JP2003004904A - Antireflection film having antidazzle layer with high refractive index and low reflective display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film which has both properties of antireflection property and antidazzle property and excellent transparency and which prevents deterioration in coating films. SOLUTION: A light transmitting low refractive index layer having the refractive index lower than that of the transparent base film is laminated on at least one surface of the base film. A light transmitting antidazzle layer having the refractive index higher than that of the transparent base film or of the low refractive index layer is laminated between the base film and the low refractive index layer. The antidazzle layer is formed from a coating composition containing metal oxide superfine particles coated with an inorganic compound and/or organic compound which reduces or eliminates photocatalytic activity, a light transmitting binder resin, a dispersant, an organic solvent and a light transmitting diffusing agent. The metal oxide superfine particles have 0.01 to 0.1 μm primary particle size and 1.90 to 2.90 refractive index. The difference Δn in the refractive index between the light transmitting resin having a high refractive index by dispersing the metal oxide superfine particles and the light transmitting diffusing agent in the antidazzle layer satisfies 0.01<=n<=0.5. The average particle size d of the light transmitting diffusing agent satisfies 0.1 μm<=d<=5 μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film applied to the surface of a display device and a low reflection display device having the antireflection film applied to the surface. More specifically, an antireflection film that can be applied to the surface of a high-definition image display such as a CRT used for image display in a word processor, a computer, a television, a liquid crystal panel, and the like, and a low reflection film obtained by applying the antireflection film to the surface. Regarding display device.

[0002]

2. Description of the Related Art The display surface of an image display device such as a liquid crystal display (LCD) or a cathode ray tube display device (CRT) is provided with a reflection of a light beam emitted from an external light source such as a fluorescent lamp in order to enhance its visibility. It is required to be small.

It has been conventionally known that the reflectance is reduced by coating the surface of a transparent object with a transparent coating having a small refractive index. It is also known that the antireflection effect is further improved by forming a high refractive index layer or a medium refractive index layer on the display surface of the image display device and further forming a low refractive index layer thereon.

It is also known that ultrafine metal oxide particles having a high refractive index are dispersed in a light-transmitting binder resin to form a coating film having a high refractive index, but the transparency of the coating film is deteriorated. There's a problem. Further, since the ultrafine particles of metal oxide having a high refractive index generally have a photocatalytic action, there is a problem that the deterioration of the coating film is caused and the weather resistance is poor.

On the other hand, in the image display device as described above, an antiglare film having fine irregularities is provided on the display surface in order to prevent glare when incident light from an external light source is reflected on the display surface. It is known to prevent glare by diffusing the reflected light.

In order to prevent these glare, a coating solution obtained by dispersing a light-transmitting diffusing agent such as silica or resin beads in a light-transmitting binder resin is applied to the surface of the display, or obtained by coating. The film was attached to the surface of the display. The antiglare layer thus formed on the surface of the display can have irregularities due to the particle shape of the light transmissive diffusing agent (Japanese Patent Laid-Open No. H06-6 / 1999).
-18706 and Japanese Patent Laid-Open No. 10-20103).

[0007]

Liquid crystal display (L
In order to impart both antireflection and antiglare properties to the surface of an image display device such as a CD) or a cathode ray tube display (CRT), the present invention has both of these properties and is transparent. It is an object of the present invention to provide an antireflection film having excellent properties and preventing deterioration of a coating film.

[0008]

In order to achieve the above-mentioned object, the antireflection film of the present invention comprises (1) a transparent substrate film having a refractive index lower than that of the transparent substrate film on at least one surface thereof. At least a light-transmissive low-refractive index layer is laminated, and a light-transmittance having a higher refractive index than the transparent base film and the low-refractive index layer is provided between the transparent base film and the low-refractive index layer. (2) The antiglare layer is a metal oxide ultrafine particle coated with an inorganic compound and / or an organic compound that reduces or eliminates photocatalytic activity. A light-transmissive binder resin, a dispersant, an organic solvent, and a light-transmissive diffusing agent, and (3) the primary particle diameter of the metal oxide ultrafine particles themselves. 0.0 A ～0.1Myuemu, refractive index 1.
By having 90 to 2.90, the transparency and the refractive index of the antiglare layer are enhanced, and (4) the light transmittance of the antiglare layer in which ultrafine metal oxide particles are dispersed to have a high refractive index. The difference Δn in refractive index between the resin and the light transmissive diffusing agent is 0.01 ≦ n
≦ 0.5 and the average particle diameter d of the light transmissive diffusing agent is 0.1
It is characterized in that μm ≦ d ≦ 5 μm.

In the antireflection film of the present invention, at least a transparent substrate film and a light-transmitting antiglare layer having a refractive index higher than that of the low refractive index layer are laminated on the transparent substrate film, and further thereon. Further, since the low refractive index layer is formed, the antireflection property is exhibited. Moreover, the antiglare layer in the antireflection film of the present invention contains a light transmissive diffusing agent, and in the antiglare layer, a light transmissive resin having metal oxide ultrafine particles dispersed therein to have a high refractive index. Since the difference Δn in the refractive index of the light-transmitting diffuser itself is 0.01 ≦ n ≦ 0.5, the antiglare property and the transparency can be enhanced in a well-balanced manner.

The reason why the refractive index difference Δn is set to 0.01 or more as described above is that if it is less than 0.01, a very large number of light-transmitting diffusing agents are required to exhibit the light diffusing property in the antiglare layer. Must be contained in the light-transmitting binder resin, and when this is done, the adhesiveness and coatability of the antiglare layer to the transparent substrate film deteriorates, while when Δn is greater than 0.5, This is because the content of the light-transmitting diffusion agent in the light-transmitting resin is small, and an antiglare layer having uniform and appropriate unevenness cannot be obtained.

Since the primary particle diameter of the ultrafine metal oxide particles themselves contained in the antiglare layer in the antireflection film of the present invention is in the range of 0.01 to 0.1 μm, the transparency of the antiglare layer is high. Since the refractive index of the ultrafine metal oxide particles themselves is 1.90 to 2.90, the refractive index of the antiglare layer is increased and the refractive index is high. The antireflection film has an excellent antireflection effect.

The average particle size d of the light transmissive diffusing agent contained in the antiglare layer in the antireflection film of the present invention is 0.
1 μm ≦ d ≦ 5 μm. By having the light-transmitting diffusing agent having such an average particle diameter, the surface of the antiglare layer has appropriate irregularities. The average particle diameter d of the light transmissive diffusing agent is 0.1μ
When it is less than m, it becomes difficult to disperse the light transmissive diffusing agent in the light transmissive resin, and it is impossible to form an antiglare layer having uniform and appropriate unevenness on the surface due to aggregation, and 5 μm.
When it exceeds, the diffusing effect inside the antiglare layer is reduced, so that the internal haze value is lowered and surface glare occurs. Further, when it exceeds 5 μm, the film thickness is inevitably increased, so that the curing shrinkage in the manufacturing process of the light transmissive resin increases, and cracks and curls occur.

The high refractive index metal oxide ultrafine particles contained in the antiglare layer in the antireflection film of the present invention include:
Examples thereof include zinc oxide, titanium oxide, zirconium oxide, and cerium oxide. By the way, since such high-refractive-index metal oxide ultrafine particles generally have a photocatalytic action, they have a serious problem of deteriorating a coating film. Since it is coated with an inorganic compound and / or an organic compound that reduces or eliminates the activity, deterioration of the coating film in which the metal oxide ultrafine particles are dispersed is prevented.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is an example showing a basic layer structure of the antireflection film of the present invention. In FIG. 1, reference numeral 12 denotes a transparent base film, and one surface of the transparent base film 12 has a light-transmitting low refractive index layer 2 having a refractive index lower than that of the transparent base film 12.
0 is laminated, and a light-transmitting antiglare layer having a refractive index higher than those of the transparent substrate film 12 and the low refractive index layer 20 is provided between the transparent substrate film 12 and the low refractive index layer 20. 18 are stacked. The antiglare layer 18 is a matrix resin in which the light transmissive diffuser 14 is present in a dispersed state in the light transmissive resin 16.

Transparent Substrate Film Examples of materials for the transparent substrate film that can be used in the antireflection film of the present invention include transparent resin films, transparent resin plates, transparent resin sheets and transparent glass plates.

The material for the transparent resin film, transparent resin plate and transparent resin sheet is triacetyl cellulose (TA
C), polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyacrylic resin, polyurethane resin, polyester, polycarbonate, polysulfone, polyether, polymethylpentene, polyetherketone, (meta ) Acrylonitrile can be used, but is not particularly limited. The thickness of the base material is usually 25 μm to
It is about 1000 μm.

In particular, TAC is suitable for a transparent base film for optical use because it has no birefringence. Further, when the antiglare layer or the low refractive index layer is coated on the transparent substrate film by various coating methods, PET is preferable in terms of workability such as heat resistance, solvent resistance and mechanical strength. .

The haze value of the surface of the antiglare layer antiglare layer can obtain clear display representation to reduce the blurring of the display as low, and the more glare and so-called surface glare (scintillation haze value is too low A glittering sparkle called is generated,
There is a disadvantage that the visibility of the display screen is deteriorated. On the other hand, if the haze value is too high, there is a disadvantage that the display surface becomes whitish (whitening, reduction in black density). In order to avoid these disadvantages, the surface haze value ha is 7
<Ha <30 is preferable, and 7 <ha <15 is most preferable. Even if the surface haze value ha is optimized, if the internal haze value hi is low, surface glare is likely to occur. In order to avoid surface glare caused by such internal haze, the internal haze value hi of the antiglare layer is preferably 1 <hi.
It is desirable that <15, and more preferably 3 ≦ hi <12. Furthermore, the sum of the surface haze value and the internal haze value of the antiglare layer is preferably 50 or less, more preferably 30.
If it is set as follows, it is possible to prevent a decrease in black density (contrast).

The difference Δn in refractive index between the coating composition in which the metal oxide fine particles are dispersed in the antiglare layer to have a high refractive index and the light transmissive diffusing agent is preferably 0.01 ≦ n ≦ 0.5,
More preferably, 0.1 ≦ n ≦ 0.15. If Δn is 0.01 or less, surface glare cannot be effectively suppressed,
When it is 0.5 or more, it becomes whitish and the contrast is lost.

The antiglare layer in the antireflection film of the present invention has a refractive index of 1.55 when the thickness of the coating composition excluding the light transmissive diffusing agent is 0.2 to 8 μm.
1.80, and the haze value specified in JIS-K7361-1 does not differ from the haze value of the transparent substrate film, or the difference from the haze value of the transparent substrate film is 1.
It is characterized by being within%. That is, the antiglare layer in the antireflection film of the present invention has a high refractive index and is almost as transparent as the transparent substrate film.

The coating composition for forming the antiglare layer contains at least the following components (1) to (5):
(1) A metal oxide coated with an inorganic compound that reduces or eliminates photocatalytic activity and an organic compound and / or an organometallic compound having an anionic polar group, and has a primary particle size in the range of 0.01 to 0.1 μm. Ultrafine particles, (2) ionizing radiation curable binder resin component, (3) dispersant having anionic polar group, (4) organic solvent, and
(5) It is preferable to include a light transmissive diffusing agent.

1) Ultrafine Metal Oxide Particles The ultrafine metal oxide particles in the antiglare layer have a high refractive index and are zinc oxide ultrafine particles which are colorless or hardly colored (refractive index: 1. 95), titanium oxide (refractive index: 2.3 to 2.7), zirconium oxide (refractive index: 2.10), antimony oxide (refractive index: 2.0).
4), cerium oxide (refractive index: 2.20) has a high refractive index and can be preferably used for increasing the refractive index of the antiglare layer. In particular, zinc oxide ultrafine particles are preferable because they are excellent in transparency, light resistance and wet heat resistance when dispersed in a coating film.

The metal oxide ultrafine particles have a primary particle size of
0.01 μm or more and 0.1 μm or less, preferably 0.01
A material having a size of from μm to 0.04 μm is used. The above particle size range belongs to what is called “ultrafine particles”, and is generally called “fine particles” from several μm to several 1
It is distinguished from those with a particle size of 00 μm.

That is, in the present invention, the ultrafine metal oxide particles having an average particle size of less than 0.01 μm cause agglomeration and the like, which makes it difficult to disperse them uniformly in the coating composition. A coated film in which ultrafine oxide particles are uniformly dispersed cannot be obtained. Further, ultrafine metal oxide particles having an average fine particle diameter of more than 0.1 μm impair the transparency of the coating film, which is not preferable. The primary particle diameter of the metal oxide ultrafine particles may be visually measured by a scanning electron microscope (SEM) or the like, or may be mechanically measured by a particle size distribution meter or the like using a dynamic light scattering method or the like.

Since zinc oxide, titanium oxide, zirconium oxide, antimony oxide, and cerium oxide have photocatalytic activity, a coating solution containing these metal oxide ultrafine particles which has not been surface-treated is used. When a coating film is formed by photocatalytic action, the chemical bond between the binders forming the coating film is broken and the coating film strength is reduced, or the coating film becomes yellow and the transparency and haze of the coating film tend to deteriorate. There is an inconvenience. In order to eliminate such inconvenience, the present invention coats the surface of the metal oxide ultrafine particles with an inorganic compound and / or an organic compound capable of reducing or eliminating the photocatalytic activity.

The inorganic compounds and / or organic compounds that reduce or eliminate the photocatalytic activity include oxides or hydroxides of metals selected from Al, Si, Zr and Sn, and / or silicone resins having siloxane bonds. An organic compound consisting of is preferably used.

For example, zinc oxide coated with silicone resin is commercially available, and zinc oxide coated with methylhydrogenpolysiloxane is MZ.
It can be obtained from Teika Ltd. under the trade name of 505S.

2) Binder Resin Component The ionizing radiation-curable binder resin component in the coating composition used for forming the antiglare layer of the antireflection film of the present invention is the coating composition used for forming the antiglare layer. Is added for the purpose of imparting film-forming property and adhesion to the base film and the adjacent layer. The ionizing radiation-curable binder resin component exists in the state of an unpolymerized monomer or oligomer in the coating composition, and therefore has excellent coating suitability for the coating composition and easily forms a uniform large-area thin film. . Further, sufficient strength of the coating film can be obtained by polymerizing and curing the binder resin component in the coating film after coating.

The ionizing radiation-curable binder resin component is a monomer having a functional group that causes a polymerization reaction directly by irradiation with ionizing radiation such as ultraviolet rays or electron beams, or indirectly by the action of a polymerization initiator. Alternatively, an oligomer can be used. In the present invention, a radically polymerizable monomer or oligomer having an ethylenic double bond can be mainly used, and a photopolymerization initiator is optionally combined. However, it is also possible to use other ionizing radiation-curable binder resin components, for example, a photo-chatin-polymerizable monomer or oligomer such as an epoxy group-containing compound may be used. If necessary, a photo-chaotic initiator is used in combination with the photo-chaotic polymerizable binder resin component. The monomer or oligomer that is the binder resin component is preferably a polyfunctional binder resin component having two or more polymerizable functional groups so that cross-linking occurs between the molecules of the binder resin component.

Specific examples of the radically polymerizable monomer and oligomer having an ethylenic double bond include 2
-Monofunctional (meth) acrylates such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, carboxypolycaprolactone acrylate, acrylic acid, methacrylic acid and acrylamide. ; Pentaerythritol triacrylate, ethylene glycol diacrylate,
Diacrylates such as pentaerythritol diacrylate monostearate; Tri (meth) acrylates such as trimethylolpropane triacrylate and pentaerythritol triacrylate; Multifunctional compounds such as pentaerythritol tetraacrylate derivatives and dipentaerythritol pentaacrylate. ) Acrylate or an oligomer obtained by polymerizing these radically polymerizable monomers can be exemplified. Here, “(meth) acrylate” means acrylate and / or methacrylate.

Further, a resin containing molecules or atoms having a high refractive index component may be used as the binder. Examples of the molecule and atom of the component that improves the refractive index include halogen atoms other than F, atoms of S, N and P, and aromatic rings.

In order to make the above ionizing radiation curable resin composition into an ultraviolet curable resin composition, a photopolymerization initiator is further added. Examples of the photopolymerization initiator that initiates radical polymerization include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and benzyldimethyl. Ketone, 1- (4-dodecylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one , Benzophenone and the like. Among these, 1-hydroxy-cyclohexyl-phenyl-ketone and 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one is preferably used in the present invention because it initiates and accelerates the polymerization reaction upon irradiation with ionizing radiation even in a small amount. These can be used alone or in combination of both. They also exist in commercial products, for example 1-hydroxy-cyclohexyl-phenyl-ketone is Irgacure 184
It is available from Nippon Ciba Geigy under the trade name (Irgacure 184).

3) Dispersant Since the dispersant having an anionic polar group has, for example, an anionic polar group having a high affinity for zinc oxide, in order to impart dispersibility to zinc oxide. In particular, it is preferably incorporated into the coating composition for forming the antiglare property. Examples of the anionic polar group include a carboxyl group, a phosphoric acid group and a hydroxyl group.

As the dispersant having an anionic polar group, specifically, a product group supplied by Big Chemie Japan under the trade name of DisperBig, that is, Disper
byk-111, Disperbyk-110, Disperbyk-116, Disperbyk-140,
Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperby
k-164, Disperbyk-170, Disperbyk-171, Disperbyk-174, Di
Examples include sperbyk-180, Disperbyk-182, and the like.

Among these, the main chain having an ethylene oxide chain skeleton has a molecular structure in which a side chain having an anionic polar group or a side chain having an anionic polar group as described above is bonded, It is preferable to use a compound having a number average molecular weight of 2,000 to 20,000 based on polystyrene equivalent molecular weight since particularly good dispersibility can be obtained. The number average molecular weight is GPC (gel permeation chromatography)
It can be measured by the method. As a material that meets such a condition, there is Disperbyk 163 (trade name) in the above-mentioned Disperbyk (trade name, manufactured by Big Chemie Japan) series.

4) Organic Solvent The organic solvent for dissolving and dispersing the solid component of the coating composition for forming the antiglare layer is not particularly limited,
Various substances, for example, alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatics such as toluene and xylene Hydrocarbons; or mixtures thereof can be used.

In the present invention, it is preferable to use a ketone type organic solvent. When the coating composition used to form the antiglare layer is prepared using a ketone-based organic solvent, it can be easily and uniformly applied to the surface of the base material, and the solvent evaporates after application. Since the speed is appropriate and uneven drying is unlikely to occur, a large-area coating film having a uniform thickness can be easily obtained. As the ketone-based organic solvent, a single solvent composed of one kind of ketone-based organic solvent, a mixed solvent composed of two or more kinds of ketone-based organic solvents, and one or more kinds of other ketone-based organic solvents and other organic solvents It is possible to use those containing the above and not losing the property as a ketone-based organic solvent. Preferably, a ketone-based organic solvent in which 70% by weight or more, particularly 80% by weight or more of the organic solvent is occupied by one or more ketone-based organic solvents is used.

In the coating composition for forming the antiglare layer, the total solid content excluding the light transmissive diffusing agent is 0.5 to
The amount of the organic solvent is preferably 50 to 99.5 parts by weight with respect to 50 parts by weight. If it is less than 50% by weight, the pigment or binder component cannot be dispersed stably and uniformly, and if it exceeds 99.5% by weight, it does not make sense as a pigment dispersion liquid.

5) Light-transmitting diffuser The light-transmitting diffuser is preferably inorganic fine particles (silica beads) or organic fine particles, more preferably organic fine particles of styrene (refractive index 1.60) or acrylic (refractive index). 1.45) or a styrene-acrylic copolymer (refractive index 1.45 to 1.60) is used. The average particle diameter d of these organic fine particles is 0.1 μm ≦ d ≦ 5 μm.
The light transmissive diffusing agent is preferably added to the coating composition at the final stage of preparation of the coating composition, for example, immediately before coating, in order to prevent the light transmissive diffusing agent from settling and to apply the uniform dispersion liquid. The addition amount is 3 to 3 with respect to 100 parts by weight of the coating composition before the addition of the light transmissive diffusing agent.
0 parts by weight is preferred (ie 3% to 23% by weight of the final coating composition). If the amount of the light-transmitting diffuser added is excessive, the antiglare effect can be obtained, but the haze becomes high and the visibility is impaired. If the added amount is too small, the antiglare effect cannot be obtained.

6) Other Components The coating composition used for forming the antiglare layer of the antireflection film of the present invention may further contain other components in addition to the above components. For example, an ultraviolet shielding agent, an ultraviolet absorbing agent, an antioxidant, a light stabilizer, and a surface conditioner (leveling agent) can be used if necessary.

Preparation of coating composition: In the coating composition used for forming the antiglare layer of the antireflection film of the present invention, not only one kind of ultrafine metal oxide particles but also light resistance and transparency are not impaired. In addition, two or more kinds of high-refractive-index metal oxide fine particles may be used in combination. For example, when zinc oxide is used as the main metal oxide ultrafine particles, titanium oxide, zirconium oxide, or cerium oxide having a higher refractive index than zinc oxide may be further added. Further, ITO, ATO or the like may be further added for the purpose of imparting conductivity.

The blending ratio of each component in the coating composition used for forming the antiglare layer of the antireflection film of the present invention can be appropriately adjusted, but preferably 10 parts by weight of the metal oxide ultrafine particles are used. It is desirable to mix the binder resin component in an amount of 4 to 20 parts by weight and the anionic polar group-containing dispersant in an amount of 2 to 10 parts by weight. When the photopolymerization initiator is added to the binder resin, the photopolymerization initiator is usually added in a proportion of 3 to 8 parts by weight with respect to 100 parts by weight of the binder resin component.

The amount of the organic solvent contained in the coating composition is such that each component can be uniformly dissolved and dispersed, does not cause aggregation during storage after preparation, and is not too dilute during coating. The addition amount is adjusted appropriately so that A high-concentration coating composition was prepared by reducing the amount of the solvent used within the range where such conditions were satisfied, stored in a state where the capacity was not taken, and the necessary amount was taken out at the time of use and suitable for coating work. It is preferable to dilute to a concentration. In the present invention, when the total amount of the solid content and the organic solvent is 100 parts by weight, the essential components and other components are included, and the total solid content excluding the light-transmitting diffuser is 0.5 to 50 parts by weight. , 50 to 95.5 parts by weight of the organic solvent, and more preferably 70 to 90 parts by weight of the organic solvent based on 10 to 30 parts by weight of the total solid content excluding the light transmissive diffusing agent. In particular, a coating composition having excellent dispersion stability and suitable for long-term storage can be obtained.

In order to prepare a coating composition for forming an antiglare layer using each of the above components, dispersion treatment may be carried out according to a general method for preparing a coating liquid. For example, each essential component and each desired component are mixed in an arbitrary order, a light-transmitting diffusing agent such as beads is added to the obtained mixture, and the mixture is appropriately dispersed by a paint shaker or a bead mill to obtain a coating composition. The thing is obtained.

Characteristics of coating composition: The coating composition used for forming the antiglare layer of the antireflection film of the present invention has excellent dispersibility and stability of ultrafine metal oxide particles, and has an extremely high haze. It has small features. That is, by controlling the compounding amount of the metal oxide ultrafine particles in the coating composition to control the refractive index, the coating composition is applied to the surface of a substrate such as a substrate, dried, and cured. A film having a predetermined refractive index, high transparency, and a small haze can be obtained even when the film is thickened to about 3 to 8 μm. Therefore, the coating composition used for the antiglare layer of the antireflection film of the present invention is also suitable for forming a layer other than the antiglare layer, and contains metal oxide ultrafine particles, particularly zinc oxide ultrafine particles. Considering the range of the refractive index that can be adjusted by changing the amount, it is also suitable when forming the medium refractive index layer.

Further, since the coating composition used for forming the antiglare layer of the antireflection film of the present invention is excellent in dispersion stability over a long period of time, it has a long pot life and is used after being stored for a long period of time. However, it is possible to form a coating film having high transparency and small haze.

Furthermore, the coating composition used for forming the antiglare layer of the antireflection film of the present invention has excellent coating suitability and can be easily and thinly and widely applied uniformly on the surface of the article to be coated. It is possible to form a uniform large-area thin film. In particular, when a ketone-based organic solvent having a slow evaporation rate is used, the viscosity is appropriate and unevenness in drying of the coating film hardly occurs, so that a uniform large-area thin film can be easily formed.

The coating composition used for forming the antiglare layer of the antireflection film of the present invention is applied to the surface of an article to be coated such as a transparent film substrate, dried, and cured by ionizing radiation to give a substantial composition. A colorless and transparent coating film having a small haze can be formed.

Coating method: The coating composition for forming the antiglare layer is, for example, spin coating method, dipping method, spraying method, slide coating method, bar coating method,
It can be coated on the substrate by various methods such as a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method and a bead coater method. After coating the coating composition on the surface of an article to be coated such as a transparent substrate film in a desired coating amount, it is usually heated and dried by a heating means such as an oven, and then ionized by ultraviolet rays or electron beams. A coating film is formed by irradiating with radiation and curing.

Low Refractive Index Layer The low refractive index layer used in the present invention has, for example, a refractive index of 1.46 or less obtained from a coating liquid containing an inorganic substance such as silica or magnesium fluoride, a fluorine resin or the like. It can be formed using a coating film. Coating and the silicon-containing polyvinylidene fluoride copolymer, formed of SiO ₂ film by a sol-gel method, the formation of the SiO ₂ film by CVD or PVD, can be suitably applied to the present invention. Since the coating film formed by the silicon-containing polyvinylidene fluoride copolymer has antifouling properties, when forming the low refractive index layer using a material other than the silicon-containing polyvinylidene fluoride copolymer, the low refractive index layer It is desirable to provide an antifouling layer on top.

For example, the formation of the low refractive index layer using a silicon-containing polyvinylidene fluoride copolymer will be specifically described below, but the present invention is not limited thereto. 100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene; and ethylene. A resin composition containing 80 to 150 parts by weight of a polymerizable compound having a polymerizable unsaturated group is prepared. Using this resin composition, a film thickness of 200
It is possible to form a low refractive index layer having a refractive index of less than 1.60 (preferably 1.45 or less), which is a thin film having a thickness of nm or less and is provided with scratch resistance.

The fluorine-containing polymer used in this low refractive index layer is a copolymer obtained by copolymerizing a monomer composition containing vinylidene fluoride and hexafluoropropylene. The proportion of each component in the vinylidene fluoride is 30 to 90% by weight, preferably 40 to 80% by weight, and particularly preferably 4%.
Hexafluoropropylene is 5 to 50% by weight, preferably 10 to 50% by weight, particularly preferably 15 to 45% by weight. The monomer composition may further contain tetrafluoroethylene in an amount of 0 to 40% by weight, preferably 0 to 35% by weight, particularly preferably 10 to 30% by weight.

Further, the monomer composition for obtaining this fluorine-containing copolymer contains other copolymer components in an amount of, for example, 20% by weight or less, preferably 10%, within the range that the object and effect of the present invention are not impaired. It may be contained in the range of not more than wt%. Here, as specific examples of the other copolymerization component, for example, fluoroethylene, trifluoroethylene, chlorotrifluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 2-promo-3,
3,3-trifluoroethylene, 3-promo-3,3-
Examples of the polymerizable monomer having a fluorine atom include difluoropropylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, and α-trifluoromethacrylic acid. it can.

The fluorine-containing copolymer obtained from such a monomer composition has a fluorine content of 60 to 70.
It is necessary that the content is 60% by weight, and the preferable fluorine content is 62 to 70% by weight, particularly preferably 64 to 68% by weight.

The fluorine-containing copolymer has good solubility in the solvent described below, especially when the fluorine-containing ratio is within the above specified range. Further, by containing such a fluorine-containing copolymer as a component, it has excellent adhesion to various substrates, has high transparency and a low refractive index, and has sufficiently excellent mechanical properties. Since a thin film having strength is formed, mechanical properties such as scratch resistance of the antireflection film surface can be made sufficiently high, which is extremely preferable.

This fluorine-containing copolymer has a molecular weight of 5,000 to 20,000 in terms of polystyrene equivalent number average molecular weight.
It is preferably 0, particularly preferably 10,000 to 100,000. By using the fluorine-containing copolymer having a molecular weight of such a size, the viscosity of the resulting fluorine-based resin composition becomes a suitable size, and therefore, the fluorine-based resin composition having surely suitable coatability. Can be

Further, the fluorine-containing copolymer preferably has a refractive index of 1.45 or less, particularly 1.42 or less, and more preferably 1.40 or less. Refractive index is 1.45
When a fluorine-containing copolymer exceeding the above is used, the thin film formed by the obtained fluorine-based paint may have a small antireflection effect.

The polymerizable compound which can be preferably used in the present invention is heated by irradiation with an active energy ray in the presence or absence of a photopolymerization initiator or in the presence of a thermal polymerization initiator. As a result, it is a compound having an ethylenically unsaturated group which causes addition polymerization. Specific examples of such a polymerizable compound include, for example, JP-A-8-
Those described in Japanese Patent Laid-Open No. 94806 can be used.

Of these compounds, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate are particularly preferable.

When the polymerizable compound used in the present invention contains three or more ethylenically unsaturated groups in one molecule, the obtained fluororesin composition has particularly excellent adhesiveness to a substrate. And a thin film having extremely good mechanical properties such as scratch resistance of the surface of the substrate.

In the present invention, the amount of the polymerizable compound used is
30 to 150 per 100 parts by weight of the fluorine-containing copolymer
Parts by weight, preferably 35 to 100 parts by weight, particularly preferably 40 to 70 parts by weight. If the proportion of the polymerizable compound used is too low, the thin film formed by the obtained coating material will have low adhesion to the substrate. On the other hand, if the proportion used is too large, the thin film formed will have a refractive index. It becomes difficult to obtain a good antireflection effect.

In the fluorine-based resin composition, the fluorine content is 30 to 55% by weight in the total amount of the polymer-forming components including the fluorine-containing copolymer and the polymerizable compound.
It is particularly preferably 35 to 50% by weight. When such conditions are satisfied, it is possible to reliably form a thin film that achieves the objects and effects of the present invention more sufficiently. A thin film formed by a fluorine-based resin composition having an excessive fluorine content tends to have low adhesion to a substrate, and mechanical properties such as scratch resistance of the surface of the substrate are slightly deteriorated. On the other hand, a thin film formed from a fluorine-based resin composition having an excessively low fluorine content tends to have a large refractive index and a low antireflection effect.

For the low refractive index layer in the antireflection film of the present invention, a silicon-containing vinylidene fluoride polymer can be preferably used, and silicon and fluorine improve the surface antifouling property and scratch resistance, Can suppress the deterioration of the physical properties of the low refractive index layer after the saponification treatment described later.

The low refractive index layer is made of vinylidene fluoride 30-9.
0 wt% and hexafluoropropylene 5-50 wt%
Fluorine-containing copolymer 1 having a fluorine content of 60 to 70% by weight obtained by copolymerizing a monomer composition containing
00 parts by weight and a resin composition comprising 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group, hexafluoropropylene 5 to 50, especially in the fluorine-containing copolymer. When it contains a monomer component by weight, a low refractive index of 1.45 or less can be realized in the low refractive index layer formed by applying this resin composition, or, in particular, the fluorine Since the contained copolymer contains 80 to 90% by weight of vinylidene fluoride as a monomer component, the solvent solubility of the obtained resin composition is increased, the coating suitability is improved, and the film thickness thereof is suitable for antireflection. It can be a thin film having a thickness of 200 nm or less. Further, in this case, the polymerizable compound 30 having an ethylenically unsaturated group is added to the resin composition to be applied.
Since it contains 150 parts by weight, the resulting coating film has excellent scratch resistance and mechanical strength. Further, since each resin component has high transparency, the low refractive index layer formed using the resin composition containing these components is excellent in transparency.

In the antireflection film of the present invention shown in FIG. 1, the air layer (refractive index 1.0) and the low refractive index layer 20 (refractive index less than 1.60, preferably 1 .45 or less), the antiglare layer 18 (refractive index of 1.5 or more), and the transparent substrate film 12 (lower than or almost the same as the refractive index of the antiglare layer 18), so efficient antireflection is performed. be able to. It is desirable that the refractive index of the antiglare layer 18 be higher than that of the transparent substrate film 12. In such a case, the transparent substrate film 1
The effect of preventing reflection at the interface between 2 and the antiglare layer 18 is further added.

FIG. 2 shows an embodiment of the present invention in which an adhesive layer is provided on the antireflection film of FIG. 1 described above. As shown in FIG. 2, an antireflection film 101 in which an adhesive layer 22 and a separator 24 are provided on the surface of the antireflection film 10 of FIG. 1 opposite to the antiglare layer 18 of the transparent substrate film 12 may be used. . The antireflection film 101 can be attached by pressing the adhesive layer 22 exposed by peeling off the separator 24 against the display surface of a display device such as a liquid crystal panel.

FIG. 3 shows an embodiment of the antireflection film of the present invention having antistatic performance. As shown in FIG. 3, a transparent conductive layer 26 is provided between the transparent base material film 12 and the antiglare layer 18, and a conductive material 27 is further contained in the antiglare layer 18. The low refractive index layer 20 may be formed on the surface of the antireflection film 102. By using the transparent conductive layer 26 and the conductive material 27, antistatic performance can be imparted.

The transparent conductive layer 26 is made by dispersing conductive fine particles in a resin composition, and the conductive fine particles are as follows.
For example, antimony-doped indium tin oxide (ATO) and indium tin oxide (IT
O), organic compound fine particles surface-treated with gold and / or nickel, etc., as the resin composition, (meth) acrylate of a polyfunctional compound such as alkyd resin and polyhydric alcohol (that is, acrylate and / or methacrylate). (Meaning) and those containing a relatively large amount of an oligomer or prepolymer and a reactive diluent can be used.

As the conductive material 27 that can be contained in the antiglare layer 18, particles surface-treated with gold and / or nickel can be used. The particles before such surface treatment can be selected from the group consisting of silica, carbon black, metal particles and resin particles.

FIG. 4 shows that in the antireflection film 10 of FIG. 1, a light-transmitting high refractive index layer 28 having a refractive index higher than that of the antiglare layer 18 is formed on the antiglare layer 18, and the antireflection film 10 is further protected. The antireflection film 103 in which the low refractive index layer 20 having a refractive index lower than that of the glare layer 18 is formed as the uppermost layer is shown. Forming the high refractive index layer as a thin film having a thickness of about 0.1 μm is advantageous in increasing the total light transmittance. For example, the high refractive index layer 28 can be easily formed by using a high refractive index metal or metal oxide. For the film formation, a thin film may be formed by a vacuum forming method or the like, or a binder resin in which fine particles having a high refractive index listed below are dispersed may be applied. Alternatively, the high refractive index layer 2
A resin containing molecules or atoms having a high refractive index component may be used as the binder resin itself used in No. 8.

Ultrafine particles having a high refractive index used for the high refractive index layer 28 include, for example, ZnO (refractive index 1.95), T
iO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 2.20), Sb ₂ O ₅ (refractive index 2.04), SnO ₂
(Refractive index 2.00), ITO (refractive index 1.95), Y ₂
O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.9
5), ZrO ₂ (refractive index 2.10), Al ₂ O ₃ (refractive index 1.63) and the like. A resin having a high refractive index containing atoms introduced with a large amount of a component having a high refractive index is used as a molecule or atom constituting the resin. Examples of the molecule and atom of the component that improves the refractive index include an aromatic ring, a halogen atom other than F, an atom of S, N, and P.

The antiglare film 10 shown in FIGS. 2, 3 and 4 above.
1, 102 and 103, the other constituent elements are the same as in FIG.
Since it is the same as the anti-glare film 10 described above, the same parts are designated by the same reference numerals and the description thereof is omitted.

In the antireflection films 10, 101, 102 and 103 shown in FIGS. 1, 2, 3 and 4, a polarizing film is laminated on the surface of the transparent substrate film 12 opposite to the antiglare layer 18. It can be used as a polarizing element. FIG. 5 shows an example of a polarizing element using the antireflection film of the present invention. The polarizing film 32 is provided on the surface of the transparent base film 12 opposite to the antiglare layer 18 side of the antireflection film 10 of FIG. And a polarizing plate 40 composed of a transparent substrate film 34 is laminated to form a polarizing element 30.

FIG. 6 shows an example of a backlight type liquid crystal display device in which the polarizing element containing the antireflection film of the present invention as a constituent element is applied to the surface of a liquid crystal panel of the liquid crystal display device. The liquid crystal display device 70 shown in FIG. 6 has the polarizing element 30 shown in FIG. 5, the liquid crystal panel 74, and the polarizing plate 50 stacked in this order, and has a backlight 78 on the back surface on the polarizing plate 50 side. Arranged transmissive liquid crystal display device 70
It is a configuration example of. As the polarizing plate 50, a polarizing plate used in a normal liquid crystal display device can be used.

The antireflection film of the present invention can be applied not only to the backlight type liquid crystal display device but also to the surface of the liquid crystal panel of the reflection type liquid crystal display device (external reflection type, internal reflection electrode type). it can. Further, the antireflection film of the present invention can be applied to the image display surface of the CRT.

[0077]

EXAMPLES Example 1 Preparation of Surface-treated Zinc Oxide Ultrafine Particle Dispersion As surface-treated zinc oxide ultrafine particles, the surface of which was coated with methylhydrogenpolysiloxane, the content of zinc oxide was 93%. , The primary particle size is 0.02-0.03μ
m, specific surface area 40 to 60 m ² / g, oil absorption 30 to 4
0 g / 100 g of zinc oxide ultrafine particles having a water-repellent surface (MZ505S: trade name, manufactured by Teika) was prepared.

As an ionizing radiation-curable binder resin component, pentaerythritol triacrylate (PET3
0: trade name, manufactured by Nippon Kayaku Co., Ltd.) was prepared. As a dispersant having an anionic polar group, a block copolymer having an affinity for a pigment (Disperbic 163: trade name,
Big Chemie Japan Co., Ltd.) was prepared. 1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184: trade name, manufactured by Nippon Ciba-Geigy) was prepared as a photopolymerization initiator. Methyl isobutyl ketone was prepared as an organic solvent.

The above zinc oxide ultrafine particles (MZ505S:
Trade name, manufactured by Teika Co., pentaerythritol triacrylate (PET30: trade name, manufactured by Nippon Kayaku Co., Ltd.), dispersant (Disperbic 163: trade name, manufactured by Disperbic Japan Co.) and methyl isobutyl ketone are put in a mayonnaise bottle. , About 4 times the amount of the mixture was used as a stirring medium, and the mixture was stirred for 10 hours with a paint shaker. After stirring, a photopolymerization initiator (IRGACURE 184: trade name, manufactured by Ciba Geigy) was added. Finally, a zinc oxide ultrafine particle dispersion liquid having the following compounding ratio was finally obtained.

Zinc oxide (MZ505S: trade name, manufactured by Teika): 10 parts by weight pentaerythritol triacrylate (PET30:
Trade name, manufactured by Nippon Kayaku Co., Ltd .: 4 parts by weight anionic polar group-containing dispersant (Disperbic 16)
3: Product name, manufactured by Big Chemie Japan Co., Ltd .: 2 parts by weight Photopolymerization initiator (Irgacure 184: Product name, manufactured by Ciba-Geigy Co., Ltd.): 0.2 parts by weight Methyl isobutyl ketone: 16.2 parts by weight

Formation of coating film of zinc oxide ultrafine particle dispersion and performance test The zinc oxide ultrafine particle dispersion immediately after being prepared in the above step,
A TAC substrate (FT-T80UZ: trade name, manufactured by Fuji Film Co., Ltd.) having a thickness of 80 μm was coated with a bar coater # 14, and was dried by heating at 60 ° C. for 1 minute, and then was irradiated with a UV irradiation device (Fusion UV Systems). H of Japan Co., Ltd.
The bulb was used as a light source and cured at an irradiation dose of 500 mJcm ² to form a transparent film having a thickness of 5 μm after curing.

Measurement of haze value and refractive index, and durability of transparent films having a thickness of 5 μm after curing formed from the zinc oxide ultrafine particle dispersion immediately after preparation and the zinc oxide ultrafine particle dispersion after standing at room temperature, respectively. As a test, a light resistance / moisture heat resistance test was performed. The haze value was measured using a turbidimeter NDH2000 (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.). In this Example 1, the internal haze value of the antiglare layer was measured as follows. Refractive index of 1.6 on TAC substrate film
Apply and harden the high refractive index matte hard coat material of 5,
After forming the antiglare layer, a polyfunctional acrylate (actually, anything is used, in this example, PET30: trade name, manufactured by Nippon Kayaku Co., Ltd. was used) so that the surface of the antiglare layer had no irregularities. Then, the internal haze value alone was measured. Further, the refractive index of the coating film after curing is a spectroscopic ellipsometer (UVSL: trade name, manufactured by Jobin-Evon Co.).
Was used to measure the refractive index of helium laser light at a wavelength of 633 nm.

In the light resistance test, a sunshine weather meter was used, and a carbon arc lamp was used as a light source.
It was performed under the conditions of a black panel temperature of 63 ° C. and 200 hours.
The moist heat resistance test was conducted under the conditions of 80 ° C. × 90% RH and 1000 hours.

For comparison, a coating film not formed, T
The haze value, the refractive index, the light resistance, and the moist heat resistance test were conducted in the same manner as above for the AC substrate alone. The results of each of the above tests are shown in Table 1 below. In Table 1, ∘ indicates no scratch, and X indicates scratch and / or peeling.

In this Example 1, in order to prevent the influence of the light transmissive diffusing agent from directly affecting the difference caused by the difference in the kind of the dispersion liquid of the metal oxide ultrafine particles, the light was intentionally measured. The properties of the obtained coating film are measured in the absence of a permeable diffuser. According to Table 1, Example 1
It can be seen that the use of the zinc oxide ultrafine particle dispersion liquid prepared in 1) provides good haze value and refractive index, and also good light resistance test.

[Comparative Example 1] Instead of the surface-treated zinc oxide ultrafine particles used in Example 1, zinc oxide not subjected to surface treatment (MZ500: trade name, manufactured by Teika) was used in the same amount as in Example 1. A coating composition was obtained in the same manner as in Example 1 except for the above. The resulting coating composition was tested as in Example 1 above.

The results obtained are shown in Table 1 below. From Table 1, it can be seen that the haze value when the thick film is formed is good, but the durability (that is, light resistance and wet heat resistance) is poor because the surface treatment is not performed.

[0088]

[Table 1]

Example 2 A zinc oxide ultrafine particle dispersion having a refractive index of 1.68 was prepared under the same compounding conditions as in Example 1, and the acrylic oxide (pentaerythritol) was further added to the zinc oxide ultrafine particle dispersion. Triacrylate / styrene beads having a particle size of 3.5 μm = 6/4), cellulose acetate propionate (ethyl acetate solution, solid content 10)
%), Toluene, a photopolymerization initiator (IRGACURE 65
1: trade name, manufactured by Nippon Ciba-Geigy Co., Ltd.) was added to prepare a matte hard coat material having a refractive index of 1.65 with a compounding ratio shown in Table 2 below.

The dispersibility of the zinc oxide ultrafine particle dispersion was stable even when a matting material of a styrene-acrylic copolymer and a binder were added.

[0091]

[Table 2]

A 1.65 high refractive index matte hard coat material prepared in the above step was applied on a TAC film substrate so that the film thickness after curing would be 5 μm, and cured by UV irradiation to a level where tack was not left. Then, the obtained coating film was made of a silicon-containing polyvinylidene fluoride copolymer.
By coating 40 low refractive index layers so that the film thickness after curing will be 90 nm and completely curing by irradiation with ultraviolet rays, the reflectance at a wavelength of 550 nm at which humans are most likely to feel glare is 0.8%. An antireflection film could be obtained. This film has a pencil hardness of 2H.

Example 3 A titanium oxide coating composition was prepared as follows. Primary particle size 0.01
~ 0.03μm, titanium oxide content 79-85%
Surface treatment with Al ₂ O ₃ and stearic acid, the specific surface area is 50-60 m ² / g, and the amount of oil supply is 24-30 g /
100 g of rutile titanium oxide (TT)
O51 (C): trade name, manufactured by Ishihara Sangyo Kaisha, Ltd. was used in the same amount as in Example 1, and a titanium oxide coating composition having a refractive index of 1.83 was obtained in the same manner as in Example 1.

The titanium oxide coating composition prepared in the above step was cured with respect to the high refractive index matte hard coat material having a refractive index of 1.65 prepared on the TAC film substrate prepared in Example 2 above. Coating thickness is 160 nm
The coating was carried out so that it was cured by irradiation with ultraviolet rays so that no tack remained.

On the cured coating film obtained in the above step, a low refractive index layer having a refractive index of 1.40 made of a silicon-containing polyvinylidene fluoride copolymer was applied so that the coating film thickness after curing would be 90 nm. Then, it was completely cured by irradiation with ultraviolet rays. As a result, 550n is the most dazzling for humans.
An antireflection film having a reflectance at m wavelength of 0.5% could be obtained. This film has a pencil hardness of 2H.

[0096]

INDUSTRIAL APPLICABILITY The antireflection film of the present invention has both properties of antireflection property and antiglare property, and further, the antiglare layer has a high refractive index by incorporating metal oxide ultrafine particles having a high refractive index. Nevertheless, since the transparency is excellent and the photocatalytic action of the metal oxide ultrafine particles is suppressed, deterioration of the coating film is prevented.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a basic layer structure of an antireflection film of the present invention.

2 is a diagram showing an embodiment of the present invention in which an adhesive layer is provided on the antireflection film of FIG.

FIG. 3 is a diagram showing an embodiment of the present invention having antistatic performance.

FIG. 4 is an anti-reflection film of FIG. 1, in which a light-transmitting high refractive index layer having a higher refractive index than the anti-glare layer is formed on the anti-glare layer. It is a figure which shows the antireflection film which formed the low and low refractive index layer in the uppermost layer.

FIG. 5 is a diagram showing an example of a polarizing element using the antireflection film of the present invention.

FIG. 6 is a diagram showing an example of a backlight type liquid crystal display device in which a polarizing element including the antireflection film of the present invention as a constituent element is applied to the surface of a liquid crystal panel of a liquid crystal display device.

[Explanation of symbols]

10, 101, 102, 103 Anti-reflection film 12, 34 Transparent substrate film 14 Light-transmitting diffuser 16 Light-transmissive resin 18 Antiglare layer 20 Low refractive index layer 22 Adhesive layer 24 separator 26 Transparent conductive layer 27 Conductive material 28 High Refractive Index Layer 30 Polarizing element 32 Polarizing film 40, 50 Polarizer 70 Liquid crystal display 74 LCD panel 78 Backlight

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/02 G09F 9/00 313 G09F 9/00 313 G02B 1/10 A F term (reference) 2H042 BA02 BA03 BA12 BA15 BA20 2K009 AA04 AA05 AA12 AA15 BB28 CC01 CC02 CC03 CC09 CC23 CC24 CC26 CC38 CC42 DD02 DD05 4F100 AA17C AA17D AA21C AA21D AA25C AA25D CAABJ CA01 BA01C01 BA23A01CBAC01B01C23A01D JN18C JN18D JN30C JN30D YY00C YY00D 5G435 AA00 AA14 FF02 HH02 HH03 KK07

Claims (17)

[Claims] (1) At least one surface of a transparent substrate film is laminated with at least a light-transmissive low refractive index layer having a refractive index lower than that of the transparent substrate film, and the transparent substrate film. An antireflection film in which at least the transparent substrate film and a light-transmissive antiglare layer having a higher refractive index than the low refractive index layer are laminated between the low refractive index layer and The antiglare layer comprises ultrafine metal oxide particles coated with an inorganic compound and / or an organic compound that reduces or eliminates photocatalytic activity, a light-transmitting binder resin, a dispersant, an organic solvent, and light-transmitting diffusion. (3) The metal oxide ultrafine particles themselves have a primary particle size of 0.
01 to 0.1 μm and a refractive index of 1.90 to 2.90.
Therefore, the transparency and the refractive index of the antiglare layer are enhanced, and (4) the light transmissive resin in which the ultrafine metal oxide particles are dispersed in the antiglare layer to have a high refractive index, and Antireflection, wherein the difference Δn in refractive index of the transmissive diffusing agent is 0.01 ≦ n ≦ 0.5, and the average particle size d of the light transmissive diffusing agent is 0.1 μm ≦ d ≦ 5 μm the film. 2. The antireflection film according to claim 1, wherein the metal oxide ultrafine particles are one or more selected from zinc oxide, titanium oxide, zirconium oxide, antimony oxide and cerium oxide. 3. The inorganic compound and / or organic compound that reduces or eliminates the photocatalytic activity is an oxide or hydroxide of a metal selected from Al, Si, Zr and Sn, and / or a silicone having a siloxane bond. The antireflection film according to claim 1 or 2, which is an organic compound made of a resin. 4. The dispersant in the coating composition for forming the antiglare layer has an anionic polar group and has a number average molecular weight of 2, based on polystyrene equivalent molecular weight.
4. The antireflection film according to claim 1, wherein the antireflection film is a compound of 000 to 20,000. 5. In the coating composition for forming the antiglare layer, 4 to 20 parts by weight of a light-transmitting binder resin is added to 10 parts by weight of the ultrafine metal oxide particles.
The antireflection film according to any one of claims 1 to 4, wherein the dispersant is contained in an amount of 4 to 10 parts by weight. 6. In the coating composition for forming the antiglare layer, one kind of ketone-based organic solvent alone,
Alternatively, the antireflection film according to any one of claims 1 to 5, further comprising a mixed solvent of two or more kinds of ketone organic solvents. 7. The coating composition for forming the antiglare layer, wherein the organic solvent is 50 to 9 relative to 0.5 to 50 parts by weight of the total solid content excluding the light transmissive diffusing agent.
The antireflection film according to claim 1, wherein the antireflection film is 9.5 parts by weight. 8. In the coating composition for forming the antiglare layer, the refractive index is 1 when the film thickness of the coating composition is 0.2 to 8 μm when the light transmissive diffusing agent is removed. 0.55-1.80 and JIS-K736
The haze value specified in 1-1 is the same as the haze value of the transparent substrate film, or the difference from the haze value of the transparent substrate film is within 1%. The antireflection film according to any one of 1. 9. The coating composition for forming the antiglare layer, wherein the light-transmitting binder resin 100 is used.
9. The antireflection film according to claim 1, wherein the photopolymerization initiator is 3 to 8 parts by weight with respect to parts by weight. 10. The antiglare layer contains a light-transmitting diffuser, so that the surface of the antiglare layer is uneven, and the surface haze value hs in the surface unevenness of the antiglare layer is 7 <hs <30. It exists, The antireflection film in any one of Claim 1 thru | or 9 characterized by the above-mentioned. 11. The anti-glare layer has an internal haze value hi due to internal diffusion of 1 <hi <30.
11. The antireflection film according to any one of 1 to 10. 12. The antireflection film according to claim 11, wherein the sum of the haze value hs on the surface irregularities of the antiglare layer and the internal haze value hi due to internal diffusion of the antiglare layer is 50 or less. . 13. The antireflection according to claim 1, wherein the average particle diameter d of the light transmissive diffusing agent in the antiglare layer is 0.1 μm ≦ d ≦ 5 μm. the film. 14. The light transmissive diffusing agent is an inorganic or organic fine particle, and 3% by weight to 23% by weight of the coating composition.
It is weight%, The antireflection film in any one of Claim 1 thru | or 13 characterized by the above-mentioned. 15. A transparent conductive layer is provided between the transparent substrate film and the antiglare layer, and a conductive material is contained in the antiglare layer. The antireflection film according to any one of 1. 16. A low-refractive index having a refractive index lower than that of the anti-glare layer, which is formed by coating a light-transmitting high-refractive index layer having a higher refractive index than the anti-glare layer on the anti-glare layer. The antireflection film according to any one of claims 1 to 15, wherein a layer is formed on the uppermost layer. 17. A low reflection display device in which the antireflection film according to any one of claims 1 to 16 is applied to the surface of a display device.