JP7368934B2 - Anti-glare film and display device - Google Patents

Description

The present invention relates to an anti-glare film and a display device.

BACKGROUND OF THE INVENTION An anti-glare film having an uneven structure is sometimes installed on the surface of display devices such as televisions, notebook PCs, and desktop PC monitors in order to soften the reflection of lighting and sunlight.

These anti-glare films often have an anti-glare layer on a transparent substrate. The anti-glare layer is often composed of a binder resin and organic particles for imparting an uneven shape to the surface of the anti-glare layer. Further, as in Patent Document 1, organic particles and inorganic particles may be used in combination as particles in the anti-glare layer.

JP2010-113219A (Claim 3, Paragraphs 0024 and 0044) JP 2016-35574 (Claim 1) JP2011-232547A (Claim 1)

In Patent Document 1, the inorganic particles play a role such as improving the hardness of the anti-glare layer. In this way, a predetermined effect can be imparted by using inorganic particles in addition to organic particles. However, when the anti-glare layer contains inorganic particles, there is a problem in that a phenomenon in which minute variations in brightness appear in image light (hereinafter sometimes referred to as "glare") tends to occur.

The reason why glare tends to occur when the anti-glare layer contains inorganic particles is thought to be that the inorganic particles tend to aggregate easily. However, in Patent Document 1, there is no study on suppressing glare when inorganic particles are included in the anti-glare layer, and the inorganic particles are actively aggregated as described in paragraphs 0024 and 0044.

Further, Patent Documents 2 and 3 describe that glare is suppressed by setting the average interval Sm of unevenness, the average inclination angle θa, the arithmetic mean roughness Ra, and the maximum height Rz to specific ranges. However, even when the parameters of Patent Documents 2 and 3 are satisfied, glare frequently occurs.

An object of the present invention is to provide an anti-glare film that provides anti-glare properties and suppresses glare in a system containing organic particles and inorganic particles in an anti-glare layer.

The present invention provides the following anti-glare films and display devices [1] to [2].
[1] An anti-glare layer containing organic particles, inorganic particles and a binder resin is provided on one surface of a transparent substrate, and the average particle diameter of the organic particles is larger than the average particle diameter of the inorganic particles. , and the average local peak spacing S of JIS B0601:1994 with a cutoff value of 0.8 mm of the anti-glare layer _{is 0.8} , and the average local peak spacing of JIS B0601:1994 with a cutoff value of 2.5 mm is S _2.5 . An anti-glare film that satisfies the following formula (1).
S _2.5 / S _0.8 ≦1.30 (1)
[2] The anti-glare film according to [1] above is disposed on a display element so that the surface on the anti-glare layer side faces the opposite side from the display element, and the anti-glare film is placed on the outermost surface. A display device placed in

In the present invention, the term "anti-glare property" refers to a level of anti-glare property that does not cause glare, and does not mean a high level of anti-glare property that completely prevents glare.

The anti-glare film and display device of the present invention can provide anti-glare properties and suppress glare in a system containing organic particles and inorganic particles in the anti-glare layer.

1 is a sectional view showing an embodiment of an anti-glare film of the present invention. FIG. 2 is a cross-sectional view of an anti-glare film of Comparative Example 1. It is a figure explaining the calculation method of average inclination angle (theta)a. It is a figure explaining the measuring method of glare.

Embodiments of the present invention will be described below.
[Anti-glare film]
The anti-glare film of the present invention has an anti-glare layer containing organic particles, inorganic particles and a binder resin on one side of a transparent substrate, and the average particle diameter of the organic particles is the average particle diameter of the inorganic particles. JIS B0601:1994 local peak average spacing S _0.8 that is larger than the particle diameter and has a cutoff value of 0.8 mm for the anti-glare layer, and JIS B0601:1994 local peak average spacing of JIS B0601:1994 that has a cutoff value of 2.5 mm. The spacing S _2.5 satisfies the relationship of formula (1) below.
S _2.5 / S _0.8 ≦1.30 (1)

FIG. 1 is a sectional view showing an embodiment of the anti-glare film of the present invention.
The anti-glare film 100 in FIG. 1 has an anti-glare layer 2 on a transparent substrate 1, which includes organic particles 21, inorganic particles, and a binder resin. Note that in FIG. 1, inorganic particles and binder resin are not shown.
Note that a layer (not shown) may be formed between the transparent base material 1 and the anti-glare layer 2 or on the surface of the transparent base material 1 opposite to the anti-glare layer 2, as long as the features of the present invention are not impaired. good.
Moreover, in this embodiment, it is preferable that no other layer is provided on the anti-glare layer 2, and that the anti-glare layer is located on the outermost surface.

<Transparent base material>
The transparent base material preferably has light transmittance, smoothness, heat resistance, and excellent mechanical strength. Such transparent substrates include polyester, triacetylcellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal. , polyetherketone, polymethyl methacrylate, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP). The transparent base material may be made by laminating two or more plastic films together.
Among the above, polyesters (polyethylene terephthalate, polyethylene naphthalate, etc.) that have been subjected to stretching processing, particularly biaxial stretching processing, are preferred from the viewpoint of mechanical strength and dimensional stability. Further, polyester is suitable because it has low permeability to solvents and monomers and can easily form a surface shape that satisfies the above formula (1).

The thickness of the transparent substrate is preferably 5 to 300 μm, more preferably 20 to 200 μm, and even more preferably 30 to 120 μm.
When it is desired to make the anti-glare film thin, the preferable upper limit of the thickness of the transparent base material is 60 μm, and the more preferable upper limit is 50 μm. Further, when the transparent base material is a low moisture permeable base material such as polyester, COP, or acrylic, the preferable upper limit of the thickness of the transparent base material for thinning is 40 μm, and the more preferable upper limit is 20 μm. Even in the case of a large screen, it is preferable that the upper limit of the thickness of the transparent base material is within the above-mentioned range, since distortion can be made less likely to occur. The thickness of the transparent substrate can be measured using a Digimatic Standard Outside Micrometer (manufactured by Mitutoyo, product number "MDC-25SX"). The thickness of the transparent base material may be as long as the average value measured at any 10 points is the above value, and the variation in thickness is preferably within the range of ±8% of the average value, and within the range of ±4% of the average value. It is more preferable that it is within the range of ±3% of the average value (if the average value of the thicknesses is 50 μm, it is preferable that each thickness falls within the range of 46 to 54 μm; It is preferable that each thickness falls within the range of 48 to 52 μm, and more preferably that each thickness falls within the range of 48.5 to 51.5 μm).
The surface of the transparent base material may be subjected to physical treatment such as corona discharge treatment or chemical treatment, or an easily adhesive layer may be formed in order to improve adhesiveness.

<Anti-glare layer>
One surface of the transparent base material has an antiglare layer containing organic particles, inorganic particles, and a binder resin.
In this embodiment, from the viewpoint of thinning and manufacturing efficiency, it is preferable that no other layer is provided on the anti-glare layer and the anti-glare layer is located on the outermost surface.
In addition, when the anti-glare layer has a thin functional layer such as a low reflection layer or an antifouling layer with a thickness of several nm or more and less than 500 nm, the surface shape of the outermost surface on the anti-glare layer side is determined by the formula ( 1) etc. is preferably satisfied. A thin functional layer is preferable because it does not significantly change the surface shape of the anti-glare layer. The thin film functional layer can be formed by sputtering, coating, etc., and may be formed by laminating a plurality of thin films such as a multilayer antireflection layer.

Inorganic particles tend to aggregate in the anti-glare layer, and in particular, the smaller the particle size, the more likely they are to aggregate. It is thought that glare is caused by aggregation of inorganic particles in the anti-glare layer. The glare caused by agglomeration of inorganic particles will be explained with reference to FIGS. 1 and 2.
FIG. 1 is a sectional view showing an embodiment of an anti-glare film of the present invention, and FIG. 2 is a sectional view of an anti-glare film of Comparative Example 1. In the anti-glare film 10 of FIG. 1, irregularities are formed on the surface of the anti-glare layer 2 mainly by organic particles 21. On the other hand, in the anti-glare film 10 of FIG. 2, irregularities are formed on the surface of the anti-glare layer 2 not only in the areas where the organic particles 21 are present but also in the areas where the organic particles 21 are not present. In FIG. 2, the unevenness formed in the area where the organic particles 21 are not present has a steeper shape than the unevenness caused by the organic particles. This steep unevenness is thought to be caused by agglomeration of inorganic particles, and is thought to be the cause of glare.
Incidentally, glare can be prevented by, for example, bonding the surface of the anti-glare film on which the anti-glare layer is not formed and a glass plate via a transparent adhesive, and then bonding the surface of the black matrix on the side on which the matrix is not formed with the glass plate. An evaluation sample is prepared by fixing the plate with water, and when a white surface light source is irradiated from the side of the evaluation sample on which the black matrix is fixed, evaluation can be performed from the anti-glare layer side. The transparent adhesive for bonding the anti-glare film and the glass plate is preferably an optically transparent adhesive (OCA) having a thickness of 20 to 30 μm, a total light transmittance of 90% or more, and a haze of 0.6% or less. As the optically transparent adhesive (OCA), the product name "Panaclean PD-S1" manufactured by Panac Co., Ltd. used in the examples can be mentioned.

In this embodiment, the anti-glare layer has an average local peak spacing S of JIS B0601:1994 of 0.8 with a cutoff value _{of 0.8 mm} , and an average local peak spacing S of JIS B0601:1994 of JIS B0601:1994 with a cutoff value of 2.5 mm _{. 5} satisfies the relationship of formula (1) below, thereby suppressing glare.
S _2.5 / S _0.8 ≦1.30 (1)
The technical significance of equation (1) will be explained below.

First, the average spacing S of local peaks is calculated by extracting a reference length from the roughness curve in the direction of the average line, finding the length of the average line corresponding to the distance between adjacent local peaks, and It is defined as "an average value."
A typical roughness curve is a combination of irregularities with various periods. For example, irregularities caused by organic particles with a large particle size tend to have a long period, and irregularities caused by inorganic particles with a small particle size tend to have a short period. In addition, the unevenness caused by aggregated inorganic particles tends to have a different period because the size and shape of the aggregates are non-uniform. In other words, the average local peak spacing S is calculated from a roughness curve that is a combination of irregularities of various periods.
Further, the cutoff value is an index indicating the degree to which unevenness with a long period is excluded from the roughness curve, and the smaller the cutoff value is, the greater the degree to which unevenness with a long period is excluded. Therefore, the average local peak spacing S _0.8 with a cutoff value of 0.8 mm is a value that excludes unevenness with a long period, whereas the average local peak spacing S _2.5 with a cutoff value of 2.5 mm is a value that excludes unevenness with a long period. can be said to be a numerical value that includes irregularities with a long period. In other words, in S _0.8 and S _2.5 , the average local peak spacing S is calculated based on roughness curves with different degrees of mixing of periods of irregularities.
When the degree of coexistence of the periods of unevenness in the roughness curve is large, the unevenness with a short period may be canceled out by the unevenness with a long period. For example, if a part where the height of irregularities with a long period continues to increase overlaps an irregularity with a short period, the component where the height of the irregularities with a short period decreases is replaced by the component where the height of the irregularities with a long period increases. It may be canceled. In this case, the average local peak spacing S for some of the irregularities with a short period is not counted. Therefore, the greater the degree of mixing of the periods of irregularities in the roughness curve, the greater the rate of change in the average local peak spacing S due to the difference in cutoff values.
In a system containing organic particles and inorganic particles in the anti-glare layer, the greater the proportion of agglomerated inorganic particles, the greater the degree of coexistence of periods of irregularities in the roughness curve.
Therefore, the above formula (1) on the condition that S _2.5 /S _0.8 is 1.30 or less indicates that the rate of aggregation of inorganic particles is small, and further indicates that glare can be suppressed. ing.
The reason why 0.8 mm and 2.5 mm were adopted as the cut-off values is that the average distance between local peaks is This is for comparison.

In the above formula (1), S _2.5 /S _0.8 is preferably 1.25 or less, more preferably 1.20 or less, and even more preferably 1.18 or less.
Although the lower limit of S _2.5 /S _0.8 is not particularly limited, it is preferably 1.05 or more, and more preferably 1.10 or more.
In this specification, the numerical values related to the above formula (1) and other surface shapes, and optical properties (total light transmittance, haze, image clarity) are expressed as 14, excluding the minimum and maximum values of the measured values at 16 locations. Means the average value of measured values at a location.
In this specification, the 16 measurement points are the intersection points when a line is drawn that divides the area inside the margin into 5 equal parts in the vertical and horizontal directions, using a 1 cm area from the outer edge of the measurement sample as a margin. It is preferable to center the measurement on 16 locations. For example, if the measurement sample is a rectangle, a 1 cm area from the outer edge of the rectangle is set as a margin, and the area inside the margin is divided into 5 equal parts vertically and horizontally, and measurements are taken at 16 points at the intersection of dotted lines. , it is preferable to calculate the parameters using their average values. Note that when the measurement sample has a shape other than a quadrilateral, such as a circle, ellipse, triangle, or pentagon, it is preferable to draw a quadrilateral inscribed in these shapes and perform measurements at 16 locations using the above method with respect to the quadrilateral.

Note that when another layer is formed on the general-purpose anti-glare layer, irregularities with a short period are reduced, making it easier to satisfy the above formula (1). However, forming another layer on top of the anti-glare layer complicates the process, increases cost, increases total thickness, and reduces resolution.
This embodiment is useful in that it can satisfy the above formula (1) without forming any other layer on the anti-glare layer.
When the anti-glare layer has a thin functional layer such as a low-reflection layer or an antifouling layer with a thickness of several nm or more and less than 500 nm, the surface shape of the outermost surface on the anti-glare layer side satisfies the above formula (1), etc. It is preferable to satisfy the following.

Further, in the present embodiment, it is preferable that S _0.8 satisfy the relationship of formula (2) below.
50μm≦ _S0.8 (2)

By setting S _0.8 to 50 μm or more, glare can be further suppressed. In the above formula (2), S _0.8 is preferably 55 μm or more, more preferably 60 μm or more.
When S _0.8 exceeds 0.12 mm (120 μm), which is the resolution limit of the human eye, the smoothness of the image decreases and the image appears grainy. Therefore, S _0.8 is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 75 μm or less.

Furthermore, in this embodiment, it is preferable that the arithmetic mean roughness Ra of JIS B0601:1994 with a cutoff value of 0.8 mm of the anti-glare layer satisfies the relationship of formula (3) below.
0.03μm≦Ra≦0.20μm (3)

By setting Ra to 0.03 μm or more, antiglare properties can be easily imparted. Further, by setting Ra to 0.20 μm or less, it is possible to easily suppress a decrease in contrast.
In the above formula (3), Ra is more preferably 0.04 μm or more and 0.15 μm or less, and even more preferably 0.04 μm or more and 0.10 μm or less.

Furthermore, in the present embodiment, it is preferable that the ten-point average roughness Rz of JIS B0601:1994 with a cutoff value of 0.8 mm of the anti-glare layer satisfies the relationship of formula (4) below.
0.10μm≦Rz≦0.40μm (4)

By setting Rz to 0.10 μm or more, unevenness is prevented from becoming excessively uniform, and scratches and defects in the anti-glare layer can be made less noticeable. Moreover, by setting Rz to 0.40 μm or less, glare can be easily suppressed, and a decrease in contrast can be easily suppressed.
In the above formula (4), Rz is more preferably 0.12 μm or more and 0.35 μm or less, and even more preferably 0.15 μm or more and 0.30 μm or less.

Further, in the present embodiment, it is preferable that the average inclination angle θa of the anti-glare layer with a cutoff value of 0.8 mm satisfies the relationship of formula (5) below.
0.15 degrees≦θa≦0.50 degrees (5)

By setting θa to 0.15 degrees or more, antiglare properties can be easily imparted. Further, by setting θa to 0.50 degrees or less, it is possible to easily suppress a decrease in contrast.
In the above formula (5), θa is more preferably 0.20 degrees or more and 0.40 degrees or less, and even more preferably 0.25 degrees or more and 0.35 degrees or less.

The average inclination angle θa is, for example, a value defined in the instruction manual (revised July 20, 1995) of the surface roughness measuring instrument (product name: SE-3400) manufactured by Kosaka Institute, and is shown in FIG. As shown in , the arctangent θa of the sum of the heights of the convex portions (h ₁ +h ₂ +h ₃ +...+h _n ) existing in the reference length L is equal to tan ^-1 {(h ₁ +h ₂ +h ₃ +・...+h _n )/L}. In this specification, the reference length is divided into 1500 parts to obtain height data of 1500 points, and the average inclination angle θa is calculated based on the height data of the 1500 points.
Note that θa can be measured using the same definition and calculation method as described above with models that comply with the JIS 1994 measurement standard, such as SE600, SE600K31, SE700, and SE4000 manufactured by Kosaka Institute. .
Other parameters (S, Ra, Rz) can be similarly measured if the model complies with the JIS1994 measurement standard.

<Organic particles>
The organic particles have the role of providing anti-glare properties by making the surface of the anti-glare layer uneven. In order to effectively fulfill this role, in this embodiment, the average particle diameter of the organic particles is made larger than the average particle diameter of the inorganic particles.

Examples of organic particles include particles made of polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine resin, polyester resin, etc. Can be mentioned. Among these, polystyrene is preferred. Polystyrene is highly lipophilic and has properties significantly different from highly hydrophilic inorganic particles, so it is suitable for making it difficult to crowd inorganic particles around polystyrene. Moreover, since the lipophilicity of polystyrene is extremely high, even if the inorganic particles have been subjected to hydrophobization treatment, it is possible to easily make it difficult for the inorganic particles to crowd around the polystyrene.
The shape of the organic particles is preferably spherical from the viewpoint of suppressing glare and suppressing a decrease in contrast.

The organic particles preferably have an average particle diameter of 0.5 to 3.0 μm, more preferably 0.8 to 2.5 μm, and even more preferably 1.0 to 2.0 μm.
By setting the average particle diameter of the organic particles to 0.5 μm or more, it is possible to easily impart anti-glare properties to the extent that reflections are not an issue. Further, by setting the average particle diameter of the organic particles to 3.0 μm or less, the unevenness on the surface of the anti-glare layer can be smoothed, making it easier to suppress glare. The reason why antiglare properties can be imparted even when the average particle diameter of the organic particles is made small as described above is mainly due to the sedimentation suppressing action of the inorganic particles, which will be described later.

The organic particles preferably have a variation coefficient of particle distribution of 25% or less, more preferably 20% or less, from the viewpoint of smoothing the unevenness on the surface of the anti-glare layer and easily suppressing glare. % or less is more preferable.

The ratio between the average particle diameter of the organic particles and the thickness of the anti-glare layer (average particle diameter of organic particles/thickness of the anti-glare layer) is 0.15 to 0.70 from the viewpoint of the balance between anti-glare properties and glare suppression. It is preferably 0.25 to 0.60, even more preferably 0.30 to 0.55.
By setting the above ratio to 0.1 or more, it is possible to easily provide anti-glare properties to the extent that reflections are not a problem. Further, by setting the above ratio to 0.7 or less, unevenness on the surface of the anti-glare layer can be smoothed and glare can be easily suppressed.

The average particle diameter of organic particles can be calculated by the following operations (x1) to (x3).
(x1) A transmission observation image of the anti-glare film of the present invention is captured using an optical microscope. The magnification is preferably 500 to 2000 times.
(x2) Extract ten arbitrary particles from the observed image and calculate the particle diameter of each particle. The particle diameter is measured as the distance between the two straight lines in a combination such that when the cross section of the particle is sandwiched between two arbitrary parallel straight lines, the distance between the two straight lines becomes the maximum.
(x3) Perform the same operation five times on the observed image of the same sample on another screen, and use the value obtained from the number average of the particle diameters of a total of 50 particles as the average particle diameter of the particles.

The content of the organic particles is preferably 0.4 to 4.0 parts by mass, more preferably 0.5 to 3.5 parts by mass, and 0.6 parts by mass based on 100 parts by mass of the binder resin. More preferably, the amount is 3.0 parts by mass.
When the content of organic particles is significantly increased, anti-glare properties are improved, external haze and internal haze are increased, and glare tends to become less noticeable. However, if the content of organic particles is increased too much, the contrast and resolution of the display element tend to decrease.
By setting the content of organic particles within the above range, it is possible to easily achieve a good balance between anti-glare properties, suppression of glare, suppression of reduction in contrast, and suppression of reduction in resolution.

<Inorganic particles>
The inorganic particles exhibit functions such as suppressing agglomeration of organic particles and suppressing sedimentation of organic particles in the coating solution for forming an anti-glare layer. Since the inorganic particles exhibit this effect, even if the average particle diameter of the organic particles is within the above-mentioned range, anti-glare properties can be easily exhibited.
In order to effectively fulfill these roles, in this embodiment, the average particle diameter of the inorganic particles is made smaller than the average particle diameter of the organic particles.

Examples of inorganic particles include inorganic oxide particles such as silica, alumina, zirconia, and titania. The shape of the inorganic particles may be spherical or amorphous.

Among inorganic particles, silica is preferred from the viewpoint of transparency.
Further, among silicas, fumed silica is suitable because it is easy to obtain a particle size suitable for obtaining internal diffusion by Rayleigh scattering, and it is easy to perform hydrophobization treatment described below.
Fumed silica is amorphous silica having a particle size of 200 nm or less produced by a dry method, and can be obtained by reacting a volatile compound containing silicon in a gas phase. Specifically, examples include those produced by hydrolyzing silicon compounds such as silicon tetrachloride (SiCl ₄ ) in a flame of oxygen and hydrogen.

When using inorganic oxide particles such as silica as the inorganic particles, the inorganic oxide fine particles are preferably amorphous. This is because when the inorganic oxide particles are crystalline, the Lewis acid salts of the inorganic oxide particles become strong due to lattice defects contained in their crystal structure, making it impossible to control excessive aggregation of the inorganic oxide particles. This is because there is a risk that it will disappear.

The inorganic particles are preferably inorganic particles whose surfaces have been subjected to hydrophobization treatment. By hydrophobicizing the surface of the inorganic particles, aggregation of the inorganic particles in the anti-glare layer forming coating solution can be suppressed, and the relationship of the above formula (1) can be easily satisfied.
Note that inorganic particles whose surfaces have been subjected to hydrophobization treatment have a reaction product between a functional group on the surface of the inorganic particles and a surface treatment agent on the surface of the inorganic particles. Examples of functional groups on the surface of inorganic particles include silanol groups of silica particles.

Surface treatment agents include trimethylsilyl chloride, dimethyldichlorosilane, trimethylsilyltrifluoromethanesulfonate, chloromethyltrimethylsilane, hexamethyldisilazane, triethylsilane, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilane, t-butyl Examples include one or more selected from dimethylsilyl chloride, octylsilane, hexadecylsilane, allyltrimethylsilane, trimethylvinylsilane, aminosilane, methacrylsilane, polydimethylsiloxane, and the like.

The surface treatment agent preferably has an alkyl group with a large number of carbon atoms in the molecule, from the viewpoint of increasing the degree of hydrophobization and further suppressing glare. Specifically, the surface treatment agent preferably has an alkyl group having 5 or more carbon atoms in the molecule, and more preferably has an alkyl group having 6 or more carbon atoms in the molecule. The alkyl group may be linear or branched, but is preferably linear.
Note that if the number of carbon atoms in the alkyl group in the molecule is too large, the rate at which the functional groups on the surface of the inorganic particles can react with the surface treatment agent decreases due to the bulkiness of the molecule of the surface treatment agent. Therefore, the number of carbon atoms in the alkyl group of the surface treatment agent is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less.

Furthermore, if only inorganic particles that have been hydrophobized with the same surface treatment agent are used, they may aggregate because they have common properties. For this reason, it is preferable to use inorganic particles that have been hydrophobically treated with different surface treatment agents. For example, inorganic particles (inorganic particles A) that have been hydrophobized with a surface treatment agent having an alkyl group with a large number of carbon atoms in the molecule, and inorganic particles (inorganic particles A) that have been hydrophobized with a surface treatment agent that has an alkyl group with a small number of carbon atoms in the molecule. It is preferable to use together with inorganic particles (inorganic particles B). In addition, inorganic particles (inorganic particles B) that have been hydrophobized with a surface treatment agent that has an alkyl group with a small number of carbon atoms in their molecules have moderate hydrophilicity, so the presence of inorganic particles B improves the dispersibility of organic particles. It can also be made better.
The number of carbon atoms in the alkyl group of the surface treatment agent of the inorganic particles A is preferably 4 to 20, more preferably 4 to 16, even more preferably 6 to 12.
The number of carbon atoms in the alkyl group of the surface treatment agent of the inorganic particles B is preferably 3 or less, more preferably 2 or less, and even more preferably 1.
The alkyl groups of inorganic particles A and inorganic particles B may be linear or branched, but are preferably linear.

When the anti-glare layer contains an anti-static agent selected from ion conductive anti-static agents and conductive polymers, which will be described later, the inorganic particles may be attracted by the anti-static agent and tend to aggregate. Even in such a case, as described above, it is preferable to use inorganic particles that have been hydrophobically treated with different surface treatment agents in combination, since aggregation of the inorganic particles can be easily suppressed.

The inorganic particles preferably have an average primary particle diameter (particle diameter of primary particles or agglomerated particle mixture) of 3 to 400 nm, more preferably 5 to 350 nm, and even more preferably 8 to 300 nm.
By setting the average primary particle diameter of the inorganic particles within the above range and suppressing agglomeration of the inorganic particles, it is possible to make it difficult to form steep irregularities caused by the inorganic particles, and to reduce the particle diameter (primary particles or particles of agglomerated particle mixture). Internal diffusion due to Rayleigh scattering can be caused in a region with a small diameter). Therefore, glare can be easily suppressed.

The average primary particle diameter of the inorganic particles (particle diameter of primary particles or agglomerated particle mixture) can be calculated by the following operations (y1) to (y3).
(y1) A cross section of the anti-glare film of the present invention is imaged using TEM or STEM. It is preferable that the accelerating voltage of TEM or STEM is 10 kV to 30 kV, and the magnification is 50,000 to 300,000 times.
(y2) Extract ten arbitrary particles from the observed image and calculate the particle diameter of each particle. The particle diameter is measured as the distance between the two straight lines in a combination such that when the cross section of the particle is sandwiched between two arbitrary parallel straight lines, the distance between the two straight lines becomes the maximum.
(y3) Perform the same operation five times on the observed image of the same sample on another screen, and use the value obtained from the number average of the particle diameters of a total of 50 particles as the average particle diameter of the particles.

The content of the inorganic particles is preferably 0.2 to 7.0 parts by mass, more preferably 0.3 to 5.0 parts by mass, and 0.4 parts by mass based on 100 parts by mass of the binder resin. More preferably, the amount is 3.0 parts by mass.
By setting the content of inorganic particles within the above-mentioned range, aggregation of organic particles can be easily suppressed while providing an appropriate internal haze. Therefore, glare can be easily suppressed. Furthermore, by setting the content of inorganic particles within the above range, sedimentation of organic particles in the anti-glare layer forming coating liquid can be suppressed. Therefore, the amount of organic particles added necessary to obtain a predetermined antiglare property can be reduced, and a decrease in resolution can be suppressed.
From the same viewpoint, [content of inorganic particles/content of organic particles] is preferably 0.5 to 5.0, more preferably 0.6 to 3.0, and 0.7 More preferably, it is 2.0 to 2.0.

<Binder resin>
Examples of the binder resin include thermoplastic resins, cured products of curable resin compositions, and mixtures thereof. Among these, from the viewpoint of scratch resistance, cured products of curable resin compositions are preferred. Furthermore, examples of the curable resin composition include thermosetting resin compositions and ionizing radiation-curable resin compositions, with ionizing radiation-curable resin compositions being preferred from the viewpoint of scratch resistance. That is, it is optimal that the binder resin contains a cured product of an ionizing radiation-curable resin composition.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

The ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as "ionizing radiation-curable compound"). Examples of the ionizing radiation-curable functional group include ethylenically unsaturated bond groups such as (meth)acryloyl group, vinyl group, and allyl group, as well as epoxy group and oxetanyl group.
As the ionizing radiation curable resin, a compound having an ethylenically unsaturated bond group is preferable, a compound having two or more ethylenically unsaturated bond groups is more preferable, and among them, a compound having two or more ethylenically unsaturated bond groups, More preferred are polyfunctional (meth)acrylate compounds. As the polyfunctional (meth)acrylate compound, both monomers and oligomers can be used.
Note that ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quantum that can polymerize or crosslink molecules, and ultraviolet rays (UV) or electron beams (EB) are usually used, but other Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

Among polyfunctional (meth)acrylate compounds, examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, and 1,6-hexane. Examples include diol diacrylate.
Examples of trifunctional or higher-functional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples include pentaerythritol tetra(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate, and the like.
Furthermore, the above (meth)acrylate monomers may have a part of their molecular skeleton modified, such as ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. can also be used.

Examples of the polyfunctional (meth)acrylate oligomer include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.
Urethane (meth)acrylates are obtained, for example, by reacting polyhydric alcohols and organic diisocyanates with hydroxy (meth)acrylates.
In addition, preferred epoxy (meth)acrylates include (meth)acrylates obtained by reacting trifunctional or higher functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with (meth)acrylic acid; (meth)acrylate obtained by reacting the above aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. with a polybasic acid and (meth)acrylic acid, and a difunctional or more aromatic epoxy resin, It is a (meth)acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin, etc., a phenol, and (meth)acrylic acid.
The above-mentioned ionizing radiation-curable resins can be used alone or in combination of two or more.

When the ionizing radiation curable resin is an ultraviolet curable resin, the antiglare layer forming coating solution preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
As the photopolymerization initiator, one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, α-aminoalkylphenone, thioxanthone, etc. Can be mentioned.
In addition, the photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and accelerate the curing speed, and includes, for example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more types may be selected.

The content of the binder resin is preferably 90.0 to 99.0% by mass, and 92.0 to 98% by mass based on the total solid content of the antiglare layer, from the viewpoint of the balance between coating film strength and antiglare property. It is more preferably .5% by mass, and even more preferably from 95.0 to 98.0% by mass.

<Leveling agent>
The anti-glare layer preferably contains a leveling agent from the viewpoint of making the surface of the anti-glare layer appropriately smooth and making it easier to satisfy the above formula (1). Examples of the leveling agent include fluorine-based leveling agents, silicone-based leveling agents, and fluorosilicone copolymer-based leveling agents. Among these, silicone leveling agents are preferred, and non-reactive silicone leveling agents are more preferred. In the present invention, since the aggregation of inorganic particles is suppressed, it is difficult to obtain abrasion resistance based on aggregation of inorganic particles, but by imparting slipperiness with a silicone leveling agent, it is easy to improve the abrasion resistance. can. In particular, since a non-reactive silicone leveling agent tends to collect on the surface, the scratch resistance can be improved more easily.
The content of the leveling agent is preferably 0.01 to 0.30% by mass, more preferably 0.02 to 0.10% by mass, based on the total solid content of the anti-glare layer.

<Antistatic agent>
The anti-glare layer is electrically charged (charged when the protective film is peeled off when a protective film is laminated on the surface of the anti-glare layer, and when the separator is peeled off when the adhesive layer and separator are laminated on the back side of the transparent base material). It is preferable to contain an antistatic agent in order to suppress electrification during manufacturing, electrification generated during other manufacturing processes, processing processes, etc.).

As the antistatic agent, one or more selected from electron conductive antistatic agents such as ATO, ion conductive antistatic agents, conductive polymers, etc. can be used. Among these, from the viewpoint of transparency, ion conductive antistatic agents and conductive polymers are preferred, and conductive polymers with less humidity dependence are more preferred. Note that the conductive polymer also functions as a binder resin.
Note that the ion conductive antistatic agent and the conductive polymer may attract inorganic particles and increase the degree of aggregation of the inorganic particles. In other words, it is difficult to simultaneously satisfy anti-glare properties, glare suppression, and antistatic properties in a single anti-glare layer. Therefore, when containing an ion-conductive antistatic agent and/or a conductive polymer as an antistatic agent in the anti-glare layer, as mentioned above, it is necessary to use a surface treatment agent with a large number of carbon atoms in the alkyl group and a surface treatment agent with a large number of carbon atoms in the alkyl group. It is preferable to use inorganic particles that have been surface treated in combination with a surface treatment agent having a small number of carbon atoms.

Examples of the ion conductive antistatic agent include cationic, anionic, and amphoteric ion conductive compounds. Examples of these ion conductive antistatic agents include general-purpose surfactants, quaternary ammonium salts, lithium salts, ionic liquids, and the like.

The ion-conducting antistatic agent is preferably one that is reactive with the curable resin composition, and more preferably one that is reactive with the ionizing radiation-curable compound.
Examples of the ion-conducting antistatic agent having reactivity with the ionizing radiation-curable compound include ion-conducting antistatic agents having an ionizing radiation-curable functional group. Examples of the ionizing radiation-curable functional group include ethylenically unsaturated bond groups such as a (meth)acryloyl group, a vinyl group, and an allyl group, an epoxy group, and an oxetanyl group. Among these, a (meth)acryloyl group is preferred.

Examples of the conductive polymer include a π-conjugated conductive polymer doped with a polyanion.
Examples of the π-conjugated conductive polymer include chain conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyacetylene. Examples of the polyanion include polystyrene sulfonic acid, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyacrylic acid ethyl sulfonic acid, and polymethacrylic carboxylic acid. Among these, a conductive polymer (PEDOT/PSS) using polythiophene as a π-conjugated conductive polymer and polystyrene sulfonic acid as a polyanion, which has excellent conductivity, is preferable.

From the viewpoint of electrical conductivity, the content of the polyanion is preferably in the range of 0.1 to 10 moles per mole of the π-conjugated conductive polymer.

The content of the antistatic agent cannot be determined unconditionally because it varies depending on the target surface resistivity and the type of antistatic agent used, but it should be 0.40% by mass or less in the total solid content of the antiglare layer. It is preferably 0.30% by mass or less, more preferably 0.20% by mass or less. Note that the content of the antistatic agent is preferably 0.10% by mass or more based on the total solid content of the antiglare layer.

<Other additives>
The anti-glare layer contains refractive index modifiers such as high refractive index particles and low refractive index particles, antifouling agents, ultraviolet absorbers, light stabilizers, antioxidants, viscosity modifiers, and other additives such as thermal polymerization initiators. May contain.

The thickness of the anti-glare layer is not particularly limited, but is preferably 1.0 to 10.0 μm, more preferably 2.0 to 8.0 μm, and even more preferably 3.0 to 5.0 μm.
The thickness of the anti-glare layer can be calculated, for example, by measuring the thickness at 20 locations from a cross-sectional image taken using a scanning transmission electron microscope (STEM) and calculating the average value of the values at 20 locations. It is preferable that the accelerating voltage of STEM is 10 kV to 30 kV, and the magnification of STEM is 1000 to 7000 times.
The variation in the thickness of the anti-glare layer is preferably within ±15%, more preferably within ±10%, even more preferably within ±7%, and even more preferably within ±7% with respect to the average film thickness. It is even more preferable that it is within the range.

The anti-glare layer can be formed by applying an anti-glare layer forming coating solution containing organic particles, inorganic particles and a binder resin, drying, and curing if necessary. The anti-glare layer forming coating solution preferably contains a solvent in order to improve coating suitability.

<Solvent>
Examples of solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic group hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (ethanol, butanol, isopropyl alcohol, cyclohexanol, etc.) , cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), and mixtures thereof may be used.

If it takes time to dry the solvent, the inorganic particles will aggregate, making it difficult to satisfy the above formula (1). Therefore, the solvent preferably contains 60% by mass or more of the total solvent, and 70% by mass of a solvent with an evaporation rate (relative evaporation rate when the evaporation rate of n-butyl acetate is 100) of 150 or more. It is more preferable to include the above. Examples of solvents with a relative evaporation rate of 160 or higher include methyl isobutyl ketone (MIBK). The relative evaporation rate of MIBK is 160.
Moreover, from the viewpoint of easily adjusting the surface resistivity of the surface of the anti-glare layer to the range described below, it is preferable that an alcohol-based solvent is included as the solvent. The alcoholic solvent preferably accounts for 5 to 40% by weight, more preferably 20 to 30% by weight of the total solvent.

When applying and drying the anti-glare layer forming coating solution containing a solvent, the drying temperature should be 50 to 90°C and the drying wind speed should be 5 to 30 m/min from the viewpoint of speeding up drying and suppressing agglomeration of inorganic particles. It is preferable.

<Physical properties of anti-glare film>
The anti-glare film preferably has a total light transmittance of 80% or more according to JIS K7361-1:1997, more preferably 85% or more, and even more preferably 90% or more.
The light incident surface when measuring total light transmittance, haze, and image clarity is the surface opposite to the anti-glare layer. Furthermore, when measuring the total light transmittance, haze, and image clarity, a location free from defects such as wrinkles, dirt, and foreign matter is selected and measured.

The anti-glare film preferably has a JIS K7136:2000 haze of 1.0 to 7.0%, more preferably 2.0 to 5.0%, from the viewpoint of anti-glare properties, resolution and contrast balance. The content is more preferably 2.5% to 4.0%.

Furthermore, when haze is divided into internal haze and surface haze, the ratio of internal haze to surface haze [internal haze/surface haze] is preferably 1.5 to 7.0, and 1.7 to 5. It is more preferably .0, and even more preferably from 2.0 to 4.5.
The internal haze is mainly effective for suppressing glare, and the surface haze is mainly effective for anti-glare properties. Therefore, by setting the ratio of internal haze to surface haze within the above range, it is possible to achieve a good balance between glare suppression and anti-glare properties.
Internal haze and surface haze can be calculated by the method described in Examples.

The anti-glare film preferably has a transmitted image clarity C _0.125 of 65.0% or more, with an optical comb width of 0.125 mm measured in accordance with JIS K7374:2007, and 70.0%. % or more, more preferably 75.0% or more.
In addition, the anti-glare film has a transmission image clarity C _2.0 measured in accordance with JIS K7374:2007 at an optical comb width of 2.0 mm using an image clarity measuring device, and the above C _0.125 , which is C _2.0 /C _0.125 . It is preferable that the relationship of ≦1.30 is satisfied, and it is more preferable that the relationship of C _2.0 /C _0.125 ≦1.25 is satisfied. By satisfying the relationship C _2.0 /C _0.125 ≦1.30, glare can be easily suppressed. Note that a small C _2.0 /C _0.125 means that there is little variation in the tilt angle on the surface of the anti-glare layer, and it is thought that this small variation in the tilt angle contributes to suppressing glare.

The surface resistivity of the anti-glare layer surface is preferably 1.0×10 ¹³ Ω/□ or less, more preferably 1.0×10 ¹² Ω/□ or less. The measurement of surface resistivity is preferably carried out with an applied voltage of 500V. Further, the measurement environment is preferably a temperature of 25±4° C. and a humidity of 50±10%.
The surface resistivity of the anti-glare layer surface was determined by preparing samples cut out from areas free of defects such as wrinkles, dirt, and foreign matter, and measuring 8 samples excluding the minimum and maximum values of the measured values of 10 samples. Means the average value of measured values.

The anti-glare film may be in the form of a sheet, or may be in the form of a roll obtained by winding up a long sheet into a roll. Further, the size of the leaves is not particularly limited, but generally the size is about 2 to 500 inches diagonally. The width and length of the roll are not particularly limited, but generally the width is about 500 to 3000 mm and the length is about 500 to 5000 m.
Further, the shape of each leaf is not particularly limited, and may be, for example, a polygon (triangle, quadrangle, pentagon, etc.), a circle, or a random amorphous shape.

[Display device]
The display device of the present invention has the above-mentioned anti-glare film of the present invention disposed on the display element so that the surface on the anti-glare layer side faces the side opposite to the display element, and the anti-glare film is placed on the outermost surface. It is something that is arranged.

Examples of display elements include liquid crystal display elements, EL display elements (organic EL display elements, inorganic EL display elements), plasma display elements, and further, LED display elements such as micro LED display elements. These display elements may have a touch panel function inside the display element.
Examples of the liquid crystal display method of the liquid crystal display element include an IPS method, a VA method, a multi-domain method, an OCB method, an STN method, and a TSTN method.

Moreover, the display device of this embodiment may be a display device with a touch panel that has a touch panel between a display element and an anti-glare film. In this case, an anti-glare film may be placed on the outermost surface of a display device with a touch panel, and the anti-glare film may be placed so that the surface of the anti-glare layer faces the opposite side of the display element.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way. Note that "parts" and "%" are based on mass unless otherwise specified.

1. Measurement and evaluation of physical properties of anti-glare films The physical properties of anti-glare films of Examples and Comparative Examples were measured and evaluated as follows. The results are shown in Table 1.

1-1. Measurement of Surface Shape The anti-glare films of Examples and Comparative Examples were cut into 10 cm square pieces. The cutting locations were selected from random locations after visually confirming that there were no abnormalities such as dust or scratches. The cut anti-glare film was attached to a black board (manufactured by Kuraray Co., Ltd., product name: Como Glass, product number: 10 cm long x 10 cm wide) via an optically transparent adhesive sheet (product name: Panaclean PD-S1) manufactured by Panac Co., Ltd. A sample was prepared by bonding DFA502K (thickness: 2.0 mm).
Using a surface roughness measuring instrument (model number: SE-3400/manufactured by Kosaka Laboratory Co., Ltd.), set the sample so that it is fixed and in close contact with the measurement stage, and then perform the following measurements under the following measurement conditions. Regarding the items, the surface shape of the anti-glare layer of each sample was measured. Based on the description in the main text of the specification, measurements were performed at 16 locations for each sample, and the average value of the 14 locations excluding the minimum and maximum values was calculated as S _2.5 /S _0.8 of each example and comparative example. S _2.5 , S _0.8 , Ra and Rz. The atmosphere at the time of measurement was a temperature of 23° C.±5° C. and a humidity of 40 to 65%. Furthermore, before starting the measurement, each sample was left in an atmosphere of 23° C.±5° C. and humidity of 40 to 65% for 10 minutes or more. The results are shown in Table 1.
<Measurement conditions>
[Stylus of surface roughness detection part]
Product name: SE2555N manufactured by Kosaka Institute (tip radius of curvature: 2 μm, apex angle: 90 degrees, material: diamond)
[Measurement conditions of surface roughness measuring instrument]
・JIS1994
・Feeding speed of stylus: 0.5mm/s
・Vertical magnification: 50,000 times ・Horizontal magnification: 5 times ・Skid: Used (contact with measurement surface)
・Cutoff filter type: Gaussian ・Dynamic range: Wide ・Overscale: Error mode ・Dead band level: 10%
・tp/PC curve: Normal ・Sampling mode: c=1500
・Operation mode: Normal ・Leveling: All data ・Evaluation length: 5 times the cutoff ・Preliminary length: 0.5 times the cutoff ・Detector: PUDJ2US (Lever horizontal height 7.85mm, length 30mm )
<Measurement items>
・JIS B0601:1994 average local peak spacing S _2.5 with a cutoff value of 2.5 mm
・JIS B0601:1994 average local peak spacing S _0.8 with a cutoff value of 0.8 mm
- Arithmetic mean roughness Ra of JIS B0601:1994 with cutoff value 0.8 mm
・JIS B0601:1994 ten-point average roughness Rz with cutoff value 0.8 mm
・Average inclination angle θa with cutoff value 0.8 mm

1-2. Haze and total light transmittance The antiglare films of Examples and Comparative Examples were cut into 10 cm square pieces. The cutting locations were selected from random locations after visually confirming that there were no abnormalities such as dust or scratches. Using a haze meter (HM-150, manufactured by Murakami Color Research Institute), the JIS K7136:2000 haze (total haze) and the JIS K7361-1:1997 total light transmittance of each sample were measured. Based on the description in the main text of the specification, measurements were performed at 16 locations for each sample, and the average value of the 14 locations excluding the minimum and maximum values was taken as the haze and total light transmittance of each example and comparative example. The atmosphere at the time of measurement was a temperature of 23° C.±5° C. and a humidity of 40 to 65%. Furthermore, before starting the measurement, each sample was left in an atmosphere of 23° C.±5° C. and humidity of 40 to 65% for 10 minutes or more. The light incident surface was placed on the transparent substrate side to prevent fingerprints and wrinkles.
Furthermore, the internal haze and surface haze were calculated by the following means.
Attach an 80 μm thick triacetyl cellulose film (manufactured by Fujifilm, TD80UL) to the surface of the anti-glare film using a transparent adhesive, avoiding wrinkles, fingerprints, dirt, dust, and air as much as possible. By this, the uneven shape was flattened and the haze was measured in a state where the influence of haze due to the surface shape was eliminated, and the internal haze was determined. Then, the surface haze was determined by subtracting the internal haze value from the overall haze value.

1-3. Transmission image clarity Using an image clarity measuring device manufactured by Suga Test Instruments Co., Ltd. (product name: ICM-1T), the 0. Two types of transmission image definition (C _2.0 , C _0.125 ) were measured through optical combs having widths of 125 mm and 2 mm. Based on the description in the main text of the specification, measurements were performed at 16 locations for each sample, and the average value of the 14 locations excluding the minimum and maximum values was taken as the transmission image clarity of each example and comparative example. The atmosphere at the time of measurement was a temperature of 23° C.±5° C. and a humidity of 40 to 65%. Furthermore, before starting the measurement, each sample was left in an atmosphere of 23° C.±5° C. and humidity of 40 to 65% for 10 minutes or more. The light incident surface was the side on which the anti-glare layer was formed, and was installed to prevent fingerprints and wrinkles.

1-4. Surface Resistivity The surface resistivity (Ω/□) of the surface of the anti-glare layer of the anti-glare film was measured based on JIS K6911:1995. The measuring device used was Mitsubishi Chemical's product name "Hirester UP MCP-HT450" and the probe was Mitsubishi Chemical's product name "URS Probe MCP-HTP14," and the measurement was performed at an applied voltage of 500 V. was carried out. The measurement environment was a temperature of 25±4° C. and a humidity of 50±10%. During measurement, the sample was placed on a flat surface so that it did not float. The measurement was performed on 10 samples cut into 5 cm squares, and the average value of the 8 samples excluding the minimum and maximum values was taken as the surface resistivity of each example and comparative example. If the surface resistivity is 1.0×10 ¹¹ Ω/□ or less, it is considered to be an acceptable level. In addition, those whose surface resistivity exceeded 1.0×10 ¹⁴ Ω/□ were indicated as “-” as not measurable.

1-5. Anti-glare property A black acrylic plate is pasted to the transparent base material side of the anti-glare film via a transparent adhesive to avoid stains such as wrinkles, fingerprints, dirt, and air as much as possible, and a sample for anti-glare property evaluation is made. was created. The sample was visually inspected in a bright room environment and evaluated by 15 subjects based on the following criteria to determine whether it had enough anti-glare properties that the observer and the background of the observer would not be bothered. .
A: 10 or more people answered good B: 5 to 9 people answered good C: 4 or less people answered good

1-6. Glare The side of the anti-glare film on which the anti-glare layer is not formed and the 2.9 mm thick glass plate are coated with a transparent adhesive (25 μm thick) to prevent stains such as wrinkles and fingerprints, dust and air smudges as much as possible. , Panac PD-S1). Next, the surface of the grid-like black matrix (glass thickness: 0.7 mm, black matrix pixel density equivalent to 200 ppi) on which no matrix is formed is opposite to the surface of the glass plate on which the anti-glare film is pasted. The side surfaces were fixed with water to prepare a sample for glare evaluation. The amount of water dropped may be approximately 0.1 mL per 10 cm square black matrix.
A white surface light source 500 (manufactured by HAKUBA, LIGHTBOX, average brightness 1000 cd/m ² ) is irradiated with light from the side on which the black matrix of the evaluation sample is fixed in a dark room to generate pseudo-glare, thereby forming an anti-glare layer. Photographs were taken from the 2nd side with a CCD camera 600 (KP-M1, C-mount adapter, close-up ring: PK-11A Nikon, camera lens: 50 mm, F1.4s NIKKOR) (see Figure 4). The distance between the white surface light source 500 and the glass plate 400 was 70 mm, the distance between the CCD camera 600 and the anti-glare layer 2 was 220 mm, and the focus of the CCD camera was adjusted to match the anti-glare film.
Using image processing software (ImagePro Plus ver. 6.2; manufactured by Media Cybernetics), images taken with a CCD camera were transferred to an image board (Pro-Series Capture Kit Spectrim Pro For Windows 2000 & XP P ro Version 5.1) through The images were imported into a personal computer and image data consisting of a collection of luminances of each pixel was obtained. In addition, the following analysis was performed using the same software. When importing, set the brightness to 32, contrast to 40, hue to 32, and saturation to 32 among the imported screen data displayed in Menu → Import → Video/Digital, and set other items to default settings. I obeyed.
First, an evaluation location of 200×160 pixels (10 mm×8 mm) was selected from the captured image data, and the evaluation location was converted to 16-bit gray scale.
Next, I selected the low-pass filter from the emphasis tab of the filter command and applied the filter under the conditions of "3 x 3, number of times 3, strength 10". This removed components derived from the black matrix pattern.
Next, flattening was selected and shading correction was performed under the conditions of "background: dark, object width 10".
Next, contrast enhancement was performed using a contrast enhancement command with "contrast: 96, brightness: 48". The obtained image data was converted to 8-bit gray scale (256 gradation gray scale). In other words, the obtained image data was converted into 256 gradations of luminance (no unit because it is a converted value) with a maximum value of 255 and a minimum value of 0. For the image data thus obtained, the standard deviation of the brightness of each pixel was calculated for an area of 150 x 110 pixels (7.5 mm x 5.5 mm), and the value was taken as the glare value. Note that the brightness of the light source was adjusted so that the average brightness in this area was 120 to 140. A glare value of 20.0 or less can be said to be a passing level.

2. Production of anti-glare film [Example 1]
Anti-glare layer forming coating solution 1 with the following formulation was applied onto a 50 μm thick polyester film (manufactured by Toyobo Co., Ltd., trade name: Cosmoshine A4300), dried at 70°C for 30 seconds at a wind speed of 5 m/s, and then exposed to ultraviolet rays. It was irradiated and cured to form an anti-glare layer to obtain an anti-glare film. The thickness of the anti-glare layer was 4.0 μm.

<Ink 1 for forming anti-glare layer>
・Pentaerythritol polyacrylate 70.0 parts by mass ・Urethane acrylate UV1700B (manufactured by Nippon Gosei Kagaku Co., Ltd.) 30.0 parts by mass ・Organic particles (polystyrene particles) 0.8 parts (average particle diameter: 1.3 μm, coefficient of variation: 12 %)
・Inorganic particles (fumed silica) 1.5 parts (shape: amorphous, average primary particle diameter: 12 nm, manufactured by Nippon Aerosil Co., Ltd.)
(Mixture of silica surface-treated with octylsilane (silica A) and silica surface-treated with methylsilane (silica B). Mass ratio of silica A: silica B = 3:1)
- Antistatic agent (PEDOT/PSS) 0.5 parts by mass (organic solvent dispersed poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid, CLEVIOS P, manufactured by H.C. Stark)
・Polymerization initiator 6.0 parts by mass (Irgacure 184, manufactured by BASF Japan)
・Reactive silicone leveling agent 0.1 part by mass (UV3500, manufactured by Bikkemie)
・MIBK 150.0 parts by mass ・n-BuOH 50.0 parts by mass

[Example 2]
The organic particles in the anti-glare layer forming ink 1 of Example 1 were changed to the following ones, the blending amount was changed to 2.0 parts, the blending amount of the inorganic particles was changed to 2.0 parts, and pentaerythritol poly An antiglare film was obtained in the same manner as in Example 1, except that the amount of acrylate was changed to 60 parts and the amount of antistatic agent was changed to 40 parts.
<Organic particles of Example 2>
Polystyrene particles with an average particle diameter of 2.0 μm. Coefficient of variation 12%.

[Example 3]
The organic particles in the anti-glare layer forming ink 1 of Example 1 were changed to the following ones, the blending amount was changed to 2.5 parts, the blending amount of the inorganic particles was changed to 2.0 parts, and pentaerythritol poly An antiglare film was obtained in the same manner as in Example 1, except that the amount of acrylate was changed to 60 parts and the amount of antistatic agent was changed to 40 parts.
<Organic particles of Example 3>
Polystyrene particles with an average particle diameter of 2.0 μm. Coefficient of variation 12%.

[Comparative example 1]
An anti-glare film was prepared in the same manner as in Example 1, except that the amount of organic particles in Ink 1 for forming an anti-glare layer in Example 1 was changed to 3.0 parts, and the amount of inorganic particles was changed to 5.0 parts. I got it.

From the results in Table 1, it can be confirmed that the anti-glare films of Examples 1 and 2 have anti-glare properties and can suppress glare.
In addition, when the inorganic particles (silica) in the example were changed to silica whose surface was amino-treated, S _2.5 /S _0.8 exceeded 1.30 and the desired surface shape could not be obtained. was there.

1: Transparent base material 21: Organic particles 2: Anti-glare layer 100: Anti-glare film 200: Transparent adhesive layer 300: Black matrix 400: Glass plate 500: White surface light source 600: CCD camera 700: Post 800: Horizontal stand

Claims (10)

An anti-glare layer containing organic particles, inorganic particles, and a binder resin is provided on one side of the transparent substrate, and the anti-glare layer further includes an ion-conductive antistatic agent and a conductive polymer. the inorganic particles have an average primary particle diameter of 3 to 400 nm, the organic particles have an average particle diameter larger than the inorganic particles, and the anti-glare The average local peak spacing S 0.8 of JIS B0601:1994 with a layer cutoff value of _{0.8 mm} and the average local peak spacing S 2.5 of JIS B0601:1994 with a cutoff value of _2.5 mm are calculated using the following formula ( An anti-glare film that satisfies the relationship 1).
S _2.5 / S _0.8 ≦1.30 (1) The anti-glare film according to claim 1, wherein the S _0.8 satisfies the following formula (2).
50μm≦ _S0.8 (2) The anti-glare film according to claim 1 or 2, wherein the organic particles have an average particle diameter of 0.5 to 3.0 μm. The anti-glare film according to any one of claims 1 to 3 , containing 0.4 to 4.0 parts by mass of the organic particles based on 100 parts by mass of the binder resin. The anti-glare film according to any one of claims 1 to 4 , containing 0.2 to 7.0 parts by mass of the inorganic particles based on 100 parts by mass of the binder resin. The anti-glare film according to any one of claims 1 to 5 , wherein [content of the inorganic particles/content of the organic particles] is 0.5 to 5.0. The inorganic particles include inorganic particles A that have been made hydrophobic with a surface treatment agent having an alkyl group having 4 to 20 carbon atoms in the molecule, and hydrophobic particles A that have been treated with a surface treatment agent that has an alkyl group having 3 or less carbon atoms in the molecule. The anti-glare film according to any one of claims 1 to 6 , comprising chemically treated inorganic particles B. The anti-glare film according to any one of claims 1 to 7 , wherein the inorganic particles are silica. The anti-glare film according to any one of claims 1 to 8 , which has a haze of 1.0 to 7.0% according to JIS K7136:2000. The anti-glare film according to any one of claims 1 to 9 is disposed on a display element so that the surface on the anti-glare layer side faces the opposite side from the display element, and the anti-glare film A display device in which a is placed on the top surface.