JP2009157234A - Anti-glare and antireflection film and liquid crystal display having the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glare film for a liquid crystal display that suppresses glare, improves black level and image definition, and improves visibility of an image, and to provide a liquid crystal display. <P>SOLUTION: This anti-glare and antireflection film is constituted by laminating an anti-glare hard coat layer and an antireflection layer containing at least a low refractive index layer in this order on a transparency substrate made of cellulosic material. The anti-glare hard coat layer is obtained by curing a composition containing active energy beam curing resin, a photo-polymerization initiator, and translucent organic fine particles. The refractive index difference between the translucent fine particles and the cured binder containing active energy beam curing resin and the photo-polymerization initiator is 0-0.05. The arithmetic average roughness (Ra) in the surface is 0.01-0.30 μm, and concavo-convex average interval (Sm) is 10-300 μm. Total Hayes value is 10% or less, and the ratio of the inner Hayes value to the total Hayes value is 50% or more. The low refractive index layer is obtained by curing a composition containing hollow silica fine particles modified by fluorine containing compound having polymerizable double bond in molecules and a silane coupling agent having polymerizable double bond in molecules. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention mainly relates to an antiglare antireflection film used by being attached to the outermost surface on the image display side of a liquid crystal display, and a liquid crystal display including the same. Anti-glare anti-reflection, especially excellent in scratch resistance and abrasion resistance, suppresses glare when installed on a liquid crystal display that displays high-definition images, and suppresses lowering of black density and deterioration of image sharpness The present invention relates to a film and a liquid crystal display including the film.

With the development of home-use game machines and high-definition displays, there is an increasing demand to increase image definition by improving the surface strength of liquid crystal displays and reducing the surface reflected light.
In general, an antiglare antireflection film is disposed on the surface of the liquid crystal display in order to diffuse light from the outside. This antiglare antireflection film has an extremely thin antireflection layer on the outermost layer, and has a problem of low surface strength.
As an attempt to solve this problem, a thin film having excellent mechanical strength by maintaining excellent adhesion to the substrate by adjusting the fluorine content of the fluorine-containing copolymer contained in the low refractive index layer The method of forming is mentioned (for example, refer patent document 1). That is, the antireflection material includes a conductive layer in which transparent conductive ultrafine particles of metal oxide are dispersed on a transparent substrate, a high refractive index layer having a higher refractive index than the conductive layer, and the conductive layer. A low refractive index layer having a refractive index lower than that of the organic layer, and the low refractive index layer includes a fluorine-containing copolymer having a fluorine content of 60 to 70%, and an ethylenically unsaturated group. It is disclosed that a resin composition comprising a polymerizable compound having a desirable value is desirable.
Moreover, in the anti-glare antireflection film of a liquid crystal display, light is diffused so that an anti-glare action can be exhibited, so that the surface unevenness needs to be increased. However, when the unevenness is increased in order to improve the antiglare property, there is a problem that the haze value of the antiglare layer is increased and the image sharpness is lowered accordingly. Furthermore, the antiglare antireflection film has a problem in that a sparkle called scintillation is generated on the film surface and visibility of the display screen is lowered.
As an attempt to solve such a problem, an antiglare film in which scintillation is suppressed based on an internal scattering effect is disclosed focusing on internal haze (see, for example, Patent Document 2). That is, in the antiglare film, an antiglare layer is provided on a transparent support, the haze of the antiglare layer is 4.0 to 50%, and the haze is 1.0 to 40%. And a total of 3.0 to 30% surface scattering.
JP 2003-294904 A (column 11) JP 2001-91707 A (2nd-3rd columns, 8th columns)

However, in the antireflection material described in Patent Document 1, since it is necessary to adjust the fluorine content to 60 to 70% as the low refractive index layer, it is difficult to greatly reduce the refractive index of the low refractive index layer. There was a problem.
Moreover, in the anti-glare film described in Patent Document 2, since the shape, interval, and the like are not considered for the fine irregularities on the surface of the anti-glare layer, the diffusion of light on the surface of the anti-glare layer is sufficiently controlled. I couldn't. For this reason, when an anti-glare film is used for a liquid crystal display, the glare on the surface of the anti-glare film cannot be sufficiently suppressed, and the required image visibility cannot be obtained. Furthermore, the haze value (total haze or total haze) of the antiglare film is specifically 15.0 to 40.1% (Examples 1 to 1 described in Table 1 on page 8 of Patent Document 2). 4). For this reason, the antiglare film has a problem that the light transmittance is poor, and as a result, the image definition is inferior and the black density of the image is lowered. In particular, in the case of a high-definition liquid crystal display, there is a problem that image visibility is insufficient.

  Therefore, the object of the present invention is excellent in scratch resistance and abrasion resistance, can suppress glare, can increase black density and image sharpness, and improve image visibility. It is in providing an anti-glare antireflection film that can be used and a liquid crystal display including the same.

  In order to achieve the above object, the antiglare antireflection film of the first invention of the present invention is a reflection comprising an antiglare hard coat layer and at least a low refractive index layer on a transparent substrate made of a cellulosic material. The anti-glare hard coat layer is composed of a cured product of a composition containing an active energy ray-curable resin, a photopolymerization initiator, and translucent organic fine particles. The refractive index difference between the cured product of the binder containing the active energy ray-curable resin and the photopolymerization initiator and the translucent organic fine particles is adjusted to 0 to 0.05, and JIS B 0601 on the surface of the antireflection layer is adjusted. -The arithmetic average roughness (Ra) measured in accordance with 1994 is 0.01 to 0.30 μm, the average interval of unevenness (Sm) is 10 to 300 μm, the overall haze value is 10% or less, and The entire The ratio of the internal haze value to the noise value is 50% or more, and the low refractive index layer comprises a fluorine-containing compound having a polymerizable double bond in the molecule and a silane cup having a polymerizable double bond in the molecule. It is a cured film of a composition (fluorine-containing curable coating liquid) containing hollow silica fine particles modified with a ring agent.

  The antiglare antireflection film of the second invention of the present invention is characterized in that the low refractive index layer further contains metal oxide fine particles having an average particle diameter of 10 to 100 nm.

  The antiglare antireflection film of the third invention of the present invention was cured by further including 0.1 to 20% by mass of a polydiorganosiloxane having a polymerizable double bond in the molecule of the low refractive index layer. It is characterized by that.

In the antiglare antireflection film of the fourth invention of the present invention, the fluorine-containing compound having a polymerizable double bond in the molecule has two or more polymerizable unsaturated groups represented by the following formula (I). It is a polyfunctional monomer having.

  The antiglare antireflection film of the fifth invention of the present invention is characterized in that the translucent organic fine particles are a (meth) acrylic resin, a styrene-acrylic copolymer resin or a cross-linked product thereof.

  In the antiglare antireflection film of the sixth invention of the present invention, the ratio a / A of the average particle diameter (a) of the translucent organic fine particles to the film thickness (A) of the antiglare hard coat layer is 0.00. It is 3 to 1.5.

  A liquid crystal display according to a seventh aspect of the present invention is characterized in that the antiglare antireflection film is provided on the outermost surface on the image display side.

The antiglare antireflection film of the first invention of the present invention is a refraction of a cured product of a binder containing an active energy ray-curable resin and a photopolymerization initiator and a light-transmitting organic fine particle in an antiglare hard coat layer. Since the rate difference is adjusted, light scattering in the antiglare hard coat layer can be suppressed and the light transmission can be improved, and the image definition and the black density of the image can be improved. Further, by setting the average roughness (Ra) and the average interval (Sm) of the unevenness on the surface of the antireflection layer to an appropriate range, the diffusion of light is controlled, and excessive scattering of light is suppressed. Suppression is suppressed. In addition, the overall haze value is adjusted to be low, the light transmittance is improved, and the image definition and the black density of the image can be improved. Moreover, the balance between the antiglare property, the glare and the image definition can be improved by regulating the external haze value appropriately by defining the ratio of the internal haze value to the overall haze value.
Therefore, the antiglare film can suppress glare when used in a liquid crystal display, can increase black density and image definition, and can improve image visibility. Furthermore, the hollow silica fine particles are integrated with the fluorine-containing compound by copolymerizing the (meth) acryloyloxy group of the silane coupling agent contained in the composition of the low refractive index layer and the polymerizable double bond of the fluorine-containing compound. And the strength and hardness of the cured film (= low refractive index layer) obtained from the fluorine-containing curable coating liquid can be improved, and the scratch resistance and abrasion resistance of the film surface can be improved. In addition, since the content of hollow silica fine particles modified with a silane coupling agent is higher than before, the formed film can exhibit low refractive index and low reflectance due to the hollow portion of fluorine and hollow silica fine particles. .

  The antiglare antireflection film of the second invention of the present invention has metal oxide fine particle projections formed on the outermost layer, and can reduce the contact area with the material to be scratched or worn, Steel wool and wear resistance are improved.

  In the antiglare antireflection film of the third invention of the present invention, the polydiorganosiloxane is coated by coating the low refractive index layer with polydiorganosiloxane having a polymerizable double bond in the molecule. Since it is oriented on the film surface and improves the surface slip, the steel wool resistance and wear resistance are improved. In addition, polydiorganosiloxane has a polymerizable double bond in the molecule, so it binds and crosslinks with hollow silica fine particles modified with a fluorine-containing compound or a silane coupling agent, and does not reduce the strength of the coating film. Therefore, the steel wool resistance and wear resistance are more effectively improved.

  The antiglare antireflection film of the fourth invention of the present invention is a polyfunctional compound in which the fluorine-containing compound having a polymerizable double bond has two or more polymerizable unsaturated groups represented by the formula (I). Since the fluorine-containing compound has two or more polymerizable unsaturated groups, it can be highly cross-linked with the polymerizable double bond contained in the film, thereby improving the strength and hardness of the resulting film. Further, the scratch resistance and wear resistance of the coating surface can be improved.

  In the antiglare antireflection film of the fifth invention of the present invention, the refractive index of the light-transmitting organic fine particles can be easily adjusted by the kind and composition of the resin.

  In the antiglare antireflection film of the sixth invention of the present invention, the ratio a / A of the average particle diameter (a) of the translucent organic fine particles to the film thickness (A) of the antiglare hard coat layer is defined. The unevenness on the surface of the antiglare hard coat layer can be easily set to be within the specified range.

  In the liquid crystal display of the seventh aspect of the present invention, the antiglare antireflection film is provided on the outermost surface on the image display side. Therefore, the above-described effect can be exhibited in a liquid crystal display, and the effect can be effectively exhibited particularly in a high-definition liquid crystal display.

Hereinafter, embodiments that are considered to be the best modes of the present invention will be described in detail.
The antiglare antireflection film of the present invention is constituted by laminating an antiglare hard coat layer and at least a low refractive index layer in this order on a transparent substrate made of a cellulosic material. Has been.
This antiglare antireflection film is used by being disposed on the outermost surface on the side of displaying an image of a liquid crystal display, particularly a high-definition liquid crystal display. And the refractive index difference of the hardened | cured material of the binder in the anti-glare hard-coat layer containing a binder (binder) and translucent microparticles | fine-particles and translucent microparticles | fine-particles is set to 0-0.05, and in visible region The minimum reflectance wavelength at which the reflectance is the lowest value 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 including 0.1 to 20% by mass of metal oxide fine particles or polydiorganosiloxane having a polymerizable double bond in the molecule and a fluorine-containing polyfunctional monomer having two or more polymerizable unsaturated groups, Excellent scratch resistance and abrasion resistance. Light transmission can be maintained by reducing the difference in refractive index between the cured binder and the light-transmitting fine particles, and the minimum reflectance wavelength is controlled. Therefore, the black color is excellent in black display images.

The antiglare antireflection film of the first invention of the present invention satisfies the following requirements <A> to <F>.
<A> An antireflection layer including an antiglare hard coat layer and at least a low refractive index layer is laminated in this order on a transparent substrate made of a cellulose-based material.
<I> The antiglare hard coat layer is formed of a cured product of a composition containing an active energy ray-curable resin, a photopolymerization initiator, and translucent organic fine particles.
<C> The refractive index difference between the cured product of the binder containing the active energy ray-curable resin and the photopolymerization initiator and the translucent organic fine particles is adjusted to 0 to 0.05.
<D> The arithmetic average roughness (Ra) measured in accordance with JIS B 0601-1994 on the surface of the antireflection layer is 0.01 to 0.30 μm, and the average interval (Sm) of the unevenness is 10 to 300 μm. .
<O> The overall haze value is 10% or less, and the ratio of the internal haze value to the overall haze value is 50% or more.
<F> The low refractive index layer contains a fluorine-containing compound having a polymerizable double bond in the molecule and hollow silica fine particles modified with a silane coupling agent having a polymerizable double bond in the molecule. It is a cured film of a product (fluorine-containing curable coating liquid).

Next, the antiglare antireflection film of the first invention of the present invention is constituted by using the following raw materials.
[1] Transparent substrate, [2] Antiglare hard coat layer, [3] Antireflection layer, [4] Low refractive index layer [5] Active energy ray-curable resin, [6] Photopolymerization initiator, 7) Translucent organic fine particles [8] Fluorine-containing compounds having a polymerizable double bond in the molecule [9] Hollow silica fine particles modified with a silane coupling agent having a polymerizable double bond in the molecule

[1] Transparent base material The cellulosic material forming the transparent base material is excellent in light transmittance and excellent in light transmittance and has no optical anisotropy. For this reason, it is the most suitable thing as a base material of the anti-glare film arrange | positioned and used on the surface of a liquid crystal display. As the cellulose material, derivatives of triacetyl cellulose (TAC), diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose, etc. can be used. Most preferably it is used. The thickness of the transparent substrate is usually 10 to 5000 μm, preferably 25 to 1000 μm, more preferably 35 to 500 μm. When this thickness is less than 10 μm, the handleability of the antiglare film tends to deteriorate and the strength tends to decrease. On the other hand, when the thickness is greater than 5000 μm, the thickness becomes unnecessarily thick, and the handleability of the antiglare film is deteriorated.

[2] Antiglare hard coat layer The antiglare hard coat layer has irregularities on its surface, light is reflected and diffused on the irregularities (surface diffusibility), and can exhibit antiglare properties. It has a function. This anti-glare hard coat layer is formed by curing an anti-glare hard coat layer forming composition containing translucent organic fine particles in a binder containing an active energy ray-curable resin and a photopolymerization initiator. The hard coat layer has the required strength and hardness. Here, the binder or the antiglare hard coat layer forming composition is usually mixed with a diluent solvent, and the viscosity of the binder or the antiglare hard coat layer forming composition is adjusted.

[5] Active energy ray-curable resin 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. Polymer (hereinafter referred to as non-polymerizable polymer), metal oxide, surfactant, diluent solvent, photosensitizer, stabilizer, ultraviolet absorber, infrared absorber, antioxidant, surface conditioner, A particle dispersant or the like is used.

  Specific examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid t. -Butyl, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ( Cetyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid Dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic Pentamethylpiperidyl phosphate, ethyl (meth) acrylate hexahydrophthalate, ethyl (meth) acrylate 2-hydroxypropyl phthalate, 2-hydroxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, (meta ) (Meth) acrylic acid esters such as phenoxyethyl acrylate, (meth) acrylic acid methoxydiethylene glycol, (meth) acrylic acid methoxytriethylene glycol, (meth) acrylic acid methoxypolyethylene glycol, styrene, α-methylstyrene, p -Methoxystyrene, m-methoxystyrene, di-t-butyl fumarate, di-n-butyl fumarate, diethyl fumarate, monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, N-isopropyl acrylate Mido, 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 (meth) 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 (meth) 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 tripropylene glycol, tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid pentaerythritol, (meth) acrylic acid esters such as hexa (meth) acrylic acid dipentaerythritol, 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. Furthermore, as the active energy ray curable resin, it is preferable to use a urethane acrylate resin from the viewpoint of good flexibility when the film is thickened.

[7] Translucent organic fine particles The translucent organic fine particles are used to develop [2] a light diffusing function in the antiglare hard coat layer, an antiglare function by forming irregularities on the surface, and the like. The translucent organic fine particles are formed from a resin obtained by polymerizing at least one monomer selected from, for example, vinyl chloride, (meth) acrylic monomer, styrene, and ethylene.
As such translucent resin fine particles, as in the fifth aspect of the present invention, a (meth) acrylic resin, a styrene-acrylic monomer copolymer resin (hereinafter simply referred to as “refractive index adjustment”) is easy. It is preferably a styrene-acrylic copolymer resin) or a cross-linked product thereof. In the case of a styrene-acrylic copolymer resin, it is more preferable in that the refractive index can be arbitrarily adjusted by changing the copolymer composition of both monomers. Furthermore, in addition to styrene-acrylic copolymer resin or (meth) acrylic resin (refractive index 1.49), vinyl chloride resin, polystyrene resin (refractive index 1.54), polyethylene resin, melamine resin (refractive index 1.57). It is also possible to form translucent organic fine particles from a resin containing polycarbonate resin or the like.

  [7] The translucent organic fine particles are [2] monodispersed with uniform particle diameters in order to uniformly diffuse or scatter light in and on the antiglare hard coat layer. Is preferred. The average particle diameter of the light-transmitting organic 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. Here, the average particle diameter is a value calculated from a particle number distribution obtained by measuring the distribution by a Coulter counter method, converting the measured distribution into a particle number distribution. The Coulter counter method is a particle size measurement method using electric resistance, and is a method of measuring an average particle diameter by measuring a change in electric resistance between two electrodes that occurs when particles pass through pores. .

As in the sixth aspect of the present invention, [2] the ratio of the average particle diameter (a) of the translucent organic fine particles to the film thickness (A) of the antiglare hard coat layer (A) is 0. .3-1.5 is preferable, and 0.5-1.5 is more preferable. When this ratio a / A is less than 0.3, the amount of translucent organic fine particles added to form desired irregularities on the surface of the antiglare hard coat layer increases, and the haze value increases. Image sharpness tends to decrease. On the other hand, when it exceeds 1.5, the unevenness on the surface of the antiglare hard coat layer becomes too large, so that the haze value becomes large, the image sharpness deteriorates, and the glare becomes undesirably strong.
The content of the translucent organic fine particles is [5] usually 1 to 70 parts by mass, preferably 2 to 60 parts by mass, more preferably 3 to 50 parts by mass, most preferably 100 parts by mass of the active energy ray-curable resin. Preferably it is 10-40 mass parts. When the content of the light-transmitting organic fine particles is less than 1 part by mass, the function of the light-transmitting organic 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 film is placed on the surface of the liquid crystal display, whitening or the like occurs and image recognizability decreases. .

[6] Photopolymerization initiator The photopolymerization initiator is [5] an active energy ray-curable resin for irradiating active energy rays such as ultraviolet rays to initiate polymerization, 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, mihilaben Examples include zoylbenzoate and tetramethylchuram monosulfide.
The content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin. 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.

[Diluted solvent]
The dilution solvent used for the preparation of the binder or antiglare hard coat layer forming composition is used to adjust the viscosity of the binder or antiglare hard coat layer forming composition, and is non-polymerizable. If there is no particular limitation. With such a diluting solvent, the composition for forming an antiglare hard coat layer can be easily applied onto a transparent substrate [1].
Examples of the diluent solvent include 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, Examples include diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, decane, dodecane, propylene glycol monomethyl ether, and 3-methoxybutanol.

[Non-swelling solvent]
Furthermore, in order to make the surface of the antiglare hard coat layer uniform and free of defects, it is preferable to use [7] a non-swelling solvent of translucent organic fine particles. The non-swelling solvent means a solvent that does not swell the translucent organic fine particles. As this non-swellable solvent, an alcohol solvent is preferable, and the amount added is preferably 10 to 60% by mass in the total amount of the solvent. When this addition amount is less than 10% by mass, it becomes difficult to form a uniform antiglare hard coat layer. On the other hand, when it exceeds 60 mass%, the dispersibility of the translucent organic fine particles deteriorates, and it becomes difficult to form a uniform [2] antiglare hard coat layer.
After the above composition for forming an antiglare hard coat layer is applied onto a transparent substrate, the antiglare hard coat layer is laminated on the transparent support by irradiating and curing the active energy ray. can do.

[3] Antireflection layer The antireflection layer includes at least [4] a low refractive index layer. In order to further enhance the antireflection effect, the low refractive index layer and [2] an antiglare hard coat layer are used. Between these layers, a high refractive index layer having a refractive index higher than that of the low refractive index layer and that of the antiglare hard coat layer can be provided. The high refractive index layer preferably has a refractive index of 1.50 or more, and the thickness of the film is preferably 50 to 500 nm. Examples of the inorganic material contained in the high refractive index layer include zinc oxide fine particles, zirconium oxide fine particles, indium oxide-tin fine particles (ITO fine particles), and antimony oxide fine particles (ATO fine particles).

[4] The low refractive index layer, which is a requirement of <F>, is [8] a fluorine-containing compound having a polymerizable double bond in the molecule and [9] a silane coupling having a polymerizable double bond in the molecule. It is a cured film of a composition (= fluorine-containing curable coating liquid) containing hollow silica fine particles modified with an agent. More specifically, the fluorine-containing curable coating liquid is polymerized and cured with a high energy beam such as an electron beam, or the fluorine-containing curable coating liquid is polymerized and cured in the presence of a thermal decomposition type polymerization initiator or a photopolymerization initiator. By doing so, a low refractive index layer is obtained.
Fluorine atoms (also referred to simply as fluorine in the present invention) have a very low polarizability, so fluorine-containing monomers have low molecular cohesion and can obtain low surface energy properties after film formation, while film forming properties are improved. It has the property of being scarce. Here, the film forming property represents a property that a fluorine-containing cured film (hereinafter also simply referred to as a film) is formed without being repelled when a fluorine-containing monomer is applied onto a substrate such as a synthetic resin film. For example, it is determined that a film having a uniform thickness can be formed at a stage where a solution diluted with a solvent is applied to a substrate and heated to remove the solvent, so that the film formability is good. For example, the critical surface tension when the trifluoromethyl group is oriented is 6 dyn / cm, whereas the tetrafluoroethylene group is 18 dyn / cm, so that fluorine can be formed in the form of a methylene fluoride group or a fluorinated methine group. By introducing it, the film forming property is improved. 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 [8] having a polymerizable double bond in the molecule, [1-8] fluorine atoms are contained in the molecule as methylene fluoride groups or fluorinated methine groups. Examples thereof include fluorine-containing monomers having an introduced structure, and fluorine-containing reactive polymers having [8-2] solvent-soluble and polymerizable double bonds.

  [8-1] The fluorine-containing monomer having a structure in which a fluorine atom is introduced into a molecule as a methylene fluoride group or a fluorinated methine group, All known monomers can be used as long as they are monomers introduced therein. 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.

この含フッ素多官能（メタ）アクリル酸エステルの具体例としては、例えば１，３−ビス｛（メタ）アクリロイルオキシ｝−２，２−ジフルオロプロパン、１，４−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３−テトラフルオロブタン、１，５−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４−ヘキサフルオロペンタン、１，６−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４，５，５−オクタフルオロヘキサン、１，７−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４，５，５，６，６−デカフルオロヘプタン、１，８−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４，５，５，６，６，７，７−ドデカフルオロオクタン、１，９−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４，５，５，６，６，７，７，８，８−テトラデカフルオロノナン、１，１０−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９−ヘキサデカフルオロデカン、１，１１−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９，１０，１０−オクタデカフルオロウンデカン、１，１２−ビス｛（メタ）アクリロイルオキシ｝−２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１１，１１−エイコサフルオロドデカン、１，８−ビス｛（メタ）アクリロイルオキシ｝−２，７−ジヒドロキシ−４，４，５，５−テトラフルオロオクタン、１，７−ビス｛（メタ）アクリロイルオキシ｝−２，８−ジヒドロキシ−４，４，５，５−テトラフルオロオクタン、２，７−ビス｛（メタ）アクリロイルオキシ｝−１，８−ジヒドロキシ−４，４，５，５−テトラフルオロオクタン、１，１０−ビス｛（メタ）アクリロイルオキシ｝−２，９−ジヒドロキシ−４，４，５，５，６，６，７，７−オクタフルオロデカン、１，９−ビス｛（メタ）アクリロイルオキシ｝−２，１０−ジヒドロキシ−４，４，５，５，６，６，７，７−オクタフルオロデカン、２，９−ビス｛（メタ）アクリロイルオキシ｝−１，１０−ジヒドロキシ−４，４，５，５，６，６，７，７−オクタフルオロデカン、１，２，７，８−テトラキス｛（メタ）アクリロイルオキシ｝−４，４，５，５−テトラフルオロデカン、１，２，８，９−テトラキス｛（メタ）アクリロイルオキシ｝−４，４，５，５，６，６−ヘキサフルオロノナン、１，２，９，１０−テトラキス｛（メタ）アクリロイルオキシ｝−４，４，５，５，６，６，７，７−オクタフルオロデカン、１，２，１０，１１−テトラキス｛（メタ）アクリロイルオキシ｝−４，４，５，５，６，６，７，７，８，８−デカフルオロウンデカン、１，２，１１，１２−テトラキス｛（メタ）アクリロイルオキシ｝−４，４，５，５，６，６，７，７，８，８，９，９−ドデカフルオロドデカン、１，１０−ビス（α−フルオロアクリロイルオキシ）−２，９−ジヒドロキシ−４，４，５，５，６，６，７，７−オクタフルオロデカン、１，９−ビス（α−フルオロアクリロイルオキシ）−２，１０−ジヒドロキシ−４，４，５，５，６，６，７，７−オクタフルオロデカン、２，９−ビス（α−フルオロアクリロイルオキシ）−１，１０−ジヒドロキシ−４，４，５，５，６，６，７，７−オクタフルオロデカン、１，２，９，１０−テトラキス（α−フルオロアクリロイルオキシ）−４，４，５，５，６，６，７，７−オクタフルオロデカン、１，２，１１，１２−テトラキス（α−フルオロアクリロイルオキシ）−４，４，５，５，６，６，７，７，８，８，９，９−ドデカフルオロドデカン等が挙げられる。使用に際しては、これらは単独又は混合物として用いられる。
含フッ素多官能(メタ)アクリル酸エステルは、公知の方法により製造される。例えば相当する含フッ素エポキシ化合物と(メタ)アクリル酸との開環反応や、相当する含フッ素多価アルコール又は前記開環反応で中間体として得られる水酸基（ヒドロキシル基）を有する含フッ素(メタ)アクリル酸エステルと(メタ)アクリル酸クロライドとのエステル化反応により製造される。 As in the fourth aspect of the present invention, the [8] fluorine-containing compound having a polymerizable double bond in the molecule has two or more polymerizable unsaturated groups represented by the following formula (I). A polyfunctional monomer is preferred.

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

[8-2] 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. Is. 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.

[9] The hollow silica fine particles modified with a silane coupling agent having a polymerizable double bond in the molecule are modified with a silane coupling agent represented by the following formula (II), for example. In the present invention, both acryl and methacryl are referred to as (meth) acryl.
ZR ¹ (OR ² ) ₃ (II)
(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.)
Since the hollow silica fine particles modified with the silane coupling agent represented by the formula (II) contain air, 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 before modification are fine particles in which silica (silicon dioxide SiO ₂ ) is formed in a substantially spherical shape and has a hollow portion (spherical cavity) in the outer shell, and the average particle size 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. At that time, 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, toluene, xylene and the like. Examples include aromatic hydrocarbons, 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 ([9] modified hollow silica fine particles) obtained by modification in this way is 20 to 60% by mass in the total amount with the above [8] fluorine-containing compound. It is desirable that it is 60 mass%. 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, excessive modified hollow silica fine particles cannot react with the fluorine-containing compound, and the polymer remains, and the scratch resistance and wear resistance of the fluorine-containing cured film surface are reduced. Show the trend. 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 [9] modified hollow silica fine particles will be further described. 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 are produced by surface treatment with the silane coupling agent. 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 [8] 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 hollow portions (spherical cavities) 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. Become.

The hollow silica fine particles used as the raw material for the modified hollow silica fine particles are fine particles having silica (silicon dioxide SiO ₂ ) formed in a substantially spherical shape and having a hollow portion (spherical cavity) in the outer shell as described above. Specifically, it can be produced through the following first to fourth steps.
That is, in the first step, an aqueous solution of silicate or acidic silicic acid solution and an alkali-soluble inorganic compound aqueous solution are placed 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 required. At the same time, a core particle dispersion in which the molar ratio of silica and inorganic compound other than silica is in the range of 0.3 to 1.0 is prepared.
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 for moisture to be adsorbed 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 [8] The water resistance of a film obtained by curing a fluorine-containing curable coating liquid combined with a fluorine-containing compound can be improved. The upper limit of the hydrothermal treatment temperature in the fifth step 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. Further, 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, when 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 lowered, which is not industrially preferable.

  [9] 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. On the other hand, the silane coupling agent is reacted with the hollow silica fine particles under the condition that the water content is 0.1 to 50% by 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.

[9] The average particle size 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 after curing of the fluorine-containing curable coating liquid. 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 in the 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 cured film formed by blending modified hollow silica fine particles having a thermal mass decrease of less than 2% by mass, whitening occurs and the scratch resistance and abrasion 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 curable coating liquid are preferably decreased. Absent.

  In addition, 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 cured film obtained by using the hollow silica fine particles 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 surface of the film before and after being left, It can be suppressed to 0.3% or less.

上記の含フッ素（メタ）アクリル酸エステルは、自身が成膜性を発揮しないものの、前記成膜性を有する〔八〕含フッ素化合物に親和性を示し、その成膜性を低下させることがない。そのため、含フッ素硬化性塗液は優れた成膜性を発揮することができる。また、成膜性を有しない式（III）で示される含フッ素（メタ）アクリル酸エステルは、高い防汚性を発現することができる成分である。さらに、含フッ素（メタ）アクリル酸エステルは重合性二重結合をもつため、前記含フッ素化合物と共重合反応を行ない、それらの機能を導入した含フッ素硬化皮膜（低屈折率層）となる。
係る含フッ素（メタ）アクリル酸エステルは、その分子末端にトリフルオロメチル基（ＣＦ₃−）をもつ炭素数１０のフルオロアルキル基（Ｒf）を有しており、この含フッ素（メタ）アクリル酸エステルは少量でもトリフルオロメチル基が表面に配向される。特に含フッ素硬化皮膜中であってもトリフルオロメチル基が表面に十分に配向される。従って、得られる含フッ素硬化皮膜は、防汚性、低屈折率性等の特性を発揮することができる。
これに対し、炭素数９以下のフルオロアルキル基を有する含フッ素（メタ）アクリル酸エステルは、末端のトリフルオロメチル基が表面に十分に配向されず、その効果が得られない。炭素数１１以上のフルオロアルキル基を有する含フッ素（メタ）アクリル酸エステルは、製造や入手が困難である。つまり、炭素数１０のフルオロアルキル基を有する含フッ素（メタ）アクリル酸エステルのみが他の鎖長のフルオロアルキル基を有する含フッ素（メタ）アクリル酸エステルと比較しても特異的な機能を発揮できるのである。
前記式（III）で示される含フッ素（メタ）アクリル酸エステルとして具体的には、１−(メタ)アクリロイルオキシ−２−ヒドロキシ−４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１１，１１，１２，１２，１３，１３，１３−ヘンエイコサフルオロトリデカン、２−(メタ)アクリロイルオキシ−１−ヒドロキシ−４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１１，１１，１２，１２，１３，１３，１３−ヘンエイコサフルオロトリデカン及び１，２−ビス(メタ)アクリロイルオキシ−４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１１，１１，１２，１２，１３，１３，１３−ヘンエイコサフルオロトリデカン等が挙げられる。これらの含フッ素（メタ）アクリル酸エステルは単独で、或いは混合物として用いることができる。
前記式（III）で示される含フッ素(メタ)アクリル酸エステルの含有量は、前記含フッ素化合物と変性中空シリカ微粒子との合計量１００質量部に対して０．５〜３０質量部であることが好ましい。この含有量が０．５質量部未満の場合には含フッ素硬化皮膜表面の防汚性が低下し、３０質量部を越える場合には透明均一で良好な含フッ素硬化皮膜を得ることが困難となる傾向にある。 The fluorine-containing curable coating liquid preferably further contains a fluorine-containing (meth) acrylic acid ester represented by the following formula (III) that does not have film-forming properties.

Although the above fluorine-containing (meth) acrylic acid ester itself does not exhibit film-forming properties, it has an affinity for [8] fluorine-containing compounds having the film-forming properties and does not deteriorate the film-forming properties. . Therefore, the fluorine-containing curable coating liquid can exhibit excellent film forming properties. Moreover, the fluorine-containing (meth) acrylic acid ester represented by the formula (III) having no film-forming property is a component that can exhibit high antifouling properties. Further, since the fluorine-containing (meth) acrylic acid ester has a polymerizable double bond, it undergoes a copolymerization reaction with the fluorine-containing compound to form a fluorine-containing cured film (low refractive index layer) in which those functions are introduced.
Such fluorine-containing (meth) acrylic acid ester has a C10 fluoroalkyl group (Rf) having a trifluoromethyl group (CF _3- ) at the molecular end, and this fluorine-containing (meth) acrylic acid. Even in a small amount of the ester, the trifluoromethyl group is oriented on the surface. In particular, even in the fluorine-containing cured film, the trifluoromethyl group is sufficiently oriented on the surface. 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.
Specific examples of the fluorine-containing (meth) acrylic acid ester represented by the formula (III) include 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 ( (Meth) acryloyloxy-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-heneicosa Examples include fluorotridecane. 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 formula (III) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the fluorine-containing compound and the modified hollow silica fine particles. Is preferred. When the content is less than 0.5 parts by mass, the antifouling property of the fluorine-containing cured film is lowered, and when it exceeds 30 parts by mass, it is difficult to obtain a transparent uniform and good fluorine-containing cured film. Tend to be.

As in the second aspect of the present invention, the [4] low refractive index layer preferably further includes metal oxide fine particles having an average particle diameter of 10 to 100 nm.
Examples of the metal oxide fine particles include lanthanum fluoride, magnesium fluoride, cerium fluoride, hollow silicon oxide fine particles, colloidal silicon oxide fine particles, and aluminum oxide. In particular, aluminum oxide is preferable from the viewpoint of improving wear resistance and scratch resistance. The average particle diameter of these fine particles preferably does not greatly exceed the thickness of the low refractive index layer, and is usually 0.1 μm or less, particularly preferably 10 to 100 nm. If the average particle diameter exceeds 0.1 μm, the optical performance of the low refractive index layer changes unintentionally, such as light scattering, which is not preferable. Further, the influence on the transparency due to the refractive index of the fine particles and the content in the layer is also important, and a refractive index and a content that lower the transparency are not preferable.
The compounding amount of the metal oxide fine particles is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass in the composition for forming a low refractive index layer.

前記一般式（IV）中のＡ及びＢは、直鎖状または分岐状の有機基であり、アルキル鎖（炭素数１〜３０）、パーフルオロアルキル鎖（炭素数１〜１０）、アリールアルキル鎖、脂肪族乃至芳香族（ポリ）エステル鎖（該有機鎖の部分的な分子量１００〜３０００）、脂肪族乃至芳香族（ポリ）エーテル鎖（該有機鎖の部分的な分子量１００〜３０００）または脂肪族乃至芳香族（ポリ）ウレタン鎖（該有機鎖の部分的な分子量１００〜３０００）からなる群より選出される少なくとも１種の骨格を有しており、該有機基中には重合性反応基が導入されていてもよく、分子内においてＡとＢは同一でも異なっていてもよく、Ａ同士またはＢ同士においても同一でも異なっていてもよい。更に、重合性反応基は、合成の簡便さからＢ（両末端）に導入されている方がより好ましい。
また、一般式（IV）中のｃは、ポリシロキサン骨格の長さをｃ＋１の形で表すものであり、３〜２５０、好ましくは６〜１００の整数である。 As in the third invention of the present invention, the [4] low refractive index layer further contains 0.1 to 20% by mass of a polydiorganosiloxane having a polymerizable double bond in the molecule and cured. It is desirable that
The polydiorganosiloxane having a polymerizable double bond in the molecule is preferably a compound having at least three polymerizable reactive groups in one molecule, more preferably 4 to 20, represented by the general formula (IV). Is done.

A and B in the general formula (IV) are linear or branched organic groups, and are an alkyl chain (1 to 30 carbon atoms), a perfluoroalkyl chain (1 to 10 carbon atoms), an arylalkyl chain. , Aliphatic to aromatic (poly) ester chain (partial molecular weight of the organic chain 100 to 3000), aliphatic to aromatic (poly) ether chain (partial molecular weight of the organic chain 100 to 3000) or fat Having at least one skeleton selected from the group consisting of aromatic or aromatic (poly) urethane chains (partial molecular weight of the organic chain 100 to 3000), and a polymerizable reactive group in the organic group May be introduced, A and B may be the same or different in the molecule, and A or B may be the same or different. Furthermore, it is more preferable that the polymerizable reactive group is introduced into B (both ends) for the convenience of synthesis.
Further, c in the general formula (IV) represents the length of the polysiloxane skeleton in the form of c + 1, and is an integer of 3 to 250, preferably 6 to 100.

  Examples of the polymerizable reactive group to be introduced include a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and an epoxy group, and a (meth) acryloyloxy group is particularly preferable. Examples of the bonding method between the polymerizable reactive group and the polysiloxane skeleton include conventionally known bonding methods such as (poly) ether type, (poly) ester type, (poly) urethane type, (poly) ester type and (poly). ) Bonding method combining urethane type, bonding method combining (poly) ether type and (poly) urethane type, bonding method combining (poly) ester type and (poly) ether type, etc. are all used Is possible.

前記一般式（Ｖ）中のＸは、３〜２５０の整数、好ましくは６〜１００の整数であり、Ｙ及びＺはＹ＋Ｚが３以上、好ましくはＹ＋Ｚが４〜２０であることを満たすような整数であり、ｍ及びｎはいずれも１〜１０の整数であり、ｍとｎが同じでも異なっていてもよいが、同じである場合の方が簡便に調製できる点で好ましい。
また、一般式（Ｖ）中のＲ₁は、直鎖状アルキル基（炭素数１〜３０）、パーフルオロアルキル基（炭素数１〜１０）、アリールアルキル基、ポリエステル基（該側鎖の部分的な分子量２００〜２０００であり、Ｓｉ原子にはアルキル鎖を介して結合している）、ポリエーテル基（該側鎖の部分的な分子量２００〜２０００であり、Ｓｉ原子にアルキル鎖を介して結合している）、ポリウレタン基（該側鎖の部分的な分子量２００〜２０００であり、Ｓｉ原子にアルキル鎖を介して結合している）のいずれかであり、分子内においてＲ₁は同一でも異なっていてもよいが、調製が簡便であることから同一である方がより好ましい。また、使用における樹脂との相溶性などの観点から、Ｒ₁はメチル基である場合が最も汎用的で好ましい。
一般式（Ｖ）中のＲ₂は、炭素数３〜３０、好ましくは３〜１５の直鎖または分岐鎖であり、該鎖上にはウレタン結合を少なくとも２つ以上有し、該ウレタン結合を介してポリシロキサン骨格及びＲ₃と結合しており（ただし、Ｒ₃はポリジオルガノシロキサン１分子中に３つ以上含まれるように結合している）、分子内においてＲ₂は同一でも異なっていてもよいが、調製が簡便であることから同一である方がより好ましい。
一般式（Ｖ）中のＲ₃は、ポリエステル骨格、好ましくは３つ以上のエステル結合を含むポリエステル骨格を有する部位であり、末端には前述のような重合性反応基、好ましくは（メタ）アクリロイル基が結合しており、分子内においてＲ₃は同一でも異なっていてもよいが、調製が簡便であることから同一である方がより好ましい。また、使用における樹脂との相溶性などの観点から、Ｒ₃は３以上のカプロラクトンからなるポリカプロラクトン骨格を有する場合が最も汎用的で好ましい。
一般式（Ｖ）中のＲ₄は、水素、フッ素、メチル基のいずれかであり、分子内においてＲ₄は同一でも異なっていてもよいが、調製が簡便であることから同一である方がより好ましい。 For example, in the case of a bonding method combining a polyester type and a polyurethane type, the structure of the polydiorganosiloxane molecule has a basic skeleton as shown in the following general formula (V), and the side chain extends from the polysiloxane site. Among them, a polymerizable reactive group is bonded to the terminal of three or more side chains.

X in the general formula (V) is an integer of 3 to 250, preferably an integer of 6 to 100, and Y and Z satisfy Y + Z of 3 or more, preferably Y + Z of 4 to 20. M and n are each an integer of 1 to 10, and m and n may be the same or different, but the case where they are the same is preferable in terms of easy preparation.
R ₁ in the general formula (V) is a linear alkyl group (1 to 30 carbon atoms), a perfluoroalkyl group (1 to 10 carbon atoms), an arylalkyl group, or a polyester group (part of the side chain). The molecular weight is 200 to 2000, and is bonded to the Si atom via an alkyl chain), a polyether group (partial molecular weight of the side chain is 200 to 2000, and the Si atom is connected via an alkyl chain). Or a polyurethane group (with a partial molecular weight of 200 to 2000 of the side chain and bonded to the Si atom via an alkyl chain), and R ₁ may be the same in the molecule. Although they may be different, the same is more preferable because preparation is simple. From the viewpoint of compatibility with the resin in use, it is most general and preferable that R ₁ is a methyl group.
R ₂ in the general formula (V) is a linear or branched chain having 3 to 30 carbon atoms, preferably 3 to 15 carbon atoms, and has at least two urethane bonds on the chain. through which combined with a polysiloxane backbone and R ₃ are (wherein, R ₃ is attached to include three or more in the polydiorganosiloxane molecule), R ₂ in the molecule are identical or different However, the same is more preferable because the preparation is simple.
R ₃ in the general formula (V) is a portion having a polyester skeleton, preferably a polyester skeleton containing three or more ester bonds, and the terminal is a polymerizable reactive group, preferably (meth) acryloyl. The groups are bonded, and R ₃ may be the same or different in the molecule, but the same is more preferable because preparation is simple. From the viewpoint of compatibility with the resin in use, it is most general and preferable that R ₃ has a polycaprolactone skeleton composed of 3 or more caprolactones.
R ₄ in the general formula (V) is any one of hydrogen, fluorine, and methyl group, and R ₄ may be the same or different in the molecule, but the same one is preferred because preparation is simple. More preferred.

Next, some more specific examples in the case of using the bonding method combining the polyester type and the polyurethane type as described above will be described together with an example of the manufacturing method. However, the following production method examples do not mean that the polydiorganosiloxane capable of obtaining the effects of the present invention is limited to the following examples.
For example, prepared by ring-opening polymerization of ε-caprolactone using polydimethylsiloxane represented by general formula (VI) obtained by a conventionally known method, triisocyanate represented by general formula (VII), and ethylene glycol monomethacrylate The polydimethylsiloxane compound represented by the general formula (IX) is obtained by a conventionally known urethane bond forming reaction using the polymerizable reactive group-containing polyester (VIII) to be produced at a molar ratio of 1: 2: 4.
At this time, polydimethylsiloxane (VI) is added to triisocyanate (VII), urethane bonds are formed at both ends of polydimethylsiloxane (VI), and then the polymerizable reactive group-containing polyester (VII) is used. By performing urethane bond formation, by-products (for example, by-products consisting only of polydimethylsiloxane (VI) and triisocyanate (VII), polymerizable reactive group-containing polyester (VIII) and triisocyanate (VII) only) The desired polydimethylsiloxane compound (IX) can be obtained in high yield by suppressing the formation of by-products.
Here, d in the general formula (VI) and the general formula (IX) is an integer of 15 to 20, e is an integer of 1 to 5, and f in the general formula (VII) and the general formula (IX). Is an integer of 4 to 8, and g in general formula (VIII) and general formula (IX) is an integer of 3 to 5.

In addition, for example, polydimethylsiloxane represented by the general formula (X) obtained by a conventionally known method, diisocyanate represented by the general formula (XI), and ε-caprolactone using pentaerythritol triacrylate Polydimethylsiloxane represented by the general formula (XIII) by a conventionally known urethane bond forming reaction using a polymerizable reactive group-containing polyester (XII) prepared by ring-opening polymerization in a molar ratio of 1: 2: 2. A compound is obtained. At this time, after adding polydimethylsiloxane (X) to diisocyanate (XI) and forming urethane bonds at both ends of polydimethylsiloxane (X), urethane with polymerizable reactive group-containing polyester (XII) By performing bond formation, by-products (for example, by-products consisting only of polydimethylsiloxane (X) and diisocyanate (XI), and by-products consisting only of polymerizable reactive group-containing polyester (XII) and diisocyanate (XI)) The desired polydimethylsiloxane compound (XIII) can be obtained in high yield.
Here, h in general formula (X) and general formula (XIII) is an integer of 25-35, i is an integer of 1-5, j in general formula (XI) and general formula (XIII) Is an integer of 5 to 10, and k in the general formula (XIII) and the general formula (XIII) is an integer of 3 to 5.

Furthermore, for example, a polydimethylsiloxane having 12 acryloyloxy groups from the polydimethylsiloxane represented by the general formula (X), triisocyanate (VII), and polymerizable reactive group-containing polyester (XII) by combining the above two examples. You can also get it.
In addition to this, it is also possible to synthesize by a method in which a polyester portion having a polymerizable reactive group and a polyurethane portion are bonded and then introduced into a siloxane skeleton, or a method in which a polymerizable reactive group is finally introduced. is there.

Usually, the polydiorganosiloxane having a polymerizable double bond in the molecule represented by the general formula (IV) can be used alone or in combination of two or more.
Also, organopolysiloxanes having one or two polymerizable reactive groups in one molecule, such as one-end methacryloxy-modified polydimethylsiloxane, polysiloxane having a perfluoroalkyl group and one end methacryloxy group, or both-end methacryloxy-modified polydimethyl. A combination of siloxane and the polydiorganosiloxane having a specific structure of the present invention can also be used.

  Further, 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. Further, 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 ( A (meth) acrylate etc. can be mixed and used in the ratio of 60 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 used when polymerizing and curing the fluorine-containing curable coating liquid is the same type of photopolymerization initiation as the [6] photopolymerization initiator used when forming the antiglare hard coat layer described above. Agent is used. 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.

  [4] The low refractive index layer is obtained by polymerizing and curing the fluorine-containing curable coating liquid with a high energy beam such as an electron beam, or in the presence of a thermal decomposition type polymerization initiator or a photopolymerization initiator. Can be obtained by polymerization and curing. 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, 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.

[5] The active energy ray source used for irradiating the active energy ray for curing the active energy ray curable resin includes, for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive material. An elemental source or the like is used.
And [2] The irradiation amount of the active energy ray for forming the antiglare hard coat layer is preferably 50 to 5000 mJ / cm ² as the integrated light amount at the wavelength of 365 nm of ultraviolet rays. When the irradiation amount is less than 50 mJ / cm ² , curing of the antiglare hard coat layer forming composition 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.

[4] The irradiation amount of the active energy ray of the fluorine-containing curable coating liquid for forming the low refractive index layer is preferably 10 mJ / cm ² or more, more preferably 100 mJ / cm ² 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 / cm ² , 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 at the time of polymerization curing and post-curing.

  The thickness of the [4] 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. When this film thickness is less than 50 nm or exceeds 200 nm, the anti-reflection effect decreases.

  The refractive index of the [4] low refractive index layer is preferably low from the viewpoint of obtaining a suitable antireflection effect, 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 of the present invention thus obtained, the refractive index difference between the cured binder and the translucent fine particles, which is a requirement of the above <c>, is 0 to improve image sharpness. It is adjusted to 0.05. The difference in refractive index is preferably set to 0 to 0.03, more preferably 0 to 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 measured by the diffuse illumination (integrating sphere) method of the antiglare antireflection film of the present invention becomes the minimum value is 450 nm to 560 nm, preferably 460 nm to 550 nm, more preferably 470 nm. It is set to any of the range of 540 nm. 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.

In addition, as a requirement of the <o>, the overall haze value is 10% or less, and the ratio of the internal haze value to the overall haze value is 50% or more.
Thus, by adjusting the overall haze value to be low, the light transmittance is improved, and the image definition and the black density of the image can be improved. Furthermore, the balance with anti-glare property, glare, and image definition can be improved by regulating the external haze value appropriately by defining the ratio of the internal haze value to the overall haze value.

Furthermore, the reflectance showing the reflection of the antiglare antireflection film of the present invention is preferably 5% or less, and more preferably 3.5% or less. This visibility reflectance is obtained by measuring the reflectance (%) using a spectrophotometer equipped with a diffuse illumination type (integrating sphere) measuring device.
In addition, in the antiglare antireflection film of the present invention, it is necessary to adjust the concavo-convex shape of the antiglare antireflection film surface in order to exhibit light diffusibility. 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, which is a requirement of <d>, is 0.01. It is -0.30 micrometer, and the average space | interval (Sm) of an unevenness | corrugation is 10-300 micrometers. The arithmetic average roughness is preferably 0.01 to 0.20 μm, and most preferably 0.05 to 0.15 μm. Furthermore, by setting the Ra of the unevenness on the surface 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.

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.
Note that the surface roughness, haze value, image definition value, glare, black density, and luminous reflectance in each example were measured by the methods described below.

(1) Evaluation of Abrasion Resistance A commercially available flannel cloth was installed at the tip of an eraser abrasion tester manufactured by Honko Seisakusho via a silicone rubber cushion, and the film surface was worn under a load of 500 gf. The film to be worn was used in a state of being attached to a glass plate with an appropriate adhesive. The test was terminated when the wear surface was scratched, and the evaluation result was determined by the number of durable wear.
(2) Evaluation of scratch resistance A steel wool of # 0000 is fixed to the tip of an eraser abrasion tester manufactured by Honko Seisakusho, and a load of 2.5N (250 gf) and 1N (100 gf) is applied to the scratched body. The scratches on the surface after 10 reciprocating rubs on the surface of a film were visually observed and evaluated in the following four stages.
◎: almost no scratch ○: 5-15 scratches △: 15-30 scratches ×: 31 or more scratches In addition, as in the case of (1) evaluation of wear resistance, the film was passed through an appropriate adhesive. Tested in condition.

(3) Surface Roughness Using a surface roughness measuring machine manufactured by Kosaka Laboratory Co., Ltd., Surfcoder SE500, under the conditions of a scanning range of 4 mm and a scanning speed of 0.2 mm / s, in accordance with the provisions of JIS B 0601-1994. The arithmetic average roughness Ra (μm), the average interval Sm (μm) of the unevenness, and the ten-point average roughness Rz (μm) were measured in conformity.
(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. The internal haze value is a haze value measured by dropping water droplets on the surface of the antiglare hard coat layer and pressing glass there.
(5) Image Sharpness Value Through an optical comb having a width of 2 mm using an image sharpness measuring device based on JIS K 7105-1981 (image clarity measuring device manufactured by Suga Test Instruments Co., Ltd., ICM-1T) ( 5-1) Image sharpness value (%) and (5-2) Image sharpness value (%) measured by 60 ° reflection were measured.
(6) Glare An anti-glare film was placed on the outermost surface on the image display side of a high-definition liquid crystal touch panel as a high-definition liquid crystal display, and the glare was measured visually and evaluated in the following three stages.
3: No glare, 2: Some glare, 1: Glare.
(7) Black density A black adhesive film was attached to the back of the sample of the antiglare film attached to the glass, and the blackness in a state where the fluorescent lamp was reflected was evaluated.
○: Black is conspicuous, Δ: Some white parts are present but black as a whole, ×: White as a whole.
(8) Visibility reflectance In order to remove the back surface reflection of the measurement surface, the back surface is roughened with sandpaper, and a spectrophotometer equipped with an integrating sphere reflectance measuring device [trade name: U-best50, manufactured by JASCO Corporation] Was used to measure the reflectance (%) and the value was corrected by the visibility.

[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.
[1] As a 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.
[2] 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 the sulfuric acid having a concentration of 0.5% by mass is maintained while maintaining this temperature. An aqueous sodium solution was 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 to form a composite oxide fine particle dispersion (core particles 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%.
[3] As the third step, pure water was added to the composite oxide fine particle dispersion, and concentrated hydrochloric acid (concentration 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 (I) having a solid content concentration of 20% by mass.
[4] In the fourth step, a mixture of the silica-based fine particles (I) in water, pure water, ethanol and 28% by mass ammonia water is heated to 35 ° C., and then ethyl silicate (SiO ₂ A silica coating (second silica coating layer) was formed by adding 28% by mass). Subsequently, while adding 5 L of pure water, it was filtered through an ultrafiltration membrane to prepare a dispersion of silica-based fine particles (II) having a solid content concentration of 20% by mass.
[5] Finally, as a fifth step, the dispersion of silica-based fine particles (II) was again hydrothermally treated 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 by an ultrafiltration membrane. 100 g of organosol having a SiO ₂ content of 20% by mass (the water content was SiO ₂ content) 0.5 mass%) was prepared. Thereto, 28 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 [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM5103 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]
The organosol in which the modified hollow silica fine particles obtained in Production Example 1 are dispersed is 50 parts by mass in terms of solid content, 1,10-diaacryloyloxy-2,2,3,3,4,4,5,5,5. 6,6,7,7,8,8,9,9-hexadecafluorodecane (fluorine content 53 mass%) [manufactured by Kyoeisha Chemical Co., Ltd., trade name “16-FDA”] 50 parts by mass, photopolymerization 5 parts by mass of an initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 907), a polyether-modified polydimethylsiloxane additive having no polymerizable reactive group (trade name “BYK-300”, Big Chemie ( 10 parts by weight) 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).

Example 1
Urethane acrylate [molecular weight 1400, viscosity at 60 ° C. 2500 to 4500 Pa · s, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple UV7600B] 100 parts by mass, 1- [4- (2-hydroxyethoxy) phenyl as a photopolymerization initiator ] 2-Hydroxy-2-methyl-1-propan-1-one [Ciba Specialty Chemicals, Irgacure 2959] 3 parts by mass and methyl isobutyl ketone (MIBK) 83.4 parts by mass To prepare a binder, and fine particles of a cross-linked acrylic-styrene copolymer resin (XX-09V, monodispersed fine particles having a uniform particle diameter, average particle size as a translucent organic fine particle, manufactured by Sekisui Plastics Co., Ltd.) Diameter (a) is 5.0 μm] 30 parts by mass was mixed to prepare a composition for forming an antiglare hard coat layer.
This anti-glare hard coat layer forming composition was applied on a triacetyl cellulose (TAC) film having a thickness of 80 μm as a transparent substrate by a roll coater so that the dry film thickness was 8.5 μm. For 2 minutes. The dry film thickness is substantially the film thickness (A) of the antiglare hard coat layer. 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 produce an antiglare hard coat layer. The cured product obtained by curing the binder had a refractive index of 1.500, and the translucent fine particles had a refractive index of 1.498. Therefore, the difference in refractive index between the cured binder and the translucent fine particles was 0.002.
Furthermore, on the obtained composition for forming an antiglare hard coat layer, the coating liquid obtained in Production Example 2 was applied with a microgravure coater, dried, and then cured by irradiation with ultraviolet rays to prevent reflection. A layer was formed to obtain an antiglare antireflection film. The arithmetic average roughness (Ra) on the surface of the obtained antireflection layer was 0.14 μm, the average interval (Sm) of the unevenness was 150 μm, and the overall haze value of the antiglare film was 2.2%.

Example 2
In the preparation of the composition for a low refractive index layer shown in Production Example 2, a liquid in which 1 part by weight of alumina fine particles was mixed was used, and a film was prepared according to Example 1 except that. The arithmetic average roughness (Ra) on the surface of the obtained antiglare antireflection layer is 0.14 μm, the average interval of unevenness (Sm) is 150 μm, and the overall haze value of the antiglare film is 2.2%. there were.

Example 3
A polyether-modified polydimethylsiloxane additive having no polymerizable reactive group described in the preparation of the composition for a low refractive index layer shown in Production Example 2 (trade name “BYK-300”, Big Chemie Co., Ltd.) Instead of a polyether-modified polydimethylsiloxane additive having 4 polymerizable reactive groups (acryloyloxy group) (trade name “BYK-UV 3570”, manufactured by Big Chemie Co., Ltd.) A film was prepared according to Example 1 except that a liquid in which 1 part by weight of alumina fine particles was mixed was used. The arithmetic average roughness (Ra) on the surface of the obtained antiglare antireflection layer is 0.14 μm, the average interval of unevenness (Sm) is 150 μm, and the overall haze value of the antiglare film is 2.2%. there were.

Example 4
A polyether-modified polydimethylsiloxane additive having no polymerizable reactive group described in the preparation of the composition for a low refractive index layer shown in Production Example 2 (trade name “BYK-300”, Big Chemie Co., Ltd.) Instead of a polyether-modified polydimethylsiloxane additive having 4 polymerizable reactive groups (acryloyloxy group) (trade name “BYK-UV 3570”, manufactured by Big Chemie Co., Ltd.) , Using a mixture of 1 part by weight of alumina fine particles, 50 parts by weight of 1,2,9,10-tetraacryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane, Except for the above, a film was prepared according to Example 1. The arithmetic average roughness (Ra) on the surface of the obtained antiglare antireflection layer is 0.14 μm, the average interval of unevenness (Sm) is 150 μm, and the overall haze value of the antiglare film is 2.2%. there were.

<< Comparative Example 1 >>
100 parts by mass of urethane acrylate [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light UV7600B], 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane- as a photopolymerization initiator A binder was prepared by mixing 3 parts by weight of 1-one [Ciba Specialty Chemicals Co., Ltd., Irgacure 2959] and 130 parts by weight of methyl isobutyl ketone (MIBK). 30 parts by mass of fine particles of silica particles (Fuji Silysia Chemical Co., Ltd., Pyrospher C-1504, average particle size: 4.0 μm) were mixed to prepare a composition for forming an antiglare hard coat layer.
This anti-glare hard coat layer forming composition was applied on a 80 μm thick triacetyl cellulose (TAC) film as a transparent substrate with a roll coater so as to have a dry film thickness of 5.0 μm, and 80 ° C. For 2 minutes. Thereafter, ultraviolet rays were irradiated by a 120 W high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) (integrated light amount 400 mJ / cm ² ) and cured to produce an antiglare film. The refractive index of the cured product obtained by curing the binder was 1.500, and the refractive index of the translucent fine particles was 1.410. Therefore, the difference in refractive index between the cured binder and the light-transmitting fine particles was 0.090.
Furthermore, on the obtained anti-glare hard coat layer, the coating liquid obtained in Production Example 2 was applied with a micro gravure coater, dried, and then cured by irradiating with ultraviolet rays to produce an anti-glare antireflection film. Got. The arithmetic average roughness (Ra) on the surface of the obtained antiglare antireflection layer was 0.20 μm, the average interval of unevenness (Sm) was 200 μm, and the overall haze value of the antiglare film was 30.0%. .

About the anti-glare antireflection film obtained in Examples 1 to 4 and Comparative Example 1 above, scratch resistance, abrasion resistance, surface roughness, haze value, image sharpness value, glare, black density and The visibility reflectance was measured, and the results are shown in Table 1.

As is clear from Table 1, the antiglare antireflection films of Examples 1 to 4 are adjusted for the difference in refractive index between the cured product of the binder and the translucent organic fine particles in the antiglare hard coat layer. It was confirmed that light transmission in the antiglare hard coat layer can be suppressed and the light transmission can be improved, and the image definition and the black density of the image can be improved. In addition, since the average roughness (Ra) and the average interval (Sm) of the unevenness on the surface of the antireflection layer are set to appropriate ranges, the diffusion of light is controlled, and excessive scattering of light is suppressed, thereby causing glare. It was suppressed. In addition, the overall haze value was adjusted low, the light transmission was improved, and the image definition and the black density of the image could be improved. Moreover, since the ratio of the internal haze value to the overall haze value is regulated and the external haze value is adjusted appropriately, the balance between antiglare property, glare and image definition can be improved. Therefore, when used in a liquid crystal display, it is possible to suppress glare, increase black density and image sharpness, improve image visibility, especially in a high-definition liquid crystal display The effect is demonstrated effectively. Furthermore, the hollow silica fine particles are integrated with the fluorine-containing compound by copolymerizing the (meth) acryloyloxy group of the silane coupling agent contained in the composition of the low refractive index layer and the polymerizable double bond of the fluorine-containing compound. It was confirmed that the strength and hardness of the low refractive index layer obtained from the fluorine-containing curable coating liquid can be improved, and the scratch resistance and wear resistance of the coating surface can be improved.
On the other hand, Comparative Example 1 had a large difference in refractive index between the cured binder and the light-transmitting organic fine particles, so that light scattering could not be suppressed and the light transmittance was low. Further, since the average roughness (Ra) on the surface of the antireflection layer is large, the light diffuses, the light is excessively scattered and glaring occurs, and the overall haze value is also large. The sharpness and black density were poor. Further, the fact that the ratio of the internal haze value to the overall haze value is not appropriate is also considered to contribute to the problem of antiglare property and glare.

Claims (7)

  An antiglare hard coat layer and an antireflection layer comprising at least a low refractive index layer are laminated in this order on a transparent substrate made of a cellulosic material, and the antiglare hard coat layer is A cured product of a composition containing an active energy ray-curable resin, a photopolymerization initiator, and translucent organic fine particles, and a cured product of the binder containing the active energy ray-curable resin and the photopolymerization initiator and a transparent material. The refractive index difference with the light organic fine particles is adjusted to 0 to 0.05, and the arithmetic average roughness (Ra) measured according to JIS B 0601-1994 on the surface of the antireflection layer is 0.01 to 0. .30 [mu] m and the average interval of irregularities (Sm) is 10 to 300 [mu] m, the overall haze value is 10% or less, and the ratio of the internal haze value to the overall haze value is 50% or more, The refractive index layer is a cured film of a composition containing a fluorine-containing compound having a polymerizable double bond in the molecule and hollow silica fine particles modified with a silane coupling agent having a polymerizable double bond in the molecule. An antiglare antireflection film characterized by being.   2. The antiglare antireflection film according to claim 1, wherein the low refractive index layer further contains metal oxide fine particles having an average particle diameter of 10 to 100 nm.   The low refractive index layer is further cured by further containing 0.1 to 20% by mass of a polydiorganosiloxane having a polymerizable double bond in the molecule. The antiglare antireflection film described in 1. The fluorine-containing compound having a polymerizable double bond is a polyfunctional monomer having two or more polymerizable unsaturated groups represented by the following formula (I). 2. An antiglare antireflection film as set forth in claim 1.

  The antiglare antireflection film according to any one of claims 1 to 4, wherein the translucent organic fine particles are a (meth) acrylic resin, a styrene-acrylic copolymer resin, or a cross-linked product thereof. .   The ratio a / A of the average particle diameter (a) of the translucent organic fine particles to the film thickness (A) of the antiglare hard coat layer is 0.3 to 1.5. 6. The antiglare antireflection film according to any one of 5 above.   A liquid crystal display comprising the antiglare antireflection film according to any one of claims 1 to 6 on the outermost surface on the image display side.