WO2021095745A1

WO2021095745A1 - Anti-glare film, method for designing anti-glare film, method for producing anti-glare film, optical member, and image display device

Info

Publication number: WO2021095745A1
Application number: PCT/JP2020/041988
Authority: WO
Inventors: 寛也遠藤; 尚樹橋本; 豪彦安藤
Original assignee: 日東電工株式会社
Priority date: 2019-11-11
Filing date: 2020-11-10
Publication date: 2021-05-20
Also published as: TW202124165A; KR20220098353A; JP2021076749A; CN114651196A

Abstract

The present invention provides an anti-glare film wherein the haze value is not susceptible to change.　An anti-glare film 10 which is obtained by superposing an anti-glare layer (B) 12 on a light-transmitting base material (A) 11, and which is characterized in that: the anti-glare layer (B) 12 contains a resin (B1) 12a for the anti-glare layer formation and at least one filler (B2) 12b for the haze adjustment; the filler (B2) 12b for the haze adjustment is configured from a copolymer of a polystyrene (Pst) and a polymethyl methacrylate (PMMA); the peak area ratio of the PMMA peak to the Pst peak, namely (PMMA peak)/(Pst peak) is 0.51 or more as determined by the Raman spectroscopy spectrum of the filler (B2) 12b for the haze adjustment by itself; the peak areas are calculated using the minimum point between adjacent peaks as the boundary; and the total haze value of the anti-glare film 10 is within the range of from 5% to 45%.

Description

Anti-glare film, anti-glare film design method, anti-glare film manufacturing method, optical member and image display device

The present invention relates to an antiglare film, a method for designing an antiglare film, a method for manufacturing an antiglare film, an optical member, and an image display device.

Various image display devices such as a cathode ray tube display device (CRT), a liquid crystal display device (LCD), a plasma display panel (PDP), and an electroluminescence display (ELD) are provided with fluorescent lamps and sunlight on the surface of the image display device. Anti-glare treatment is applied to prevent contrast deterioration due to reflection of external light and reflection of images, and in particular, as the screen size of image display devices increases, anti-glare films are used. The number of image display devices installed is increasing.

There are many documents describing antiglare films, for example, Patent Documents 1 and 2.

JP-A-2009-109683 Japanese Unexamined Patent Publication No. 2003-202416

In the antiglare film, the haze value needs to be within an appropriate range from the viewpoint of antiglare and display characteristics.

However, due to the influence of ultraviolet rays, temperature, humidity, etc., the haze value of the antiglare film may change significantly, and as a result, the antiglare property or display characteristics may deteriorate.

Therefore, an object of the present invention is to provide an antiglare film whose haze value is hard to change, a method for designing an antiglare film, a method for manufacturing an antiglare film, an optical member, and an image display device.

In order to achieve the above object, the first antiglare film of the present invention is
An antiglare film in which an antiglare layer (B) is laminated on a light transmissive base material (A).
The antiglare layer (B) contains a resin for forming an antiglare layer (B1) and at least one kind of haze adjusting filler (B2).
The haze adjusting filler (B2) is a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate).
The peak area ratio of PMMA peak / Pst peak according to the Raman spectroscopic spectrum of the haze adjusting filler (B2) alone is 0.51 or more, and the peak area is calculated with the minimum point between the adjacent peaks as a boundary. It is the peak area,
The total haze value of the antiglare film is in the range of 5 to 45%.

In order to achieve the above object, the second antiglare film of the present invention is used.
An antiglare film in which an antiglare layer (B) is laminated on a light transmissive base material (A).
The antiglare layer (B) contains a resin for forming an antiglare layer (B1) and at least one kind of haze adjusting filler (B2).
The haze adjusting filler (B2) is a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate), and does not contain a filler having a refractive index of more than 1.535.
The total haze value of the antiglare film is in the range of 5 to 45%.

In the following, the term "antiglare film of the present invention" refers to both the first antiglare film of the present invention and the second antiglare film of the present invention unless otherwise specified. including.

The method for designing the antiglare film of the present invention is
A method for designing an antiglare film in which an antiglare layer (B) is laminated on a light transmissive base material (A).
The antiglare layer (B) contains a resin for forming an antiglare layer (B1) and at least one kind of haze adjusting filler (B2).
The haze adjusting filler (B2) is a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate).
By designing the antiglare film so as to satisfy the following conditions (1) and (2), it is characterized in that the change in the haze value of the antiglare film is suppressed.

(1) The peak area ratio of PMMA peak / Pst peak according to the Raman spectroscopic spectrum of the haze adjusting filler (B2) alone is 0.51 or more, and the peak area borders a minimum point between adjacent peaks. It is the peak area calculated as.
(2) The total haze value of the antiglare film is in the range of 5 to 45%.

The method for producing the first antiglare film of the present invention is
The step of designing the antiglare film according to the method for designing the antiglare film of the present invention is included.
The antiglare film is the antiglare film of the present invention.

The method for producing the second antiglare film of the present invention is
The step of forming the antiglare layer (B) for forming the antiglare layer (B) on the light transmissive base material (A) is included.
The antiglare layer (B) forming step is a coating step of applying a coating liquid on the light transmissive base material (A) and drying the coated coating liquid to form a coating film. Including the coating film forming step
The method for producing an antiglare film of the present invention, wherein the coating liquid contains the antiglare layer forming resin (B1) forming material and the haze adjusting filler (B2).

In the following, the term "method for producing the antiglare film of the present invention" refers to the method for producing the first antiglare film of the present invention and the second prevention of the present invention unless otherwise specified. Includes both with a method of making a dazzling film.

The optical member of the present invention is an optical member including the antiglare film of the present invention.

The image display device of the present invention is an image display device including the antiglare film of the present invention or the optical member of the present invention.

According to the present invention, it is possible to provide an antiglare film whose haze value is hard to change, a method for designing an antiglare film, a method for manufacturing an antiglare film, an optical member, and an image display device.

FIG. 1 is a cross-sectional view showing an example of the antiglare film of the present invention.

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

In the antiglare film of the present invention, for example, the refractive index of the haze adjusting filler (B2) is smaller than the refractive index of the antiglare layer forming resin (B1), and the antiglare layer forming resin is formed. The difference in refractive index between (B1) and the haze adjusting filler (B2) may be more than 0.001 and less than 0.15 in absolute value.

In the antiglare film of the present invention, for example, the haze adjusting filler (B2) may be particles.

The method for producing an antiglare film of the present invention may include, for example, a step of forming the antiglare layer (B) and a curing step of curing the coating film.

The optical member of the present invention may be, for example, a polarizing plate.

[1. Anti-glare film]

The cross-sectional view of FIG. 1 shows an example of the configuration of the antiglare film of the present invention. As shown in the figure, in the antiglare film 10, the antiglare layer (B) 12 is laminated on one surface of the light transmissive base material (A) 11. The antiglare layer (B) 12 contains particles (haze adjusting filler (B2)) 12b and a thixotropy-imparting agent 12c in the resin layer 12a. The resin layer 12a is formed of the antiglare layer forming resin (B1). The particles 12b correspond to the haze adjusting filler (B2) in the antiglare film of the present invention.

As described above, the haze adjusting filler (B2) is a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate). In FIG. 1, the haze adjusting filler (B2) is only one type of particles 12b. However, the present invention is not limited to this, and the haze adjusting filler (B2) may be of one type or a plurality of types. That is, in the present invention, as the haze adjusting filler (B2), only one type of filler composed of a copolymer of polystyrene and PMMA may be used, or a plurality of types may be used. Further, the haze adjusting filler (B2) may be, for example, particles, but may be other than particles.

Further, the thixotropy-imparting agent 12c is optional in the antiglare film of the present invention, and may or may not be contained. Further, the antiglare film of the present invention may or may not contain a filler other than the haze adjusting filler (B2). Examples of the other filler include the thixotropy-imparting agent 12c shown in FIG. Further, examples of the other filler include particles other than the haze adjusting filler (B2).

Further, the antiglare film of the present invention may or may not contain layers other than the light transmissive base material (A) and the antiglare layer (B). When the antiglare film of the present invention contains the other layer, the other layer may be one layer or two or more layers, and the position thereof is not particularly limited. For example, the light-transmitting base material (A) may be laminated on the light-transmitting base material (A) via the other layer. Further, for example, the other layer may be laminated on the surface of the antiglare layer (B) opposite to the light transmissive base material (A). The other layer is not particularly limited, and may be, for example, a low refractive index layer, an antireflection layer, a high refractive index layer, a hard coat layer, an adhesive layer, or the like.

As described above, the antiglare film of the present invention has a total haze value in the range of 5 to 45%. If the total haze value is too small, the anti-glare property will decrease. If the total haze value is too large, the display characteristics are likely to be deteriorated, such as the image becoming unclear and the contrast in a dark place being lowered. The total haze value may be, for example, 7% or more, 10% or more, 12% or more, or 15% or more, for example, 40% or less, 35% or less, 32% or less, 30% or less, 27% or less, or. It may be 25% or less. In the antiglare film of the present invention, the "total haze value" is the haze value (cloudiness) of the entire antiglare film according to JIS K 7136 (2000 version).

Further, as shown in FIG. 1, for example, irregularities are formed on the surface of the antiglare layer (B) (the surface opposite to the light transmissive base material (A)). By controlling the uneven shape, for example, the haze value (cloudiness) of the antiglare film, the display characteristics, and the like can be controlled. The uneven shape of the surface of the antiglare layer (B) (for example, surface roughness, average height of unevenness, average distance between convex portions, etc.) is not particularly limited, and is, for example, according to a general antiglare film. Alternatively, it can be set as appropriate with reference to it.

Hereinafter, each of the light transmissive base material (A), the antiglare layer (B), and the other layers will be described with further examples. In the following, the case where the antiglare layer (B) is an antiglare hard coat layer will be mainly described, but the present invention is not limited thereto.

[1-1. Light-transparent substrate (A)]
The light-transmitting base material (A) is not particularly limited, and examples thereof include a transparent plastic film base material. The transparent plastic film base material is not particularly limited, but is preferably one having excellent visible light transmittance (preferably 90% or more) and excellent transparency (preferably one having a haze value of 1% or less). For example, the transparent plastic film base material described in JP-A-2008-90263 can be mentioned. As the transparent plastic film base material, one having less birefringence optically is preferably used. The antiglare film of the present invention can also be used as a protective film for a polarizing plate, and in this case, as the transparent plastic film base material, triacetyl cellulose (TAC), polycarbonate, acrylic polymer, etc. A film formed of a polyolefin or the like having a cyclic or norbornene structure is preferable. Further, in the present invention, as will be described later, the transparent plastic film base material may be the polarizer itself. With such a configuration, the protective layer made of TAC or the like is unnecessary and the structure of the polarizing plate can be simplified, so that the number of manufacturing steps of the polarizing plate or the image display device can be reduced and the production efficiency can be improved. Further, with such a configuration, the polarizing plate can be made thinner. When the transparent plastic film base material is a polarizer, for example, the antiglare layer (B) serves as a protective layer. Further, with such a configuration, the antiglare film also functions as a cover plate when mounted on the surface of a liquid crystal cell, for example.

In the present invention, the thickness of the light transmissive base material (A) is not particularly limited, but in consideration of workability such as strength and handleability and thin layer property, for example, 10 to 500 μm and 20 to 300 μm. , Or in the range of 30-200 μm. The refractive index of the light transmissive substrate (A) is not particularly limited. The refractive index is, for example, in the range of 1.30 to 1.80 or 1.40 to 1.70.

In the present invention, the "refractive index" refers to a refractive index having a wavelength of 550 nm unless otherwise specified. Further, in the present invention, the method for measuring the refractive index is not particularly limited, but in the case of the refractive index of a fine substance such as particles, for example, the Becke method can be used for measurement. The Becke method is the refractive index of a standard refracting solution when the contour of the sample disappears or becomes blurred when the measurement sample is dispersed in a standard refracting solution on a slide glass and observed under a microscope. It is a measurement method to be performed. The method for measuring the refractive index of a measurement object whose refractive index cannot be measured by the Becke method (for example, an antiglare film, an antiglare layer, or a resin constituting the antiglare layer) is not particularly limited, but for example, It can be measured using a general refractometer (equipment for measuring the refractive index). The refractometer is also not particularly limited, and examples thereof include an Abbe refractometer. Examples of the Abbe refractometer include a multi-wavelength Abbe refractometer DR-M2 / 1550 (trade name) manufactured by Atago Co., Ltd.

In the antiglare film of the present invention, for example, the resin contained in the light transmissive base material (A) may contain an acrylic resin.

In the antiglare film of the present invention, for example, the light transmissive base material (A) may be an acrylic film.

[1-2. Anti-glare layer (B)]
In the antiglare film of the present invention, the antiglare layer (B) contains, as described above, the antiglare layer forming resin (B1) and at least one kind of haze adjusting filler (B2).

As the antiglare layer (B), for example, as will be described later, a coating liquid containing the antiglare layer forming resin (B1), the haze adjusting filler (B2) and a solvent is applied to the light-transmitting base material. It is formed by coating on at least one surface of (A) to form a coating film, and then removing the solvent from the coating film.

[1-2-1. Antiglare layer forming resin (B1)]
The antiglare layer forming resin (B1) (hereinafter, may be simply referred to as “resin (B1)” or “resin”) is not particularly limited, and for example, only one type of resin may be used. Two or more kinds of resins may be used together. The resin (B1) may contain, for example, an acrylate resin (also referred to as an acrylic resin), or may contain, for example, a urethane acrylate resin. The resin (B1) may be, for example, a copolymer of a curable urethane acrylate resin and a polyfunctional acrylate.

The resin (B1) is not limited to the acrylate resin and the like, and examples thereof include thermosetting resins and ionizing radiation curable resins that are cured by ultraviolet rays or light. As the resin (B1), a commercially available thermosetting resin, an ultraviolet curable resin, or the like can also be used.

As the thermosetting resin or the ultraviolet curable resin, for example, a curable compound having at least one of an acrylate group and a methacrylate group that is cured by heat, light (ultraviolet rays, etc.) or an electron beam can be used. Silicone resin, polyester resin, polyether resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin, oligomers such as methacrylate and prepolymers of polyfunctional compounds such as polyhydric alcohol Can be mentioned. These may be used alone or in combination of two or more.

As the resin (B1), for example, a reactive diluent having at least one group of an acrylate group and a methacrylate group can also be used. 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. As the reactive diluent, trifunctional or higher functional acrylates and trifunctional or higher functional methacrylates are preferable. This is because the hardness of the antiglare layer (B) can be made excellent. Examples of the reactive diluent include butanediol glycerin ether diacrylate, isocyanuric acid acrylate, and isocyanuric acid methacrylate. These may be used alone or in combination of two or more.

The refractive index of the resin (B1) is not particularly limited, but may be, for example, 1.48 or more, 1.49 or more, 1.50 or more, or 1.51 or more, and for example, 1.60 or less, 1.59 or less. , 1.58 or less, or 1.57 or less.

[1-2-2. Haze adjustment filler (B2)]
The haze adjusting filler (B2) is, for example, a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate) as described above. The haze adjusting filler (B2) is not particularly limited except that it is a filler composed of a copolymer of polystyrene and PMMA. For example, as described above, one type may be used alone. Two or more types may be used together. Further, as described above, the haze adjusting filler (B2) may be, for example, particles.

The polystyrene content in the haze adjusting filler (B2) is not particularly limited, but at least one of the following conditions (a) and (b) is satisfied. The following condition (a) is the condition of the first antiglare film of the present invention, and the following condition (b) is the condition of the second antiglare film of the present invention. In the Raman spectrum, the apex of PMMA peak (maximum), for example expressed in 1724 cm ^-1, a peak of polystyrene, expressed for example 1600 cm ^-1. Further, since polystyrene has a higher refractive index than PMMA, the higher (larger) the polystyrene content in the haze adjusting filler (B2), the higher the refractive index of the haze adjusting filler (B2) alone tends to be. ..

(A) The peak area ratio of PMMA peak / Pst peak according to the Raman spectroscopic spectrum of the haze adjusting filler (B2) alone is 0.51 or more. However, the peak area is a peak area calculated with the minimum point between adjacent peaks as a boundary.
(B) The refractive index of the haze adjusting filler (B2) alone is 1.535 or less.

For example, if the polystyrene content in the filler (for example, particles) is too high, the haze value of the antiglare film tends to change. The cause of this is unknown, but it is considered that polystyrene in the filler is decomposed by light irradiation (UV irradiation), humidification heat, etc., which changes the refractive index of the filler and the haze value of the antiglare film.

The antiglare film of the present invention is excellent in light resistance, heat resistance, humidification heat resistance, etc. by selecting an appropriate filler as the haze adjusting filler (B2), and the haze value is hard to change. It becomes a film.

The haze adjusting filler (B2), for example, makes the surface of the antiglare layer (B) to be formed uneven to impart antiglare properties, and also controls the haze value of the antiglare layer (B). Main function. The haze value of the antiglare layer (B) can be designed, for example, by controlling the difference in refractive index between the haze adjusting filler (B2) and the antiglare layer forming resin (B1). As described above, the haze adjusting filler (B2) is not particularly limited except that it is a filler composed of a copolymer of polystyrene and PMMA.

As described above, the refractive index of the haze adjusting filler (B2) may be, for example, 1.535 or less, for example, 1.525 or less, 1.515 or less, 1.505 or less, or 1.495 or less. Further, the refractive index of the haze adjusting filler (B2) may be, for example, 1.42 or more, 1.43 or more, 1.44 or more, or 1.45 or more.

The refractive index of the haze adjusting filler (B2) may be smaller than the refractive index of the antiglare layer forming resin (B1), or may be the same as the refractive index of the antiglare layer forming resin (B1). It may be larger than the refractive index of the antiglare layer forming resin (B1). The difference in refractive index between the antiglare layer forming resin (B1) and the haze adjusting filler (B2) is not particularly limited, but as described above, for example, the absolute value is more than 0.001 and less than 0.15. There may be. The difference in refractive index between the antiglare layer forming resin (B1) and the haze adjusting filler (B2) is preferably as large as possible from the viewpoint of increasing internal scattering in order to improve glare. Further, the difference in refractive index between the antiglare layer forming resin (B1) and the haze adjusting filler (B2) is preferably as small as possible from the viewpoint of suppressing internal scattering in order to obtain high transparency. The absolute value of the difference in refractive index between the antiglare layer forming resin (B1) and the haze adjusting filler (B2) may be, for example, 0.002 or more, 0.003 or more, 0.004 or more, or 0.005 or more. It may be, for example, 0.14 or less, 0.13 or less, 0.12 or less, or 0.11 or less.

The weight average particle size of the haze adjusting filler (B2) is not particularly limited, but may be, for example, 1.0 μm or more, 2.0 μm or more, 3.0 μm or more, or 4.0 μm or more, for example, 7.0 μm or less. , 8.0 μm or less, 9.0 μm or less, or 10.0 μm or less. In the present invention, the weight average particle size of the particles can be measured by, for example, the Coulter counting method. For example, using a particle size distribution measuring device (trade name: Coulter Multisizer, manufactured by Beckman Coulter) using the pore electric resistance method, an electrolytic solution corresponding to the volume of the particles when the particles pass through the pores. By measuring the electric resistance, the number and volume of the particles are measured, and the weight average particle diameter is calculated. When the haze adjusting filler (B2) is a particle, its shape is not particularly limited, and may be, for example, a bead-shaped substantially spherical shape or an irregular shape such as powder. , Approximately spherical particles are preferable, and substantially spherical particles having an aspect ratio of 1.5 or less are preferable, and spherical particles are most preferable.

The content of the haze adjusting filler (B2) in the antiglare layer (B) is not particularly limited, but is, for example, 1% by mass or more and 3% by mass with respect to the total mass of the antiglare layer forming resin (B1). % Or more, 5% by mass or more, or 7% by mass or more, for example, 20% by mass or less, 18% by mass or less, 16% by mass or less, or 14% by mass or less. Further, the antiglare layer (B) may or may not contain particles other than the haze adjusting filler (B2), as will be described later. For example, in the method for producing an antiglare film of the present invention, the surface shape of the antiglare layer (B) may be adjusted by adjusting the content of the haze adjusting filler (B2) and the other particles. ..

[1-2-3. Other components in the antiglare layer (B)]
The antiglare layer (B) may or may not contain other components other than the antiglare layer forming resin (B1) and the haze adjusting filler (B2). Examples of the other component include fillers other than the haze adjusting filler (B2). The other filler is not particularly limited, and examples thereof include particles other than the haze adjusting filler (B2), a thixotropic agent, and inorganic nanoparticles. For example, when the antiglare layer (B) contains the thixotropy-imparting agent, it is possible to easily control the aggregated state of particles such as the haze adjusting filler (B2).

In the antiglare film of the present invention, the thixotropy-imparting agent may be at least one selected from the group consisting of, for example, organic clay, oxidized polyolefin and modified urea. Further, the thixotropy-imparting agent may be, for example, a thickener.

The organic clay is preferably a layered clay that has been organically treated in order to improve the affinity with the resin. The organic clay may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN, Somasif ME-100, Somasif MAE, Somasif MTE, Somasif MEE, and Somasif MPE (trade names, all of which are Corp Chemical Co., Ltd.). Made by); Esben, Esben C, Esben E, Esben W, Esben P, Esben WX, Esben N-400, Esben NX, Esben NX80, Esben NO12S, Esben NEZ, Esben NO12, Esben NE, Esben NZ, Esben NZ70, Olga Knight, Organite D, Organite T (trade name, all manufactured by Hojun Co., Ltd.); Kunipia F, Kunipia G, Kunipia G4 (trade name, all manufactured by Kunimine Kogyo Co., Ltd.); Chixogel VZ, Clayton HT, Clayton 40 (Product names, all manufactured by Rockwood Additives) and the like.

The above-mentioned polyolefin oxide may be prepared in-house or a commercially available product may be used. Examples of the commercially available product include Disparon 4200-20 (trade name, manufactured by Kusumoto Kasei Co., Ltd.), Fronon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

The modified urea is a reaction product of an isocyanate monomer or an adduct thereof and an organic amine. The modified urea may be prepared in-house or a commercially available product may be used. Examples of the commercially available product include BYK410 (manufactured by Big Chemie) and the like.

The thixotropy-imparting agent may be used alone or in combination of two or more.

The ratio of the thixotropy-imparting agent in the antiglare layer (B) is preferably in the range of 0.2 to 5 parts by weight, more preferably in the range of 0.4 to 4 parts by weight, based on 100 parts by weight of the resin. is there.

In the antiglare film of the present invention, for example, even if the thixotropy-imparting agent is contained in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight (mass) of the resin of the antiglare layer (B). Good.

[2. Manufacturing method of antiglare film]
The method for producing the antiglare film of the present invention is not particularly limited and may be produced by any method, but it is preferably produced by the method for producing the antiglare film of the present invention.

The method for producing the antiglare film can be carried out as follows, for example.

First, the antiglare layer (B) is formed on the light transmissive base material (A) (antiglare layer (B) forming step). As a result, a laminate of the light-transmitting base material (A) and the antiglare layer (B) is produced. As described above, the antiglare layer (B) forming step includes a coating step of applying a coating liquid on the light transmissive base material (A) and a drying coating of the coated coating liquid. It includes a coating film forming step of forming a film. Further, for example, as described above, the antiglare layer (B) forming step may further include a curing step of curing the coating film. The curing can be performed, for example, after the drying, but is not limited thereto. The curing can be performed by, for example, heating, light irradiation, or the like. The light is not particularly limited, but may be, for example, ultraviolet rays or the like. The light source for light irradiation is not particularly limited, but may be, for example, a high-pressure mercury lamp or the like.

The coating liquid contains a resin and a solvent as described above. The coating liquid is, for example, an antiglare layer forming material (coating liquid) containing the antiglare layer forming resin (B1), the haze adjusting filler (B2), the thixotropy-imparting agent, and the solvent. May be good.

The coating liquid preferably exhibits thixotropic properties, and the Ti value defined by the following formula is preferably in the range of 1.3 to 3.5, more preferably 1.4 to 3. It is in the range of 2, and more preferably in the range of 1.5 to 3.

Ti value = β1 / β2

In the above formula, β1 is a viscosity measured under the condition of a shear rate of 20 (1 / s) using a HAAKE Leostress RS6000, and β2 is a viscosity measured using a HAAKE Leostress RS6000 with a shear rate of 200 (1 / s). It is the viscosity measured under the conditions of.

If the Ti value is 1.3 or more, problems such as appearance defects and deterioration of antiglare and white blur characteristics are unlikely to occur. Further, when the Ti value is 3.5 or less, problems such as the particles not agglomerating and becoming dispersed are unlikely to occur.

Further, the coating liquid may or may not contain a thixotropy-imparting agent, but it is preferable to contain the thixotropy-imparting agent because it tends to exhibit thixotropy. Further, as described above, when the coating liquid contains the thixotropy-imparting agent, an effect of preventing the sedimentation of the particles (thixotropy effect) can be obtained. Further, the surface shape of the antiglare film can be freely controlled in a wider range by the shear aggregation of the thixotropy-imparting agent itself.

The solvent is not particularly limited, and various solvents can be used, and one type may be used alone or two or more types may be used in combination. The optimum solvent type and solvent ratio may be appropriately selected in order to obtain the antiglare film of the present invention according to the composition of the resin, the types and contents of the particles and the thixotropy-imparting agent. The solvent is not particularly limited, and is, for example, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, t-butyl alcohol (TBA), 2-methoxyethanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopenta. Ketones such as non; esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; cellosolves such as ethyl cellosolve and butyl cellosolve; Aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene can be mentioned. Further, for example, the solvent may contain a hydrocarbon solvent and a ketone solvent. The hydrocarbon solvent may be, for example, an aromatic hydrocarbon. The aromatic hydrocarbon may be at least one selected from the group consisting of, for example, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and benzene. The ketone solvent may be, for example, at least one selected from the group consisting of cyclopentanone and acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, isophorone, and acetophenone. The solvent preferably contains, for example, the hydrocarbon solvent (eg toluene) in order to dissolve the thixotropy-imparting agent (eg, thickener). The solvent may be, for example, a solvent in which the hydrocarbon solvent and the ketone solvent are mixed at a mass ratio of 90:10 to 10:90. The mass ratio of the hydrocarbon solvent to the ketone solvent may be, for example, 80:20 to 20:80, 70:30 to 30:70, or 40:60 to 60:40. In this case, for example, the hydrocarbon solvent may be toluene and the ketone solvent may be methyl ethyl ketone. Further, the solvent may contain, for example, toluene and further contain at least one selected from the group consisting of ethyl acetate, butyl acetate, IPA, methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol, and TBA. Good.

For example, when an acrylic film is used as the light-transmitting base material (A) to form an intermediate layer (permeation layer), a good solvent for the acrylic film (acrylic resin) can be preferably used. As the solvent, for example, as described above, a solvent containing a hydrocarbon solvent and a ketone solvent may be used. The hydrocarbon solvent may be, for example, an aromatic hydrocarbon. The aromatic hydrocarbon may be at least one selected from the group consisting of, for example, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and benzene. The ketone solvent may be, for example, at least one selected from the group consisting of cyclopentanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, isophorone, and acetophenone. The solvent may be, for example, a solvent in which the hydrocarbon solvent and the ketone solvent are mixed at a mass ratio of 90:10 to 10:90. The mass ratio of the hydrocarbon solvent to the ketone solvent may be, for example, 80:20 to 20:80, 70:30 to 30:70, or 40:60 to 60:40. In this case, for example, the hydrocarbon solvent may be toluene and the ketone solvent may be methyl ethyl ketone.

When, for example, triacetyl cellulose (TAC) is used as the light-transmitting base material (A) to form an intermediate layer (permeation layer), a good solvent for TAC can be preferably used. Examples of the solvent include ethyl acetate, methyl ethyl ketone, cyclopentanone and the like.

Further, by appropriately selecting the solvent, the thixotropy to the antiglare layer forming material (coating liquid) can be satisfactorily exhibited when the thixotropy-imparting agent is contained. For example, when organic clay is used, toluene and xylene can be preferably used alone or in combination. For example, when using an oxide polyolefin, methyl ethyl ketone, ethyl acetate, and propylene glycol monomethyl ether are preferably used alone. It can be used or used in combination. For example, when modified urea is used, butyl acetate and methyl isobutyl ketone can be preferably used alone or in combination.

Various leveling agents can be added to the antiglare layer forming material. As the leveling agent, for example, a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing uneven coating (uniformizing the coated surface). In the present invention, when the surface of the antiglare layer (B) is required to have antifouling properties, or as described later, an antireflection layer (low refractive index layer) or a layer containing an interlayer filler is placed on the antiglare layer (B). The leveling agent can be appropriately selected depending on the case where it is formed in. In the present invention, for example, by incorporating the thixotropy-imparting agent, the thixotropy can be exhibited in the coating liquid, so that uneven coating is less likely to occur. In this case, for example, it has an advantage that the options of the leveling agent can be expanded.

The blending amount of the leveling agent is, for example, 5 parts by weight or less, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin.

Pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, antioxidants, etc. are added to the antiglare layer forming material as needed, as long as the performance is not impaired. May be done. One type of these additives may be used alone, or two or more types may be used in combination.

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

Examples of the method of applying the coating liquid onto the light transmissive substrate (A) to form a coating film include a fanten coating method, a die coating method, a spin coating method, a spray coating method, and a gravure coating method. , Roll coating method, bar coating method and other coating methods can be used.

Next, as described above, the coating film is dried and cured to form an antiglare layer (B). The drying may be, for example, natural drying, air drying by blowing wind, heat drying, or a method in which these are combined.

The drying temperature of the coating liquid for forming the antiglare layer (B) may be, for example, in the range of 30 to 200 ° C. The drying temperature may be, for example, 40 ° C. or higher, 50 ° C. or higher, 60 ° C. or higher, 70 ° C. or higher, 80 ° C. or higher, 90 ° C. or higher, or 100 ° C. or higher, 190 ° C. or lower, 180 ° C. or lower, 170. It may be ℃ or less, 160 ℃ or less, 150 ℃ or less, 140 ℃ or less, 135 ℃ or less, 130 ℃ or less, 120 ℃ or less, or 110 ℃ or less. The drying time is not particularly limited, but may be, for example, 30 seconds or more, 40 seconds or more, 50 seconds or more, or 60 seconds or more, 150 seconds or less, 130 seconds or less, 110 seconds or less, or 90 seconds or less. You may.

The means for curing the coating film is not particularly limited, but ultraviolet curing is preferable. The irradiation amount of the energy radiation source is preferably ^{50 to 500 mJ / cm 2} as the integrated exposure amount at the ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ / cm ² or more, curing tends to proceed sufficiently, and the hardness of the antiglare layer (B) formed tends to increase. Further, if it is 500 mJ / cm ² or less, coloring of the formed antiglare layer (B) can be prevented.

As described above, a laminate of the light transmissive base material (A) and the antiglare layer (B) can be produced. This laminate may be used as it is as the antiglare film of the present invention, or for example, the other layer may be formed on the antiglare layer (B) to obtain the antiglare film of the present invention. The method for forming the other layer is not particularly limited, and is, for example, the same as or similar to the method for forming a general low refractive index layer, antireflection layer, high refractive index layer, hard coat layer, adhesive layer, or the like. Can be done with.

[3. Optical member and image display device]
The optical member of the present invention is not particularly limited, but may be, for example, a polarizing plate. The polarizing plate is also not particularly limited, but may include, for example, the antiglare film and the polarizer of the present invention, and may further contain other components. Each component of the polarizing plate may be bonded by, for example, an adhesive or an adhesive.

The image display device of the present invention is not particularly limited, and any image display device may be used, and examples thereof include a liquid crystal display device and an organic EL display device.

The image display device of the present invention is, for example, an image display device having the antiglare film of the present invention on the surface on the viewing side, and the image display device may have a black matrix pattern.

In the antiglare film of the present invention, for example, the light transmissive base material (A) side can be attached to an optical member used in an LCD via an adhesive or an adhesive. At the time of this bonding, the surface of the light transmissive base material (A) may be subjected to various surface treatments as described above. As described above, according to the method for producing an antiglare film of the present invention, the surface shape of the antiglare film can be freely controlled in a wide range. Therefore, the optical properties that can be obtained by laminating the antiglare film with other optical members using an adhesive, an adhesive, or the like cover a wide range corresponding to the surface shape of the antiglare film. ..

Examples of the optical member include a polarizer or a polarizing plate. The polarizing plate generally has a transparent protective film on one side or both sides of the polarizing element. When the transparent protective films are provided on both sides of the polarizer, the transparent protective films on the front and back sides may be made of the same material or different materials. Polarizing plates are usually arranged 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.

The configuration of the polarizing plate on which the antiglare film is laminated is not particularly limited, but for example, the transparent protective film, the polarizer and the transparent protective film are laminated in this order on the antiglare film. Alternatively, the polarizing element and the transparent protective film may be laminated in this order on the antiglare film.

The configuration of the image display device of the present invention is not particularly limited, and may be, for example, the same configuration as a general image display device. For example, in the case of an LCD, it can be manufactured by appropriately assembling optical members such as a liquid crystal cell and a polarizing plate, and if necessary, each component such as a lighting system (backlight or the like) and incorporating a drive circuit.

The use of the image display device of the present invention is not particularly limited, and it can be used for any purpose. Applications include, for example, OA devices such as personal computer monitors, laptop computers, and copiers, mobile phones, clocks, digital cameras, mobile information terminals (PDAs), portable devices such as portable game machines, video cameras, televisions, and microwave ovens. Home electrical equipment such as, back monitor, car navigation system monitor, in-vehicle equipment such as car audio, exhibition equipment such as information monitor for commercial stores, security equipment such as monitoring monitor, nursing care monitor, medical monitor Nursing care / medical equipment, etc.

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.

In the following Examples and Comparative Examples, the number of copies of the substance is parts by mass (parts by weight) unless otherwise specified.

In the following examples and comparative examples, the haze adjusting filler (B2) used in the examples and the haze adjusting filler used in the comparative examples are measured for refractive index and Raman spectroscopy by the following methods. The spectrum was measured by the method.

(Measurement of refractive index of filler)
The refractive index at a wavelength of 550 nm was measured by the Becke method described above. As the standard refracting liquid, Cargill standard refracting liquid manufactured by Moritex Co., Ltd. was used.

(Measurement of refractive index other than filler)
The refractive index at a wavelength of 550 nm was measured using the above-mentioned multi-wavelength Abbe refractometer DR-M2 / 1550 (trade name) manufactured by Atago Co., Ltd.

(Spectral measurement by Raman spectroscopy)
The spectrum was measured by Raman spectroscopy using alpha300RSA (trade name) manufactured by WITEC. Peak peak vertex (maximum) of 1724 cm ^-1 peak PMMA, the apex of the peak (maximum) of the peak of 1600 cm ^-1 was identified as peaks of polystyrene. The peak area was calculated with the minimum point between adjacent peaks as the boundary. The peak area ratio was calculated based on the peak area.

[Example 1]
As the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%) and pentaeristol triacrylate are used. A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) as a main component was prepared. This resin is a material for forming the antiglare layer forming resin (B1), and as described later, it can be cured by light irradiation to form the antiglare layer forming resin (B1). Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.525 per 100 parts by weight of resin solid content of the resin. ) Is 3 parts by weight, silicone particles (manufactured by Momentive Performance Materials Japan (same as above), trade name "Tospearl 130", weight average grain shape: 3 μm, refractive index: 1.42) is 1.5 parts by weight, As the thixotropy-imparting agent, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay, and a photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907") are used. 0.15 parts by weight of a leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LE303", solid content 40%) was mixed in an amount of 3 parts by weight. The crosslinked polymethyl methacrylate particles "techpolymer" are particles composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate), and correspond to a haze adjusting filler (B2). The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 55% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

Further, using this antiglare layer forming material (coating liquid), an antiglare layer (B) forming step of forming the antiglare layer (B) on the light transmissive base material (A) was performed. That is, first, the antiglare layer forming material (coating liquid) corresponds to a triacetyl cellulose base material (thickness 60 μm, FUJIFILM Corporation, trade name TG60UL, light transmissive base material (A)). Painted on top. Then, an ultraviolet ray having a wavelength of 365 nm is irradiated with a high-pressure mercury lamp so that the integrated light intensity is 300 mJ / cm ^2, and the resin in the antiglare layer forming material (coating liquid) is cured, and further, at 80 ° C. The mixture was heated for 60 seconds and dried to form an antiglare layer (B) in which a haze adjusting filler (B2) was dispersed in an antiglare layer forming resin (B1) having a thickness of 8 μm. As described above, the antiglare film of this example was produced. In the antiglare film of this embodiment, the antiglare layer (B) is laminated on the light transmissive base material (A), and the antiglare layer (B) is formed of the antiglare layer forming resin (B1). It contained a haze adjusting filler (B2).

[Example 2]
Antiglare layer forming material in the same manner as in Example 1 except that the blending amounts of the "techpolymer" (filler for haze adjustment (B2)), the "Tospearl 130", and the "Lucentite SAN" were changed. (Coating liquid) was prepared. Specifically, it is as follows. As the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%) and pentaeristol triacrylate are used. A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.525 per 100 parts by weight of resin solid content of the resin. ) Is 5 parts by weight, silicone particles (manufactured by Momentive Performance Materials Japan (same as above), trade name "Tospearl 130", weight average grain shape: 3 μm, refractive index: 1.42) is 1.4 parts by weight, As the thixotropy-imparting agent, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay, and a photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907") are used. 0.15 parts by weight of a leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LE303", solid content 40%) was mixed in an amount of 3 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 52% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

Further, the same as in Example 1 except that the antiglare layer forming material (coating liquid) prepared in this example was used instead of the antiglare layer forming material (coating liquid) prepared in Example 1. The antiglare layer (B) forming step was carried out to produce the antiglare film of this example. In the antiglare film of this embodiment, the antiglare layer (B) is laminated on the light transmissive base material (A), and the antiglare layer (B) is formed of the antiglare layer forming resin (B1). It contained a haze adjusting filler (B2).

[Example 3]
The antiglare layer forming material (coating liquid) was used in the same manner as in Example 1 except that the blending amount of the "techpolymer" (filler for haze adjustment (B2)) was changed from 3 parts by weight to 4 parts by weight. Prepared. Specifically, it is as follows. As the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%) and pentaeristol triacrylate are used. A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.525 per 100 parts by weight of resin solid content of the resin. ) Is 4 parts by weight, silicone particles (manufactured by Momentive Performance Materials Japan (same as above), trade name "Tospearl 130", weight average grain shape: 3 μm, refractive index: 1.42) is 1.5 parts by weight, As the thixotropy-imparting agent, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay, and a photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907") are used. 0.15 parts by weight of a leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LE303", solid content 40%) was mixed in an amount of 3 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 52% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

[Example 4]
As the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%) and pentaeristol triacrylate are used. A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.535 per 100 parts by weight of resin solid content of the resin. ) Is 4 parts by weight, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay as the thixotropy-imparting agent, and a photopolymerization initiator (manufactured by BASF). The name "OMNIRAD907") was mixed in 3 parts by weight, and the leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LE303", solid content 40%) was mixed in 0.15 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 52% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared. The antiglare layer forming material (coating liquid) does not contain the silicone particles "Tospearl 130", and the refractive index of the "techpolymer" (haze adjusting filler (B2)) is 1.535. It was different from Examples 1 to 3 in that.

[Example 5]
As the "techpolymer" (filler for haze adjustment (B2)), a "techpolymer" having a refractive index of 1.515 was used instead of the "techpolymer" having a refractive index of 1.535. A material for forming an antiglare layer (coating liquid) was prepared in the same manner as in Example 4 except that the blending amount of the "techpolymer" was changed to 8 parts by weight. Specifically, first, as the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%), and , A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) containing pentaeristol triacrylate as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.515) per 100 parts by weight of the resin solid content of the resin. ) Is 8 parts by weight, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay as the thixotropy-imparting agent, and a photopolymerization initiator (manufactured by BASF). The name "OMNIRAD907") was mixed in 3 parts by weight, and the leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LE303", solid content 40%) was mixed in 0.15 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 45% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

[Example 6]
As the "techpolymer" (filler for haze adjustment (B2)), a "techpolymer" having a refractive index of 1.505 was used instead of the "techpolymer" having a refractive index of 1.535. A material for forming an antiglare layer (coating liquid) was prepared in the same manner as in Example 4 except that the blending amount of the "techpolymer" was changed to 8 parts by weight. Specifically, first, as the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%), and , A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) containing pentaeristol triacrylate as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.505 per 100 parts by weight of resin solid content of the resin. ) Is 8 parts by weight, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay as the thixotropy-imparting agent, and a photopolymerization initiator (manufactured by BASF). The name "OMNIRAD907") was mixed in 3 parts by weight, and the leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LE303", solid content 40%) was mixed in 0.15 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 45% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

[Comparative Example 1]
As the "techpolymer", the antiglare layer is the same as in Example 4 except that the "techpolymer" having a refractive index of 1.555 is used instead of the "techpolymer" having a refractive index of 1.535. A forming material (coating liquid) was prepared. Specifically, first, as the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%), and , A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) containing pentaeristol triacrylate as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.555 per 100 parts by weight of resin solid content of the resin. ) Is 4 parts by weight, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay as the thixotropy-imparting agent, and a photopolymerization initiator (manufactured by BASF). The name "OMNIRAD907") was mixed in 3 parts by weight, and the leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., trade name "LE303", solid content 40%) was mixed in 0.15 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 50% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

Further, the protection of Example 1 except that the antiglare layer forming material (coating liquid) prepared in this comparative example was used instead of the antiglare layer forming material (coating liquid) prepared in Example 1. A step similar to the step of forming the glare layer (B) was carried out to produce an antiglare film of this comparative example.

[Comparative Example 2]
A material for forming an antiglare layer (coating liquid) was prepared in the same manner as in Comparative Example 1 except that the blending amount of the "techpolymer" having a refractive index of 1.555 was changed to 5.5 parts by weight. Specifically, first, as the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%), and , A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) containing pentaeristol triacrylate as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.555 per 100 parts by weight of resin solid content of the resin. ) Is 5.5 parts by weight, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay as the thixotropy-imparting agent, and a photopolymerization initiator (manufactured by BASF). , Product name "OMNIRAD907") was mixed in 3 parts by weight, and a leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., product name "LE303", solid content 40%) was mixed in 0.15 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 50% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

[Comparative Example 3]
A material for forming an antiglare layer (coating liquid) was prepared in the same manner as in Comparative Example 1 except that the blending amount of the "techpolymer" having a refractive index of 1.555 was changed to 7.2 parts by weight. Specifically, first, as the resin contained in the antiglare layer forming material, 50 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "UV1700TL", solid content 80%), and , A mixture of 50 parts by weight of a polyfunctional acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 300", 100% solid content) containing pentaeristol triacrylate as a main component was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Sekisui Kasei Kogyo Co., Ltd., trade name "Techpolymer", weight average particle size: 3 μm, refractive index: 1.555 per 100 parts by weight of resin solid content of the resin. ) Is 7.2 parts by weight, 1.5 parts by weight of synthetic smectite (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN"), which is an organic clay as the thixotropy-imparting agent, and a photopolymerization initiator (manufactured by BASF). , Product name "OMNIRAD907") was mixed in 3 parts by weight, and a leveling agent (manufactured by Kyoeisha Chemical Co., Ltd., product name "LE303", solid content 40%) was mixed in 0.15 parts by weight. The organic clay was diluted with toluene so that the solid content was 6%. This mixture is diluted with a mixed solvent of toluene / ethyl acetate / cyclopentanone (CPN) (weight ratio 35/41/24) so that the solid content concentration becomes 50% by weight, and an ultrasonic disperser is used. , Anti-glare layer forming material (coating liquid) was prepared.

[Comparative Example 4]
As a resin contained in the antiglare layer forming material, 100 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by DIC Corporation, trade name "Luxidia 17-806", solid content 80%) was prepared. Crosslinked polymethyl methacrylate particles (manufactured by Soken Kagaku Co., Ltd., trade name "SX-350H", weight average particle size: 3.5 μm, refractive index: 1. 59) 13 parts by weight, silicone particles (manufactured by Momentive Performance Materials Japan Co., Ltd., synthetic smectite which is an organic clay as the thixotropy-imparting agent (manufactured by Corp Chemical Co., Ltd., trade name "Lucentite SAN") 2.5 parts by weight, photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907") by 5 parts by weight, leveling agent (manufactured by DIC Co., Ltd., trade name "Megafuck F470N", solid content 30%) 0.5 parts by weight was mixed. The organic clay was diluted with ethyl acetate so that the solid content was 4.6%, and this mixture was used so that the solid content concentration was 32% by weight. The antiglare layer forming material (coating liquid) was prepared by diluting with a toluene / ethyl acetate mixed solvent (weight ratio 93/7) using an ultrasonic disperser.

[FD (fade) test]
The antiglare films of each of the Examples and Comparative Examples were subjected to a fade (FD) test under the following test conditions using an ultraviolet fade meter U48HB (trade name of Suga Test Instruments Co., Ltd.). The test results are shown in Table 1 below. In Table 1 below, "0H" represents the state before the fade test, and "500H" represents the state after the fade test (after 500 hours have passed). Further, in Tables 1 to 3 below, "haze value" represents the total haze value of the antiglare film, "Pst" represents polystyrene, "PMMA" represents polymethylmethacrylate, and Pst / PMMA represents polystyrene. Represents a copolymer of and polymethacrylic acid.

(Fade test conditions)
In-layer temperature: 40 ° C
Intralayer humidity: 20% RH
Lamp: (wavelength) 300 nm-700 nm, (illuminance) 500 W / m ²
Test time: 500 hours

[Heat resistance test]
The antiglare films of each of the Examples and Comparative Examples were allowed to stand in an oven at 100 ° C. for 500 hours to perform a heat resistance test. The test results are shown in Table 2 below. In Table 2 below, "0H" represents the state before the heat resistance test, and "500H" represents the state after the heat resistance test (after 500 hours have passed).

[Humidification heat test]
The antiglare films of each of the Examples and Comparative Examples were allowed to stand in an oven at 60 ° C. and 95% RH for 500 hours for a humidification heat test. The test results are shown in Table 2 below. In Table 3 below, "0H" represents the state before the humidification heat test, and "500H" represents the state after the humidification heat test (after 500 hours have passed).

As shown in Tables 1 to 3, the antiglare film of the example containing no particles (filler) having a polystyrene content of more than 30% by volume changes the total haze value even after heating or humidification for 500 hours. The absolute value of the amount was as small as 1.4% at the maximum. On the other hand, the antiglare film of the comparative example containing particles (filler) having a polystyrene content of more than 30% by volume has an absolute value of change in the total haze value of 1 after heating or humidifying for 500 hours. It changed significantly to 5.5% or more.

As described above, according to the present invention, it is possible to provide an antiglare film whose haze value is hard to change, a method for producing the antiglare film, an optical member, and an image display device. The antiglare film of the present invention is suitable for use under high temperature or high humidity conditions because the haze value does not easily change even under heating or humidifying conditions, for example. However, the present invention is not limited to this application and can be used in a wide range of applications.

This application claims priority based on Japanese application Japanese Patent Application No. 2019-20427 filed on November 11, 2019, and incorporates all of its disclosures herein.

10 Anti-glare film 11 Light-transmitting base material (A)
12 Anti-glare layer (B)
12a Antiglare layer forming resin (B1)
12b Haze adjustment filler (B2)
12c thixotropy imparting agent

Claims

An antiglare film in which an antiglare layer (B) is laminated on a light transmissive base material (A).
The antiglare layer (B) contains a resin for forming an antiglare layer (B1) and at least one kind of haze adjusting filler (B2).
The haze adjusting filler (B2) is a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate).
The peak area ratio of PMMA peak / Pst peak according to the Raman spectroscopic spectrum of the haze adjusting filler (B2) alone is 0.51 or more, and the peak area is calculated with the minimum point between the adjacent peaks as a boundary. It is the peak area,
An antiglare film characterized in that the total haze value of the antiglare film is in the range of 5 to 45%.
An antiglare film in which an antiglare layer (B) is laminated on a light transmissive base material (A).
The antiglare layer (B) contains a resin for forming an antiglare layer (B1) and at least one kind of haze adjusting filler (B2).
The haze adjusting filler (B2) is a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate), and does not contain a filler having a refractive index of more than 1.535.
An antiglare film characterized in that the total haze value of the antiglare film is in the range of 5 to 45%.
The antiglare according to claim 1 or 2, wherein the difference in refractive index between the antiglare layer forming resin (B1) and the haze adjusting filler (B2) exceeds 0.001 and is less than 0.15 in absolute value. Sex film.
The antiglare film according to any one of claims 1 to 3, wherein the haze adjusting filler (B2) is a particle.
A method for designing an antiglare film in which an antiglare layer (B) is laminated on a light transmissive base material (A).
The antiglare layer (B) contains a resin for forming an antiglare layer (B1) and at least one kind of haze adjusting filler (B2).
The haze adjusting filler (B2) is a filler composed of a copolymer of Pst (polystyrene) and PMMA (polymethyl methacrylate).
A design method characterized by suppressing a change in the haze value of the antiglare film by designing the antiglare film so as to satisfy the following conditions (1) and (2).

(1) The peak area ratio of PMMA peak / Pst peak according to the Raman spectroscopic spectrum of the haze adjusting filler (B2) alone is 0.51 or more, and the peak area borders a minimum point between adjacent peaks. It is the peak area calculated as.
(2) The total haze value of the antiglare film is in the range of 5 to 45%.
The step of designing the antiglare film by the design method according to claim 5 is included.
The method for producing an antiglare film, wherein the antiglare film is the antiglare film according to any one of claims 1 to 4.
The step of forming the antiglare layer (B) for forming the antiglare layer (B) on the light transmissive base material (A) is included.
The antiglare layer (B) forming step is a coating step of applying a coating liquid on the light transmissive base material (A) and drying the coated coating liquid to form a coating film. Including the coating film forming step
The prevention according to any one of claims 1 to 4, wherein the coating liquid contains the antiglare layer forming resin (B1) forming material and the haze adjusting filler (B2). A method for producing a dazzling film.
The manufacturing method according to claim 7, wherein the antiglare layer (B) forming step further includes a curing step of curing the coating film.
The manufacturing method according to claim 7 or 8, further comprising the step of designing the antiglare film by the design method according to claim 5.
An optical member including the antiglare film according to any one of claims 1 to 4.
The optical member according to claim 10, which is a polarizing plate.
An image display device including the antiglare film according to any one of claims 1 to 4 or the optical member according to claim 10 or 11.