JP2015014735A - Antiglare film, polarizing plate, liquid crystal panel, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiglare film capable of suppressing glare and having low total haze and internal haze.SOLUTION: An antiglare film 10 includes a light-transmitting substrate and an antiglare layer 12 disposed on the light-transmitting substrate and having a rugged surface 12A; and the antiglare film 10 has a surface 10A that is a rugged surface. The antiglare film 10 has a total haze value of 0% or more and 5% or less and an internal haze value of 0% or more and 5% or less. A transmissive image clarity C(0.125) of the antiglare film measured by using an optical comb having a width of 0.125 mm and a transmissive image clarity C(0.25) of the antiglare film measured by using an optical comb having a width of 0.25 mm satisfy expressions (1):C(0.25)-C(0.125)≥2% and (2):C(0.125)≥65%.

Description

  The present invention relates to an antiglare film, a polarizing plate, a liquid crystal panel, and an image display device.

  An image display surface in an image display device such as a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED) or the like is usually an observer and In order to suppress reflection of an observer's background or the like, an antiglare film having irregularities on the surface and an antireflection film having an antireflection layer on the outermost surface are provided.

  The antiglare film suppresses reflection of the observer and the background of the observer by scattering external light on the uneven surface of the antiglare layer. The antiglare film mainly includes a light-transmitting base material and an antiglare layer having an uneven surface provided on the light-transmitting base material.

  The antiglare layer usually contains a binder resin and organic fine particles which are present in the binder resin and form an uneven surface.

  However, when such an antiglare film is disposed on the surface of the image display device, the image light is scattered by the uneven surface of the antiglare layer, and so-called glare may occur. For such problems, it has been proposed to suppress glare by increasing the internal haze of the antiglare film (see, for example, Patent Document 1).

  On the other hand, in recent years, an ultra-high definition image display device called 4K2K (horizontal pixel number 3840 × vertical pixel number 2160) having a horizontal pixel number of 3000 or more has been developed.

  In such an ultra-high-definition image display device, an anti-glare film is provided on the image display surface as in the case of the above-described image display device. Optical transparency is required. Here, increasing the total haze and internal haze of the antiglare film causes a decrease in luminance and light transmittance, so in the ultra-high-definition image display device, as a means for suppressing glare as described above, A means of increasing the internal haze of the antiglare film cannot be adopted. Also, if the internal haze of the antiglare film is increased, the image light may diffuse in the antiglare film, and some image light may become stray light.As a result, the darkroom contrast is lowered and the image is blurred. There is also a risk. Therefore, at present, an antiglare film that can suppress glare and has low total haze and low internal haze is desired as an antiglare film incorporated in an ultrahigh-definition image display device.

JP 2010-102186 A

  The present invention has been made to solve the above problems. That is, it aims at providing the glare-proof film, polarizing plate, liquid crystal panel, and image display apparatus which can suppress glare and have a low total haze and internal haze.

According to one aspect of the present invention, there is provided an antiglare film comprising a light transmissive substrate and an antiglare layer provided on the light transmissive substrate and having an uneven surface, wherein the antiglare film is provided. The surface of the antiglare film has an uneven surface, the total haze value of the antiglare film is from 0% to 5%, the internal haze value of the antiglare film is from 0% to 5%, and the width is 0.125 mm The transmitted image definition of the anti-glare film measured using the optical comb is C (0.125), and the transmitted image definition of the anti-glare film measured using an optical comb having a width of 0.25 mm is used. An antiglare film characterized by satisfying the following formulas (1) and (2) when C (0.25) is satisfied.
C (0.25) -C (0.125) ≧ 2% (1)
C (0.125) ≧ 65% (2)

  According to another aspect of the present invention, the polarizing element formed on the surface of the antiglare film opposite to the surface on which the antiglare layer of the light transmissive substrate of the antiglare film is formed. A polarizing plate is provided.

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

  According to another aspect of the present invention, there is provided an image display device comprising the antiglare film or the polarizing plate and having a horizontal pixel number of 3000 or more.

  According to the antiglare film of one embodiment of the present invention and the polarizing plate, the liquid crystal panel, and the image display device of another embodiment, the total haze value of the antiglare film is 0% or more and 5% or less. The internal haze value is 0% or more and 5% or less, and the transmitted image clarity of the antiglare film measured using an optical comb having a width of 0.125 mm is C (0.125), When the transmitted image definition of the anti-glare film measured using an optical comb is C (0.25), the above formulas (1) and (2) are satisfied, so that glare can be suppressed, and An antiglare film, a polarizing plate, a liquid crystal panel, and an image display device having low total haze and internal haze can be provided.

It is a schematic block diagram of the anti-glare film which concerns on 1st Embodiment. It is the figure which expanded a part of FIG. It is the schematic diagram which showed a mode that the transmission image definition of the anti-glare film which concerns on 1st Embodiment was measured with the transmission image definition measuring apparatus. It is a schematic block diagram of the polarizing plate which concerns on 1st Embodiment. It is a schematic block diagram of the liquid crystal panel which concerns on 1st Embodiment. It is a schematic block diagram of the liquid crystal display which is an example of the image display apparatus which concerns on 1st Embodiment. It is a schematic block diagram of the anti-glare film which concerns on 2nd Embodiment.

(First embodiment)
Hereinafter, an antiglare film according to a first embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of an antiglare film according to the present embodiment, FIG. 2 is an enlarged view of a part of FIG. 1, and FIG. 3 shows the transmitted image definition of the antiglare film according to the present embodiment. It is the schematic diagram which showed a mode that it measured with the transmitted-image definition measuring apparatus. In the present specification, terms such as “film”, “sheet”, and “plate” are not distinguished from each other only based on the difference in names. Therefore, for example, “film” is a concept including a member that can also be called a sheet or a plate. As a specific example, “antiglare film” includes members called “antiglare sheet”, “antiglare plate” and the like.

≪Anti-glare film≫
As shown in FIG. 1, the antiglare film 10 includes a light transmissive substrate 11 and an antiglare layer 12 provided on the light transmissive substrate 11 and having an uneven surface 12A. The antiglare film 10 includes a light transmissive substrate 11 and a photopolymerizable monomer having a weight average molecular weight of 1000 or less near the interface of the antiglare layer 12 in the light transmissive substrate 11 as shown in FIG. It is preferable that a mixed region 11A in which a resin included as a monomer unit is mixed is formed. In this specification, the “weight average molecular weight” is a value obtained by dissolving in a solvent such as tetrahydrofuran (THF) and converting to polystyrene by a conventionally known gel permeation chromatography (GPC) method.

  The surface 10A of the antiglare film 10 is an uneven surface. In this embodiment, since the functional layer such as the low refractive index layer is not provided on the antiglare layer 12, the uneven surface 12A of the antiglare layer 12 is the surface 10A of the antiglare film 10. “Functional layer” is a layer intended to exhibit some function in an antiglare film, and specifically, for example, exhibits functions such as antireflection, antistatic, or antifouling properties. The layer for doing is mentioned. The functional layer is not limited to a single layer but may be a laminate of two or more layers.

  In the antiglare film 10, the total haze value is 0% or more and 5% or less, and the internal haze value is 0% or more and 5% or less. The total haze value and the internal haze value are values when measured as the whole antiglare film. For example, in the present embodiment, since no functional layer such as a low refractive index layer is provided on the antiglare layer 12, the total haze value and the internal haze value of the antiglare film 10 are the light-transmitting substrate 11 and It is a value measured using the antiglare film 10 composed of the antiglare layer 12. Further, for example, when a functional layer such as a low refractive index layer is provided on the antiglare layer as in the second embodiment, the total haze value and the internal haze value of the antiglare film are light transmissive. It is the value measured using the anti-glare film which consists of a conductive base material, an anti-glare layer, and a functional layer.

  The total haze value and the internal haze value can be measured by a method based on JIS K7136 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory). Specifically, the total haze value of the antiglare film is measured using a haze meter in accordance with JIS K7136. Thereafter, a triacetyl cellulose base material (manufactured by Fuji Film, TD60UL) is attached to the surface of the antiglare film via a transparent optical adhesive layer. Thereby, the uneven shape on the surface of the antiglare film is crushed, and the surface of the antiglare film becomes flat. And in this state, an internal haze value is calculated | required by measuring a haze value according to JISK7136 using a haze meter (HM-150, Murakami Color Research Laboratory make). This internal haze does not take into account the uneven shape of the surface of the antiglare film.

  The total haze value of the antiglare film 10 is preferably 1% or less, and more preferably 0.3% or more and 0.5% or less. The internal haze value is preferably substantially 0%. Here, “the internal haze value is substantially 0%” is not limited to the case where the internal haze value is completely 0%, even if the internal haze value exceeds 0%. It is within the range of errors, and includes a range in which the internal haze value can be regarded as almost 0% (for example, an internal haze value of 0.3% or less).

  When the total haze value of the antiglare film 10 is 0% or more and 5% or less and the internal haze value is 0% or more and 5% or less, the surface haze value of the antiglare film 10 is 0% or more and 5% or less. It has become. The surface haze value of the antiglare film 10 is preferably 0% or more and 1% or less, and more preferably 0% or more and 0.3% or less. The surface haze value is caused only by the uneven surface shape of the anti-glare film, and the surface haze value obtained only by the uneven surface shape of the anti-glare film is obtained by subtracting the internal haze value from the overall haze value. It is done.

In the anti-glare film 10, the transmitted image clarity of the anti-glare film 10 measured using an optical comb having a width of 0.125 mm is C (0.125), and measured using an optical comb having a width of 0.25 mm. When the transmitted image clarity of the antiglare film 10 is C (0.25), the following expressions (1) and (2) are satisfied.
C (0.25) -C (0.125) ≧ 2% (1)
C (0.125) ≧ 65% (2)

  The “transparent image clarity of the antiglare film” means the transmitted image clarity measured for the entire antiglare film. In the present embodiment, since a functional layer such as a low refractive index layer is not provided on the antiglare layer 12, the transmitted image clarity of the antiglare film 10 is determined from the light transmissive substrate 11 and the antiglare layer 12. It is the transmitted image clarity measured using the anti-glare film 10 which becomes. Further, for example, when a functional layer such as a low refractive index layer is provided on the antiglare layer as in the second embodiment, the transmitted image definition of the antiglare film is a light transmissive substrate. , The transmitted image clarity measured using an antiglare film comprising an antiglare layer and a functional layer.

  In the present invention, the antiglare film needs to satisfy the above formulas (1) and (2) for the following reason. First, in an antiglare film, an uneven shape is formed on the surface of the antiglare layer in order to obtain an antiglare property, and the unevenness in the uneven shape may act like a lens (lens effect). And when such a lens effect arises, the black matrix which partitions pixels, such as a liquid crystal display, and the transmitted light from a pixel will be emphasized at random, and it will be thought that this produces glare. It is considered that the antiglare film having a low transmitted image definition has more irregularities acting as a lens and tends to deteriorate glare than the antiglare film having a high transmitted image definition. In this regard, the present inventors have conducted extensive research. Specifically, when the value of C (0.125) is less than 65%, the unevenness acting as a lens becomes excessive, resulting in glare. Will get worse. Further, when the present inventors conducted further earnest studies, the reason is not clear, but an anti-glare film having a small difference between the value of C (0.25) and the value of C (0.125) It has been found that the lens effect is stronger and the glare tends to be worse than that of a large antiglare film. Specifically, if the difference between the value of C (0.25) and the value of C (0.125) is less than 2%, the lens effect becomes too strong and the glare deteriorates. For these reasons, it is said that the antiglare film needs to satisfy the above formulas (1) and (2). In general, from the viewpoint of suppressing glare, it is better for those skilled in the art to reduce the difference between the value of C (0.25) and the value of C (0.125), and if this difference is large, glare Is expected to worsen. This is supported by, for example, Japanese Patent Application Laid-Open No. 2010-269504. In this gazette, from the viewpoint of suppressing glare, the ratio between the transmitted image definition using a 0.125 mm optical comb and the transmitted image definition using a 2.0 mm optical comb is 0.70 or more, And it is described that this ratio is preferably 0.80 or more and 0.93 or less. That is, in this publication, although an optical comb of 0.25 mm is not used, it is described that the above ratio is preferably 0.80 or more than 0.70 or more. Therefore, an optical comb of 0.125 mm is used. It shows a directionality that a smaller difference between the transmitted image definition used and the transmitted image definition using an optical comb of 2.0 mm is preferable. On the other hand, contrary to this prediction, in the present invention, in order to suppress glare, the difference between the value of C (0.25) and the value of C (0.125) is set to 2% or more. Therefore, it can be said that the anti-glare film satisfying the above (1) and (2) exceeds the range that can be predicted in view of the technical level of the conventional anti-glare film.

  The difference between the value of C (0.25) and the value of C (0.125) is preferably 3% or more, and more preferably 4% or more. The value of C (0.125) is preferably 75% or more. The value of C (0.125) is preferably 90% or less, more preferably 85% or less, and even more preferably 80% or less in order to ensure antiglare properties.

  The transmission image definition can be measured by a transmission image definition measuring device based on the image definition transmission method of JIS K7374. As such a measuring apparatus, Suga Test Instruments Co., Ltd. image clarity measuring device ICM-1T etc. are mentioned.

As shown in FIG. 3, the transmitted image definition measuring apparatus 100 includes a light source 101, a slit 102, a lens 103, a lens 104, an optical comb 105, and a light receiver 106. The transmitted sharpness measuring apparatus 100 converts light emitted from the light source 101 and passing through the slit 102 into parallel light by the lens 103, and irradiates the parallel light to the light-transmitting substrate side of the anti-glare film 10 to thereby prevent glare. The light transmitted from the uneven surface 12A of the antiglare layer 12 of the film 10 is condensed by the lens 104, and the light that has passed through the optical comb 105 is received by the light receiver 106. The light received by the light receiver 106 Based on this amount, the transmitted image definition C is calculated by the following equation (3).
C (n) = {(M−m) / (M + m)} × 100 (%) (3)
In formula (3), C (n) is the transmitted image definition (%) when the width of the optical comb is n (mm), M is the maximum amount of light when the width of the optical comb is n (mm), and m is This is the minimum light amount when the width of the optical comb is n (mm).

  The optical comb 105 is movable along the longitudinal direction of the optical comb 105 and has a light shielding portion and a transmission portion. The ratio of the width of the light shielding portion and the transmission portion of the optical comb 105 is 1: 1. Here, in JIS K7374, five types of optical combs having a width of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm are defined as optical combs.

<Light transmissive substrate>
The light-transmitting substrate 11 is not particularly limited as long as it has light-transmitting properties. For example, a cellulose acylate substrate, a cycloolefin polymer substrate, a polycarbonate substrate, an acrylate polymer substrate, a polyester substrate, or A glass substrate is mentioned.

  As a cellulose acylate base material, a cellulose triacetate base material and a cellulose diacetate base material are mentioned, for example. As a cycloolefin polymer base material, the base material which consists of polymers, such as a norbornene-type monomer and a monocyclic cycloolefin monomer, is mentioned, for example.

  Examples of the polycarbonate substrate include aromatic polycarbonate substrates based on bisphenols (bisphenol A and the like), aliphatic polycarbonate substrates such as diethylene glycol bisallyl carbonate, and the like.

  Examples of the acrylate polymer base material include a poly (meth) methyl acrylate base material, a poly (meth) ethyl acrylate base material, and a (meth) methyl acrylate- (meth) butyl acrylate copolymer base material. Can be mentioned.

  Examples of the polyester base material include base materials containing at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as constituent components.

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

  Among these, a cellulose acylate base material is preferable because of excellent retardation and easy adhesion with a polarizer, and among the cellulose acylate base materials, a triacetyl cellulose base material (TAC base material) is preferable. A triacetyl cellulose base material is a light-transmitting base material capable of setting an average light transmittance to 50% or more in a visible light region of 380 to 780 nm. The average light transmittance of the triacetyl cellulose base material is preferably 70% or more, and more preferably 85% or more.

  In addition, as a triacetyl cellulose base material, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like may be used in combination with components other than acetic acid as a fatty acid forming an ester with cellulose. Good. Further, these triacetylcelluloses may be added with other additives such as other cellulose lower fatty acid esters such as diacetylcellulose, or plasticizers, ultraviolet absorbers, and lubricants as necessary.

  A cycloolefin polymer substrate is preferred from the standpoint of retardation and heat resistance, and a polyester substrate is preferred from the standpoint of mechanical properties and heat resistance.

  The thickness of the light-transmitting substrate 11 is not particularly limited, but can be 5 μm or more and 1000 μm or less. The lower limit of the thickness of the light-transmitting substrate 11 is preferably 15 μm or more from the viewpoint of handling properties, etc., and 25 μm The above is more preferable. The upper limit of the thickness of the light transmissive substrate 11 is preferably 80 μm or less from the viewpoint of thinning.

<Mixed area>
As described above, the mixed region 11A is a region in which the light-transmitting substrate 1 and a resin containing a photopolymerizable monomer having a weight average molecular weight of 1000 or less as a monomer unit are mixed. This photopolymerizable monomer is the same as the photopolymerizable monomer having a weight average molecular weight of 1000 or less contained as a monomer unit in a binder resin 14 described later of the antiglare layer 12.

  The thickness of the mixed region 11A is preferably 0.01 μm or more and 1 μm or less. In the present embodiment, since the generation of interference fringes can be sufficiently suppressed by the uneven surface 12A described later of the antiglare layer 12, even when the thickness of the mixed region 11A is so thin, the generation of interference fringes is suppressed. it can. In addition, since the thickness of the mixing area | region formed with the conventional antireflection film is 3 micrometers or more, it can be said that the thickness of the mixing area | region 11A is sufficiently thin compared with the mixing area | region formed with the conventional antireflection film. In addition, by forming the mixed region 11A, the adhesion between the light transmissive substrate 11 and the antiglare layer 12 can be further improved. As described above, since the generation of interference fringes can be sufficiently suppressed by the uneven surface 12A of the antiglare layer 12, it is not necessary to form such a mixed region 11A in the antiglare film 10. Even when the mixed region is not formed in this way, the generation of interference fringes can be suppressed. For example, it is difficult to form a mixed region such as an acrylic substrate, a cycloolefin polymer substrate, or a polyester substrate. Even if it exists, it can be used as a light-transmitting substrate.

<Anti-glare layer>
The antiglare layer 12 is a layer that exhibits antiglare properties. The antiglare layer 12 may exhibit antiglare properties and other functions. Specifically, the anti-glare layer 12 may be a layer that exhibits anti-glare properties and, for example, functions such as hard coat properties, antireflection properties, antistatic properties, and antifouling properties.

  When the antiglare layer 12 is a layer that exhibits hard coat properties in addition to the antiglare property, the antiglare layer 12 has a pencil hardness test (4.9 N) defined by JIS K5600-5-4 (1999). It has a hardness equal to or higher than “H” in terms of load.

  As described above, the surface of the antiglare layer 12 is an uneven surface 12A. The “surface of the antiglare layer” means a surface opposite to the surface on the light transmissive substrate side of the antiglare layer (the back surface of the antiglare layer).

  If the internal haze value is in the range of 0% or more and 5% or less, the internal haze value does not affect the transmitted image definition, so the transmitted image definition is affected by the uneven shape on the surface of the antiglare film. On the other hand, in this embodiment, the surface 10 </ b> A of the antiglare film 10 is an uneven surface 12 </ b> A of the antiglare layer 12. Therefore, in this embodiment, whether or not the transmitted image definition of the antiglare film 10 satisfies the above formulas (1) and (2) is determined by the concave and convex shape of the concave and convex surface 12A of the antiglare layer 12. Hereinafter, the uneven surface of the antiglare layer in which the antiglare film satisfies the above formulas (1) and (2) is referred to as a “specific uneven surface”.

  The unique irregular surface can be formed by appropriately adjusting the number of irregularities, the size of the irregularities, the inclination angle of the irregularities, etc. As a method for adjusting these, for example, (A) a binder after curing A method of forming an uneven surface using a composition for an antiglare layer containing a photopolymerizable compound and fine particles as a resin, (B) a method of forming an uneven surface by a transfer method using a mold, and (C) sand blasting. Examples thereof include a method of forming an uneven surface by roughening the surface of the antiglare layer, or a method (D) of forming an uneven surface by imparting unevenness to the surface of the antiglare layer with an embossing roll. Among these, the method (A) is preferable because the production is easy.

  In the above method (A), when the photopolymerizable compound is polymerized (crosslinked) to become a binder resin, the photopolymerizable compound undergoes curing shrinkage in the portion where fine particles are not present, and thus shrinks as a whole. To do. On the other hand, in the portion where the fine particles are present, since the fine particles do not cause curing shrinkage, only the photopolymerizable compounds existing above and below the fine particles cause curing shrinkage. Thereby, since the film thickness of the anti-glare layer is thicker in the part where the fine particles are present than in the part where the fine particles are not present, the surface of the anti-glare layer becomes an uneven surface. Therefore, the antiglare layer having a specific uneven surface can be formed by appropriately selecting the kind and particle size of the fine particles and the kind of the photopolymerizable compound and adjusting the coating film forming conditions.

  As shown in FIG. 2, the antiglare layer 12 includes a binder resin 14 and fine particles 15 and is formed by the method (A).

(Binder resin)
The binder resin contains a polymerized product (crosslinked product) of a photopolymerizable compound. The binder resin may contain a solvent-drying resin or a thermosetting resin in addition to a polymerized product (crosslinked product) of a photopolymerizable compound. The photopolymerizable compound has at least one photopolymerizable functional group. In the present specification, the “photopolymerizable functional group” is a functional group capable of undergoing a polymerization reaction by light irradiation. Examples of the photopolymerizable functional group include ethylenic double bonds such as a (meth) acryloyl group, a vinyl group, and an allyl group. The “(meth) acryloyl group” means to include both “acryloyl group” and “methacryloyl group”. The light irradiated when polymerizing the photopolymerizable compound includes visible light and ionizing radiation such as ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays.

  Examples of the photopolymerizable compound include a photopolymerizable monomer, a photopolymerizable oligomer, and a photopolymerizable polymer, and these can be appropriately adjusted and used. As the photopolymerizable compound, a combination of a photopolymerizable monomer and a photopolymerizable oligomer or photopolymerizable polymer is preferable. In the case where the mixed region 11A is formed, at least a photopolymerizable monomer is included as a photopolymerizable compound.

Photopolymerizable monomer The photopolymerizable monomer has a weight average molecular weight of 1000 or less. When the weight average molecular weight of the photopolymerizable monomer is 1000 or less, it is possible to allow the photopolymerizable monomer to penetrate into the light transmissive substrate 11 together with the solvent that penetrates into the light transmissive substrate 11. Thereby, the light-transmitting substrate 11 and the photopolymerization for relaxing the refractive index of the light-transmitting substrate 11 and the anti-glare layer 12 in the vicinity of the interface of the anti-glare layer 12 in the light-transmitting substrate 11. A mixed region 11A in which a resin containing a polymerizable monomer as a monomer unit is mixed can be formed. In addition, you may use not only one type but multiple types of such photopolymerizable monomers.

  The photopolymerizable monomer is preferably a polyfunctional monomer having two or more photopolymerizable functional groups (that is, bifunctional).

  Examples of the bifunctional or higher monomer include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditri Methylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Lapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin tetra ( (Meth) acrylate, adamantyl di (meth) acrylate, isoboronyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and these are PO, EO And the like modified.

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

Photopolymerizable oligomer The photopolymerizable oligomer has a weight average molecular weight of more than 1,000 and 10,000 or less.
As the photopolymerizable oligomer, a polyfunctional oligomer having 3 (trifunctional) or more photopolymerizable functional groups is preferable. The photopolymerizable oligomer is preferably a bifunctional or higher polyfunctional oligomer. Polyfunctional oligomers include polyester (meth) acrylate, urethane (meth) acrylate, polyester-urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, and isocyanurate (meth). Examples include acrylate and epoxy (meth) acrylate.

Photopolymerizable polymer The photopolymerizable polymer has a weight average molecular weight exceeding 10,000, and the weight average molecular weight is preferably from 10,000 to 80,000, more preferably from 10,000 to 40,000. When the weight average molecular weight exceeds 80000, the viscosity is high, so that the coating suitability is lowered, and the appearance of the obtained antiglare film may be deteriorated. Examples of the polyfunctional polymer include urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester-urethane (meth) acrylate, and epoxy (meth) acrylate.

  The solvent-drying resin is a resin that forms a film only by drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin. When the solvent-drying type resin is added, film defects on the coating surface of the coating liquid can be effectively prevented when forming the antiglare layer 12. It does not specifically limit as solvent dry type resin, Generally, a thermoplastic resin can be used.

  Examples of thermoplastic resins include styrene resins, (meth) acrylic resins, vinyl acetate resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, polyester resins, polyamide resins. , Cellulose derivatives, silicone resins and rubbers or elastomers.

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

  The thermosetting resin is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation Examples thereof include resins, silicon resins, polysiloxane resins, and the like.

(Fine particles)
The fine particles may be either inorganic fine particles or organic fine particles. Among these, for example, silica (SiO ₂ ) fine particles, alumina fine particles, titania fine particles, tin oxide fine particles, antimony-doped tin oxide (abbreviation: ATO) fine particles. Inorganic oxide fine particles such as zinc oxide fine particles are preferred. The inorganic oxide fine particles can form an aggregate in the antiglare layer, and a specific uneven surface can be formed by the degree of aggregation of the aggregate.

  Examples of the organic fine particles include plastic beads. Specific examples of the plastic beads include polystyrene beads, melamine resin beads, acrylic beads, acrylic-styrene beads, silicone beads, benzoguanamine beads, benzoguanamine / formaldehyde condensation beads, polycarbonate beads, polyethylene beads, and the like.

  It is preferable that the organic fine particles have moderately adjusted resistance to curing shrinkage of the fine particles in the curing shrinkage described above. In order to adjust the resistance to shrinkage, create multiple anti-glare films that contain organic fine particles with different hardness, and change the degree of three-dimensional crosslinking in advance. By evaluating, it is preferable to select a degree of cross-linking suitable for providing a specific uneven surface.

  When inorganic oxide particles are used as the fine particles, the inorganic oxide particles are preferably subjected to surface treatment. By subjecting the inorganic oxide fine particles to surface treatment, the distribution of the fine particles in the functional layer 12 can be suitably controlled, and the chemical resistance and saponification resistance of the fine particles themselves can be improved.

  As the surface treatment, a hydrophobizing treatment for making the surface of the fine particles hydrophobic is preferable. Such a hydrophobization treatment can be obtained by chemically reacting the surface of the fine particles with a surface treatment agent such as silanes or silazanes. Specific examples of the surface treatment agent include dimethyldichlorosilane, silicone oil, hexamethyldisilazane, octylsilane, hexadecylsilane, aminosilane, methacrylsilane, octamethylcyclotetrasiloxane, and polydimethylsiloxane. When the fine particles are inorganic oxide fine particles, hydroxyl groups are present on the surface of the inorganic oxide fine particles. However, by performing the hydrophobic treatment as described above, the hydroxyl groups present on the surface of the inorganic oxide fine particles are reduced. In addition, the specific surface area of the inorganic oxide fine particles measured by the BET method can be reduced, and the inorganic oxide fine particles can be prevented from excessively agglomerating, so that a functional layer having a specific uneven surface can be formed.

  When inorganic oxide particles are used as the fine particles, the inorganic oxide fine particles are preferably amorphous. This is because when the inorganic oxide particles are crystalline, the Lewis acid salt of the inorganic oxide fine particles becomes strong due to lattice defects contained in the crystal structure, and excessive aggregation of the inorganic oxide fine particles can be controlled. It is because there is a risk of disappearing.

  The content of fine particles with respect to the antiglare layer is not particularly limited, but is preferably 0.1% by mass or more and 5.0% by mass or less. Since the content of fine particles is 0.1% by mass or more, a peculiar uneven surface can be formed more reliably, and the content of fine particles is 5.0% by mass or less, so Aggregation does not occur excessively, and it is possible to suppress internal diffusion and / or generation of large irregularities on the surface of the functional layer, thereby suppressing cloudiness. The lower limit of the content of fine particles is more preferably 0.5% by mass or more, and the upper limit of the content of fine particles is more preferably 3.0% by mass or less.

  The fine particles are preferably spherical in shape in a single particle state. Since the single particles of the fine particles are spherical, an image having excellent contrast can be obtained when the optical film is disposed on the image display surface of the image display device. Here, “spherical” means, for example, a true spherical shape, an elliptical spherical shape, etc., but a so-called indeterminate shape is not included.

  When organic fine particles are used as the fine particles, the difference in refractive index with the binder resin can be reduced by changing the copolymerization ratio of resins having different refractive indexes, for example, less than 0.01 can suppress the diffusion of light by the fine particles. This is preferable. The average primary particle size of the organic fine particles is preferably less than 8.0 μm, and more preferably 5.0 μm or less.

  The antiglare layer 12 shown in FIG. 2 is formed using the fine particles 15 that form loose aggregates among the methods (A). The “loose aggregate” is an aggregate having a structure including a bent portion 15A formed by continuous primary particles and an inner region 15B sandwiched between the bent portions 15A. Means. Here, in this specification, the “bent portion” is a concept including a curved portion. Examples of the shape having the bent portion 15 </ b> A include a V shape, a U shape, an arc shape, a C shape, a string shape, and a hook shape. Both ends of the bent portion 15A may be closed. For example, the fine particles 15 may have an annular structure having the bent portion 15A.

  The bent portion 15A may be formed by agglomerates of a single fine particle that is formed by a series of primary particles and is bent, but a trunk formed by a series of primary particles and a branch from the trunk However, it may be constituted by branch portions formed by continuous primary particles, or may be constituted by two branch portions branched from the trunk portion and connected at the trunk portion. The “stem” is the longest part of the aggregate of fine particles.

  The inner region 15 </ b> B is filled with the binder resin 14. The bent portion 15 </ b> A is preferably present so as to sandwich the inner region 15 </ b> B from the thickness direction of the antiglare layer 12.

  Agglomerates that aggregate in a lump form act as a single solid upon curing shrinkage (polymerization shrinkage) of the photopolymerizable compound that becomes the binder resin after curing, so the uneven surface of the antiglare layer corresponds to the shape of the aggregate To do. On the other hand, the aggregate in which the fine particles 15 are gently aggregated has the bent portion 15A and the inner region 15B sandwiched between the bent portions 15A, and therefore acts as a solid having a buffering action upon curing shrinkage. Therefore, the aggregate in which the fine particles 15 are gradually aggregated is easily and uniformly crushed during the curing shrinkage. As a result, the shape of the uneven surface 12A is more gradual than when fine particles are aggregated in a lump, and large unevenness is less likely to occur in part.

  As fine particles that form a gentle aggregate, for example, inorganic oxide fine particles having an average primary particle size of 1 nm to 100 nm are preferable. Since the average primary particle size of the fine particles is 1 nm or more, an antiglare layer having a specific uneven surface can be formed more easily, and since the average primary particle size is 100 nm or less, Light diffusion can be suppressed, and excellent darkroom contrast can be obtained. The lower limit of the average primary particle size of the fine particles is more preferably 5 nm or more, and the upper limit of the average primary particle size of the fine particles is more preferably 50 nm or less. The average primary particle size of the fine particles is a value measured using an image processing software from an image of a cross-sectional electron microscope (a transmission type such as TEM or STEM and preferably having a magnification of 50,000 times or more).

  When inorganic oxide fine particles are used as the fine particles forming a gentle aggregate, the average particle diameter of the aggregates of the inorganic oxide fine particles is preferably 100 nm or more and 2.0 μm or less. If the thickness is 100 nm or more, a specific uneven surface can be easily formed. If the thickness is 2.0 μm or less, the diffusion of light due to the aggregate of fine particles can be suppressed, and an image image of an optical film excellent in dark room contrast. A display device can be obtained. The average particle diameter of the fine particle aggregate is preferably 200 nm or less at the lower limit, and preferably 1.5 μm or less at the upper limit.

  The average particle diameter of the aggregates of the inorganic oxide fine particles was selected from a 5 μm square region containing a large amount of aggregates of the inorganic oxide fine particles based on observation with a cross-sectional electron microscope (about 10,000 to 20,000 times). The particle diameter of the aggregate of inorganic oxide fine particles was measured, and the average particle diameter of the aggregate of the top 10 inorganic oxide fine particles was measured. The “particle diameter of the aggregate of the inorganic oxide fine particles” is the maximum distance between the two straight lines when the cross section of the aggregate of the inorganic oxide fine particles is sandwiched between any two parallel straight lines. It is measured as the distance between straight lines in a combination of two straight lines. The particle diameter of the aggregate of inorganic oxide fine particles may be calculated using image analysis software.

  When the inorganic oxide fine particles are used as the fine particles forming a gentle aggregate, the unevenness on the uneven surface of the antiglare layer is preferably formed only from the inorganic oxide fine particles. “Unevenness on the uneven surface of the antiglare layer is formed only by the inorganic oxide fine particles” means that the unevenness on the uneven surface of the antiglare layer is other than the inorganic oxide fine particles in addition to the inorganic oxide fine particles. In the case of being formed due to the fine particles, it means that it is not substantially contained. As used herein, “substantially free” means fine particles that do not form unevenness on the uneven surface of the antiglare layer, or a slight amount that does not affect the antiglare property even if unevenness is formed. If so, it means that the antiglare layer may contain fine particles other than the inorganic oxide fine particles.

Among the inorganic oxide fine particles, fumed silica is particularly preferable from the viewpoint that a gentle aggregate can be formed and a unique uneven surface can be easily formed. Fumed silica is amorphous silica having a particle size of 200 nm or less prepared by a dry method, and can be obtained by reacting a volatile compound containing silicon in a gas phase. Specific examples include those produced by hydrolyzing a silicon compound such as silicon tetrachloride (SiCl ₄ ) in a flame of oxygen and hydrogen. Examples of commercially available fumed silica include AEROSIL R805 manufactured by Nippon Aerosil Co., Ltd.

  Although fumed silica has hydrophilicity and hydrophobicity, among these, from the viewpoint of reducing water absorption and facilitating dispersion in the functional layer composition, hydrophobicity is expected. What is shown is preferred. Hydrophobic fumed silica can be obtained by chemically reacting a surface treatment agent as described above with silanol groups present on the surface of fumed silica. From the viewpoint of easily obtaining the aggregate as described above, the fumed silica is most preferably treated with octylsilane.

The BET specific surface area of fumed silica is preferably 100 m ² / g or more and 200 m ² / g or less. By setting the BET specific surface area of the fumed silica to 100 m ² / g or more, the fumed silica does not disperse excessively and it becomes easy to form an appropriate aggregate, and the BET specific surface area of the fumed silica is 200 m ² / g. By making it below, it becomes difficult for fumed silica to form excessively large aggregates. The lower limit of the BET specific surface area of fumed silica is more preferably 120 m ² / g, still more preferably 140 m ² / g. The upper limit of the BET specific surface area of fumed silica is more preferably 180 m ² / g, still more preferably 165 m ² / g.

  Such an antiglare layer 12 can be formed by the following method, for example. First, the following antiglare layer composition is applied to the surface of the light transmissive substrate 11. Examples of the method for applying the antiglare layer composition include known coating methods such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, and die coating.

  The antiglare layer composition contains at least the photopolymerizable compound and the fine particles. In addition, you may add the said thermoplastic resin, the said thermosetting resin, a solvent, and a polymerization initiator to the composition for glare-proof layers as needed. Further, the antiglare layer composition includes conventionally known dispersants, surfactants and antistatic agents depending on purposes such as increasing the hardness of the antiglare layer, suppressing cure shrinkage, and controlling the refractive index. , Silane coupling agents, thickeners, anti-coloring agents, colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modification A quality agent, a lubricant, etc. may be added.

(solvent)
The solvent is used for adjusting the viscosity for easy application of the antiglare layer composition, adjusting the evaporation rate and dispersibility for fine particles, and adjusting the degree of aggregation of the fine particles when forming the antiglare layer. It can be used for the purpose of easily forming a peculiar uneven surface. Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketones (acetone, methyl ethyl ketone (MEK), cyclohexanone. , Methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone, etc.), ethers (1,4-dioxane, dioxolane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate) ), Cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc., and mixtures thereof may be used. .

  In addition, as shown in FIG. 1, when the mixed region 11 </ b> A is formed in the vicinity of the interface with the antiglare layer 12 in the light transmissive substrate 11, it is permeable to the light transmissive substrate 11 as a solvent. In addition, a material containing a penetrating solvent that dissolves or swells the light-transmitting substrate 11 is used, and a photopolymerizable compound containing a photopolymerizable monomer having a weight average molecular weight of 1000 or less is used. By using the permeable solvent and the photopolymerizable monomer, not only the permeable solvent but also the photopolymerizable monomer penetrates into the light transmissive substrate 11, so that the interface with the antiglare layer 12 in the light transmissive substrate 11. A mixed region 11A in which a light transmissive substrate 11 and a resin containing a photopolymerizable monomer as a monomer unit are mixed can be formed in the vicinity.

  Examples of the permeable solvent include ketones (acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone), esters (methyl formate, methyl acetate, ethyl acetate, propyl acetate). , Butyl acetate, ethyl lactate, etc.), ethers (1,4-dioxane, dioxolane, tetrahydrofuran, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), phenol (Phenol, orthochlorophenol) and the like. Moreover, these mixtures may be sufficient. In the case of using a triacetyl cellulose base material as the light transmissive base material, among these, examples of the permeable solvent include methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate. At least one selected from the group consisting of the above is preferred, and orthochlorophenol is preferred when a polyester substrate is used as the light-transmitting substrate.

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

  The polymerization initiator is not particularly limited as long as it can release a substance that initiates radical polymerization by light irradiation. The polymerization initiator is not particularly limited, and known ones can be used. Specific examples include, for example, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, thioxanthones, propiophenone. , Benzyls, benzoins, acylphosphine oxides. In addition, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

  As the polymerization initiator, when the binder resin is a resin system having a radically polymerizable unsaturated group, it is preferable to use acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether or the like alone or in combination. .

  The content of the polymerization initiator in the antiglare layer composition is preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound. By setting the content of the polymerization initiator within this range, the hard coat performance can be sufficiently maintained, and curing inhibition can be suppressed.

  Although it does not specifically limit as a content rate (solid content) of the raw material in the composition for glare-proof layers, Usually, 5 to 70 mass% is preferable, and it is more preferable to set it as 25 to 60 mass%. .

(Leveling agent)
As the leveling agent, for example, silicone oil, fluorine-based surfactant and the like are preferable because it prevents the antiglare layer from having a Benard cell structure. When a resin composition containing a solvent is applied and dried, a surface tension difference or the like is generated between the coating film surface and the inner surface in the coating film, thereby causing many convections in the coating film. The structure generated by this convection is called a Benard cell structure, and causes problems such as the skin and coating defects in the antiglare layer to be formed.

  In the Benard cell structure, the unevenness on the surface of the antiglare layer may become too large. When the leveling agent as described above is used, this convection can be prevented, so that not only a glare-proof layer free from defects and unevenness can be obtained, but also the uneven shape of the surface of the glare-proof layer can be easily adjusted.

  The method for preparing the composition for the antiglare layer is not particularly limited as long as each component can be uniformly mixed. For example, the composition can be performed using a known apparatus such as a paint shaker, a bead mill, a kneader, or a mixer.

  After coating the antiglare layer composition on the surface of the light-transmitting substrate 11, it is transported to a heated zone for drying the coating-like antiglare layer composition, and various known methods are used. The antiglare layer composition is dried and the solvent is evaporated. Here, the distribution state of the fine particles can be adjusted by selecting the solvent relative evaporation rate, solid content concentration, coating solution temperature, drying temperature, drying air velocity, drying time, solvent atmosphere concentration in the drying zone, and the like.

  In particular, a method of adjusting the distribution state of the fine particles by selecting the drying conditions is simple and preferable. The specific drying temperature is preferably 30 to 120 ° C., and the drying wind speed is preferably 0.2 to 50 m / s. The drying treatment appropriately adjusted within this range is performed once or a plurality of times to thereby form fine particles. The distribution state can be adjusted to a desired state.

  Moreover, when the composition for anti-glare layer is dried, the permeable solvent which has permeated the light-transmitting substrate evaporates, but the photopolymerizable compound remains in the light-transmitting substrate.

  Thereafter, the coating-like antiglare layer composition is irradiated with light such as ultraviolet rays, and the photopolymerizable compound is polymerized (crosslinked) to cure the antiglare layer composition. In addition to the formation, the mixed region 11A is formed.

  When ultraviolet rays are used as the light for curing the composition for the antiglare layer, ultraviolet rays emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like can be used. Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

  In addition, the anti-glare layer having a specific uneven surface can also be formed by using a photopolymerizable compound and a solvent-drying resin as a material for forming the binder resin. Specifically, for example, using a composition for an antiglare layer containing a photopolymerizable compound, a solvent-drying resin, and fine particles, the composition for an antiglare layer on a light transmissive substrate by the same method as described above. The coating film is formed, and the antiglare layer composition is cured in the same manner as described above. When a photopolymerizable compound and a solvent-drying resin are used in combination as a material for forming the binder resin, the viscosity can be increased as compared with the case where only the photopolymerizable compound is used, and curing shrinkage (polymerization shrinkage). Therefore, the uneven surface of the antiglare layer is formed without following the shape of the fine particles during drying and curing, and a unique uneven surface can be formed. However, since the uneven shape of the uneven surface of the antiglare layer is affected by the film thickness of the antiglare layer, etc., even when the antiglare layer is formed by such a method, the film thickness of the antiglare layer, etc. Needless to say, it is necessary to adjust the above.

  In the present embodiment, the antiglare layer 12 has a single-layer structure. However, if the above formulas (1) and (2) are satisfied, the antiglare layer has a multilayer structure of two or more layers. May be. Specifically, the antiglare layer may have a two-layer structure including a base uneven layer having an uneven surface and a surface adjustment layer formed on the base uneven layer. The foundation uneven layer may be the antiglare layer 12. The surface adjustment layer is used to fill the fine unevenness present on the surface of the underlying uneven layer to obtain a smooth uneven surface, and / or to adjust the interval, size, etc. of the unevenness present on the surface of the uneven layer. Is a layer. The surface adjustment layer has an uneven surface, and the uneven surface of the surface adjustment layer has a unique uneven surface. However, when the antiglare layer has a multi-layer structure, the manufacturing process is complicated, and the management of the manufacturing process may be difficult as compared with the case of a single layer structure. .

  The film thickness of the surface adjustment layer is preferably from 0.5 μm to 20 μm from the viewpoint of adjusting the unevenness. The upper limit of the film thickness of the surface adjustment layer is preferably 12 μm or less, and more preferably 8 μm or less. The lower limit of the thickness of the surface adjustment layer is preferably 3 μm or more.

  The antiglare layer composed of the underlying uneven layer and the surface adjustment layer can be formed by the following method using the underlying uneven layer composition and the surface adjustment layer composition as the antiglare layer composition. .

  As the composition for the base uneven layer, the same composition as the composition for the antiglare layer described in the column of the composition for antiglare layer can be used. Moreover, as a composition for surface adjustment layers, the composition which contains at least the photopolymerizable compound similar to the photopolymerizable compound demonstrated in the column of the said binder resin can be used. In addition to the photopolymerizable compound, the surface adjustment layer composition may contain a leveling agent, a solvent, and the like similar to the leveling agent and solvent described in the column of the antiglare layer composition.

  When forming an antiglare layer composed of a base uneven layer and a surface adjustment layer, first, the composition for the base uneven layer is applied on the transparent substrate, and then the composition for the base uneven layer is formed on the light transparent substrate. Form a coating of objects. Then, after drying this coating film, the coating film is irradiated with light such as ultraviolet rays to polymerize (crosslink) the photopolymerizable compound, thereby curing the foundation uneven layer composition to form a foundation uneven layer. To do. Then, the composition for surface adjustment layers is apply | coated on a base uneven | corrugated layer, and the coating film of the composition for surface adjustment layers is formed. And after drying this coating film, the coating film is irradiated with light such as ultraviolet rays to polymerize (crosslink) the photopolymerizable compound, thereby curing the composition for the surface adjustment layer to form a surface adjustment layer. To do. Thereby, an anti-glare layer having a specific uneven surface can be formed without using fine particles forming a gentle aggregate. However, the uneven shape of the uneven surface of the antiglare layer is also affected by the drying conditions of the coating film and the film thickness of the underlying uneven layer and the surface adjustment layer. Even if it exists, it cannot be overemphasized that it is necessary to adjust the drying conditions of a coating film, the film thickness of a base uneven | corrugated layer, and a surface adjustment layer suitably.

≪Physical properties of anti-glare film≫
The antiglare film 10 preferably has a total light transmittance of 85% or more. When the total light transmittance is 85% or more, color reproducibility and visibility can be further improved when the antiglare film 10 is mounted on the surface of the image display device. The total light transmittance is more preferably 90% or more. The total light transmittance can be measured by a method based on JIS K7361 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).

  In the surface 10A of the antiglare film 10, the average interval Sm of the unevenness constituting the surface 10A is preferably 0.1 mm or more and 0.8 mm or less, and is 0.3 mm or more and 0.6 mm or less. It is more preferable. On the surface of the antiglare film, the average inclination angle θa of the unevenness constituting this surface is preferably 0.01 ° or more and 0.1 ° or less, and is 0.03 ° or more and 0.08 ° or less. More preferably.

  In the surface 10A of the antiglare film 10, the arithmetic average roughness Ra of the unevenness constituting this surface is preferably 0.02 μm or more and 0.12 μm or less, and is 0.04 μm or more and 0.10 μm or less. More preferably. On the surface of the antiglare film, the maximum height roughness Ry of the unevenness constituting the surface is preferably 0.1 μm or more and 0.8 μm or less, and is 0.3 μm or more and 0.6 μm or less. It is more preferable. On the surface of the antiglare film, the 10-point average roughness Rz of the unevenness constituting this surface is preferably 0.1 μm or more and 0.7 μm or less, and is 0.2 μm or more and 0.5 μm or less. It is more preferable.

The definitions of the above “Sm”, “Ra”, “Ry” and “Rz” shall conform to JIS B0601-1994. The definition of “θa” is in accordance with the surface roughness measuring instrument: SE-3400 / Kosaka Laboratory Co., Ltd. instruction manual (revised 1995.07.20). Specifically, θa is represented by the following formula (4).
θa = tan ⁻¹ Δa (4)
In the formula, Δa represents the slope as an aspect ratio, and is a value obtained by dividing the total sum of the differences between the minimum and maximum portions of each unevenness (corresponding to the height of each convex portion) by the reference length.

Sm, θa, Ra, Ry, and Rz can be measured under the following measurement conditions using, for example, a surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory).
1) Stylus of surface roughness detector (trade name SE2555N (2μ standard) manufactured by Kosaka Laboratory Ltd.)
・ Tip radius of curvature 2μm, apex angle 90 degrees, material diamond 2) Measurement conditions of surface roughness measuring instrument ・ Reference length (cutoff value λc of roughness curve): 2.5 mm
Evaluation length (reference length (cutoff value λc) × 5): 12.5 mm
・ Feeding speed of stylus: 0.5mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

  According to this embodiment, the transmitted image definition of the antiglare film 10 measured using an optical comb having a width of 0.125 mm is C (0.125), and the optical comb is measured using an optical comb having a width of 0.25 mm. When the transmitted image definition of the anti-glare film 10 is C (0.25), the anti-glare film 10 satisfies the above formulas (1) and (2). Even if it has a low total haze of 0% to 5% and a low internal haze of 0% to 5%, glare can be suppressed for the reasons described above.

  When the antiglare layer 12 is formed using inorganic oxide fine particles (for example, fumed silica) having an average primary particle size of 1 nm or more and 100 nm or less as the fine particles, a lower total haze value (for example, 1% or less) The anti-glare film 10 having a lower total haze value) and a lower internal haze value (for example, an internal haze value of substantially 0%) can be obtained. That is, the total haze and the internal haze of the antiglare film are the ratio of the transmitted light that deviates by 2.5 degrees or more from the incident light due to forward scattering in the transmitted light transmitted through the antiglare film. If the ratio of transmitted light deviating by 5 degrees or more can be reduced, the overall haze value and internal haze are lowered. On the other hand, since the inorganic oxide fine particles having an average primary particle size of 100 nm or less do not aggregate in a lump in the antiglare layer 12 and form a gentle aggregate, the light transmitted through the antiglare layer 12 is antiglare. Difficult to diffuse in layer 12. Therefore, when the anti-glare layer 12 is formed using inorganic oxide fine particles having an average primary particle size of 1 nm or more and 100 nm or less, generation of transmitted light deviated by 2.5 degrees or more from incident light can be suppressed. Thus, the antiglare film 10 having a lower total haze value and lower internal haze value can be obtained.

  When the unevenness on the uneven surface 12A of the antiglare layer 12 is formed due to only the inorganic oxide fine particles, it is easy to form the uneven surface 12A having gentle and uniform unevenness that can obtain antiglare properties. Therefore, the anti-glare film 10 which has a low total haze value and an internal haze value and can further suppress glare can be obtained.

  According to the present embodiment, the anti-glare film 10 has a total haze value of 0% or more and 5% or less, and an internal haze value of 0% or more and 5% or less. Can be suppressed. Further, since the diffusion of the image light inside the anti-glare film 10 can be suppressed, a part of the image light does not become stray light, and as a result, there is no possibility that the darkroom contrast is lowered and the image may be blurred. Nor. Thereby, the anti-glare film 10 can be used by being incorporated in an ultra-high-definition image display device having a horizontal pixel number of 3000 or more such as 4K2K (horizontal pixel number 3840 × vertical pixel number 2160).

  According to this embodiment, since the anti-glare film 10 includes the anti-glare layer 12 having the uneven surface 12A, the light reflected at the interface between the light transmissive substrate 11 and the anti-glare layer 12 and the anti-glare layer Interference with light reflected by the twelve irregular surfaces 12A can be suppressed. Thereby, generation | occurrence | production of an interference fringe can be suppressed. In addition, when the mixed region 11A is formed, reflection at the interface between the light transmissive substrate 11 and the antiglare layer 12 can be suppressed, so that the generation of interference fringes can be further suppressed.

  When the unevenness on the uneven surface 12A of the antiglare layer 12 is formed only by the inorganic oxide fine particles, it is easy to prevent the inclination angle of the unevenness constituting the uneven surface 12A from increasing. Thereby, since excessive diffusion of external light does not occur, it is possible to suppress a decrease in bright room contrast. Further, since it is possible to prevent the image light from becoming stray light, a good dark room contrast can be obtained. Furthermore, since it has an appropriate specular reflection component, when a moving image is displayed, the shine and brightness of the image increase, and a dynamic feeling can be obtained. As a result, it is possible to obtain a black feeling having both excellent contrast and dynamic feeling.

  In addition, it is also possible to provide the glare improvement method with the anti-glare film which satisfy | fills said Formula (1) and (2).

≪Polarizing plate≫
The antiglare film 10 can be used by being incorporated into a polarizing plate, for example. FIG. 4 is a schematic configuration diagram of a polarizing plate incorporating the antiglare film according to the present embodiment. As shown in FIG. 4, the polarizing plate 20 includes an antiglare film 10, a polarizing element 21, and a protective film 22. The polarizing element 21 is formed on the surface opposite to the surface on which the antiglare layer 12 is formed in the light transmissive substrate 11. The protective film 22 is provided on the surface opposite to the surface on which the antiglare film 10 of the polarizing element 21 is provided. The protective film 22 may be a retardation film.

  Examples of the polarizing element 21 include a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, which are dyed and stretched with iodine or the like. When laminating the antiglare film 10 and the polarizing element 21, it is preferable to saponify the light transmissive substrate 11 in advance. By performing the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

≪LCD panel≫
The antiglare film 10 and the polarizing plate 20 can be used by being incorporated in a liquid crystal panel. FIG. 5 is a schematic configuration diagram of a liquid crystal panel incorporating the antiglare film according to the present embodiment.

  The liquid crystal panel 30 shown in FIG. 5 has a protective film 31, such as a triacetyl cellulose film (TAC film), a polarizing element 32, a retardation film 33, an adhesive, from the light source side (backlight unit side) to the viewer side. The agent layer 34, the liquid crystal cell 35, the adhesive layer 36, the retardation film 37, the polarizing element 21, and the antiglare film 10 are sequentially laminated. In the liquid crystal cell 35, a liquid crystal layer, an alignment film, an electrode layer, a color filter, and the like are disposed between two glass substrates.

  Examples of the retardation films 33 and 37 include a triacetyl cellulose film and a cycloolefin polymer film. The retardation film 37 may be the same as the protective film 22. Examples of the adhesive constituting the adhesive layers 34 and 36 include a pressure sensitive adhesive (PSA).

  Further, in the liquid crystal panel 30 shown in FIG. 5, the protective film 31 can be replaced with the antiglare film 10. In this case, the antiglare film 10 instead of the protective film 31 is disposed such that the uneven surface 12A of the antiglare layer 12 is on the light source side.

≪Image display device≫
The anti-glare film 10, the polarizing plate 20, and the liquid crystal panel 30 are used by being incorporated in an ultra-high-definition image display device having a horizontal pixel count of 3000 or more such as 4K2K (horizontal pixel count 3840 × vertical pixel count 2160). be able to. Examples of the image display device include a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, and electronic paper. Can be mentioned. FIG. 6 is a schematic configuration diagram of a liquid crystal display which is an example of an image display device incorporating the antiglare film according to the present embodiment.

  The image display device 40 shown in FIG. 6 is a liquid crystal display having 3000 horizontal pixels or more. The image display device 40 includes a backlight unit 41 and a liquid crystal panel 30 including an anti-glare film 10 disposed closer to the viewer than the backlight unit 41. A known backlight unit can be used as the backlight unit 41.

  In the image display device 40 shown in FIG. 6, the protective film 31 can be replaced with the antiglare film 10. In this case, the antiglare film 10 instead of the protective film 31 is disposed such that the uneven surface 12A of the antiglare layer 12 is on the light source side.

(Second Embodiment)
Hereinafter, an antiglare film according to a second embodiment of the present invention will be described with reference to the drawings. In the second embodiment, the contents overlapping with those of the first embodiment are omitted unless otherwise specified. FIG. 7 is a schematic configuration diagram of an antiglare film according to the present embodiment.

≪Anti-glare film≫
As shown in FIG. 7, the antiglare film 50 includes at least a light transmissive substrate 51, an antiglare layer 52 provided on the light transmissive substrate 51, and having an uneven surface 52A, and an antiglare layer. And functional layer 53 provided on 52. Since the light transmissive substrate 51 is the same as the light transmissive substrate 11 described in the first embodiment, the description thereof is omitted in this embodiment. In the vicinity of the interface of the antiglare layer 52 in the light transmissive substrate 51, there is a mixed region 51A in which the binder resin component of the light transmissive substrate 51 and the antiglare layer 52 are mixed as shown in FIG. Preferably it is formed.

  The surface 50A of the antiglare film 50 is an uneven surface. In the present embodiment, since the functional layer 53 is provided on the antiglare layer 52, the surface 53A of the functional layer 53 is the surface 50A of the antiglare film 50.

  In the antiglare film 50, the total haze value is 0% or more and 5% or less, and the internal haze value is 0% or more and 5% or less. The total haze value of the antiglare film 50 is preferably 1% or less, and more preferably 0.3% or more and 0.5% or less. The internal haze value is preferably substantially 0%.

  When the total haze value of the antiglare film 50 is 0% or more and 5% or less and the internal haze value is 0% or more and 5% or less, the surface haze value of the antiglare film 50 is 0% or more and 5% or less. It has become. The surface haze value of the antiglare film 50 is preferably 0% or more and 1% or less, and more preferably 0% or more and 0.3% or less.

The antiglare film 50 is measured using an optical comb having a width of 0.25 mm, where C (0.125) is the transmitted image definition of the antiglare film 50 measured using an optical comb having a width of 0.125 mm. When the transmitted image clarity of the antiglare film 10 is C (0.25), the following expressions (1) and (2) are satisfied.
C (0.25) -C (0.125) ≧ 2% (1)
C (0.125) ≧ 65% (2)

  In the present embodiment, since the functional layer 53 is provided on the antiglare layer 52, the transmitted image clarity of the antiglare film 50 is determined from the light transmissive substrate 51, the antiglare layer 52, and the functional layer 53. It is the transmitted image clarity measured using the anti-glare film 50 which becomes.

  The difference between the value of C (0.25) and the value of C (0.125) is preferably 3% or more, and more preferably 4% or more. The value of C (0.125) is preferably 75% or more. The value of C (0.125) is preferably 90% or less, more preferably 85% or less, and even more preferably 80% or less in order to ensure antiglare properties.

  In the present embodiment, if the antiglare film 50 satisfies the above (1) and (2), the uneven shape on the surface 50A of the antiglare film 50 and the uneven shape on the uneven surface 52A of the antiglare layer 52 are different. May be. Here, when a low refractive index layer is used as the functional layer 53, since the low refractive index layer is thin, the uneven shape on the uneven surface of the antiglare layer is almost the same on the surface of the low refractive index layer. It is maintained as it is. Accordingly, the uneven shape on the surface 50A of the antiglare film 50 (the surface 53A of the functional layer 53) is substantially the uneven shape on the uneven surface 52A of the antiglare layer 52. Hereinafter, a case where a low refractive index layer is used as the functional layer 53 will be described.

  The antiglare film 50 preferably has the same physical properties as those described in the section of the physical properties of the antiglare film.

<Anti-glare layer>
In this embodiment, since the glare-proof layer 52 is the same as the glare-proof layer 12 demonstrated in 1st Embodiment, description shall be abbreviate | omitted in this embodiment.

<Low refractive index layer>
The low refractive index layer is for reducing the reflectance when external light (for example, a fluorescent lamp, natural light, etc.) is reflected on the surface of the antiglare film. The low refractive index layer has a lower refractive index than the antiglare layer. Specifically, for example, the low refractive index preferably has a refractive index of 1.45 or less, and more preferably has a refractive index of 1.42 or less.

The thickness of the low-refractive index layer is not limited, but it may be set appropriately from the range of about 30 nm to 1 μm. The thickness d _A (nm) of the low refractive index layer preferably satisfies the following formula (5).
d _A = mλ / (4n _A ) (5)
In the above formula, n _A represents the refractive index of the low refractive index layer, m represents a positive odd number, preferably 1, and λ is a wavelength, preferably a value in the range of 480 nm to 580 nm.

The low refractive index layer preferably satisfies the following formula (6) from the viewpoint of reducing the reflectance.
120 <n _A d _A <145 (6)

  The effect can be obtained with a single layer of the low refractive index layer, but it is also possible to appropriately provide two or more low refractive index layers for the purpose of adjusting a lower minimum reflectance or a higher minimum reflectance. When two or more low refractive index layers are provided, it is preferable to provide a difference in the refractive index and thickness of each low refractive index layer.

  The low refractive index layer is preferably 1) a resin containing low refractive index particles such as silica and magnesium fluoride, 2) a fluorine-based resin which is a low refractive index resin, and 3) fluorine containing silica or magnesium fluoride. 4) It can be composed of any one of a thin film of a low refractive index material such as silica and magnesium fluoride. As for the resin other than the fluorine resin, the same resin as the binder resin constituting the antiglare layer described above can be used.

  Further, the silica is preferably hollow silica fine particles, and such hollow silica fine particles can be produced by, for example, a production method described in Examples of JP-A-2005-099778.

  As the fluorine-based resin, a polymerizable compound containing at least a fluorine atom in the molecule or a polymer thereof can be used. Although it does not specifically limit as a polymeric compound, For example, what has hardening reactive groups, such as a photopolymerizable functional group and a thermosetting polar group, is preferable. Moreover, the compound which has these reactive groups simultaneously may be sufficient. In contrast to this polymerizable compound, a polymer has no reactive groups as described above.

  As the photopolymerizable compound, fluorine-containing monomers having an ethylenically unsaturated bond can be widely used. More specifically, to illustrate fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) Can do. As those having a (meth) acryloyloxy group, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ) Ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, α-trifluoro (Meth) acrylate compounds having a fluorine atom in the molecule, such as methyl methacrylate and α-trifluoroethyl methacrylate; a C 1-14 fluoroalkyl group having at least 3 fluorine atoms in the molecule, fluoro A cycloalkyl group or a fluoroalkylene group and at least two (medium There are also fluorine-containing polyfunctional (meth) acrylic acid ester compounds having an acryloyloxy group.

  Preferable examples of the thermosetting polar group include hydrogen bond forming groups such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. These are excellent not only in adhesion to the coating film but also in affinity with inorganic ultrafine particles such as silica. Examples of the polymerizable compound having a thermosetting polar group include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, phenol, polyimide, and the like. Examples include fluorine-modified products of each resin.

  The polymerizable compound having both the photopolymerizable functional group and the thermosetting polar group includes acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, fully or partially. Examples thereof include fluorinated vinyl esters, fully or partially fluorinated vinyl ketones, and the like.

  Examples of the fluorine-based resin include the following. Polymer of monomer or monomer mixture containing at least one fluorine-containing (meth) acrylate compound of a polymerizable compound having an ionizing radiation curable group; at least one fluorine-containing (meth) acrylate compound; and methyl (meth) Copolymers with (meth) acrylate compounds that do not contain fluorine atoms in the molecule such as acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; fluoroethylene , Fluorine-containing compounds such as vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, hexafluoropropylene Monomer homopolymer or Copolymer such as. Silicone-containing vinylidene fluoride copolymers obtained by adding a silicone component to these copolymers can also be used. The silicone components in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl-modified (poly) dimethylsiloxane, azo group-containing (poly) dimethylsiloxane, Dimethyl silicone, phenylmethyl silicone, alkyl aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, methyl hydrogen silicone, silanol group containing silicone, alkoxy group containing silicone, phenol group containing silicone, methacryl modified silicone, acrylic Modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone Over emissions, fluorine-modified silicones, polyether-modified silicone and the like. Among these, those having a dimethylsiloxane structure are preferable.

  Furthermore, non-polymers or polymers composed of the following compounds can also be used as the fluororesin. That is, a fluorine-containing compound having at least one isocyanate group in the molecule is reacted with a compound having at least one functional group in the molecule that reacts with an isocyanate group such as an amino group, a hydroxyl group, or a carboxyl group. Compound obtained: a compound obtained by reacting a fluorine-containing polyol such as fluorine-containing polyether polyol, fluorine-containing alkyl polyol, fluorine-containing polyester polyol, fluorine-containing ε-caprolactone-modified polyol with a compound having an isocyanate group Can be used.

  Moreover, each binder resin as described in the said glare-proof layer 12 can also be mixed and used with the polymeric compound and polymer which have the above-mentioned fluorine atom. Furthermore, various additives and solvents can be used as appropriate in order to improve the curing agent for curing reactive groups and the like, to improve the coating property, and to impart antifouling properties.

  In the formation of the low refractive index layer, the viscosity of the composition for the low refractive index layer formed by adding the above-described material is 0.5 to 5 mPa · s (25 ° C.), preferably 0.7, which provides preferable coating properties. It is preferable to be in the range of ˜3 mPa · s (25 ° C.). An antireflection layer excellent in visible light can be realized, a uniform thin film with no coating unevenness can be formed, and a low refractive index layer particularly excellent in adhesion can be formed.

  The curing means of the low refractive index layer composition may be the same as that described in the antiglare layer 12 according to the first embodiment. When a heating means is used for the curing treatment, it is preferable to add a thermal polymerization initiator that generates, for example, a radical by heating to start polymerization of the polymerizable compound, to the fluororesin composition.

  According to the present embodiment, the transmitted image definition of the antiglare film 50 measured using an optical comb having a width of 0.125 mm is C (0.125), and measured using an optical comb having a width of 0.25 mm. When the transmitted image clarity of the anti-glare film 10 is C (0.25), the anti-glare film 50 satisfies the above formulas (1) and (2), and thus is the same as in the first embodiment. For this reason, even if the antiglare film 50 has a low total haze of 0% to 5% and a low internal haze of 0% to 5%, glare can be suppressed. .

  According to the present embodiment, when a low refractive index layer is formed as the functional layer 53 on the antiglare layer 52, the external light reflectance in the antiglare film 50 can be reduced. Since the external light reflectance is reduced, the light transmittance of the antiglare film 50 is relatively increased, whereby the light transmittance of the antiglare film 50 can be improved.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited to these descriptions.

<Preparation of composition for antiglare layer>
First, each component was mix | blended so that it might become a composition shown below, and the composition for glare-proof layers was obtained.
(Anti-glare layer composition 1)
Silica fine particles (octylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.5 parts by mass Silica fine particles (methylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.2 parts by mass / pentaerythritol tetraacrylate (PETTA) (product name “PETA”, manufactured by Daicel Cytec): 50 parts by mass / urethane acrylate (product name “V-4000BA”, manufactured by DIC): 50 parts by mass -Polymerization initiator (Irgacure 184, manufactured by BASF Japan): 5 parts by mass-Polyether-modified silicone (product name "TSF4460", manufactured by Momentive Performance Materials): 0.025 parts by mass-Toluene: 70 parts by mass・ Isopropyl alcohol: 40 parts by mass Non: 40 parts by weight

(Anti-glare layer composition 2)
Silica fine particles (octylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.3 parts by mass Silica fine particles (methylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.5 parts by mass / pentaerythritol tetraacrylate (PETTA) (product name “PETA”, manufactured by Daicel Cytec): 50 parts by mass / urethane acrylate (product name “V-4000BA”, manufactured by DIC): 50 parts by mass -Polymerization initiator (Irgacure 184, manufactured by BASF Japan): 5 parts by mass-Polyether-modified silicone (product name "TSF4460", manufactured by Momentive Performance Materials): 0.025 parts by mass-Toluene: 70 parts by mass・ Isopropyl alcohol: 40 parts by mass Non: 40 parts by weight

(Anti-glare layer composition 3)
Silica fine particles (octylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.7 parts by mass Silica fine particles (methylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.2 parts by mass / pentaerythritol tetraacrylate (PETTA) (product name “PETA”, manufactured by Daicel Cytec): 50 parts by mass / urethane acrylate (product name “V-4000BA”, manufactured by DIC): 50 parts by mass -Polymerization initiator (Irgacure 184, manufactured by BASF Japan): 5 parts by mass-Polyether-modified silicone (product name "TSF4460", manufactured by Momentive Performance Materials): 0.025 parts by mass-Toluene: 70 parts by mass・ Isopropyl alcohol: 40 parts by mass Non: 40 parts by weight

(Anti-glare layer composition 4)
Spherical acrylic = styrene copolymer beads (refractive index 1.52, average primary particle size 5 μm, manufactured by Sekisui Plastics): 4 parts by mass Isocyanuric acid EO-modified diacrylate (product name “M-215”, Toa Gosei Co., Ltd.) 50 parts by mass / PMMA resin (solvent dry resin, molecular weight 75,000, manufactured by Mitsubishi Rayon Co.): 50 parts by mass / polymerization initiator (Irgacure 184, manufactured by BASF Japan): 3 parts by mass / polyether modified Silicone (product name “TSF4460”, manufactured by Momentive Performance Materials): 0.025 parts by mass, toluene: 70 parts by mass, isopropyl alcohol: 40 parts by mass, cyclohexanone: 40 parts by mass

(Anti-glare layer composition 5)
(1) Composition for underlying concavo-convex layer / spherical acrylic = styrene copolymer beads (refractive index 1.52, average primary particle size 5 μm, manufactured by Sekisui Plastics): 8 parts by mass / pentaerythritol tetraacrylate (PETTA) (product Name “PETA” (manufactured by Daicel Cytec): 50 parts by mass / urethane acrylate (product name “V-4000BA”, manufactured by DIC): 50 parts by mass / polymerization initiator (Irgacure 184, manufactured by BASF Japan): 5 Parts by mass, polyether-modified silicone (product name “TSF4460”, manufactured by Momentive Performance Materials): 0.015 parts by mass, toluene: 70 parts by mass, isopropyl alcohol: 40 parts by mass, cyclohexanone: 40 parts by mass (2 ) Composition for surface adjustment layer / Pentaerythritol tetraacrylate (PETT) ) (Product name “PETA”, manufactured by Daicel Cytec Co., Ltd.): 50 parts by mass / urethane acrylate (Product name “V-4000BA”, manufactured by DIC): 50 parts by mass / polymerization initiator (Irgacure 184, manufactured by BASF Japan) ): 5 parts by mass-polyether-modified silicone (product name “TSF4460”, manufactured by Momentive Performance Materials): 0.035 parts by mass-Toluene: 110 parts by mass-cyclohexanone: 40 parts by mass

(Anti-glare layer composition 6)
Silica fine particles (octylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.5 parts by mass Silica fine particles (methylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.2 parts by mass / pentaerythritol tetraacrylate (PETTA) (product name “PETA”, manufactured by Daicel Cytec): 50 parts by mass / urethane acrylate (product name “V-4000BA”, manufactured by DIC): 50 parts by mass -Polymerization initiator (Irgacure 184, manufactured by BASF Japan): 5 parts by mass-Polyether-modified silicone (product name "TSF4460", manufactured by Momentive Performance Materials): 0.025 parts by mass-Toluene: 90 parts by mass・ Isopropyl alcohol: 20 parts by mass Non: 40 parts by weight

(Anti-glare layer composition 7)
Silica fine particles (octylsilane-treated fumed silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.7 parts by massPentaerythritol tetraacrylate (PETTA) (product name “PETA”, manufactured by Daicel Cytec Co., Ltd.): 50 parts by mass / urethane acrylate (product name “V-4000BA”, manufactured by DIC): 50 parts by mass / polymerization initiator (Irgacure 184, manufactured by BASF Japan): 5 parts by mass / polyether-modified silicone (product name “TSF4460”) ”, Manufactured by Momentive Performance Materials): 0.025 parts by mass, toluene: 90 parts by mass, isopropyl alcohol: 20 parts by mass, cyclohexanone: 40 parts by mass

(Anti-glare layer composition 8)
Spherical acrylic = styrene copolymer beads (refractive index 1.52, average primary particle size 5 μm, manufactured by Sekisui Plastics Co., Ltd.): 4 parts by mass Pentaerythritol tetraacrylate (PETTA) (product name “PETA”, Daicel Cytec) 70 parts by mass / EO isocyanuric acid EO-modified diacrylate (product name “M-215”, manufactured by Toa Gosei Co., Ltd.): 30 parts by mass / polymerization initiator (Irgacure 184, manufactured by BASF Japan): 3 parts by mass / poly Ether-modified silicone (product name “TSF4460”, manufactured by Momentive Performance Materials): 0.025 parts by mass, toluene: 70 parts by mass, isopropyl alcohol: 40 parts by mass, cyclohexanone: 40 parts by mass

(Anti-glare layer composition 9)
(1) Composition for underlying concavo-convex layer / spherical acrylic = styrene copolymer beads (refractive index 1.52, average primary particle diameter 5 μm, manufactured by Sekisui Plastics): 10 parts by mass / pentaerythritol tetraacrylate (PETTA) (product Name “PETA” (manufactured by Daicel Cytec): 50 parts by mass / urethane acrylate (product name “V-4000BA”, manufactured by DIC): 50 parts by mass / polymerization initiator (Irgacure 184, manufactured by BASF Japan): 5 Parts by mass, polyether-modified silicone (product name “TSF4460”, manufactured by Momentive Performance Materials): 0.015 parts by mass, toluene: 70 parts by mass, isopropyl alcohol: 40 parts by mass, cyclohexanone: 40 parts by mass (2 ) Composition for surface adjustment layer / Pentaerythritol tetraacrylate (PET A) (Product name “PETA”, manufactured by Daicel-Cytec): 50 parts by mass / urethane acrylate (Product name “V-4000BA”, manufactured by DIC): 50 parts by mass / polymerization initiator (Irgacure 184, BASF Japan) Manufactured): 5 parts by mass-polyether-modified silicone (product name "TSF4460", manufactured by Momentive Performance Materials): 0.035 parts by mass-toluene: 110 parts by mass-cyclohexanone: 40 parts by mass

(Anti-glare layer composition 10)
Spherical acrylic = styrene copolymer beads (refractive index 1.52, average primary particle size 5 μm, manufactured by Sekisui Plastics): 5 parts by mass Isocyanuric acid EO-modified diacrylate (product name “M-215”, Toa Gosei Co., Ltd.) 50 parts by mass / PMMA resin (solvent dry resin, molecular weight 75,000, manufactured by Mitsubishi Rayon Co.): 50 parts by mass / polymerization initiator (Irgacure 184, manufactured by BASF Japan): 3 parts by mass / polyether modified Silicone (product name “TSF4460”, manufactured by Momentive Performance Materials): 0.025 parts by mass, toluene: 70 parts by mass, isopropyl alcohol: 40 parts by mass, cyclohexanone: 40 parts by mass

<Preparation of composition for low refractive index layer>
Each component was mix | blended so that it might become the composition shown below, and the composition for low refractive index layers was obtained.
(Composition for low refractive index layer)
Hollow silica fine particles (solid content of hollow silica fine particles: 20% by mass, solution: methyl isobutyl ketone, average particle size: 50 nm): 40 parts by mass Pentaerythritol triacrylate (PETA) (Product name: PETIA, Daicel Cytec) 10 parts by mass / polymerization initiator (Irgacure 127; manufactured by BASF Japan): 0.35 parts by mass / modified silicone oil (X22164E; manufactured by Shin-Etsu Chemical Co., Ltd.): 0.5 parts by mass / methyl isobutyl ketone (MIBK) ): 320 parts by mass-Propylene glycol monomethyl ether acetate (PGMEA): 161 parts by mass

<Example 1>
A 60 μm-thick triacetyl cellulose resin film (manufactured by Fuji Film Co., Ltd., TD60UL) as a light-transmitting substrate was prepared, and the antiglare layer composition 1 was applied to one side of the triacetyl cellulose resin film. Formed. Next, 50 ° C. dry air was passed through the formed coating film at a flow rate of 0.2 m / s for 15 seconds, and then 70 ° C. dry air was passed through for 30 seconds at a flow rate of 10 m / s. By evaporating, the solvent in the coating film is evaporated, and the coating film is cured by irradiating ultraviolet rays under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) so that the integrated light quantity becomes 100 mJ / cm ^2. The anti-glare layer (when cured) was formed, and an anti-glare film according to Example 1 was produced.

<Example 2>
In Example 2, 70 ° C. dry air was circulated for 15 seconds at a flow rate of 1.0 m / s, and then 70 ° C. dry air was further circulated for 30 seconds at a flow rate of 10 m / s. In the same manner as in Example 1, an antiglare film was produced.

<Example 3>
In Example 3, an antiglare film was produced in the same manner as in Example 1 except that the antiglare layer composition 2 was used instead of the antiglare layer composition 1.

<Example 4>
In Example 4, after using the antiglare layer composition 3 in place of the antiglare layer composition 1, 70 ° C. dry air was circulated at a flow rate of 5.0 m / s for 15 seconds. Further, an antiglare film was produced in the same manner as in Example 1 except that 70 ° C. dry air was circulated for 30 seconds at a flow rate of 10 m / s.

<Example 5>
In Example 5, an antiglare film was prepared in the same manner as in Example 1 except that the antiglare layer composition 4 was used in place of the antiglare layer composition 1 and the thickness at curing was 5 μm. Produced.

<Example 6>
In Example 6, a 60 μm-thick triacetyl cellulose resin film (manufactured by FUJIFILM Corporation, TD60UL) as a light-transmitting substrate was prepared, and the antiglare layer composition 5 was formed on one side of the triacetyl cellulose resin film. The base uneven layer composition was applied to form a coating film. Next, 70 ° C. dry air was passed through the formed coating film at a flow rate of 1.0 m / s for 15 seconds, and then 70 ° C. dry air was passed through for 30 seconds at a flow rate of 10 m / s. By evaporating, the solvent in the coating film is evaporated, and the coating film is cured by irradiating ultraviolet rays with an integrated light amount of 50 mJ / cm ² under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). A base uneven layer (at the time of curing) was formed. Further, the surface adjustment layer composition of the antiglare layer composition 5 was applied to the underlying uneven layer to form a coating film, and 70 ° C. dry air was circulated for 15 seconds at a flow rate of 1.0 m / s. Thereafter, the solvent in the coating film was evaporated by passing 70 ° C. dry air at a flow rate of 10 m / s for 30 seconds to dry, and the accumulated light quantity was 100 mJ under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). / Cm ² is irradiated to cure the coating film to form a surface adjustment layer, and an anti-glare layer is formed so that the total thickness of the base uneven layer and the surface adjustment layer is 6 μm (when cured). An antiglare film according to Example 6 was produced.

<Example 7>
In Example 7, an antiglare layer was formed on the triacetyl cellulose resin film in the same manner as in Example 1 except that the cumulative amount of ultraviolet light was 50 mJ / cm ² . Next, the composition for the low refractive index layer is applied to the surface of the antiglare layer so that the film thickness after drying (40 ° C. × 1 minute) is 0.1 μm, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) Then, an ultraviolet ray was irradiated at an integrated light amount of 100 mJ / cm ² and cured to form a low refractive index layer, and an optical film according to Example 7 was produced.

<Comparative Example 1>
In Comparative Example 1, after the antiglare layer composition 6 was used instead of the antiglare layer composition 1, drying air was circulated at 50 ° C. for 15 seconds at a flow rate of 1.0 m / s. Further, an antiglare film was produced in the same manner as in Example 1 except that 70 ° C. dry air was circulated for 30 seconds at a flow rate of 10 m / s.

<Comparative example 2>
In Comparative Example 2, an antiglare film was produced in the same manner as in Example 1 except that the antiglare layer composition 7 was used instead of the antiglare layer composition 1.

<Comparative Example 3>
In Comparative Example 3, an antiglare film was produced in the same manner as in Example 1 except that the antiglare layer composition 6 was used instead of the antiglare layer composition 1.

<Comparative Example 4>
In Comparative Example 4, the antiglare layer was prepared in the same manner as in Example 1 except that the antiglare layer composition 8 was used in place of the antiglare layer composition 1 and the thickness at curing was 4.5 μm. A film was prepared.

<Comparative Example 5>
In Comparative Example 5, an antiglare film was produced in the same manner as in Example 6 except that the antiglare layer composition 9 was used instead of the antiglare layer composition 5.

<Comparative Example 6>
In Comparative Example 6, an antiglare film was prepared in the same manner as in Example 1 except that the antiglare layer composition 10 was used in place of the antiglare layer composition 1 and the thickness upon curing was 5 μm. Produced.

<Measurement of transmitted image clarity>
In each antiglare film obtained in Examples and Comparative Examples, the transmitted image definition was measured as follows. First, a image clarity measuring device (model number: ICM-1T, manufactured by Suga Test Instruments Co., Ltd.) was prepared. And each anti-glare film which concerns on an Example and a comparative example is installed so that the triacetyl cellulose resin film side may become the light source side of a image clarity measuring device, and it conforms to the measuring method of the image definition by the transmission method of JIS K7374 Then, the transmitted image definition was measured. As the optical comb, those having a width of 0.125 mm and a width of 0.25 mm were used. Then, the transmission image definition (C (0.25)) measured using an optical comb having a width of 0.25 mm and the transmission image definition (C (0. 0) measured using an optical comb having a width of 0.125 mm). 125)) (C (0.25) -C (0.125)). Further, for reference, the transmission image definition of each antiglare film according to Examples and Comparative Examples was measured in the same manner as described above using optical combs of 0.5 mm width, 1.0 mm width, and 2.0 mm width. , Transmitted image definition (C (0.125)) measured using a 0.125 mm wide optical comb, and transmitted image definition (C (0.5) measured using a 0.5 mm wide optical comb. )), Transmitted image clarity measured with a 1.0 mm wide optical comb (C (1.0)), and transmitted image sharpness measured with a 2.0 mm wide optical comb (C ( 2.0)).

<Glare evaluation (1)>
In each antiglare film obtained in Examples and Comparative Examples, a glass plate (thickness 3 mm) was bonded to the surface of the antiglare film where the antiglare layer was not formed with a transparent adhesive. Furthermore, the glass surface in which the anti-glare film in this glass plate was not bonded, and the glass surface in which the matrix of 350 ppi black matrix (glass thickness 0.7mm) was not formed were bonded together with water. For the sample thus obtained, a white surface light source (LIGHTBOX manufactured by HAKUBA, average luminance of 1000 cd / m ² ) was installed on the black matrix side, thereby causing pseudo glare. This was photographed from the antiglare film side with a CCD camera (KP-M1, C mount adapter, close-up ring; PK-11A Nikon, camera lens; 50 mm, F1.4s NIKKOR). The distance between the CCD camera and the antiglare film was 250 mm, and the focus of the CCD camera was adjusted to match the antiglare film. Images taken with a CCD camera were taken into a personal computer and analyzed with image processing software (ImagePro Plus ver. 6.2; manufactured by Media Cybernetics) as follows. First, an evaluation location of 200 × 160 pixels was selected from the captured image, and converted to a 16-bit gray scale at the evaluation location. Next, the low-pass filter was selected from the enhancement tab of the filter command, and the filter was applied under the conditions of 3 × 3, number of times 3, and strength 10. As a result, components derived from the black matrix pattern were removed. Next, flattening was selected, and shading correction was performed under the condition of background: dark, object width 10. Next, contrast enhancement was performed with a contrast enhancement command with a contrast of 96 and a brightness of 48. The obtained image was converted to an 8-bit gray scale, and the variation in the value for each pixel was calculated as a standard deviation value for 150 × 110 pixels in the image, thereby glaring was digitized. It can be said that the smaller the numerical value of the glare value, the less the glare.

<Glare evaluation (2)>
In each antiglare film obtained in Examples and Comparative Examples, glare was evaluated as follows. 15 light subjects (white surface light source) with a luminance of 1500 cd / m ² , 350 ppi black matrix glass, and anti-glare film are stacked in order from the bottom, and 15 subjects are visually inspected from various distances up and down and left and right from a distance of about 30 cm. Evaluation was performed. It was determined whether or not the glare was worrisome and was evaluated according to the following criteria.
◎: 13 or more people who answered good ○: 10-12 people who answered good △: 7-9 people who answered good ×: 6 or less people who answered good

<Overall haze, internal haze, surface haze measurement>
About each anti-glare film obtained by the said Example and comparative example, the whole haze, the internal haze, and the surface haze were measured as follows. First, the overall haze value of the antiglare film was measured according to JIS K7136 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory). Thereafter, a triacetyl cellulose base material (manufactured by Fuji Film, TD60UL) was attached to the surface of the antiglare layer via a transparent optical adhesive layer. Thereby, the uneven shape of the uneven surface in the antiglare layer was crushed, and the surface of the antiglare film became flat. In this state, the haze value was measured according to JIS K7136 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) to determine the internal haze value. And the surface haze value was calculated | required by subtracting an internal haze value from the whole haze value.

<Measurement of Sm, θa, Ra, Ry, and Rz>
On the surface of each antiglare film obtained in Examples and Comparative Examples (the surface of the antiglare layer when there is no low refractive index layer, the surface of the low refractive index layer when there is a low refractive index layer), Sm , Θa, Ra, Ry, and Rz were measured. The definitions of Sm, Ra, Ry and Rz shall be in accordance with JIS B0601-1994, and θa shall follow the surface roughness measuring instrument: SE-3400 / Kosaka Laboratory Co., Ltd. instruction manual (revised 1995.07.20). Shall.

Specifically, Sm, θa, Ra, Ry, and Rz were measured under the following measurement conditions using a surface roughness measuring instrument (model number: SE-3400 / manufactured by Kosaka Laboratory Ltd.).
1) Stylus of surface roughness detector (trade name SE2555N (2μ standard) manufactured by Kosaka Laboratory Ltd.)
・ Tip radius of curvature 2μm, apex angle 90 degrees, material diamond 2) Measurement conditions of surface roughness measuring instrument ・ Reference length (cutoff value λc of roughness curve): 2.5 mm
Evaluation length (reference length (cutoff value λc) × 5): 12.5 mm
・ Feeding speed of stylus: 0.5mm / s
・ Preliminary length: (cutoff value λc) × 2
・ Vertical magnification: 2000 times ・ Horizontal magnification: 10 times

The results are shown in Tables 1 and 2.

  As shown in Table 1, in Comparative Examples 1 to 6, the difference between C (0.25) and C (0.125) of the antiglare film is 2% or more, and C (0.125) is Since an antiglare film of 65% or more was not obtained, glare could not be suppressed.

  On the other hand, in Examples 1-7, the difference between C (0.25) and C (0.125) of the antiglare film is 2% or more, and C (0.125) is 65% or more. Since an anti-glare film was obtained, glare could be suppressed even in an anti-glare film having a total haze value and an internal haze of 0% or more and 5% or less.

  In addition, when the sum of the transmitted image clarity in the anti-glare film which concerns on an Example and the anti-glare film which concerns on a comparative example is compared, the sum of the transmitted image clarity of the anti-glare film which concerns on an Example from Table 1 is a comparative example It can be understood that some of them are larger than the sum of the transmitted image clarity of the antiglare film, but some are smaller. From this result, it can be understood that the glare prevention property cannot be evaluated by the sum of the transmitted image clarity.

  Moreover, since the result of the glare evaluation 1 corresponds to the result of the glare evaluation 2, the measurement method used in the glare evaluation 1 is determined to be reliable.

DESCRIPTION OF SYMBOLS 10, 50 ... Anti-glare film 10A, 50A ... Surface 11, 51 ... Light transmissive base material 11A, 51A ... Mixed area | region 12, 52 ... Anti-glare layer 12A, 52A ... Uneven surface 14 ... Binder resin 15 ... Fine particle 20 ... Polarization Plate 21 ... Polarizing element 30 ... Liquid crystal panel 40 ... Image display device 53 ... Functional layer

Claims (12)

An antiglare film comprising a light transmissive substrate and an antiglare layer provided on the light transmissive substrate and having an uneven surface,
The surface of the antiglare film is an uneven surface,
The total haze value of the antiglare film is 0% or more and 5% or less, and the internal haze value of the antiglare film is 0% or more and 5% or less,
The transmitted image clarity of the antiglare film measured using an optical comb having a width of 0.125 mm is defined as C (0.125), and the transmission of the antiglare film measured using an optical comb having a width of 0.25 mm. An antiglare film characterized by satisfying the following formulas (1) and (2) when the image definition is C (0.25).
C (0.25) -C (0.125) ≧ 2% (1)
C (0.125) ≧ 65% (2)   The antiglare film according to claim 1, wherein the uneven surface of the antiglare layer is the surface of the antiglare film.   The antiglare film according to claim 1, further comprising a functional layer provided on the antiglare layer, wherein a surface of the functional layer is the surface of the antiglare film.   The anti-glare film according to any one of claims 1 to 3, wherein the anti-glare layer contains a binder resin and fine particles.   The antiglare film according to claim 4, wherein the fine particles are inorganic oxide fine particles.   The anti-glare film according to claim 5, wherein an average primary particle size of the inorganic oxide fine particles is 1 nm or more and 100 nm or less.   The anti-glare film according to claim 5 or 6, wherein the inorganic oxide fine particles are inorganic oxide fine particles having a surface hydrophobized.   The inorganic oxide fine particles form aggregates in the antiglare layer, and the average particle diameter of the aggregates is 100 nm or more and 2.0 μm or less, according to any one of claims 5 to 7. Antiglare film.   The anti-glare film according to any one of claims 1 to 8, wherein the total haze value of the anti-glare film is 0% or more and 1% or less, and the internal haze value of the anti-glare film is substantially 0%. the film. An antiglare film according to any one of claims 1 to 9,
A polarizing plate comprising: a polarizing element formed on a surface of the light transmissive substrate of the antiglare film opposite to a surface on which the antiglare layer is formed.   A liquid crystal display panel provided with the anti-glare film as described in any one of Claims 1 thru | or 9, or the polarizing plate of Claim 10.   An image display device comprising the antiglare film according to claim 1 or the polarizing plate according to claim 10 and having a number of horizontal pixels of 3000 or more.

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