JP2013178534A - Hard-coated antidazzle film, and polarizing plate using the same, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard-coated antidazzle film, a polarizing film and the like, having excelling antidazzle properties and excelling reflection properties even with a low haze degree value and, when reflection is reduced, capable of preventing specific "tinting" to improve the black density when displaying black.SOLUTION: The hard-coated antidazzle film including a hard-coating antidazzle layer and a reflection layer has a reflection intensity ratio of 3 or less. The hard-coating antidazzle layer contains fine particles. An asperity-shaped surface of the hard-coating antidazzle layer has an average angle θa of inclination in a predetermined range and arithmetic average surface roughness Ra. The surface shape of the antireflection layer has the number of convexities exceeding a roughness mean line of a surface roughness profile. And, the number and size of the convexities exceeding a standard line that is in parallel to the mean line and is located at a height of 0.1 μm are within predetermined ranges.

Description

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

  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 used for applications that use LCDs and in-vehicle applications such as mobile phones and car navigation displays, due to technological innovations such as high viewing angle, high definition, high-speed response, and color reproducibility. It has spread. In these applications, further improvement in visibility is required. One of the reasons why sufficient visibility cannot be obtained is interface reflection at the interface between the polarizing plate disposed on the outermost surface portion of the display and air. Therefore, in order to further improve the visibility, a method of performing a low reflection treatment on the surface of the polarizing plate is generally used (for example, see Patent Documents 1 and 2).

  In addition, there is a technique of performing anti-glare processing in order to prevent a decrease in contrast due to reflection of external light. An antiglare hard coat film can be used for the antiglare treatment (see, for example, Patent Document 3). Even in the case of using an antiglare hard coat film, from the viewpoint of antireflection, it has been studied to perform a low reflection treatment for the purpose of further improving the visibility (see, for example, Patent Document 4). It is important to ensure anti-glare properties even after imparting low reflection characteristics. On the other hand, in recent years, anti-glare hard coat films have been required to have a low haze value for the purpose of achieving high contrast. When the haze value of the antiglare hard coat film is lowered, there is a problem that the luminance variation existing in the pixels constituting the display is more emphasized to cause a visible failure (glare failure), and the image quality deteriorates.

Japanese Patent Laid-Open No. 11-295503 JP 2002-122705 A JP 2008-90263 A JP 2006-317957 A

  If the low reflection treatment and the anti-glare treatment are used together in order to achieve both of the above characteristics, there will be a problem of “colored” which appears to be blue or red on the display, and thus the visibility may be lowered instead. It turned out to be. Then, an object of this invention is to provide the glare-proof hard coat film which improves visibility, without degrading the characteristic of image display apparatuses, such as LCD. In other words, it has excellent anti-glare properties and excellent reflection characteristics even at a low haze value, and prevents “coloring” peculiar to the case of low reflection to prevent black in black display. An object of the present invention is to provide an antiglare hard coat film capable of improving the darkness, a polarizing plate and an image display device using the same.

In order to achieve the above object, the antiglare hard coat film of the present invention has the following reflection strength having an antiglare hard coat layer and an antireflection layer on at least one surface of a transparent plastic film substrate. An anti-glare hard coat film having a ratio of 3 or less,
The antiglare hard coat layer contains fine particles,
In the uneven shape of the antireflection layer surface, the average inclination angle θa is in the range of 0.5 ≦ θa ≦ 1.5, and
The following arithmetic average surface roughness Ra is in the range of 0.05 to 0.15 μm,
In any length of 4 mm on the surface of the antireflection layer, it has 80 or more convex portions exceeding the roughness average line of the surface roughness profile, and
Convex part that exceeds the reference line located at a height of 0.1 μm parallel to the average line, and the length of the line segment that crosses the convex part of the reference line is 50 μm or more It is characterized by not including a shape part.
Reflection intensity ratio: on the outermost surface of the antiglare hard coat film at an angle of 10 ° from the vertical direction
Of the reflection intensity when light is applied so that the light intensity at 1000 Lx is
Ratio value when the reflection intensity of a hard coat film having a refractive index of 1.53 is set to 1. Ra: arithmetic average surface roughness (μm) specified in JIS B 0601 (1994 edition)

  The polarizing plate of the present invention has the antiglare hard coat film of the present invention and a polarizer.

  The image display device of the present invention includes the antiglare hard coat film of the present invention.

  The image display device of the present invention includes the polarizing plate of the present invention.

  According to the anti-glare hard coat film of the present invention, it has low reflection characteristics, and furthermore, by realizing a characteristic uneven shape, it is excellent in anti-glare while suppressing “coloring” when low reflection is performed. In addition, the glare is suppressed and the haze value can be lowered. Therefore, the visibility can be improved as compared with a conventional low reflection antiglare hard coat film. Further, by preventing “coloring”, 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 having a measurement length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Example 3. (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. 4 is a profile showing a range of 2 to 3 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. 5 is a profile showing a range of 0 to 1 mm in a measured length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Comparative Example 2. FIG. 6 is a profile showing the range of 0 to 1 mm in the measured length of 4 mm of the cross-sectional surface shape of the antiglare hard coat film of Comparative Example 3. FIG. 7 is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Comparative Example 4 in a range of 0 to 1 mm in a measurement length of 4 mm. 8 is a profile showing a cross-sectional surface shape of the antiglare hard coat film of Comparative Example 5 in a range of 0 to 1 mm in a measurement length of 4 mm. FIG. 9 is a schematic diagram illustrating an example of the relationship between the roughness curve, the height h, and the reference length L. FIG. 10 is a schematic diagram for explaining a method of measuring the number of convex portions exceeding the roughness average line of the surface roughness profile in the present invention. FIG. 11 is a schematic diagram for explaining a method for measuring the number of convex portions exceeding the reference line of the surface roughness in the present invention.

  In the antiglare hard coat film of the present invention, the antireflection layer preferably has a thickness in the range of 170 to 350 nm.

  In the antiglare hard coat film of the present invention, the haze value is preferably in the range of 4 to 30.

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.

  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: a weight average particle diameter formed by bonding inorganic oxide particles and an organic compound containing a polymerizable unsaturated group , Particles below 200nm

  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, more preferably in the range of 5 to 17 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 preferably has a haze value in the range of 4 to 30%. The haze value is the haze value (cloudiness) of the entire antiglare hard coat film according to JIS K 7136 (2000 version). The haze value is more preferably in the range of 6 to 30%, and still more preferably in the range of 8 to 30%. In order to set the haze value in the above range, the fine particles and the hard coat layer forming material are adjusted 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 0.06. Is 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.

The antiglare hard coat film of the present invention has an average inclination angle θa in the range of 0.5 ≦ θa ≦ 1.5 in the uneven shape on the surface of the antireflection layer. In the present invention, the average inclination angle θa is a value defined by the following mathematical formula (1). The average inclination angle θa is, for example, a value measured by a method described in an example described later.
Average inclination angle θa = tan ⁻¹ Δa (1)

In the mathematical formula (1), Δa is a peak length and a valley between adjacent peaks in the reference length L of the roughness curve defined in JIS B 0601 (1994 version) as shown in the following mathematical formula (2). This is a value obtained by dividing the sum (h1 + h2 + h3... + Hn) of the difference (height h) from the lowest point by the reference length L. The roughness curve is a curve obtained by removing a surface waviness component longer than a predetermined wavelength from a cross-sectional curve with a phase difference compensation type high-pass filter. The cross-sectional curve is a contour that appears at the cut end when the target surface is cut along a plane perpendicular to the target surface. FIG. 9 shows an example of the roughness curve, the height h, and the reference line L.
Δa = (h1 + h2 + h3... + Hn) / L (2)

  The θa is preferably in the range of 0.6 to 1.4, more preferably in the range of 0.65 to 1.35. When θa is less than 0.5, the antiglare property is weak, and when it exceeds 1.5, glare tends to be strong.

  The antiglare hard coat film of the present invention has an arithmetic average surface roughness Ra in the range of 0.05 to 0.15 μm as defined in JIS B 0601 (1994 version) in the uneven shape of the antiglare hard coat layer surface. Furthermore, at a length of 4 mm at an arbitrary position on the surface of the antireflection layer, the surface roughness profile has 80 or more convex portions exceeding the roughness average line, and is parallel to the average line. Including a convex portion having a length exceeding a reference line located at a height of 0.1 μm, and a length of a line segment that crosses the convex portion of the reference line is 50 μm or more. Not in. The Ra is preferably in the range of 0.07 to 0.12 μm, more preferably in the range of 0.08 to 0.10 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 0.05 μm or more. . In addition, in order to ensure antiglare properties, the Ra needs to be 0.15 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. When the number of convex portions exceeding the roughness average line is 80 or more, and the Ra is an antiglare hard coat film of 0.15 μm or less, when used for an image display device or the like, 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. As for the number of the said convex-shaped parts, the range of 80-110 is more preferable, More preferably, it is the range of 90-100. If the number of the convex portions is less than 80, glare is likely to occur, and if it exceeds 110, coloring of the entire surface tends to be strong.

  The antiglare hard coat film of the present invention has a convex portion that exceeds the reference line located at a height of 0.1 μm parallel to the roughness average line of the surface roughness profile. The reference line located at a height of 0.1 μm crosses the convex part, and the size of the convex part is the length of the line segment of the reference line that crosses the convex part. Is less than 50 μm. Furthermore, it is preferable that 50 or more of the convex portions having a length of the line segment of 20 μm or less are formed at a length of 4 mm at an arbitrary position on the surface of the antiglare hard coat layer. When the number of the convex portions having a length of 20 μm or less is 50 or more, it is preferable in terms of antiglare property, and glare is hardly generated. Further, if there is a convex portion having a line segment length of 50 μm or more, glare is likely to occur. There are no convex portions having a length of 50 μm or more in the line segment, and 80 or more convex portions exceeding the roughness average line are formed, and the Ra is 0.15 μm or less. In the case of an antiglare hard coat film, since there are many relatively uniform fine irregularities, excellent uniform scattering becomes possible, and glare can be suppressed even in a high-definition panel. The number of convex portions having a length of 20 μm or less is preferably in the range of 50 to 90, and more preferably in the range of 60 to 80. If the number of convex portions having a length of 20 μm or less is too large, white blur tends to be strong.

  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 50 μm or more. In addition, there are a predetermined number of fine irregularities independently, and preferably 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 layer constituting 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. The coating material is applied to at least one surface of the transparent plastic film substrate to form a coating film, and the coating film is cured to form the anti-glare hard coating layer. it can. In the production of the antiglare hard coat layer in the present invention, a transfer method using a mold, a method of imparting a concavo-convex shape by an appropriate method such as sand blasting or embossing roll can be used together.

  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. In order to obtain the antiglare hard coat layer in the present invention, there are optimum solvent types and solvent ratios according to 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 5 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 2.0 / 1 (weight ratio), and an antiglare hard coat layer capable of realizing the characteristics of the present invention is obtained. It is done. In the case of butyl acetate / MEK, an antiglare hard coat layer capable of realizing the characteristics of the present invention is obtained in the range of at least 1.5 / 1 to 3.0 / 1 (weight ratio). 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 material for forming the antiglare hard coat layer may include pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, and antioxidants as long as the performance is not impaired. An agent, thixotropic agent, etc. 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.

  In the antiglare hard coat film of the present invention, an antireflection layer (low refractive index layer) is disposed on the antiglare hard coat layer. 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 factor that reduces the visibility of images. 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.

The reflectance of the optical thin layer can be lowered as the thickness of the optical thin layer increases. However, the cost increases by increasing the thickness of the optical thin layer. For example, when a reflectance of about 0.3% is desired, a configuration of about 5 layers is preferable. On the anti-glare hard coat layer, a first SiO ₂ layer, a first TiO ₂ layer, a second SiO ₂ layer, a second TiO ₂ layer, a third SiO ₂ layer and five layers are formed in order. In this case, the thickness of the first SiO ₂ layer is preferably 10 to 40 nm, more preferably 10 to 30 nm, and the first TiO ₂ layer is preferably 10 to 40 nm, more preferably 10 to 30 nm, and the second SiO ₂ layer. _{The two} layers are preferably 10 to 40 nm, more preferably 15 to 35 nm, and the second TiO ₂ layer is preferably 70 to 140 nm, more preferably 110 to 130 nm, and the third SiO ₂ layer is preferably 70 to 90 nm, more Preferably it is 75-85 nm. The antireflection layer preferably has a total film thickness of 170 to 350 nm, more preferably 220 to 310 nm. The antireflection layer is thinner than the antiglare hard coat layer, and has a thickness that hardly affects the uneven shape of the surface by itself. Therefore, it can be said that the characteristic surface shape of the antiglare hard coat film of the present invention is mainly formed by the antiglare hard coat layer.

  One of the characteristics of the antiglare hard coat film of the present invention is that it has a low reflectance. The antiglare hard coat film of the present invention has the following characteristics, for example. Light is applied to the surface of the antiglare hard coat film from an angle of 10 ° from the vertical direction so that the light intensity on the outermost surface of the antiglare hard coat film is 1000 Lx. When the reflection intensity of the hard coat film having a refractive index of 1.53 is 1, the reflection intensity ratio on the surface of the antiglare hard coat film of the present invention can be 3 or less. In the antiglare hard coat film of the configuration of the present invention having a reflection intensity ratio of 3 or less, “coloring” can be prevented. In this case, the reflected hues x and y can be realized such that 0.2 ≦ x ≦ 0.4 and 0.2 ≦ y ≦ 0.4, and “colored” is not observed. In addition, when the antiglare property is too strong, “colored” may be seen. Therefore, also from that viewpoint, θa is defined as 1.5 or less, and Ra is defined as 0.15 μm or less.

  Further, in the antiglare hard coat film of the present invention, in order to prevent the adhesion of contaminants and improve the ease of removing the adhered contaminants, the fluorine group-containing silane compound or the fluorine group-containing organic compound is used. It is also preferable to laminate a contamination prevention layer to be formed on the antireflection layer.

  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.

  As described above, forming the antiglare hard coat layer on at least one surface of the transparent plastic film substrate, and further forming the antireflection layer on the surface of the formed antiglare hard coat layer. Thus, the antiglare hard coat film of the present invention can be produced. 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.

  An example of the antiglare hard coat film of the present invention is one in which an antiglare hard coat layer and an antireflection layer are formed on one surface of a transparent plastic film substrate. 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 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.

(Haze value)
The haze value was measured using a haze meter (trade name “HM-150”, manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS K 7136 (2000 version) haze (cloudiness). .

(Average inclination angle θa and arithmetic average 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 a surf coder ET4000 (manufactured by Kosaka Laboratory Co., Ltd.), and the average inclination angle θa and arithmetic average surface roughness Ra were measured. Asked. The high-precision fine shape measuring instrument automatically calculates the average inclination angle θa and the arithmetic average surface roughness Ra. The average inclination angle θa and the arithmetic average surface roughness Ra are based on JIS B 0601 (1994 edition).

(Number of convex parts exceeding the roughness average line of the surface roughness profile)
In the roughness profile (F profile) obtained by measuring the surface shape, the measured value was obtained by measuring the number of convex portions exceeding the roughness average line of the profile on an arbitrary 4 mm straight line. FIG. 10 is a schematic diagram for explaining a method for measuring the number of the convex portions. The convex part 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 average line. For example, when there are a plurality of peaks in the portion exceeding the average line, such as 1, 2, 4, 6, 8 in the profile, the number of convex portions is counted as one. In FIG. 10, the total number of convex portions is ten.

(Number of convex parts exceeding the surface roughness reference line)
In the roughness profile (F 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. Of the convex portions that exceed the reference line on a straight line having an arbitrary measurement area of 4 mm, the length of the reference line that crosses the convex portion is 50 μm or more and the reference line that crosses the convex portion. The measured value was obtained by measuring the number of convex portions having a line segment length of 20 μm or less. FIG. 11 is a schematic diagram for explaining a method of measuring the number of the convex portions. The convex part 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. 11, the number of convex portions of 50 μm or more is one of the peaks 3 in the profile, and the number of convex portions of 20 μm or less is a total of five peaks 1, 4, 5, 6, and 8 in the profile. It becomes.

(Reflection intensity ratio)
(1) A black acrylic plate (Mitsubishi Rayon Co., Ltd., thickness 2.0 mm, 50 mm × 50 mm) having a thickness of about 20 μm is formed on the surface of the antiglare hard coat film on which the antiglare hard coat layer is not formed. A sample was prepared by pasting with an acrylic adhesive to eliminate back surface reflection.
(2) With respect to the sample, a light receiver (manufactured by MINOLTA, SPECTRORADIOTER CS1000A) is set to be parallel to the upper side by 50 cm, and ring illumination (diameter 37 mm: MHF-G150LR made by MORITEX) is set at a height of 105 mm. did. The irradiation angle of the light applied to the panel from the ring illumination light at this set position was set to 10 °.
(3) An illuminometer (manufactured by TOPCOM, ILLUMINANCE METER) was used to adjust the illuminance to 1000 Lx.
(4) The Y value and chromaticity coordinates of the CIE1931 color system (2-degree visual field XYZ color system) at the center of the blackboard with the antiglare hard coat film were measured, and the Y value was defined as the reflection intensity.
(5) As a reference value, the reflection intensity was measured by the method of (1) to (4) above using a hard coat film produced in the same manner as Comparative Example 5 except that no antireflection layer was provided. The value was normalized to 100 (actual value: 59). The characteristic values related to the surface roughness of the reference hard coat film were an Ra value of 0.002 μm and a θa value of 0.05 °.
(6) The ratio of the reflection intensity of the sample when the reflection intensity of the reference hard coat film was set to 1 was calculated as the reflection intensity ratio.

(Reflection hue evaluation)
In the measurement of the reflection intensity ratio, the chromaticity coordinates (x, y) obtained in (4) were used for the reflection hue evaluation.

(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: There is no reflection of a face, and there is no influence on visibility.
A: Although there is a reflection of the face, there is no practical problem.
B: There is a reflection of the face and I am a little worried.
C: The face is clearly reflected and I am quite worried.

(Glare evaluation)
The surface on which the antiglare hard coat layer of the antiglare hard coat film was not formed was bonded to a glass plate having a thickness of 1.1 mm with an adhesive to obtain a measurement sample. This sample was set on a mask pattern placed on a backlight (made by Hakuba Photo Industry Co., Ltd., trade name “Light Viewer 5700”). As the mask pattern, a lattice pattern (150 ppi) having an opening of 146 μm × 47 μm, a vertical line width of 19 μm, and a horizontal line width of 23 μm was used. The distance from the mask pattern to the antiglare hard coat layer was 1.1 mm, and the distance from the backlight to the mask pattern was 1.5 mm. And the glare of the said glare-proof hard coat film was determined visually by the following criteria.
Judgment criteria AA: There is almost no glare.
A: There is a slight glare, but a level that does not matter.
B: Glare is strong.

(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) 6 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 content concentration was 45% by weight and the butyl acetate / MEK ratio was 2/1 (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 rays having an integrated light quantity of 300 mJ / cm ² were irradiated with a high-pressure mercury lamp, and the coating film was cured to form an antiglare hard coat layer having a thickness of 9 μm.

On the formed antiglare hard coat layer, by sputtering, a SiO ₂ layer (thickness 20 nm), a TiO ₂ layer (thickness 20 nm), a SiO ₂ layer (thickness 25 nm), a TiO ₂ layer (thickness 120 nm), and SiO _{2 are} sequentially formed. A layer (thickness 80 nm) and a five-layer antireflection layer were formed, and the antiglare hard coat film of Example 1 was obtained.

(Example 2)
As the fine particles, silicone fine particles (manufactured by Momentive Performance Materials, trade name “Tospearl 145”, weight average particle size: 4.5 μm, refractive index: 1.425) are used as resin solid content 100 of the hard coat layer forming material. An antiglare hard coat film of Example 2 was obtained in the same manner as in Example 1 except that 5 parts by weight was mixed per part by weight.

(Example 3)
In the same manner as in Example 1, except that 10 parts by weight of the same acrylic and styrene crosslinked particles as in Example 1 were mixed per 100 parts by weight of resin solid content of the same hard coat layer forming material as in Example 1. An antiglare hard coat film of Example 3 was obtained.

(Comparative Example 1)
Example 1 except that a material for forming an antiglare hard coat layer comprising an ultraviolet curable resin and fine particles was applied to one side of the transparent plastic film substrate to form an antiglare hard coat layer having a thickness of 5 μm. In the same manner as above, an antiglare hard coat film of Comparative Example 1 was obtained.

(Comparative Example 2)
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. A 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 hard coat layer forming material, an irregular shape having a weight average particle diameter of 4.2 μm 4.3 parts by weight of silica particles (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “Silicia 436”, refractive index: 1.46), and photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name “Irgacure 184”) )) 5 parts by weight were dissolved or dispersed in toluene so that the solid content concentration was 44% by weight to prepare an antiglare hard coat layer forming material.

The antiglare hard coat layer forming material was applied to one side of the transparent plastic film substrate using a bar 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 , and the coating film was cured to form an antiglare hard coat layer having a thickness of 5 μm. On the formed anti-glare hard coat layer, an antireflection layer similar to that of Example 1 was formed, and an anti-glare hard coat film of Comparative Example 2 was obtained.

(Comparative Example 3)
The same hard coat layer forming material as in Comparative Example 2 was prepared. 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 , and the coating film was cured to form an antiglare hard coat layer having a thickness of 4 μm. On the formed anti-glare hard coat layer, an antireflection layer similar to that of Example 1 was formed, and an anti-glare hard coat film of Comparative Example 3 was obtained.

(Comparative Example 4)
100 parts by weight of urethane acrylate UV curable resin, amorphous silica particles having a weight average particle diameter of 1.5 μm (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “Sirohovic 100”, refractive index: 1.46) 11 .6 parts by weight, leveling agent (trade name; MegaFuck F470N, manufactured by Dainippon Ink & Chemicals, Inc.), 0.5 part by weight of synthetic smectite, photopolymerization initiator (trade name; Irgacure 907, 5 parts by weight of Ciba Specialty Chemicals Co., Ltd.) is diluted with a mixed solvent of butyl acetate and toluene (butyl acetate: toluene = 13: 87, weight ratio) so that the solid content concentration becomes 42% by weight, and hard coat A layer forming material was prepared.

Next, the hard coat layer forming material was applied onto the transparent plastic film substrate with a bar coater to form a coating film, and the coating film was heated at 100 ° C. for 1 minute and dried. Furthermore, the coating film was irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm ² with a metal halide lamp and cured to form an antiglare hard coat layer having a thickness of 5 μm. On the formed anti-glare hard coat layer, the same anti-reflection layer as in Example 1 was formed, and the anti-glare hard coat film of Comparative Example 4 was obtained.

(Comparative Example 5)
In Comparative Example 2, a low reflection hard coat film of Comparative Example 5 was obtained in the same manner as Comparative Example 2 except that the amorphous silica particles were not added.

  Various properties of the antiglare hard coat films of Examples 1 to 3 and Comparative Examples 1 to 4 thus obtained and the low reflection hard coat film of Comparative Example 5 were measured or evaluated. The results are shown in FIGS. 1 to 8 and Table 1 below.

  As shown in Table 1, in the examples, good results were obtained with respect to all of reflected light intensity, coloring, anti-glare property and glare. In general, when the anti-glare hard coat layer is subjected to a low reflection treatment, the diffused light caused by the anti-glare layer is colored, so that the whole is more likely to be colored, but in these examples, it is exposed to light. Only the part had anti-glare property and the other part looked black, showing good characteristics. On the other hand, in the comparative example, good results were obtained for some of the reflected light intensity, coloring, anti-glare properties, and glare, but not for all the characteristics. That is, in Comparative Examples 1 to 4, the line segment has a convex portion with a length of 50 μm or more, and the reflection hue y is outside the range of 0.2 ≦ y ≦ 0.4. Although the glare was strong, it was colored. In Comparative Examples 2 to 4, it can be inferred that θa exceeds 1.5, which affects the glare characteristics. Also, the reflection intensity ratio exceeds 3. In Comparative Example 5, θa is less than 0.5. Ra is also 0 μm, the number of convex portions having a length of 20 μm or less is 0, and there is no antiglare property. By measuring the number of θa, Ra and the number of convex portions defined in the present invention, it is also possible to grasp the tendency of visibility such as reflected light intensity, coloring, anti-glare property and glare without visual evaluation. is there.

  FIGS. 1-8 is the profile of the cross-sectional surface shape of the anti-glare hard coat film or low reflection 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 50 μm or more). The anti-glare hard coat film having an uneven surface shape as in the above examples is in the range defined by the size and number of the θa, the Ra, and the convex portions, and is used as an anti-glare hard coat film. It can be seen that it can be used satisfactorily.

According to the anti-glare hard coat film of the present invention, it has excellent anti-glare properties while suppressing "coloring" when low reflection is performed, and glare is suppressed, and further, a low haze value is possible. Therefore, the visibility can be improved as compared with the conventional low reflection antiglare hard coat film. Further, by preventing “coloring”, it is possible to improve the darkness of black when the image display device displays black. 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. Furthermore, by measuring the size and number of θa, Ra, and convex portions defined in the present invention, the tendency of visibility such as reflected light intensity, coloring, anti-glare property, and glare is grasped without visual evaluation. This is also effective as an index for evaluating an antiglare film.

Claims (11)

An antiglare hard coat film having an antiglare hard coat layer and an antireflection layer on at least one surface of the transparent plastic film substrate and having a reflection intensity ratio of 3 or less,
The antiglare hard coat layer contains fine particles,
In the uneven shape of the antireflection layer surface, the average inclination angle θa is in the range of 0.5 ≦ θa ≦ 1.5, and
The following arithmetic average surface roughness Ra is in the range of 0.05 to 0.15 μm,
In any length of 4 mm on the surface of the antireflection layer, it has 80 or more convex portions exceeding the roughness average line of the surface roughness profile, and
Convex part that exceeds the reference line located at a height of 0.1 μm parallel to the average line, and the length of the line segment that crosses the convex part of the reference line is 50 μm or more An anti-glare hard coat film characterized by not containing a shaped part.
Reflection intensity ratio: on the outermost surface of the antiglare hard coat film at an angle of 10 ° from the vertical direction
Of the reflection intensity when light is applied so that the light intensity at 1000 Lx is
Ratio value when the reflection intensity of a hard coat film having a refractive index of 1.53 is set to 1. Ra: arithmetic average surface roughness (μm) specified in JIS B 0601 (1994 edition) The anti-glare hard coat film according to claim 1, wherein the antireflection layer has a thickness in a range of 170 to 350 nm. The antiglare hard coat film according to claim 1 or 2, wherein the haze value is in the range of 4 to 30. 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 antiglare hard coat film described in 1.
(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 5. 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 4 or 5, 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 an amount 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 7, 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. A polarizing plate comprising the antiglare hard coat film according to any one of claims 1 to 8 and a polarizer. An image display device comprising the antiglare hard coat film according to any one of claims 1 to 8. An image display device comprising the polarizing plate according to claim 9.

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