JP2013178533A - Hard-coated antiglare film, polarizing plate and image display device using the same, and method for manufacturing hard-coated antiglare film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard-coated antiglare film having superior antiglare properties, capable of highly precisely accommodating thereto even when a haze value is low, and improving depth of black in a black display by preventing white blur from an oblique direction, and to provide a polarizing plate and the like.SOLUTION: The hard-coated antiglare film includes a hard-coating antiglare layer that contains fine particles formed on at least one side of a transparent film substrate. The hard-coated antiglare film has a total haze value Ht within a range of 10-35%. The total haze value Ht and an internal haze value Hin satisfy a relationship of 0.5≤Hin/Ht≤0.9. An asperity-shaped surface of the hard-coating antiglare layer has arithmetic average surface roughness Ra within the range of 0.1-0.3 μm.

Description

  The present invention relates to an antiglare hard coat film, a polarizing plate and an image display device using the same, and a method for producing an antiglare hard coat film.

  Along with recent technological advances, liquid crystal display devices (LCD), plasma displays (PDP), electroluminescence displays (ELD), etc. have been developed and put to practical use in addition to conventional cathode ray tube display devices (CRT). It has become. Among these, LCDs are changing from notebook personal computers (notebook PCs) and monitors to televisions due to technological innovations related to high viewing angle, high definition, high-speed response, and color reproducibility. It is changing. In general, a liquid crystal panel in which polarizing plates are arranged on both sides of a liquid crystal cell is used for the LCD. The surface of the liquid crystal panel is generally subjected to a hard coat treatment to prevent the polarizing plate from being scratched. For the hard coat treatment, a hard coat film is often used. The hard coat film is subjected to an anti-glare treatment for preventing a decrease in contrast due to reflection of external light such as fluorescent light or sunlight on the liquid crystal panel surface or reflection of an image, and in particular, image display. As the screen size of the apparatus has increased, image display apparatuses equipped with an antiglare hard coat film have been increasing.

  In recent years, in order to improve image quality, high-definition image display devices with small pixel sizes and image display devices compatible with so-called full HD (high definition) are increasing. Has a high definition of 140 ppi or more. When a conventional anti-glare hard coat film is arranged on such a high-definition image display device, the luminance variation existing in the pixels is more emphasized, causing a visible failure (glare failure), and the image quality is remarkably improved. It was getting worse. Conventionally, in order to produce a high-definition anti-glare laminate, there has been a method of eliminating glare by increasing the haze value of the anti-glare layer. Due to the strong scattering, there is a problem that the contrast is greatly reduced. In addition, when the surface irregularities are greatly roughened to improve the antiglare property, there is a problem of so-called white blurring in the oblique direction in which the reflected light becomes too scattered when viewed from an oblique direction, and the image appears blurred. In the anti-glare treatment, a method of producing an uneven shape on the film surface by adding inorganic or organic particles is performed. The improvement in anti-glare property, the improvement in contrast, and the improvement in white blur are generally considered to be in a reciprocal relationship, but various proposals have been made to achieve both of these characteristics. For example, studies have been made to make a three-dimensional structure aggregate part formed from the particles present in the antiglare layer (see, for example, Patent Documents 1 to 3). A fine pattern may appear on the hard coat film. Although effective means for improving some characteristics have been proposed (for example, refer to Patent Documents 4 and 5), no effective means for solving all the above three problems has been found.

JP 2005-316413 A JP 2007-264113 A JP 2007-249191 A JP 2003-4903 A Japanese Patent No. 4001320

  SUMMARY OF THE INVENTION An object of the present invention is to provide an antiglare hard coat film that improves visibility without degrading the characteristics of an image display device such as an LCD that is becoming increasingly fine and high in contrast. In other words, it has excellent anti-glare properties, can handle high definition even at low haze values, prevents white blurring from an oblique direction, and improves black density during black display An object of the present invention is to provide an antiglare hard coat film capable of producing an antiglare hard coat film, a polarizing plate and an image display device using the same, and a method for producing the antiglare hard coat film.

To achieve the above object, the antiglare hard coat film of the present invention is an antiglare hard coat film having an antiglare hard coat layer containing fine particles on at least one surface of a transparent plastic film substrate. And the total haze value Ht of the antiglare hard coat film is in the range of 10 to 35%,
The total haze value Ht and the internal haze value Hin satisfy the relationship of the following formula (1),
In the uneven shape of the antiglare hard coat layer surface, the following arithmetic average surface roughness Ra is in the range of 0.1 to 0.3 μm,
The length of the line segment of the portion where the convex portion exceeding the roughness average line of the surface roughness profile crosses the convex portion of the average line at a length of 4 mm at an arbitrary location on the surface of the antiglare hard coat layer. Does not include a convex portion with a length of 80 μm or more, and has a convex portion that exceeds a reference line that is parallel to the average line and located at a height of 0.1 μm, and the convex portion of the reference line The length of the line segment that crosses the shape portion is 20 μm or less, and there are 50 or more convex portions at a length of 4 mm at any location on the surface of the antiglare hard coat layer. .
0.5 ≦ Hin / Ht ≦ 0.9 (1)
Total haze value Ht: Anti-glare hardware according to JIS K 7136 (2000 edition)
Haze value of entire coat film (cloudiness) (%)
Inner haze value Hin: Haze value (%) of the entire antiglare hard coat film measured when the antiglare hard coat film surface is smooth.
Ra: arithmetic average surface roughness (μm) specified in JIS B 0601 (1994 edition)

  The polarizing plate of the present invention is a polarizing plate having a polarizer and an antiglare hard coat film, wherein the antiglare hard coat film is the antiglare hard coat film of the present invention. .

  The image display device of the present invention is an image display device comprising an antiglare hard coat film, wherein the hard coat film is the antiglare hard coat film of the present invention.

  The image display device of the present invention is an image display device including a polarizing plate, wherein the polarizing plate is the polarizing plate of the present invention.

The method for producing an antiglare hard coat film of the present invention is a method for producing the antiglare hard coat film of the present invention,
Preparing a hard coat layer forming material containing the fine particles, the following components (A) and (B), and an antiglare hard coat layer forming material containing a solvent;
Coating the antiglare hard coat layer forming material on at least one surface of the transparent plastic film substrate to form a coating film;
Curing the coating film to form the antiglare hard coat layer,
The fine particles are added in a range of 5 to 20 parts by weight with respect to 100 parts by weight of the hard coat layer forming material,
As the solvent, a mixed solvent of butyl acetate and methyl ethyl ketone (MEK) is used, and the ratio of butyl acetate / MEK in the mixed solvent is within a range of 1.5 / 1 to 6.0 / 1 by weight ratio. It is characterized by.
(A) component: a curable compound having at least one of an acrylate group and a methacrylate group (B) component: a weight average particle diameter formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group Particles of 200nm or less

The method for producing an antiglare hard coat film of the present invention is a method for producing the antiglare hard coat film of the present invention,
Preparing a hard coat layer forming material containing the fine particles, the following components (A) and (B), and an antiglare hard coat layer forming material containing a solvent;
Coating the antiglare hard coat layer forming material on at least one surface of the transparent plastic film substrate to form a coating film;
Curing the coating film to form the antiglare hard coat layer,
The fine particles are added in a range of 5 to 20 parts by weight with respect to 100 parts by weight of the hard coat layer forming material,
As the solvent, a mixed solvent of methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK) is used, and the MIBK / MEK ratio of the mixed solvent is within a range of 1.5 / 1 to 6.0 / 1 by weight. It is characterized by being.
(A) component: a curable compound having at least one of an acrylate group and a methacrylate group (B) component: a weight average particle diameter formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group Particles of 200nm or less

  According to the antiglare hard coat film of the present invention, for example, even a higher-definition liquid crystal panel or the like having a resolution of about 200 ppi can suppress glare, and can also have a low haze value. Compared with the conventional high-definition antiglare hard coat film, the contrast of light and darkness can be greatly improved. The antiglare hard coat film of the present invention has excellent antiglare properties by realizing a characteristic uneven shape, and can prevent white blurring from an oblique direction. By preventing the white blurring, light scattering in the front direction of the image display device can be suppressed, so that the black luminance can be suppressed and the contrast in a bright place can be improved. Thereby, it is possible to improve the darkness of black when the image display device displays black. Therefore, the image display apparatus using the antiglare hard coat film or polarizing plate of the present invention has excellent display characteristics.

FIG. 1A is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Example 1 in a range of 0 to 1 mm in a measurement length of 4 mm. FIG. 1B is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Example 1 in a range of 1 to 2 mm out of a measurement length of 4 mm. FIG.1 (c) is the profile which showed the range of 2-3 mm among the measurement length 4mm of the cross-sectional surface shape of the glare-proof hard coat film of Example 1. FIG. FIG.1 (d) is the profile which showed the range of 3-4 mm among the measurement length 4mm of the cross-sectional surface shape of the glare-proof hard coat film of Example 1. FIG. FIG. 2 is a profile having a measurement length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Example 2. (A) is in the range of 0-1 mm, (b) is in the range of 1-2 mm, (c) is in the range of 2-3 mm, and (d) is in the range of 3-4 mm. FIG. 3 is a profile showing the range of 3 to 4 mm of the measured length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Comparative Example 1. FIG. 4 is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Comparative Example 2 in a range of 3 to 4 mm out of a measured length of 4 mm. FIG. 5 is a profile showing the range of 3 to 4 mm of the measured length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Comparative Example 3. FIG. 6 is a profile showing the range of 3 to 4 mm of the measured length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Comparative Example 4. FIG. 7 is a profile showing the range of 3 to 4 mm of the measured length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Comparative Example 5. FIG. 8 is a profile showing the range of 3 to 4 mm of the measured length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Comparative Example 6. FIG. 9 is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Comparative Example 7 in a range of 0 to 1 mm out of a measured length of 4 mm. FIG. 10 is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Comparative Example 8 in a range of 1 to 2 mm out of a measured length of 4 mm. FIG. 11 is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Comparative Example 9 in a range of 3 to 4 mm out of a measured length of 4 mm. FIG. 12 is a schematic cross-sectional view illustrating a method for measuring an internal haze value in Examples and Comparative Examples. FIG. 13 is a schematic diagram illustrating a method for measuring the number of convex portions in the present invention.

In the antiglare hard coat film of the present invention, the antiglare hard coat layer is formed using the fine particles and a hard coat layer forming material containing the following components (A) and (B). It is preferable.
(A) component: a curable compound having at least one of an acrylate group and a methacrylate group (B) component: a weight average particle diameter formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group Particles of 200nm or less

  In the component (B), the inorganic oxide particles preferably include at least one particle selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide and zirconium oxide.

  In the hard coat layer forming material, the component (B) is preferably contained in the range of 100 to 200 parts by weight with respect to 100 parts by weight of the component (A).

  A spherical or irregular shape in which the difference in refractive index between the hard coat layer forming material and the fine particles is in the range of 0.01 to 0.04, and the fine particles have a weight average particle size in the range of 0.5 to 8 μm. It is preferable that the fine particles are contained in a range of 5 to 20 parts by weight with respect to 100 parts by weight of the hard coat layer forming material.

  In the antiglare hard coat film of the present invention, the thickness of the antiglare hard coat layer is preferably in the range of 1.2 to 3 times the weight average particle diameter of the fine particles.

  In the antiglare hard coat film of the present invention, an antireflection layer is preferably formed on the antiglare hard coat layer.

  Next, the present invention will be described in detail. However, the present invention is not limited by the following description.

  The antiglare hard coat film of the present invention has an antiglare hard coat layer on at least one surface of a transparent plastic film substrate.

  The transparent plastic film substrate is not particularly limited, but preferably has a visible light transmittance (preferably a light transmittance of 90% or more) and a transparency (preferably a haze value of 1% or less). For example, the transparent plastic film base material of Unexamined-Japanese-Patent No. 2008-90263 is mention | raise | lifted. As the transparent plastic film substrate, those having a small optical birefringence are preferably used. The antiglare hard coat film of the present invention can also be used for a polarizing plate as a protective film, for example. In this case, as the transparent plastic film substrate, triacetyl cellulose (TAC), polycarbonate, acrylic A film formed from a polymer, a polyolefin having a cyclic or norbornene structure, or the like is preferable. In the present invention, as described later, the transparent plastic film substrate may be a polarizer itself. With such a configuration, a protective layer made of TAC or the like is not required, and the structure of the polarizing plate can be simplified. Therefore, the number of manufacturing steps of the polarizing plate or the image display device can be reduced, and the production efficiency can be improved. Moreover, if it is such a structure, a polarizing plate can be made thinner. When the transparent plastic film substrate is a polarizer, the antiglare hard coat layer serves as a conventional protective layer. Moreover, if it is such a structure, when it mounts | wears with the liquid crystal cell surface, for example, an anti-glare hard coat film will serve as a cover plate.

  In the present invention, the thickness of the transparent plastic film substrate is not particularly limited, but is preferably in the range of 10 to 500 μm, more preferably in consideration of workability such as strength and handleability and thin layer properties. Is in the range of 20-300 μm, optimally in the range of 30-200 μm. The refractive index of the transparent plastic film substrate is not particularly limited. The refractive index is, for example, in the range of 1.30 to 1.80, and preferably in the range of 1.40 to 1.70.

  The antiglare hard coat layer is formed using the fine particles and the hard coat layer forming material. Examples of the hard coat layer forming material include a thermosetting resin and an ionizing radiation curable resin that is cured by ultraviolet rays or light. As the hard coat layer forming material, a commercially available thermosetting resin, ultraviolet curable resin, or the like can be used. Examples of the hard coat layer forming material include the following components (A) and (B): The thing containing is preferable.

(A) component: a curable compound having at least one of an acrylate group and a methacrylate group (B) component: particles formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group

  As said (A) component, the curable compound which has at least one group of the acrylate group and methacrylate group which harden | cure with a heat | fever, light (ultraviolet rays etc.) or an electron beam etc. can be used, for example. Examples of the component (A) include acrylates of polyfunctional compounds such as silicone resins, polyester resins, polyether resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols. And oligomers or prepolymers such as styrene and methacrylate. These may be used alone or in combination of two or more.

  As said (A) component, the reactive diluent which has at least one group of an acrylate group and a methacrylate group can also be used, for example. As the reactive diluent, for example, the reactive diluent described in JP-A-2008-88309 can be used, and includes, for example, monofunctional acrylate, monofunctional methacrylate, polyfunctional acrylate, polyfunctional methacrylate and the like. The reactive diluent is preferably a trifunctional or higher acrylate or a trifunctional or higher methacrylate. This is because the hardness of the antiglare hard coat layer can be made more excellent. Examples of the component (A) include butanediol glycerin ether diacrylate, isocyanuric acid acrylate, isocyanuric acid methacrylate, and the like. As the component (A), one type may be used alone, or two or more types may be used in combination.

  The component (B) is as described above. In the component (B), examples of the inorganic oxide particles include fine particles such as silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. These may be used alone or in combination of two or more.

  In the antiglare hard coat film of the present invention, the component (B) has a weight average particle diameter of 1 nm to 200 nm from the viewpoints of preventing light scattering, preventing the hard coat layer from lowering transmittance, preventing coloring, and transparency. It is preferable that it is what is called a nanoparticle which is the range of these. The said weight average particle diameter can be measured by the method as described in the below-mentioned Example, for example. The weight average particle diameter is more preferably in the range of 1 nm to 100 nm. The inventors have found that when the component (B), which is a nanoparticle, is added to the component (A), the movement of the fine particles in the coating and drying process changes due to, for example, selection of a solvent described later. It was. That is, in a system to which nanoparticles were added, there was a tendency that surface irregularities due to the fine particles were hardly formed when a specific solvent was used, and that the irregularities were easily formed when another specific solvent was used. If the nanoparticles were not contained, the difference in surface irregularities depending on the type of solvent was not large. From these phenomena, when the nanoparticles are contained, repulsive force acts on the nanoparticles and the fine particles, so that the fine particles are easily dispersed relatively uniformly, and the movement of the fine particles in the coating and drying process is controlled. Therefore, it can be presumed that the number of added parts of the fine particles can be reduced, and the surface uneven shape of the present invention can be effectively produced. However, the present invention is not limited or limited by this inference.

  In the component (B), the inorganic oxide particles are bonded (surface modified) with an organic compound containing a polymerizable unsaturated group. The polymerizable unsaturated group is reactively cured with the component (A), thereby improving the hardness of the hard coat layer. As the polymerizable unsaturated group, for example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, and acrylamide group are preferable. The organic compound containing a polymerizable unsaturated group is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. It is also preferable that the organic compound containing a polymerizable unsaturated group has a photosensitive group.

  The blending amount of the component (B) is preferably in the range of 100 to 200 parts by weight with respect to 100 parts by weight of the component (A). By making the blending amount of the component (B) 100 parts by weight or more, curling and folding of the antiglare hard coat film can be more effectively prevented, and by making it 200 parts by weight or less, scratch resistance is obtained. Property and pencil hardness can be made high. The blending amount of the component (B) is more preferably in the range of 100 to 150 parts by weight with respect to 100 parts by weight of the component (A).

  By adjusting the blending amount of the component (B), for example, the refractive index of the antiglare hard coat layer can be adjusted. When the antireflection layer described later is not provided, the refractive index of the antiglare hard coat layer is preferably lowered in order to suppress the reflectance. In the case of providing an antireflection layer (low refractive index layer), it is possible to uniformly reduce reflection in the wavelength region of visible light by increasing the refractive index of the antiglare hard coat layer.

  The fine particles for forming the antiglare hard coat layer provide the antiglare property by making the surface of the formed antiglare hard coat layer uneven, and also the haze value of the antiglare hard coat layer. The main function is to control. The haze value of the antiglare hard coat layer can be designed by controlling the refractive index difference between the fine particles and the hard coat layer forming material. Examples of the fine particles include inorganic fine particles and organic fine particles. The inorganic fine particles are not particularly limited, and examples thereof include silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles and the like. Can be given. The organic fine particles are not particularly limited. For example, polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin Examples thereof include powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluorinated ethylene resin powder. These inorganic fine particles and organic fine particles may be used alone or in combination of two or more.

  The weight average particle diameter of the fine particles is preferably in the range of 0.5 to 8 μm. When the weight average particle diameter of the fine particles is larger than the above range, image sharpness is deteriorated. When the fine particle diameter is smaller than the above range, sufficient antiglare property cannot be obtained, and the problem that glare is likely to increase is likely to occur. The weight average particle diameter of the fine particles is more preferably in the range of 2 to 6 μm, still more preferably in the range of 3 to 6 μm. The weight average particle diameter of the fine particles is preferably in the range of 30 to 80% of the thickness of the antiglare hard coat layer. The weight average particle diameter of the fine particles can be measured by, for example, a Coulter counting method. For example, by using a particle size distribution measuring device (trade name: Coulter Multisizer, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method, the electrolyte solution corresponding to the volume of the particulates when the particulates pass through the pores By measuring the electrical resistance, the number and volume of the fine particles are measured, and the weight average particle diameter is calculated.

  The shape of the fine particles is not particularly limited, and may be, for example, a bead-like substantially spherical shape or an irregular shape such as a powder, but is preferably substantially spherical, more preferably an aspect ratio. Is substantially spherical fine particles having a particle size of 1.5 or less, and most preferably spherical fine particles.

  The blending ratio of the fine particles is preferably in the range of 5 to 20 parts by weight, and more preferably in the range of 10 to 20 parts by weight with respect to 100 parts by weight of the hard coat layer forming material.

  The thickness of the antiglare hard coat layer is preferably in the range of 1.2 to 3 times the weight average particle diameter of the fine particles, and more preferably in the range of 1.2 to 2 times. Furthermore, the thickness of the antiglare hard coat layer is preferably in the range of 8 to 12 μm from the viewpoint of coating properties and pencil hardness, and the weight average particle diameter of the fine particles is adjusted to be within this thickness range. It is preferable to do. When the thickness is within the predetermined range, it is easy to realize the surface shape of the antiglare hard coat film of the present invention in which a large number of fine irregularities exist independently, and the antiglare hard coat layer has sufficient hardness. (For example, the pencil hardness is 4H or more). Further, when the thickness is larger than the predetermined range, there is a problem that the curl is large and the line running property at the time of coating is lowered, and further, there is a problem that the antiglare property is lowered. Further, when the thickness is smaller than the predetermined range, there is a problem that glare cannot be prevented and the sharpness is lowered.

  The antiglare hard coat film of the present invention has a total haze value Ht of 10 to 35%. The total haze value is the haze value (cloudiness) of the entire antiglare hard coat film according to JIS K 7136 (2000 version). The total haze value is more preferably in the range of 15 to 30%, and still more preferably in the range of 20 to 25%. In order to set the total haze value in the above range, the fine particles and the hard coat layer forming material are set so that the refractive index difference between the fine particles and the hard coat layer forming material is in the range of 0.01 to 0.04. And are preferably selected. When the total haze value is within the above range, a clear image can be obtained and the contrast in a dark place can be improved. If the total haze value is too low, glare failure is likely to occur.

  In the antiglare hard coat film of the present invention, the total haze value Ht and the internal haze value Hin satisfy the relationship of 0.5 ≦ Hin / Ht ≦ 0.9. The internal haze value Hin is a haze value of the entire antiglare hard coat film measured when the antiglare hard coat film surface is smooth. In order to form the smooth surface, for example, the hard coat layer forming material may be applied to the surface of the antiglare hard coat film. By forming the smooth surface and measuring the haze value, a haze value (internal haze value) obtained by subtracting the influence of the surface scattering component can be obtained. When Hin / Ht is 0, the internal haze value is 0, and all the hazes indicate external (surface) haze. In this case, generally, the unevenness of the surface is large and glare occurs. On the other hand, when Hin / Ht is 1, it indicates a state where the ratio of internal haze is 1. In this case, the external (surface) haze value is 0, that is, generally the surface is a smooth surface, and the antiglare property cannot be obtained. The value of Hin / Ht is preferably in the range of 0.5 to 0.7, and more preferably in the range of 0.5 to 0.6. If the value is less than 0.5, glare is likely to occur, and if it exceeds 0.9, sufficient antiglare property cannot be imparted.

  The antiglare hard coat film of the present invention has an arithmetic average surface roughness Ra defined by JIS B 0601 (1994 edition) in the uneven shape of the antiglare hard coat layer surface in the range of 0.1 to 0.3 μm. In addition, at a length of 4 mm at any location on the surface of the antiglare hard coat layer, a portion where the convex portion exceeding the roughness average line of the surface roughness profile crosses the convex portion of the average line The line segment does not include a convex part having a length of 80 μm or more, and has a convex part that exceeds the reference line parallel to the average line and located at a height of 0.1 μm, The length of a line segment that crosses the convex portion of the reference line has a length of 20 μm or less, and the convex portion has 50 or more at any length of 4 mm on the surface of the antiglare hard coat layer. . The Ra is preferably in the range of 0.1 to 0.2 μm, more preferably in the range of 0.1 to 0.15 μm. In order to prevent the reflection of external light and images on the surface of the antiglare hard coat film, a certain degree of surface roughness is required, but the reflection can be improved by Ra of 0.1 μm or more. . Further, in order to prevent white blurring, the Ra needs to be 0.3 μm or less, and the surface is not rough as a whole, but swells or fine irregularities appear to be sparse. It is preferable to have a rough surface. If the number of convex portions having a length of 20 μm or less is small, it is not preferable in terms of antiglare properties, and glare is likely to occur. The number of the convex portions of 20 μm or less is preferably in the range of 60 to 100, more preferably in the range of 80 to 100. If the number of convex portions of 20 μm or less is less than 50, glare is likely to occur, and if it exceeds 100, white blur tends to be strong. Further, if there is a convex portion having a line segment length of 80 μm or more, glare is likely to occur. There are no convex portions having a length of 80 μm or more in the line segment, and 50 or more convex portions having the length of 20 μm or less are formed, and the Ra is in the range of 0.1 to 0.3 μm. In the antiglare hard coat film, a large number of relatively uniform fine irregularities exist, so that excellent uniform scattering can be achieved, and glare can be suppressed even in a high-definition panel. Further, scattering of reflected light when viewed from an oblique direction is suppressed, white blur is improved, and contrast in a bright place can be improved.

  The antiglare hard coat film of the present invention has a large number of fine irregularities independently as defined by the size and number of Ra and the convex portions, and there are convex portions having a length of 80 μm or more. In addition, there are a predetermined number of fine irregularities independently, and by having internal scattering defined by the haze value in the above range, it is possible to achieve both improvement of antiglare property and elimination of glare.

  The antiglare hard coat film of the present invention is prepared, for example, by preparing an antiglare hard coat layer forming material containing the fine particles, the hard coat layer forming material, and a solvent, and the antiglare hard coat layer forming material is transparent. It can be produced by coating on at least one surface of a plastic film substrate to form a coating film, and curing the coating film to form the antiglare hard coat layer. In the production of the antiglare hard coat film of the present invention, a transfer method using a mold, a method of imparting a concavo-convex shape by an appropriate method such as sandblasting, embossing roll, or the like can also be used.

  The solvent is not particularly limited, and various solvents can be used. One type may be used alone, or two or more types may be used in combination. There are optimum solvent types and solvent ratios for obtaining the antiglare hard coat film of the present invention depending on the hard coat layer forming material composition, the kind of fine particles, the content and the like.

  For example, for the hard coat layer forming material used in the examples described later, when 10 parts by weight of fine particles are added, the solid content concentration is 45% by weight, and the thickness of the antiglare hard coat layer is about 10 μm, The ratio of methyl isobutyl ketone (MIBK) / methyl ethyl ketone (MEK) is at least 1.5 / 1 to 6.0 / 1 (weight ratio), and an antiglare hard coat film having the characteristics of the present invention is obtained. More preferably, it is in the range of 1.5 / 1 to 3.0 / 1 (weight ratio). In the case of butyl acetate / MEK, an antiglare hard coat film having the characteristics of the present invention is obtained in the range of at least 1.5 / 1 to 6.0 / 1 (weight ratio). More preferably, it is in the range of 3.0 / 1 to 5.5 / 1 (weight ratio). When the solvent ratio is less than 1.5 / 1, the number of surface irregularities increases, but white blurring and surface unevenness are likely to occur. When the ratio is greater than 6.0 / 1, the number of surface irregularities decreases. It becomes easy to glaring. When the component (B) is a nanoparticle as in the hard coat layer forming material used in the examples described later, for example, depending on the type and mixing ratio of the solvent, the nanoparticle and the fine particle are dispersed. It is presumed that the unevenness tendency of the antiglare hard coat layer surface changes due to the change. However, the present invention is not limited or limited by this inference. For example, in the case of the hard coat layer forming material described later, when the solvent is MEK, cyclopentanone, ethyl acetate, acetone or the like, irregularities are easily formed on the surface, and the solvent is MIBK, toluene, butyl acetate, 2 In the case of -propanol, ethanol, etc., it is difficult to form irregularities on the surface. Therefore, in order to obtain an antiglare hard coat film having the characteristics of the present invention, it is also preferable to control the surface shape according to the type of solvent and the ratio of the solvent.

  Various leveling agents can be added to the antiglare hard coat layer forming material. Examples of the leveling agent include a fluorine-based or silicone-based leveling agent, and a silicone-based leveling agent is preferable. As the silicone leveling agent, reactive silicone is particularly preferable. By adding the reactive silicone, slipperiness is imparted to the surface, and scratch resistance is maintained over a long period of time. In addition, when a reactive silicone having a hydroxyl group is used, an antireflection layer (low refractive index layer) containing a siloxane component is formed on the antiglare hard coat layer as described later. The adhesion between the antireflection layer and the antiglare hard coat layer is improved.

  The blending amount of the leveling agent is, for example, 5 parts by weight or less, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the entire resin component.

  The anti-glare hard coat layer forming material may include pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, and antioxidants as long as the performance is not impaired. Further, a thixotropic agent or the like may be added. These additives may be used alone or in combination of two or more.

  As the antiglare hard coat layer forming material, for example, a conventionally known photopolymerization initiator as described in JP-A-2008-88309 can be used.

  Examples of the method for coating the antiglare hard coat layer forming material on the transparent plastic film substrate include, for example, a phanten coating method, a die coating method, a spin coating method, a spray coating method, a gravure coating method, a roll coating method, A coating method such as a bar coating method can be used.

  The antiglare hard coat layer forming material is applied to form a coating film on the transparent plastic film substrate, and the coating film is cured. Prior to the curing, the coating film is preferably dried. The drying may be, for example, natural drying, air drying by blowing air, heat drying, or a combination of these.

The means for curing the coating film of the antiglare hard coat layer forming material is not particularly limited, but ultraviolet curing is preferable. The irradiation amount of the energy ray source is preferably 50 to 500 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ / cm ² or more, the curing becomes more sufficient, and the hardness of the formed antiglare hard coat layer becomes more sufficient. Moreover, if it is 500 mJ / cm < ² > or less, coloring of the anti-glare hard-coat layer formed can be prevented.

  As described above, the antiglare hard coat film of the present invention can be produced by forming the antiglare hard coat layer on at least one surface of the transparent plastic film substrate. In addition, you may manufacture the anti-glare hard coat film of this invention with manufacturing methods other than the above-mentioned method. The hardness of the antiglare hard coat film of the present invention is affected by the thickness of the layer in pencil hardness, but has a hardness of 2H or more, for example.

  As an example of the antiglare hard coat film of the present invention, one having an antiglare hard coat layer formed on one surface of a transparent plastic film substrate can be mentioned. The antiglare hard coat layer contains fine particles, whereby the surface of the antiglare hard coat layer has an uneven shape. In this example, the antiglare hard coat layer is formed on one side of the transparent plastic film substrate. However, the present invention is not limited to this, and the antiglare hard coat is formed on both sides of the transparent plastic film substrate. It may be an antiglare hard coat film in which a layer is formed. In addition, the antiglare hard coat layer of this example is a single layer, but the present invention is not limited thereto, and the antiglare hard coat layer has a multilayer structure in which two or more layers are laminated. May be.

  In the antiglare hard coat film of the present invention, an antireflection layer (low refractive index layer) may be disposed on the antiglare hard coat layer. For example, when an anti-glare hard coat film is attached to an image display device, light reflection at the interface between air and the anti-glare hard coat layer is one of the factors that lower the image visibility. The antireflection layer reduces the surface reflection. The antiglare hard coat layer and the antireflection layer may be formed on both surfaces of the transparent plastic film substrate. Further, the antiglare hard coat layer and the antireflection layer may each have a multilayer structure in which two or more layers are laminated.

  In the present invention, the antireflection layer is an optical thin film in which thickness and refractive index are strictly controlled, or a laminate of two or more optical thin films. The antireflection layer exhibits an antireflection function by canceling out the reversed phases of incident light and reflected light using the interference effect of light. The wavelength region of visible light that exhibits the antireflection function is, for example, 380 to 780 nm, and the wavelength region with particularly high visibility is in the range of 450 to 650 nm, and the reflectance at 550 nm, which is the central wavelength, is minimized. Thus, it is preferable to design the antireflection layer.

  In designing the antireflection layer based on the light interference effect, as a means for improving the interference effect, for example, there is a method of increasing the refractive index difference between the antireflection layer and the antiglare hard coat layer. In general, in a multilayer antireflection layer having a structure in which two to five optical thin layers (thin films whose thickness and refractive index are strictly controlled) are laminated, a plurality of components having different refractive indexes are formed in a predetermined thickness. Thus, the degree of freedom in optical design of the antireflection layer is increased, the antireflection effect can be further improved, and the spectral reflection characteristics can be made uniform (flat) in the visible light region. Since the optical thin film requires high thickness accuracy, each layer is generally formed by a dry method such as vacuum evaporation, sputtering, or CVD.

  Further, in order to prevent the adhesion of contaminants and improve the ease of removing the adhered contaminants, a contamination prevention layer formed of a fluorine group-containing silane compound or a fluorine group-containing organic compound is provided on the antireflection layer. It is preferable to laminate them.

  In the antiglare hard coat film of the present invention, it is preferable to perform a surface treatment on at least one of the transparent plastic film substrate and the antiglare hard coat layer. If the surface of the transparent plastic film substrate is surface-treated, the adhesion to the antiglare hard coat layer, the polarizer or the polarizing plate is further improved. Further, if the surface of the antiglare hard coat layer is surface-treated, the adhesion with the antireflection layer, the polarizer or the polarizing plate is further improved.

  In the antiglare hard coat film in which the antiglare hard coat layer is formed on one surface of the transparent plastic film substrate, the other surface may be subjected to a solvent treatment in order to prevent curling. Good. Further, in the antiglare hard coat film in which the antiglare hard coat layer is formed on one surface of the transparent plastic film base material, a transparent resin layer is formed on the other surface in order to prevent curling. May be.

  In the antiglare hard coat film of the present invention, the transparent plastic film substrate side can usually be bonded to an optical member used in an LCD via an adhesive or an adhesive. In addition, in this bonding, various surface treatments as described above may be performed on the surface of the transparent plastic film substrate.

  Examples of the optical member include a polarizer and a polarizing plate. Generally, the polarizing plate has a transparent protective film on one side or both sides of the polarizer. When providing a transparent protective film on both surfaces of a polarizer, the same material may be sufficient as the transparent protective film of front and back, and a different material may be sufficient as it. The polarizing plates are usually disposed on both sides of the liquid crystal cell. Further, the polarizing plates are arranged so that the absorption axes of the two polarizing plates are substantially orthogonal to each other.

  Next, an optical member in which the antiglare hard coat film of the present invention is laminated will be described by taking a polarizing plate as an example. A polarizing plate having the function of the present invention can be obtained by laminating the antiglare hard coat film of the present invention with a polarizer or a polarizing plate using an adhesive or a pressure-sensitive adhesive.

  The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and iodine and dichroic dyes. Examples thereof include a polyene-based oriented film such as a film obtained by adsorbing a chromatic substance and uniaxially stretched, a dehydrated polyvinyl alcohol product or a dehydrochlorinated polyvinyl chloride product.

  As the transparent protective film provided on one side or both sides of the polarizer, those having excellent transparency, mechanical strength, thermal stability, moisture shielding property, retardation value stability and the like are preferable. Examples of the material for forming the transparent protective film include the same materials as those for the transparent plastic film substrate.

  Examples of the transparent protective film include polymer films described in JP-A No. 2001-343529 (WO01 / 37007). The polymer film can be produced by extruding the resin composition into a film. The polymer film has a small phase difference and a small photoelastic coefficient, and therefore, when applied to a protective film such as a polarizing plate, it can eliminate problems such as unevenness due to distortion and has a low moisture permeability. Excellent in humidification durability.

  The transparent protective film is preferably a film made of a cellulose resin such as triacetyl cellulose or a film made of a norbornene resin from the viewpoints of polarization characteristics and durability. Examples of the commercial product of the transparent protective film include trade name “Fujitac” (manufactured by FUJIFILM Corporation), trade name “ZEONOR” (manufactured by ZEON Corporation), trade name “ARTON” (manufactured by JSR Corporation), and the like. . The thickness of the transparent protective film is not particularly limited, but is, for example, in the range of 1 to 500 μm from the viewpoints of workability such as strength, handleability, and thin layer properties.

  The configuration of the polarizing plate in which the antiglare hard coat film is laminated is not particularly limited. For example, the transparent protective film, the polarizer and the transparent protective film are arranged in this order on the antiglare hard coat film. The structure which laminated | stacked by this, and the structure which laminated | stacked the said polarizer and the said transparent protective film in this order on the said glare-proof hard coat film may be sufficient.

  The image display device of the present invention has the same configuration as the conventional image display device except that the antiglare hard coat film of the present invention is used. For example, in the case of an LCD, it can be manufactured by appropriately assembling each component such as a liquid crystal cell, an optical member such as a polarizing plate, and an illumination system (backlight or the like) as necessary and incorporating a drive circuit.

  The liquid crystal display device of the present invention is used for any appropriate application. Applications include, for example, OA devices such as personal computer monitors, laptop computers, and copy machines, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, etc. Household electrical equipment, back monitor, car navigation system monitor, car audio and other in-vehicle equipment, display equipment for commercial store information monitors, security equipment such as monitoring monitors, nursing care monitors, medical monitors, etc. Nursing care / medical equipment.

  Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited by the following examples and comparative examples. The various properties in the following examples and comparative examples were evaluated or measured by the following methods.

(Total haze value Ht)
The measurement method of all haze values is based on the haze (cloudiness) of JIS K 7136 (2000 version) and is measured using a haze meter (trade name “HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd.). did.

(Inside haze value Hin)
As shown in FIG. 12, the surface unevenness of the antiglare hard coat layer 2 on the transparent plastic film substrate 1 is smooth using the respective hard coat layer forming materials used in the examples and comparative examples. The value measured in the same manner as the total haze value was taken as the internal haze value. When the hard coat layer forming material contained fine particles having a weight average particle diameter of 50 nm or more, the smooth surface 4 was formed using a resin not containing the fine particles.

(External noise value)
The external haze value was determined by the following formula.
External haze value = Total haze value-Internal haze value

(Arithmetic mean surface roughness Ra)
A glass plate (thickness 1.3 mm) made by MATSUNAMI is bonded to the surface of the antiglare hard coat film on which the antiglare hard coat layer is not formed, and a high precision fine shape measuring instrument (trade name; The surface shape of the antiglare hard coat layer was measured under the condition of a cut-off value of 0.8 mm using Surfcorder ET4000 (manufactured by Kosaka Laboratory Ltd.), and the arithmetic average surface roughness Ra was determined. The high precision fine shape measuring instrument automatically calculates the arithmetic average surface roughness Ra. The arithmetic average surface roughness Ra is based on JIS B 0601 (1994 edition).

(Number of convex parts exceeding the surface roughness reference line)
In the roughness profile obtained by the measurement of the surface shape, a line parallel to the roughness average line of the profile and located at a height of 0.1 μm was used as a reference line. On the straight line of an arbitrary measurement area of 4 mm, the number of convex portions having a length of a line segment that crosses the convex portion of the average line is 80 μm or more, and among the convex portions exceeding the reference line, A measurement value was obtained by measuring the number of convex portions having a length of a reference line crossing the convex portions of 20 μm or less. FIG. 13 is a schematic diagram for explaining a method of measuring the number of convex portions. The convex part of 20 μm or less to be measured is hatched. The number of convex portions is measured not by the number of peaks but by the number of portions crossing the reference line. For example, when there are a plurality of peaks in the portion exceeding the reference line, such as 3 and 9 in the profile, the number of convex portions is counted as one. In FIG. 13, the number of convex portions of 80 μm or more is three peaks 10, 11, 12 in the profile, and the number of convex portions of 20 μm or less is peaks 1, 4, 5, 6 in the profile. , 8 for a total of 5.

(Anti-glare evaluation)
(1) A black acrylic plate (Mitsubishi Rayon Co., Ltd., thickness: 2.0 mm) is bonded to the surface of the antiglare hard coat film on which the antiglare hard coat layer is not formed, and the back surface is reflected. A sample was prepared without the.
(2) In general, the antiglare property of the sample prepared above was visually determined in an office environment (about 1000 Lx) using a display.
Judgment criteria AA: The anti-glare property is so excellent that the entire image is not reflected, and can be suitably used for products requiring high anti-glare properties such as notebook PCs.
A: The anti-glare property is so good that the boundary of the contour of the image is not known, and it can be applied to a product such as a notebook PC that requires high anti-glare property.
B: Although there is anti-glare property, the boundary of the contour of the image is known, so it is difficult to apply to a product such as a notebook PC that requires high anti-glare property.

(White blur evaluation)
(1) A black acrylic plate (manufactured by Nitto Resin Co., Ltd., thickness 1.0 mm) is bonded to the surface of the antiglare hard coat film on which the antiglare hard coat layer is not formed, A sample with no reflection was produced.
(2) Generally, in an office environment using a display (about 1000 Lx), the white blur phenomenon is visually observed when viewed from a direction of 60 ° with the vertical direction as a reference (0 °) with respect to the plane of the sample prepared above. And evaluated according to the following criteria.
Criteria AA: Almost no white blur.
A: There is white blur but the effect on visibility is small.
B: White blurring is strong and the visibility is remarkably lowered.

(Glare evaluation)
(1) A notebook PC (manufactured by Samsung Electronics, “NT-R610”, FHD (1920 × 1080 pixels), 16 inches, approximately 140 to 150 ppi) was prepared. The polarizing plate constituting the panel surface of the notebook PC is a non-glare type (no antiglare property).
(2) The surface on which the antiglare hard coat layer of the antiglare hard coat film was not formed was bonded to the white polarizing plate of the notebook PC panel with an adhesive. And the glare of the said glare-proof hard coat film was determined visually by the following criteria.
Judgment criteria AA: There is a glare, but the level on the visibility is small.
A: Although there is glare, there is no problem in practical use.
B: A level with severe glare and practical problems.

(Refractive index of transparent plastic film substrate and hard coat layer)
The refractive index of the transparent plastic film substrate and the hard coat layer was selected from the Abgo refractometer (trade name: DR-M2 / 1550) manufactured by Atago Co., and monobromonaphthalene was selected as an intermediate solution. Measurement was performed by a specified measurement method shown in the apparatus so that measurement light was incident on the measurement surface of the hard coat layer.

(Refractive index of fine particles)
Fine particles were placed on a slide glass, a refractive index standard solution was dropped onto the fine particles, and a cover glass was placed over to prepare a sample. The sample was observed with a microscope, and the refractive index of the refractive index standard solution in which the contour of the fine particles was most hardly visible at the interface with the refractive index standard solution was defined as the refractive index of the fine particles.

(Weight average particle diameter of fine particles)
The weight average particle diameter of the fine particles was measured by a Coulter counting method. Specifically, using a particle size distribution measuring device (trade name: Coulter Multisizer, manufactured by Beckman Coulter, Inc.) using the pore electrical resistance method, electrolysis corresponding to the volume of the particulates when the particulates pass through the pores. By measuring the electrical resistance of the liquid, the number and volume of fine particles were measured, and the weight average particle diameter was calculated.

(Thickness of the antiglare hard coat layer)
Anti-glare hard coat layer by measuring the total thickness of the anti-glare hard coat film using a micro gauge thickness gauge manufactured by Mitutoyo Co., Ltd. and subtracting the thickness of the transparent plastic film substrate from the total thickness. The thickness of was calculated.

Example 1
A hard coat layer forming material (JSR Co., Ltd.) containing the component (A) in which nano-silica particles (component (B)) formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group are dispersed. Product name “OPSTAR Z7540”, solid content: 56 wt%, solvent: butyl acetate / methyl ethyl ketone (MEK) = 76/24 (weight ratio)). The hard coat layer forming material is composed of (A) component: dipentaerythritol and isophorone diisocyanate polyurethane, (B) component: silica fine particles whose surface is modified with organic molecules (weight average particle size of 100 nm or less), (A) component Total: (B) component = 2: 3. The refractive index of the cured film of the hard coat layer forming material was 1.485. Crosslinked particles of acryl and styrene as the fine particles per 100 parts by weight of resin solid content of the hard coat layer forming material (manufactured by Sekisui Plastics Co., Ltd., trade name “Techpolymer SSX1055QXE”, weight average particle size: 5.5 μm , Refractive index: 1.515), 10 parts by weight, leveling agent (manufactured by DIC Corporation, trade name “GRANDIC PC-4100”), 0.1 part by weight, photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Trade name “Irgacure 127”) was mixed. This mixture was diluted so that the solid concentration was 45% by weight and the butyl acetate / MEK ratio was 5/1 (weight ratio) to prepare an antiglare hard coat layer forming material.

A triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., trade name “TD80UL”, thickness: 80 μm, refractive index: 1.48) was prepared as a transparent plastic film substrate. The antiglare hard coat layer forming material was applied to one side of the transparent plastic film substrate using a comma coater to form a coating film. Subsequently, the said coating film was dried by heating at 100 degreeC for 1 minute. Thereafter, ultraviolet light with an integrated light quantity of 300 mJ / cm ² was irradiated with a high-pressure mercury lamp, the coating film was cured to form an antiglare hard coat layer having a thickness of 9 μm, and the antiglare hard coat film of Example 1 was formed. Got.

(Example 2)
An antiglare hard coat film of Example 2 was obtained in the same manner as in Example 1 except that 12 parts by weight of the fine particles were mixed per 100 parts by weight of resin solid content of the hard coat layer forming material. .

(Comparative Example 1)
In the same manner as in Example 1, except that 8 parts by weight of the fine particles were mixed per 100 parts by weight of resin solid content of the hard coat layer forming material to form an antiglare hard coat layer having a thickness of 11 μm. The antiglare hard coat film of Example 1 was obtained.

(Comparative Example 2)
As a crosslinked particle of acrylic and styrene, “Techpolymer SSX105NXE” (manufactured by Sekisui Plastics Co., Ltd., weight average particle size: 5.0 μm, refractive index: 1.505) is used. An antiglare hard coat film of Comparative Example 2 was obtained in the same manner as in Example 1 except that the amount was 14 parts by weight per 100 parts by weight of resin solid content of the forming material.

(Comparative Example 3)
As a crosslinked particle of acrylic and styrene, “Techpolymer SSX105NXE” (manufactured by Sekisui Plastics Co., Ltd., weight average particle size: 5.0 μm, refractive index: 1.505) is used. An antiglare hard coat film of Comparative Example 3 was obtained in the same manner as in Example 1 except that the amount was 17 parts by weight per 100 parts by weight of resin solid content of the forming material.

(Comparative Example 4)
As a hard coat layer forming material, an ultraviolet curable resin (made by DIC Corporation, trade name “Unidic 17-806”) made of isocyanuric acid triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate and isophorone diisocyanate polyurethane, solid Min: 80% by weight, solvent: butyl acetate). The refractive index of the cured film of the hard coat layer forming material was 1.53. An irregular shape having a leveling agent (trade name “Megafac F-470N” manufactured by DIC Corporation) of 0.5 parts by weight and a weight average particle diameter of 2.5 μm per 100 parts by weight of resin solid content of the hard coat layer forming material. Silica particles (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “Silo Hovic 702”, refractive index: 1.46) 8 parts by weight, amorphous silica particles having a weight average particle size of 1.5 μm (Fuji Silysia Chemical Co., Ltd.) 7 parts by weight of a product name “Silo Hovic 100”, refractive index: 1.46), and 5 parts by weight of a photopolymerization initiator (Ciba Specialty Chemicals, trade name “Irgacure 184”) An antiglare hard coat layer forming material was prepared by dissolving or dispersing in a mixed solvent (toluene: butyl acetate = 85: 15 (weight ratio)) so that the concentration was 38 wt%.

The antiglare hard coat layer forming material was applied to one side of the transparent plastic film substrate using a comma coater to form a coating film. Subsequently, the said coating film was dried by heating at 100 degreeC for 1 minute. Thereafter, the metal halide lamp was irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm ² , the coating film was cured to form an antiglare hard coat layer having a thickness of 4 μm, and the antiglare hard coat film of Comparative Example 4 was formed. Obtained.

(Comparative Example 5)
Leveling agent (manufactured by DIC Corporation, trade name “Megafac F-470N”) 0.5 parts by weight per 100 parts by weight of resin solid content of the same hard coat layer forming material as in Comparative Example 4; 5 μm amorphous silica particles (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “Silo Hovic 702”, refractive index: 1.46) 8 parts by weight, and photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Inc.) Name “Irgacure 184”) is dissolved or dispersed in a mixed solvent (toluene: butyl acetate = 85: 15 (weight ratio)) so that the solid content concentration is 38% by weight, and an antiglare hard coat An antiglare hard coat film of Comparative Example 5 was obtained in the same manner as in Comparative Example 4 except that the layer forming material was prepared.

(Comparative Example 6)
In the same manner as in Example 1, except that the same acrylic and styrene crosslinked particles as in Example 1 were mixed in an amount of 6 parts by weight per 100 parts by weight of resin solid content of the same hard coat layer forming material as in Example 1. The anti-glare hard coat film of Comparative Example 6 was obtained.

前記式（１）において、Ｒ^１は、−Ｈ若しくは−ＣＨ_３であり、Ｒ^２は、−ＣＨ_２ＣＨ_２ＯＸ若しくは下記一般式（２）で表される基であり、前記Ｘは、−Ｈ若しくは下記一般式（３）で表されるアクリロイル基である。

前記一般式（２）において、前記Ｘは、−Ｈ若しくは下記一般式（３）で表されるアクリロイル基であり、前記Ｘは、同一であってもよいし、異なっていてもよい。

(Comparative Example 7)
As a hard coat layer forming material, a resin containing the following components (manufactured by DIC Corporation, trade name “GRANDIC PC1097”, solid content: 66% by weight) was prepared. The refractive index of the cured film of the hard coat layer forming material was 1.53. Acrylic particles (manufactured by Sekisui Plastics Co., Ltd., trade name “SSX-108TNL”, weight average particle diameter: 8 μm, refractive index: 1.495) per 100 parts by weight of resin solid content of the hard coat layer forming material. 20 parts by weight and 0.1 part by weight of a leveling agent (manufactured by DIC Corporation, trade name “GRANDIC PC-F479”) were mixed. This mixture was diluted with ethyl acetate so that the solid content concentration was 55% by weight to prepare an antiglare hard coat layer forming material.
Isophorone diisocyanate urethane acrylate (100 parts by weight)
Dipentaerythritol hexaacrylate (38 parts by weight)
Pentaerythritol tetraacrylate (40 parts by weight)
Pentaerythritol triacrylate (15.5 parts by weight)
Polymer having a repeating unit represented by the following general formula (1), a copolymer or a mixture of the polymer and the copolymer (30 parts by weight)
Photopolymerization initiator: 1.8 parts by weight of trade name “Irgacure 184” (manufactured by Ciba Specialty Chemicals) and 5.6 parts by weight of lucillin type photopolymerization initiator; mixed solvent; butyl acetate: ethyl acetate = 3: 4 (weight ratio)

In the formula (1), R ¹ is —H or —CH ₃ , R ² is —CH ₂ CH ₂ OX or a group represented by the following general formula (2), and the X is — H or an acryloyl group represented by the following general formula (3).

In the general formula (2), X is —H or an acryloyl group represented by the following general formula (3), and the Xs may be the same or different.

The antiglare hard coat layer forming material was applied to one side of the transparent plastic film substrate using a comma coater to form a coating film. Subsequently, the said coating film was dried by heating at 100 degreeC for 1 minute. Thereafter, ultraviolet light with an integrated light quantity of 300 mJ / cm ² was irradiated with a high-pressure mercury lamp, the coating film was cured to form an antiglare hard coat layer having a thickness of 24 μm, and the antiglare hard coat film of Comparative Example 7 Got.

(Comparative Example 8)
The above-mentioned “Unidic 17-806” (trade name) was prepared as a hard coat layer forming material. Leveling agent (manufactured by DIC Corporation, trade name “Defenser MCF323”) 0.5 parts by weight, polystyrene particles (manufactured by Soken Chemical Co., Ltd., trade name “100 parts by weight of resin solid content of the hard coat layer forming material” Chemisnow SX350H ”, weight average particle diameter: 3.5 μm, refractive index: 1.59) 14 parts by weight and photopolymerization initiator (trade name“ Irgacure 184 ”manufactured by Ciba Specialty Chemicals), 5 parts by weight An antiglare hard coat layer dissolved or dispersed in a mixed solvent (toluene: butyl acetate: ethyl acetate = 86.5: 1.0: 12.5 (weight ratio)) so that the partial concentration becomes 45% by weight. A forming material was prepared.

The antiglare hard coat layer forming material was applied to one side of the transparent plastic film substrate using a comma coater to form a coating film. Subsequently, the said coating film was dried by heating at 100 degreeC for 1 minute. Thereafter, the metal halide lamp was irradiated with ultraviolet rays having an integrated light quantity of 300 mJ / cm ² , the coating film was cured to form an antiglare hard coat layer having a thickness of 5 μm, and the antiglare hard coat film of Comparative Example 8 was formed. Obtained.

(Comparative Example 9)
As the fine particles, 10 parts by weight of “Techpolymer XX94AA” (manufactured by Sekisui Plastics Co., Ltd., weight average particle size: 6.0 μm, refractive index: 1.495), which is a crosslinked particle of acrylic and styrene, is mixed. The antiglare hard coat film of Comparative Example 9 was obtained in the same manner as in Comparative Example 8, except that an antiglare hard coat layer having a thickness of 9 μm was formed.

  Various characteristics were measured or evaluated for the antiglare hard coat films of Examples 1 and 2 and Comparative Examples 1 to 9 thus obtained. The results are shown in FIGS. 1 to 11 and Table 1 below.

  As shown in Table 1, in the examples, good results were obtained for all of antiglare properties, glare and white blur. On the other hand, in the comparative examples, although good results were obtained for some of the antiglare properties, glare and white blur, good results were not obtained for all the characteristics. That is, it can be seen that Comparative Examples 1, 7, and 9 have convex portions with a length of the line segment of 80 μm or more, and the glare characteristics are not good. In Comparative Example 8, although the length of the line segment has a convex portion of 80 μm or more, the total haze value is very high as 45%. I understand that it is strong. When the total haze value is about 45%, the contrast is also lowered. In Comparative Examples 2 to 5, the ratio of the internal haze value to the total haze value is small. That is, since the contribution of internal scattering is small, good glare characteristics cannot be obtained. Further, in Comparative Example 6, sufficient antiglare property is not obtained, but this is considered to be caused by a small Ra. By measuring the Ra, the number of convex portions and the haze value defined in the present invention, it is possible to grasp the tendency of visibility such as antiglare property, glare and white blurring without visual evaluation.

  FIGS. 1-11 is the profile of the cross-sectional surface shape of the anti-glare hard coat film obtained by the said Example and comparative example. In the anti-glare hard coat film obtained in the above examples, compared to the anti-glare hard coat film obtained in the comparative example, the entire surface is not rough, but fine irregularities are sparse, Further, there is no locally large convex portion (the length of the line segment is 80 μm or more). The anti-glare hard coat film having a concavo-convex shape as in the above examples is in a range defined by the Ra and the size and number of the convex portions, and further satisfies a predetermined haze value. Thus, it can be seen that it can be used favorably as an antiglare hard coat film.

According to the anti-glare hard coat film of the present invention, it is possible to solve all of the conflicting issues of high contrast, ensuring anti-glare properties, preventing white blur, and supporting high definition. Therefore, the antiglare hard coat film of the present invention can be suitably used, for example, for optical members such as polarizing plates, image display devices such as liquid crystal panels and LCDs, and its application is not limited and can be applied to a wide range of fields. is there. Further, by measuring the number of Ra and the number of convex portions defined in the present invention, it is possible to grasp the tendency of visibility such as anti-glare property, glare and white blur without visual evaluation. It is also effective as an index for evaluating a dazzling film.

Claims (12)

An antiglare hard coat film having an antiglare hard coat layer containing fine particles on at least one surface of a transparent plastic film substrate, wherein the total haze value Ht of the antiglare hard coat film is 10 to 35 % In range,
The total haze value Ht and the internal haze value Hin satisfy the relationship of the following formula (1),
In the uneven shape of the antiglare hard coat layer surface, the following arithmetic average surface roughness Ra is in the range of 0.1 to 0.3 μm,
The length of the line segment of the portion where the convex portion exceeding the roughness average line of the surface roughness profile crosses the convex portion of the average line at a length of 4 mm at an arbitrary location on the surface of the antiglare hard coat layer. Does not include a convex portion with a length of 80 μm or more, and has a convex portion that exceeds a reference line that is parallel to the average line and located at a height of 0.1 μm, and the convex portion of the reference line The length of the line segment that crosses the shape portion is 20 μm or less, and there are 50 or more convex portions at a length of 4 mm at any location on the surface of the antiglare hard coat layer. Antiglare hard coat film.
0.5 ≦ Hin / Ht ≦ 0.9 (1)
Total haze value Ht: Anti-glare hardware according to JIS K 7136 (2000 edition)
Haze value of entire coat film (cloudiness) (%)
Inner haze value Hin: When the antiglare hard coat film surface is smooth.
Total haze value of antiglare hard coat film measured (%)
Ra: arithmetic average surface roughness (μm) specified in JIS B 0601 (1994 edition) 2. The antiglare hard coat according to claim 1, wherein the antiglare hard coat layer is formed using the fine particles and a hard coat layer forming material containing the following components (A) and (B). the film.
(A) component: a curable compound having at least one of an acrylate group and a methacrylate group (B) component: a weight average particle diameter formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group Particles of 200nm or less 3. The component (B), wherein the inorganic oxide particles include at least one particle selected from the group consisting of silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Antiglare hard coat film. The antiglare hard according to claim 2 or 3, wherein in the hard coat layer forming material, the component (B) is contained in a range of 100 to 200 parts by weight with respect to 100 parts by weight of the component (A). Coat film. A spherical or irregular shape in which the difference in refractive index between the hard coat layer forming material and the fine particles is in the range of 0.01 to 0.04, and the fine particles have a weight average particle size in the range of 0.5 to 8 μm. The fine particles are contained in a range of 5 to 20 parts by weight with respect to 100 parts by weight of the hard coat layer forming material. Antiglare hard coat film. The antiglare hard coat film according to any one of claims 1 to 5, wherein a thickness of the antiglare hard coat layer is in a range of 1.2 to 3 times a weight average particle diameter of the fine particles. The antiglare hard coat film according to any one of claims 1 to 6, wherein an antireflection layer is formed on the antiglare hard coat layer. A polarizing plate comprising the antiglare hard coat film according to any one of claims 1 to 7 and a polarizer. An image display device comprising the antiglare hard coat film according to any one of claims 1 to 7. An image display device comprising the polarizing plate according to claim 8. A manufacturing method for manufacturing the antiglare hard coat film according to any one of claims 1 to 7,
Preparing a hard coat layer forming material containing the fine particles, the following components (A) and (B), and an antiglare hard coat layer forming material containing a solvent;
Coating the antiglare hard coat layer forming material on at least one surface of the transparent plastic film substrate to form a coating film;
Curing the coating film to form the antiglare hard coat layer,
The fine particles are added in a range of 5 to 20 parts by weight with respect to 100 parts by weight of the hard coat layer forming material,
As the solvent, a mixed solvent of butyl acetate and methyl ethyl ketone (MEK) is used, and the ratio of butyl acetate / MEK in the mixed solvent is within a range of 1.5 / 1 to 3.0 / 1 by weight. A method for producing an antiglare hard coat film characterized by
(A) component: a curable compound having at least one of an acrylate group and a methacrylate group (B) component: a weight average particle diameter formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group Particles of 200nm or less A manufacturing method for manufacturing the antiglare hard coat film according to any one of claims 1 to 7,
Preparing a hard coat layer forming material containing the fine particles, the following components (A) and (B), and an antiglare hard coat layer forming material containing a solvent;
Coating the antiglare hard coat layer forming material on at least one surface of the transparent plastic film substrate to form a coating film;
Curing the coating film to form the antiglare hard coat layer,
The fine particles are added in a range of 5 to 20 parts by weight with respect to 100 parts by weight of the hard coat layer forming material,
As the solvent, a mixed solvent of methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK) is used, and the MIBK / MEK ratio of the mixed solvent is within a range of 1.5 / 1 to 6.0 / 1 by weight. The manufacturing method of the anti-glare hard coat film characterized by these.
(A) component: a curable compound having at least one of an acrylate group and a methacrylate group (B) component: a weight average particle diameter formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group Particles of 200nm or less

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