JP2009047938A - Anti-glare anti-reflection film and display using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide anti-glare anti-reflection film capable of suppressing dazzling and having deep black and good balance and to provide a display using it. <P>SOLUTION: The anti-glare anti-reflection film is produced by laminating an anti-glare hard coat layer and a low-refractive index layer on a translucent base film in this order. The anti-glare hard coat layer contains a binder and translucent particles. The difference in refractive index between the hardened material of the binder and translucent particles is 0 to 0.05. The wavelength at minimum refractive index at which the refractive index in the visible region in 5° regular reflection is minimum ranges from 450 to 560 nm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antiglare antireflection film that is used by being attached to the outermost surface of the viewing side of various displays, in particular, an antiglare antireflection film excellent in suppressing image sharpness, blackening, and glare, and the same It relates to the display used.

  Electronic image display devices such as a cathode ray tube display (CRT), plasma display (PDP), and liquid crystal display (LCD) have little reflection of light emitted from an external light source such as a fluorescent lamp in order to improve the visibility. Is required.

  When light from the outside is reflected on the surface (display surface), a front image is reflected there, and the internal image becomes very difficult to see, so the reflection on the display surface is reduced. Further, an antiglare film and an antireflection film are arranged. The conventional antiglare film has a low reflection effect due to the light diffusing action due to the uneven shape of the surface, and the antireflection film has a low reflection effect due to the optical interference action by providing layers with different refractive indexes on the surface. What you get is known.

  However, when obtaining a low reflection effect only by the light diffusing action, it is necessary to make the concavo-convex shape larger or finer in order to obtain a sufficient effect, resulting in an increase in haze (cloudiness value), glare, and display There has been a problem that a phenomenon that the image is blurred in white (white blur) occurs and the image sharpness is lowered. In addition, when the anti-reflection effect is obtained only by the optical interference action, the reflected light is reduced and the glare is reduced and the display image is clear, but the image of the illumination device is clearly reflected and the display image is difficult to see. There was a problem.

Therefore, anti-glare antireflection films have been developed that are designed to complement the respective disadvantages by utilizing the effects of both light diffusion and optical interference. That is, an antiglare antireflection film is disclosed in which the shape of the surface irregularities is limited to such an extent that glare is suppressed, and a low refractive index layer is provided thereon (see, for example, Patent Document 1). Further, an antiglare antireflection film comprising a hard coat layer and a low refractive index layer and having a hard coat layer having a haze of 40% or more is disclosed (for example, see Patent Document 2).
JP 2002-196117 A (page 5) JP 2005-187770 A

  However, in the antiglare antireflection film described in Patent Document 1, glare is suppressed by defining Sm, Ra and Rz, but the refractive index of the hard coat layer is not controlled. Since the haze was high and the film thickness of the refractive index of the low refractive index layer was not optimized, the blackness in the black display image was not good. In the antiglare antireflection film described in Patent Document 2, Ra is set small and the haze of the hard coat layer is set high, and the diffusion effect is suppressed, so that the image sharpness is improved to some extent. Although the effect was obtained, the haze was high and the black margin in the black display image was not sufficient.

  Accordingly, an object of the present invention is to provide an antiglare antireflection film having a low haze, good image clarity, and excellent blackness in a black display image, and a display using the same. .

  In order to achieve the above object, the antiglare antireflection film of the first invention in the present invention is constituted by laminating an antiglare hard coat layer and a low refractive index layer in this order on a transparent substrate film. Has been. And the refractive index difference of the hardened | cured material of a binder and translucent microparticles | fine-particles in the anti-glare hard-coat layer containing a binder and translucent microparticles | fine-particles is 0-0.05, and the visible region in 5 degree regular reflection The minimum reflectance wavelength at which the reflectance at the minimum is set in the range of 450 to 560 nm.

  In the antiglare antireflection film of the second invention, the arithmetic average roughness (Ra) measured in accordance with JIS B 0601-1994 on the surface of the antiglare antireflection film is 0.00 in the first invention. It is characterized by having an average interval (Sm) of 01 to 0.30 μm and unevenness of 10 to 300 μm.

  The anti-glare antireflection film of the third invention is characterized in that, in the first or second invention, the anti-glare hard coat layer contains inorganic fine particles having an average particle diameter smaller than that of the translucent fine particles. To do.

  The antiglare antireflection film of the fourth invention is a fluorine-containing cured coating obtained by curing the fluorine-containing curable coating liquid in the first to third inventions by the low refractive index layer. The fluorine-containing curable coating liquid has a film-forming property and contains a fluorine-containing compound having a polymerizable double bond and hollow silica fine particles modified with a silane coupling agent represented by the following chemical formula (1) The content of the hollow silica fine particles is 20 to 60% by mass in the total amount of the fluorine-containing compound and the hollow silica fine particles.

(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group.)

  The display of 5th invention is equipped with the anti-glare antireflection film which concerns on any one of 1st to 4th invention on the outermost surface at the side which displays an image, It is characterized by the above-mentioned.

According to the present invention, the following effects can be exhibited.
In the antiglare antireflection film of the first invention, the refractive index difference between the cured binder and the light transmitting fine particles in the antiglare hard coat layer containing the binder and the light transmitting fine particles is 0 to 0.05. It is limited to a small range. For this reason, the light transmittance within the antiglare hard coat layer can be improved. Moreover, the minimum reflectance wavelength at which the reflectance in the visible region with 5 ° regular reflection is the lowest is set in the range of 450 to 560 nm. Therefore, reflection on the film surface is suppressed and the reflection color is controlled. Accordingly, the antiglare antireflection film has a low haze, good image sharpness, and excellent blackness in black display images.

  In the antiglare antireflection film of the second invention, the arithmetic average roughness (Ra) measured in accordance with JIS B 0601-1994 on the surface of the antiglare antireflection film is 0.01 to 0.30 μm and The average interval (Sm) of the unevenness is suppressed to a small range of 10 to 300 μm. For this reason, in addition to the effect of 1st invention, light transmittance can be maintained and glare can be suppressed, exhibiting the spreading | diffusion of the light in the anti-glare antireflection film surface.

  In the antiglare antireflection film of the third invention, the binder contains inorganic fine particles having an average particle size smaller than that of the light transmissive fine particles. Therefore, in addition to the effects of the first or second invention, the refractive index of the cured product of the binder can be adjusted, and the antiglare property can be adjusted by floating the translucent fine particles on the surface.

  In the antiglare antireflection film of the fourth invention, the fluorine-containing curable coating liquid used for the low refractive index layer has a film-forming property, and contains a fluorine-containing compound having a polymerizable double bond, and the chemical formula (1) Hollow silica fine particles modified with a silane coupling agent represented by the formula (1)), and the content of the hollow silica fine particles is set to 20 to 60% by mass in the total amount of the fluorine-containing compound and the hollow silica fine particles. . For this reason, in addition to the effects of any one of the first to third inventions, the (meth) acryloyloxy group of the silane coupling agent and the polymerizable double bond of the fluorine-containing compound are copolymerized to form hollow silica. The fine particles are integrally bonded to the fluorine-containing compound, the strength and hardness of the film obtained from the fluorine-containing curable coating liquid can be improved, and the scratch resistance and wear resistance of the film surface can be improved. In this case, since the content of the hollow silica fine particles modified with the silane coupling agent is higher than the conventional amount, the above effect can be sufficiently exhibited. Furthermore, a low refractive index and a low reflectance can be exhibited by the hollow part of fluorine and hollow silica fine particles with respect to the formed film.

  In the display of the fifth aspect, the antiglare antireflection film according to any one of the first to fourth aspects is provided on the outermost surface on the image display side. Therefore, it is possible to provide a display that is excellent in the transparency of the display image, has a good image sharpness, and is excellent in blackness in the case of a black display image.

Hereinafter, embodiments that are considered to be the best modes of the present invention will be described in detail.
The antiglare antireflection film of this embodiment is constituted by laminating an antiglare hard coat layer and a low refractive index layer in this order on a transparent substrate film. The refractive index difference between the cured binder and the light-transmitting fine particles in the antiglare hard coat layer containing the binder (binder) and the light-transmitting fine particles is set to 0 to 0.05, and reflection in the visible region The minimum reflectance wavelength at which the rate is the lowest is set in the range of 450 to 560 nm. Note that the difference in refractive index between the cured binder and the translucent fine particles being zero means that the refractive index of the cured binder and the translucent fine particles are the same.

  Thus, by reducing the difference in refractive index between the cured binder and the light-transmitting fine particles, the light transmission can be maintained, and at the same time, by controlling the minimum reflectance wavelength, It is excellent in black margins.

Next, each component of the antiglare antireflection film will be described in order.
As the transparent substrate film, a transparent resin film, a transparent resin sheet, a transparent glass plate or the like is used, and is not particularly limited. Specific examples of the resin material for forming the transparent base film include poly (meth) acrylic resins, poly (meth) acrylonitrile resins, polystyrene resins, polysulfone resins, polyethersulfone resins, and polyether resins. Resin, polymethylpentene resin, triacetate cellulose (TAC) resin, polyethylene terephthalate (PET) resin, polyurethane resin, regenerated cellulose resin, diacetyl cellulose resin, acetate butyrate cellulose resin, polyester resin, acrylonitrile -Styrene-butadiene terpolymer resin, polycarbonate resin, polyether ketone resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polyethylene resin, polypropylene resin , Polyamide (nylon) resin, polyimide resin, and norbornene resin. Among these, poly (meth) acrylic resins, polystyrene resins, triacetate cellulose (TAC) resins, polyethylene terephthalate (PET) resins, and polycarbonate resins are preferable from the viewpoints of versatility and application results. When providing a polarizing layer as a functional layer, triacetate cellulose (TAC) resin is usually used.

  The thickness of the transparent substrate film is usually 10 to 5000 μm, preferably 25 to 1000 μm, and more preferably 35 to 500 μm. When this thickness is thinner than 10 μm, workability is deteriorated and the strength of the transparent substrate film tends to be lowered. On the other hand, if the thickness is greater than 5000 μm, the thickness becomes unnecessarily thick and the handleability deteriorates, which is not preferable.

Next, the antiglare hard coat layer will be described.
The antiglare hard coat layer has irregularities on its surface, and light is reflected and diffused on the irregularities (surface diffusibility), and has a function capable of exhibiting antiglare properties. Such an antiglare hard coat layer is formed by curing a composition for forming an antiglare hard coat layer containing light-transmitting fine particles in a binder. The binder of the composition for forming an antiglare hard coat layer preferably contains an active energy ray-curable resin and a photopolymerization initiator. In order to adjust the refractive index of the cured binder and to adjust the antiglare property, it is preferable to include inorganic fine particles having an average particle diameter smaller than that of the light-transmitting fine particles. Furthermore, a diluting solvent is usually blended in the binder or the antiglare hard coat layer forming composition.

  The active energy ray-curable resin requires a polymerizable component as a constituent component, and may contain other components as necessary. Examples of such polymerizable components include monofunctional monomers, polyfunctional monomers, oligomers having vinyl groups and (meth) acryloyl groups, and polymers having vinyl groups and (meth) acryloyl groups. Or 2 or more types are selected and used. Other components include photodegradable or thermal decomposable polymerization initiators, oligomers that do not contain vinyl groups or (meth) acryloyl groups (hereinafter referred to as non-polymerizable oligomers), vinyl groups or (meth) acryloyl groups. Polymers (hereinafter referred to as non-polymerizable polymers), metal oxides, surfactants, diluent solvents, photosensitizers, stabilizers, ultraviolet absorbers, infrared absorbers, antioxidants and the like are used.

  Specific examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, Isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Cetyl acid, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate Oxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid Tamethylpiperidyl, (meth) acrylic acid ethyl hexahydrophthalate, (meth) acrylic acid 2-hydroxypropyl ethyl phthalate, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid butoxyethyl, (meth) acrylic (Meth) acrylic acid esters such as phenoxyethyl acid, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, styrene, α-methylstyrene, p-methoxy Styrene, m-methoxystyrene, di-t-butyl fumarate, di-n-butyl fumarate, diethyl fumarate, monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, N-isopropylacrylamide, N -Vinyl-2-pyrrolidone and the like are preferable.

  Examples of the polyfunctional monomer include esterified products of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified acrylate, and the like. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, Divalent alcohols such as hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2′-thiodiethanol, 1,4-cyclohexanedimethanol; trimethylolpropane, glycerol, pentaerythritol, di Examples thereof include trivalent or higher alcohols such as glycerol, dipentaerythritol, and ditrimethylolpropane.

  The urethane-modified acrylate can be obtained by a urethanization reaction between an organic isocyanate having a plurality of isocyanate groups in one molecule and a (meth) acrylic acid derivative having a hydroxyl group. Examples of organic isocyanates having a plurality of isocyanate groups in one molecule include two isocyanates in one molecule such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and dicyclohexylmethane diisocyanate. Organic isocyanate having a group, organic isocyanate having three isocyanate groups in one molecule obtained by subjecting these organic isocyanates to isocyanurate modification, adduct modification, biuret modification, and the like.

  Among them, di (meth) acrylic acid hexanediol, di (meth) acrylic acid neopentyl glycol, di (meth) acrylic acid diethylene glycol, di (meth) acrylate from the viewpoint of improving the strength of the cured product (coating film) and availability. (Meth) acrylic acid esters such as tripropylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexamethylene diisocyanate And an adduct of 2-hydroxyethyl (meth) acrylate, an adduct of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate, an adduct of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate, Adduct-modified isophorone diiso Aneto and (meth) adducts of adduct and biuret modified isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl acrylate is preferable.

  The light-transmitting fine particles are for exhibiting a light diffusion function in the antiglare hard coat layer, an antiglare function by forming irregularities on the surface, and the like. Examples of the light-transmitting fine particles include inorganic fine particles and resin fine particles (plastic beads). However, resin fine particles are preferable from the viewpoint of easy adjustment of the refractive index difference from the transparency and the antiglare hard coat layer. As the material for forming such resin fine particles, vinyl chloride resin, (meth) acrylic resin (refractive index 1.49), polystyrene resin (refractive index 1.54), melamine resin (refractive index 1.57), polyethylene Resins, polycarbonate resins, acrylic-styrene copolymer resins and the like can be mentioned. These resins include cross-linked resins. In the acrylic-styrene copolymer resin, the refractive index can be arbitrarily adjusted by changing the copolymerization ratio of both monomers.

  The translucent fine particles are preferably monodispersed with a uniform particle diameter in order to uniformly scatter or diffuse light in the antiglare hard coat layer and on the surface thereof. The average particle diameter of the light-transmitting fine particles is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 1 to 10 μm in order to sufficiently exhibit its function. When this average particle diameter is less than 0.1 μm, the antiglare property on the surface of the antiglare hard coat layer tends to be insufficient. On the other hand, when it exceeds 20 μm, the haze value of the antiglare hard coat layer becomes too high, and the transparency tends to be impaired.

  The ratio of the average particle diameter of the translucent fine particles to the thickness of the antiglare hard coat layer is preferably 10 to 100%. When this ratio is less than 10%, the amount of translucent fine particles added to form desired irregularities on the surface of the antiglare hard coat layer is increased, and the haze value is increased, so that the image clarity is deteriorated. Tend to. On the other hand, when it exceeds 100%, the unevenness on the surface of the antiglare hard coat layer becomes too large, so that the haze value becomes large, image sharpness is deteriorated, and glare is increased.

  The content of the translucent fine particles is usually 1 to 70 parts by mass, preferably 2 to 60 parts by mass, more preferably 3 to 50 parts by mass, and most preferably 30 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin. 40 parts by mass. When the content of the light-transmitting fine particles is less than 1 part by mass, the function of the light-transmitting fine particles cannot be sufficiently exhibited, and satisfactory antiglare properties cannot be obtained. On the other hand, when the amount is more than 70 parts by mass, the haze value of the antiglare hard coat layer becomes too high, and when the antiglare antireflection film is placed on the display surface, image recognizability such as whitening is lowered.

The inorganic fine particles express the function of adjusting the refractive index of the cured product of the binder, and the function of adjusting the antiglare property by suppressing the sedimentation of the translucent fine particles or floating on the surface. Among inorganic fine particles, colloidally dispersed inorganic fine particles and inorganic oxide fine particles are particularly preferable. Examples of the material for forming the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide, indium oxide, and antimony oxide. Silica sol is particularly preferable in consideration of the refractive index, price, and the like. The silica sol may be surface-modified as necessary. The average particle size of the inorganic fine particles is preferably 0.001 or more and less than 0.1 μm, and more preferably 0.01 to 0.1 μm. When this average particle diameter is smaller than 0.001 μm, the function of adjusting the refractive index of the cured product of the binder and the function of adjusting the antiglare property cannot be sufficiently exhibited. On the other hand, when the thickness is 0.1 μm or more, the haze value tends to increase, and a phenomenon such as whitening increases, which is not preferable.

Here, the refractive index of the active energy ray curable resin is generally about 1.5, which is about the same as that of glass, but the refractive index of the active energy ray curable resin is high in comparison with the refractive index of the translucent fine particles. In this case, it is preferable to use silica (SiO ₂ , refractive index 1.45) which is an inorganic fine particle having a low refractive index. Conversely, when the refractive index of the active energy ray-curable resin is low, titanium dioxide (TiO ₂ , refractive index 2.3 to 2.7), yttrium oxide (Y ₂ O ₃ ), which are inorganic fine particles having a high refractive index. Refractive index 1.87), lanthanum oxide (La ₂ O ₃ , refractive index 1.95), zirconium oxide (ZrO ₂ , refractive index 2.05), alumina (Al ₂ O ₃ , refractive index 1.63), etc. It is preferable to use it. In these cases, the inorganic fine particles are added to such an extent that the antiglare hard coat layer forming composition can form a film and an antiglare hard coat layer is obtained.

  The content of the inorganic fine particles is usually 50 to 150 parts by weight, preferably 60 to 130 parts by weight, more preferably 70 to 120 parts by weight, and most preferably 80 to 100 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin. Part. When this content is less than 50 parts by mass, the antiglare hard coat layer cannot obtain sufficient antiglare properties. On the other hand, when it exceeds 150 parts by mass, the haze value of the antiglare hard coat layer becomes too high, and when an antiglare antireflection film is placed on the display surface, image recognition such as whitening is deteriorated.

  The diluting solvent used in the preparation of the antiglare hard coat layer forming composition or binder is mainly used for applying the antiglare hard coat layer forming composition on the transparent substrate film. It is used for adjusting the viscosity of the layer forming composition or the binder and is not particularly limited as long as it is non-polymerizable. Diluent solvents such as toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, dialkyl Examples include acetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, decane, dodecane, propylene glycol monomethyl ether, and 3-methoxybutanol.

  The fluorine-containing curable coating liquid is a hollow silica fine particle (hereinafter, modified) having a film-forming property and a fluorine-containing compound having a polymerizable double bond and a silane coupling agent represented by the following chemical formula (1). Also referred to as hollow silica fine particles). In the present invention, both acryl and methacryl are referred to as (meth) acryl.

(In the formula, Z is a (meth) acryloyloxy group, R1 is an alkylene group having 1 to 4 carbon atoms, and R2 is a hydrogen atom, a methyl group or an ethyl group.)

  In fluorine-containing compounds, fluorine atoms (also referred to simply as fluorine in the present invention) have a very low polarizability, so fluorine-containing monomers have low molecular cohesive force and can obtain low surface energy after film formation. The film has a property of being poor in film formability. Here, the film formability represents the property that a fluorine-containing cured film (hereinafter also simply referred to as a film) is formed without being repelled when applied on a substrate such as a synthetic resin film. It is judged that a film having a uniform thickness can be formed with good thickness when the solution diluted in step 1 is applied to a substrate and heated to remove the solvent. For example, when the trifluoromethyl group is oriented, the critical surface tension is 6 dyn / cm, while the tetrafluoroethylene group is 18 dyn / cm, so that fluorine in the form of a methylene fluoride group or a fluorinated methine group is used. The film-formability is improved by introducing. Further, from the viewpoint of increasing the cohesive force of molecules, a technique of polymerizing is also effective. Therefore, as the fluorine-containing compound having the film forming property and having a polymerizable double bond, a fluorine-containing monomer having a structure in which a fluorine atom is introduced into the molecule as a methylene fluoride group or a fluorinated methine group, Examples thereof include a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond.

  In the fluorine-containing monomer having a structure in which the fluorine atom is introduced into the molecule as a methylene fluoride group or a fluorinated methine group, almost all of the fluorine atoms are introduced into the molecule as a methylene fluoride group or a fluorinated methine group. As long as it is a monomer, all known monomers can be used. That is, the polymerizable double bond may be either one (monofunctional) monomer, two or more (polyfunctional) monomers, or a mixture thereof. These fluorine-containing compounds can increase the strength and hardness of the film obtained by curing the fluorine-containing curable coating liquid, and can improve the scratch resistance and wear resistance of the film surface. Among the fluorine-containing compounds, a fluorine-containing polyfunctional (meth) acrylic acid ester is preferable because a crosslinked structure can be formed and the strength and hardness of the cured film are high.

  Specific examples of the fluorine-containing polyfunctional (meth) acrylic acid ester include, for example, 1,3-bis {(meth) acryloyloxy} -2,2-difluoropropane, 1,4-bis {(meth) acryloyloxy}. -2,2,3,3-tetrafluorobutane, 1,5-bis {(meth) acryloyloxy} -2,2,3,3,4,4-hexafluoropentane, 1,6-bis {(meta ) Acryloyloxy} -2,2,3,3,4,4,5,5-octafluorohexane, 1,7-bis {(meth) acryloyloxy} -2,2,3,3,4,4, 5,5,6,6-decafluoroheptane, 1,8-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5,6,6,7,7-dodeca Fluorooctane, 1,9-bis {(meth) acrylo Ruoxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorononane, 1,10-bis {(meth) acryloyloxy} -2 , 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane, 1,11-bis {(meth) acryloyloxy} -2 , 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10-octadecafluoroundecane, 1,12-bis {(meth) acryloyl Oxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-eicosafluorododecane, 1, 8-bis {(meth) acryloyloxy} -2,7-dihydroxy-4,4,5,5-tetrafluorooctane, 1,7-bis {( Ta) acryloyloxy} -2,8-dihydroxy-4,4,5,5-tetrafluorooctane, 2,7-bis {(meth) acryloyloxy} -1,8-dihydroxy-4,4,5,5 -Tetrafluorooctane, 1,10-bis {(meth) acryloyloxy} -2,9-dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, 1,9-bis { (Meth) acryloyloxy} -2,10-dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, 2,9-bis {(meth) acryloyloxy} -1,10- Dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, 1,2,7,8-tetrakis {(meth) acryloyloxy} -4,4,5,5-tetrafluorodecane 1, 2, 8 , 9-Tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6-hexafluorononane, 1,2,9,10-tetrakis {(meth) acryloyloxy} -4,4,5 , 5,6,6,7,7-octafluorodecane, 1,2,10,11-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6,7,7,8, 8-decafluoroundecane, 1,2,11,12-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane 1,10-bis (α-fluoroacryloyloxy) -2,9-dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, 1,9-bis (α-fluoroacryloyl) Oxy) -2,10-dihydroxy-4 , 4,5,5,6,6,7,7-octafluorodecane, 2,9-bis (α-fluoroacryloyloxy) -1,10-dihydroxy-4,4,5,5,6,6 7,7-octafluorodecane, 1,2,9,10-tetrakis (α-fluoroacryloyloxy) -4,4,5,5,6,6,7,7-octafluorodecane, 1,2,11 , 12-tetrakis (α-fluoroacryloyloxy) -4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane and the like. In use, these are used alone or as a mixture.

  The fluorine-containing polyfunctional (meth) acrylic acid ester is produced by a known method. For example, a ring-opening reaction between a corresponding fluorine-containing epoxy compound and (meth) acrylic acid, a corresponding fluorine-containing polyhydric alcohol, or a fluorine-containing (meta) group having a hydroxyl group (hydroxyl group) obtained as an intermediate by the ring-opening reaction. ) Produced by an esterification reaction between an acrylic ester and (meth) acrylic chloride.

  The solvent-soluble fluorine-containing reactive polymer having a polymerizable double bond has a main chain derived from a fluorine-containing ethylenic monomer and has a reactive group for crosslinking and curing. As the solvent-soluble solvent, ester solvents such as ethyl acetate and propyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as isopropyl alcohol and 2-butanol are preferable. Examples of the reactive group include a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and an epoxy group. Such a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond has a high molecular weight, so it has good film forming properties while containing fluorine, and is crosslinked and cured using reactive groups after film formation. By doing so, a solvent-insoluble cured layer can be obtained.

  Such a solvent-soluble fluorine-containing reactive polymer having a polymerizable double bond usually has a content of a group having a polymerizable double bond of 1 to 20% by mass, preferably 5 to 15% by mass. Weight) The average molecular weight is usually 1 to 500,000, preferably 3 to 200,000. Specific examples of the fluorine-containing reactive polymer include those disclosed in republished patent WO02 / 018457.

  The content of the fluorine-containing compound having film-forming properties and having a polymerizable double bond is preferably 40 to 80% by mass in the total amount (solid content) with the modified hollow silica fine particles. More preferably, it is -60 mass%. When the content of the fluorine-containing compound is less than 40% by mass, the strength and hardness of the film obtained by curing the fluorine-containing curable coating liquid tend to be insufficient, and the film surface has scratch resistance and abrasion resistance. descend. On the other hand, when the content exceeds 80% by mass, the content of the modified hollow silica fine particles is relatively decreased, the balance is deteriorated, the scratch resistance and wear resistance of the coating surface are lowered, and the reflectance of the coating is also increased.

  Since the hollow silica fine particles modified by the silane coupling agent represented by the chemical formula (1) contain air therein, the film formed by curing the fluorine-containing curable coating liquid has a low refractive index. In addition, the reflectance can be reduced, and the scratch resistance and abrasion resistance of the film can be improved by inorganic fine particles called silica fine particles. Examples of the silane coupling agent include γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, and γ-acryloyloxypropyltriethoxysilane.

  The hollow silica fine particles are fine particles in which silica (silicon dioxide, SiO2) is formed in a substantially spherical shape and has a hollow portion in the outer shell, and the average particle diameter is about 10 to 100 nm. The thickness of the outer shell of the hollow silica fine particles is about 1 to 50 nm, and the proportion of the hollow portion in the hollow silica fine particles is 10 to 60%. The refractive index of the hollow silica fine particles is a low refractive index of 1.1 to 1.4.

  The modification of the hollow silica fine particles with the silane coupling agent is performed as follows. First, for example, the above-mentioned silane coupling agent is added to and mixed with hollow silica fine particles dispersed in an organic solvent, and distilled water is added to this mixture to perform ordinary hydrolysis and condensation reactions. The solid content of the hollow silica fine particles is preferably 1 to 70% by mass, and more preferably 15 to 40% by mass. In this case, the order of adding the silane coupling agent is not particularly limited. As for the compounding quantity of the distilled water to mix, it is desirable that it is 3-5 times by mass with respect to a silane coupling agent. The operation for carrying out the hydrolysis reaction and the condensation reaction is carried out by refluxing the organic solvent for 3 to 7 hours under normal pressure with stirring.

  Examples of the organic solvent used for the modification of the hollow silica fine particles include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene. Examples of the hydrocarbons include amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more. The resulting modified hollow silica fine particles can be isolated by centrifugation or the like, but can also be subjected to a subsequent step while the organic solvent is present.

  The content of hollow silica fine particles (referred to as modified hollow silica fine particles) obtained by modification in this way is 20 to 60% by mass and 40 to 60% by mass in the total amount with the fluorine-containing compound. Is desirable. When the content is less than 20% by mass, the content of the modified hollow silica fine particles is small, and it becomes impossible to sufficiently reduce the refractive index and the reflectance of the resulting film, and the scratch resistance and Wear resistance is reduced. On the other hand, when it exceeds 60% by mass, the excessive modified hollow silica fine particles cannot react with the fluorine-containing compound, and the polymer remains, so that the scratch resistance and wear resistance of the fluorine-containing cured film surface tend to decrease. Indicates. As a result of the copolymerization and bonding of the (meth) acryloyloxy group contained in the silane coupling agent of the modified hollow silica fine particles and the polymerizable double bond of the fluorine-containing compound, the function of the modified hollow silica fine particles and the fluorine-containing compound are obtained. Are expressed synergistically and continuously.

The modified hollow silica fine particles will be further described. The modified hollow silica fine particles are produced by subjecting the surface of the hollow silica fine particles having an average particle diameter of 5 to 100 nm and a specific surface area of 50 to 1000 m ² / g with the silane coupling agent. Is done. Specifically, an organosilyl group (monoorganosilyl, diorganosilyl, or triorganosilyl group) is bonded to the surface of the hollow silica fine particle by a hydrolysis reaction between the silanol group on the surface of the hollow silica fine particle and the silane coupling agent. In addition, it has an organic group directly bonded to a large number of silicon atoms on its surface.

  Since the modified hollow silica fine particles are modified by the silane coupling agent, an excellent effect not found in conventional silica fine particles or hollow silica fine particles can be exhibited. This excellent effect is mainly based on the fact that the modified hollow silica fine particles are excellent in compatibility with the fluorine-containing compound. For this reason, when the modified hollow silica fine particles are mixed with a fluorine-containing compound, aggregation of the modified hollow silica fine particles can be suppressed, and a film having no transparency and excellent transparency can be obtained. Further, in the film, the polymerizable double bond group of the silane coupling agent and the fluorine-containing compound is chemically bonded to form a strong film, so that the scratch resistance and wear resistance of the film can be dramatically improved. . In addition, since the modified hollow silica fine particles contain a hollow portion (cavity) inside, the coating obtained by curing the coating liquid combined with the fluorine-containing compound has a lower refractive index and lower reflectance than the conventional coating. .

Specifically, the hollow silica fine particles used as the raw material for the modified hollow silica fine particles can be produced through the following first to fourth steps.
That is, in the first step, an aqueous solution of silicate or an acidic silicate solution and an aqueous solution of an alkali-soluble inorganic compound in an alkaline aqueous solution having a pH of 10 or more, or an alkaline aqueous solution having a pH of 10 or more in which seed particles are dispersed as necessary. At the same time, a core particle dispersion is prepared in which the molar ratio of silica to an inorganic compound other than silica is in the range of 0.3 to 1.0.

  Next, in the second step, a silica source is added to the core particle dispersion to form a first silica coating layer on the core particle surface.

  Next, in the third step, an acid is added to the dispersion in which the first silica coating layer is formed to remove a part or all of the elements constituting the core particles.

  Finally, in the fourth step, an aqueous alkali solution and an organosilicon compound or a partial hydrolyzate thereof are added to the dispersion of the hollow silica fine particles obtained in the third step, and the second silica coating layer is formed on the hollow silica fine particles. Form.

  Furthermore, it is preferable to add a fifth step in which the hollow silica fine particle dispersion obtained in the fourth step is hydrothermally treated at 200 ° C. for at least 5 hours. By this hydrothermal treatment, hollow silica fine particles having a dense outer shell can be obtained. By densifying the outer shell, it becomes difficult to adsorb moisture, and the water resistance of the hollow silica fine particles can be improved. As a result, the modified hollow silica fine particles obtained by modifying the hollow silica fine particles and the fluorine-containing compound It is possible to improve the water resistance of a film obtained by curing a fluorine-containing curable coating liquid in combination. The upper limit of the hydrothermal treatment temperature is preferably 280 ° C. Even when the temperature exceeds 280 ° C., the outer shell of the hollow silica fine particles is not further densified, and the hollow silica fine particles may aggregate instead. The hydrothermal treatment time varies depending on the hydrothermal treatment temperature, but is preferably 5 hours or more and 20 hours or less, more preferably 10 hours or more and 20 hours or less. A hydrothermal treatment time of less than 5 hours is not preferable because the outer shell cannot be sufficiently densified. On the other hand, if it exceeds 20 hours, the outer shell of the hollow silica fine particles is not further densified, and the productivity of the hollow silica fine particles is reduced, which is not industrially preferable.

  In the method for producing modified hollow silica fine particles, an organosol having a silica concentration of 1 to 70% by mass is prepared, and the silane coupling agent and the alkali catalyst are added within a range of 30 to 300 ° C. The said silane coupling agent is made to react with hollow silica fine particles on the conditions whose quantity is 0.1-50 mass%. In the method for producing an organosol, a silica sol composed of hollow silica fine particles prepared using water as a dispersion medium is solvent-substituted to obtain an organosol. An organic solvent is used as a type of the solvent for solvent substitution. The type of organic solvent is not particularly limited as long as it does not adversely affect the surface coating of the hollow silica fine particles by the silane coupling agent. As examples of such organic solvents, solvents such as alcohols, glycols, esters, ketones, nitrogen compounds, and aromatics can be used. Usually, alcohols such as methanol, ethanol and isopropyl alcohol are selected.

  The addition amount of the silane coupling agent is usually 1 to 50 parts by mass and preferably 3 to 25 parts by mass with respect to 100 parts by mass of the hollow silica fine particles. If the amount added is less than 1 part by mass, the proportion of untreated hollow silica fine particles increases, and if it exceeds 50 parts by mass, the silane coupling agent becomes excessive, which is not economical.

  The kind of the alkali catalyst is not particularly limited, and ammonia, an alkali metal hydroxide, an amine compound, and the like are preferably used. These alkalis may be added in the form of an aqueous solution. The addition amount of the alkali catalyst is not particularly limited, and is preferably 20 to 2000 ppm with respect to the organosol in which the hollow silica fine particles are dispersed, although it depends on the kind of the alkali catalyst. When this addition amount is less than 20 ppm, the reaction of the silane compound on the surface of the hollow silica fine particles may not sufficiently proceed. On the other hand, when it exceeds 2000 ppm, the dispersibility when the hollow silica fine particles are dispersed in the binder may be reduced due to the excess alkali, and there is a problem that the alkali catalyst remains in the composition. .

  The amount of water in the reaction solution is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, based on the amount of silica. If the moisture content is in the range of 10 to 50% by mass, the surface of the hollow silica fine particles reacts with the silane coupling agent to effect surface treatment effectively. When the water content is less than 10% by mass, the surface treatment efficiency is low and stable surface treatment is not performed, and when it exceeds 50% by mass, the tendency of the silane coupling agents to react with each other increases, resulting in the surface treatment of the hollow silica fine particles. It becomes insufficient.

  About reaction temperature when making a silane coupling agent react with hollow silica fine particles, if it is less than 30 degreeC, reaction rate will be slow and it is not practical. On the other hand, when the boiling point of the solvent of the organosol is exceeded, the evaporation of the solvent may cause an increase in the water content, etc., but this is not preferable. However, when the reaction is performed using a pressure vessel, the temperature is up to 300 ° C. Can be reacted. The reaction temperature is preferably in the temperature range from 40 ° C. to less than the boiling point of the solvent.

  The reaction time for reacting the silane coupling agent with the hollow silica fine particles is less than 0.1 hour, and the reaction may not sufficiently proceed, which is not practical. On the other hand, even if the reaction is carried out for more than 100 hours, no improvement is seen in the yield and the like, and it is not necessary to continue the reaction further. This reaction time is preferably 3 to 30 hours. The surface-treated hollow silica fine particles may be further substituted with an organic solvent using the same method as described above, if necessary.

  The average particle diameter of the modified hollow silica fine particles is preferably 5 to 100 nm. Modified hollow silica fine particles having an average particle diameter in this range can obtain a transparent film. It is difficult to produce modified hollow silica fine particles having an average particle size of less than 5 nm. On the other hand, when the thickness exceeds 100 nm, light scattering is increased, and reflection is increased in the thin film, so that the antireflection function cannot be exhibited. A more preferable average particle diameter range of the modified hollow silica fine particles is 30 to 80 nm.

The specific surface area of the modified hollow silica fine particles is preferably in the range of 50 to 1000 m ² / g in order to obtain the dispersibility and stability of the modified hollow silica fine particles in the solvent or film formation. When the specific surface area is less than 50 m ² / g, it is difficult to obtain modified hollow silica fine particles having a low refractive index. On the other hand, when it exceeds 1000 m ² / g, the dispersion stability of the modified hollow silica fine particles is lowered, which is not desirable. A more preferable range of the specific surface area of the modified hollow silica fine particles is 50 to ²⁰⁰ m ² / g.

  In the modified hollow silica fine particles, the amount of the silane coupling agent bonded to the hollow silica fine particles by the modification treatment can be easily known by a thermal mass measurement method (TG). This thermal mass measurement method (Thermogravimetry Analysis) measures the mass change of the sample with respect to the temperature rise (or fall) of the sample, and the mass change curve with respect to the temperature change is called a TG curve. ing.

  The modified hollow silica fine particles preferably exhibit a mass loss of 2% by mass or more in thermal mass measurement in a temperature range of 200 to 500 ° C. In a fluorine-containing curable film formed by blending modified hollow silica fine particles having a thermal mass reduction of less than 2% by mass, whitening occurs and scratch resistance and wear resistance are insufficient. About thermal mass reduction | decrease, what shows the thermal mass reduction | decrease of 3 mass% or more in a temperature range 200-500 degreeC is further more preferable. However, if the thermal mass reduction exceeds 10% by mass, the reaction between the particles tends to occur, so that the stability as the sol of the modified hollow silica fine particles and the stability as the fluorine-containing cured coating liquid are not preferable. .

  The water resistance of a fluorine-containing cured film can be evaluated by the reflectance of the film. In a film having no water resistance, when water droplets are left on the film for 30 minutes, moisture is adsorbed and the refractive index increases, resulting in an increase in the reflectance of light on the film surface. In the fluorine-containing curable film obtained by using hollow silica fine particles that have been subjected to hydrothermal treatment for 5 hours or more, even when water droplets are left on the film for 30 minutes, the change in light reflectance on the film surface before and after being left is left. , 0.3% or less.

  The fluorine-containing curable coating liquid preferably further contains a fluorine-containing (meth) acrylic acid ester represented by the following chemical formula (2) that does not have film-forming properties.

(In the formula, X and Y are either a (meth) acryloyloxy group or a hydroxyl group, and at least one is a (meth) acryloyloxy group.)

  Although the above fluorine-containing (meth) acrylic acid ester itself does not exhibit film-forming properties, it exhibits affinity for the fluorine-containing compound having the film-forming properties and does not deteriorate the film-forming properties. . For this reason, the fluorine-containing curable coating liquid can exhibit excellent film forming properties. Moreover, the fluorine-containing (meth) acrylic acid ester represented by the chemical formula (2) having no film-forming property is a component that can exhibit high antifouling properties. Furthermore, since the fluorine-containing (meth) acrylic acid ester has a polymerizable double bond, it has the film-forming property, and undergoes a copolymerization reaction with a fluorine-containing compound having a polymerizable double bond, Become.

  Such fluorine-containing (meth) acrylic acid ester has a fluoroalkyl group having 10 carbon atoms having a trifluoromethyl group (CF3-) at its terminal, and this fluorine-containing (meth) acrylic acid ester is trivalent even in a small amount. Fluoromethyl groups are oriented on the surface. In particular, the trifluoromethyl group is sufficiently oriented on the surface even in a film made of a fluorine-containing compound having a film forming property and a high fluorine content having a polymerizable double bond. Therefore, the obtained fluorine-containing cured film can exhibit properties such as antifouling property and low refractive index. On the other hand, in the fluorine-containing (meth) acrylic acid ester having a fluoroalkyl group having 9 or less carbon atoms, the terminal trifluoromethyl group is not sufficiently oriented on the surface, and the effect cannot be obtained. The fluorine-containing (meth) acrylic acid ester having a fluoroalkyl group having 11 or more carbon atoms is difficult to produce and obtain. In other words, only fluorine-containing (meth) acrylate having a C10 fluoroalkyl group exhibits a specific function compared to other fluorine-containing (meth) acrylates having fluoroalkyl groups of other chain lengths. It can be done.

  Specifically, as the fluorine-containing (meth) acrylic acid ester represented by the chemical formula (2), 1- (meth) acryloyloxy-2-hydroxy-4,4,5,5,6,6,7,7,8 , 8, 9, 9, 10, 10, 11, 11, 12, 12, 13, 13, 13-heneicosafluorotridecane, 2- (meth) acryloyloxy-1-hydroxy-4, 4, 5, 5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluorotridecane and 1,2-bis (meta Acrylyloxy-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosafluoro And tridecane. These fluorine-containing (meth) acrylic acid esters can be used alone or as a mixture.

  The content of the fluorine-containing (meth) acrylic acid ester represented by the chemical formula (2) is preferably 0.5 to 30% by mass with respect to the total amount of the fluorine-containing compound and the modified hollow silica fine particles. When this content is less than 0.5% by mass, the antifouling property of the fluorine-containing cured film surface is lowered, and when it exceeds 30% by mass, it is difficult to obtain a transparent uniform and good fluorine-containing cured film. Tend to be.

  In addition, the fluorine-containing curable coating liquid may contain a diluting solvent as long as the reaction is not inhibited for the purpose of adjusting the viscosity of the coating liquid and surface leveling after coating. Examples of the diluting solvent include alcohol solvents such as methanol, ethanol, isopropanol, 2-butanol and isobutanol, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Furthermore, in the fluorine-containing curable coating liquid, for the purpose of adjusting the fluorine content, polyfunctional (meth) acrylic acid esters not containing fluorine, such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (Meth) acrylate and the like can be mixed and used at a ratio of 60% by mass or less. When the blending amount exceeds 60% by mass, the refractive index of the film is increased, which is not preferable when used as, for example, an antiglare antireflection film.

  The photopolymerization initiator is used for initiating polymerization by irradiating an active energy ray-curable resin with active energy rays such as ultraviolet rays, and a known compound is used. Examples of such photopolymerization initiators include benzophenones, acetophenones, α-amyloxime esters, Michler benzoyl benzoate, tetramethylchuram monosulfide, and thioxanthones. Specifically, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy-1,2-diphenylethane-1 -One, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, α-amyloxime ester, Michler Emissions benzoyl benzoate, tetramethylthiuram monosulfide, and the like.

  The content of the photopolymerization initiator with respect to the active energy ray-curable resin is preferably 0.01 to 20 parts by mass and preferably 1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin. Is more preferable. When this content is less than 0.01 part by mass, the cured product (coating film) obtained from the antiglare hard coat layer forming composition is not completely cured and is not preferable because curing is insufficient. . On the other hand, if it exceeds 20 parts by mass, curing is sufficient, but no further effect can be expected, and the amount is unnecessarily large and wasted.

  The blending ratio of the photopolymerization initiator to the fluorine-containing curable coating liquid is preferably 0.1 to 20% by mass with respect to the solid content in the fluorine-containing curable coating liquid. When the blending ratio of the photopolymerization initiator is less than 0.1% by mass, the polymerization curing of the fluorine-containing curable coating liquid becomes insufficient, and when it exceeds 20% by mass, the refractive index of the film after polymerization curing increases. Therefore, it is not preferable.

  The composition for forming an antiglare hard coat layer is applied on a transparent substrate film, and then cured by irradiating an active energy ray so that the antiglare hard coat layer is laminated on the transparent substrate film. .

  The low refractive index layer polymerizes and cures the fluorine-containing curable coating liquid with high energy rays such as electron beams, or polymerizes and cures the fluorine-containing curable coating liquid in the presence of a thermal decomposition type polymerization initiator or photopolymerization initiator. It is obtained by doing. In these, the method of apply | coating the fluorine-containing sclerosing | hardenable coating liquid which added the photoinitiator to the base-material surface, and irradiating an ultraviolet irradiation in inert gas atmosphere to the formed film | membrane and polymerizing and hardening is preferable.

  The formation method of each layer is not particularly limited, and a commonly applied coating method such as a roll coating method, a spin coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, a knife coating method, or a die coating method. Any known method such as a gravure coating method, a curtain flow coating method, a reverse coating method, a kiss coating method, or a comma coating method may be employed. In application, in order to improve adhesion, pretreatment such as corona discharge treatment can be applied to the surface of the transparent substrate film in advance.

  As an active energy ray source used for irradiation of active energy rays, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive element or the like is used.

It is preferable that the irradiation amount of the active energy ray of the composition for forming an antiglare hard coat layer is 50 to 5000 mJ / cm ² as an integrated light amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is less than 50 mJ / cm ² , curing of the composition for forming an antiglare hard coat layer becomes insufficient, which is not preferable. On the other hand, when it exceeds 5000 mJ / cm ² , the active energy ray-curable resin tends to be colored, which is not preferable.

  The irradiation amount of the active energy ray of the fluorine-containing curable coating liquid is preferably 10 mJ or more, and more preferably 100 mJ or more. The upper limit of the irradiation amount is determined according to a conventional method in this type of ultraviolet irradiation. When the irradiation dose is less than 10 mJ, sufficient hardness cannot be obtained for the film obtained after polymerization and curing. Further, post-curing by ultraviolet irradiation may be performed after the polymerization curing. In order to obtain good polymerization curability, it is preferable to suppress the oxygen concentration at the time of ultraviolet irradiation to 1000 ppm or less by blowing an inert gas such as nitrogen or argon during both polymerization curing and post-curing. The film after curing has a refractive index of preferably 1.5 or less, particularly preferably 1.45 or less, and its lower limit is about 1.3 in consideration of uses such as an antiglare antireflection film. The film thickness is preferably 50 to 200 nm. When this film thickness is less than 50 nm or exceeds 200 nm, the anti-reflection effect decreases.

  This antiglare antireflection film may be one in which one or more functional layers are provided between the low refractive index layer and the antiglare hard coat layer. Examples of the functional layer include a layer made of a high refractive index material, a hard coat layer, an antistatic layer, an ultraviolet ray preventing layer, an antiglare layer for antiglare, a near infrared ray preventing layer, and an electromagnetic wave shielding layer. When a layer made of a high refractive index material is provided as a functional layer in order to enhance the antireflection effect, the high refractive index material preferably has a refractive index of 1.55 or more, and the film thickness is 50 to 500 nm. Is preferred. The low-refractive index material layer and the high-refractive index material layer may be provided one by one on the substrate, but a plurality of layers may be provided. When providing a plurality of layers, the outermost layer is provided with the low refractive index layer. By laminating layers having different refractive indexes with an optical film thickness of about 100 nm, the interface reflection light generated at the thin film interface interferes with the reflection light on the outermost surface to cancel out, thereby producing a dereflection effect. it can. Therefore, layers having different refractive indexes are laminated on the substrate surface in order from the substrate side, and a low refractive index layer made of a fluorine-containing cured film is provided on the outermost surface.

  The thickness of the low refractive index layer is not particularly limited, but is preferably ¼ (about 100 nm) of the visible light wavelength because surface reflection is reduced by the interference effect and the transmittance is improved. Further, from the viewpoint of obtaining a suitable antireflection effect, the low refractive index layer preferably has a low refractive index, but if it is too low, the reflected light is colored, which is not preferable. Therefore, in consideration of antireflection and coloring prevention, the refractive index of the low refractive index layer is preferably 1.30 to 1.50, and particularly when the antireflection effect is emphasized, More preferably, it is 1.30 to 1.45.

  In the antiglare antireflection film thus obtained, the refractive index difference between the cured binder and the translucent fine particles is 0 to 0.05, preferably 0 to 0.03, in order to improve image sharpness. More preferably, it is set to 0-0.01. By setting the refractive index difference between the cured binder and the light-transmitting fine particles in such a range, light scattering inside the anti-glare hard coat layer can be suppressed, and light transmittance is improved. Can be made. When this difference in refractive index is larger than 0.05, light scattering inside the antiglare hard coat layer is increased, and transmission of light is hindered, resulting in poor image clarity.

  Further, the minimum reflectance wavelength at which the reflectance in the visible region at 5 ° regular reflection of the antiglare antireflection film is the lowest is 450 nm to 560 nm, preferably 460 nm to 550 nm, more preferably 470 nm to 540 nm. It is set to either. By setting the minimum reflectance wavelength in such a range, the reflection color of the antiglare antireflection film is controlled to be close to black, and the blackness in the black display image is improved.

  Moreover, it is preferable that the reflectance which shows reflection of a glare-proof antireflection film is 5% or less, and it is more preferable that it is 3.5% or less. This visibility reflectance is obtained by measuring the reflectance (%) using a spectrophotometer equipped with a 5 ° specular reflection measuring device.

  In addition, in the antiglare antireflection film, in order to exhibit light diffusibility, it is necessary to adjust the uneven shape of the antiglare antireflection film surface. That is, regarding the uneven shape of the antiglare antireflection film surface, the arithmetic average roughness (Ra) defined in JIS B 0601-1994 on the antiglare antireflection film surface is 0.01 to 0.30 μm, and 0 It is preferably 0.01 to 0.20 μm, and most preferably 0.05 to 0.15 μm. By setting the surface roughness Ra of the antiglare antireflection film in such a range, when the antiglare antireflection film is placed on a display for image display, an appropriate light diffusibility is maintained, Moreover, there is no glare and it is possible to ensure good visibility of the display.

  When Ra is less than 0.01 μm, the light diffusibility on the surface of the antiglare and antireflection film is insufficient and the antiglare property is deteriorated. On the other hand, when Ra exceeds 0.30 μm, the haze value of the antiglare antireflection film is increased, whitening occurs, and the image sharpness deteriorates.

  Moreover, the average interval (Sm) of the unevenness | corrugation prescribed | regulated to JISB0601-1994 in the anti-glare antireflection film surface needs to be 10-300 micrometers, and it is preferable that it is 30-200 micrometers, 100-180 micrometers. It is particularly preferred that If this Sm is in the range of 10 to 300 μm, glare is suppressed when an antiglare antireflection film is placed on a display for image display, and good visibility of the display can be secured. . Sm represents the interval between the irregularities in the direction along the surface of the antiglare antireflection film, and this interval is important for suppressing glare particularly on the antiglare antireflection film surface. When Sm is less than 10 μm, the light diffusibility on the surface of the antiglare and antireflection film is insufficient and glare cannot be suppressed. On the other hand, when Sm exceeds 300 μm, the haze value of the antiglare antireflection film is increased to cause a whitening phenomenon, and the desired image sharpness cannot be obtained.

About the relationship between said arithmetic mean roughness (Ra) and the average space | interval (Sm) of an unevenness | corrugation, it is preferable that ratio of Sm / Ra is 1000-1300. That is, the interval of the unevenness is about 10 ³ times the height of the irregularity, carefully first diffusion of light irregularity is formed in such a shape, it is possible to suppress the glare. When the ratio of Sm / Ra is smaller than 1000, the interval between the projections and depressions with respect to the height of the projections and depressions is narrowed, the haze value tends to increase, and the image sharpness is deteriorated. On the other hand, when the ratio of Sm / Ra is larger than 1300, the interval of the unevenness with respect to the unevenness height becomes too wide, and the light diffusion tends to be insufficient.

  A haze value is applied as an index of antiglare property. The haze value (haze value, haze) is measured in accordance with JIS K 7136, and is a value obtained by dividing the scattered light transmittance by the total light transmittance in percentage. The haze value is preferably 1 to 50%, more preferably 1 to 30%, particularly preferably 1.5 to 10%, and most preferably 1.5 to 5%. . When the haze value is less than 1%, the antiglare effect is insufficient, and it is difficult to prevent the reflection of an image when the antiglare antireflection film is disposed on the display surface. On the other hand, if it is larger than 50%, the display image becomes white when the contrast is lowered or the antiglare antireflection film is arranged on the display surface.

  The haze value is due to external haze caused by external scattering due to irregularities on the surface of the antiglare hard coat layer, and the difference in refractive index between the light-transmitting fine particles present inside the antiglare hard coat layer and the antiglare hard coat layer. Can be classified as internal haze due to internal scattering. Since the anti-glare antireflection film aims to suppress image clarity and glare while maintaining anti-glare properties, adjustment of external haze and internal haze is important. Since the antiglare property is mainly caused by the external haze, the surface unevenness needs to be increased to some extent in order to exhibit the antiglare property. On the other hand, since image clarity and glare are correlated with external haze and internal haze, it is necessary to keep both low.

  Next, a display is comprised by providing the anti-glare antireflection film mentioned above in the outermost surface of the side which displays the image of a display. This display is provided with an antiglare and antireflection film, so that image reflection can be suppressed and visibility can be improved. Furthermore, since the unevenness of the antiglare antireflection film surface is set to a small range as described above with respect to the display pixel size, there is no lens action and the image visibility is excellent. Specifically, the display displays images on personal computers, word processors, televisions, mobile phones, mobile terminals, game machines, automatic cash withdrawals, cash dispensers, vending machines, navigation devices, security system terminals, etc. Members (CRT, plasma display, liquid crystal display, electroluminescence display, field emission display, projection display, toner-based display used for electronic paper, etc.) and the like. Examples of the display include glass cases such as show cases and show windows used for display for display, plastic cases, and the like.

Hereinafter, the embodiment will be described more specifically with reference to production examples, examples and comparative examples, but the present invention is not limited to the scope of these examples.
As shown in FIG. 1, the antiglare and antireflective film of this example is obtained by sequentially forming a hard coat layer 12 and a low refractive index layer 13 on one surface of a transparent substrate film 10. is there.

The reflectivity, reflectivity wavelength, surface roughness, haze value, image sharpness value, and glare in each example were measured by the following methods.
(1) Measurement of reflectance A spectrophotometer [trade name: U-best50, manufactured by JASCO Corporation] with a back surface roughened with sandpaper and a 5 ° specular reflection measuring device in order to remove the back surface reflection of the measurement surface. ] Was used to read the reflectance (%) at a wavelength of 600 nm.
(2) Measurement of minimum reflectance wavelength A spectrophotometer [trade name: U, manufactured by JASCO Corporation] with a back surface roughened with sandpaper to remove the back surface reflection of the measurement surface and equipped with a 5 ° specular reflection measuring device. -Best 50] was used to measure the reflectance and obtain a reflection spectrum. The wavelength at which the reflectance in the visible light region of the reflection spectrum is the lowest was read.
(3) Surface roughness Co., Ltd., manufactured by Kosaka Laboratory Co., Ltd., using a surface roughness measuring machine, Surfcoder SE500, conforming to JIS B 0601-1994, under conditions of a scanning range of 4 mm and a scanning speed of 0.2 mm / s. Then, the arithmetic average roughness Ra (μm) and the average interval Sm (μm) of the irregularities were measured.
(4) Haze value A haze value (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze value (%) as an optical property.
(5) Black Margin A black film using a black adhesive was pasted on the back surface and visually evaluated in a 1000 lux bright room.
1: sufficiently black 2: slightly tinted (white) 3: tinted (white) (6) Value of image definition Measurement of image definition based on JIS K 7105-1981 A value (%) of image definition was measured through an optical comb having a width of 2 mm using an apparatus (image clarity measuring device manufactured by Suga Test Instruments Co., Ltd., ICM-1T).
(7) Glare An anti-glare antireflection film was placed on the surface of a high-definition display or high-definition touch panel, and the glare was measured visually and evaluated in the following three stages.
1: No glare, 2: Slight glare, 3: Glare

(Production Example 1, Preparation of Modified Hollow Silica Sol as Inorganic Fine Particles)
A modified hollow silica sol was prepared according to the following first to fifth steps.
As the first step, a silica sol having an average particle diameter of 5 nm of silica (SiO ₂ ) having a concentration of 20% by mass and pure water were mixed to prepare a reaction mother liquor and heated to 80 ° C. The pH of this reaction mother liquor is 10.5, and 1.17% by mass sodium silicate aqueous solution as SiO ₂ and 0.83% by mass sodium aluminate aqueous solution as alumina (Al ₂ O ₃ ) are added to the reaction mother liquor. Added simultaneously. Meanwhile, the temperature of the reaction mother liquor was kept at 80 ° C. The pH of the reaction mother liquor rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate and remained almost unchanged thereafter. After completion of the addition, the reaction mother liquor was cooled to room temperature and filtered through an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ primary particle dispersion (core particle dispersion) having a solid content concentration of 20% by mass.

Next, as a second step, pure water is added to the SiO ₂ .Al ₂ O ₃ primary particle dispersion and heated to 98 ° C., and an aqueous sodium sulfate solution having a concentration of 0.5 mass% is maintained while maintaining this temperature. Added. Subsequently, an aqueous solution of sodium silicate having a concentration of 1.17% by mass as SiO ₂ and an aqueous solution of sodium aluminate having a concentration of 0.5% by mass as Al ₂ O ₃ were added, and a composite oxide fine particle dispersion (the core particles were subjected to 1) A fine particle dispersion having a silica coating layer was obtained. And this was filtered with the ultrafiltration membrane, and it was set as the complex oxide fine particle dispersion liquid of solid content concentration 13 mass%.

  As a third step, pure water was added to this composite oxide fine particle dispersion, and concentrated hydrochloric acid (35.5% by mass) was added dropwise to adjust the pH to 1.0, followed by dealumination. Subsequently, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt was separated with an ultrafiltration membrane to obtain an aqueous dispersion of silica-based fine particles (1) having a solid content concentration of 20% by mass.

As the fourth step, a mixture of the aqueous dispersion of the silica-based fine particles (1), pure water, ethanol and 28% by mass ammonia water is heated to 35 ° C., and then ethyl silicate (SiO ₂ 28% by mass). Was added to form a silica coating (second silica coating layer). Subsequently, while adding 5 L of pure water, it was filtered through an ultrafiltration membrane to prepare a dispersion of silica-based fine particles (2) having a solid content concentration of 20% by mass.

Finally, as a fifth step, the dispersion of silica-based fine particles (2) was again subjected to hydrothermal treatment at 200 ° C. for 11 hours. Then, it filtered with the ultrafiltration membrane, adding pure water 5L, and adjusted solid content concentration to 20 mass%. Then, using an ultrafiltration membrane, the dispersion medium of this dispersion was replaced with ethanol to obtain an organosol having a solid content concentration of 20% by mass. This organosol was an organosol (hollow silica sol A) in which hollow silica fine particles having an average particle diameter of 60 nm and a specific surface area of 110 m ² / g were dispersed.

200 g of the hollow silica sol A (silica solid content concentration: 20% by mass) was prepared, and the solvent was replaced with methanol in an ultrafiltration membrane. 100 g of organosol having a SiO ₂ content of 20% by mass (water content was SiO ₂ content) 0.5 mass%) was prepared. Thereto, a 28% by mass aqueous ammonia solution was added to 100 g of the organosol so as to be 100 ppm as ammonia, and mixed well. Further, γ-acryloyloxypropyltrimethoxysilane [trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd. 3.6 g was added to obtain a reaction solution. This was heated to 50 ° C. and heated at 50 ° C. for 6 hours with stirring. After completion of the heating, the reaction solution was cooled to room temperature, and further the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an organosol composed of coated hollow fine particles having a SiO ₂ concentration of 20% by mass. This organosol has an average particle size of 60 nm, a refractive index of 1.25, a porosity of 40 to 45%, a specific surface area of 130 m ² / g, and a mass reduction ratio by thermal mass measurement (TG) of 3.6%. It was an organosol in which hollow silica fine particles were dispersed.

(Production Example 2, Preparation of Composition for Low Refractive Index Layer)
50 parts by mass, 1,10-diaacryloyloxy-2,2,3,3,4,4,5,5,6 in terms of solid content of the organosol in which the modified hollow silica fine particles obtained in Production Example 1 were dispersed. , 6,7,7,8,8,9,9-hexadecafluorodecane (fluorine content 53 mass%) [manufactured by Kyoeisha Chemical Co., Ltd., trade name “16-FDA”] 50 parts by mass, photopolymerization started 5 parts by mass of an agent [manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 907] and 2000 parts by mass of isopropyl alcohol were mixed to obtain a composition for a low refractive index layer (fluorine-containing curable coating liquid).

(Production Example 3, Preparation of Antiglare Hard Coat Layer-Forming Composition)
51 parts by mass of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA], 49 parts by mass of silica sol [manufactured by Nissan Chemical Co., Ltd., XBA-ST, a mixed solvent of xylene and butanol, 30% by mass] As a photopolymerization initiator, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one [manufactured by Ciba Specialty Chemicals, Inc., Irgacure] 2959] 3 parts by mass and 83.4 parts by mass of methyl isobutyl ketone (MIBK) were mixed to prepare a binder, and fine particles of cross-linked acrylic resin (MX-500, manufactured by Soken Chemical Co., Ltd.) as translucent fine particles. 17 parts by mass of monodispersed fine particles having a uniform diameter and an average particle diameter of 5 μm) are mixed to form a composition for forming an antiglare hard coat layer. Prepared.

Example 1
The composition for forming an antiglare hard coat layer prepared in Production Example 3 is used as a transparent substrate film on a polyethylene terephthalate (PET) film having a thickness of 100 μm so that the dry film thickness becomes 6.2 μm using a roll coater. And dried at 80 ° C. for 2 minutes. Then, ultraviolet rays were irradiated with a 120 W high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) (integrated light amount 400 mJ / cm ² ) and cured to prepare an antiglare hard coat layer. The refractive index of the cured product obtained by curing the binder was 1.50, and the refractive index of the translucent fine particles was 1.49. Therefore, the difference in refractive index between the cured binder and the light-transmitting fine particles was 0.01.

After applying the composition for low refractive index layer prepared in Production Example 2 on the surface of the antiglare hard coat layer so that the thickness when dried becomes 0.090 μm, an ultraviolet irradiation device ( An anti-glare antireflection film was obtained by irradiating 400 mJ ultraviolet rays using a 120 W high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., curing the low refractive index layer composition, and forming a low refractive index layer. The refractive index of this low refractive index layer was 1.34.
The arithmetic average roughness (Ra) on the surface of the antiglare antireflection film was 0.13 μm, the average interval (Sm) of irregularities was 148 μm, and the haze value of the antiglare antireflection film was 2.8%.

(Example 2)
An antiglare hard coat layer was produced in the same manner as in Example 1.
After applying the composition for a low refractive index layer prepared in Production Example 2 on the surface of the antiglare hard coat layer so that the thickness when dried is 0.100 μm, an ultraviolet irradiation device ( An anti-glare antireflection film was obtained by irradiating 400 mJ ultraviolet rays using a 120 W high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., curing the low refractive index layer composition, and forming a low refractive index layer. The refractive index of this low refractive index layer was 1.34.
The arithmetic average roughness (Ra) on the surface of the antiglare antireflection film was 0.13 μm, the average interval (Sm) of irregularities was 148 μm, and the haze value of the antiglare antireflection film was 2.8%.

(Example 3)
An antiglare hard coat layer was produced in the same manner as in Example 1.
After applying the composition for a low refractive index layer prepared in Production Example 2 on the surface of the antiglare hard coat layer so that the thickness when dried is 0.085 μm, an ultraviolet irradiation device ( An anti-glare antireflection film was obtained by irradiating 400 mJ ultraviolet rays using a 120 W high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., curing the low refractive index layer composition, and forming a low refractive index layer. The refractive index of this low refractive index layer was 1.34.
The arithmetic average roughness (Ra) on the surface of the antiglare antireflection film was 0.13 μm, the average interval (Sm) of irregularities was 148 μm, and the haze value of the antiglare antireflection film was 2.8%.

(Comparative Example 1)
An antiglare hard coat layer was produced in the same manner as in Example 1.
After applying the composition for a low refractive index layer prepared in Production Example 2 on the surface of the antiglare hard coat layer so that the thickness when dried becomes 0.082 μm, an ultraviolet irradiation device ( An anti-glare antireflection film was obtained by irradiating 400 mJ ultraviolet rays using a 120 W high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., curing the low refractive index layer composition, and forming a low refractive index layer. The refractive index of this low refractive index layer was 1.34.
The arithmetic average roughness (Ra) on the surface of the antiglare antireflection film was 0.13 μm, the average interval (Sm) of irregularities was 148 μm, and the haze value of the antiglare antireflection film was 2.8%.

(Comparative Example 2)
An antiglare hard coat layer was produced in the same manner as in Example 1.
After applying the composition for a low refractive index layer prepared in Production Example 2 on the surface of the antiglare hard coat layer so that the thickness when dried is 0.105 μm, an ultraviolet irradiation device ( An anti-glare antireflection film was obtained by irradiating 400 mJ ultraviolet rays using a 120 W high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., curing the low refractive index layer composition, and forming a low refractive index layer. The refractive index of this low refractive index layer was 1.34.
The arithmetic average roughness (Ra) on the surface of the antiglare antireflection film was 0.13 μm, the average interval (Sm) of irregularities was 148 μm, and the haze value of the antiglare antireflection film was 2.8%.

(Comparative Example 3)
100 parts by mass of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA], 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1- as a photopolymerization initiator A binder was prepared by mixing 3 parts by mass of propan-1-one [Ciba Specialty Chemicals, Inc., Irgacure 2959] and 83.4 parts by mass of methyl isobutyl ketone (MIBK). 17 parts by mass of crosslinked styrene fine particles (manufactured by Soken Chemicals Co., Ltd., SX-500; average particle size 5 μm) were mixed as a fine particle to prepare a composition for forming an antiglare hard coat layer.

This antiglare hard coat layer forming composition was applied on a PET film having a thickness of 100 μm as a transparent support with a roll coater so that the dry film thickness was 6.2 μm, and dried at 80 ° C. for 2 minutes. . Thereafter, ultraviolet rays were irradiated with a 120 W high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) (integrated light amount 400 mJ / cm ² ) and cured to obtain an antiglare hard coat layer. The refractive index of the cured product of the binder in the antiglare hard coat layer was 1.51, and the refractive index of the translucent fine particles was 1.60. Therefore, the difference in refractive index between the cured binder and the light-transmitting fine particles was 0.09.

An antiglare antireflection film was obtained by forming a low refractive index layer on the surface of the antiglare hard coat layer in the same manner as in Example 1. The refractive index of this low refractive index layer was 1.34.
The arithmetic average roughness (Ra) on the surface of the antiglare antireflection film was 0.20 μm, the average interval (Sm) of unevenness was 200 μm, and the haze value of the antireflection film was 30.0%.

  For the antiglare antireflection films of Examples 1 to 3 and Comparative Examples 1 to 3, the thickness of the antiglare hard coat layer, the thickness of the low refractive index layer, the refraction of the cured product of the binder and the translucent fine particles Table 1 collectively shows the difference in reflectance, the reflectance, the minimum reflectance wavelength, the arithmetic average roughness Ra, the average interval Sm between the irregularities, the haze value, the blackness, the image sharpness value, and the glare.

  As shown in Table 1, in Examples 1 and 2, the refractive index difference between the cured binder and the translucent fine particles is 0 to 0.01, and the minimum reflectance wavelength is in the range of 470 to 540 nm. Met. Therefore, the antiglare antireflection films of Examples 1 and 2 show no glare in the evaluation of glare, and no color is seen in the evaluation of black tightness, and can exhibit both characteristics in a well-balanced manner. It was. Furthermore, since the haze value can be suppressed to 1.5 to 5.0% and the reflectance can be suppressed to 3.5% or less, the image clarity is excellent.

  In Example 3, the refractive index difference between the cured binder and the light-transmitting fine particles was 0.002 to 0.01, but the minimum reflectance wavelength was 456 nm. Therefore, the antiglare antireflection film of Example 3 did not show glare in the evaluation of glare, but slightly colored in the evaluation of black spots.

  On the other hand, in Comparative Examples 1 and 2, the minimum reflectance wavelength was outside the range of the present invention. Therefore, the anti-glare antireflection films of Comparative Examples 1 and 2 showed a tint in the evaluation of black spots, which was an inappropriate result as an anti-glare antireflection film.

  In Comparative Example 3, the difference in refractive index between the cured binder and the translucent fine particles was outside the scope of the present invention. Therefore, the anti-glare antireflection film of Comparative Example 3 showed glare in the evaluation of glare, and was an inappropriate result as an anti-glare antireflection film.

  The present invention can be used for antiglare reflection prevention of a display using liquid crystal, plasma, or the like.

Sectional drawing of the anti-glare anti-reflective film which concerns on one specific Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Transparent base film 12 ... Anti-glare hard coat layer 13 ... Low refractive index layer

Claims (5)

  An antiglare antireflection film comprising an antiglare hard coat layer and a low refractive index layer laminated in this order on a transparent base film, and an antiglare hard coat layer containing a binder and translucent fine particles The refractive index difference between the cured binder and the light-transmitting fine particles is 0 to 0.05, and the minimum reflectance wavelength at which the reflectance in the visible region at 5 ° regular reflection is the lowest is in the range of 450 to 560 nm. An anti-glare antireflection film characterized by being set to   The arithmetic average roughness (Ra) measured in accordance with JIS B 0601-1994 on the surface of the antiglare antireflection film is 0.01 to 0.30 μm, and the average interval (Sm) of unevenness is 10 to 300 μm. The antiglare antireflection film according to claim 1,   The antiglare antireflection film according to claim 1 or 2, wherein the antiglare hard coat layer contains inorganic fine particles having an average particle diameter smaller than that of the light transmissive fine particles. The low refractive index layer is a fluorine-containing cured coating obtained by curing a fluorine-containing curable coating liquid, and the fluorine-containing curable coating liquid has film-forming properties and has a polymerizable double bond. The compound and hollow silica fine particles modified with a silane coupling agent represented by the following chemical formula (1) are contained, and the content of the hollow silica fine particles is 20 to 60 in the total amount of the fluorine-containing compound and the hollow silica fine particles. The antiglare antireflection film according to claim 1, wherein the antiglare antireflection film is in mass%.
(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group.) A display comprising the antiglare antireflection film according to any one of claims 1 to 4 on an outermost surface on a side to display an image.