same manner as in Example B1 except that the composition B2 for the anti-glare layer was used instead of the composition B1 for the anti-glare layer, and the thickness of the anti-glare layer at the time of curing was 3 μm. Anti-glare film.

<Example B3>

In Example B3, an anti-glare film was produced in the same manner as in Example B1 except that the anti-glare layer composition B3 was used instead of the anti-glare layer composition B1.

<Comparative example B1>

In Comparative Example B1, instead of the composition B1 for the anti-glare layer, the composition B4 for the anti-glare layer was used, and the thickness of the anti-glare layer at the time of curing was 6 μm. Other than that, an anti-glare film was produced in the same manner as in Example B1.

<Comparative example B2>

Comparative Example B2 was prepared in the same manner as in Example B1, except that the antiglare layer composition B5 was used instead of the antiglare layer composition B1 and the thickness of the antiglare layer at the time of curing was 3 μm. Anti-glare film.

<Comparative example B3>

Comparative Example B3 was produced in the same manner as in Example B1, except that the anti-glare layer composition B6 was used instead of the anti-glare layer composition B1, and the thickness of the anti-glare layer at the time of curing was 3 μm. Anti-glare film.

<Cross section observation of anti-glare film>

The anti-glare film related to the foregoing embodiment B1 and the anti-glare film related to the foregoing embodiment A1 are the same, so the cross-sectional photos of FIGS. 21 and 22 can also be said to be cross-sectional photos of the anti-glare film related to the embodiment B1.

From the photograph in FIG. 21, in the anti-glare film related to Example B1, it was confirmed that: organic fine particle aggregates exist; inorganic fine particle aggregates exist, and the inorganic fine particle aggregates exist at least on the uneven surface of the anti-glare layer or in the vicinity thereof. Position, the position of the surface of the organic microparticle agglomerates, and the position separated from the organic microparticle agglomerates and between the organic microparticle agglomerates; and the inorganic microparticle agglomerates existing on or near the uneven surface of the antiglare layer The aggregation diameter in a direction orthogonal to the thickness direction is larger than the aggregation diameter in the thickness direction of the anti-glare layer.

In addition, as a result of image analysis of the photograph shown in FIG. 22, in the anti-glare film according to Example B1, it was confirmed that the position exists on the surface of the organic fine particle aggregates and is separated from the organic fine particle aggregates and between the organic fine particle aggregates. The inorganic fine particle agglomerates at the sacral position have a buckled portion having an inner region buried with an adhesive resin.

<Penetration image clarity>

For each anti-glare film obtained in Examples B1 to B3 and Comparative Examples B1 to B3, an image sharpness measuring device (model: ICM-1T, SUGA) was set according to the image sharpness measuring method using the transmission method of JIS K7374. Test Machine Co., Ltd.), the triethyl cellulose base material side was set to face the light source, and the clarity of the transmitted image was measured. In terms of optical combs, the clarity of the transmitted image was measured using 0.125 mm, 0.25 mm width, 0.5 mm width, 1.0 mm, and 2.0 mm width, respectively. In addition, the transmitted image sharpnesses measured separately are totaled to obtain an arithmetic mean value, and the absolute value of the difference between the arithmetic average value and the value of each of the transmitted image sharpness values is further obtained.

<Anti-glare properties>

On the side opposite to the surface on which the anti-glare layer of the triacetam cellulose substrate of each of the anti-glare films obtained in Examples B1 to B3 and Comparative Examples B1 to B3 was formed, a transparent adhesive was used for adhesion to prevent A black acrylic plate with back reflection was used as a sample. This sample was evaluated visually in a bright room environment, using 15 subjects, and anti-glare to the extent that the reflection of the observer and the background of the observer was not taken into consideration according to the following criteria. estimate.

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Glare>

For each anti-glare film obtained in Examples B1 to B3 and Comparative Examples B1 to B3, glare was evaluated in the following manner. The light box (white surface light source) with a brightness of 1500cd / m ² , a black matrix glass of 140ppi, and an anti-glare film are stacked in the order from the bottom, and a distance of about 30cm is selected from various angles from top to bottom and left and right. Fifteen subjects underwent a visual assessment. Whether or not to care about glare was evaluated based on the following criteria.

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Black look>

Regarding each anti-glare film obtained in Examples B1 to B3 and Comparative Examples B1 to B3, the black color feeling was evaluated in the following manner. The polarizing plate on the outermost surface of the LCD TV "KDL-40X2500" manufactured by Sony Corporation was peeled off, and a polarizing plate without surface coating was attached. Next, the obtained anti-glare films related to Examples B1 to B3 and Comparative Examples B1 to B3 were made so that the anti-glare layer side became the outermost surface by using a transparent adhesive film for anti-glare film (total transmittance 91). % Or more, haze 0.3% or less, products with a film thickness of 20 to 50 μm, such as MHM series Column: NICHIEI company, etc.). This LCD TV was set up in a room with an illumination of about 1000Lx, and the DVD "Opera Phantom of the Opera" was played by MEDIA FACTORY company. The LCD TV was separated from the LCD TV by a distance of 1.5 ~ 2.0m. Thus, the black color feeling was evaluated by the functional evaluation. The black color feeling is determined based on whether the contrast is high when the animation image is played, whether the image is shiny and bright, and whether it feels a sense of dynamism. The evaluation criteria are as follows.

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Measurement of total haze, internal haze, and surface haze>

The anti-glare films obtained in the above-mentioned Examples B1 to B3 and Comparative Examples B1 to B3 were measured in the following manner to measure the total haze, the internal haze, and the surface haze. First, the total haze value of the anti-glare film was measured using a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) in accordance with JIS K7136. Then, on the surface of the anti-glare layer, a triethyl cellulose base material (manufactured by Fujifilm, TD60UL) was applied through a transparent optical adhesive layer. Thereby, the uneven shape on the uneven surface of the anti-glare layer is crushed, and the surface of the anti-glare film becomes flat. In this state, a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) was used to measure the haze value in accordance with JIS K7136, and the haze of the adhesive layer itself was further subtracted to determine the interior. Haze value. Then, the internal haze value is subtracted from the full haze value to obtain the surface haze value.

<Measurement of Sm, θa, and Ra>

The surface of each anti-glare film obtained in Examples B1 to B3 and Comparative Examples B1 to B3 was measured for Sm, θa, and Ra. The definition of Sm and Ra is based on JIS B0601-1994, and θa is based on a surface roughness tester: SE-3400 / (Stock) Kosaka Research Institute operating manual (revised 1995.07.20).

Sm, θa, and Ra were specifically measured using a surface roughness measuring device (model: SE-3400 / Kosaka Research Institute, Ltd.) under the following measurement conditions.

1) Stylus of surface roughness detection unit (trade name SE2555N (2μ standard), manufactured by Kosaka Research Institute, Ltd.)

． Tip curvature radius 2μm, apex angle 90 °, diamond material

2) Measurement conditions of surface roughness measuring device

． Reference length (cutoff value of roughness curve λc): 2.5mm

． Evaluation length (reference length (cut-off value λc) × 5): 12.5mm

． Stylus travel speed: 0.5mm / s

． Preliminary length: (cut value λc) × 2

． Vertical magnification: 2000 times

． Horizontal magnification: 10 times

<Buckling resistance test>

For each anti-glare film obtained in Examples B1 to B3 and Comparative Examples B1 to B3, a buckling resistance test was performed using a buckling tester having a mandrel, The minimum diameter of the mandrel where no cracks occur is shown in Table 2. The buckling resistance test was performed in accordance with JIS K5600-5-1 (1999).

<Scratch resistance>

For each anti-glare film obtained in Examples B1 to B3 and Comparative Examples B1 to B3, steel wool # 0000 (product name: BONSTAR, manufactured by NIPPON STEEL WOOL Co., Ltd.) was used, and the load was 700 g / cm ² while loading. After rubbing back and forth 10 times at a speed of 100mm / sec, a black tape was pasted on the opposite side of the anti-glare layer on the triethyl cellulose substrate, and the presence or absence of abrasion was visually observed under a 3-wavelength fluorescent lamp. And an assessment was made. The evaluation criteria of the abrasion resistance evaluation are as follows.

(Circle): The grade which abrasion was not confirmed or a little abrasion was confirmed, but there was no problem practically.

×: Most scratches were confirmed.

The results are shown in Tables 3 to 5 below.

As shown in Table 4, in Comparative Example B1, good anti-glare properties were obtained, but glare was deteriorated. The reason for this is conceivable: In Comparative Example B1, since the absolute value of the difference between the optical comb and the arithmetic mean of the image clarity is large, the flat portion is small and glare is easily generated. Further, in Comparative Example B2, the glare and black color feeling were good, but the antiglare property was deteriorated. The reason for this is conceivable: In Comparative Example B2, the arithmetic mean of the clarity of the penetrating image is large, so there are too many flat parts. Further, in Comparative Example B3, the antiglare property was good, and glare was not noticed, but the black color feeling was low. The reason for this is thought to be that in Comparative Example B3, the unevenness on the surface of the anti-glare layer was formed by using acrylic-styrene copolymer particles as organic fine particles and amorphous silicon dioxide, and the haze was high, so glare was suppressed. , But the arithmetic mean of the clarity of the transmitted image is small, so there are almost no flat parts. In contrast, in Examples B1 to B3, the anti-glare property was good, the glare was not noticed, and the black color feeling was good.

<< Example C >> <Preparation of composition for anti-glare layer>

First, each component was formulated so that it might become a composition shown below, and the composition for anti-glare layers was obtained.

(Composition C1 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 3 parts by mass

． Fuming silica (inorganic fine particles, hexamethyldisilazane treatment, average primary particle size 50 nm, manufactured by NIPPON AEROSIL): 1 part by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Isocyanurate ethoxy modified diacrylate (product name "M-215", manufactured by Toa Kosei Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Methyl isobutyl ketone (MIBK): 30 parts by mass

(Composition C2 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 4 parts by mass

． Fuming silica (inorganic fine particles, hexamethyldisilazane treatment, average primary particle size 50 nm, manufactured by NIPPON AEROSIL): 1 part by mass

． Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Urethane acrylate (product name "UV1700B", Japan Synthetic Chemical company): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Cyclohexanone: 30 parts by mass

(Composition C3 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 2 parts by mass

． Fuming silica (inorganic fine particles, octyl silane treatment, average primary particle size 12 nm, manufactured by NIPPON AEROSIL): 2 parts by mass

． Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by DAICEL-ALLNEX): 60 parts by mass

． Urethane acrylate (product name "UV1700B", manufactured by Nippon Synthetic Chemical Co., Ltd.): 40 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 105 parts by mass

． Isopropanol: 30 parts by mass

． Cyclohexanone: 15 parts by mass

(Composition C4 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 3.5 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 4.5 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 65 parts by mass

． Isocyanuric acid modified triacrylate (product name "M-313", manufactured by Toa Kosei Co., Ltd.): 35 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 110 parts by mass

． Cyclohexanone: 50 parts by mass

(Composition C5 for anti-glare layer)

． Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle size (laser diffraction scattering method) 2.3 μm, manufactured by Fuji Silia Chemical Co., Ltd.): 2 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 100 parts by mass

． Polymerization initiator (product name "IRGACURE184", BASF JAPAN Company system): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 150 parts by mass

． Methyl isobutyl ketone (MIBK): 35 parts by mass

The above-mentioned amorphous silicon dioxide particles were produced by a gel method.

(Composition C6 for anti-glare layer)

． Acrylic-styrene copolymer particles (organic fine particles, average primary particle diameter 3.0 μm, refractive index 1.52, manufactured by Sekisui Chemical Industry Co., Ltd.): 7 parts by mass

． Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle size (laser diffraction scattering method) 2.7 μm, manufactured by Fuji Silia Chemical Co., Ltd.): 2 parts by mass

． Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by DAICEL-ALLNEX): 100 parts by mass

． Polymerization initiator (product name "IRGACURE184", manufactured by BASF Japan): 5 parts by mass

． Polyether modified polysiloxane (product name "TSF4460", manufactured by MOMENTIVE PERFORMANCE MATERIALS): 0.025 parts by mass

． Toluene: 120 parts by mass

． Cyclohexanone: 30 parts by mass

The above-mentioned amorphous silica particles are produced by a gel method. By.

<Example C1>

A 60 μm-thick triethyl cellulose base material (manufactured by Fujifilm Corporation, TD60UL) was prepared as a light-transmitting base material, and one side of the triethyl cellulose base material was coated with a composition 1 for an anti-glare layer to form Coating film. Next, the formed coating film was dried at 70 ° C for 15 seconds at a flow rate of 0.2 m / s, and then dried at 70 ° C for 30 seconds at a flow rate of 10 m / s to dry the coating. The solvent in the film was evaporated, and the coating film was hardened by irradiating ultraviolet rays under a nitrogen environment (oxygen concentration of 200 ppm or less) so that the accumulated light amount became 100 mJ / cm ² to form an anti-glare layer having a thickness of 4 μm at the time of hardening. An anti-glare film related to Example C1 was provided.

<Example C2>

Example C2 was produced in the same manner as in Example C1 except that the composition C2 for the anti-glare layer was used instead of the composition C1 for the anti-glare layer, and the thickness of the anti-glare layer at the time of curing was 3 μm. Anti-glare film.

<Example C3>

In Example C3, an anti-glare film was produced in the same manner as in Example C1 except that the composition C3 for an anti-glare layer was used instead of the composition C1 for an anti-glare layer.

<Comparative example C1>

Comparative Example C1 was produced in the same manner as in Example C1, except that the composition for anti-glare layer C4 was used instead of the composition for anti-glare layer C1, and the thickness of the anti-glare layer at the time of curing was 6 μm. Anti-glare film.

<Comparative Example C2>

Comparative Example C2 was produced in the same manner as in Example C1, except that the composition C5 for the anti-glare layer was used instead of the composition C1 for the anti-glare layer, and the thickness of the anti-glare layer at the time of curing was 3 μm. Anti-glare film.

<Comparative Example C3>

Comparative Example C3 was produced in the same manner as in Example C1, except that the composition C6 for the anti-glare layer was used instead of the composition C1 for the anti-glare layer, and the thickness of the anti-glare layer at the time of curing was 3 μm. Anti-glare film.

<Cross section observation of anti-glare film>

The anti-glare film related to the above-mentioned embodiment C1 is the same as the anti-glare film related to the above-mentioned embodiment A1. Therefore, the cross-sectional photos of FIG. 21 and FIG.

From the photograph of FIG. 21, in the anti-glare film related to the above-mentioned Example C1, it was confirmed that: organic fine particle aggregates exist; inorganic fine particle aggregates exist, and the inorganic fine particle aggregates exist at least on the uneven surface of the anti-glare layer or in the vicinity thereof. Position of the organic fine particle aggregates, and the position between the organic fine particle aggregates and the organic fine particle aggregates And the inorganic fine particle aggregates existing on the uneven surface of the anti-glare layer or in the vicinity thereof, the aggregate diameter in a direction orthogonal to the thickness direction is larger than the aggregate diameter in the thickness direction of the anti-glare layer.

In addition, as a result of image analysis of the photo of FIG. 22, in the anti-glare film related to the above-mentioned Example C1, it was confirmed that the position on the surface of the organic fine particle aggregate and the organic fine particle aggregate separated from the organic fine particle aggregate were confirmed. The inorganic fine particle aggregates at the intermediate positions have a buckling portion having an inner region buried with an adhesive resin.

<Tilt angle>

On the side opposite to the surface on which the anti-glare layer of the triacetam cellulose substrate of each of the anti-glare films obtained in Examples C1 to C3 and Comparative Examples C1 to C3 was formed, a transparent adhesive was attached to the glass plate. As a sample, a white interference microscope (New View 6300, manufactured by Zygo) was used as a sample, and the uneven shape of the surface of the anti-glare film was measured under the following conditions, and the tilt angle distribution was calculated by the method described above from the results. In addition, in terms of analysis software, the Microscope Application of MetroPro ver8.3.2 was used.

[Measurement conditions]

Objective lens: 10 times

Zoom: 2 times

Measurement area: 573μm × 573μm

Resolution (interval between each point): 0.58μm

[Analysis conditions]

Delete: None

Filter: High Pass

Filter type: GaussSpline

Low wavelength: 300μm

Remove Spikes: on

Spike height (xRMS): 2.5

In addition, the low wavelength corresponds to the cutoff value λc of the roughness parameter.

<Anti-glare properties>

On the side opposite to the surface on which the anti-glare layer of the triethyl cellulose base material of each of the anti-glare films obtained in Examples C1 to C3 and Comparative Examples C1 to C3 was formed, a transparent adhesive was used for adhesion to prevent A black acrylic plate with back reflection was used as a sample. This sample was visually observed in a bright room environment, and 15 subjects were used to evaluate the anti-glare level to the extent that the background reflection of the observer and the observer would not be taken into consideration according to the following criteria. .

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Glare>

For each anti-glare film obtained in Examples C1 to C3 and Comparative Examples C1 to C3, glare was evaluated in the following manner. A light box (white surface light source) with a brightness of 1500cd / m ² , a black matrix glass of 140ppi, and an anti-glare film are made to overlap from the bottom, and a distance of about 30cm is selected from various angles from top to bottom and left and right. Fifteen subjects underwent a visual assessment. Whether or not to care about glare was evaluated based on the following criteria.

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Black look>

Regarding each anti-glare film obtained in Examples C1 to C3 and Comparative Examples C1 to C3, the black color feeling was evaluated in the following manner. The polarizing plate on the outermost surface of the LCD TV "KDL-40X2500" manufactured by Sony Corporation was peeled off, and a polarizing plate without surface coating was attached. Next, the obtained anti-glare films related to Examples C1 to C3 and Comparative Examples C1 to C3 were made on the side of the anti-glare layer so as to be the outermost surface, and the transparent adhesive film for anti-glare film (total transmittance 91) % Or more, haze of 0.3% or less, and a film thickness of 20 to 50 μm (for example, MHM series: manufactured by NICHIEI). This LCD TV was set up in a room with an illumination of about 1000Lx, and the DVD "Opera Phantom of the Opera" was played by MEDIA FACTORY company. The LCD TV was separated from the LCD TV by a distance of 1.5 ~ 2.0m. Thus, the black color feeling was evaluated by the functional evaluation. The black color feeling is determined based on whether the contrast is high when the animation image is played, whether the image is shiny and bright, and whether it feels a sense of dynamism. The evaluation criteria are as follows.

◎: 10 or more people answered well

○: 5-9 people answered well

×: 4 or less people answered well

<Measurement of total haze, internal haze, and surface haze>

The anti-glare films obtained in the above-mentioned Examples C1 to C3 and Comparative Examples C1 to C3 were measured for the total haze, internal haze, and surface haze in the following manner. First, the total haze value of the anti-glare film was measured using a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) in accordance with JIS K7136. Then, on the surface of the anti-glare layer, a triethyl cellulose base material (manufactured by Fujifilm, TD60UL) was applied through a transparent optical adhesive layer. Thereby, the uneven shape on the uneven surface of the anti-glare layer is crushed, and the surface of the anti-glare film becomes flat. In this state, a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) was used to measure the haze value in accordance with JIS K7136, and the haze of the adhesive layer itself was further subtracted to determine the interior. Haze value. Then, the internal haze value is subtracted from the full haze value to obtain the surface haze value.

<Measurement of Sm, θa, and Ra>

The surface of each anti-glare film obtained in Examples C1 to C3 and Comparative Examples C1 to C3 was measured for Sm, θa, and Ra. The definition of Sm and Ra is based on JIS B0601-1994, and θa is based on a surface roughness tester: SE-3400 / (Stock) Kosaka Research Institute operating manual (revised 1995.07.20).

Sm, θa, and Ra, specifically, using a rough surface The degree measuring device (model: SE-3400 / made by Kosaka Laboratories, Ltd.) was measured under the following measurement conditions.

1) Stylus of surface roughness detection unit (trade name SE2555N (2μ standard), manufactured by Kosaka Research Institute, Ltd.)

． Tip curvature radius 2μm, apex angle 90 °, diamond material

2) Measurement conditions of surface roughness measuring device

． Reference length (cutoff value of roughness curve λc): 2.5mm

． Evaluation length (reference length (cut-off value λc) × 5): 12.5mm

． Stylus travel speed: 0.5mm / s

． Preliminary length: (cut value λc) × 2

． Vertical magnification: 2000 times

． Horizontal magnification: 10 times

<Buckling resistance test>

For each anti-glare film obtained in Examples C1 to C3 and Comparative Examples C1 to C3, a buckling resistance test was performed using a buckling tester having a mandrel, and the minimum diameter of the mandrel without cracks is described in Table 2. The buckling resistance test was performed in accordance with JIS K5600-5-1 (1999).

<Scratch resistance>

For each of the anti-glare films obtained in Examples C1 to C3 and Comparative Examples C1 to C3, steel wool # 0000 (product name: BONSTAR, manufactured by NIPPON STEEL WOOL Co., Ltd.) was used, and a load of 700 g / cm ² was used while loading. After rubbing back and forth 10 times at a speed of 100mm / sec, a black tape was pasted on the opposite side of the anti-glare layer on the triethyl cellulose substrate, and the presence or absence of abrasion was visually observed under a 3-wavelength fluorescent lamp. And an assessment was made. The evaluation criteria of the abrasion resistance evaluation are as follows.

(Circle): The grade which abrasion was not confirmed or a little abrasion was confirmed, but there was no problem practically.

×: Most scratches were confirmed.

The results are shown in Tables 6 and 7 below.

As shown in Table 6, in Comparative Example C1, good anti-glare properties were obtained, but glare was deteriorated. This system is conceivable because, in Comparative Example C1, the 99th percentile / third quartile is small, so the flat portion is small and glare is easily generated. Further, in Comparative Example C2, the glare and black color feeling were good, but the antiglare property was deteriorated. The reason for this is conceivable: In Comparative Example C2, the 99th percentile / 3rd quartile is large, so the tilt angle is too biased toward the flat side. Further, in Comparative Example C3, the antiglare property was good, and glare was not noticed, but the black color feeling was low. This system is thought to be because, in Comparative Example C3, the system has high haze and can suppress glare, but the 99th percentile / 3rd quartile is very small and there are almost no flat portions. In this regard, in Examples C1 to C3, the anti-glare property is good, the glare is not noticed, and the black color feeling is good.

Claims (18)

An anti-glare film includes a light-transmitting substrate and an anti-glare layer provided on the light-transmitting substrate. The surface of the anti-glare layer becomes an uneven surface. The anti-glare layer includes: a binder resin; and In the binder resin, a plurality of first inorganic fine particle aggregates are aggregated by three or more inorganic fine particles, and the first inorganic fine particle aggregates are formed by connecting the inorganic fine particles and have The flexion in the inner region where the adhesive resin is buried. The anti-glare layer further includes a plurality of organic fine particle aggregates aggregated by two or more organic fine particles, and the first inorganic fine particle aggregates exist at least on a surface of the organic fine particle aggregates, and from the organic fine particles. The agglomerates are separated and the positions between the organic fine particle agglomerates. For example, in the anti-glare film according to item 1 of the application, wherein the proportion of the first inorganic fine particle aggregates in the anti-glare layer is higher than the anti-glare layer on the light-transmitting substrate side of the anti-glare layer. Rugged surface side. For example, the anti-glare film according to item 1 of the patent application scope, wherein the anti-glare layer further includes a plurality of individual organic fine particles unevenly stored on the side of the light-transmitting substrate, and the first inorganic fine particle aggregates exist at least A position on the surface of the organic fine particles, and a position separated from the organic fine particles and between the organic fine particles. For example, the anti-glare film according to the first item of the patent application scope, wherein the anti-glare layer further includes a plurality of second inorganic fine particle aggregates that are aggregated by two or more inorganic fine particles, and the second inorganic fine particle aggregates exist. The aggregation diameter of the second inorganic fine particle aggregates at or near the uneven surface and in a direction orthogonal to the thickness direction is larger than the aggregation diameter of the second inorganic fine particle aggregates in the thickness direction of the anti-glare layer. For example, the anti-glare film according to item 4 of the patent application range, wherein the second inorganic fine particle aggregate has a smaller diameter in the thickness direction than the first inorganic fine particle aggregate. For example, in the anti-glare film according to the first patent application scope, in the first inorganic fine particle aggregate, the inorganic fine particles having one or more inorganic fine particles connected to one or more of the inorganic fine particles are connected to one of the inorganic fine particles. The proportion is above 95%. For example, the anti-glare film according to the first patent application range, wherein the average diameter of the first inorganic fine particle aggregate is 100 nm or more and 2.0 μm or less. An anti-glare film includes a light-transmitting substrate and an anti-glare layer provided on the light-transmitting substrate and having an uneven surface. The anti-glare layer includes: a plurality of organic fine particles, a plurality of inorganic fine particles, and a binder resin. The arithmetic mean value of the transmitted image clarity of the anti-glare film measured with a light comb of 0.125 mm width, 0.25 mm width, 0.5 mm width, 1.0 mm width, and 2.0 mm width is 70% or more and 95% or less And the absolute value of the difference between the arithmetic mean and the sharpness of the transmitted image measured using each of the optical combs is within 10%, and at least a part of the organic microparticles among the plurality of organic microparticles are in the order of 2 or more The above-mentioned organic fine particles exist as agglomerated organic fine particle aggregates, and at least a part of the plurality of inorganic fine particles of the inorganic fine particles are agglomerated first inorganic fine particle aggregates of three or more of the inorganic fine particles. Existing in form, the first inorganic fine particle aggregate is formed by connecting the inorganic fine particles, and includes a buckling having an inner region buried with the binder resin. . An anti-glare film includes a light-transmitting substrate and an anti-glare layer provided on the light-transmitting substrate and having an uneven surface. The anti-glare layer includes: a plurality of organic fine particles, a plurality of inorganic fine particles, and a binder resin. When the frequency distribution of the inclination angle of the surface of the anti-glare film with respect to the surface of the light-transmitting substrate is determined at 0.01 degrees, the cumulative percentage of the frequency of the inclination angle with respect to the third quartile The 99th percentile ratio is 3.0 or more and 5.0 or less. At least a part of the organic fine particles of the plurality of organic fine particles are in the form of an aggregate of organic fine particles in which two or more of the organic fine particles are aggregated. At least a part of the inorganic fine particles of the inorganic fine particles exist as a first inorganic fine particle aggregate in which three or more of the inorganic fine particles are aggregated. The first inorganic fine particle aggregate is made by the inorganic fine particles. It is formed by joining and includes a buckling portion having an inner region buried with the adhesive resin. For example, the anti-glare film according to claim 8 or 9, wherein the first inorganic fine particle aggregates exist at least on the surface of the organic fine particle aggregates, and are separated from the organic fine particle aggregates and the organic fine particles aggregate. Interbody position. For example, the anti-glare film according to item 10 of the patent application, wherein a part of the inorganic fine particles among the plurality of inorganic fine particles exists in the form of a plurality of second inorganic fine particle aggregates in which two or more inorganic fine particles are aggregated, The second inorganic fine particle aggregate is located at or near the uneven surface, and the aggregation diameter of the second inorganic fine particle aggregate in a direction orthogonal to the thickness direction is larger than the thickness direction of the antiglare layer. Aggregation diameter of the second inorganic fine particle aggregate. For example, the anti-glare film according to item 8 or 9 of the patent application scope, wherein the proportion of the first inorganic fine particle aggregates in the anti-glare layer is higher than that of the anti-glare layer on the light-transmitting substrate side. The uneven surface side of the glare layer. For example, when the anti-glare film according to any one of claims 1, 8 and 9 is applied, wherein the thickness of the anti-glare layer is T and the average particle diameter of the organic fine particles is R, the following relationship is satisfied: 0.2 < R / T <0.7. For example, the anti-glare film according to any one of claims 1, 8 and 9, wherein the average primary particle diameter of the inorganic fine particles is 1 nm or more and 100 nm or less. For example, the anti-glare film according to claim 8 or 9, wherein the average diameter of the first inorganic fine particle aggregate is 100 nm or more and 2.0 μm or less. A polarizing plate, comprising: an anti-glare film according to any one of claims 1, 8 and 9 of the scope of patent application; and an anti-glare layer formed on the light-transmitting substrate formed on the anti-glare film. The polarizing element on the opposite side of the surface. A liquid crystal display panel includes an anti-glare film according to any one of claims 1, 8 and 9. An image display device includes an anti-glare film according to any one of claims 1, 8, and 9.