JP2018189975A - Anti-glare film, polarizing plate, liquid crystal panel, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-glare film that can obtain anti-glareness to the extent that a reflection is not annoying, and can obtain good glare prevention and good black color feeling, a polarizing plate, a liquid crystal panel, and an image display device.SOLUTION: According to one aspect of the present invention, there is provided an anti-glare film 10 comprising an optically transparent substrate 11; and an anti-glare layer 12 that is provided on the optically transparent substrate 11 and a concavo-convex surface 12A, where the anti-glare layer 12 includes a plurality of organic fine particles 13, a plurality of inorganic fine particles 14, and a binder resin 15, and when the frequency distribution of the inclination angle of a surface 10A of the anti-glare film 10 with respect to a surface 11A of the optically transparent substrate 11 is determined for every 0.01 degrees, the ratio of the 99th percentile to the third quartile in the cumulative percentage of the frequency of the inclination angle is 3.0 or more and 5.0 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an antiglare film, a polarizing plate, a liquid crystal panel, and an image display device.

  An image display surface in an image display device such as a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED) or the like is usually an observer and In order to suppress reflection of an observer's background or the like, an antiglare film having irregularities on the surface and an antireflection film having an antireflection layer on the outermost surface are provided (for example, see Patent Document 1).

  The antiglare film mainly includes a light-transmitting base material and an antiglare layer having an uneven surface provided on the light-transmitting base material. The antiglare film suppresses reflection of the observer and the background of the observer by scattering external light on the uneven surface of the antiglare layer.

  Some anti-glare films have an anti-glare property that prevents reflection. However, not only the anti-glare film with almost no reflection, but also the anti-glare film having an anti-glare property that does not bother the reflection is disposed on the surface of the image display device, the uneven surface of the anti-glare layer There is a possibility that the image light is scattered and so-called glare occurs. In order to prevent the occurrence of glare, it has been proposed to increase the haze. However, if the haze is increased, the occurrence of glare can be prevented, but the contrast may be lowered.

  In addition, currently, anti-glare films have a performance that combines excellent contrast and dynamism when displaying a movie (for example, the hair of a person displayed in an image in the case of a youth scene under a blue sky). Is black with a smooth feeling, moist black, and the skin has a gloss that is unique to the youth and looks vibrant.

JP 2011-215515 A

  The present invention has been made to solve the above problems. That is, an anti-glare film, a polarizing plate, a liquid crystal panel, and an image display device that can obtain an anti-glare property that does not bother the reflection, and that can provide a good anti-glare property and a good black feeling. The purpose is to provide.

  According to one aspect of the present invention, there is provided an antiglare film comprising a light transmissive substrate and an antiglare layer provided on the light transmissive substrate and having an uneven surface, wherein the antiglare layer is provided. Includes a plurality of organic fine particles, a plurality of inorganic fine particles, and a binder resin, and the frequency distribution of the inclination angle of the surface of the antiglare film with respect to the surface of the light-transmitting substrate was determined every 0.01 degrees. When the ratio of the 99th percentile to the 3rd quartile in the cumulative percentage of the frequency of the inclination angle is 3.0 or more and 5.0 or less, an antiglare film is provided.

  According to another aspect of the present invention, the above-described anti-glare film and polarized light formed on the surface of the light-transmitting substrate of the anti-glare film opposite to the surface on which the anti-glare layer is formed. There is provided a polarizing plate comprising a child.

  According to another aspect of the present invention, there is provided a liquid crystal display panel comprising the above antiglare film or the above polarizing plate.

  According to the other aspect of this invention, an image display apparatus provided with said anti-glare film or said polarizing plate is provided.

  According to the antiglare film of one embodiment of the present invention, and the polarizing plate, liquid crystal panel, and image display device of another embodiment, the frequency distribution of the inclination angle of the surface of the antiglare film with respect to the surface of the light transmissive substrate is obtained. When calculated every 0.01 degrees, since the ratio of the 99th percentile to the 3rd quartile in the cumulative percentage of the frequency of the inclination angle is 3.0 or more and 5.0 or less, the reflection is a concern. In addition to being able to obtain an antiglare property that does not occur, good glare prevention and good blackness can be obtained.

It is a schematic block diagram of the anti-glare film which concerns on embodiment. It is the figure which expanded a part of FIG. It is the figure which expanded a part of FIG. It is a schematic block diagram of the polarizing plate which concerns on embodiment. It is a schematic block diagram of the liquid crystal panel which concerns on embodiment. It is a schematic block diagram of the liquid crystal display which is an example of the image display apparatus which concerns on embodiment. It is a cross-sectional photograph of the anti-glare film based on Example 1 image | photographed using the scanning transmission electron microscope function of a scanning electron microscope. It is a cross-sectional photograph of the anti-glare film based on Example 1 which image | photographed using the scanning transmission electron microscope function of a scanning electron microscope, raising magnification from FIG.

  Hereinafter, an antiglare film and the like according to an embodiment of the present invention will be described with reference to the drawings. First, in the present specification, terms such as “film”, “sheet”, and “plate” are not distinguished from each other only based on the difference in names. Therefore, for example, “film” is a concept including a member that can also be called a sheet or a plate. As a specific example, “antiglare film” includes members called “antiglare sheet”, “antiglare plate” and the like. In the present specification, the “weight average molecular weight” is a value obtained by dissolving in a solvent such as tetrahydrofuran (THF) and converting to polystyrene by a conventionally known gel permeation chromatography (GPC) method.

<<< Anti-Glare Film >>>
FIG. 1 is a schematic configuration diagram of an antiglare film according to the present embodiment, FIG. 2 is an enlarged view of a part of FIG. 1, and FIG. 3 is an enlarged view of a part of FIG.

  As shown in FIG. 1, the antiglare film 10 is composed of a light transmissive substrate 11, an antiglare layer 12 provided on the light transmissive substrate 11, and having an uneven surface 12 </ b> A. It has.

  The surface 10A of the antiglare film 10 is an uneven surface. In this embodiment, since the functional layer such as the low refractive index layer is not provided on the antiglare layer 12, the uneven surface 12A of the antiglare layer 12 is the surface 10A of the antiglare film 10. “Functional layer” is a layer intended to exhibit some function in an antiglare film, and specifically, for example, exhibits functions such as antireflection, antistatic, or antifouling properties. The layer for doing is mentioned. The functional layer is not limited to a single layer but may be a laminate of two or more layers.

  In the anti-glare film 10, when the frequency distribution of the inclination angle of the surface 10A of the anti-glare film 10 with respect to the surface 11A of the light-transmitting substrate 11 is obtained every 0.01 degrees, the first in the cumulative percentage of the inclination angle frequency. The ratio of the 99th percentile to the 3rd quartile (99th percentile / third quartile) is 3.0 or more and 5.0 or less. The lower limit of the 99th percentile / third quartile is preferably 4.0 or higher, and the upper limit of the 99th percentile / third quartile is 4.5 or lower. preferable.

  “Inclination angle” is an inclination angle on the surface of the antiglare film. That is, as in this embodiment, when a functional layer such as a low refractive index layer is not provided on the antiglare layer, the measured “tilt angle” is the tilt angle of the uneven surface of the antiglare layer. is there. Further, when a functional layer such as a low refractive index layer is provided on the antiglare layer, the “inclination angle” is not the inclination angle of the uneven surface of the antiglare layer, but the inclination angle of the surface of the functional layer. is there. The “tilt angle” is an absolute value.

  The inclination angle can be obtained by measuring the surface shape of the surface of the antiglare film. Examples of the apparatus for measuring the surface shape include a contact-type surface roughness meter and a non-contact-type surface roughness meter (for example, an interference microscope, a confocal microscope, an atomic force microscope, etc.). Among these, an interference microscope is preferable from the viewpoint of simplicity of measurement. Examples of such an interference microscope include “New View” series manufactured by Zygo.

In order to calculate the inclination angle using the interference microscope, for example, the inclination St of each point over the entire surface of the antiglare film is obtained, and the inclination St is converted into the inclination angle θ _i by the following formula (1).
θ _i = tan ⁻¹ St (1)

The slope St can be obtained from the following equation (2).
However, when one of two orthogonal directions on the measurement surface is the x-axis and the other is the y-axis, Sx is an inclination in the x-axis direction with respect to the x-axis, and Sy is an inclination in the y-axis direction with respect to the y-axis, It is calculated from the following formulas (3) and (4).
Sx = (Z _{i + 1, j} −Z _{i−1, j} ) / 2Δ (3)
Sy = (Z _{i, j + 1} −Z _{i, j−1} ) / 2Δ (4)
In equations (3) and (4), Z _{i, j} is the height at the i-th in the x-axis direction and the j-th in the y-axis direction, and Δ is the sampling interval.

  In the measurement of the surface shape of the surface 10A, it is preferable to calculate the inclination angle from the concavo-convex shape excluding the waviness component with a high-pass filter having 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. If the sampling interval is too small, high-frequency components of unevenness on the noise will be picked up, and the tilt angle may be excessively estimated. If the sampling interval is too large, the surface angle can be accurately estimated. It is because there is a risk of disappearing. The wider measurement area is preferable, and the measurement is preferably performed in a region of at least 200 μm × 200 μm or more, more preferably 500 μm × 500 μm or more.

  In the antiglare film 10, an arithmetic average value of transmitted image clarity measured using an optical comb of 0.125 mm width, 0.25 mm width, 0.5 mm width, 1.0 mm width, 2.0 mm width, It is preferable that the absolute value of the difference from the transmitted image sharpness measured using each optical comb is within 10%. When this difference is within 10%, glare can be more reliably suppressed.

  The “transparent image clarity of the antiglare film” means the transmitted image clarity measured for the entire antiglare film. In the present embodiment, since a functional layer such as a low refractive index layer is not provided on the antiglare layer 12, the transmitted image clarity of the antiglare film 10 is determined from the light transmissive substrate 11 and the antiglare layer 12. It is the transmitted image clarity measured using the anti-glare film 10 which becomes. In addition, when a functional layer such as a low refractive index layer is provided on the antiglare layer, the transmitted image clarity of the antiglare film is an antiglare layer composed of a light transmissive substrate, an antiglare layer, and a functional layer. It is the transmission image definition measured using the glare film.

  The transmission image definition can be measured by a transmission definition measuring device based on the image definition transmission method of JIS K7374. As such a measuring apparatus, Suga Test Instruments Co., Ltd. image clarity measuring device ICM-1T etc. are mentioned.

  The optical comb 105 is movable along the longitudinal direction of the optical comb 105 and has a light shielding portion and a transmission portion. The ratio of the width of the light shielding portion and the transmission portion of the optical comb 105 is 1: 1. Here, in JIS K7374, five types of optical combs having a width of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm are defined as optical combs. The anti-glare film 10 is arranged so that the light that has become parallel light by the lens 103 is incident on the back surface of the anti-glare film 10 at an incident angle of 90 °.

  It is preferable that the average value of the transmitted image definition of the antiglare film 10 measured using the five types of optical combs is 80% or more. The transmitted image definition of the antiglare film 10 measured using an optical comb having a width of 0.125 mm is preferably 70% or more, and the antiglare film measured using an optical comb having a width of 0.25 mm. 10 is preferably 70% or more, and the image clarity of the antiglare film 10 measured using an optical comb having a width of 0.5 mm is 80% or more. Preferably, the transmitted image definition of the antiglare film 10 measured using an optical comb having a width of 1.0 mm is preferably 80% or more, and the antiglare measured using an optical comb having a width of 2.0 mm. The transmitted image definition of the glare film 10 is preferably 90% or more.

  In the surface 10A of the antiglare film 10, the average interval Sm of the unevenness constituting the surface 10A is preferably 0.1 mm or more and 0.6 mm or less, and is 0.2 mm or more and 0.4 mm or less. Is more preferable. In the surface 10A of the antiglare film 10, the average inclination angle θa of the unevenness constituting the surface 10A is preferably 0.05 ° or more and 0.30 ° or less, and is 0.15 ° or more and 0.25 ° or less. It is more preferable that

  In the surface 10A of the antiglare film 10, the arithmetic average roughness Ra of the unevenness constituting the surface 10A is preferably 0.02 μm or more and 0.20 μm or less, and is 0.04 μm or more and 0.10 μm or less. More preferably.

The definitions of “Sm” and “Ra” are based on JIS B0601-1994. The definition of “θa” is in accordance with the surface roughness measuring instrument: SE-3400 / Kosaka Laboratory Co., Ltd. instruction manual (revised 1995.07.20). Specifically, θa is represented by the following formula (5).
θa = tan ⁻¹ Δa (5)
In the formula, Δa represents the slope as an aspect ratio, and is a value obtained by dividing the total sum of the differences between the minimum and maximum portions of each unevenness (corresponding to the height of each convex portion) by the reference length.

Sm, θa, and Ra can be measured under the following measurement conditions using, for example, a surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory Ltd.).
1) Surface roughness detector stylus (trade name SE2555N (2μ standard) manufactured by Kosaka Laboratory Ltd.), tip radius of curvature 2μm, apex angle 90 degrees, material diamond 2) Measurement conditions of surface roughness measuring instrument Reference length (roughness curve cut-off value λc): 2.5 mm
Evaluation length (reference length (cutoff value λc) × 5): 12.5 mm
・ Feeding speed of stylus: 0.5mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

  The antiglare film 10 preferably has a total light transmittance of 85% or more. When the total light transmittance is 85% or more, color reproducibility and visibility can be further improved when the antiglare film 10 is mounted on the surface of the image display device. The total light transmittance is more preferably 90% or more. The total light transmittance can be measured by a method based on JIS K7361 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).

  The haze value (total haze value) of the entire antiglare film 10 is preferably 2% or less. When the total haze value is 2% or less, desired optical characteristics can be obtained, and the visibility when the antiglare film 10 is placed on the image display surface can be further improved. The total haze value is more preferably 1% or less. The total haze value can be measured by a method based on JIS K7136 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).

  When the antiglare film has an internal haze value, the glare prevention property is improved. On the other hand, when the internal haze value is too large, stray light may be generated and the blackness may be inferior. From the viewpoint of improving the feeling, the internal haze value of the antiglare film 10 is preferably 0.1% or more and 2.0% or less. The internal haze value of the antiglare film 10 is more preferably 0.5% or more and 1.5% or less.

  The surface haze value of the antiglare film 10 is preferably 0% or more and 0.3% or less. The surface haze value is caused only by the uneven shape of the uneven surface in the antiglare layer, and can be determined as follows. First, the total haze value of the antiglare film is measured according to JIS K7136 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory). Thereafter, a light transmissive resin base material is attached to the surface of the antiglare layer via an adhesive layer, an adhesive tape, or the like. Thereby, the uneven shape of the uneven surface in the antiglare layer is crushed, and the surface of the antiglare film becomes flat. In this state, the haze value is measured according to JIS K7136 using a haze meter, and the internal haze value is obtained by subtracting the haze of the adhesive layer or the adhesive tape itself. This internal haze value does not take into account the uneven shape of the uneven surface in the antiglare layer, so by subtracting the internal haze value from the total haze value, the surface haze value resulting from only the uneven surface shape in the antiglare layer Is required.

<< light transmissive substrate >>
The light-transmitting substrate 11 is not particularly limited as long as it has light-transmitting properties. For example, a cellulose acylate substrate, a cycloolefin polymer substrate, a polycarbonate substrate, an acrylate polymer substrate, a polyester substrate, or A glass substrate is mentioned.

  As a cellulose acylate base material, a cellulose triacetate base material and a cellulose diacetate base material are mentioned, for example. As a cycloolefin polymer base material, the base material which consists of polymers, such as a norbornene-type monomer and a monocyclic cycloolefin monomer, is mentioned, for example.

  Examples of the polycarbonate substrate include aromatic polycarbonate substrates based on bisphenols (bisphenol A and the like), aliphatic polycarbonate substrates such as diethylene glycol bisallyl carbonate, and the like.

  Examples of the acrylate polymer base material include a poly (meth) methyl acrylate base material, a poly (meth) ethyl acrylate base material, and a (meth) methyl acrylate- (meth) butyl acrylate copolymer base material. Can be mentioned.

  Examples of the polyester base material include base materials containing at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as constituent components.

  Examples of the glass substrate include glass substrates such as soda lime silica glass, borosilicate glass, and alkali-free glass.

  Among these, a cellulose acylate base material is preferable because of excellent retardation and easy adhesion with a polarizer, and among the cellulose acylate base materials, a triacetyl cellulose base material (TAC base material) is preferable. A triacetyl cellulose base material is a light-transmitting base material capable of setting an average light transmittance to 50% or more in a visible light region of 380 to 780 nm. The average light transmittance of the triacetyl cellulose base material is preferably 70% or more, and more preferably 85% or more.

  In addition, as a triacetyl cellulose base material, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like may be used in combination with components other than acetic acid as a fatty acid forming an ester with cellulose. Good. Further, these triacetylcelluloses may be added with other additives such as other cellulose lower fatty acid esters such as diacetylcellulose, or plasticizers, ultraviolet absorbers, and lubricants as necessary.

  A cycloolefin polymer substrate is preferred from the standpoint of retardation and heat resistance, and a polyester substrate is preferred from the standpoint of mechanical properties and heat resistance.

  The thickness of the light-transmitting substrate 11 is not particularly limited, but can be 5 μm or more and 1000 μm or less. The lower limit of the thickness of the light-transmitting substrate 11 is preferably 15 μm or more from the viewpoint of handling properties, etc., and 25 μm The above is more preferable. The upper limit of the thickness of the light transmissive substrate 11 is preferably 80 μm or less from the viewpoint of thinning.

<< Anti-glare layer >>
The antiglare layer 12 is a layer that exhibits antiglare properties, and includes a plurality of organic fine particles 13, a plurality of inorganic fine particles 14, and a binder resin 15 as shown in FIG. 2. The antiglare layer 12 may exhibit antiglare properties and other functions. Specifically, the anti-glare layer 12 may be a layer that exhibits anti-glare properties and, for example, functions such as hard coat properties, antireflection properties, antistatic properties, and antifouling properties.

  When the antiglare layer 12 is a layer that exhibits hard coat properties in addition to the antiglare property, the antiglare layer 12 has a pencil hardness test (4.9 N) defined by JIS K5600-5-4 (1999). It has a hardness equal to or higher than “H” in terms of load.

  The surface of the antiglare layer 12 is an uneven surface 12A. Here, the “surface of the antiglare layer” means a surface of the antiglare layer opposite to the surface on the light transmissive substrate side (the back surface of the antiglare layer).

  In the present embodiment, since the uneven surface 12A of the antiglare layer 12 is the surface 10A of the antiglare film 10, the inclination angle of the uneven surface 12 of the antiglare layer 12 with respect to the surface 11A of the light transmissive substrate 11 is increased. When the frequency distribution is obtained every 0.01 degrees, the ratio of the 99th percentile to the third quartile in the cumulative percentage of the frequency of the inclination angle (99th percentile / third quartile) is 3. It is 0 or more and 5.0 or less.

  When the antiglare layer 12 has a hard coat property, the thickness of the antiglare layer 12 is preferably 2.0 μm or more and 7.0 μm or less. If the thickness of the antiglare layer 12 is within this range, a desired hardness can be obtained. In addition, the antiglare layer can be made thin, while cracking and curling of the antiglare layer can be suppressed. The thickness of the antiglare layer 12 is a value measured using an image processing software from an image of a cross-sectional electron microscope (TEM, STEM). Here, since the surface of the antiglare layer is an uneven surface, the thickness varies depending on the location, but the “thickness of the antiglare layer” means an average value of the thickness of the antiglare layer. The lower limit of the thickness of the antiglare layer is more preferably 2.5 μm or more, and the upper limit is more preferably 5 μm or less.

<Organic fine particles>
At least some of the organic fine particles 13 are preferably present as an organic fine particle aggregate 13A in which two or more organic fine particles 13 are aggregated. When the number of the organic fine particles 13 constituting the organic fine particle aggregate 13A is two or more, the area of the peak of the convex portion having a gentle slope increases on the concave and convex surface 12A, and the convex rising surface of the convex portion having a steep slope is obtained. Since the area is reduced, deterioration of contrast can be suppressed.

  In the antiglare layer 12, the maximum height of the organic fine particle aggregate 13 </ b> A in the thickness direction of the antiglare layer 12 is preferably less than the thickness of the antiglare layer 12. Since the maximum height of the organic fine particle aggregate 13A is less than the thickness of the antiglare layer 12, a sharp uneven surface is not generated, and a decrease in contrast and blackness can be suppressed while exhibiting antiglare properties. it can.

Examples of the organic fine particles 13 include plastic beads. Specific examples of the plastic beads include polystyrene beads, melamine resin beads, acrylic beads, acrylic-styrene beads, silicone beads, benzoguanamine beads, benzoguanamine / formaldehyde condensation beads, polycarbonate beads, polyethylene beads, and the like. It is also preferable to subject the surface of the organic fine particles 13 to a hydrophilic treatment.
By subjecting the surface of the organic fine particles 13 to a hydrophilic treatment, it is possible to control the state of aggregation with the inorganic fine particles 14.

The average primary particle size of the organic fine particles 13 is preferably 1 μm or more and 5 μm or less. The average primary particle size of the organic fine particles is observed as an almost the same particle size of any same kind in observation of an electron microscope (transmission type such as TEM, STEM, etc.) of a cross section passing through the vicinity of the center of the organic fine particles. The value is calculated as an average value obtained by selecting 30 organic fine particles and measuring the maximum particle size of the cross section. It may be calculated using image analysis software. When the average primary particle size of the organic fine particles 13 is 1 μm or more, the antiglare property can be more reliably ensured.
Moreover, when the average primary particle diameter of the organic fine particles 13 is 5 μm or less, a decrease in contrast can be suppressed. The lower limit of the average primary particle size of the organic fine particles 13 is more preferably 1.5 μm or more, and the upper limit of the average primary particle size of the organic fine particles 13 is more preferably 4.0 μm or less.

Further, when the thickness of the antiglare layer 12 is T and the average primary particle size of the organic fine particles 13 is R, the organic fine particles preferably satisfy the relationship of the following formula (6).
0.2 <R / T <0.7 (6)

  When R / T satisfies the above formula (6), the anti-glare property and the blackness can be more reliably achieved.

  The number of the organic fine particles 13 constituting the organic fine particle aggregate 13A is preferably 2 or more and 3 or less. When the number of the organic fine particles 13 constituting the organic fine particle aggregate 13A is 3 or less, the generation of the organic fine particle aggregate larger than the thickness T of the antiglare layer 12 can be prevented more reliably, and the steep convex portion is formed. It can suppress forming.

  For example, the organic fine particle aggregate 13A may be obtained by interspersing groups that react with each other on the surface of the organic fine particle to control the aggregation state of the organic fine particle to obtain the organic fine particle aggregate 13A. By using a solvent having a different affinity and volatility with the binder resin, the agglomeration may be controlled by changing the affinity during drying to obtain an organic fine particle aggregate 13A. You may obtain by controlling the hydrophilization process of the organic fine particle to comprise, the hydrophobization process of the inorganic fine particle 14, and the hydroxyl group presence ratio of the binder resin 15.

<Inorganic fine particles>
The inorganic fine particles 14 are not particularly limited. For example, inorganic oxide fine particles such as silica (SiO ₂ ) fine particles, alumina fine particles, titania fine particles, tin oxide fine particles, antimony-doped tin oxide (abbreviated as ATO) fine particles, and zinc oxide fine particles. Is mentioned.

When silica particles are used as the inorganic fine particles 14, fumed silica fine particles are preferable from the viewpoint of easily forming an antiglare layer having a smooth uneven surface among the silica particles. Fumed silica is amorphous silica having a particle size of 200 nm or less prepared by a dry method, and can be obtained by reacting a volatile compound containing silicon in a gas phase. Specific examples include those produced by hydrolyzing a silicon compound such as silicon tetrachloride (SiCl ₄ ) in a flame of oxygen and hydrogen. Examples of commercially available fumed silica fine particles include AEROSIL R805 manufactured by Nippon Aerosil Co., Ltd.

  When inorganic oxide particles are used as the inorganic fine particles 14, the inorganic oxide fine particles are preferably amorphous. This is because when the inorganic oxide particles are crystalline, the Lewis acid salt of the inorganic oxide fine particles becomes strong due to lattice defects contained in the crystal structure, and excessive aggregation of the inorganic oxide fine particles can be controlled. It is because there is a risk of disappearing.

  Further, when fumed silica fine particles are used as the inorganic fine particles 14, the fumed silica fine particles include hydrophilic ones and hydrophobic ones, but among these, the amount of moisture absorption is reduced and anti-glare. From the viewpoint of facilitating dispersion in the layer composition, those exhibiting hydrophobicity are preferred. Hydrophobic fumed silica can be obtained by chemically reacting the above-mentioned surface treatment agent with silanol groups present on the surface of the fumed silica fine particles.

  The inorganic fine particles 14 are preferably spherical in shape in a single particle state. Since the single particles of the inorganic fine particles 14 are spherical, an image with better contrast can be obtained when the antiglare film is disposed on the image display surface of the image display device. Here, “spherical” means, for example, a true spherical shape, an elliptical spherical shape, etc., but a so-called indeterminate shape is not included.

The average primary particle size of the inorganic fine particles 14 is preferably 1 nm or more and 100 nm or less.
Since the average primary particle size of the inorganic fine particles 14 is 1 nm or more, an antiglare layer having a smooth uneven surface can be more easily formed, and the average primary particle size is 100 nm or less. Light diffusion by the inorganic fine particles can be suppressed, and excellent contrast can be obtained. The lower limit of the average primary particle size of the inorganic fine particles 14 is more preferably 10 nm or more, and the upper limit of the average primary particle size of the inorganic fine particles 14 is more preferably 50 nm or less.

  The average primary particle size of the inorganic fine particles 14 is a value measured using an image processing software from an image of a cross-sectional electron microscope (a transmission type such as TEM or STEM and preferably having a magnification of 50,000 times or more).

  It is preferable that at least some of the inorganic fine particles 14 exist as a first inorganic fine particle aggregate 14 </ b> A in which three or more inorganic fine particles 14 are aggregated.

  The first inorganic fine particle aggregate 14A is present in the binder resin 15 and is composed of three or more inorganic fine particles 14 as described above. As shown in FIG. 3, the first inorganic fine particle aggregate 14 </ b> A preferably has a bent portion 14 </ b> B formed by continuous inorganic fine particles 14. Here, in this specification, the “bent portion” is a concept including a curved portion. Examples of the shape having the bent portion 14B include a V shape, a U shape, an arc shape, a C shape, a string shape, and a hook shape. Both ends of the bent portion 14B may be closed. For example, the first inorganic fine particle aggregate 14 may have an annular structure having the bent portion 14B.

  The bent portion 14B may be formed of a single inorganic fine particle aggregate formed by bending inorganic fine particles, and may be composed of a trunk formed by continuous inorganic fine particles and a branch from the trunk. In addition, it may be constituted by branch portions formed by continuous inorganic fine particles, or may be constituted by two branch portions branched from the trunk portion and connected at the trunk portion. The “stem” is the longest portion of the first inorganic fine particle aggregate.

  The bent portion 14B has an inner region 14C as shown in FIG. The “inner region” is a region sandwiched between bent portions. This inner region 14 </ b> C is filled with a binder resin 15. The bent portion 14 </ b> C preferably exists so as to sandwich the inner region 14 </ b> C from the thickness direction of the antiglare layer 12.

  Since the inorganic fine particle aggregate in which the inorganic fine particles are aggregated in a lump shape acts as a single solid upon curing shrinkage (polymerization shrinkage) of the photopolymerizable compound that becomes a binder resin after curing, the uneven surface of the antiglare layer is inorganic. Corresponds to the shape of the fine particle aggregate. On the other hand, since the first inorganic fine particle aggregate 14A has the bent portion 14B having the inner region 14C, it acts as a solid having a buffering action upon curing shrinkage. Accordingly, the first inorganic fine particle aggregate 14A is easily and uniformly crushed during the curing shrinkage. Thereby, the shape of the uneven surface 12A becomes gentler than the shape before curing shrinkage.

  In the first inorganic fine particle aggregate 14A, it is preferable that the proportion of inorganic fine particles in which one or more and three or less inorganic fine particles are in contact with one inorganic fine particle is 95% or more. When the proportion of inorganic fine particles in contact with one or more inorganic particles is 95% or more with respect to one inorganic fine particle, four or more inorganic fine particles are in contact with 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 14 does not become a lump. The proportion of the inorganic fine particles is more preferably 97% or more, and further preferably 99% or more.

The presence ratio of the first inorganic fine particle aggregate 14 </ b> A in the antiglare layer 12 is higher on the light transmissive substrate 11 side of the antiglare layer 12 than on the uneven surface 12 </ b> A side of the antiglare layer 12. preferable.
Here, whether the first inorganic fine particle aggregate is present on the light transmissive substrate side in the antiglare layer or is present on the uneven surface side, with a half of the thickness of the antiglare layer as a boundary, Judgment is made based on whether it exists on the light-transmitting substrate side from this boundary or on the uneven surface side from this boundary. In addition, the existence ratio of the first inorganic fine particle aggregates is higher on the light transmissive substrate side of the antiglare layer than on the uneven surface side of the antiglare layer, which is a cross-sectional electron microscope (TEM, STEM). It can be confirmed by the image. The presence ratio of the first inorganic fine particle aggregate 14A is higher on the light transmissive substrate 11 side of the antiglare layer 12 than on the uneven surface 12A side of the antiglare layer 12, so that the uneven surface 12A is steep. It becomes smooth without having a slope, and has a diffusion performance very close to regular reflection and / or regular transmission. Thereby, the anti-glare layer 12 has anti-glare properties, but not only has excellent contrast in a bright room, but also can suppress the occurrence of stray light of image light, so it has excellent contrast in a dark room, An antiglare film 10 having a high contrast and a black feeling can be obtained.

Specifically, in the cross section along the thickness direction of the antiglare layer 12, the first inorganic fine particle aggregates present on the light transmissive substrate 11 side in the antiglare layer 12 in the first inorganic fine particle aggregate 14 </ b> A. When the number of the aggregates 14A is Nb and the number of the first inorganic fine particle aggregates 14A existing on the uneven surface 12A side in the antiglare layer 12 is Nf, Nb / Nf satisfies the following formula (7) Is preferred.
1.5 <Nb / Nf (7)

  When Nb / Nf satisfies the above formula (7), the above antiglare property and excellent blackness can be more reliably obtained.

  The first inorganic fine particle aggregate 14A is preferably present at least at the position of the surface of the organic fine particle aggregate 13A and at a position apart from the organic fine particle aggregate 13A and between the organic fine particle aggregates 13A. On the uneven surface 12A, the position corresponding to the organic fine particle aggregate 13A is a convex portion. However, the presence of the first inorganic fine particle aggregate 14A on the surface of the organic fine particle aggregate 13A causes the organic fine particle aggregate 13 to be present. The specific gravity of the convex surface of the concave / convex surface 12A changes smoothly by showing a buffering effect on the curing shrinkage of the binder resin 15, and the rugged surface of the concave / convex surface 12A changes smoothly. 12A becomes smooth. Furthermore, since the positions corresponding to the organic fine particle aggregates 13 are convex portions on the concavo-convex surface 12 </ b> A, the organic fine particle aggregates 13 are concave portions, but are separated from the organic fine particle aggregates 13 and the organic fine particle aggregates 13. The presence of the first inorganic fine particle aggregate 14A in the middle position increases the position of the concave portion on the concave / convex surface 12A, thereby reducing the height difference between the convex portion and the concave portion on the concave / convex surface 12A. 12A becomes smoother and, as described above, extremely loose irregularities are formed between the irregular surfaces 12A, so that the antiglare property can be ensured without degrading the contrast.

  The average aggregate diameter of the first inorganic fine particle aggregate 14A is preferably 100 nm or more and 2.0 μm or less. If the average aggregate diameter of the first inorganic fine particle aggregate 14A is 100 nm or more, the smooth uneven surface 12A can be easily formed, and the average aggregate diameter of the first inorganic fine particle aggregate 14A is 2.0 μm. If it is below, the diffusion of light by the first inorganic fine particle aggregate 14A can be suppressed, and the antiglare film 10 excellent in contrast can be obtained. The lower limit of the average aggregate diameter of the first inorganic fine particle aggregate 14A is preferably 200 nm or more, and the upper limit is preferably 1.5 μm or less.

  The average aggregate diameter of the first inorganic fine particle aggregates is selected from a 5 μm square area containing a large amount of the first inorganic fine particle aggregates from observation with a cross-sectional electron microscope (about 10,000 to 20,000 times). The aggregate diameter of the first inorganic fine particle aggregates is measured, and the aggregate diameters of the top 10 first inorganic fine particle aggregates are averaged. The “average aggregate diameter of the first inorganic fine particle aggregate” is the maximum distance between the two straight lines when the cross section of the first inorganic fine particle aggregate is sandwiched between any two parallel straight lines. It is measured as the distance between straight lines in a combination of two straight lines. The average aggregate diameter of the first inorganic fine particle aggregates may be calculated using image analysis software.

  The first inorganic fine particle aggregate 14 </ b> A preferably has a larger aggregate diameter in the direction orthogonal to the thickness direction than the aggregate diameter in the thickness direction of the antiglare layer 12. The “aggregation diameter in the thickness direction” is a distance between two straight lines when the cross section of the first inorganic fine particle aggregate is sandwiched between two parallel straight lines perpendicular to the thickness direction of the antiglare layer. Measured. In addition, the “aggregation diameter in a direction perpendicular to the thickness direction” means that two cross-sections when the cross section of the first inorganic fine particle aggregate is sandwiched between two parallel straight lines parallel to the thickness direction of the anti-glare layer. Measured as the distance between straight lines. These agglomerated diameters may also be calculated using image analysis software.

  The first inorganic fine particle aggregate 14 </ b> A can be obtained, for example, by controlling the hydrophilicity treatment of the organic fine particles 13, the hydrophobic treatment of the inorganic fine particles 14, and the hydroxyl group existing ratio of the binder resin 15. Hydroxyl groups are present on the surface of the inorganic fine particles 14, but when the first inorganic fine particles 14 are subjected to a hydrophobization treatment, the number of hydroxyl groups present on the surface of the inorganic fine particles 14 is reduced and the inorganic fine particles are excessively aggregated. Can be suppressed. Further, by applying a hydrophobic treatment to the surface of the inorganic fine particles 14, the chemical resistance and saponification resistance of the inorganic fine particles themselves can be improved.

  Such a hydrophobic treatment can be performed using a surface treatment agent such as silanes and silazanes. Specific examples of the surface treatment agent include dimethyldichlorosilane, silicone oil, hexamethyldisilazane, octylsilane, hexadecylsilane, aminosilane, methacrylsilane, octamethylcyclotetrasiloxane, and polydimethylsiloxane.

  In addition, since the first inorganic fine particle aggregate 14A can be obtained by a method other than the above method, the method for obtaining the first inorganic fine particle aggregate 14A is not limited to the above method. For example, the surface of the inorganic fine particles may be interspersed with each other to control the aggregation state of the inorganic fine particles to obtain the first inorganic fine particle aggregate 14A, or between the inorganic fine particles and the binder resin. By using solvents having different affinity and volatility, the first inorganic fine particle aggregate 14A may be obtained by controlling the aggregation by changing the affinity during drying.

  As the inorganic fine particles 14 in the antiglare layer 12, together with the first inorganic fine particle aggregate 14A, as shown in FIG. 2 and FIG. 3, a second inorganic fine particle aggregate 14D in which two or more inorganic fine particles 14 are aggregated. May be present. The second inorganic fine particle aggregate 14D exists on the uneven surface 12A or in the vicinity thereof. Also, in the second inorganic fine particle aggregate 14D, the ratio of the inorganic fine particles in contact with one or more and three or less inorganic fine particles to one inorganic fine particle is 95% or more. preferable. Further, the second inorganic fine particle aggregate 14D preferably has a larger aggregate diameter in the direction perpendicular to the thickness direction than the aggregate diameter in the thickness direction of the antiglare layer 12, and further aggregates two-dimensionally. It is preferable. Further, since the second inorganic fine particle aggregate 14D is present on the uneven surface 12A or in the vicinity thereof compared to the first inorganic fine particle aggregate 14A, it is more antiglare than the first inorganic fine particle aggregate 14A. Since the aggregation diameter in the thickness direction of the layer 12 is small, the uneven surface 12A can be made smoother.

  Since the second inorganic fine particle aggregate 14D is present on or near the irregular surface 12A, the hardness of the surface of the antiglare layer 12 can be increased. Therefore, a relatively soft binder resin can be used as the binder resin 15. Thus, the antiglare film 10 having excellent flexibility can be obtained.

  The average aggregate diameter of the second inorganic fine particle aggregate 14D is preferably 100 nm or more and 2.0 μm or less for the same reason as the average aggregate diameter of the first inorganic fine particle aggregate 14A. The lower limit of the average aggregate diameter of the second inorganic fine particle aggregate 14D is more preferably 200 nm or more, and the upper limit is more preferably 1.5 μm or less.

  Since the inorganic fine particles 14 constituting the second inorganic fine particle aggregate 14D may be the same as the inorganic fine particles 14 constituting the first inorganic fine particle aggregate 14A, description thereof will be omitted here. . Further, the second inorganic fine particle aggregate 14 is similar to the first inorganic fine particle aggregate 14A, for example, the hydrophilic treatment of the organic fine particles 13, the hydrophobic treatment of the inorganic fine particles 14, and the presence of the hydroxyl groups of the binder resin 15. It can be obtained by controlling the ratio. However, in order to make the aggregation state of the second inorganic fine particle aggregate 14D different from the aggregation state of the first inorganic fine particle aggregate 14A, for example, in the second inorganic fine particle aggregate 14D, the first inorganic fine particle aggregate 14D A surface treatment agent different from the aggregate 14A or a surface treatment agent concentration different from the first inorganic fine particle aggregate 14A may be used.

  In the antiglare layer 12, the organic fine particles 13 and the inorganic fine particles 14 in the uneven surface 12 </ b> A of the antiglare layer 12 in a cross section along the thickness direction of the antiglare layer 12 (the normal direction of the light transmissive substrate 11). The ratio of the length of the region other than the region corresponding to is preferably 15% or more and 70% or less. When this ratio is 15% or more, the anti-glare film has an appropriate specular transmission (regular reflection) component, and it is possible to ensure image shine, brightness, and contrast, and this ratio is 70% or less. Therefore, since excessive regular reflection does not occur, antiglare property can be ensured. 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-mentioned “length of the region other than the region corresponding to the organic fine particles and the inorganic fine particles” refers to the organic fine particles (organic fine particle aggregation) when viewed from the thickness direction of the antiglare layer in the cross section along the thickness direction of the antiglare layer. It means the length (linear distance) of a region other than the region of the concavo-convex surface overlapping with the aggregate) and the inorganic fine particles (the first inorganic fine particle aggregate and the second inorganic fine particle aggregate). The region other than the region corresponding to the organic fine particles and inorganic fine particles is a region where there is no diffusing element contributing to internal diffusion and / or surface diffusion, and the image light transmitted through this region consists only of components in the normal transmission direction. Similarly, the outside light is composed of only a regular reflection component. On the contrary, the region corresponding to the organic fine particles and the inorganic fine particles is a region having a diffusing element contributing to internal diffusion and / or surface diffusion, and the image light transmitted through this region is composed of a diffusing component. Similarly, it has a diffuse reflection component. For example, in the case of FIG. 3, the lengths of the regions other than the regions corresponding to the organic fine particles 13 and the inorganic fine particles 14 are L _{1 to} L ₄ . Moreover, the ratio of this length is a value measured using an image processing software from an image of a cross-sectional electron microscope (TEM, STEM).

<Binder resin>
The binder resin 15 includes a polymerized product (crosslinked product) of a photopolymerizable compound. The binder resin may contain a solvent-drying resin or a thermosetting resin in addition to a polymerized product (crosslinked product) of a photopolymerizable compound. The photopolymerizable compound has at least one photopolymerizable functional group.
In the present specification, the “photopolymerizable functional group” is a functional group capable of undergoing a polymerization reaction by light irradiation. Examples of the photopolymerizable functional group include ethylenic double bonds such as a (meth) acryloyl group, a vinyl group, and an allyl group. The “(meth) acryloyl group” means to include both “acryloyl group” and “methacryloyl group”. The light irradiated when polymerizing the photopolymerizable compound includes visible light and ionizing radiation such as ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays.

  Examples of the photopolymerizable compound include a photopolymerizable monomer, a photopolymerizable oligomer, and a photopolymerizable prepolymer, which can be appropriately adjusted and used. As the photopolymerizable compound, a combination of a photopolymerizable monomer and a photopolymerizable oligomer or photopolymerizable prepolymer is preferable.

  It is preferable that the hydrophilicity of the binder resin 15 is controlled. For example, an anti-glare film is prepared and checked using a binder resin whose hydrophilicity is controlled by changing the mixing ratio of a photopolymerizable compound having a hydroxyl group and a photopolymerizable compound not having a hydroxyl group in advance. Thus, an antiglare film in which the degree of aggregation and uneven distribution of organic fine particles and inorganic fine particles is controlled can be obtained.

(Photopolymerizable monomer)
The photopolymerizable monomer has a weight average molecular weight of 1000 or less. In addition, you may use not only one type but multiple types of photopolymerizable monomers.

  The photopolymerizable monomer is preferably a polyfunctional monomer having two or more photopolymerizable functional groups (that is, bifunctional).

  Examples of the bifunctional or higher monomer include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and 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, ditri Methylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Lapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin tetra ( (Meth) acrylate, adamantyl di (meth) acrylate, isoboronyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and these are PO, EO And the like modified.

  Among these, from the viewpoint of obtaining an antiglare layer having high hardness, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), and the like. preferable.

(Photopolymerizable oligomer)
The photopolymerizable oligomer has a weight average molecular weight of more than 1000 and 10,000 or less.
As the photopolymerizable oligomer, a polyfunctional oligomer having 3 (trifunctional) or more photopolymerizable functional groups is preferable. The photopolymerizable oligomer is preferably a bifunctional or higher polyfunctional oligomer. Polyfunctional oligomers include polyester (meth) acrylate, urethane (meth) acrylate, polyester-urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, and isocyanurate (meth). Examples include acrylate and epoxy (meth) acrylate.

(Photopolymerizable prepolymer)
The photopolymerizable prepolymer has a weight average molecular weight exceeding 10,000, and the weight average molecular weight is preferably 10,000 or more and 80,000 or less, and more preferably 10,000 or more and 40,000 or less. When the weight average molecular weight exceeds 80000, the viscosity is high, so that the coating suitability is lowered, and the appearance of the obtained antiglare film may be deteriorated. Examples of the polyfunctional polymer include urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester-urethane (meth) acrylate, and epoxy (meth) acrylate.

  The solvent-drying resin is a resin that forms a film only by drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin. When the solvent-drying type resin is added, film defects on the coating surface of the coating liquid can be effectively prevented when the antiglare layer 12 is formed. It does not specifically limit as solvent dry type resin, Generally, 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 resins, polyamide resins. , Cellulose derivatives, silicone resins and rubbers or elastomers.

  The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, from the viewpoint of transparency and weather resistance, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) and the like are preferable.

  The thermosetting resin is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation Examples thereof include resins, silicon resins, polysiloxane resins, and the like.

  In this embodiment, when the frequency distribution of the inclination angle of the surface 10A of the antiglare film 10 with respect to the surface 11A of the light transmissive substrate 11 is obtained every 0.01 degrees, the cumulative percentage of the frequency of the inclination angle is the first. The ratio of the 99th percentile to the 3rd quartile (99th percentile / third quartile) is 3.0 or more and 5.0 or less, so anti-glare is not noticeable. Can be obtained, and also good antiglare property and good blackness can be obtained. That is, since the 99th percentile indicates the maximum value of the tilt angle, and the third quartile is a representative value of the main tilt angle in the tilt angle distribution, the 99th percentile / third quartile. The large is that the main part of the concavo-convex shape on the surface of the antiglare film is biased toward a smaller inclination angle, that is, there are many flat parts on the surface of the antiglare film. In the present embodiment, since the 99th percentile / third quartile is 3.0 or more, the 99th percentile / third quartile is large, and the antiglare film 10 has a surface 10A. There are many flat parts. Since there are many flat portions on the surface 10 </ b> A of the antiglare film 10, the occurrence of glare can be suppressed, so that good glare prevention can be obtained. Further, since there are many flat portions on the surface 10A of the anti-glare film 10, an appropriate specular reflection component can be provided, so that when a moving image is displayed, the shine and brightness of the image increase, and a dynamic feeling is provided. Can be obtained. In addition, it is possible to suppress a decrease in bright room contrast without causing excessive diffusion of outside light, and it is also possible to prevent the image light from becoming stray light, so that a good dark room contrast can be obtained. . On the other hand, if the 99th percentile / third quartile is too large, too many flat portions are present on the surface of the antiglare film, resulting in poor antiglare properties. In the present embodiment, since the 99th percentile / third quartile is 5.0 or less, the surface 10A of the antiglare film 10 does not have too many flat portions, and the reflection is reflected. An anti-glare property that does not matter is obtained. Thereby, while being able to obtain the anti-glare property to such an extent that the reflection is not a concern, it is possible to obtain good glare prevention and good blackness. Note that anti-glare properties that do not bother the viewer (observer) and the background of the viewer are not concerned are, for example, the presence of an observer, but only the outline is blurred. In addition, although the presence of an object in the background of the observer is recognized, it means antiglare properties such that the outline and boundary are unclear. In this way, only the outline of the observer is blurred, and the reflection is less noticeable for the observer.

  According to the present embodiment, since the first inorganic fine particle aggregate 14A has the bent portion 14B having the inner region 14C, as described above, the first inorganic fine particle aggregate 14A is subjected to curing shrinkage. In addition, it can be easily and uniformly crushed. As a result, the first inorganic fine particle aggregate 14A has an action of forming the uneven surface 12A, but the shape of the uneven surface 12A becomes gentler than the amount of cure shrinkage, and the uneven surface 12A is an observer (observer). And anti-glare that does not bother the reflection of the background of the observer, and it is possible to effectively prevent the occurrence of a sudden change part of the inclination angle change rate that causes a dramatic change in brightness. Preventive properties can be obtained. Moreover, since the inclination angle of the unevenness constituting the uneven surface 12A does not increase, excessive diffusion of external light does not occur. Thereby, the fall of bright room contrast can be suppressed. Further, since it is possible to prevent the image light from becoming stray light, a good dark room contrast can be obtained. Furthermore, since it has an appropriate specular reflection component, when a moving image is displayed, the shine and brightness of the image increase, and a dynamic feeling can be obtained. As a result, it is possible to obtain a more black feeling having both excellent contrast and dynamic feeling.

<<< Method for Producing Antiglare Film >>>
The antiglare film 10 can be formed as follows, for example. First, the antiglare layer composition is applied on the light transmissive substrate 11. Examples of the method for applying the antiglare layer composition include known coating methods such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, and die coating.

<< Composition for anti-glare layer >>
The composition for the antiglare layer contains at least the organic fine particles 13, the inorganic fine particles 14, and the photopolymerizable compound, and preferably the organic fine particle aggregate 13A, the first inorganic fine particle aggregate 14A, and the second inorganic fine particle. The fine particle aggregate 14D is included. In addition, you may add the said thermoplastic resin, the said thermosetting resin, a solvent, and a polymerization initiator to the composition for glare-proof layers as needed. Further, the antiglare layer composition includes conventionally known dispersants, surfactants and antistatic agents depending on purposes such as increasing the hardness of the antiglare layer, suppressing cure shrinkage, and controlling the refractive index. , Silane coupling agents, thickeners, anti-coloring agents, colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modification A quality agent, a lubricant, etc. may be added.

<Solvent>
Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketones (acetone, methyl ethyl ketone (MEK), cyclohexanone. , Methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone, etc.), ethers (1,4-dioxane, dioxolane, diisopropyl ether dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic Hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl formate, methyl acetate, ethyl acetate, vinegar) Propyl, butyl acetate, ethyl lactate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide etc.), amides (dimethylformamide, dimethylacetamide etc.), etc. A mixture thereof may be used.

<Polymerization initiator>
The polymerization initiator is a component that is decomposed by light irradiation to generate radicals to initiate or advance polymerization (crosslinking) of the photopolymerizable compound.

  The polymerization initiator is not particularly limited as long as it can release a substance that initiates radical polymerization by light irradiation. The polymerization initiator is not particularly limited, and known ones can be used. Specific examples include, for example, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, thioxanthones, propiophenone. , Benzyls, benzoins, acylphosphine oxides. In addition, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

  As the polymerization initiator, when the binder resin is a resin system having a radically polymerizable unsaturated group, it is preferable to use acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether or the like alone or in combination. .

  The content of the polymerization initiator in the antiglare layer composition is preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound. By setting the content of the polymerization initiator within this range, the hard coat performance can be sufficiently maintained, and curing inhibition can be suppressed.

  Although it does not specifically limit as a content rate (solid content) of the raw material in the composition for glare-proof layers, Usually, 5 to 70 mass% is preferable, and it is more preferable to set it as 25 to 60 mass%. .

  The method for preparing the composition for the antiglare layer is not particularly limited as long as each component can be uniformly mixed. For example, the composition can be performed using a known apparatus such as a paint shaker, a bead mill, a kneader, or a mixer.

  After coating the antiglare layer composition on the light-transmitting substrate 11, it is transported to a heated zone for drying the coating-like antiglare layer composition and is antiglare by various known methods. The layer composition is dried and the solvent is evaporated. Here, by selecting the affinity between the solvent and the solid content, the solvent relative evaporation rate, the solid content concentration, the coating solution temperature, the drying temperature, the drying air velocity, the drying time, the solvent atmosphere concentration in the drying zone, etc. The distribution state of the fine particle aggregate 13A, the first inorganic fine particle aggregate 14A, and the second inorganic fine particle aggregate 14D can be adjusted.

  In particular, a method of adjusting the distribution state of fine particle aggregates by selecting drying conditions is simple and preferable. The specific drying temperature is preferably 30 to 120 ° C., and the drying wind speed is preferably 0.2 to 50 m / s. The drying treatment appropriately adjusted within this range is performed once or a plurality of times to thereby form fine particles. The distribution state of the aggregate can be adjusted to a desired state.

  Thereafter, the coating-like antiglare layer composition is irradiated with light such as ultraviolet rays, and the photopolymerizable compound is polymerized (crosslinked) to cure the antiglare layer composition. Form. Here, as described above, since the first inorganic fine particle aggregate 14A has the bent portion 14B having the inner region 14C, it acts as a solid having a buffering action upon curing shrinkage. Accordingly, the first inorganic fine particle aggregate 14A is easily and uniformly crushed during the curing shrinkage.

  When ultraviolet rays are used as the light for curing the composition for the antiglare layer, ultraviolet rays emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like can be used. Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

<<< Polarizing plate >>>
The antiglare film 10 can be used by being incorporated into a polarizing plate, for example. FIG. 4 is a schematic configuration diagram of a polarizing plate incorporating the antiglare film according to the present embodiment. As shown in FIG. 4, the polarizing plate 20 includes an antiglare film 10, a polarizer 21, and a protective film 22. The polarizer 21 is formed on the surface of the light transmissive substrate 11 opposite to the surface on which the antiglare layer 12 is formed. The protective film 22 is provided on the surface of the polarizer 21 opposite to the surface on which the antiglare film 10 is provided. The protective film 22 may be a retardation film.

  Examples of the polarizer 21 include a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, and an ethylene-vinyl acetate copolymer saponified film that are dyed and stretched with iodine or the like. When laminating the antiglare film 10 and the polarizer 21, it is preferable to saponify the light-transmitting substrate 11 in advance. By performing the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

<<< LCD panel >>>
The antiglare film 10 and the polarizing plate 20 can be used by being incorporated in a liquid crystal panel. FIG. 5 is a schematic configuration diagram of a liquid crystal panel incorporating the antiglare film according to the present embodiment.

  The liquid crystal panel shown in FIG. 5 includes a protective film 31, such as a triacetyl cellulose film (TAC film), a polarizer 32, a retardation film 33, an adhesive, from the light source side (backlight unit side) to the viewer side. The layer 34, the liquid crystal cell 35, the adhesive layer 36, the retardation film 37, the polarizer 21, and the antiglare film 10 are stacked in this order. In the liquid crystal cell 35, a liquid crystal layer, an alignment film, an electrode layer, a color filter, and the like are disposed between two glass substrates.

  Examples of the retardation films 33 and 37 include a triacetyl cellulose film and a cycloolefin polymer film. The retardation film 37 may be the same as the protective film 22. Examples of the adhesive constituting the adhesive layers 34 and 36 include a pressure sensitive adhesive (PSA).

<<< Image display device >>>
The antiglare film 10, the polarizing plate 20, and the liquid crystal panel 30 can be used by being incorporated in an image display device. Examples of the image display device include a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, and electronic paper. Can be mentioned. FIG. 6 is a schematic configuration diagram of a liquid crystal display which is an example of an image display device incorporating the antiglare film according to the present embodiment.

  The image display device 40 shown in FIG. 6 is a liquid crystal display. The image display device 40 includes a backlight unit 41 and a liquid crystal panel 30 including an anti-glare film 10 disposed closer to the viewer than the backlight unit 41. A known backlight unit can be used as the backlight unit 41.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited to these descriptions.

<Preparation of composition for antiglare layer>
First, each component was mix | blended so that it might become a composition shown below, and the composition for glare-proof layers was obtained.
(Anti-glare layer composition 1)
Acrylic-styrene copolymer particles (organic fine particles, average primary particle size 2.0 μm, refractive index 1.52, manufactured by Sekisui Plastics Co., Ltd.): 3 parts by mass Fumed silica (inorganic fine particles, hexamethyldisilazane treatment) , Average primary particle size 50 nm, manufactured by Nippon Aerosil Co., Ltd .: 1 part by mass, pentaerythritol triacrylate (PETA) (product name “PETIA”, manufactured by Daicel Cytec Co., Ltd.): 60 parts by mass, ethoxy modified diacrylate of isocyanuric acid (product) Name “M-215”, manufactured by Toa Gosei Co., Ltd .: 40 parts by mass, polymerization initiator (product name “Irgacure 184”, manufactured by BASF Japan): 5 parts by mass, polyether-modified silicone (product name “TSF4460”, Momentive)・ Performance Materials Co., Ltd.): 0.025 mass parts ・ Toluene: 120 mass parts ・ Methyliso Ethyl ketone (MIBK): 30 parts by weight

(Anti-glare layer composition 2)
Acrylic-styrene copolymer particles (organic fine particles, average primary particle size 2.0 μm, refractive index 1.52, manufactured by Sekisui Plastics Co., Ltd.): 4 parts by mass Fumed silica (inorganic fine particles, hexamethyldisilazane treatment) , Average primary particle size 50 nm, manufactured by Nippon Aerosil Co., Ltd .: 1 part by mass / pentaerythritol tetraacrylate (PETTA) (product name “PETA”, manufactured by Daicel Cytec Co., Ltd.): 60 parts by mass / urethane acrylate (product name “UV1700B”) , Manufactured by Nippon Synthetic Chemical Co., Ltd.): 40 parts by mass, polymerization initiator (product name “Irgacure 184”, manufactured by BASF Japan): 5 parts by mass, polyether-modified silicone (product name “TSF4460”, Momentive Performance Materials) Manufactured by the company): 0.025 parts by mass, toluene: 120 parts by mass, cyclohexanone: 3 Parts by weight

(Anti-glare layer composition 3)
Acrylic-styrene copolymer particles (organic fine particles, average primary particle size 2.0 μm, refractive index 1.52, manufactured by Sekisui Plastics Co., Ltd.): 2 parts by mass Fumed silica (inorganic fine particles, octylsilane treatment, average Primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd .: 2 parts by mass, pentaerythritol tetraacrylate (PETTA) (product name “PETA”, manufactured by Daicel Cytec): 60 parts by mass, urethane acrylate (product name “UV1700B”, Japan) Synthetic Chemical Co., Ltd.): 40 parts by mass, polymerization initiator (product name “Irgacure 184”, manufactured by BASF Japan): 5 parts by mass, polyether-modified silicone (product name “TSF4460”, manufactured by Momentive Performance Materials, Inc.) ): 0.025 parts by mass-Toluene: 105 parts by mass-Isopropyl alcohol: 30 The amount part Cyclohexanone: 15 parts by weight

(Anti-glare layer composition 4)
Acrylic-styrene copolymer particles (organic fine particles, average primary particle size 3.5 μm, refractive index 1.52, manufactured by Sekisui Plastics Co., Ltd.): 4.5 parts by mass Pentaerythritol triacrylate (PETA) (Product name “PETIA” (manufactured by Daicel Cytec): 65 parts by mass • Isocyanuric acid-modified triacrylate (product name “M-313”, manufactured by Toagosei Co., Ltd.): 35 parts by mass • polymerization initiator (product name “Irgacure 184”, BASF Japan Ltd.): 5 parts by mass, polyether-modified silicone (product name “TSF4460”, manufactured by Momentive Performance Materials): 0.025 parts by mass, toluene: 110 parts by mass, cyclohexanone: 50 parts by mass

(Anti-glare layer composition 5)
Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 2.3 μm, manufactured by Fuji Silysia Chemical Ltd.): 2 parts by mass Pentaerythritol triacrylate (PETA) (product name “PETIA” , Manufactured by Daicel Cytec Co., Ltd.): 100 parts by mass, polymerization initiator (product name “Irgacure 184”, manufactured by BASF Japan): 5 parts by mass, polyether-modified silicone (product name “TSF4460”, Momentive Performance Materials) (Made by company): 0.025 mass partToluene: 150 mass partmethyl isobutyl ketone (MIBK): 35 mass part In addition, the said amorphous silica particle was produced by the gel method.

(Anti-glare layer composition 6)
Acrylic-styrene copolymer particles (organic fine particles, average primary particle size 3.0 μm, refractive index 1.52, manufactured by Sekisui Plastics Co., Ltd.): 7 parts by mass Amorphous silica particles (inorganic fine particles, hydrophobic treatment, Average particle diameter (laser diffraction scattering method) 2.7 μm, manufactured by Fuji Silysia Chemical Ltd.): 2 parts by mass / pentaerythritol triacrylate (PETA) (product name “PETIA”, manufactured by Daicel Cytec): 100 parts by mass / polymerization Initiator (Product name “Irgacure 184”, manufactured by BASF Japan): 5 parts by mass. Polyether-modified silicone (Product name “TSF4460”, manufactured by Momentive Performance Materials): 0.025 parts by mass. Toluene: 120 Part by mass / cyclohexanone: 30 parts by mass The amorphous silica particles were prepared by a gel method.

<Example 1>
Triacetyl cellulose substrate thickness 60μm as the light transmitting substrate (Fuji off Lee Lum Inc., TD60UL) was prepared, and on one surface of a triacetyl cellulose substrate, an antiglare layer composition 1 was applied, A coating film was formed. Next, 70 ° C. dry air was passed through the formed coating film at a flow rate of 0.2 m / s for 15 seconds, and then 70 ° C. dry air was passed through for 30 seconds at a flow rate of 10 m / s. By evaporating the solvent in the coating film, the coating film is cured by irradiating ultraviolet rays with an integrated light amount of 100 mJ / cm ² under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). An antiglare layer having a thickness of 4 μm was formed to produce an antiglare film according to Example 1.

<Example 2>
In Example 2, the antiglare layer composition 2 was used in place of the antiglare layer composition 1, and the antiglare layer was cured in the same manner as in Example 1, except that the thickness of the antiglare layer was 3 μm. A dazzling film was prepared.

<Example 3>
In Example 3, an antiglare film was produced in the same manner as in Example 1 except that the antiglare layer composition 3 was used instead of the antiglare layer composition 1.

<Comparative Example 1>
In Comparative Example 1, the antiglare layer composition 4 was used in place of the antiglare layer composition 1, and the antiglare layer was cured in the same manner as in Example 1 except that the thickness of the antiglare layer was 6 μm. A dazzling film was prepared.

<Comparative Example 2>
In Comparative Example 2, the antiglare layer composition 5 was used in place of the antiglare layer composition 1, and the antiglare layer was cured in the same manner as in Example 1 except that the thickness of the antiglare layer during curing was 3 μm. A dazzling film was prepared.

<Comparative Example 3>
In Comparative Example 3, an antiglare layer composition 6 was used in place of the antiglare layer composition 1, and the antiglare layer was cured in the same manner as in Example 1 except that the thickness of the antiglare layer was 3 μm. A dazzling film was prepared.

<Section observation of anti-glare film>
The cross section of the antiglare film obtained in Example 1 and Example 2 above was photographed using the scanning transmission electron microscope (STEM) function of a scanning electron microscope (SEM) (S-4800, manufactured by Hitachi High-Tech), The obtained STEM cross-sectional photograph was observed. FIG. 8 is a cross-sectional photograph of the antiglare film according to Example 1 taken using the scanning transmission electron microscope function of the scanning electron microscope, and FIG. 9 is an enlarged photograph thereof.

  From the photograph in FIG. 7, the presence of organic fine particle aggregates, the presence of inorganic fine particle aggregates, and the presence of inorganic fine particle aggregates at least at the uneven surface of the antiglare layer or in the vicinity thereof, In the inorganic fine particle aggregate existing on the surface of the surface of the antiglare layer or in the vicinity thereof, and being present at the position between the surface of the organic fine particle aggregate and at a position between the organic fine particle aggregates. It was confirmed that the aggregate diameter in the direction perpendicular to the thickness direction was larger than the aggregate diameter in the thickness direction of the antiglare layer.

  Further, as a result of image analysis of the photograph of FIG. 8, the inorganic fine particle aggregates separated from the organic fine particle aggregates and at the positions between the organic fine particle aggregates and the organic fine particle aggregates It was confirmed to have a bend with an inner region filled with.

<Inclination angle>
Attached to a glass plate via a transparent adhesive on the surface opposite to the surface on which the antiglare layer is formed in the triacetylcellulose base material of each antiglare film obtained in Examples and Comparative Examples. Using the white interference microscope (New View 6300, manufactured by Zygo) as a sample, the uneven shape of the surface of the antiglare film was measured under the following conditions, and the inclination angle distribution was calculated from the result by the above-described method. The analysis software used was MicroScope Application 8.3.2 Microscope Application.

[Measurement condition]
Objective lens: 10 times Zoom: 2 times measurement area: 573 μm × 573 μm
Resolution (interval per point): 0.58 μm

[Analysis conditions]
Removed: None
Filter: HighPass
FilterType: GaussSpline
Low wavelength: 300 μm
Remove spikes: on
Spike Height (xRMS): 2.5
Note that Low wavelength corresponds to the cutoff value λc in the roughness parameter.

<Anti-glare properties>
In order to prevent back surface reflection via a transparent adhesive on the surface opposite to the surface on which the antiglare layer is formed in the triacetyl cellulose base material of each antiglare film obtained in Examples and Comparative Examples. A black acrylic plate was used as a sample. By visually observing this sample in a bright room environment, it was evaluated according to the following criteria whether or not 15 subjects were able to obtain an anti-glare property to the extent that the observer and the background of the observer were not concerned. .
◎: More than 10 people answered good ○: 5-9 people answered good ×: Less than 4 people answered good

<Glitter>
In each antiglare film obtained in Examples and Comparative Examples, glare was evaluated as follows. 15 test subjects were visually inspected from various angles from the top and bottom of the light box (white surface light source) with a luminance of 1500 cd / m ² , 140 ppi black matrix glass, and anti-glare film from the bottom, from a distance of about 30 cm. Evaluation was performed. It was determined whether or not the glare was worrisome and was evaluated according to the following criteria.
◎: More than 10 people answered good ○: 5-9 people answered good ×: Less than 4 people answered good

<Blackness>
In each antiglare film obtained in the examples and comparative examples, the blackness was evaluated as follows. The polarizing plate on the outermost surface of the liquid crystal television “KDL-40X2500” manufactured by Sony Corporation was peeled off, and a polarizing plate without surface coating was attached. Subsequently, the anti-glare films according to Examples and Comparative Examples obtained thereon were prepared so that the anti-glare layer side was the outermost surface. The transparent adhesive film for the anti-glare film (total light transmittance of 91% or more, haze 0. 3% or less and a product having a film thickness of 20 to 50 μm, for example, MHM series (manufactured by Niei Engineering Co., Ltd.)) Install this LCD TV in a room with an illuminance of about 1000 Lx, display the DVD “Media Phantom” by Media Factory, and place it about 1.5 to 2.0 meters away from the LCD TV. The black color was evaluated by sensory evaluation by 15 subjects viewing this video. The blackness was determined by whether or not a moving image was displayed and whether the image had a high contrast and the image was shining or shining and felt a dynamic feeling.
The evaluation criteria are as follows.
◎: More than 10 people answered good ○: 5-9 people answered good ×: Less than 4 people answered good

<All haze, internal haze, surface haze measurement>
About each anti-glare film obtained by the said Example and comparative example, total haze, internal haze, and surface haze were measured as follows. First, the total haze value of the antiglare film was measured according to JIS K7136 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory). Thereafter, a triacetyl cellulose base material (manufactured by Fuji Film, TD60UL) was attached to the surface of the antiglare layer via a transparent optical adhesive layer. Thereby, the uneven shape of the uneven surface in the antiglare layer was crushed, and the surface of the antiglare film became flat. In this state, using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory), the haze value was measured according to JIS K7136, and the internal haze value was obtained by subtracting the haze of the adhesive layer itself.
Then, the surface haze value was determined by subtracting the internal haze value from the total haze value.

<Measurement of Sm, θa, and Ra>
Sm, θa, and Ra were measured on the surface of each antiglare film obtained in Examples and Comparative Examples. The definitions of Sm and Ra shall conform to JIS B0601-1994, and θa shall conform to the surface roughness measuring instrument: SE-3400 / manufactured by Kosaka Laboratory Co., Ltd. (revised 1995.07.20).

Specifically, Sm, θa, and Ra were measured under the following measurement conditions using a surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory Ltd.).
1) Surface roughness detector stylus (trade name SE2555N (2μ standard) manufactured by Kosaka Laboratory Ltd.), tip radius of curvature 2μm, apex angle 90 degrees, material diamond 2) Measurement conditions of surface roughness measuring instrument Reference length (roughness curve cut-off value λc): 2.5 mm
Evaluation length (reference length (cutoff value λc) × 5): 12.5 mm
・ Feeding speed of stylus: 0.5mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

<Bend resistance test>
Each anti-glare film obtained in the examples and comparative examples was subjected to a bending resistance test using a bending tester having a mandrel, and the minimum diameter of the mandrel in which no crack was generated is shown in Table 2. The bending resistance test was performed according to JIS K5600-5-1 (1999).

<Abrasion resistance>
In each anti-glare film obtained in Examples and Comparative Examples, 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 at a speed of 100 mm / second. After rubbing 10 times, a black tape was applied to the surface of the triacetylcellulose substrate opposite to the surface on which the antiglare layer was formed, and the presence or absence of scratches was evaluated by visual observation under a three-wavelength fluorescent lamp. The evaluation criteria for the scratch resistance evaluation were as follows.
○: Scratches were not confirmed, or some scratches were confirmed, but there was no practical problem.
X: Many scratches were confirmed.

The results are shown in Tables 1 and 2.

  As shown in Table 1, in Comparative Example 1, although good antiglare property was obtained, glare was inferior. This is presumably because, in Comparative Example 1, the 99th percentile / third quartile was small, and the flat portion was small and glare was likely to occur. In Comparative Example 2, the glare and blackness were good, but the antiglare property was inferior. This is considered to be because in the comparative example 2, since the 99th percentile / third quartile is large, the tilt angle is excessively biased toward the flat side. In Comparative Example 3, the antiglare property was good and the glare was not noticed, but the blackness was low. This is considered to be because, in Comparative Example 3, although the haze was high, glare could be suppressed, but the 99th percentile / third quartile was very small and there was almost no flat part. On the other hand, Examples 1-3 were good in anti-glare property, were not worried about glare, and black feeling was good.

The present invention includes the following inventions.
[1] An antiglare film comprising a light transmissive substrate and an antiglare layer provided on the light transmissive substrate and having an uneven surface,
The antiglare 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 antiglare film with respect to the surface of the light transmissive substrate is determined every 0.01 degrees, the 99th hundredth relative to the third quartile in the cumulative percentage of the frequency of the inclination angle. An antiglare film having a quantile ratio of 3.0 or more and 5.0 or less.
[2] At least some of the organic fine particles are present as an organic fine particle aggregate in which two or more organic fine particles are aggregated, and at least some of the inorganic fine particles are among the plurality of inorganic fine particles. Exists as a first inorganic fine particle aggregate in which three or more of the inorganic fine particles are aggregated, and the first inorganic fine particle aggregate is formed by the continuous inorganic fine particles and is filled with the binder resin. The antiglare film according to [1], including a bent portion having an inner region.
[3] The first inorganic fine particle aggregate is present at least at a position on the surface of the organic fine particle aggregate and at a position apart from the organic fine particle aggregate and between the organic fine particle aggregates. 2].
[4] Among the plurality of inorganic fine particles, some of the inorganic fine particles exist as 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 present at the uneven surface or in the vicinity thereof, and is orthogonal to the thickness direction compared to the aggregate diameter of the second inorganic fine particle aggregate in the thickness direction of the antiglare layer. The antiglare film according to [3], wherein the second inorganic fine particle aggregate has a large aggregate diameter in a direction to be aligned.
[5] The proportion of the first inorganic fine particle aggregates present in the antiglare layer is higher on the light transmissive substrate side of the antiglare layer than on the concave and convex surface side of the antiglare layer. ] The anti-glare film as described in any one of.
[6] When the thickness of the antiglare layer is T and the average particle size of the organic fine particles is R,
0.2 <R / T <0.7
The antiglare film according to [1], which satisfies the relationship:
[7] The antiglare film according to [1], wherein the inorganic fine particles have an average primary particle diameter of 1 nm to 100 nm.
[8] In the cross section along the thickness direction of the antiglare layer, the ratio of the length of the uneven surface other than the region corresponding to the organic fine particles and the inorganic fine particles is 15% or more and 70% or less. The antiglare film according to [1].
[9] The antiglare film according to [1],
A polarizing plate comprising: a polarizing element formed on a surface of the light transmissive substrate of the antiglare film opposite to a surface on which the antiglare layer is formed.
[10] A liquid crystal display panel comprising the antiglare film according to [1] or the polarizing plate according to [9].
[11] An image display device comprising the antiglare film according to [1] or the polarizing plate according to [9].

DESCRIPTION OF SYMBOLS 10 ... Anti-glare film 10A ... Surface 11 ... Light-transmitting base material 12 ... Anti-glare layer 12A ... Uneven surface 13 ... Organic fine particle 13A ... Organic fine particle aggregate 14 ... Inorganic fine particle 14A ... First inorganic fine particle aggregate 14B ... Bending Part 14C ... Inner region 14D ... Second inorganic fine particle aggregate 15 ... Binder resin 20 ... Polarizing plate 21 ... Polarizer 30 ... Liquid crystal panel 40 ... Image display device

Claims (1)

An antiglare film comprising a light transmissive substrate and an antiglare layer provided on the light transmissive substrate and having an uneven surface,
The antiglare 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 antiglare film with respect to the surface of the light transmissive substrate is determined every 0.01 degrees, the 99th hundredth relative to the third quartile in the cumulative percentage of the frequency of the inclination angle. An antiglare film having a quantile ratio of 3.0 or more and 5.0 or less.