CN112241033B - Anti-glare film, polarizing plate, liquid crystal panel, and image display device - Google Patents

Abstract

The invention relates to an anti-glare film, a polarizing plate, a liquid crystal panel, and an image display device, and aims to provide an anti-glare film, a polarizing plate, a liquid crystal panel, and an image display device, which can obtain anti-glare properties without causing glare and can obtain good anti-dazzling properties and good black color. According to one embodiment of the present invention, an anti-glare film (10) is provided, which comprises a light-transmitting substrate (11) and an anti-glare layer (12) provided on the light-transmitting substrate (11), wherein the surface of the anti-glare layer (12) is an uneven surface (12A); the antiglare layer (12) comprises a binder resin (16) and 2 or more first inorganic particulate aggregates (13), wherein the first inorganic particulate aggregates (13) are present in the binder resin (16) and are formed by aggregating 3 or more inorganic particulate; the first inorganic particle aggregate (13) comprises a bent portion (13A), wherein the bent portion (13A) is formed by the connection of the inorganic particles and has an inner region (13B) filled with a binder resin (16).

Description

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

The present application is a divisional application, which is filed under the name of "antiglare film, polarizing plate, liquid crystal panel, and image display device" in chinese national application No. 201410379744.9, application date 8/4/2014.

[ technical field ] A

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

[ background of the invention ]

In general, an anti-glare film having irregularities on the surface or an anti-reflection film having an anti-reflection layer on the outermost surface is provided on the image display surface of an image display device such as a Liquid Crystal Display (LCD), a cathode ray tube display (CRT), a Plasma Display (PDP), an electroluminescence display (ELD), or a Field Emission Display (FED) in order to suppress reflection of an observer and the background of the observer (for example, see japanese patent application laid-open publication No. 2011-215515).

The antiglare film mainly comprises a light-transmitting substrate and an antiglare layer having an uneven surface provided on the light-transmitting substrate. The antiglare film scatters external light on the uneven surface of the antiglare layer, and suppresses reflection of an observer, a background of the observer, and the like.

The antiglare film has an antiglare property to an extent that the image is inconspicuous. However, when an antiglare film having an antiglare property to prevent reflection of light is provided on the surface of the image display device in addition to an antiglare film having substantially no reflection of light, screen image light may be scattered by the uneven surface of the antiglare layer, and so-called glare may occur. In order to prevent the occurrence of glare, it has been proposed to increase the haze, and when the haze is increased, the occurrence of glare is prevented, but the contrast may be decreased.

In addition, in the antiglare film, there is a demand for a "black color" which is a performance of having both an excellent contrast and a sense of excitement when a moving image is displayed (for example, when a scene of youth in a blue sky is taken as an example, hair displayed in an image is black having a dry feeling, eye drops are black having a moist feeling, and skin looks vigorous with luster unique to youth).

[ summary of the invention ]

[ problem to be solved by the invention ]

The present invention has been made to solve the above problems. That is, it is an object of the present invention to provide an antiglare film, a polarizing plate, a liquid crystal panel, and an image display device, which can provide antiglare properties to a degree that does not cause glare, and can provide good glare prevention and good black color.

[ means for solving the problems ] to solve the problems

According to one aspect of the present invention, there is provided an antiglare film comprising a light-transmitting substrate and an antiglare layer provided on the light-transmitting substrate, wherein: the surface of the anti-dazzle layer is a concave-convex surface; the antiglare layer contains a binder resin and 2 or more (on the bark) of first inorganic particulate aggregates which are present in the binder resin and are formed by aggregating 3 or more inorganic particulate; the first inorganic microparticle aggregates include bent portions formed by connecting the inorganic microparticles and having inner regions filled with the binder resin.

According to another aspect of the present invention, there is provided an antiglare film comprising a light-transmitting substrate and an antiglare layer provided on the light-transmitting substrate and having a surface having irregularities, wherein: the above-mentioned antiglare layer contains 2 or more (on the letter) organic fine particles, 2 or more (on the letter) inorganic fine particles, and a binder resin; the arithmetic mean value of the sharpness of the transmitted image of the antiglare film measured by using 0.125mm wide, 0.25mm wide, 0.5mm wide, 1.0mm wide, and 2.0mm wide combs is 70% to 95%, and the absolute value of the difference between the arithmetic mean value and the sharpness of the transmitted image measured by using each comb is 10% or less.

According to another aspect of the present invention, there is provided an antiglare film comprising a light-transmitting substrate and an antiglare layer provided on the light-transmitting substrate and having an uneven surface, wherein: the antiglare layer comprises 2 or more organic fine particles, 2 or more 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 obtained at intervals of 0.01 degrees, the ratio of the 99 th percentile to the 3 rd quartile in the cumulative percentage of the frequencies of the inclination angles is 3.0 to 5.0.

According to another aspect of the present invention, there is provided a polarizing plate comprising the antiglare film and a polarizing element (polarizer) formed on a surface of the light-transmitting substrate of the antiglare film opposite to a surface on which the antiglare layer is formed.

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

According to another aspect of the present invention, there is provided an image display device including the antiglare film or the polarizing plate.

[ Effect of the invention ]

According to an embodiment of the present invention, an antiglare film, and another embodiment of a polarizing plate, a liquid crystal panel, and an image display device, the antiglare layer includes a binder resin and 2 or more first inorganic fine particle aggregates in which 3 or more inorganic fine particles are aggregated and exist in the binder resin; the first inorganic fine particle aggregates include bent portions formed by the connection of the inorganic fine particles and having inner regions filled with the binder resin, and thus can provide antiglare properties to a degree that does not cause discomfort to a person, and can provide good glare resistance and a good black color.

According to the antiglare film of another aspect of the present invention, and the polarizing plate, the liquid crystal panel and the image display device of another aspect of the present invention, an arithmetic average value of the sharpness of the transmitted image of the antiglare film measured using 0.125mm wide, 0.25mm wide, 0.5mm wide, 1.0mm wide and 2.0mm wide combs is 70% or more and 95% or less, and a difference between the arithmetic average value and the sharpness of the transmitted image measured using each comb is 10% or less, whereby it is possible to obtain antiglare properties of a degree that does not cause human interference, and to obtain good glare resistance and good black feeling.

According to the antiglare film of another aspect of the present invention, and the polarizing plate, the liquid crystal panel, and the image display device of another aspect of the present invention, 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 obtained at every 0.01 degrees, the ratio of the 99 th percentile to the 3 rd quartile in the cumulative percentage of the frequencies of the inclination angles is 3.0 or more and 5.0 or less, and thus, antiglare properties of a degree that does not cause glare can be obtained, and good antiglare properties and good black color feeling can be obtained.

[ description of the drawings ]

Fig. 1 is a schematic configuration diagram of an antiglare film of a first embodiment.

Fig. 2 is an enlarged view of a portion of fig. 1.

Fig. 3 is a schematic configuration diagram of a polarizing plate of the first embodiment.

Fig. 4 is a schematic configuration diagram of a liquid crystal panel of the first embodiment.

Fig. 5 is a schematic configuration diagram of a liquid crystal display panel as an example of the image display device of the first embodiment.

Fig. 6 is a schematic configuration diagram of another antiglare film of the second embodiment.

Fig. 7 is an enlarged view of a portion of fig. 6.

Fig. 8 is a schematic configuration diagram of an antiglare film of a third embodiment.

Fig. 9 is an enlarged view of a portion of fig. 8.

Fig. 10 is an enlarged view of a portion of fig. 9.

Fig. 11 is a schematic view showing a mode of measuring the transmitted image clarity of the antiglare film of the third embodiment by a transmitted image clarity measuring device.

Fig. 12 is a schematic configuration diagram of a polarizing plate of the third embodiment.

Fig. 13 is a schematic configuration diagram of a liquid crystal panel of the third embodiment.

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

Fig. 15 is a schematic configuration diagram of an antiglare film of the fourth embodiment.

Fig. 16 is an enlarged view of a portion of fig. 15.

Fig. 17 is an enlarged view of a portion of fig. 16.

Fig. 18 is a schematic configuration diagram of a polarizing plate of the fourth embodiment.

Fig. 19 is a schematic configuration diagram of a liquid crystal panel of the fourth embodiment.

Fig. 20 is a schematic configuration diagram of a liquid crystal display panel as an example of an image display device according to a fourth embodiment.

FIG. 21 is a photograph of a cross-section of the antiglare film of example A1, the cross-section taken using a scanning transmission electron microscope function of a scanning electron microscope.

Fig. 22 is a cross-sectional photograph of the antiglare film of example a1, taken at a higher magnification than fig. 21, using the scanning transmission electron microscope function of a scanning electron microscope.

FIG. 23 is a photograph of a cross-section of the antiglare film of example A2, the cross-section taken using the scanning transmission electron microscope function of a scanning electron microscope.

Fig. 24 is a cross-sectional photograph of the antiglare film of example a2, taken at a higher magnification than in fig. 23, using the scanning transmission electron microscope function of a scanning electron microscope.

[ detailed description ] embodiments

[ first embodiment ]

The antiglare film and the like according to the first embodiment of the present invention will be described below with reference to the drawings. First, in the present specification, terms such as "film", "sheet", "plate", and the like are not distinguishable from each other only by the difference in designation. Thus, for example, "membrane" is a concept that also includes components that can also be referred to as sheets or plates. As a specific example, the "antiglare film" also includes a member called an "antiglare sheet" or an "antiglare plate". In the present specification, the "weight average molecular weight" refers to a value obtained by dissolving a compound in a solvent such as Tetrahydrofuran (THF) and converting the compound into polystyrene by a conventionally known Gel Permeation Chromatography (GPC) method.

< < anti-glare film > >)

Fig. 1 is a schematic configuration diagram of an antiglare film of the present embodiment, and fig. 2 is a partial enlarged view of fig. 1. As shown in fig. 1, the antiglare film 10 includes at least a light-transmitting substrate 11 and an antiglare layer 12 provided on the light-transmitting substrate 11.

< light-transmitting substrate >

The light-transmitting substrate 11 is not particularly limited as long as it has light-transmitting properties, and examples thereof include a cellulose acylate substrate, a cycloolefin polymer substrate, a polycarbonate substrate, an acrylate polymer substrate, a polyester substrate, and a glass substrate.

Examples of the cellulose acylate substrate include cellulose triacetate substrates and cellulose diacetate substrates. Examples of the cycloolefin polymer substrate include substrates formed of polymers of norbornene monomers, monocyclic cycloolefin monomers, and the like.

Examples of the polycarbonate substrate include aromatic polycarbonate substrates based on bisphenols (e.g., bisphenol a) and aliphatic polycarbonate substrates such as diethylene glycol bis allyl carbonate.

Examples of the acrylate polymer base include a polymethyl (meth) acrylate base, a polyethyl (meth) acrylate base, and a methyl (meth) acrylate-butyl (meth) acrylate copolymer base.

Examples of the polyester substrate include substrates containing at least one polyester selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as a component.

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

Among them, a cellulose acylate substrate is preferable because of excellent retardation (retadation) and easy adhesion to a polarizing element, and further, a cellulose triacetate substrate (TAC substrate) is preferable among the cellulose acylate substrates. The cellulose triacetate base material is a light-transmitting base material which can make the average light transmittance more than 50% in the visible light range of 380 nm-780 nm. The cellulose triacetate base material preferably has an average light transmittance of 70% or more, more preferably 85% or more.

The cellulose triacetate base material may be, in addition to pure cellulose triacetate, a material such as cellulose acetate propionate or cellulose acetate butyrate, which also contains a component other than acetic acid as a fatty acid that forms an ester with cellulose. If necessary, other cellulose lower fatty acid esters such as diacetyl cellulose, and various additives such as a plasticizer, an ultraviolet absorber, and a slipping agent may be added to these triacetylcelluloses.

A cycloolefin polymer base material is preferable from the viewpoint of excellent retardation and heat resistance; in addition, a polyester substrate is preferable from the viewpoint of mechanical properties and heat resistance.

The thickness of the light-transmitting substrate 11 is not particularly limited, and may be 5 μm or more and 1000 μm or less; from the viewpoint of handling properties and the like, the lower limit of the thickness of the light-transmissive substrate 11 is preferably 15 μm or more, and more preferably 25 μm or more. From the viewpoint of making the film thinner, the upper limit of the thickness of the light-transmissive substrate 11 is preferably 80 μm or less.

< anti-glare layer >)

The antiglare layer 12 is a layer exhibiting antiglare properties. The antiglare layer 12 can exert other functions as well as antiglare properties. Specifically, the antiglare layer 12 may be a layer that exhibits functions such as hard coat property, antireflection property, antistatic property, and antifouling property while exhibiting antiglare property.

When the antiglare layer 12 is a layer exhibiting hard coatability in addition to antiglare properties, the antiglare layer 12 has a hardness of "H" or more in a pencil hardness test (4.9N load) prescribed in JIS K5600-5-4 (1999).

The surface of the antiglare layer 12 is an uneven surface 12A. In the present specification, the "front surface of the antiglare layer" refers to a surface of the antiglare layer opposite to the surface on the light-transmitting substrate side (the back surface of the antiglare layer). In the present embodiment, since a functional layer such as a 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 as shown in fig. 1. The "functional layer" in the present specification means a layer intended to exert a certain function in the antiglare film, and specifically includes, for example, a layer for exerting a function such as antireflection property, antistatic property, or antifouling property. The functional layer may be a single layer or a stack of 2 or more layers.

The antiglare layer 12 shown in fig. 1 includes 2 or more first inorganic fine particle aggregates 13 formed by aggregating 3 or more inorganic fine particles, 2 or more second inorganic fine particle aggregates 14 formed by aggregating 2 or more inorganic fine particles, 2 or more organic fine particle aggregates 15 formed by aggregating 2 or more organic fine particles, and a binder resin 16. The antiglare layer 12 may not contain the second inorganic fine particle aggregates 14 and the organic fine particle aggregates 15.

In the antiglare layer 12, the ratio of the length of the region other than the region corresponding to the first inorganic fine particle aggregates 13, the second inorganic fine particle aggregates 14, and the organic fine particle aggregates 15 in the uneven surface 12A of the antiglare layer 12 is preferably 15% to 70% in a cross section along the thickness direction of the antiglare layer 12 (the direction of the normal to the light-transmissive substrate 11). When the ratio is 15% or more, the antiglare film generates a proper positive transmittance (or positive reflectance) component, and can secure the gloss, brilliance, and contrast of an image; further, by setting the ratio to 70% or less, excessive regular reflection does not occur, and thus the antiglare property can be ensured. The lower limit of the ratio is preferably 20% or more, and the upper limit of the ratio is preferably 60% or less.

The above-mentioned "length of the region other than the regions corresponding to the first inorganic particulate aggregates, the second inorganic particulate aggregates, and the organic particulate aggregates" means the length (linear distance) of the region other than the region of the uneven surface overlapping with the first inorganic particulate aggregates, the second inorganic particulate aggregates, and the organic particulate aggregates when viewed from the thickness direction of the antiglare layer in a cross section along the thickness direction of the antiglare layer. The regions other than the regions corresponding to the first inorganic fine particle aggregates, the second inorganic fine particle aggregates, and the organic fine particle aggregates are regions where no diffusion element contributing to internal diffusion and/or surface diffusion is present, and the screen image light transmitted through the regions is formed only by a component in the normal transmission direction, and the external light is similarly formed only by a normal reflection component. On the other hand, the regions corresponding to the first inorganic fine particle aggregates, the second inorganic fine particle aggregates, and the organic fine particle aggregates are regions having diffusion elements contributing to internal diffusion and/or surface diffusion, and the screen image light transmitted through the regions contains a diffusion component (component diffused when passing through the antiglare film), and the external light similarly has a diffuse reflection component (component diffused when the external light is reflected on the surface of the antiglare film). For example, in the case of fig. 2, the length of the region other than the regions corresponding to the first inorganic fine particle aggregates 13, the second inorganic fine particle aggregates 14, and the organic fine particle aggregates 15 is L ₁ ～L ₄ . And, the ratio of the lengthThe values obtained from image measurements with a cross-sectional electron microscope (TEM, STEM) using image processing software.

In the antiglare layer 12, when the inclination angle of the uneven surface 12A with respect to the surface of the light-transmissive substrate 11 is measured at 0.1 degree intervals in a cross section along the thickness direction of the antiglare layer 12, the ratio of the 99 th percentile to the 3 rd quartile (99 th percentile/3 rd quartile) in the cumulative percentage of the frequencies of the inclination angles is preferably 4.0 or more and less than 5.0. By setting the ratio to 4.0 or more, the inclination angle change rate is not excessively increased, and glare can be prevented; further, by making the ratio smaller than 5.0, the ratio of the portion having an excessive inclination angle in the uneven surface 12A can be controlled, and thus the decrease in contrast can be suppressed.

When the antiglare layer 12 has hard coat properties, the thickness of the antiglare layer 12 is preferably 2.0 μm or more and 7.0 μm or less. When the thickness of the antiglare layer 12 is within this range, a desired hardness can be obtained. Further, the antiglare layer can be made thinner, and the occurrence of cracking and curling of the antiglare layer can be suppressed. The thickness of the antiglare layer is a value measured from an image of a cross-sectional electron microscope (TEM, STEM) using image processing software. Here, since the surface of the antiglare layer is uneven, the thickness varies depending on the position, and 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.

On the uneven surface 12A of the antiglare layer 12, the average spacing Sm of the unevenness constituting the uneven surface 12A is preferably 0.1mm to 0.6mm, more preferably 0.2mm to 0.4 mm. On the uneven surface 12A of the antiglare layer 12, the average inclination angle θ a of the unevenness constituting the uneven surface 12A is preferably 0.05 ° to 0.30 °, more preferably 0.15 ° to 0.25 °.

On the uneven surface 12A of the antiglare layer 12, the arithmetic average roughness Ra of the unevenness constituting the uneven surface 12A is preferably 0.02 μm or more and 0.20 μm or less, and more preferably 0.04 μm or more and 0.10 μm or less.

The above-mentioned "Sm" and "Ra" are defined in accordance with JIS B0601-1994. "θ a" is defined as the surface roughness meter: SE-3400/(Proc. Xiao Shu) (1995.07.20 revision). Specifically, θ a is represented by the following formula (1).

θa＝tan ^-1 Δa…(1)

In the formula, Δ a is a value indicating the slope in terms of the vertical-horizontal ratio, and is a value obtained by dividing the sum of the differences between the minimum portion and the maximum portion of each irregularity (corresponding to the height of each projection) by the reference length.

Sm, θ a and Ra can be measured under the following measurement conditions using, for example, a surface roughness tester (model: SE-3400/(manufactured by Xiaoguka research Co., Ltd.).

1) Stylus of surface roughness detecting section (trade name SE2555N (2. mu. Standard), manufactured by Xiaoban Ltd.)

Diamond with 2 μm radius of curvature at tip and 90 ° apex angle

2) Measurement conditions of surface roughness measuring apparatus

Reference length (sampling length value λ c of roughness curve): 2.5mm

Evaluation length (reference length (sampling length value λ c) × 5): 12.5mm

Feed speed of stylus: 0.5mm/s

Preliminary length ( long さ): (sampling length value. lamda.c). times.2

Longitudinal magnification: 2000 times of

Transverse magnification: 10 times of

< first inorganic microparticle agglomeration >

The first inorganic fine particle aggregates 13 are present in the binder resin 16, and are composed of 3 or more inorganic fine particles as described above. In the present invention, as shown in fig. 2, the first inorganic fine particle aggregates 13 have the curved portions 13A formed by the connection of the inorganic fine particles. Here, in the present specification, the term "bent portion" refers to a concept including a bent portion. Examples of the shape having the inflection portion 13A include a V-shape, a U-shape, an arc shape, a C-shape, a coil shape, and a cage shape. Both ends of the inflection portion 13A may be closed, and for example, the first inorganic particulate aggregate 13 may have a ring-shaped structure having the inflection portion 13A.

The inflection portion 13A may be formed of 1 inorganic fine particle aggregate which is formed by inorganic fine particles being connected and has a curved shape, or may be formed of a main portion which is formed by inorganic fine particles being connected, and a branch portion which is branched from the main portion and formed by inorganic fine particles being connected, or may be formed of 2 branch portions which are branched from the main portion and connected to the main portion. The "trunk portion" in the present specification means the longest portion in the first inorganic fine particle aggregate.

As shown in fig. 2, the flexed portion 13A has an inner region 13B. The "inner region" in the present specification means a region sandwiched by the flexed portion. The inner region 13B is filled with a binder resin 16. The inflection portion 13A is preferably present so as to sandwich the inner region 13B from the thickness direction of the antiglare layer 12.

The inorganic fine particle aggregates in which the inorganic fine particles are aggregated into a mass form act as a single solid when the photopolymerizable compound that becomes the binder resin 16 after curing shrinks (polymerization shrinkage), and therefore the uneven surface of the antiglare layer corresponds to the shape of the inorganic fine particle aggregates. In contrast, the first inorganic fine particle aggregates 13 have the flexed parts 13A, and the flexed parts 13A include the inner regions 13B, and thus function as a solid having a cushioning effect during solidification and shrinkage. Therefore, the first inorganic fine particle aggregates 13 easily and uniformly collapse (ulceration れる) upon curing shrinkage. Therefore, the shape of the uneven surface 12A becomes gentler than the shape before curing and shrinking.

In the first inorganic fine particle aggregates 13, the ratio of 1 to 3 inorganic fine particles to 1 inorganic fine particle in contact with each other is preferably 95% or more. When the ratio of 1 to 3 inorganic fine particles to 1 inorganic fine particle is 95% or more, the ratio of 4 or more to 1 inorganic fine particle is extremely small, and the entire shape of the first inorganic fine particle aggregates 13 does not become a block. The proportion of the inorganic fine particles is more preferably 97% or more, and still more preferably 99% or more.

In the antiglare layer 12, the proportion of the first inorganic fine particle aggregates 13 is preferably higher on the light-transmitting substrate 11 side of the antiglare layer 12 than on the uneven surface 12A side of the antiglare layer 12. Here, whether the first inorganic fine particle aggregates are present on the light-transmitting substrate side or on the uneven surface side in the antiglare layer is determined by determining whether the first inorganic fine particle aggregates are present on the light-transmitting substrate side or on the uneven surface side with respect to the boundary at a position corresponding to half the thickness of the antiglare layer. The presence ratio of the first inorganic fine particle aggregates on the light-transmitting substrate side of the antiglare layer is higher than that on the uneven surface side of the antiglare layer, and can be confirmed by an image of a cross-sectional electron microscope (TEM, STEM). Since the proportion of the first inorganic fine particle aggregates 13 present on the light-transmitting substrate 11 side of the antiglare layer 12 is higher than that on the uneven surface 12A side of the antiglare layer 12, the uneven surface 12A is smoother without having a steep slope, and has diffusion performance extremely close to regular reflection and/or regular transmission. Thus, although the antiglare layer 12 has antiglare properties, it is excellent in bright room contrast, and in addition, it is possible to suppress the occurrence of stray light of screen image light, and therefore, it is also excellent in dark room contrast, and an antiglare film 10 having extremely high contrast and a black color feeling can be obtained.

Specifically, when Nb is the number of the first inorganic fine particle aggregates 13 present on the light-transmitting substrate 11 side of the antiglare layer 12 in the first inorganic fine particle aggregates 13 and Nf is the number of the first inorganic fine particle aggregates 13 present on the uneven surface 12A side of the antiglare layer 12 in a cross section along the thickness direction of the antiglare layer 12, Nb/Nf preferably satisfies the following formula (2).

1.5<Nb/Nf…(2)

When Nb/Nf satisfies the above formula (2), the antiglare property and excellent black color feeling can be more reliably obtained.

The first inorganic particulate aggregates 13 are present at least at a position on the surface of the organic particulate aggregates 15 and at a position separated from the organic particulate aggregates 15 and between the organic particulate aggregates 15. In the uneven surface 12A, the position corresponding to the organic fine particle aggregates 15 is a convex portion, and the first inorganic fine particle aggregates 13 are present at the position on the surface of the organic fine particle aggregates 15, so that the relative density of the organic fine particle aggregates 15 is increased, and floating up of the surface can be suppressed, and the buffering effect against the curing shrinkage of the binder resin 16 is exhibited, so that the edge (bottom) of the convex portion of the uneven surface 12A is gently changed, and the uneven surface 12A is thereby smoothed. Further, since the positions corresponding to the organic fine particle aggregates 15 in the uneven surface 12A are convex, the organic fine particle aggregates 15 form concave portions therebetween; however, since the first inorganic fine particle aggregates 13 are present at a position separated from the organic fine particle aggregates 15 and between the organic fine particle aggregates 15, the position of the concave portion on the uneven surface 12A becomes high, and thus the difference in level between the convex portion and the concave portion on the uneven surface 12A is reduced, whereby the uneven surface 12A becomes smoother, and at the same time, extremely gentle unevenness is formed between the uneven surfaces 12A as described above, and thus, antiglare properties can be reliably provided without deteriorating the contrast.

The average aggregate diameter of the first inorganic fine particle aggregates 13 is preferably 100nm or more and 2.0 μm or less. When the average aggregate diameter of the first inorganic fine particle aggregates 13 is 100nm or more, the smooth uneven surface 12A can be easily formed; when the average aggregate diameter of the first inorganic fine particle aggregates 13 is 2.0 μm or less, light diffusion by the first inorganic fine particle aggregates 13 can be suppressed, and the antiglare film 10 having excellent contrast can be obtained. The lower limit of the average particle diameter of the first inorganic fine particle aggregates 13 is preferably 200nm or more, and the upper limit thereof is preferably 1.5 μm or less.

The average aggregate diameter of the first inorganic fine particle aggregates is a particle diameter obtained by: a5 μm square region including a large number of first inorganic fine particle aggregates was selected by observation (about 1 ten thousand to 2 ten thousand times) with a cross-sectional electron microscope, the aggregation diameters of the first inorganic fine particle aggregates in the region were measured, the aggregation diameters of the first 10 largest first inorganic fine particle aggregates were averaged, and the obtained particle diameter was the average aggregation diameter. The "diameter of agglomeration of the first inorganic particulate aggregates" is measured as follows: when the cross section of the first inorganic particulate aggregate is sandwiched by 2 arbitrary parallel straight lines, the inter-straight line distance in the combination of the 2 straight lines when the inter-straight line distance is the maximum is measured as the aggregation diameter. The average diameter of the first inorganic particle aggregates may be calculated by using image analysis software.

The first inorganic fine particle aggregates 13 preferably have a larger aggregation diameter in a direction perpendicular to the thickness direction of the antiglare layer 12 than in the thickness direction. The "diameter of aggregation in the thickness direction" is measured as follows: the cross section of the first inorganic fine particle aggregate was sandwiched by 2 parallel straight lines perpendicular to the thickness direction of the antiglare layer, and the distance between the 2 straight lines at that time was measured as the aggregation diameter. The "diameter of the aggregate in the direction orthogonal to the thickness direction" is measured as follows: the cross section of the first inorganic fine particle aggregate was sandwiched by 2 parallel straight lines parallel to the thickness direction of the antiglare layer, and the distance between the 2 straight lines at this time was measured as the aggregation diameter. These condensation diameters can also be calculated using image analysis software.

The first inorganic fine particle aggregates 13 can be obtained by controlling, for example, the hydrophobization treatment of the inorganic fine particles constituting the first inorganic fine particle aggregates 13 and the second inorganic fine particle aggregates 14, the hydrophilization treatment of the organic fine particles constituting the organic fine particle aggregates 15, and the presence ratio of the hydroxyl group of the binder resin 16. Although hydroxyl groups are present on the surfaces of the inorganic fine particles, when the inorganic fine particle aggregates are subjected to a hydrophobic treatment, the hydroxyl groups present on the surfaces of the inorganic fine particles are reduced, and excessive aggregation of the inorganic fine particles can be suppressed. Further, by subjecting the surfaces of the inorganic fine particles to a hydrophobic treatment, the chemical resistance and saponification resistance of the inorganic fine particles themselves can be improved.

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

Since the first inorganic fine particle aggregates 13 can be obtained by a method other than the above-described method, the method for obtaining the first inorganic fine particle aggregates 13 is not limited to the above-described method. For example, the first inorganic fine particle aggregates 13 can be obtained by dispersing mutually reactive groups on the surfaces of the inorganic fine particles to control the aggregation state of the inorganic fine particles; the first inorganic fine particle aggregates 13 can be obtained by controlling aggregation by changing the affinity during drying using a solvent having a different affinity and volatility from those of the inorganic fine particles and the binder resin.

The inorganic fine particles constituting the first inorganic fine particle aggregates 13 are not particularly limited, and examples thereof include Silica (SiO) ₂ ) Inorganic oxide fine particles such as fine particles, alumina fine particles, titania fine particles, tin oxide fine particles, antimony-doped tin oxide (ATO) fine particles, and zinc oxide fine particles.

When silica particles are used as the inorganic fine particles, fumed silica fine particles are preferable in that an antiglare layer having smooth uneven surfaces can be easily formed among the silica particles. Fumed silica refers to amorphous silica having a particle diameter of 200nm or less produced by a dry method, and can be obtained by reacting a volatile compound containing silicon in a vapor phase. Specifically, for example, silicon tetrachloride (SiCl) ₄ ) And the like formed by hydrolysis of a silicon compound in a flame of oxygen and hydrogen. Commercially available products of fumed silica fine particles include AEROSIL R805 manufactured by NIPPON AEROSIL CORPORATION, and the like.

When inorganic oxide particles are used as the inorganic fine particles, 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 is reinforced by the lattice defect contained in the crystal structure thereof, and there is a possibility that excessive aggregation of the inorganic oxide fine particles cannot be controlled.

In addition, in the case of using the fumed silica fine particles as the inorganic fine particles, the fumed silica fine particles include silica fine particles exhibiting hydrophilicity and silica fine particles exhibiting hydrophobicity; among them, silica fine particles exhibiting hydrophobicity are preferable in terms of a small amount of moisture absorption and easy dispersion in the composition for an antiglare layer. The hydrophobic fumed silica can be obtained by chemically reacting silanol groups present on the surfaces of the fumed silica fine particles with the surface-treating agent as described above.

The inorganic fine particles are preferably spherical in shape in a single particle state. By forming the single particles of the inorganic fine particles into such a spherical shape, an image having a further excellent contrast can be obtained when the antiglare film is disposed on the image display surface of an image display device. The term "spherical" as used herein includes, for example, a regular spherical shape and an elliptical spherical shape, but does not include a so-called amorphous shape.

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

The average primary particle size of the inorganic fine particles is a value measured from an image of a cross-sectional electron microscope (preferably, a transmission type microscope such as TEM and STEM having a magnification of 5 ten thousand times or more) using image processing software.

< second inorganic Fine particle agglomerate >

The second inorganic fine particle aggregates 14 are present on or near the uneven surface 12A. In the second inorganic fine particle aggregates 14, it is also preferable that the ratio of 1 to 3 inorganic fine particles to the inorganic fine particles in contact with the 1 inorganic fine particle is 95% or more. Further, the aggregation diameter of the second inorganic fine particle aggregates 14 in the direction orthogonal to the thickness direction of the antiglare layer 12 is preferably larger than the aggregation diameter in the thickness direction, and the second inorganic fine particle aggregates 14 are more preferably two-dimensionally aggregated. Further, since the second inorganic fine particle aggregates 14 are present closer to the uneven surface 12A or the vicinity thereof than the first inorganic fine particle aggregates 13, the uneven surface 12A can be made smoother by making the aggregate diameter in the thickness direction of the antiglare layer 12 smaller than that of the first inorganic fine particle aggregates 13.

Since the hardness of the surface of the antiglare layer 12 can be increased by the presence of the second inorganic fine particle aggregates 14 on the uneven surface 12A or in the vicinity thereof, a relatively soft binder resin can be used as the binder resin 16, and thus the antiglare film 10 having excellent flexibility can be obtained.

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

Since the inorganic fine particles constituting the second inorganic fine particle aggregates 14 may be the same as the inorganic fine particles constituting the first inorganic fine particle aggregates 13, the description thereof will be omitted. The second inorganic fine particle aggregates 14 can be obtained in the same manner as the first inorganic fine particle aggregates 13, and can be obtained, for example, by controlling the hydrophobization treatment of the inorganic fine particles constituting the first inorganic fine particle aggregates 13 and the second inorganic fine particle aggregates 14, the hydrophilization treatment of the organic fine particles constituting the organic fine particle aggregates 15, and the presence ratio of the hydroxyl groups of the binder resin 16. Here, in order to make the aggregation state of the second inorganic particulate aggregates 14 different from the aggregation state of the first inorganic particulate aggregates 13, for example, in the second inorganic particulate aggregates 14, a surface treatment agent different from the first inorganic particulate aggregates 13 or a surface treatment agent concentration different from the first inorganic particulate aggregates 13 may be used.

< organic microparticle aggregate >

The organic microparticle aggregates 15 are composed of 2 or more organic microparticles as described above. In the antiglare layer 12, the maximum height of the organic particulate aggregates 15 in the thickness direction of the antiglare layer 12 is preferably smaller than the thickness of the antiglare layer 12. Since the maximum height of the organic fine particle aggregates 15 is smaller than the thickness of the antiglare layer 12, a steep uneven surface is not generated, and the antiglare property is exhibited while the decrease in contrast and black tone is suppressed.

Examples of the organic fine particles include plastic beads. Specific examples of the plastic beads include polystyrene beads, melamine resin beads, acrylic-styrene beads, silicone 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 to a hydrophilization treatment. The surface of the organic fine particles is hydrophilized, whereby the state of aggregation with the inorganic fine particles can be controlled.

The average primary particle diameter of the organic fine particles is preferably 1 μm or more and 5 μm or less. The average primary particle diameter of the organic fine particles is a value obtained as follows: in the observation with an electron microscope (preferably, transmission type such as TEM or STEM) of a cross section passing through the vicinity of the center of the organic fine particles, 30 organic fine particles having substantially the same particle size are selected from the same species, the maximum particle size of the cross section is measured, and the average value is calculated as the average primary particle size. In addition, the calculation may be performed using image analysis software. The antiglare property can be more reliably ensured by making the average primary particle diameter of the organic fine particles to be 1 μm or more. Further, by setting the average primary particle diameter of the organic fine particles to 5 μm or less, a decrease in contrast can be suppressed. The lower limit of the average primary particle diameter of the organic fine particles is more preferably 1.5 μm or more, and the upper limit of the average primary particle diameter of the organic fine particles is more preferably 4.0 μm or less.

When the thickness of the antiglare layer 12 is T and the average primary particle diameter of the organic fine particles is R, R/T preferably satisfies the following formula (3).

0.2<R/T<0.7…(3)

By making R/T satisfy the above formula (3), both the antiglare property and the black color feeling can be more surely achieved.

The number of organic fine particles constituting the organic fine particle aggregates 15 is preferably 2 to 3. By setting the number of organic fine particles constituting the organic fine particle aggregates 15 to 2 or more, the area of the gently inclined peak of the convex portion in the uneven surface 12A increases, and the area of the steeply inclined vertical surface of the convex portion decreases, so that deterioration of contrast can be suppressed. Further, by setting the number of organic fine particles constituting the organic fine particle aggregates 15 to 3 or less, it is possible to more reliably prevent the occurrence of organic fine particle aggregates larger than the thickness T of the antiglare layer 12 and to suppress the formation of sharp protrusions.

The organic fine particle aggregates 15 can be obtained, for example, by dispersing groups that react with each other on the surface of the organic fine particles, and controlling the state of aggregation of the organic fine particles; further, the organic fine particle aggregate 15 can be obtained by controlling the aggregation by changing the affinity during drying using a solvent having a different affinity and volatility from those of the organic fine particles and the binder resin; the organic microparticle aggregates 15 can also be obtained by controlling the hydrophobizing treatment of the inorganic microparticles constituting the first inorganic microparticle aggregates 13 and the second inorganic microparticle aggregates 14, the hydrophilizing treatment of the organic microparticles constituting the organic microparticle aggregates 15, and the proportion of hydroxyl groups of the binder resin 16 present.

< Binder resin >

The binder resin 16 contains a polymer (crosslinked product) of a photopolymerizable compound. The binder resin may contain a solvent-drying resin or a thermosetting resin in addition to the polymer (crosslinked product) of the photopolymerizable compound. The photopolymerizable compound has at least 1 photopolymerizable functional group. In the present specification, the "photopolymerizable functional group" is a functional group which can undergo a polymerization reaction by irradiation with light. Examples of the photopolymerizable functional group include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. The term "(meth) acryloyl group" means a meaning including both "acryloyl group" and "methacryloyl group". Examples of the light irradiated when polymerizing the photopolymerizable compound include visible light and ionizing radiation such as ultraviolet rays, X-rays, electron rays, α rays, β rays and γ rays.

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

The hydrophilicity of the binder resin 16 is preferably controlled. For example, an antiglare film in which the degree of aggregation and dispersion (dispersion) of organic fine particles and inorganic fine particles are controlled can be obtained by producing an antiglare film using the following binder resin and confirming the production; the binder resin is a binder resin in which the degree of hydrophilicity is controlled by changing the mixing ratio of the photopolymerizable compound having a hydroxyl group and the photopolymerizable compound having no hydroxyl group.

(photopolymerizable monomer)

The photopolymerizable monomer has a weight average molecular weight of 1000 or less. The photopolymerizable monomer may be used alone, or two or more kinds thereof may be used.

As the photopolymerizable monomer, a polyfunctional monomer having 2 (i.e., 2 functions) or more photopolymerizable functional groups is preferable.

Examples of the monomer having a 2-or more-functional group include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, and mixtures thereof, Polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin tetra (meth) acrylate, adamantyl di (meth) acrylate, isobornyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and modified products thereof by PO, EO, and the like.

Among them, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA) and the like are preferable in terms of obtaining an antiglare layer having high hardness.

(photopolymerizable oligomer)

The weight average molecular weight of the photopolymerizable oligomer is greater than 1000 and 10000 or less.

The photopolymerizable oligomer is preferably a polyfunctional oligomer having 3 (3 functions) or more photopolymerizable functional groups. The photopolymerizable oligomer is preferably a polyfunctional oligomer having 2 or more functions. Examples of the polyfunctional oligomer include polyester (meth) acrylate, urethane (meth) acrylate, polyester-urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, isocyanurate (meth) acrylate, and epoxy (meth) acrylate.

(photopolymerizable prepolymer)

The weight average molecular weight of the photopolymerizable prepolymer is greater than 10000, and is preferably 10000 to 80000, and more preferably 10000 to 40000. When the weight average molecular weight is more than 80000, the viscosity is high, so that the coatability is lowered, and the appearance of the obtained optical laminate 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 such that a coating film can be formed only by drying a solvent added for adjusting a solid content at the time of coating, such as a thermoplastic resin. When the solvent-drying resin is added, film defects on the coating surface of the coating liquid can be effectively prevented when the antiglare layer 12 is formed. The solvent-drying type resin is not particularly limited, and a thermoplastic resin can be usually used.

Examples of the thermoplastic resin 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 and elastomers.

The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly, a general-purpose solvent capable of dissolving 2 or more polymers or curable compounds). In particular, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (such as cellulose esters) and the like are preferable from the viewpoint of transparency and weather resistance.

The thermosetting resin is not particularly limited, and examples thereof include phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins, epoxy resins, aminoalkyd resins, melamine-urea-formaldehyde cocondensated resins, silicone resins, and polysiloxane resins.

< Properties of antiglare film >

The total light transmittance of the antiglare film 10 is preferably 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 attached to the surface of an image display device. The total light transmittance is more preferably 90% or more. The total light transmittance in the present specification can be measured by a method in accordance with JIS K7361 using a haze meter (product number, HM-150, manufactured by murakamura color technology research).

The haze value of the entire antiglare film 10 (overall haze value) is preferably 2% or less. When the overall haze value is 2% or less, desired optical characteristics can be obtained, and the visibility when the antiglare film 10 is provided on the image display surface can be further improved. The overall haze value is more preferably 1% or less. The overall haze value in the present specification can be measured by a haze meter (product No. HM-150, manufactured by color technology research on village) according to a method based on JIS K7136.

The internal haze value of the antiglare film 10 is preferably 0% or more and 2.0% or less. Here, the meaning of "the internal haze value is 0%" in the present specification is not limited to the case where the internal haze value is completely 0%, and includes a range in which the measurement error is within even the case where the internal haze value is greater than 0% and the internal haze value can be regarded as substantially 0% (for example, an internal haze value of 0.3% 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 haze value of the entire antiglare film was measured according to JIS K7136 using a haze meter (HM-150, manufactured by murakamura color technology research). Then, the light-transmitting resin base material is adhered to the surface of the antiglare layer with an adhesive layer, tape, or the like. This collapses the uneven shape of the uneven surface in the antiglare layer, and flattens the surface of the antiglare film. In this state, the internal haze value can be determined by measuring the haze value according to JIS K7136 using a haze meter and subtracting the haze value of the pressure-sensitive adhesive layer or the tape itself. Since the internal haze value does not take into account the uneven shape of the uneven surface in the antiglare layer, the surface haze value due to the uneven shape of the surface only in the antiglare layer can be obtained by subtracting the internal haze value from the entire haze value.

In the antiglare film 10, the difference between the average value of the sharpness of the transmitted image measured by using the optical combs having a width of 0.125mm, a width of 0.5mm, a width of 1.0mm, and a width of 2.0mm and the sharpness of the transmitted image measured by using each optical comb is preferably 10% or less. By setting this difference to 10% or less, glare can be suppressed more reliably.

The transmission image clarity can be measured by a transmission clarity measuring apparatus based on the transmission method of image clarity according to JIS K7105. Examples of such a measuring apparatus include an image sharpness measuring instrument ICM-1T manufactured by SUGA TEST INSTRUMENTS, Inc.

The average value of the transmitted image sharpness of the antiglare film 10 measured using the 4 types of combs is preferably 80% or more. The transmission image clarity of the antiglare film 10 measured with a 0.125mm wide comb is preferably 80% or more, the transmission image clarity of the antiglare film 10 measured with a 0.5mm wide comb is preferably 80% or more, the transmission image clarity of the antiglare film 10 measured with a 1.0mm wide comb is preferably 80% or more, and the transmission image clarity of the antiglare film 10 measured with a 2.0mm wide comb is preferably 90% or more.

According to the present embodiment, since the first inorganic fine particle aggregate 13 has the curved portion 13A including the inner region 13B, as described above, the first inorganic fine particle aggregate 13 is easily and uniformly collapsed when it is cured and shrunk. As a result, the first inorganic fine particle aggregates 13 have a function of forming the uneven surface 12A, the shape of the uneven surface 12A becomes gentle compared to the solidification shrinkage amount, the uneven surface 12A has an antiglare property to the extent that the reflection of the observer (observer) and the background of the observer is not noticeable, and the occurrence of a portion where the inclination angle change rate is abruptly changed, which causes an abrupt change in brightness, can be effectively prevented, so that a good anti-dazzling property can be obtained. The antiglare property to such an extent that the observer (observer) and the background of the observer are not reflected is, for example, an antiglare property such as: the presence of a viewer can be found, but only its contour exhibits an unclear state of blur; and also the presence of items located at the background of the viewer, but with unclear outlines or borders. In this way, the contour or the like of the observer is merely blurred, and appears in a state where it is not noticeable to the observer.

Further, since the inclination angle of the irregularities constituting the irregular surface 12A does not become large, excessive diffusion of external light does not occur. This can suppress a decrease in the bright room contrast. Further, since the screen image light can be prevented from forming stray light, a good dark room contrast can be obtained. Further, since the liquid crystal display device has an appropriate positive reflection component, when a moving image is displayed, the gloss or brilliance of the image increases, and a sense of snap can be obtained. Thus, a black color sense having both excellent contrast and a sense of snap can be obtained.

[ method for producing anti-glare film ]

The antiglare film 10 can be formed, for example, as follows. First, the composition for an antiglare layer is applied to the light-transmitting substrate 11. Examples of the method for applying the composition for an antiglare layer include known application methods such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure printing, and die coating.

The composition for an antiglare layer contains at least a first inorganic fine particle aggregate 13, a second inorganic fine particle aggregate 14, an organic fine particle aggregate 15, and the photopolymerizable compound. The thermoplastic resin, the thermosetting resin, a solvent, and a polymerization initiator may be added to the composition for an antiglare layer, if necessary. Further, in the composition for an antiglare layer, conventionally known dispersants, surfactants, antistatic agents, silane coupling agents, thickeners, anti-coloring agents, colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, adhesion imparting agents, polymerization inhibitors, antioxidants, surface modifiers, slip agents, and the like may be added for the purpose of improving the hardness of the antiglare layer, suppressing curing shrinkage, controlling the refractive index, and the like.

< solvent >

Examples of the solvent include alcohols (e.g., methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, benzyl alcohol, PGME, ethylene glycol), ketones (e.g., acetone, Methyl Ethyl Ketone (MEK), cyclohexanone, methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone, etc.), ethers (e.g., 1, 4-dioxane, dioxolane, diisopropyl ether dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., toluene, xylene, etc.), halogenated carbons (e.g., methylene chloride, dichloroethane), esters (e.g., methyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide), and the like), Amides (dimethylformamide, dimethylacetamide, etc.), etc., and mixtures thereof may also be used.

< polymerization initiator >

The polymerization initiator is a component that is decomposed by light irradiation to generate a radical to initiate polymerization (crosslinking) of the photopolymerizable compound or to proceed the polymerization (crosslinking).

The polymerization initiator is not particularly limited as long as it can emit a substance that initiates radical polymerization by light irradiation. The polymerization initiator is not particularly limited, and known ones can be used, and specific examples thereof include acetophenones, benzophenones, Michler's benzoyl benzoate, α -amorolyl ester, thioxanthones, benzophenones, biphenylcarbonyls, benzoins and acylphosphine oxides. Further, it is preferable to use the photosensitizer in admixture, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

When the binder resin is a resin system having a radical polymerizable unsaturated group, the polymerization initiator is preferably selected from acetophenones, benzophenones, thioxanthones, benzoin methyl ether and the like, either singly or in combination.

The content of the polymerization initiator in the composition for an antiglare layer is preferably 0.5 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound. When the content of the polymerization initiator is within this range, the hard coating performance can be sufficiently ensured and the curing failure can be suppressed.

The content ratio (solid content) of the raw material in the composition for an antiglare layer is not particularly limited, and is usually preferably 5 mass% to 70 mass%, more preferably 25 mass% to 60 mass%.

The method for producing the composition for an antiglare layer is not particularly limited as long as the components can be uniformly mixed, and for example, the production can be carried out using a known apparatus such as a paint shaker, a bead mill, a kneader, or a mixer.

After the composition for an antiglare layer is applied to the light-transmitting substrate 11, the coated composition for an antiglare layer is transferred to a heated region to be dried by various known methods and the solvent is evaporated. Here, the distribution state of the first inorganic particle aggregates 13, the second inorganic particle aggregates 14, and the organic particle aggregates 15 can be adjusted by selecting the affinity of the solvent and the solid content, the relative evaporation rate of the solvent, the solid content concentration, the temperature of the coating liquid, the drying temperature, the wind speed of the drying wind, the drying time, the concentration of the solvent atmosphere in the drying region, and the like.

The method of adjusting the distribution state of the fine particle aggregates by selecting the drying conditions is particularly simple and preferable. The drying temperature is preferably 30 to 120 ℃ and the drying air speed is preferably 0.2 to 50m/s, and the distribution of the fine particle aggregates can be adjusted to a desired state by performing the drying treatment appropriately adjusted within this range 1 time or 2 or more times.

Thereafter, the composition for an antiglare layer in the form of a coating film is irradiated with light such as ultraviolet rays to polymerize (crosslink) the photopolymerizable compound, thereby curing the composition for an antiglare layer to form the antiglare layer 12. Here, as described above, the first inorganic fine particle aggregates 13 have the bent portions 13A, and the bent portions 13A have the inner regions 13B, and thus function as a solid having a cushioning effect during solidification and shrinkage. Thus, the first inorganic particulate aggregates 13 collapse easily and uniformly upon solidification shrinkage.

When ultraviolet rays are used as light for curing the composition for an 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. The wavelength of the ultraviolet light may be in a wavelength range of 190nm to 380 nm. Specific examples of the electron beam source include various electron beam accelerators such as a Cockcroft-Walton (Cockcroft-Walton) type, a Van der Graaff (バンデグラフト) type, a resonance transformer type, an insulated core transformer type, a linear type, a denameter (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. 3 is a schematic configuration diagram of a polarizing plate incorporating the antiglare film of the present embodiment. As shown in fig. 3, the polarizing plate 20 includes an antiglare film 10, a polarizing element 21, and a protective film 22. The polarizing element 21 is formed on the surface of the light-transmitting 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 polarizing element 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 polarizing element 21 include a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, and an ethylene-vinyl acetate copolymer saponified film, which are dyed with iodine or the like and stretched. When the antiglare film 10 and the polarizing element 21 are laminated, the light-transmitting substrate 11 is preferably subjected to saponification treatment in advance. By the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

< < liquid Crystal Panel > >)

The antiglare film 10 and the polarizing plate 20 can be incorporated into a liquid crystal panel and used. Fig. 4 is a schematic configuration diagram of a liquid crystal panel incorporating the antiglare film of the present embodiment.

The liquid crystal panel shown in fig. 4 has a structure in which a protective film 31 such as a cellulose triacetate film (TAC film), a polarizing element 32, a phase difference film 33, an adhesive layer 34, a liquid crystal cell 35, an adhesive layer 36, a phase difference film 37, a polarizing element 21, and an antiglare film 10 are stacked in this order from the light source side (backlight unit side) toward the viewer side. In the liquid crystal cell 35, a liquid crystal layer, an alignment film, an electrode layer, a color filter, and the like are arranged between 2 glass substrates.

Examples of the retardation films 33 and 37 include cellulose triacetate films and cycloolefin polymer films. The retardation film 37 may be the same as the protective film 22. As the adhesive constituting the adhesive layers 34 and 36, Pressure Sensitive Adhesive (PSA) can be mentioned.

< < image display apparatus > >)

The antiglare film 10, the polarizing plate 20, and the liquid crystal panel 30 can be incorporated into an image display device and used. Examples of the image display device include a Liquid Crystal Display (LCD), a cathode ray tube display (CRT), a Plasma Display Panel (PDP), an electroluminescence display panel (ELD), a field emission display panel (FED), a touch panel, a tablet computer, and electronic paper. Fig. 5 is a schematic configuration diagram of a liquid crystal display panel as an example of an image display device incorporating the antiglare film of the present embodiment.

The image display device 40 shown in fig. 5 is a liquid crystal display panel. The image display device 40 includes a backlight unit 41 and a liquid crystal panel 30 including an antiglare film 10 disposed closer to the viewer than the backlight unit 41. As the backlight unit 41, a known backlight unit can be used.

[ second embodiment ]

An antiglare film according to a second embodiment of the present invention is described below with reference to the drawings. Unless otherwise specified, the same contents as those in the first embodiment are omitted. Fig. 6 is a schematic configuration diagram of another antiglare film of the present embodiment, and fig. 7 is a partial enlarged view of fig. 6.

< < anti-glare film > >)

As shown in fig. 6, the antiglare film 50 includes at least a light-transmitting substrate 51 and an antiglare layer 52 provided on the light-transmitting substrate 51. The light-transmissive substrate 51 is the same as the light-transmissive substrate 11 described in the first embodiment, and thus the description thereof is omitted in this embodiment.

< anti-glare layer >

The antiglare layer 52 contains a first inorganic fine particle aggregate 53 in which 3 or more inorganic fine particles are aggregated, a second inorganic fine particle aggregate 54 in which 2 or more inorganic fine particles are aggregated, organic fine particles 55 in a state of unagglomerated single particles, and a binder resin 56. The antiglare layer 52 may not contain the second inorganic fine particle aggregates 54 and the organic fine particles 55.

In the antiglare layer 52, the organic fine particles 55 are biased (biased) toward the light-transmissive substrate 51. The organic fine particles were observed as being biased toward the translucent base material by an image obtained by a cross-sectional electron microscope (TEM, STEM).

Here, for example, by comparing the average value of the thickness of the binder resin 56 between the light-transmitting substrate 51 and the organic fine particles 55 with the average value of the thickness of the binder resin 56 between the uneven surface 52A and the organic fine particles 55, it can be shown how much the organic fine particles 55 are uneven.

Specifically, in the antiglare layer 52, when Tb is the average value of the thickness of the binder resin 56 between the light-transmitting substrate 51 and the organic fine particles 55 and Tf is the average value of the thickness of the binder resin 56 between the uneven surface 52A and the organic fine particles 55, Tf/Tb preferably satisfies the following formula (4).

2.5<Tf/Tb…(4)

By making Tf/Tb satisfy the above expression (4), the uneven surface 52A is smooth, and occurrence of a large tilt angle that deteriorates contrast and glare can be prevented.

In the uneven surface 52A of the antiglare layer 52, the average interval Sm of the unevenness constituting the uneven surface 52A is preferably 0.1mm to 0.6mm, more preferably 0.2mm to 0.4 mm. In the uneven surface 52A of the antiglare layer 52, the average inclination angle θ a of the unevenness constituting the uneven surface 52A is preferably 0.05 ° or more and 0.30 ° or less, and more preferably 0.15 ° or more and 0.25 ° or less.

In the uneven surface 52A of the antiglare layer 52, the arithmetic mean roughness Ra of the unevenness constituting the uneven surface 52A is preferably 0.02 μm or more and 0.20 μm or less, more preferably 0.04 μm or more and 0.10 μm or less. The definitions and measurement methods of "Sm", "Ra", and "θ a" are the same as those of the first embodiment.

< first inorganic microparticle agglomeration >

In the present embodiment, similarly to the first embodiment, the ratio of 1 to 3 inorganic fine particles in the first inorganic fine particle aggregates 53 to 1 inorganic fine particle in contact with each other is 95% or more. As shown in fig. 7, the first inorganic fine particle aggregates 53 have curved portions 53A formed by connection of inorganic fine particles. As shown in fig. 7, the bent portion 53A has an inner region 53B.

The inorganic fine particle aggregates are the same as the first inorganic fine particle aggregates 13 described in the first embodiment except for the following description, and therefore the description thereof is omitted.

For the same reason as in the first embodiment, the first inorganic fine particle aggregates 53 are present at least at the positions on the surfaces of the organic fine particles 55 and at the positions between the organic fine particles 55 apart from the organic fine particles 55.

< second inorganic Fine particle agglomerate >

The second inorganic fine particle aggregates 54 are present on or near the uneven surface 52A. The rest is the same as the second inorganic fine particle aggregate 14 described in the first embodiment, and thus the description thereof is omitted.

< organic Fine particles >

The organic fine particles 55 have the same material and the same average primary particle diameter as those of the organic fine particles described in the first embodiment. Here, for example, since the aggregation of the organic fine particles 55 can be controlled by changing the affinity during drying by using a solvent having an affinity and volatility different from those of the organic fine particles and the binder resin, the organic fine particles 55 can be present as single-particle organic fine particles 55 in the antiglare layer 52, and the organic fine particles 55 can be biased toward the light-transmissive substrate 51.

< Binder resin >

The binder resin 56 is the same as the binder resin 16 described in the first embodiment, and therefore, the description thereof is omitted.

[ method for producing anti-glare film ]

The antiglare film 50 can be formed by the same method as the first embodiment, and thus the description is omitted.

In the present embodiment, since the first inorganic fine particle aggregates 53 including the curved portions 53A having the inner regions 53B are present in the antiglare layer 52, antiglare properties to the extent that the observer (observer) and the background of the observer are not distracted to the human eye can be obtained, and good antiglare properties and good black color feeling can be obtained for the same reason as in the first embodiment.

[ third embodiment ]

An antiglare film according to a third embodiment of the present invention is described below with reference to the drawings.

< < anti-glare film > >)

Fig. 8 is a schematic configuration diagram of the antiglare film of the present embodiment, fig. 9 is a partial enlarged view of fig. 8, fig. 10 is a partial enlarged view of fig. 9, and fig. 11 is a schematic diagram showing a mode of measuring the transmitted image sharpness of the antiglare film of the present embodiment by a transmitted image sharpness measuring apparatus.

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

The surface 60A of the antiglare film 60 is formed with irregularities. In the present embodiment, since no functional layer such as a low refractive index layer is provided on the antiglare layer 62, the uneven surface 62A of the antiglare layer 62 is the surface 60A of the antiglare film 60.

In the antiglare film 60, the absolute value of the difference between the arithmetic average of the sharpness of the transmitted image measured by using the optical combs having a width of 0.125mm, a width of 0.25mm, a width of 0.5mm, a width of 1.0mm and a width of 2.0mm and the sharpness of the transmitted image measured by using each optical comb is 10% or less.

The "transmitted image clarity of the antiglare film" in the present specification means the transmitted image clarity measured as the entire antiglare film. In the present embodiment, since no functional layer such as a low refractive index layer is provided on the antiglare layer 62, the transmitted image clarity of the antiglare film 60 is the transmitted image clarity measured using the antiglare film 60 including the light-transmissive substrate 61 and the antiglare layer 62. In addition, in the case where 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 the transmitted image clarity measured using the antiglare film including the light-transmitting substrate, the antiglare layer, and the functional layer.

The transmission image sharpness may be measured by a transmission sharpness measuring apparatus of a transmission method of image sharpness according to JIS K7374. Examples of such a measuring apparatus include an image sharpness measuring instrument ICM-1T manufactured by SUGA TEST INSTRUMENTS, Inc.

As shown in fig. 11, the transmitted image sharpness measuring apparatus 200 includes a light source 201, a slit 202, a lens 203, a lens 204, an optical comb 205, and a light receiver 206. In the transmitted sharpness measurement apparatus 200, light emitted from the light source 201 and passing through the slit 202 is collimated by the lens 203, the collimated light is irradiated to the back surface of the antiglare film 60 (the surface of the light-transmitting substrate 61 opposite to the antiglare layer 62 side), light passing through the uneven surface 62A of the antiglare layer 62 of the antiglare film 60 is focused by the lens 204, light passing through the optical comb 205 is received by the light receiver 206, and the transmitted image sharpness C is calculated by the following equation (5) based on the amount of light received by the light receiver 206.

C(n)＝{(M-m)/(M+m)}×100(％)…(5)

In the formula (5), C (n) is the transmitted image sharpness (%) when the width n (mm) of the optical comb, M is the highest light quantity when the width n (mm) of the optical comb, and M is the lowest light quantity when the width n (mm) of the optical comb.

The optical comb 205 is movable along a longitudinal direction of the optical comb 205, and has a light blocking portion and a light transmitting portion. The ratio of the widths of the light-shielding portion and the light-transmitting portion of the optical comb 205 is 1: 1. Here, in JIS K7374, 5 types of optical combs having a width of 0.125mm, 0.25mm, 0.5mm, 1.0mm and 2.0mm are defined as the optical combs. The antiglare film 60 is disposed so that light which becomes parallel light via the lens 203 is incident perpendicularly to the antiglare film 60 on the back surface of the antiglare film 60.

The arithmetic mean of the sharpness of the transmitted image of the antiglare film 60 measured using the 5 types of combs described above was 70% to 95%. The lower limit of the arithmetic average value of the transmitted image sharpness of the antiglare film 60 is preferably 80% or more, and the upper limit of the arithmetic average value of the transmitted image sharpness of the antiglare film 60 is preferably 90% or less. The transmission image clarity of the antiglare film 60 measured with a 0.125mm wide comb is preferably 70% or more, the transmission image clarity of the antiglare film 60 measured with a 0.25mm wide comb is preferably 70% or more, the transmission image clarity of the antiglare film 60 measured with a 0.5mm wide comb is preferably 80% or more, the transmission image clarity of the antiglare film 60 measured with a 1.0mm wide comb is preferably 80% or more, and the transmission image clarity of the antiglare film 60 measured with a 2.0mm wide comb is preferably 90% or more.

On the surface 60A of the antiglare film 60, the average interval Sm of irregularities constituting the surface 60A is preferably 0.1mm to 0.6mm, more preferably 0.2mm to 0.4 mm. On the surface 60A of the antiglare film 60, the average inclination angle θ a of the irregularities constituting the surface 60A is preferably 0.05 ° to 0.30 °, more preferably 0.15 ° to 0.25 °.

On the surface 60A of the antiglare film 60, the arithmetic average roughness Ra of the irregularities constituting the surface 60A is preferably 0.02 μm or more and 0.20 μm or less, more preferably 0.04 μm or more and 0.10 μm or less.

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

The total light transmittance of the antiglare film 60 is preferably 85% or more, more preferably 90% or more, for the same reason as in the first embodiment. The total light transmittance can be measured by the same method as in the first embodiment.

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

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

In the antiglare film 60, when the inclination angle of the surface 60A of the antiglare film 10 with respect to the surface 61A of the light-transmissive substrate 61 is measured at 0.1 degrees in a cross section along the thickness direction of the antiglare film 60, the ratio of the 99 th percentile to the 3 rd quartile (99 th percentile/3 rd quartile) in the cumulative percentage of the frequencies of the inclination angles is preferably 4.0 or more and less than 5.0. By setting the ratio to 4.0 or more, the inclination angle change rate is not excessively increased, and glare can be prevented; further, by making this ratio smaller than 5.0, the proportion of the portion having an excessively oblique angle in the surface 60A of the antiglare film 60 can be controlled, and thus a decrease in contrast can be suppressed.

< translucent base Material >

The light-transmissive substrate 61 is the same as the light-transmissive substrate 11 described in the first embodiment, and therefore, the description thereof is omitted.

< anti-glare layer >

The antiglare layer 62 is a layer exhibiting antiglare properties, and as shown in fig. 9, contains 2 or more organic fine particles 63, 2 or more inorganic fine particles 64, and a binder resin 65. The surface of the antiglare layer 62 is an uneven surface 62A. The antiglare layer 62 may exert other functions as well as antiglare properties. Specifically, the antiglare layer 62 may be a layer that exhibits functions such as antiglare properties and hard coat properties, antireflection properties, antistatic properties, and antifouling properties.

When the antiglare layer 62 exhibits hard coating properties in addition to antiglare properties, the antiglare layer 62 has a hardness of "H" or more in a pencil hardness test (4.9N load) specified in JIS K5600-5-4 (1999).

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

< organic Fine particles >

Of the 2 or more organic fine particles 63, it is preferable that at least a part of the organic fine particles 63 exist in the form of organic fine particle aggregates 63A, and the organic fine particle aggregates 63A are formed by aggregating 2 or more organic fine particles 63. By setting the number of the organic fine particles 63 constituting the organic fine particle aggregate 63A to 2 or more, the area of the crest of the gently inclined convex portion in the uneven surface 62A increases, and the area of the rising surface of the steeply inclined convex portion decreases, whereby deterioration of contrast can be suppressed.

In the antiglare layer 62, the maximum height of the organic fine particle aggregates 63A in the thickness direction of the antiglare layer 62 is preferably smaller than the thickness of the antiglare layer 62 for the same reason as in the first embodiment.

The organic fine particles 63 include, for example, plastic beads as exemplified in the first embodiment. For the same reason as in the first embodiment, it is also preferable to subject the surface of the organic fine particles 63 to a hydrophilization treatment.

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

When the thickness of the antiglare layer 62 is T and the average primary particle diameter of the organic fine particles 63 is R, R/T preferably satisfies the relationship of the above expression (3) for the same reason as in the first embodiment.

For the same reason as in the first embodiment, the number of the organic fine particles 63 constituting the organic fine particle aggregate 63A is preferably 2 or more and 3 or less. The organic fine particle aggregates 63A can be obtained by controlling the aggregation state as in the first embodiment, for example.

< inorganic Fine particles >

The inorganic fine particles 64 are not particularly limited, and examples thereof include inorganic oxide fine particles similar to those exemplified in the first embodiment. When silica particles are used as the inorganic fine particles 64, fumed silica fine particles are preferable in that an antiglare layer having smooth uneven surfaces can be easily formed among the silica particles.

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

When the fumed silica fine particles are used as the inorganic fine particles 64, the fumed silica fine particles exhibiting hydrophobicity are preferable for the same reason as in the first embodiment. The hydrophobic fumed silica can be obtained by chemically reacting the surface-treating agent as described above with silanol groups present on the surface of the fumed silica particles.

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

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

At least a part of the inorganic fine particles 64 among the 2 or more inorganic fine particles 64 is preferably present in the form of first inorganic fine particle aggregates 64A in which 3 or more inorganic fine particles 64 are aggregated.

The first inorganic fine particle aggregates 64A are present in the binder resin 65, and are composed of 3 or more inorganic fine particles 64 as described above. The first inorganic particle aggregates 64A preferably have curved portions 64B formed by the connection of the inorganic particles 64 as shown in fig. 10. The shape of the bent portion 64B is similar to that of the bent portion 13A.

The bent portion 64B may be formed of 1 inorganic fine particle aggregate formed by inorganic fine particles connected and bent, may be formed of a main portion formed by inorganic fine particles connected and a branch portion branched from the main portion and formed by inorganic fine particles connected, or may be formed of 2 branch portions branched from the main portion and connected to the main portion.

The inflection portion 64B has an inner region 64C as shown in fig. 10. The inner region 64C is filled with a binder resin 65. The inflected section 64C is preferably present so as to sandwich the inner region 64C from the thickness direction of the antiglare layer 62.

The inorganic fine particle aggregates in which the inorganic fine particles are aggregated into a mass form act as a single solid when the photopolymerizable compound which becomes the binder resin after curing shrinks (polymerization shrinkage), and therefore the uneven surface of the antiglare layer corresponds to the shape of the inorganic fine particle aggregates. In contrast, the first inorganic particulate aggregate 64A has the bent portion 64B, and the bent portion 64B has the inner region 64C, and thus functions as a solid having a cushioning effect when it is solidified and contracted. Therefore, the first inorganic particulate aggregates 64A collapse easily and uniformly upon curing shrinkage. Therefore, the shape of the uneven surface 62A becomes gentler than the shape before curing and shrinking.

In the first inorganic fine particle aggregates 64A, the ratio of 1 to 3 or less inorganic fine particles to 1 inorganic fine particle in contact with each other is preferably 95% or more for the same reason as in the first embodiment. The proportion of the inorganic fine particles is more preferably 97% or more, and still more preferably 99% or more.

For the same reason as in the first embodiment, in the antiglare layer 62, the proportion of the first inorganic particulate aggregates 64A present is preferably higher on the light-transmitting substrate 61 side of the antiglare layer 62 than on the uneven surface 62A side of the antiglare layer 62. Here, whether the first inorganic fine particle aggregates are present on the light-transmitting substrate side or the uneven surface side in the antiglare layer is determined by the same method as that described in the first embodiment.

Specifically, when the number of the first inorganic particulate aggregates 64A present on the light-transmitting substrate 61 side of the antiglare layer 62 in the first inorganic particulate aggregates 64A is Nb and the number of the first inorganic particulate aggregates 64A present on the uneven surface 62A side of the antiglare layer 62 is Nf in a cross section along the thickness direction of the antiglare layer 62, Nb/Nf preferably satisfies the above equation (2) for the same reason as in the first embodiment.

For the same reason as in the first embodiment, it is preferable that the first inorganic fine particle aggregates 64A are present at least at the surface of the organic fine particle aggregates 63A and at a position separated from the organic fine particle aggregates 63A and between the organic fine particle aggregates 63A.

The average particle diameter of the first inorganic particulate aggregates 64A is preferably 100nm or more and 2.0 μm or less for the same reason as in the first embodiment. The lower limit of the average aggregate diameter of the first inorganic fine particle aggregates 64A is preferably 200nm or more, and the upper limit thereof is preferably 1.5 μm or less. The average particle diameter of the first inorganic microparticle aggregates is determined by the same method as in the first embodiment.

The first inorganic particulate aggregates 64A preferably have a larger aggregation diameter in a direction perpendicular to the thickness direction of the antiglare layer 62 than in the thickness direction. The "diameter of aggregation in the thickness direction" and the "diameter of aggregation in the direction orthogonal to the thickness direction" are measured by the same method as in the first embodiment.

The first inorganic fine particle aggregates 64A can be obtained by, for example, controlling the hydrophilization treatment of the organic fine particles 63, the hydrophobization treatment of the inorganic fine particles 64, and the presence ratio of the hydroxyl groups of the binder resin 65. Although hydroxyl groups are present on the surfaces of the inorganic fine particles 64, when the first inorganic fine particles 64 are subjected to the hydrophobic property-imparting treatment, the hydroxyl groups present on the surfaces of the inorganic fine particles 64 are reduced, and the inorganic fine particles can be inhibited from excessively aggregating. Further, by subjecting the surfaces of the inorganic fine particles 64 to the hydrophobic treatment, the chemical resistance and the saponification resistance of the inorganic fine particles themselves can be improved.

Such hydrophobization treatment can be performed using a surface treatment agent such as silanes or silazanes. Specific examples of the surface treatment agent include dimethyldichlorosilane exemplified in the first embodiment.

The first inorganic fine particle aggregates 64A may be obtained by a method other than the above-described method, and may be obtained by the method described in the first embodiment.

As the inorganic fine particles 64 in the antiglare layer 62, as shown in fig. 9 and 10, 2 or more second inorganic fine particle aggregates 64D in which the inorganic fine particles 64 are aggregated may be present together with the first inorganic fine particle aggregates 64A. The second inorganic fine particle aggregates 64D are present on or near the uneven surface 62A. In the second inorganic fine particle aggregates 64D, it is also preferable that the ratio of 1 or more and 3 or less inorganic fine particles to the inorganic fine particles in contact with the 1 inorganic fine particle is 95% or more. Further, the aggregation diameter of the second inorganic fine particle aggregates 64D in the direction orthogonal to the thickness direction of the antiglare layer 62 is preferably larger than the aggregation diameter in the thickness direction, and the second inorganic fine particle aggregates 64D are more preferably two-dimensionally aggregated. Further, since the second inorganic fine particle aggregate 64D is present closer to the uneven surface 62A or its vicinity than the first inorganic fine particle aggregate 64A, the uneven surface 62A can be made smoother by making the aggregate diameter in the thickness direction of the antiglare layer 62 smaller than that of the first inorganic fine particle aggregate 64A.

When the second inorganic fine particle aggregates 64D are present on or near the uneven surface 62A, the antiglare film 60 having excellent flexibility can be obtained for the same reason as in the first embodiment.

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

Since the inorganic fine particles 64 constituting the second inorganic fine particle aggregates 64D are the same as the inorganic fine particles 64 constituting the first inorganic fine particle aggregates 64A, the description thereof is omitted here. The second inorganic fine particle aggregates 64D can be obtained by controlling the hydrophilization treatment of the organic fine particles 63, the hydrophobization treatment of the inorganic fine particles 64, and the presence ratio of the hydroxyl groups in the binder resin 65, for example, in the same manner as the first inorganic fine particle aggregates 64A. Here, in order to make the aggregation state of the second inorganic particulate aggregates 64D different from the aggregation state of the first inorganic particulate aggregates 64A, for example, in the second inorganic particulate aggregates 64D, a surface treatment agent different from the first inorganic particulate aggregates 64A or a surface treatment agent concentration different from the first inorganic particulate aggregates 64A may be used.

In the antiglare layer 62, the proportion of the length of a region other than the region corresponding to the organic fine particles 63 and the inorganic fine particles 64 in the uneven surface 62A of the antiglare layer 62 is preferably 15% to 70% in a cross section along the thickness direction of the antiglare layer 62 (the normal direction of the light-transmissive substrate 61). When the ratio is 15% or more, the antiglare film generates a suitable positive transmission (positive reflection) component, and can secure the gloss, brilliance, and contrast of an image; further, by setting the ratio to 70% or less, excessive regular reflection does not occur, and thus the antiglare property can be ensured. The lower limit of the proportion is preferably 20% or more, and the upper limit of the proportion is preferably 60% or less.

The "length of the region other than the region corresponding to the organic fine particles and the inorganic fine particles" in the present specification means a length (linear distance) of a region other than the region of the uneven surface on which the organic fine particles (organic fine particle aggregates) and the inorganic fine particles (first inorganic fine particle aggregates and second inorganic fine particle aggregates) overlap when viewed from the thickness direction of the antiglare layer in a cross section along the thickness direction of the antiglare layer. The regions other than the regions corresponding to the organic fine particles and the inorganic fine particles are regions where no diffusion element contributing to internal diffusion and/or surface diffusion is present, and the screen image light transmitted through the regions is formed only by a component in the normal transmission direction, and the external light is similarly formed only by a component in the normal reflection direction. On the other hand, the regions corresponding to the organic fine particles and the inorganic fine particles are regions having diffusion elements contributing to internal diffusion and/or surface diffusion, and the screen image light transmitted through the regions contains a diffusion component, and the external light similarly has a diffuse reflection component. For example, in the case of fig. 10, the length of the region other than the region corresponding to the organic fine particles 63 and the inorganic fine particles 64 is L ₁ ～L ₄ . The length ratio is a value measured from an image of a cross-sectional electron microscope (TEM, STEM) using image processing software.

< Binder resin >

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

According to the present embodiment, the antiglare film 60 has an arithmetic average value of the transmission image brightness measured by using 0.125mm wide, 0.25mm wide, 0.5mm wide, 1.0mm wide, and 2.0mm wide combs of 70% or more, and an absolute value of a difference between the arithmetic average value and the transmission image brightness measured by using each comb is 10% or less, and therefore, it is possible to obtain antiglare properties of a degree not to be noticeable to humans, and to obtain good glare resistance and good black color feeling. That is, since the absolute value of the difference between the arithmetic average value and the sharpness of the transmitted image measured by using each optical comb is 10% or less, the difference in sharpness of the transmitted image between the optical combs is small. This indicates that the transmitted light is diffused only at the convex portions on the surface of the antiglare film and is not diffused at the flat portions on the surface of the antiglare film. Meaning that the flat portion is substantially free of tilt. Since the flat portion is substantially free from inclination in this manner, occurrence of glare can be suppressed, and good glare prevention can be obtained. Further, since the flat portion has substantially no inclination, it can have an appropriate regular reflection component, and when a moving image is displayed, the gloss and brilliance of the image increase, and a sense of jump can be obtained. Further, since the arithmetic average value of the sharpness of the transmitted image is 70% or more, the convex portion on the surface of the antiglare film is not excessively large. Therefore, in addition to the above-described effects, it is possible to prevent the screen image light from becoming stray light while suppressing a decrease in the bright room contrast without excessive diffusion of the external light, and it is also possible to obtain a good dark room contrast. Further, by setting the arithmetic average of the sharpness of the transmitted image to 95% or less, the number of flat portions is not increased, that is, the convex portions can be appropriately formed on the surface of the antiglare film and the reflected light can be appropriately diffused, so that the antiglare property of a level of not giving a noticeable reflection can be obtained. Thus, it is possible to obtain an antiglare property to a degree that does not cause a person to be conscious, and also to obtain a good glare preventing property and a good black color feeling having both an excellent contrast and a sense of jumping. The antiglare property, which is not concerned about the degree of the viewer (observer) and the background of the viewer from being reflected therebetween, is, for example, an antiglare property such as: the presence of a viewer can be found, but only its contour exhibits an unclear state of blur; and also the presence of items located at the background of the viewer, but with unclear outlines or borders. In this way, the contour or the like of the observer is merely blurred, and appears in a state where it is not noticeable to the observer.

According to the present embodiment, since the first inorganic fine particle aggregates 64A include the curved portion 64B having the inner region 64C, a more satisfactory anti-glare property can be obtained and a black color sensation having both an excellent contrast and a sense of jump can be further obtained for the same reason as in the first embodiment.

[ method for producing anti-glare film ]

The antiglare film 60 can be formed, for example, as follows. First, a composition for an antiglare layer is applied to a light-transmitting substrate 61 in the same manner as in the first embodiment.

< composition for antiglare layer >

The composition for an antiglare layer contains at least the organic fine particles 63, the inorganic fine particles 64, and the photopolymerizable compound, and preferably contains organic fine particle aggregates 63A, first inorganic fine particle aggregates 64A, and second inorganic fine particle aggregates 64D. The thermoplastic resin, the thermosetting resin, a solvent, and a polymerization initiator may be added to the composition for an antiglare layer, if necessary. Further, a conventionally known dispersant or the like as exemplified in the first embodiment may be added to the composition for an antiglare layer.

< solvent, polymerization initiator >

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

After the composition for an antiglare layer is applied to the light-transmitting substrate 61, the coated composition for an antiglare layer is transferred to a heated region to be dried by various known methods and the solvent is evaporated. Here, the distribution state of the organic fine particle aggregates 63A, the first inorganic fine particle aggregates 64A, and the second inorganic fine particle aggregates 64D can be adjusted by selecting the affinity of the solvent with the solid content, the relative evaporation rate of the solvent, the solid content concentration, the temperature of the coating liquid, the drying temperature, the wind speed of the drying wind, the drying time, the concentration of the solvent atmosphere in the drying region, and the like.

Thereafter, the composition for an antiglare layer in the form of a coating film is irradiated with light such as ultraviolet rays to polymerize (crosslink) the photopolymerizable compound, thereby curing the composition for an antiglare layer to form an antiglare layer 62. Here, as described above, since the first inorganic fine particle aggregates 64A have the bent portions 64B and the bent portions 64B have the inner regions 64C, the first inorganic fine particle aggregates function as a solid having a cushioning effect during solidification and shrinkage. Thus, the first inorganic particulate aggregates 64A collapse easily and uniformly upon solidification shrinkage.

The method for producing the composition for an antiglare layer, the drying conditions, and the light when curing the composition for an antiglare layer are the same as those of the first embodiment, and therefore, the description thereof is omitted.

< polarizing plate, liquid crystal panel, image display device >

As shown in fig. 12 to 14, the antiglare film 60 can be incorporated into, for example, a polarizing plate 70, a liquid crystal panel 80, and an image display device 90, and used, as in the first embodiment. In fig. 12 to 14, the same reference numerals as those in fig. 3 to 5 denote the same members as those described in the first embodiment.

[ fourth embodiment ]

An antiglare film according to a fourth embodiment of the present invention is described below with reference to the drawings.

< < anti-glare film > >)

Fig. 15 is a schematic configuration diagram of the antiglare film of the present embodiment, fig. 16 is a partial enlarged view of fig. 15, and fig. 17 is a partial enlarged view of fig. 16.

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

The surface 100A of the antiglare film 100 is a concave-convex surface. In the present embodiment, since a functional layer such as a low refractive index layer is not provided on the antiglare layer 102, the uneven surface 102A of the antiglare layer 102 is the surface 100A of the antiglare film 100.

In the antiglare film 100, when the frequency distribution of the inclination angle of the surface 100A of the antiglare film 100 with respect to the surface 101A of the light-transmissive substrate 101 is obtained at 0.01 degrees, the ratio of the 99 th percentile to the 3 rd quartile (99 th percentile/3 rd quartile) in the cumulative percentage of the frequencies of the inclination angles is 3.0 to 5.0. The lower limit of the 99 th percentile/the 3 rd quartile is preferably 4.0 or more, and the upper limit of the 99 th percentile/the 3 rd quartile is preferably 4.5 or less.

The "inclination angle" is an inclination angle of the surface of the antiglare film. That is, in the case where a functional layer such as a low refractive index layer is not provided on the antiglare layer as in the present embodiment, the "inclination angle" measured is the inclination angle of the uneven surface of the antiglare layer. In the case where a functional layer such as a low refractive index layer is provided on the antiglare layer, the "inclination angle" is an inclination angle of the surface of the functional layer rather than an inclination angle of the uneven surface of the antiglare layer. In addition, the "inclination angle" is an absolute value.

The inclination angle is obtained by measuring the surface shape of the surface of the antiglare film. Examples of the device for measuring the surface shape include a contact surface roughness meter and a non-contact surface roughness meter (e.g., an interference microscope, a confocal microscope, an atomic force microscope, etc.). Among them, an interference microscope is preferable for the sake of simplicity of measurement. Examples of such an interference microscope include "New View" series manufactured by Zygo corporation.

When the inclination angle is calculated using an 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 by the following formula (6) _i 。

θ _i ＝tan ^-1 St…(6)

The slope St can be obtained from the following equation (7).

[ number 1 ]

Where one of 2 directions orthogonal to the measurement plane is defined as an x-axis and the other is defined as a y-axis, Sx is a slope in the x-axis direction with respect to the x-axis, and Sy is a slope in the y-axis direction with respect to the y-axis, and the values are calculated by the following equations (8) and (9).

Sx＝(Z _i+1,j -Z _i-1,j )/2⊿…(8)

Sy＝(Z _i,j+1 -Z _i,j-1 )/2⊿…(9)

In formulae (8) and (9), Z _i,j The height of the ith in the x-axis direction and the jth in the y-axis direction is delta, which is a sampling interval.

In the measurement of the surface shape of the surface 100A, it is preferable to calculate the inclination angle from the roughness obtained by removing the waviness (うねり) with a high-pass filter based on a sampling length value of 300 μm.

It is known that the tilt 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. This is because if the sampling interval is too small, a high-frequency component of unevenness on noise is picked up, and the tilt angle may be estimated to be too large; if the sampling interval is too large, the surface angle may not be accurately estimated. The measurement area is preferably large, and the measurement can be performed in a region of at least 200. mu. m.times.200. mu.m or more, more preferably 500. mu. m.times.500. mu.m or more.

In the antiglare film 100, the absolute value of the difference between the arithmetic average of the sharpness of the transmitted image measured by using the optical combs having a width of 0.125mm, a width of 0.25mm, a width of 0.5mm, a width of 1.0mm and a width of 2.0mm and the sharpness of the transmitted image measured by using each optical comb is preferably within 10%. By setting this difference to 10% or less, glare can be more reliably suppressed. The transmission image sharpness may be measured by using the same apparatus as that of the third embodiment.

The average value of the transmitted image sharpness of the antiglare film 100 measured using the 5 types of combs described above is preferably 80% or more. The transmission image clarity of the antiglare film 100 measured with a 0.125mm wide comb is preferably 70% or more, the transmission image clarity of the antiglare film 100 measured with a 0.25mm wide comb is preferably 70% or more, the transmission image clarity of the antiglare film 100 measured with a 0.5mm wide comb is preferably 80% or more, the transmission image clarity of the antiglare film 100 measured with a 1.0mm wide comb is preferably 80% or more, and the transmission image clarity of the antiglare film 100 measured with a 2.0mm wide comb is preferably 90% or more.

On the surface 100A of the antiglare film 100, the average spacing Sm of the irregularities constituting the surface 100A is preferably 0.1mm to 0.6mm, more preferably 0.2mm to 0.4 mm. On the surface 100A of the antiglare film 100, the average inclination angle θ a of the irregularities constituting the surface 100A is preferably 0.05 ° to 0.30 °, more preferably 0.15 ° to 0.25 °.

On the surface 100A of the antiglare film 100, the arithmetic average roughness Ra of the irregularities constituting the surface 100A is preferably 0.02 μm or more and 0.20 μm or less, more preferably 0.04 μm or more and 0.10 μm or less.

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

The total light transmittance of the antiglare film 100 is preferably 85% or more, more preferably 90% or more, for the same reason as in the first embodiment. The total light transmittance can be measured by the same method as in the first embodiment.

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

When the anti-glare film has an internal haze value, the anti-glare property is improved; on the other hand, if the internal haze value is too large, stray light occurs and the black color may be deteriorated, so the internal haze value of the antiglare film 100 is preferably 0.1% or more and 2.0% or less from the viewpoint of improvement of the antiglare property and the black color. The internal haze value of the antiglare film 100 is more preferably 0.5% or more and 1.5% or less. The internal haze value can be measured by the same method as that of the first embodiment.

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

< light-transmitting substrate >

The light-transmissive substrate 101 is the same as the light-transmissive substrate 11 described in the first embodiment, and therefore, description thereof is omitted.

< anti-glare layer >

The antiglare layer 102 is a layer exhibiting antiglare properties, and as shown in fig. 16, contains 2 or more organic fine particles 103, 2 or more inorganic fine particles 104, and a binder resin 105. The antiglare layer 102 may exert other functions as well as antiglare properties. Specifically, the antiglare layer 102 may be a layer that exhibits functions such as hard coat property, antireflection property, antistatic property, and antifouling property, as well as antiglare property.

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

The surface of the antiglare layer 102 is an uneven surface 102A. In the present embodiment, since the uneven surface 102A of the antiglare layer 102 is the surface 100A of the antiglare film 100, when a frequency distribution of the inclination angle of the uneven surface 102A of the antiglare layer 102 with respect to the surface 101A of the light-transmissive substrate 101 is obtained at every 0.01 degrees, the ratio of the 99 th percentile to the 3 rd quartile (99 th percentile/3 rd quartile) in the cumulative percentage of the frequencies of the inclination angles is 3.0 to 5.0.

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

< organic Fine particles >

For the same reason as in the third embodiment, at least a part of the organic fine particles in the 2 or more organic fine particles 103 are present in the form of organic fine particle aggregates 103A, and the organic fine particle aggregates 103A are formed by aggregating the 2 or more organic fine particles 103.

In the antiglare layer 102, the maximum height of the organic particulate aggregates 103A in the thickness direction of the antiglare layer 102 is preferably smaller than the thickness of the antiglare layer 12 for the same reason as in the first embodiment.

The organic fine particles 103 include, for example, plastic beads as exemplified in the first embodiment. For the same reason as in the first embodiment, it is also preferable to perform hydrophilization treatment on the surface of the organic fine particles 103.

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

When the thickness of the antiglare layer 102 is T and the average primary particle diameter of the organic fine particles 103 is R, R/T preferably satisfies the relationship of the above expression (3) for the same reason as in the first embodiment.

For the same reason as in the first embodiment, the number of the organic fine particles 103 constituting the organic fine particle aggregates 103A is preferably 2 to 3. The organic fine particle aggregates 103A can be obtained by controlling the aggregation state as in the first embodiment, for example.

< inorganic Fine particles >

The inorganic fine particles 104 are not particularly limited, and examples thereof include inorganic oxide fine particles similar to those exemplified in the first embodiment. When silica particles are used as the inorganic fine particles 104, fumed silica fine particles are preferable in terms of being able to easily form an antiglare layer having smooth uneven surfaces among the silica particles.

When the inorganic oxide particles are used as the inorganic fine particles 104, the inorganic oxide fine particles are preferably amorphous for the same reason as in the first embodiment. When the fumed silica fine particles are used as the inorganic fine particles 104, the fumed silica fine particles exhibiting hydrophobicity are preferable for the same reason as in the first embodiment. The hydrophobic fumed silica can be obtained by chemically reacting the surface-treating agent as described above with silanol groups present on the surface of the fumed silica particles.

For the same reason as in the first embodiment, the inorganic fine particles 104 are preferably spherical in shape in a single particle state.

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

At least a part of the inorganic fine particles 104 in the 2 or more inorganic fine particles 104 is preferably present in the form of a first inorganic fine particle aggregate 104A in which 3 or more inorganic fine particles 104 are aggregated.

The first inorganic fine particle aggregates 104A are present in the binder resin 105 and are composed of 3 or more inorganic fine particles 104 as described above. The first inorganic particle aggregates 104A preferably have curved portions 104B formed by the connection of the inorganic particles 104 as shown in fig. 17. The shape of the bent portion 104B is similar to that of the bent portion 13A.

The bent portion 104B may be formed of 1 inorganic fine particle aggregate formed by inorganic fine particles connected and curved, or may be formed of a trunk portion formed by inorganic fine particles connected, and branch portions branched from the trunk portion and formed by inorganic fine particles connected, or may be formed of 2 branch portions branched from the trunk portion and connected to the trunk portion.

The inflection portion 104B has an inner region 104C as shown in fig. 17. The inner region 104C is filled with a binder resin 105. It is preferable that the inflected section 104B is present so as to sandwich the inner region 104C from the thickness direction of the antiglare layer 102.

The inorganic fine particle aggregates in which the inorganic fine particles are aggregated into a mass form act as a single solid when the photopolymerizable compound which becomes the binder resin after curing shrinks (polymerization shrinkage), and therefore the uneven surface of the antiglare layer corresponds to the shape of the inorganic fine particle aggregates. In contrast, the first inorganic particulate aggregate 104A has the inflection portion 104B, and the inflection portion 104B has the inner region 104C, and thus acts as a solid having a cushioning effect when it is solidified and contracted. Therefore, the first inorganic particle aggregates 104A collapse easily and uniformly upon curing shrinkage. Therefore, the shape of the uneven surface 102A becomes gentler than the shape before curing and shrinking.

In the first inorganic fine particle aggregates 104A, the ratio of 1 to 3 inorganic fine particles to 1 inorganic fine particle in contact with each other is preferably 95% or more for the same reason as in the first embodiment. The proportion of the inorganic fine particles is more preferably 97% or more, and still more preferably 99% or more.

For the same reason as in the first embodiment, in the antiglare layer 102, the proportion of the first inorganic fine particle aggregates 104A present is preferably higher on the light-transmitting substrate 101 side of the antiglare layer 102 than on the uneven surface 102A side of the antiglare layer 102. Here, whether the first inorganic fine particle aggregates are present on the light-transmitting substrate side or the uneven surface side in the antiglare layer is determined by the same method as that described in the first embodiment.

Specifically, when the number of the first inorganic fine particle aggregates 104A present on the light-transmitting substrate 101 side of the antiglare layer 102 in the first inorganic fine particle aggregates 104A is Nb and the number of the first inorganic fine particle aggregates 104A present on the uneven surface 102A side of the antiglare layer 102 is Nf in a cross section along the thickness direction of the antiglare layer 102, Nb/Nf is preferably satisfied by the above formula (2) for the same reason as in the first embodiment.

For the same reason as in the first embodiment, the first inorganic particle-aggregate 104A is preferably present at least at a position on the surface of the organic particle-aggregate 103A and at a position separated from the organic particle-aggregate 103A and between the organic particle-aggregate 103A.

For the same reason as in the first embodiment, the average aggregate diameter of the first inorganic fine particle aggregates 104A is preferably 100nm or more and 2.0 μm or less. The lower limit of the average particle diameter of the first inorganic fine particle aggregates 104A is preferably 200nm or more, and the upper limit thereof is preferably 1.5 μm or less. The average particle diameter of the first inorganic microparticle aggregates is determined by the same method as in the first embodiment.

The first inorganic fine particle aggregates 104A preferably have an aggregate diameter in a direction perpendicular to the thickness direction of the antiglare layer 102 that is larger than the aggregate diameter in the thickness direction. The "diameter of aggregation in the thickness direction" and the "diameter of aggregation in the direction orthogonal to the thickness direction" are measured by the same method as in the first embodiment.

The first inorganic fine particle aggregates 104A can be obtained by controlling the hydrophilization treatment of the organic fine particles 103, the hydrophobization treatment of the inorganic fine particles 104, and the presence ratio of hydroxyl groups in the binder resin 105, for example. Although hydroxyl groups are present on the surfaces of the inorganic fine particles 104, when the first inorganic fine particles 104 are subjected to the hydrophobic property-imparting treatment, the hydroxyl groups present on the surfaces of the inorganic fine particles 104 are reduced, and the inorganic fine particles can be inhibited from excessively aggregating. Further, by subjecting the surface of the inorganic fine particles 104 to a hydrophobic treatment, the chemical resistance and saponification resistance of the inorganic fine particles themselves can be improved.

Such hydrophobization treatment can be performed using a silane-based or silazane-based surface treatment agent. Specific examples of the surface treatment agent include dimethyldichlorosilane exemplified in the first embodiment.

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

As shown in fig. 16 and 17, the inorganic fine particles 104 in the antiglare layer 102 may include a first inorganic fine particle aggregate 104A and a second inorganic fine particle aggregate 104D in which 2 or more inorganic fine particles 104 are aggregated. The second inorganic particle aggregates 104D are present on or in the vicinity of the uneven surface 102A. In the second inorganic fine particle aggregates 104D, the ratio of 1 to 3 inorganic fine particles to the inorganic fine particles in contact with the 1 inorganic fine particle is preferably 95% or more. Further, the aggregation diameter of the second inorganic fine particle aggregates 104D in the direction orthogonal to the thickness direction of the antiglare layer 102 is preferably larger than the aggregation diameter in the thickness direction, and the second inorganic fine particle aggregates 104D are more preferably two-dimensionally aggregated. Further, since the second inorganic particulate aggregates 104D are present closer to the uneven surface 102A or its vicinity than the first inorganic particulate aggregates 104A, the uneven surface 102A can be made smoother by making the aggregation diameter in the thickness direction of the antiglare layer 12 smaller than that of the first inorganic particulate aggregates 104A.

By having the second inorganic fine particle aggregates 104D present on or near the uneven surface 102A, the hardness of the surface of the antiglare layer 102 can be increased, and therefore a relatively soft binder resin can be used as the binder resin 105, and the antiglare film 100 having excellent flexibility can be obtained.

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

Since the inorganic fine particles 104 constituting the second inorganic fine particle aggregates 104D may be the same as the inorganic fine particles 104 constituting the first inorganic fine particle aggregates 104A, the description thereof will be omitted. The second inorganic fine particle aggregates 104D can be obtained in the same manner as the first inorganic fine particle aggregates 104A, and can be obtained by controlling the hydrophilization treatment of the organic fine particles 103, the hydrophobization treatment of the inorganic fine particles 104, and the presence ratio of the hydroxyl groups of the binder resin 105, for example. Here, in order to make the aggregation state of the second inorganic particle aggregates 104D different from the aggregation state of the first inorganic particle aggregates 104A, for example, in the second inorganic particle aggregates 104D, a surface treatment agent different from the first inorganic particle aggregates 104A or a surface treatment agent concentration different from the first inorganic particle aggregates 104A may be used.

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

< Binder resin >

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

In the present embodiment, when the frequency distribution of the inclination angle of the surface 100A of the antiglare film 100 with respect to the surface 101A of the light-transmissive substrate 101 is obtained at every 0.01 degrees, the ratio of the 99 th percentile to the 3 rd quartile (99 th percentile/3 rd quartile) in the cumulative percentage of the frequencies of the inclination angles is 3.0 or more and 5.0 or less, and therefore, it is possible to obtain antiglare properties of a degree that does not cause glare, and to obtain good glare resistance and good black color. That is, since the 99 th percentile indicates the maximum value of the inclination angle and the 3 rd quartile is a representative value of the main inclination angle in the inclination angle distribution, a large value of the 99 th percentile/3 rd quartile indicates that the main portion of the uneven shape on the surface of the antiglare film is deviated to the smaller one of the inclination angles, that is, that there are a large number of flat portions on the surface of the antiglare film. In the present embodiment, the 99 th percentile/3 rd quartile is 3.0 or more, and therefore the 99 th percentile/3 rd quartile is large, and many flat portions are present on the surface 100A of the antiglare film 100. By having a large number of flat portions on the surface 100A of the antiglare film 100, occurrence of glare can be suppressed, and thus good glare prevention can be obtained. Further, since a large number of flat portions are present on the surface 100A of the antiglare film 100, an appropriate regular reflection component can be present, and thus when a moving image is displayed, the gloss and brilliance of the image increase, and a sense of leap can be obtained. Further, it is possible to prevent the screen image light from becoming stray light while suppressing a decrease in the bright room contrast without causing excessive diffusion of the external light, and it is also possible to obtain a good dark room contrast. On the other hand, if the 99 th percentile/3 rd quartile is too large, the antiglare property is deteriorated because there are too many flat portions on the surface of the antiglare film. In the present embodiment, since the 99 th percentile/3 rd quartile is 5.0 or less, the surface 100A of the antiglare film 100 does not have an excessive number of flat portions, and thus antiglare properties of a degree that does not cause a person to perceive a reflection can be obtained. This makes it possible to obtain an antiglare property to a degree that does not cause glare, and also to obtain a good glare-preventing property and a good black color. The antiglare property to the extent that the reflection between the observer (observer) and the background of the observer is not noticeable is, for example, an antiglare property such as: the presence of a viewer can be found, but only its contour exhibits an unclear state of blur; and also the presence of items located at the background of the viewer, but with unclear outlines or borders. In this way, the contour or the like of the observer is merely blurred, and appears in a state where it is not noticeable to the observer.

According to the present embodiment, since the first inorganic fine particle aggregates 104A have the bent portions 104B and the bent portions 104B have the inner regions 104C, a more satisfactory anti-glare property can be obtained and a black color sensation having both an excellent contrast and a sense of jump can be further obtained for the same reason as in the first embodiment.

[ method for producing anti-glare film ]

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

< composition for antiglare layer >

The composition for an antiglare layer contains at least the organic fine particles 103, the inorganic fine particles 104, and the photopolymerizable compound, and preferably contains the organic fine particle aggregate 103A, the first inorganic fine particle aggregate 104A, and the second inorganic fine particle aggregate 104D. The thermoplastic resin, the thermosetting resin, a solvent, and a polymerization initiator may be added to the composition for an antiglare layer, if necessary. Further, a conventionally known dispersant or the like as exemplified in the first embodiment may be added to the composition for an antiglare layer.

< solvent and polymerization initiator >

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

After the composition for an antiglare layer is applied to the light-transmitting substrate 101, the coated composition for an antiglare layer is transferred to a heated region to be dried by various known methods and the solvent is evaporated. Here, the distribution state of the organic fine particle aggregates 103A, the first inorganic fine particle aggregates 104A, and the second inorganic fine particle aggregates 104D can be adjusted by selecting the affinity between the solvent and the solid content, the relative evaporation rate of the solvent, the solid content concentration, the temperature of the coating liquid, the drying temperature, the wind speed of the drying wind, the drying time, the concentration of the solvent atmosphere in the drying region, and the like.

Thereafter, the composition for an antiglare layer in the form of a coating film is irradiated with light such as ultraviolet rays to polymerize (crosslink) the photopolymerizable compound, thereby curing the composition for an antiglare layer to form the antiglare layer 102. Here, as described above, the first inorganic fine particle aggregates 104A have the bent portions 104B, and the bent portions 104B have the inner regions 104C, and thus function as a solid having a cushioning effect during solidification and shrinkage. Thus, the first inorganic particle aggregates 104A collapse easily and uniformly upon curing shrinkage.

The method of producing the composition for an antiglare layer, the drying conditions, and the light when curing the composition for an antiglare layer are the same as those in the first embodiment, and therefore, the description thereof is omitted.

< polarizing plate, liquid crystal panel, image display device >

As shown in fig. 18 to 20, the antiglare film 100 can be incorporated into, for example, a polarizing plate 110, a liquid crystal panel 120, and an image display device 130, and used, as in the first embodiment. In fig. 18 to 20, the same reference numerals as in fig. 3 to 5 denote the same members as those described in the first embodiment.

[ examples ] A

The present invention will be described in detail with reference to examples, but the present invention is not limited to these descriptions.

< example A >

< preparation of composition for antiglare layer >

First, the components were mixed in the following composition to obtain a composition for an antiglare layer.

(composition for antiglare layer A1)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by water-accumulative chemical industries): 3 parts by mass

Fumed silica (inorganic fine particles, hexamethyldisilazane-treated, average primary particle diameter 50nm, manufactured by NIPPON AEROSIL Co., Ltd.): 1 part by mass of

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 60 parts by mass

Isocyanuric acid ethoxy-modified diacrylate (product name "M-215", manufactured by Toyo Synthesis 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 "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Methyl isobutyl ketone (MIBK): 30 parts by mass

(composition for antiglare layer A2)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 4 parts by mass

Fumed silica (inorganic fine particles, hexamethyldisilazane-treated, average primary particle diameter 50nm, manufactured by NIPPON AEROSIL Co., Ltd.): 1 part by mass

Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by Daicel SciTech corporation): 60 parts by mass

Urethane acrylate (product name "UV 1700B", manufactured by japan synthetic chemical corporation): 40 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Cyclohexanone: 30 parts by mass

(composition for antiglare layer A3)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 1 part by mass

Fumed silica (inorganic fine particles, octylsilane-treated, average primary particle diameter 12nm, manufactured by NIPPON AEROSIL Co., Ltd.): 1 part by mass

Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by Daicel SciTech corporation): 60 parts by mass

Urethane acrylate (product name "UV 1700B", manufactured by japan synthetic chemical corporation): 40 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 105 parts by mass of

Isopropyl alcohol: 30 parts by mass

Cyclohexanone: 15 parts by mass

(composition for antiglare layer A4)

2.5 parts by mass of fumed silica (inorganic fine particles, octylsilane-treated, average particle diameter 12nm, manufactured by NIPPON AEROSIL Co., Ltd.)

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 70 parts by mass

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

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass of

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 105 parts by mass

Isopropanol: 35 parts by mass

Cyclohexanone: 10 parts by mass

(composition for anti-glare layer A5)

Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 4.1 μm, manufactured by Fuji silica Chemical corporation): 4 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 100 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 150 parts by mass of

Methyl isobutyl ketone (MIBK): 35 parts by mass

The amorphous silica particles are produced by a gel method.

(composition for antiglare layer A6)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 3.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 7 parts by mass

Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 2.7 μm, manufactured by Fuji silica Chemical corporation): 2 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 100 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass of

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Cyclohexanone: 30 parts by mass

The amorphous silica particles are produced by a gel method.

< example A1>

A cellulose triacetate substrate (TD 60UL, manufactured by Fuji film Co.) having a thickness of 60 μm was prepared as a light-transmitting substrate, and a coating film was formed by applying the composition A1 for an antiglare layer to one surface of the cellulose triacetate substrate. Then, the formed coating film was dried by allowing 70 ℃ dry air to flow at a flow rate of 0.2m/s for 15 seconds, and then allowing 70 ℃ dry air to flow at a flow rate of 10m/s for 30 seconds, thereby evaporating the solvent in the coating film, and the cumulative light amount was 100mJ/cm in a nitrogen atmosphere (oxygen concentration of 200ppm or less) ² The coating film was cured by irradiation with ultraviolet rays to form an antiglare layer having a thickness of 4 μm upon curing, thereby producing an antiglare film of example a 1.

< example A2>

An antiglare film was produced in the same manner as in example a1, except that in example a2, the antiglare layer composition a2 was used instead of the antiglare layer composition a1, and the thickness of the antiglare layer during curing was set to 3 μm.

< example A3>

An antiglare film was produced in the same manner as in example a1, except that in example A3, the antiglare layer composition a1 was not used, but the antiglare layer composition A3 was used.

< example A4>

An antiglare film was produced in the same manner as in example a1, except that in example a4, the antiglare layer composition a1 was not used, but the antiglare layer composition a4 was used.

< comparative example A1>

An antiglare film was produced in the same manner as in example a1, except that in comparative example a1, the antiglare layer composition a5 was used instead of the antiglare layer composition a1, and the thickness of the antiglare layer during curing was 2 μm.

< comparative example A2>

An antiglare film was produced in the same manner as in example a1, except that in comparative example a2, the antiglare layer composition a6 was used instead of the antiglare layer composition a1, and the thickness of the antiglare layer during curing was 3 μm.

< Cross-section Observation of antiglare film >

The cross-sections of the antiglare films obtained in example a1 and example a2 were photographed using a Scanning Transmission Electron Microscope (STEM) function of a Scanning Electron Microscope (SEM) (manufactured by S-4800, High-Tech co.) and the obtained STEM cross-sectional photographs were observed. Fig. 21 is a cross-sectional photograph of the antiglare film of example a1 taken using a scanning transmission electron microscope function of a scanning electron microscope, and fig. 22 is an enlarged photograph thereof. Fig. 23 is a cross-sectional photograph of the antiglare film of example a2 taken using the scanning transmission electron microscope function of a scanning electron microscope, and fig. 24 is an enlarged photograph thereof.

From the photograph of fig. 21, it was confirmed that the organic fine particle aggregates were present; inorganic particle aggregates are present, and the inorganic particle aggregates are present at least at positions on or near the uneven surface of the antiglare layer, at positions on the surface of the organic particle aggregates, and at positions separated from the organic particle aggregates and between the organic particle aggregates; and inorganic fine particle aggregates present on the uneven surface of the antiglare layer or in the vicinity thereof, wherein the aggregate diameter in the direction orthogonal to the thickness direction of the antiglare layer is larger than the aggregate diameter in the thickness direction.

Further, as a result of image analysis of the photograph of fig. 22, it was confirmed that the inorganic particulate aggregates present at the positions of the surfaces of the organic particulate aggregates and at the positions spaced apart from the organic particulate aggregates and between the organic particulate aggregates have bent portions having inner regions filled with the binder resin.

Similarly, from the photograph of fig. 23, it was confirmed that the organic fine particles alone were biased on the cellulose triacetate substrate side; inorganic fine particle aggregates are present, and the inorganic fine particle aggregates are present at least at positions on or near the uneven surface of the antiglare layer, at positions on the surface of the organic fine particles, and at positions separated from the organic fine particles and between the organic fine particles; and inorganic fine particle aggregates present on the uneven surface of the antiglare layer or in the vicinity thereof, wherein the aggregate diameter in the direction orthogonal to the thickness direction of the antiglare layer is larger than the aggregate diameter in the thickness direction.

Further, as a result of image analysis of the photograph of fig. 24, it was confirmed that the inorganic fine particle aggregates present at the positions of the surfaces of the organic fine particle aggregates and at the positions separated from the organic fine particle aggregates and between the organic fine particle aggregates have a flexed portion having an inner region filled with the binder resin.

< anti-glare Property >

Samples were prepared by attaching a black acrylic (acrylic) plate for preventing back reflection to the opposite side of the cellulose triacetate base material of each of the antiglare films obtained in examples a1 to a4 and comparative examples a1 and a2 from the side on which the antiglare layer was formed, with a transparent adhesive. The sample was visually observed by 15 subjects in a bright room environment, and whether or not the antiglare property was obtained to such an extent that the observer and the background of the observer were not intentionally reflected was evaluated based on the following criteria.

Very good: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people who answer well is below 4

< eye dazzling >

The glare was evaluated for each of the antiglare films obtained in examples a1 to a4 and comparative examples a1 and a2 as follows. With a luminance of 1500cd/m ² The lamp box (white surface light source), 140ppi black matrix glass, and antiglare film were laminated in this order from below, and in this state, visual evaluation was performed by 15 subjects from various angles, from the top and bottom, and from the left and right, at a distance of about 30 cm. Whether or not glare is not observed was determined, and evaluation was performed according to the following criteria.

Very good: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people with good answers is below 4

< feel of Black color >

The antiglare films obtained in examples a1 to a4 and comparative examples a1 and a2 were evaluated for black color as follows. The outermost surface of the liquid crystal television "KDL-40X 2500" manufactured by Sony corporation was peeled off and a surface-coating-free polarizing plate was attached. Then, the antiglare films of examples A1 to A4 and comparative examples A1 and A2 were bonded to a transparent pressure-sensitive adhesive film for optical films (a product having a total light transmittance of 91% or more, a haze of 0.3% or less, and a film thickness of 20 to 50 μm, for example, MHM series, manufactured by Nigron processing Co., Ltd.) so that the antiglare layer side was the outermost surface. The liquid crystal television was installed indoors under an environment with an illuminance of about 1000Lx, and 15 subjects of DVD "opera ghost (オペラ people with strangers) of MEDIA factor corporation viewed the screen image from a position of about 1.5 to 2.0m from the liquid crystal television, thereby evaluating the black color through sensory evaluation. The black color sensation is determined by whether the contrast is high when the moving image is displayed, whether the image has luster and brilliance, and whether a sense of jump is felt. The evaluation criteria are as follows.

Very good: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people who answer well is below 4

< measurement of Whole haze, internal haze and surface haze >

The total haze, the internal haze, and the surface haze of each of the antiglare films obtained in examples a1 to a4 and comparative examples a1 and a2 were measured as follows. First, the haze value of the antiglare film as a whole was measured in accordance with JIS K7136 using a haze meter (HM-150, manufactured by mura color technology research). Thereafter, a cellulose triacetate base material (TD 60UL manufactured by fuji photo film) was bonded to the surface of the antiglare layer via a transparent optical adhesive layer. Thereby, the uneven shape of the uneven surface of the antiglare layer is collapsed, and the surface of the antiglare film is flattened. In this state, the haze value was measured in accordance with JIS K7136 using a haze meter (HM-150, manufactured by murakamura color technology research), and the internal haze value was determined by subtracting the haze of the adhesive layer itself. And the surface haze value is found by subtracting the internal haze value from the overall haze value.

< Transmission image clarity >

For each of the antiglare films obtained in examples a1 to a4 and comparative examples a1 and a2, an image clarity measuring instrument (model number: ICM-1T, manufactured by SUGA TEST INSTRUMENTS) was set in accordance with the image clarity measurement method based on the JIS K7105 transmission method, and the transmitted image clarity was measured by placing the cellulose triacetate substrate side toward a light source. As the optical combs, optical combs having a width of 0.125mm, 0.5mm, 1.0mm and 2.0mm were used to measure the sharpness of the transmitted image. The measured transmission image sharpness values are summed up to obtain an average value.

< measurement of Sm, Theta a and Ra >

Sm, θ a, and Ra were measured on the surfaces of the antiglare films obtained in examples a1 to a4 and comparative examples a1 and a 2. Sm and Ra are defined based on the definition in JIS B0601-1994, and θ a is defined based on a surface roughness tester: definition in SE-3400/(Proc. Xiao Shuzo) (1995.07.20 revision).

Specifically, Sm, θ a and Ra were measured under the following measurement conditions using a surface roughness measuring instrument (model: SE-3400/(Katsuka corporation)).

1) Stylus of surface roughness detecting section (trade name SE2555N (2. mu. Standard), manufactured by Xiaoban Ltd.)

Diamond with 2 μm radius of curvature at tip and 90 ° apex angle

2) Measurement conditions of surface roughness measuring apparatus

Reference length (sampling length value λ c of roughness curve): 2.5mm

Evaluation length (reference length (sampling length value λ c) × 5): 12.5mm

Feed speed of stylus: 0.5mm/s

Preparatory length: (sampling length value. lamda.c). times.2

Longitudinal magnification: 2000 times of

Transverse magnification: 10 times of

< Flex resistance test >

The bending resistance test was performed on each of the antiglare films obtained in examples a1 to a4 and comparative examples a1 and a2 using a bending resistance tester having a mandrel, and the minimum diameter of the mandrel having no crack was shown in table 2. The flexing resistance test was carried out in accordance with JIS K5600-5-1 (1999).

< scratch resistance >

For the anti-glare films obtained in examples A1 to A4 and comparative examples A1 and A2, steel wool #0000 (product name: Bonstar, manufactured by Nippon Steel wool Co., Ltd.) was used and applied at a rate of 700g/cm ² After rubbing was repeated 10 times at a speed of 100 mm/sec under load, a black tape was attached to the opposite surface of the cellulose triacetate base material to the surface on which the antiglare layer was formed, and the presence or absence of a flaw was evaluated under a three-wavelength fluorescent lamp. The evaluation criteria for the scratch resistance evaluation are as follows.

O: the level of no or slight scars observed was practically no problem.

X: many scars were confirmed.

The results are shown in tables 1 and 2 below.

As shown in table 1, in comparative example a1, although good antiglare properties were obtained, the dazzling performance was poor. This is considered to be because, in comparative example a1, although the unevenness of the antiglare layer surface was formed by amorphous silica, the inclination angle was abruptly changed because the amorphous silica was massive. In comparative example a2, the glare was not felt, but the black color was low, although the antiglare property was good. This is considered to be because, in comparative example a2, although the unevenness of the antiglare layer surface was formed by the acrylic-styrene copolymer particles as the organic fine particles and the amorphous silica, and the haze was high, and the glare could be suppressed, the amorphous silica was massive, and an excessively large inclination angle was generated by the unevenness. On the other hand, examples a1 to a4 had good antiglare properties, no dazzling, and good black color.

< example B >

< preparation of composition for anti-glare layer >

First, the components were mixed in the following composition to obtain a composition for an antiglare layer.

(composition for antiglare layer B1)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 3 parts by mass

Fumed silica (inorganic fine particles, hexamethyldisilazane-treated, average primary particle diameter 50nm, manufactured by NIPPON AEROSIL Co., Ltd.): 1 part by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 60 parts by mass

Isocyanuric acid ethoxy-modified diacrylate (product name "M-215", manufactured by Toyo Synthesis 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 "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Methyl isobutyl ketone (MIBK): 30 parts by mass

(composition for antiglare layer B2)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 4 parts by mass of

Fumed silica (inorganic fine particles, hexamethyldisilazane-treated, average primary particle diameter 50nm, manufactured by NIPPON AEROSIL Co., Ltd.): 1 part by mass

Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by Daicel SciTech corporation): 60 parts by mass

Urethane acrylate (product name "UV 1700B", manufactured by japan synthetic chemical corporation): 40 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Cyclohexanone: 30 parts by mass

(composition for antiglare layer B3)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 2 parts by mass

Fumed silica (inorganic fine particles, octylsilane-treated, average primary particle diameter 12nm, manufactured by NIPPON AEROSIL Co., Ltd.): 2 parts by mass

Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by Daicel SciTech corporation): 60 parts by mass

Urethane acrylate (product name "UV 1700B", manufactured by japan synthetic chemical corporation): 40 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 105 parts by mass of

Isopropyl alcohol: 30 parts by mass

Cyclohexanone: 15 parts by mass

(composition for antiglare layer B4)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 3.5 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 4.5 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 65 parts by mass

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

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 110 parts by mass

Cyclohexanone: 50 parts by mass

(composition for antiglare layer B5)

Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 2.3 μm, manufactured by Fuji silica Chemical corporation): 2 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 100 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 150 parts by mass

Methyl isobutyl ketone (MIBK): 35 parts by mass

The amorphous silica particles are produced by a gel method.

(composition for antiglare layer B6)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 3.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 7 parts by mass

Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 2.7 μm, manufactured by Fuji silica Chemical corporation): 2 parts by mass of

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 100 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Cyclohexanone: 30 parts by mass

The amorphous silica particles are produced by a gel method.

< example B1>

A cellulose triacetate substrate (TD 60UL, manufactured by Fuji film Co.) having a thickness of 60 μm was prepared as a light-transmitting substrate, and a coating film was formed by applying the composition B1 for an antiglare layer to one surface of the cellulose triacetate substrate. Then, the formed coating film was dried by allowing 70 ℃ dry air to flow at a flow rate of 0.2m/s for 15 seconds, and then allowing 70 ℃ dry air to flow at a flow rate of 10m/s for 30 seconds, thereby evaporating the solvent in the coating film, and the cumulative light amount was 100mJ/cm in a nitrogen atmosphere (oxygen concentration of 200ppm or less) ² The coating film was cured by irradiation with ultraviolet light to form an antiglare layer having a thickness of 4 μm upon curing, thereby producing an antiglare film of example B1.

< example B2>

An antiglare film was produced in the same manner as in example B1, except that in example B2, the antiglare layer composition B2 was used instead of the antiglare layer composition B1, and the thickness of the antiglare layer during curing was set to 3 μm.

< example B3>

An antiglare film was produced in the same manner as in example B1, except that in example B3, the antiglare layer composition B1 was not used, but the antiglare layer composition B3 was used.

< comparative example B1>

An antiglare film was produced in the same manner as in example B1, except that in comparative example B1, the composition B4 for an antiglare layer was used instead of the composition B1, and the thickness of the antiglare layer during curing was set to 6 μm.

< comparative example B2>

An antiglare film was produced in the same manner as in example B1, except that in comparative example B2, the antiglare layer composition B5 was used instead of the antiglare layer composition B1, and the thickness of the antiglare layer during curing was set to 3 μm.

< comparative example B3>

An antiglare film was produced in the same manner as in example B1, except that in comparative example B3, the antiglare layer composition B6 was used instead of the antiglare layer composition B1, and the thickness of the antiglare layer during curing was set to 3 μm.

< Cross-section Observation of antiglare film >

The antiglare film of example B1 was the same as the antiglare film of example a1, and therefore the photographs of the cross-sections of fig. 21 and 22 can be said to be photographs of the cross-section of the antiglare film of example B1.

From the photograph of fig. 21, it was confirmed that the antiglare film of example B1 contained organic fine particle aggregates; inorganic particle aggregates are present, and the inorganic particle aggregates are present at least at positions on or near the uneven surface of the antiglare layer, at positions on the surface of the organic particle aggregates, and at positions separated from the organic particle aggregates and between the organic particle aggregates; and inorganic fine particle aggregates present on the uneven surface of the antiglare layer or in the vicinity thereof, wherein the aggregate diameter in the direction orthogonal to the thickness direction of the antiglare layer is larger than the aggregate diameter in the thickness direction.

Further, as a result of image analysis of the photograph of fig. 22, it was confirmed that, in the antiglare film of example B1, the inorganic fine particle aggregates present at the positions on the surface of the organic fine particle aggregates and at the positions separated from the organic fine particle aggregates and between the organic fine particle aggregates had flexed portions having inner regions filled with the binder resin.

< Transmission image clarity >

For each of the antiglare films obtained in examples B1 to B3 and comparative examples B1 to B3, an image clarity measuring instrument (model number: ICM-1T, manufactured by SUGA TEST INSTRUMENTS) was set in accordance with the image clarity measuring method based on the JIS K7374 transmission method, and the transmitted image clarity was measured by placing the cellulose triacetate substrate side toward a light source. As the optical combs, optical combs having a width of 0.125mm, 0.25mm, 0.5mm, 1.0mm and 2.0mm were used to measure the transmitted image sharpness, respectively. The measured transmission image sharpness values are summed up to obtain an arithmetic mean value, and the absolute value of the difference between the arithmetic mean value and the transmission image sharpness value is further obtained.

< anti-glare Property >

A black acrylic (acrylic) plate for preventing back reflection was attached to the side of the cellulose triacetate substrate of each of the antiglare films obtained in examples B1 to B3 and comparative examples B1 to B3 opposite to the side on which the antiglare layer was formed, with a transparent adhesive. The sample was visually observed by 15 subjects in a bright room environment, and whether or not the antiglare property was obtained to such an extent that the observer and the background of the observer were not visually perceived was evaluated according to the following criteria.

Very good: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people who answer well is below 4

< eye dazzling >

The glare of each of the antiglare films obtained in examples B1 to B3 and comparative examples B1 to B3 was evaluated as follows. With a luminance of 1500cd/m ² The lamp box (white surface light source), 140ppi black matrix glass, and antiglare film were laminated in this order from below, and in this state, visual evaluation was performed by 15 subjects from various angles, from the top and bottom, and from the left and right, at a distance of about 30 cm. Judging whether the patient is unconsciousThe glare was evaluated according to the following criteria.

Very good: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people with good answers is below 4

< feel of Black color >

The antiglare films obtained in examples B1 to B3 and comparative examples B1 to B3 were evaluated for black color as follows. The outermost surface of the liquid crystal television "KDL-40X 2500" manufactured by Sony corporation was peeled off and a surface-coating-free polarizing plate was attached. The obtained antiglare films of examples B1 to B3 and comparative examples B1 to B3 were then bonded to a transparent pressure-sensitive adhesive film for an antiglare film (a product having a total light transmittance of 91% or more, a haze of 0.3% or less, and a film thickness of 20 to 50 μm, for example, MHM series manufactured by nippon corporation) so that the antiglare layer side was the outermost surface. The liquid crystal television was installed indoors under an environment of an illuminance of about 1000Lx, a DVD "opera ghost" of MEDIA factor was played, and 15 subjects viewed the screen image at a distance of about 1.5 to 2.0m from the liquid crystal television, and evaluated the black color feeling by sensory evaluation. The black color sensation is determined by whether or not the contrast is high, the image has luster and brilliance, and a sense of snap sensation is felt when the moving image is displayed. The evaluation criteria are as follows.

Very good: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people who answer well is below 4

< measurement of Total haze, internal haze and surface haze >

The total haze, the internal haze, and the surface haze of each of the antiglare films obtained in examples B1 to B3 and comparative examples B1 to B3 were measured as follows. First, the total haze value of the antiglare film was measured in accordance with JIS K7136 using a haze meter (HM-150, manufactured by mura color technology research). Thereafter, a cellulose triacetate base material (TD 60UL, manufactured by fuji film corporation) was bonded to the surface of the antiglare layer via a transparent optical adhesive layer. Thereby, the uneven shape of the uneven surface of the antiglare layer is collapsed, and the surface of the antiglare film is flattened. In this state, the haze value was measured in accordance with JIS K7136 using a haze meter (HM-150, manufactured by murakamura color technology research), and the internal haze value was determined by subtracting the haze of the adhesive layer itself. And the surface haze value is found by subtracting the internal haze value from the full haze value.

< measurement of Sm, Theta a and Ra >

Sm, θ a, and Ra were measured on the surfaces of the antiglare films obtained in examples B1 to B3 and comparative examples B1 to B3. Sm and Ra are defined based on the definition in JIS B0601-1994, and θ a is defined based on a surface roughness tester: definition in SE-3400/(Proc. Xiao Shuzo) (1995.07.20 revision).

Specifically, Sm, θ a and Ra were measured under the following measurement conditions using a surface roughness measuring instrument (model: SE-3400/(Katsuka corporation)).

1) Stylus of surface roughness detecting section (trade name SE2555N (2. mu. Standard), manufactured by Xiaoban Ltd.)

Diamond with 2 μm radius of curvature at tip and 90 ° apex angle

2) Measurement conditions of surface roughness measuring apparatus

Reference length (sampling length value λ c of roughness curve): 2.5mm

Evaluation length (reference length (sampling length value λ c) × 5): 12.5mm

Feed speed of stylus: 0.5mm/s

Preparatory length: (sampling length value. lamda.c). times.2

Vertical magnification: 2000 times of

Transverse magnification: 10 times of

< Flex resistance test >

The bending resistance test was performed on each of the antiglare films obtained in examples B1 to B3 and comparative examples B1 to B3 using a bending resistance tester having a mandrel, and the minimum diameter of the mandrel having no crack was shown in table 5. The flexing resistance test was carried out in accordance with JIS K5600-5-1 (1999).

< scratch resistance >

For theEach of the anti-glare films obtained in examples B1 to B3 and comparative examples B1 to B3 was prepared by applying 700g/cm of steel wool No. #0000 (product name: Bonstar, manufactured by Nippon Steel wool Co., Ltd.) to a glass plate ² After rubbing was repeated 10 times at a speed of 100 mm/sec under load, a black tape was attached to the opposite surface of the cellulose triacetate substrate to the surface on which the antiglare layer was formed, and the presence or absence of scratches was visually evaluated under a three-wavelength fluorescent lamp. The evaluation criteria for the scratch resistance evaluation are as follows.

O: the level of no or slight scars observed was practically no problem.

X: many scars were confirmed.

The results are shown in tables 3 to 5 below.

As shown in table 4, in comparative example B1, although good antiglare properties were obtained, the dazzling performance was poor. This is considered to be because, in comparative example B1, the absolute value of the difference between each comb of the transmitted image sharpness and the arithmetic average value is large, and therefore, the flat portion is small and glaring is likely to occur. In comparative example B2, the glare property and the black tone were good, but the antiglare property was poor. This is considered to be because, in comparative example B2, the arithmetic average of the sharpness of the transmission image is large, and the number of flat portions is too large. In comparative example B3, the glare resistance was good, but the black color sensation was low. This is considered to be because, in comparative example B3, although the surface roughness of the antiglare layer was formed by the acrylic-styrene copolymer particles as organic fine particles and amorphous silica, and the haze was high, and glare could be suppressed, the arithmetic average of the sharpness of the transmitted image was small, and there were almost no flat portions. On the other hand, examples B1 to B3 had good antiglare properties, no fear of glare, and good black color.

< example C >

< preparation of composition for antiglare layer >

First, the components were mixed in the following composition to obtain a composition for an antiglare layer.

(composition for anti-glare layer C1)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 3 parts by mass of

Fumed silica (inorganic fine particles, hexamethyldisilazane-treated, average primary particle diameter 50nm, manufactured by NIPPON AEROSIL Co., Ltd.): 1 part by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 60 parts by mass

An ethoxy-modified diacrylate isocyanurate (product name "M-215", manufactured by Toyo Kogyo 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 "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Methyl isobutyl ketone (MIBK): 30 parts by mass

(composition for antiglare layer C2)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by water-accumulative chemical industries): 4 parts by mass

Fumed silica (inorganic fine particles, hexamethyldisilazane-treated, average primary particle diameter 50nm, manufactured by NIPPON AEROSIL Co., Ltd.): 1 part by mass

Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by Daicel SciTech corporation): 60 parts by mass

Urethane acrylate (product name "UV 1700B", manufactured by japan synthetic chemical corporation): 40 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass of

Cyclohexanone: 30 parts by mass

(composition for antiglare layer C3)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 2.0 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 2 parts by mass

Fumed silica (inorganic fine particles, octylsilane-treated, average primary particle diameter 12nm, manufactured by NIPPON AEROSIL Co., Ltd.): 2 parts by mass

Pentaerythritol tetraacrylate (PETTA) (product name "PETA", manufactured by Daicel SciTech corporation): 60 parts by mass

Urethane acrylate (product name "UV 1700B", manufactured by japan synthetic chemical corporation): 40 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 105 parts by mass

Isopropanol: 30 parts by mass

Cyclohexanone: 15 parts by mass

(composition for antiglare layer C4)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 3.5 μm, refractive index 1.52, produced by hydroboration chemical industry Co., Ltd.): 4.5 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 65 parts by mass of

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

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 110 parts by mass

Cyclohexanone: 50 parts by mass

(composition for antiglare layer C5)

Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 2.3 μm, manufactured by Fuji silica Chemical corporation): 2 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 100 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 150 parts by mass

Methyl isobutyl ketone (MIBK): 35 parts by mass

The amorphous silica particles are produced by a gel method.

(composition for anti-glare layer C6)

Acrylic acid-styrene copolymer particles (organic fine particles, average primary particle diameter 3.0 μm, refractive index 1.52, produced by water-accumulative chemical industries): 7 parts by mass

Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 2.7 μm, manufactured by Fuji silica Chemical corporation): 2 parts by mass

Pentaerythritol triacrylate (PETA) (product name "PETIA", manufactured by Daicel SciTech corporation): 100 parts by mass

Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 5 parts by mass

Polyether-modified silicone (product name "TSF 4460", manufactured by Momentive Performance Materials corporation): 0.025 parts by mass

Toluene: 120 parts by mass

Cyclohexanone: 30 parts by mass

The amorphous silica particles are produced by a gel method.

< example C1>

A cellulose triacetate substrate (TD 60UL, manufactured by Fuji photo Co., Ltd.) having a thickness of 60 μm as a light-transmitting substrate was prepared, and a coating film was formed by applying the composition 1 for an antiglare layer to one surface of the cellulose triacetate substrate. Then, the coating film thus formed was dried by allowing 70 ℃ dry air to flow for 15 seconds at a flow rate of 0.2m/s, and then allowing 70 ℃ dry air to flow for 30 seconds at a flow rate of 10m/s, thereby evaporating the solvent in the coating film, and the cumulative light amount was 100mJ/cm in a nitrogen atmosphere (oxygen concentration 200ppm or less) ² The coating film was cured by irradiation with ultraviolet rays to form an antiglare layer having a thickness of 4 μm upon curing, thereby producing an antiglare film of example C1.

< example C2>

An antiglare film was produced in the same manner as in example C1, except that in example C2, the composition C2 for an antiglare layer was used instead of the composition C1, and the thickness of the antiglare layer during curing was set to 3 μm.

< example C3>

An antiglare film was produced in the same manner as in example C1, except that in example C3, the composition C1 for an antiglare layer was not used, but the composition C3 for an antiglare layer was used.

< comparative example C1>

An antiglare film was produced in the same manner as in example C1, except that in comparative example C1, the composition C4 for an antiglare layer was used instead of the composition C1, and the thickness of the antiglare layer during curing was set to 6 μm.

< comparative example C2>

An antiglare film was produced in the same manner as in example C1, except that in comparative example C2, the composition C5 for an antiglare layer was used instead of the composition C1, and the thickness of the antiglare layer during curing was set to 3 μm.

< comparative example C3>

An antiglare film was produced in the same manner as in example C1, except that in comparative example C3, the composition C6 for an antiglare layer was used instead of the composition C1, and the thickness of the antiglare layer during curing was set to 3 μm.

< Cross-section Observation of antiglare film >

The antiglare film of example C1 is the same as the antiglare film of example a1, and thus the photographs of the cross section of fig. 21 and 22 can also be said to be photographs of the cross section of the antiglare film of example C1.

From the photograph of fig. 21, it was confirmed that organic fine particle aggregates were present in the antiglare film of example C1; inorganic particle aggregates are present, and the inorganic particle aggregates are present at least at positions on or near the uneven surface of the antiglare layer, at positions on the surface of the organic particle aggregates, and at positions separated from the organic particle aggregates and between the organic particle aggregates; and inorganic fine particle aggregates present on the uneven surface of the antiglare layer or in the vicinity thereof, wherein the aggregate diameter in the direction orthogonal to the thickness direction of the antiglare layer is larger than the aggregate diameter in the thickness direction.

Further, as a result of image analysis of the photograph of fig. 22, it was confirmed that, in the antiglare film of example C1, the inorganic fine particle aggregates present at the positions on the surface of the organic fine particle aggregates and at the positions separated from the organic fine particle aggregates and between the organic fine particle aggregates had flexed portions having inner regions filled with the binder resin.

< Angle of inclination >

A glass plate was attached to the surface of the cellulose triacetate substrate of each of the antiglare films obtained in examples C1 to C3 and comparative examples C1 to C3, which was opposite to the surface on which the antiglare layer was formed, with a transparent adhesive to prepare a sample, and the uneven shape of the surface of the antiglare film was measured under the following conditions using a white interference microscope (New View6300, manufactured by Zygo corporation), and the inclination angle distribution was calculated from the results by the above-described method. The analysis software used the Microscope Application of MetropoPro ver 8.3.2.

[ measurement conditions ]

An objective lens: 10 times of

Zooming: 2 times of

Measurement area: 573 μm × 573 μm

Resolution (interval per 1 dot): 0.58 μm

[ analysis conditions ]

Removed：None

Filter：HighPass

FilterType：GaussSpline

Low wavelength：300μm

Remove spikes：on

Spike Height(xRMS)：2.5

It should be noted that Low wavelength corresponds to the sampling length value λ c in the roughness parameter.

< anti-glare Property >

Samples were prepared by attaching a black acrylic (acrylic) plate for preventing back reflection to the opposite side of the cellulose triacetate base material of each of the antiglare films obtained in examples C1 to C3 and comparative examples C1 to C3 from the side on which the antiglare layer was formed, with a transparent adhesive. The sample was visually observed by 15 subjects in a bright room environment, and whether or not the antiglare property was obtained to such an extent that the observer and the background of the observer were not intentionally reflected was evaluated based on the following criteria.

Excellent: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people who answer well is below 4

< glare >

The glare was evaluated for each of the antiglare films obtained in examples C1 to C3 and comparative examples C1 to C3 as follows. With a luminance of 1500cd/m ² The light box (white surface light source), 140ppi black matrix glass, and antiglare film were layered in this order from below, and visual evaluation was performed by 15 subjects from various angles of up-down and left-right at a distance of about 30cm in this state. Whether or not glare is not observed was determined, and evaluation was performed according to the following criteria.

Excellent: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people who answer well is below 4

< feeling of blackness >

The antiglare films obtained in examples C1 to C3 and comparative examples C1 to C3 were evaluated for their black color tone as follows. The outermost surface of the liquid crystal television "KDL-40X 2500" manufactured by Sony corporation was peeled off and a surface-coating-free polarizing plate was attached. The obtained antiglare films of examples C1 to C3 and comparative examples C1 to C3 were then bonded to a transparent pressure-sensitive adhesive film for antiglare films (products having a total light transmittance of 91% or more, a haze of 0.3% or less, and a film thickness of 20 to 50 μm, for example, MHM series manufactured by jiro corporation) so that the antiglare layer side was the outermost surface. The liquid crystal television was installed indoors under an environment of an illuminance of about 1000Lx, a DVD "opera ghost" of MEDIA factor was played, and 15 subjects viewed the screen image at a distance of about 1.5 to 2.0m from the liquid crystal television, and evaluated the black color feeling by sensory evaluation. The black color sensation is determined by whether the contrast is high when the moving image is displayed, whether the image has luster and brilliance, and whether a sense of jump is felt. The evaluation criteria are as follows.

Very good: the number of people who answer well is more than 10

O: the number of people who answer well is 5-9

X: the number of people who answer well is below 4

< measurement of Total haze, internal haze and surface haze >

The total haze, the internal haze, and the surface haze of each of the antiglare films obtained in examples C1 to C3 and comparative examples C1 to C3 were measured as follows. First, the total haze value of the antiglare film was measured in accordance with JIS K7136 using a haze meter (HM-150, manufactured by mura color technology research). Thereafter, a cellulose triacetate base material (TD 60UL, manufactured by fuji film corporation) was bonded to the surface of the antiglare layer via a transparent optical adhesive layer. Thereby, the uneven shape of the uneven surface of the antiglare layer is collapsed, and the surface of the antiglare film is flattened. In this state, the internal haze value was determined by measuring the haze value according to JIS K7136 using a haze meter (HM-150, manufactured by murakamura color technology research) and further subtracting the haze of the adhesive layer itself. And the surface haze value is found by subtracting the internal haze value from the full haze value.

< measurement of Sm, Theta a and Ra >

Sm, θ a and Ra were measured on the surfaces of the antiglare films obtained in examples C1 to C3 and comparative examples C1 to C3. Sm and Ra are defined based on the definition in JIS B0601-1994, and θ a is defined based on a surface roughness tester: SE-3400/(revised, 1995.07.20) in the Specification of the national institute of Mingkistry, Ltd.

Specifically, Sm, θ a and Ra were measured under the following measurement conditions using a surface roughness measuring instrument (model: SE-3400/(Katsuka corporation)).

1) Stylus of surface roughness detecting section (trade name SE2555N (2. mu. Standard), manufactured by Xiaoban Ltd.)

Diamond with 2 μm radius of curvature at tip and 90 ° apex angle

2) Measurement conditions of surface roughness measuring apparatus

Reference length (sampling length value λ c of roughness curve): 2.5mm

Evaluation length (reference length (sampling length value λ c) × 5): 12.5mm

Feed speed of stylus: 0.5mm/s

Preparatory length: (sampling length value. lamda.c). times.2

Longitudinal magnification: 2000 times of

Transverse magnification: 10 times of

< Flex resistance test >

The bending resistance test was performed on each of the antiglare films obtained in examples C1 to C3 and comparative examples C1 to C3 using a bending resistance tester having a mandrel, and the minimum diameter of the mandrel having no crack was shown in table 7. Flex resistance test was carried out in accordance with JIS K5600-5-1 (1999).

< scratch resistance >

For the anti-glare films obtained in examples C1 to C3 and comparative examples C1 to C3, steel wool #0000 (product name: Bonstar, manufactured by Nippon Steel wool Co., Ltd.) was used and applied at 700g/cm ² After repeatedly scraping 10 times at a speed of 100 mm/sec under a load, the surface of the cellulose triacetate base material opposite to the surface on which the antiglare layer was formed was coatedA black tape was attached to the side surface, and the presence or absence of a flaw was visually evaluated under a three-wavelength fluorescent lamp. The evaluation criteria for the scratch resistance evaluation are as follows.

O: the level of no or slight scars observed was practically no problem.

X: many scars were confirmed.

The results are shown in tables 6 and 7 below.

As shown in table 6, in comparative example C1, although good antiglare properties were obtained, the dazzling performance was poor. This is considered to be because, in comparative example C1, the value of 99 th percentile/3 rd quartile is small, and therefore, the flat portion is small, and glare is likely to occur. In comparative example C2, although the glare and the black color sensation were good, the antiglare property was poor. This is considered to be because the inclination angle is too greatly biased to be flat in comparative example C2 because the 99 th percentile/3 rd quartile value is large. In comparative example C3, the glare was not felt, but the black color was low. This is considered to be because comparative example C3 has a very small value of 99 th percentile/3 rd quartile and almost no flat portion, although it has a high haze and thus can suppress glare. On the other hand, examples C1 to C3 had good antiglare properties, no fear of glare, and good black color.

[ description of symbols ]

10. 50, 60, 100 … anti-dazzle film

10A, 60A, 100A … surface

11. 51, 61, 101 … light-transmitting base material

12. 52, 62, 102 … antiglare layer

12A, 52A, 62A, 102A … concave-convex surface

13. 53, 64A, 104A … first inorganic particulate agglomerates

14. 54, 64D, 104D … second inorganic particulate agglomerates

15. 63A, 103A … organic microparticle agglomeration

16. 56, 65, 105 … Binder resin

20. 70, 110 … polarizer

21 … polarizing element

30. 80, 120 … liquid crystal panel

40. 90, 130 … image display device

55 … organic microparticles

Claims (11)

1. An antiglare film comprising a light-transmitting substrate and an antiglare layer provided on the light-transmitting substrate and having an uneven surface, wherein:

the antiglare layer comprises 2 or more organic fine particles, 2 or more 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-transmitting substrate is obtained at every 0.01 degrees, the ratio of the 99 th percentile to the 3 rd quartile in the cumulative percentage of the frequencies of the inclination angles is 3.0 to 5.0.

2. The antiglare film according to claim 1, wherein at least a part of the organic fine particles out of 2 or more of the organic fine particles are present in the form of organic fine particle aggregates in which 2 or more of the organic fine particles are aggregated; at least a part of the inorganic fine particles in 2 or more of the inorganic fine particles exist as first inorganic fine particle aggregates in which 3 or more of the inorganic fine particles are aggregated; the first inorganic particle aggregate includes a curved portion formed by the inorganic particles being connected to each other and having an inner region filled with the binder resin.

3. The antiglare film of claim 2, wherein the first inorganic particulate agglomerates are present at least at a location on a surface of the organic particulate agglomerates and at a location that is separate from and between the organic particulate agglomerates.

4. The antiglare film of claim 3, wherein:

a part of the 2 or more inorganic fine particles is present in the form of 2 or more second inorganic fine particle aggregates in which 2 or more inorganic fine particles are aggregated;

the second inorganic particulate aggregates are present at the position of the uneven surface or the vicinity thereof, and the aggregation diameter of the second inorganic particulate aggregates in the direction orthogonal to the thickness direction of the antiglare layer is larger than the aggregation diameter of the second inorganic particulate aggregates in the thickness direction.

5. An antiglare film according to claim 2, wherein a proportion of the first inorganic particulate aggregates present in the antiglare layer on the light-transmitting substrate side is higher than a proportion of the first inorganic particulate aggregates present on the uneven surface side of the antiglare layer.

6. The antiglare film of claim 1, wherein a relation of 0.2< R/T <0.7 is satisfied where T is a thickness of the antiglare layer and R is an average particle diameter of the organic fine particles.

7. The antiglare film according to claim 1, wherein an average primary particle diameter of said inorganic fine particles is 1nm or more and 100nm or less.

8. The antiglare film according to claim 2, wherein the average diameter of the first inorganic fine particle aggregates is 100nm or more and 2.0 μm or less.

9. A polarizing plate comprising the antiglare film according to claim 1 and a polarizing element formed on a surface of the light-transmitting substrate of the antiglare film opposite to the surface on which the antiglare layer is formed.

10. A liquid crystal display panel comprising the antiglare film of claim 1.

11. An image display panel comprising the antiglare film according to claim 1.

Images