JP2014202950A - Antidazzle film, polarizing plate, liquid crystal panel and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antidazzle film capable of suppressing glare and having low total haze and internal haze, and to provide a polarizing plate, a liquid crystal panel and an image display device.SOLUTION: An antidazzle film 10 in one embodiment includes a light-transmitting substrate 11 and an antidazzle layer 12 disposed on the light-transmitting substrate 11 and having a rugged surface 12A. The antidazzle layer 12 contains a binder resin 14 and fumed silica 15 present in the binder resin 14; and rugged features in the rugged surface 12A are formed as originated only from the fumed silica 15.

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 layer is provided. However, there is provided an antiglare film comprising a binder resin and fumed silica present in the binder resin, wherein the irregularities on the irregular surface are formed solely from the fumed silica.

  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, liquid crystal panel, and image display device of another embodiment, the antiglare layer contains fumed silica present in the binder resin, Since the unevenness on the uneven surface is formed only from fumed silica, an antiglare film, a polarizing plate, a liquid crystal panel, and an image display device that can suppress glare and have low internal haze can be provided.

It is a schematic block diagram of the anti-glare film which concerns on embodiment. It is the figure which expanded a part of FIG. It is a schematic block diagram of the polarizing plate which concerns on embodiment. It is a schematic block diagram of the liquid crystal panel which concerns on embodiment. It is a schematic block diagram of the liquid crystal display which is an example of the image display apparatus which concerns on embodiment.

  Hereinafter, an antiglare film according to an 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, and FIG. 2 is an enlarged view of a part of FIG. In the present specification, terms such as “sheet”, “film”, and “plate” are not distinguished from each other only based on the difference in names. Therefore, for example, a “sheet” is a concept including a member that can also be called a film or a plate. As a specific example, “antiglare film” includes members called “optical sheet”, “optical plate” and the like.

≪Anti-glare film≫
As shown in FIG. 1, the antiglare film 10 includes a light transmissive substrate 11, an antiglare layer 12 provided on the light transmissive substrate 11, and a low refraction provided on the antiglare layer 12. The rate layer 13 is provided. The antiglare film 10 only needs to include at least the light-transmitting substrate 11 and the antiglare layer 12, and does not need to include the low refractive index layer 13. Near the interface of the antiglare layer 12 in the light transmissive substrate 11, as shown in FIG. 1, a light transmissive substrate 11 and a resin containing a photopolymerizable monomer having a weight average molecular weight of 1000 or less as a monomer unit, It is preferable to form a mixed region 11A in which are mixed. 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.

<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.

  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). As shown in FIG. 2, the antiglare layer 12 includes a binder resin 14 and fumed silica 15 present in the binder resin 14.

  The unevenness on the uneven surface 12A of the antiglare layer 12 is formed due to the fumed silica 15 alone. "Unevenness on the uneven surface of the antiglare layer is formed only by fumed silica" means that the uneven surface on the uneven surface of the antiglare layer is caused by fine particles other than fumed silica. When it is formed, it means that it is not substantially included. 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 fumed silica.

(Binder resin)
The binder resin 14 is obtained by polymerizing (crosslinking) a photopolymerizable compound by light irradiation. 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.

(Fumed silica)
The fumed silica 15 is an aggregate of very bulky amorphous silica produced by a dry method. The fumed silica 15 is produced, for example, 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.

  As shown in FIG. 2, the fumed silica 15 is not a lump but has a structure including a bent portion 15A formed by continuous primary particles and an inner region 15B sandwiched between the bent portions 15A. Yes. 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 fumed silica 15 may have an annular structure having the bent portion 15A. As amorphous silica, colloidal silica, precipitated silica, and gel silica are also known. These are produced by a wet method. Colloidal silica is difficult to form aggregates, and even if colloidal silica forms aggregates, the colloidal silica aggregates are considered to be agglomerated and thus do not have a structure like fumed silica 15. Moreover, since the precipitation method silica or the gel method silica is produced as a massive aggregate, it does not have the structure like the fumed silica 15.

  The bent portion 15A may be formed of a single fumed silica formed by a series of primary particles and bent. However, the bent portion 15A branches from the trunk and a trunk formed by a series of primary particles. And 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 fumed silica.

  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.

  Since the inorganic fine particle aggregate in which organic fine particles and inorganic fine particles are aggregated in a lump acts as a single solid upon curing shrinkage (polymerization shrinkage) of the photopolymerizable compound that becomes a binder resin after curing, the unevenness of the antiglare layer The surface corresponds to the shape of organic fine particles or inorganic fine particle aggregates. On the other hand, the fumed silica 15 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 fumed silica 15 is easily and uniformly crushed during curing shrinkage. Thereby, the shape of the uneven surface 12A is more gradual than the case of using an inorganic fine particle aggregate in which organic fine particles or inorganic fine particles are aggregated in a lump shape, and large unevenness is less likely to occur in part.

  The average primary particle size of the fumed silica 15 is preferably 1 nm or more and 100 nm or less. Since the average primary particle size of the fine particles is 1 nm or more, the antiglare layer having the uneven surface as described above can be more easily formed, and the average primary particle size is 100 nm or less. Light diffusion due to the fine particles 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).

  The average agglomerated diameter of the fumed silica 15 is preferably 100 nm or more and 2.0 μm or less. If the average agglomerated diameter of the fumed silica 15 is 100 nm or more, the smooth uneven surface 12A can be easily formed. If the average agglomerated diameter of the fumed silica 15 is 2.0 μm or less, the fumed silica Accordingly, the antiglare film 10 having excellent contrast can be obtained. The lower limit of the average agglomerated diameter of the fumed silica 15 is preferably 200 nm or more, and the upper limit is preferably 1.5 μm or less.

  For the average agglomerated diameter of fumed silica, select a 5 μm square area containing a large amount of fumed silica from observation with a cross-sectional electron microscope (about 10,000 to 20,000 times), and measure the agglomerated diameter of fumed silica in that area. In addition, the agglomerated diameters of the top 10 fumed silicas are averaged. The above-mentioned “average agglomerated diameter of fumed silica” refers to two straight lines that maximize the distance between the two straight lines when the section of the fumed silica is sandwiched between two parallel straight lines. Measured as the distance between straight lines in the combination. Further, the average aggregate diameter of fumed silica may be calculated using image analysis software.

  The fumed silica 15 preferably has a larger aggregate diameter in the direction perpendicular to the thickness direction than the aggregate diameter in the thickness direction of the antiglare layer 12. The “aggregation diameter in the thickness direction” is measured as a distance between two straight lines when a section of fumed silica is sandwiched between two parallel straight lines perpendicular to the thickness direction of the antiglare layer. Moreover, the above-mentioned “aggregated diameter in a direction perpendicular to the thickness direction” is a distance between two straight lines when a section of fumed silica is sandwiched between two parallel straight lines parallel to the thickness direction of the antiglare layer. Measured. These agglomerated diameters may also be calculated using image analysis software.

The BET specific surface area of the fumed silica 15 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 the fumed silica 15 is more preferably 120 m ² / g, still more preferably 140 m ² / g. The upper limit of the BET specific surface area of the fumed silica 15 is more preferably 180 m ² / g, and further preferably 165 m ² / g.

  The fumed silica 15 has hydrophilicity and hydrophobicity. Among these, from the viewpoint of reducing water absorption and facilitating dispersion in the antiglare layer composition, the fumed silica 15 is hydrophobic. What shows the property is preferable. Hydrophobic fumed silica can be obtained by chemically reacting a silanol group present on the surface of fumed silica with a surface treatment agent such as silanes or silazanes. Examples of such a surface treatment agent include dimethyldichlorosilane, silicone oil, hexamethyldisilazane, octylsilane, hexadecylsilane, aminosilane, methacrylsilane, octamethylcyclotetrasiloxane, polydimethylsiloxane, and the like. The degree of aggregation of fumed silica can be adjusted by appropriately selecting the above-mentioned surface treatment agent and adjusting the hydrophobicity, and fumed silica treated with a plurality of types of surface treatment agents can also be used in combination. . From the viewpoint of easily obtaining the aggregate as described above, it is most preferable to use fumed silica treated with octylsilane.

  Although content of the fumed silica 15 with respect to the glare-proof layer 12 is not specifically limited, It is preferable that it is 0.1 to 3.0 mass%. By setting the content of fumed silica 15 to 0.1% by mass or more, a gentle uneven surface 12A can be more reliably formed, and the content of fumed silica 15 is set to 3.0% by mass or less. By doing so, the fumed silica aggregates are not generated excessively, and it is possible to further suppress the occurrence of large irregularities on the surface of the internal diffusion and / or the antiglare layer, thereby suppressing the cloudiness. The lower limit of the content of fumed silica 15 is more preferably 0.2% by mass or more, and the upper limit of the content of fumed silica 15 is more preferably 1.0% by mass or less.

(Other ingredients)
As described above, fine particles other than the fumed silica 15 may be included in the antiglare layer 12 as long as the fine particles do not form unevenness on the uneven surface 12A of the antiglare layer 12.

Such fine particles may be either inorganic fine particles or organic fine particles. Among these, for example, silica (SiO ₂ ) fine particles other than fumed silica, alumina fine particles, titania fine particles, tin oxide fine particles, antimony dope Inorganic oxide fine particles such as tin oxide (abbreviation: ATO) fine particles and zinc oxide fine particles are preferable.

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

  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.

  In addition to the antiglare layer 12, if necessary, a solvent-drying resin (a resin that forms a coating only by drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin) A thermosetting resin may be added.

  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 added to the antiglare layer 12 is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino Examples include alkyd resins, melamine-urea cocondensation resins, silicon resins, polysiloxane resins, and the like.

  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.

<Composition for anti-glare layer>
The composition for an antiglare layer contains at least the photopolymerizable compound and the fumed silica. In addition, if necessary, the fine particles other than fumed silica, the thermoplastic resin, the thermosetting resin, a solvent, and a polymerization initiator may be added to the antiglare layer composition. 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)
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. .

  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, the solvent has high permeability to the light transmissive substrate 11. In addition to using a permeable solvent that dissolves or swells the light-transmitting substrate 11, a photopolymerizable compound that includes 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 fumed silica 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 fumed silica by selecting drying conditions is simple and preferable. Specifically, the 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, and fumed. The distribution state of silica 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.

<Low refractive index layer>
The low refractive index layer 13 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 10. The low refractive index layer 13 has a lower refractive index than the antiglare layer 12. 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.

Although the thickness of the low-refractive-index layer 13 is not limited, Usually, what is necessary is just to set suitably from the range of about 30 nm-1 micrometer. The thickness d _A (nm) of the low refractive index layer 13 preferably satisfies the following formula (1).
d _A = mλ / (4n _A ) (1)
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 13 preferably satisfies the following formula (2) from the viewpoint of reducing the reflectance.
120 <n _A d _A <145 (2)

  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 13 preferably includes 1) a resin containing low refractive index particles such as silica and magnesium fluoride, 2) a fluorine resin which is a low refractive index resin, and 3) silica or magnesium fluoride. Fluorine resin, 4) A thin film of a low refractive index material such as silica or magnesium fluoride, etc. can be used. 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 13, the viscosity of the composition for low refractive index layer formed by adding the above-described material is 0.5 to 5 mPa · s (25 ° C.), preferably 0. It is preferable to set it as the thing of the range of 7-3 mPa * s (25 degreeC). 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 for the low refractive index layer composition may be the same as that described for the antiglare layer 12 described above. 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.

≪Physical properties of anti-glare film≫
The antiglare film 10 preferably has a total haze value of 1% or less and an internal haze value of 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). 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 FUJIFILM Corporation, TD60UL) is 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 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 uneven surface in the antiglare layer. The total haze value of the antiglare film 10 is more preferably 0.3% or more and 0.5% or less.

  When the total haze value of the antiglare film 10 is 1% or less and the internal haze value is substantially 0%, the surface haze value of the antiglare film 10 is 1% or less. The surface haze value of the antiglare film 10 is preferably 0% or more and 0.3% or less. The surface haze value is caused only by the uneven shape of the uneven surface in the antiglare layer, and by subtracting the internal haze value from the overall haze value, the surface haze value caused by only the uneven shape of the surface in the antiglare layer is Desired.

  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).

  The surface 10A of the antiglare film 10 reflects the shape of the uneven surface 12A of the antiglare layer 12. That is, the surface of the antiglare film 10 is an uneven surface. In the antiglare film 10 shown in FIG. 1, since the low refractive index layer 13 is formed on the antiglare layer 12, the surface 10 </ b> A of the antiglare film 10 is the surface of the low refractive index layer 13. In addition, when other layers, such as a low refractive index layer, are not formed on an anti-glare layer, the surface of an anti-glare film turns into the surface of an anti-glare layer.

  On the surface of the antiglare film, the average interval Sm of the unevenness constituting this surface is preferably 0.1 mm or more and 0.8 mm or less, more preferably 0.3 mm or more and 0.6 mm or less. 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.

  On the surface of the antiglare film, the arithmetic average roughness Ra of the unevenness constituting the surface is preferably 0.02 μm or more and 0.12 μm or less, and 0.04 μm or more and 0.10 μm or less. Is more preferable. 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 (3).
θa = tan ⁻¹ Δa (3)
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, since the anti-glare layer 12 is formed using the fumed silica 15, a low total haze value (for example, a total haze value of 1% or less) and a low internal haze value (for example, substantially Thus, an antiglare film 10 having an internal haze value of 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, the fumed silica 15 does not aggregate in a lump in the antiglare layer 12, so that light transmitted through the antiglare layer 12 is difficult to diffuse in the antiglare layer 12. Therefore, when the antiglare layer 12 is formed using the fumed silica 15, generation of transmitted light deviated by 2.5 degrees or more from incident light can be suppressed. An antiglare film 10 having a low haze value can be obtained.

  When the uneven surface of the antiglare layer is made of organic fine particles, there are uneven surfaces that make up the uneven surface that are larger than other parts, and these large uneven surfaces exhibit a strong lens effect. It is thought that glare occurs because of On the other hand, according to the present embodiment, since the irregularities on the irregular surface 12A of the antiglare layer 12 are formed only by the fumed silica 15, gentle and uniform irregularities that can obtain antiglare properties. 12A can be formed. Therefore, glare can be suppressed even if the total haze value and the internal haze value are low.

  According to this embodiment, the antiglare film 10 has a low total haze value (for example, a total haze value of 1% or less) and a low internal haze value (for example, an internal haze value of substantially 0%). Decrease in luminance and light transmission 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 the present embodiment, since the antiglare film 10 includes the antiglare layer 12 having the uneven surface 12A, the light reflected at the interface between the light transmissive substrate 11 and the antiglare layer 12 and the low refractive index. Interference with light reflected at the interface between the layer 13 and the antiglare layer 12 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.

  According to this embodiment, since the low refractive index layer 13 is formed on the antiglare layer 12, the external light reflectance in the antiglare film 10 can be reduced. Since the external light reflectance is lowered, the light transmittance of the antiglare film 10 is relatively increased, whereby the light transmittance of the antiglare film 10 can be improved.

  In the present embodiment, since the irregularities on the irregular surface 12A of the antiglare layer 12 are formed only from the fumed silica 15, the inclination angle of the irregularities constituting the irregular surface 12A does not increase. 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.

≪Polarizing plate≫
The antiglare film 10 can be used by being incorporated into a polarizing plate, for example. FIG. 3 is a schematic configuration diagram of a polarizing plate incorporating the antiglare film according to the present embodiment. As shown in FIG. 3, the polarizing plate 20 includes an antiglare film 10, a polarizing element 21, and a protective film 22. The polarizing element 21 is formed on the surface 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. 4 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. 4 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. 4, 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. 5 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. 5 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. 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.

  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)
-Fumed silica (octylsilane treatment, average particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.5 parts by mass- Fumed silica (methylsilane treatment, average 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 Ltd.): 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 Parts / cyclohexanone: 40 parts by mass

(Anti-glare layer composition 2)
-Fumed silica (octylsilane treatment, average particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.6 parts by mass- Fumed silica (methylsilane treatment, average particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.): 0.3 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 Ltd.): 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 Parts / cyclohexanone: 40 parts by mass

(Anti-glare layer composition 3)
Acrylic-styrene copolymer particles (organic fine particles, average primary particle size 3.0 μm, refractive index 1.52, manufactured by Sekisui Plastics Co., Ltd.): 4 parts by mass Pentaerythritol triacrylate (PETA) (Product name “PETIA ”, Manufactured by Daicel Cytec Co., Ltd.): 100 parts by mass, polymerization initiator (product name“ Irgacure 184 ”, manufactured by BASF Japan): 5 parts by mass, polyether-modified silicone (product name“ TSF4460 ”, Momentive Performance Material) Manufactured by Co., Ltd.): 0.025 parts by mass, toluene: 120 parts by mass, cyclohexanone: 30 parts by mass

(Anti-glare layer composition 4)
Polystyrene particles (organic fine particles, average primary particle size 3.0 μm, refractive index 1.59, manufactured by Sekisui Plastics Kogyo Co., Ltd.): 10 parts by mass Pentaerythritol triacrylate (PETA) (product name “PETIA”, Daicel Cytec) 100 parts by mass / polymerization initiator (product name “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: 120 parts by mass-Cyclohexanone: 30 parts by mass

(Anti-glare layer composition 5)
Amorphous silica particles (inorganic fine particles, hydrophobization treatment, average particle diameter (laser diffraction scattering method) 2.7 μm, manufactured by Fuji Silysia Chemical Ltd.): 4 parts by mass Pentaerythritol triacrylate (PETA) (product name “PETIA” , Manufactured by Daicel Cytec Co., Ltd.): 100 parts by mass, polymerization initiator (product name “Irgacure 184”, manufactured by BASF Japan): 5 parts by mass, polyether-modified silicone (product name “TSF4460”, Momentive Performance Materials) (Made by company): 0.025 mass partToluene: 150 mass partmethyl isobutyl ketone (MIBK): 35 mass part In addition, the said amorphous silica particle was produced by the gel method.

<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, 70 ° 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, 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, the low refractive index layer was formed by irradiating with an ultraviolet ray at an integrated light amount of 100 mJ / cm ² to form an optical film according to Example 2.

<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, except that 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 20 m / s. In the same manner as in Example 1, an antiglare film was produced.

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

<Comparative example 2>
In Comparative Example 2, the antiglare layer composition 4 was used in place of the antiglare layer composition 1, and the antiglare layer was prepared in the same manner as in Example 1 except that the film thickness upon curing was 2.5 μm. A film was prepared.

<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 5 was used instead of the antiglare layer composition 1.

<Glare measurement>
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 , 200 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, 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.
○: 10 or more people who answered good ×: 5 to 9 people who answered good XX: 4 or less people who answered good

<Blackness>
In each antiglare film obtained in the examples and comparative examples, the blackness was evaluated as follows. The polarizing plate on the outermost surface of the liquid crystal television “KDL-40X2500” manufactured by Sony Corporation was peeled off, and a polarizing plate without surface coating was attached. Subsequently, the anti-glare films according to Examples and Comparative Examples obtained thereon were coated with an optical film transparent adhesive film (total light transmittance of 91% or more, haze of 0. 3% or less and a product having a film thickness of 20 to 50 μm, for example, MHM series (manufactured by Niei Engineering Co., Ltd.)). Install this LCD TV in a room with an illuminance of about 1000 Lx, display the DVD “Media Phantom” by Media Factory, and place it about 1.5 to 2.0 meters away from the LCD TV. The black color was evaluated by sensory evaluation by 15 subjects viewing this video. The blackness was determined by whether or not a moving image was displayed and whether the image had a high contrast and the image was shining or shining and felt a dynamic feeling. The evaluation criteria are as follows.
◎: 13 or more people who answered good ○: 10-12 people who answered good ×: 9 or fewer 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 Table 1.

  As shown in Table 1, in Comparative Examples 1 and 3, since the irregularities are formed by organic fine particles or massive inorganic fine particles, large irregularities that have a strong lens effect are generated, so that glare is suppressed. I could not. Further, in Comparative Example 2, although organic fine particles were used, it had a great internal diffusion effect, so that the glare was good, but the internal haze was large and the blackness was inferior. On the other hand, in Examples 1-4, since fumed silica is used, the total haze value of the antiglare film is 1% or less, and the internal haze value of the antiglare film is substantially 0%. However, it was possible to suppress glare and the blackness was good.

DESCRIPTION OF SYMBOLS 10 ... Anti-glare film 10A ... Surface 11 ... Light-transmitting base material 11A ... Mixed area 12 ... Anti-glare layer 12A ... Uneven surface 13 ... Low refractive index layer 14 ... Binder resin 15 ... Fumed silica 20 ... Polarizing plate 21 ... Polarization Element 30 ... Liquid crystal panel 40 ... Image display device

Claims (8)

An antiglare film comprising a light transmissive substrate and an antiglare layer provided on the light transmissive substrate and having an uneven surface,
The anti-glare film, wherein the anti-glare layer includes a binder resin and fumed silica present in the binder resin, and the irregularities on the irregular surface are formed only from the fumed silica.   The anti-glare film according to claim 1, wherein the anti-glare film has a total haze value of 1% or less and an internal haze value of the anti-glare film is substantially 0%.   The anti-glare film according to claim 1 or 2, further comprising a low refractive index layer provided on the anti-glare layer and having a lower refractive index than the anti-glare layer.   The anti-glare film according to any one of claims 1 to 3, wherein the fumed silica is fumed silica whose surface has been subjected to a hydrophobic treatment.   The anti-glare film as described in any one of Claims 1 thru | or 4 whose average aggregate diameter of the said fumed silica is 100 nm or more and 2.0 micrometers or less. Antiglare film according to any one of claims 1 to 5,
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 5, or the polarizing plate of Claim 6.   An image display device comprising the antiglare film according to any one of claims 1 to 5 or the polarizing plate according to claim 6 and having a number of horizontal pixels of 3000 or more.

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