JP6689564B2 - Antireflection film, polarizing plate, and image display device - Google Patents

Description

  The present invention relates to an antireflection film, a polarizing plate, and an image display device.

  An image display surface of an image display device such as a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a field emission display (FED) usually has an observer and An antireflection film or an antiglare film having a low refractive index layer is provided in order to suppress the reflection of the background of an observer.

  The antireflection film is capable of reflecting light reflected on the surface of the low refractive index layer and light reflected at the interface between the low refractive index layer and a layer adjacent to the low refractive index layer (for example, a hard coat layer or a high refractive index layer). By canceling each other, the reflected light itself is reduced.

  The low refractive index layer usually contains a binder resin and hollow silica fine particles present in the binder resin (for example, refer to Patent Document 1). As the hollow silica fine particles, those having an average primary particle diameter of 60 nm or less are used.

JP2012-48195A

  At present, it is desired to reduce the reflectance of the antireflection film. Specifically, it is desired to reduce the reflection Y value of the antireflection film to less than 0.3%.

  When using hollow silica fine particles having an average primary particle diameter of 60 nm or less, a large amount of hollow silica fine particles must be contained in the low refractive index layer in order to achieve a reflection Y value of 0.3% or less. However, when a large amount of this hollow silica fine particle is contained in the low refractive index layer, when the surface of the low refractive index layer is subjected to a steel wool resistance test and a fingerprint antifouling evaluation test, the steel wool resistance and antifouling property are evaluated. There is a risk that the dirtiness will be extremely reduced.

  The present invention has been made to solve the above problems. That is, it is an object of the present invention to provide an antireflection film which can realize a low reflectance and has excellent steel wool resistance and antifouling property, and a polarizing plate and an image display device including the antireflection film.

According to one aspect of the present invention, a transparent substrate, a hard coat layer provided on the transparent substrate, a low refractive index lower than the hard coat layer and provided on the hard coat layer. An antireflection film comprising a refractive index layer, wherein the low refractive index layer is present on at least the surface of the low refractive index layer, hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, a binder resin. A surface modifier, wherein the surface modifier contains a silicon-containing compound and a fluorine-containing compound, and the reflection Y value of the antireflection film measured from the low refractive index layer side is less than 0.3%. When the steel wool test is conducted on the surface of the low refractive index layer by rubbing 10 cycles with a load using steel wool, the maximum load at which no scratch is confirmed on the surface of the low refractive index layer is 200. / Cm ² or more, the antireflection film is provided.

  According to another aspect of the present invention, the antireflection film, and a polarizing element formed on the surface of the transparent substrate of the antireflection film opposite to the surface on which the hard coat layer is formed, A polarizing plate is provided.

  According to another aspect of the present invention, there is provided an image display device, comprising a display element and the above-mentioned antireflection film located closer to an observer than the display element, wherein the antireflection film has the low refractive index. An image display device is provided in which the surface of the rate layer is arranged so as to be the surface of the image display device on the observer side.

  According to another aspect of the present invention, there is provided an image display device comprising a display element and the above-mentioned polarizing plate positioned closer to an observer than the display element, wherein the polarizing plate is the low refractive index layer. An image display device is provided in which the surface of the image display device is arranged on the observer side of the image display device.

According to the antireflection film of one aspect of the present invention, the polarizing plate of another aspect, and the image display device of another aspect, the hollow silica fine particles in the low refractive index layer have an average primary particle size of 65 nm or more and 85 nm or less. Since the hollow silica fine particles are used, an antireflection film having a reflection Y value of less than 0.3% can be obtained in a smaller amount as compared with the case of using hollow silica fine particles having an average primary particle diameter of 60 nm or less. Further, the hollow silica fine particles having an average primary particle diameter of 65 nm or more and 85 nm or less in the low refractive index layer can be reduced in amount as compared with the case where the hollow silica fine particles having an average primary particle diameter of 60 nm or less are used. A silicon-containing compound as a surface modifier is easily deposited (bleed out) on the surface of the low refractive index layer during the formation of the layer. Therefore, a large amount of silicon-containing compound can be present on the surface of the low refractive index layer. Further, when the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used, the amount of the hollow silica fine particles in the low refractive index layer is larger than that in the case of using hollow silica fine particles having an average primary particle size of 60 nm or less. Therefore, the amount of binder resin in the low refractive index layer can be increased. Therefore, the hardness of the low refractive index layer can be increased. Therefore, when a steel wool resistance test in which the surface of the low refractive index layer is rubbed 10 times while applying a load using steel wool is carried out, a maximum load of 200 g / cm ² at which no scratch is confirmed on the surface of the low refractive index layer is confirmed. The above can be done. Further, the hollow silica fine particles having an average primary particle diameter of 65 nm or more and 85 nm or less in the low refractive index layer can be reduced in amount as compared with the case where the hollow silica fine particles having an average primary particle diameter of 60 nm or less are used. A fluorine-containing compound as a surface modifier is likely to be deposited on the surface of the low refractive index layer when the layer is formed. Therefore, a large amount of a fluorine-containing compound can be present on the surface of the low refractive index layer, so that the antifouling property can be improved. As a result, it is possible to realize a low reflectance and obtain good steel wool resistance and antifouling property.

It is a schematic block diagram of the antireflection film which concerns on embodiment. It is a schematic block diagram of the polarizing plate which concerns on embodiment. FIG. 1 is a schematic configuration diagram of a liquid crystal panel which is an example of a display panel according to an embodiment. FIG. 1 is a schematic configuration diagram of a liquid crystal display which is an example of an image display device according to an embodiment.

  Hereinafter, an antireflection film, a polarizing plate, a display panel, and an image display device according to embodiments of the present invention will be described with reference to the drawings. In the present specification, "film" also includes members called "sheets" and "plates". As one specific example, the "antireflection film" also includes members called "antireflection sheet" and "antireflection plate". In the present specification, the “weight average molecular weight” is a value obtained by dissolving in a solvent such as tetrahydrofuran (THF) and converting it into polystyrene by a conventionally known gel permeation chromatography (GPC) method. FIG. 1 is a schematic configuration diagram of the antireflection film according to the present embodiment.

<< Anti-reflection film >>
The antireflection film 10 includes a transparent base material 11, a hard coat layer 12 provided on the transparent base material 11, a high refractive index layer 13 provided on the hard coat layer 12, and a high refractive index layer 13. The low refractive index layer 14 is provided. Although the antireflection film 10 of the present embodiment includes the high refractive index layer 13, it does not have to include the high refractive index layer 13. However, from the viewpoint of obtaining excellent scratch resistance and antifouling property, it is preferable to include the high refractive index layer 13.

  In the antireflection film 10, the reflection Y value measured from the low refractive index layer 14 side is less than 0.3%. The above-mentioned reflection Y value is more preferably 0.15% or less, further preferably 0.1% or less, from the viewpoint of further suppressing the reflection.

  The reflection Y value is based on JIS Z8722. The reflection Y value was reflected by the antireflection film by irradiating light with an incident angle of 5 degrees from the low refractive index layer side of the antireflection film using a spectrophotometer such as MPC3100 manufactured by Shimadzu Corporation. The reflected light in the regular reflection direction is received, the reflectance in the wavelength range of 380 nm to 780 nm is measured, and then calculated as the brightness perceived by human eyes (for example, software built in the MPC3100). You can In the present specification, "light having an incident angle of 5 degrees" means light that is inclined by 5 degrees with respect to the normal direction when the normal direction of the film surface of the antireflection film is 0 degree. The “film surface” means a surface that coincides with the plane direction of the target antireflection film when viewed as a whole and as a whole. When measuring the reflection Y value, it is preferable to attach a black tape to the surface of the transparent substrate opposite to the surface on which the hard coat layer is formed in order to prevent back reflection of the antireflection film.

In the antireflection film 10, the surface 14A of the low-refractive index layer 14 was scratched on the surface 14A of the low-refractive index layer 14 when subjected to a steel wool test of rubbing 10 times with steel wool while applying a load. The maximum load that is not confirmed is 200 g / cm ² or more. This maximum load is preferably 300 g / cm ² or more. In the steel wool resistance test, # 0000 (product name “Bonster”, manufactured by Nippon Steel Wool Co., Ltd.) steel wool is used.

  From the viewpoint of suppressing the cloudiness, the haze value (overall haze value) of the antireflection film 10 is preferably 0.5% or less, more preferably 0.3% or less. The lower limit of the total haze can be 0.2% or more. The haze value can be measured by a method according to JIS K7136 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory).

<Transparent substrate>
The transparent substrate 11 is not particularly limited as long as it has a light-transmitting property. For example, a cellulose acylate substrate, a cycloolefin polymer substrate, a polycarbonate substrate, an acrylate polymer substrate, a polyester substrate, or a glass substrate. There are materials.

  Examples of the cellulose acylate base material include a cellulose triacetate base material and a cellulose diacetate base material. Examples of the cycloolefin polymer base material include base materials made of polymers such as norbornene-based monomers and monocyclic cycloolefin monomers.

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

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

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

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

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

  As the triacetyl cellulose base material, in addition to pure triacetyl cellulose, it is possible to use components other than acetic acid as a fatty acid forming an ester with cellulose such as cellulose acetate propionate and cellulose acetate butyrate. Good. In addition, other cellulose lower fatty acid ester such as diacetyl cellulose or various additives such as a plasticizer, an ultraviolet absorber and a slippery lubricant may be added to these triacetyl celluloses, if necessary.

  A cycloolefin polymer base material is preferable from the viewpoint of excellent retardation and heat resistance, and a polyester base material is preferable from the viewpoint of mechanical properties and heat resistance.

  The thickness of the transparent substrate 11 is not particularly limited, but can be 5 μm or more and 100 μm or less, and the lower limit of the thickness of the transparent substrate 11 is preferably 15 μm or more, and more preferably 25 μm or more from the viewpoint of handling property and the like. . The upper limit of the thickness of the transparent substrate 11 is preferably 80 μm or less from the viewpoint of thinning.

<Hard coat layer>
The hard coat layer 12 is a layer having a hardness of “H” or more in a pencil hardness test (4.9 N load) defined by JIS K5600-5-4 (1999). By setting the pencil hardness to "H" or more, the hardness of the hard coat layer 12 can be sufficiently reflected on the surface 14A of the low refractive index layer 14, and the durability can be improved. From the viewpoint of adhesion to the high refractive index layer formed on the hard coat layer 12, toughness, and prevention of curl, the upper limit of the pencil hardness of the surface of the hard coat layer 12 is preferably about 4H.

  The thickness of the hard coat layer 12 is preferably 1 μm or more and 10 μm or less. When the film thickness of the hard coat layer 12 is in this range, desired hardness can be obtained and the hard coat layer can be thinned. The film thickness of the hard coat layer can be determined by observing the cross section of the hard coat layer with a scanning electron microscope (SEM). Specifically, the image of the scanning electron microscope is used to measure the film thickness of the hard coat layer at three locations in one image, this is performed for five images, and the average value of the measured film thickness is calculated.

  The lower limit of the film thickness of the hard coat layer 12 is more preferably 8 μm or less from the viewpoint of suppressing cracking of the hard coat layer. Further, from the viewpoint of suppressing the occurrence of curling while reducing the thickness of the hard coat layer, the thickness of the hard coat layer 12 is more preferably 0.5 μm or more and 5.0 μm or less.

  The refractive index of the hard coat layer 12 may be 1.50 or more and 1.60 or less. The lower limit of the refractive index of the hard coat layer 12 may be 1.52 or more, and the upper limit of the refractive index of the hard coat layer 12 may be 1.56 or less. The refractive index difference between the transparent substrate 11 and the hard coat layer 12 is preferably 0.10 or less, and more preferably 0.06 or less, from the viewpoint of suppressing the occurrence of interference fringes.

  The refractive index of the hard coat layer 12 is fixed in the wavelength region of 380 nm to 780 nm, and the reflection spectrum measured by the spectrophotometer and the spectrum calculated from the optical model of the thin film using the Fresnel's equation are fitted. Can be determined by The refractive index of the hard coat layer 12 may be obtained by forming an independent layer and then measuring it with an Abbe refractometer (NAR-4T manufactured by Atago Co.) or an ellipsometer. Further, as a method of measuring the refractive index after becoming the antireflection film 29, the hard coat layer 12 is scraped off by a cutter or the like to prepare a powdery sample, and the JIS K7142 (2008) B method (powdered or granular The Becke method (for a transparent material) (using a Cargill reagent having a known refractive index, the sample in the powder state is placed on a slide glass or the like, the reagent is dropped on the sample, and the sample is immersed in the reagent. Is observed by a microscope, and the bright line (Becke line) generated on the sample outline cannot be visually observed due to the difference in refractive index between the sample and the reagent. it can.

  The hard coat layer 12 can be composed of at least a resin. In addition to the resin, it may contain fine particles.

<resin>
The resin contains a cured product (polymerized product, crosslinked product) of a curable resin precursor. In the present specification, the “curable resin precursor” means a resin precursor having a photocurable property or a thermosetting property and becoming a resin by photocuring or thermosetting. The resin may include a solvent-drying resin as well as a cured product of a curable resin precursor. The photocurable resin precursor having photocurability has at least one photopolymerizable functional group. In the present specification, the “photopolymerizable functional group” is a functional group capable of undergoing a polymerization reaction by irradiation with light. Examples of the photopolymerizable functional group include ethylenic double bonds such as (meth) acryloyl group, vinyl group and allyl group. In addition, in this specification, "(meth) acryloyl group" is meant to include both "acryloyl group" and "methacryloyl group". In addition, examples of the light irradiated when the photocurable resin precursor is cured include visible light, and ionizing radiation such as ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays. The thermosetting resin precursor having thermosetting property has at least one thermosetting functional group.

  Examples of the photocurable resin precursor include a photopolymerizable monomer, a photopolymerizable oligomer, and a photopolymerizable polymer, which can be appropriately adjusted and used. The photocurable resin precursor is preferably a combination of a photopolymerizable monomer and a photopolymerizable oligomer or photopolymerizable polymer.

(Photopolymerizable monomer)
The photopolymerizable monomer has a weight average molecular weight of less than 1000. As the photopolymerizable monomer, a polyfunctional monomer having two or more (that is, bifunctional) photopolymerizable functional groups is preferable.

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

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

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

(Photopolymerizable polymer)
The photopolymerizable polymer has a weight average molecular weight of 10,000 or more, and the weight average molecular weight is preferably 10,000 or more and 80,000 or less, more preferably 10,000 or more and 40,000 or less. When the weight average molecular weight exceeds 80,000, the viscosity is high and the coating suitability is deteriorated, and the appearance of the obtained optical layered product may be deteriorated. Examples of the polyfunctional polymer include urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester-urethane (meth) acrylate, and epoxy (meth) acrylate.

  The thermosetting resin precursor is not particularly limited, and examples thereof include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea. Examples thereof include respective precursors of co-condensation resin, silicon resin, polysiloxane resin and the like.

  The solvent-drying resin is a resin such as a thermoplastic resin that forms a film only by drying the solvent added to adjust the solid content during coating. When the solvent-drying resin is added, it is possible to effectively prevent film defects on the coating surface of the coating liquid when forming the hard coat layer 14. The solvent-drying resin is not particularly limited, and generally thermoplastic resin can be used.

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

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

<Particles>
The fine particles may be inorganic fine particles, organic fine particles, or a mixture thereof. Examples of the inorganic fine particles include inorganic oxide fine particles such as silica (SiO ₂ ) fine particles, alumina fine particles, titania fine particles, tin oxide fine particles, antimony-doped tin oxide (abbreviation: ATO) fine particles, and zinc oxide fine particles.

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

  In order to form the hard coat layer 12, first, a hard coat layer composition containing at least a curable resin precursor is applied to the surface of the transparent substrate 11. Then, the film-shaped composition for hard coat layer is conveyed to a zone heated for drying, and the composition for hard coat layer is dried and the solvent is evaporated by various known methods. Thereafter, the hard coat layer composition is irradiated with light such as ultraviolet rays and / or heated to cure (polymerize or crosslink) the curable resin precursor to form a hard coat layer composition. The hard coat layer 12 is formed by curing.

  Examples of the method for applying the composition for the hard coat layer include known coating methods such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating and die coating.

  When ultraviolet rays are used as light for curing the composition for the hard coat layer, ultraviolet rays emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp or the like can be used. Further, as the wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as Cockcroft-Walt type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type.

  The fine particles, the thermoplastic resin, the solvent, and the polymerization initiator may be added to the composition for the hard coat layer, if necessary. Further, the hard coat layer composition may include a conventionally known dispersant, surfactant, antistatic agent, depending on the purpose of increasing the hardness of the hard coat layer, suppressing curing shrinkage, controlling the refractive index, and the like. , Silane coupling agent, thickener, anti-coloring agent, colorant (pigment, dye), defoaming agent, leveling agent, flame retardant, UV absorber, adhesion promoter, polymerization inhibitor, antioxidant, surface modification A quality agent, a slip agent, etc. may be added.

<solvent>
Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketones (acetone, methyl ethyl ketone (MEK), cyclohexanone). , Methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone, etc.), ethers (1,4-dioxane, dioxolane, diisopropyl ether dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic Hydrocarbons (cyclohexane etc.), aromatic hydrocarbons (toluene, xylene etc.), halogenated carbons (dichloromethane, dichloroethane etc.), esters (methyl formate, methyl acetate, ethyl acetate, vinegar) Propyl, butyl acetate, ethyl lactate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), etc. It may be a mixture of these.

<Leveling agent>
The leveling agent is not particularly limited, but a non-polymerizable fluorine-containing compound having no photopolymerizable functional group is preferable from the viewpoint of enhancing antifouling property as described later. Among the non-polymerizable fluorine-containing compounds, compounds having a weight average molecular weight of 30,000 to 40,000 are preferable. Examples of commercially available products of such a non-polymerizable fluorine-containing compound include F568 and F477 manufactured by DIC.

  The content of the leveling agent in the hard coat layer composition is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the curable resin precursor. By setting the content of the leveling agent within this range, it is possible to sufficiently secure the flatness of the surface of the hard coat layer.

<Polymerization initiator>
The polymerization initiator is a component which is decomposed by light irradiation to generate radicals to initiate or proceed with polymerization (crosslinking) of the photocurable resin precursor.

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

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

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

  The content ratio (solid content) of the raw material in the composition for hard coat layer is not particularly limited, but is usually preferably 5% by mass or more and 70% by mass or less, and more preferably 25% by mass or more and 60% by mass or less. .

<High refractive index layer>
The high refractive index layer 13 is a layer having a refractive index higher than that of the hard coat layer 12. Specifically, the refractive index of the high refractive index layer 13 may be 1.50 or more and 2.00 or less. The lower limit of the refractive index of the high refractive index layer 13 may be 1.60 or more, and the upper limit of the refractive index of the high refractive index layer 13 may be 1.75 or less. The refractive index of the high refractive index layer 13 can be measured by the same method as the refractive index of the hard coat layer 12. The refractive index difference between the hard coat layer 12 and the high refractive index layer 13 may be 0.05 or more and 0.25 or less.

  The film thickness of the high refractive index layer 13 is preferably 200 nm or less. The lower limit of the film thickness of the high refractive index layer 13 is preferably 40 nm or more, and more preferably 50 nm or more. The upper limit of the film thickness of the high refractive index layer 13 is preferably 170 nm or less, and more preferably 160 nm or less. The film thickness of the high refractive index layer can be determined by observing the cross section of the high refractive index layer with a transmission electron microscope (TEM, STEM) (the magnification is preferably 10,000 times or more). Specifically, using a transmission electron microscope image, the film thickness of the high refractive index layer is measured at three places in one image, this is performed for five images, and the average value of the measured film thickness is calculated. .

  The high refractive index layer 13 is not particularly limited as long as it is a layer having a refractive index higher than that of the hard coat layer 12, but the high refractive index layer 13 includes, for example, high refractive index fine particles and a binder resin. Can be configured.

<High refractive index fine particles>
Examples of the high refractive index fine particles forming the high refractive index layer 13 include metal oxide fine particles. Specific examples of the metal oxide fine particles include titanium oxide (TiO ₂ , refractive index: 2.3 to 2.7), niobium oxide (Nb ₂ O ₅ , refractive index: 2.33), zirconium oxide. (ZrO ₂ , refractive index: 2.10), antimony oxide (Sb ₂ O ₅ , refractive index: 2.04), tin oxide (SnO ₂ , refractive index: 2.00), tin-doped indium oxide (ITO, refractive index) 1.95 to 2.00), cerium oxide (CeO ₂ , refractive index: 1.95), aluminum-doped zinc oxide (AZO, refractive index: 1.90 to 2.00), gallium-doped zinc oxide (GZO, Refractive index: 1.90 to 2.00), zinc antimonate (ZnSb ₂ O ₆ , refractive index: 1.90 to 2.00), zinc oxide (ZnO, refractive index: 1.90), yttrium oxide (Y ₂ O _3, the refractive index: 1 87), antimony-doped tin oxide (ATO, refractive index: 1.75 to 1.85), phosphorus-doped tin oxide (PTO, refractive index: 1.75 to 1.85), and the like. Among these, zirconium oxide is preferable from the viewpoint of refractive index.

<Binder resin>
The binder resin that constitutes the high refractive index layer 13 is not particularly limited, and a thermoplastic resin may be used, but from the viewpoint of increasing the surface hardness, a thermosetting resin precursor and / or a photocurable resin. A cured product (polymerized product, cross-linked product) such as a precursor is preferable, and a cured product of a photocurable resin precursor is more preferable.

  Examples of the thermosetting resin precursor include respective precursors of acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like. A curing agent may be used when curing the thermosetting resin precursor.

  The photocurable resin precursor is not particularly limited, but photopolymerizable monomers, oligomers, and polymers can be used. Examples of the monofunctional photopolymerizable monomer include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and N-vinylpyrrolidone. Examples of the bifunctional or higher photopolymerizable monomer include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol triacrylate. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Examples thereof include acrylates and compounds obtained by modifying these compounds with ethylene oxide, polyethylene oxide and the like.

  Further, these compounds may be those in which an aromatic ring, a halogen atom other than fluorine, sulfur, nitrogen, a phosphorus atom or the like is introduced to adjust the refractive index to a high level. Further, in addition to the above compounds, relatively low molecular weight polyester resins having unsaturated double bonds, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiro acetal resins, polybutadiene resins, polythiol polyene resins, etc. Can also be used. When polymerizing (crosslinking) the photocurable resin precursor, the polymerization initiator described in the section of the hard coat layer may be used.

  The high refractive index layer 13 can be formed by, for example, a method similar to the method of forming the hard coat layer 12. Specifically, first, a composition for a high refractive index layer containing at least high refractive index fine particles, a curable resin precursor and a solvent is applied to the surface of the hard coat layer 12. The composition for high refractive index layer preferably contains a leveling agent.

<solvent>
As the solvent used for the composition for the high refractive index layer, the same solvents as those mentioned for the hard coat layer can be used.

<Leveling agent>
As the leveling agent, the same leveling agent as described for the hard coat layer can be used.

  Next, the composition for a high refractive index layer in the form of a coating film is conveyed to a zone heated for drying, the composition for a high refractive index layer is dried by various known methods, and the solvent is evaporated. Thereafter, the composition for a high refractive index layer is irradiated with light such as ultraviolet rays and / or heated to polymerize (crosslink) the curable resin precursor to cure the composition for a high refractive index layer. Then, the high refractive index layer 13 can be formed.

<Low refractive index layer>
The low refractive index layer 13 is a layer having a refractive index lower than that of the hard coat layer 12. Specifically, the refractive index of the low refractive index layer 14 may be 1.20 or more and 1.50 or less. The upper limit of the refractive index of the low refractive index layer 14 may be 1.49 or less, or 1.32 or less. The refractive index of the low refractive index layer 14 can be measured by the same method as the refractive index of the hard coat layer 12. The refractive index difference between the high refractive index layer 13 and the low refractive index layer 14 may be 0.10 or more and 0.35 or less.

  The surface 14A of the low refractive index layer 14 forms the surface 10A of the antireflection film 10. Further, the surface 14A of the low refractive index layer 14 preferably has fine irregularities. The "surface of the antireflection film" means the surface opposite to the surface of the antireflection film on the transparent substrate side, and the "surface of the low refractive index layer" means the hard coat layer side of the low refractive index layer. Means the surface opposite to the surface.

  The film thickness of the low refractive index layer 14 is preferably 120 nm or less. The lower limit of the film thickness of the low refractive index layer 14 is preferably 70 nm or more, and more preferably 75 nm or more. The upper limit of the film thickness of the low refractive index layer 14 is preferably 110 nm or less, and more preferably 100 nm or less. The film thickness of the low refractive index layer can be determined by observing the cross section of the low refractive index layer with a transmission electron microscope (TEM, STEM) (the magnification is preferably 10,000 times or more). Specifically, using a transmission electron microscope image, the film thickness of the low refractive index layer is measured at three places in one image, this is performed for five images, and the average value of the measured film thickness is calculated. .

  The low refractive index layer 14 contains hollow silica fine particles, a binder resin, and a surface modifier for modifying the properties of the surface 14A of the low refractive index layer 14. The hollow silica fine particles can be produced, for example, by the production method described in Examples of JP-A-2005-099778.

<Hollow silica fine particles>
The hollow silica fine particles forming the low refractive index layer 14 have an average primary particle diameter of 65 nm or more and 85 nm or less. The average primary particle size of the hollow silica fine particles can be obtained, for example, from an image of a sectional electron microscope (a TEM, STEM or the like having a magnification of 50,000 or more is preferable) using image processing software. it can. Further, by using an image of a cross-sectional electron microscope (a transmission electron microscope such as TEM or STEM having a magnification of 50,000 or more is preferable), the average value is manually calculated in consideration of the scale and the hollow silica fine particles. You may obtain | require the average primary particle diameter of. In this case, 10 hollow silica fine particles are selected from the larger size of the hollow silica fine particles in one image, this is performed for 5 images, and an average value is calculated from a total of 50 hollow silica fine particles. Further, when the hollow silica fine particles are present alone, that is, when the hollow silica fine particles are in the stage before being incorporated into the composition for the low refractive index layer or the low refractive index layer, the average primary particle diameter of the hollow silica fine particles is determined by laser scattering. Can be measured by the method. The measurement result by the laser scattering method and the calculation result from the image of the sectional electron microscope are almost the same. The lower limit of the average primary particle size of the hollow silica fine particles may be 68 nm or more, or 70 nm or more. The upper limit of the average primary particle size of the hollow silica fine particles may be 82 nm or less, or 80 nm or less. The average primary particle size of the hollow silica fine particles is set to 65 nm or more and 85 nm or less, because when the average primary particle size of the hollow silica fine particles is less than 65 nm, good steel wool resistance and This is because the antifouling property cannot be obtained, and when the average primary particle diameter of the hollow silica fine particles exceeds 85 nm, the void ratio of the hollow silica fine particles becomes large, so that the desired hardness may not be obtained, and the low hardness is also low. When the film thickness of the refractive index layer is about 100 nm, a part of the hollow silica fine particles may protrude from the low refractive index layer, and the low refractive index layer may become cloudy. This is because the hollow silica particles may get caught in the hollow silica fine particles protruding from the low refractive index layer, resulting in scratches.

  The hollow silica fine particles preferably have a photopolymerizable functional group on the surface. Such silica fine particles having a photopolymerizable functional group on the surface can be prepared by surface-treating the silica fine particles with a silane coupling agent or the like. As a method of treating the surface of the silica fine particles with a silane coupling agent, a dry method of spraying the silane coupling agent on the silica fine particles, or a wet method of dispersing the silica fine particles in a solvent and then adding the silane coupling agent to react Etc.

<Binder resin>
Examples of the binder resin forming the low refractive index layer 14 include the same binder resins as forming the high refractive index layer 13. However, the binder resin may be a resin having a low refractive index such as a fluororesin or an organopolysiloxane.

  The fluororesin can be obtained by polymerizing a curable fluororesin precursor. The "curable fluororesin precursor" in the present specification means a fluororesin precursor which has curability and becomes a fluororesin when cured. The curable fluororesin precursor preferably has a lower functional group equivalent than the crosslinkable fluorine-containing compound as the surface modifier. Here, the “functional group equivalent” means the weight average molecular weight per one polymerizable functional group.

  Further, in the curable fluororesin precursor, it is considered preferable that the main chain contains more fluorine atoms than the side chains from the viewpoint of suppressing the decrease in hardness. On the other hand, in the case of the crosslinkable fluorine-containing compound as the surface modifier, it is considered that it is preferable that the side chain contains more fluorine atoms than the main chain in order to easily bleed out and to improve the antifouling property.

式中、Ｒｆ_１は、少なくとも炭素原子およびフッ素原子を含み、酸素原子および／または水素原子を含んでいてもよい、鎖状または環状の（ｍ＋ｎ）価のフッ化炭化水素基を表す。Ｒｆ_２は、それぞれ独立して、少なくとも炭素原子およびフッ素原子を含み、酸素原子および／または水素原子を含んでもよい、鎖状または環状の２価のフッ化炭化水素基を表す。Ｑは重合性基を表す。ｍおよびｎは、それぞれ独立して、０以上の整数（ただし、ｍ＋ｎ≧２）を表す。 Examples of the curable fluororesin precursor include curable fluororesin precursors represented by the following formula (1).

In the formula, Rf ₁ represents a chain or cyclic (m + n) -valent fluorohydrocarbon group containing at least carbon atoms and fluorine atoms and optionally oxygen atoms and / or hydrogen atoms. Rf _2's each independently represent a linear or cyclic divalent fluorohydrocarbon group containing at least a carbon atom and a fluorine atom and optionally an oxygen atom and / or a hydrogen atom. Q represents a polymerizable group. m and n each independently represent an integer of 0 or more (however, m + n ≧ 2).

The number of hydrogen atoms / the number of fluorine atoms in Rf ₁ is preferably 1/4 or less, more preferably 1/9 or less, and particularly preferably substantially free of hydrogen atoms. Specific examples of Rf ₁ are shown in the following formulas (2) to (11), but Rf ₁ is not limited thereto.

Rf ₂ is preferably a linear or branched perfluoroalkylene group having 1 to 12 carbon atoms. Examples of the perfluoroalkylene group include a difluoromethylene group (—CF ₂ —), a perfluoromethylmethylene group (—CF (CF ₃ ) —), a perfluoroethylmethylene group (—CF (CF ₂ CF ₃ ) —). , A perfluoroethylene group (—CF ₂ CF ₂ —), a perfluoropropylene group (—CF ₂ CF ₂ CF ₂ —) and the like. Among these, a perfluoroethylene group is preferable.

The Q, a radical, cationic, or preferably a condensation-polymerizable _{group, -COC (R 0) = CH} 2, allyl, epoxy alkylene _{group, - (CH 2) x Si} (OW) 3, - _{(CH 2)} y NCO or - _{(CH 2)} and more preferably z CN. Here, R ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent, W represents an alkoxy group or a hydroxyl group, and x, y and z each represent an integer of 1 or more, 3 The individual Ws may be different from each other. The substituent of the alkyl group in R ₀ may be any substituent, but a halogen atom is preferable. When n is 2 or more, a plurality of Qs may be the same or different.

  In the curable fluororesin precursor represented by the above formula (1), the fluorine content is preferably 35% by mass or more and 35% by mass or more and 70% by mass or less of the molecular weight of the fluorine-containing compound. It is more preferably 37% by mass or more and 60% by mass or less.

式中、Ｒｆ_１、Ｒｆ_２、ｍおよびｎはそれぞれ上記式（１）と同じ意味であり、Ｒは水素原子、フッ素原子、メチル基またはトリフルオロメチル基を表し、これらの中でもＲは水素原子であることが好ましい。 The curable fluororesin precursor represented by the above formula (1) is preferably a compound represented by the following formula (1A).

In the formula, Rf ₁ , Rf ₂ , m and n each have the same meaning as in the above formula (1), R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and among these, R is a hydrogen atom. Is preferred.

  Specific examples of the curable fluororesin precursor represented by the above formula (1) are shown below, but the invention is not limited thereto.

  Among these, the compound represented by the above formula (25) is preferable from the viewpoint of obtaining a low refractive index and good steel wool resistance.

Further, as the curable fluororesin precursor, in addition to the above formula (1), a curable fluororesin precursor represented by the following formulas (33) to (36) or a group represented by the following formula (37). A curable fluororesin precursor having at least one segment selected from the above is included.

式（３７）中、ｘ、ｙはＦまたは（ＣＦ_２）_０〜１０ＣＦ_３を表す。

Wherein (37), x, y is F or _{(CF 2) 0~10} CF _3.

<Surface modifier>
The surface modifier forming the low refractive index layer 14 is present at least on the surface 14A of the low refractive index layer 14. Whether or not the surface modifier is present on the surface of the low refractive index layer can be confirmed by an X-ray photoelectron spectroscopy analyzer (XPS). The surface modifier may be present inside the low refractive index layer as well as on the surface of the low refractive index layer. The surface modifier contains a silicon-containing compound for improving the steel wool resistance of the surface of the low refractive index layer, and a fluorine-containing compound for improving the antifouling property of the surface of the low refractive index layer. .

(Silicon-containing compound)
From the viewpoint of suppressing the desorption of the silicon-containing compound from the surface of the low refractive index layer, the silicon containing compound is preferably crosslinked with the binder resin in the state of the low refractive index layer. In order to crosslink the silicon-containing compound with the binder resin, a crosslinkable silicon-containing compound having a photopolymerizable functional group is used as the silicon-containing compound. By using such a crosslinkable silicon-containing compound, the crosslinkable silicon-containing compound and the curable resin precursor constituting the binder resin are crosslinked during curing of the composition for low refractive index layer, and are crosslinked with the binder resin. A silicon-containing compound is obtained.

  The silicon-containing compound may contain fluorine. Examples of commercially available silicon-containing compounds (crosslinkable silicon-containing compounds) include X22-164E manufactured by Shin-Etsu Chemical Co., Ltd. and RS-55 manufactured by DIC. X22-164E is a fluorine-free crosslinkable silicon-containing compound, and RS-55 is a fluorine-containing crosslinkable silicon-containing compound.

  Among the silicon-containing compounds, a silicon-containing compound having a weight average molecular weight of 2,000 to 20,000 is preferable. By using a silicon-containing compound having a weight average molecular weight of 2,000 to 20,000, the lift-up effect described below can be reliably obtained.

  The total amount of the hollow silica fine particles and the curable resin precursor constituting the binder resin and the compounding ratio (weight basis) of the silicon-containing compound are preferably 95: 5 to 85:15. This range is preferable because, when the ratio of the silicon-containing compound is less than the above range, sufficient slipperiness may not be obtained and the steel wool resistance may decrease, and the ratio of the silicon-containing compound may be reduced. This is because if the ratio is larger than the above range, coating unevenness may occur.

(Fluorine-containing compound)
From the viewpoint of suppressing the release of the fluorine-containing compound from the surface of the low refractive index layer, the fluorine containing compound is preferably crosslinked with the binder resin in the state of the low refractive index layer. In order to crosslink the fluorine-containing compound with the binder resin, a crosslinkable fluorine-containing compound having a photopolymerizable functional group is used as the fluorine-containing compound. By using such a crosslinkable fluorine-containing compound, the crosslinkable fluorine-containing compound and the curable resin precursor constituting the binder resin are crosslinked during curing of the composition for the low refractive index layer, and are crosslinked with the binder resin. A fluorine-containing compound is obtained.

  The fluorine-containing compound may contain silicon. However, when the silicon-containing compound contains fluorine and the fluorine-containing compound contains silicon, the fluorine-containing compound tends to have a higher ratio of fluorine atoms to silicon atoms (F / Si) than the silicon-containing compound.

  Among the fluorine-containing compounds, a fluorine-containing compound having a weight average molecular weight of 2,000 to 10,000 is preferable. By using a fluorine-containing compound having a weight average molecular weight of 2,000 to 10,000, the lift-up effect described below can be reliably obtained.

Examples of commercially available fluorine-containing compounds (crosslinkable fluorine-containing compounds) include Daikin's Optool DAC, Kyoeisha Chemical's LINC-3A-MI20 (triacryloylheptadecafluorononenylpentaerythritol) and LINC-102A. LINC series such as (1,2-diacryloxymethylperfluorocyclohexane) and Fluorolink manufactured by Solvay Solexis
The series, RS-71 manufactured by DIC, and the like can be mentioned.

  The total amount of the hollow silica fine particles and the curable resin precursor constituting the binder resin and the compounding ratio (weight basis) of the fluorine-containing compound are preferably 95: 5 to 85:15. This range is preferable because, if the ratio of the fluorine-containing compound is less than the above range, sufficient antifouling property may not be obtained, and the ratio of the fluorine-containing compound is more than the above range. This is because if the amount is large, scratch resistance may be deteriorated and coating unevenness may occur.

  The low refractive index layer 14 can be formed by, for example, a method similar to the method of forming the hard coat layer 12. Specifically, first, a composition for a low refractive index layer containing at least low refractive index fine particles, a curable resin precursor, a surface modifier and a solvent is applied to the surface of the high refractive index layer 13.

  Next, the composition for a low refractive index layer in the form of a coating film is conveyed to a zone heated for drying, and the composition for a low refractive index layer is dried and the solvent is evaporated by various known methods. Then, the composition for the low refractive index layer is cured by irradiating the composition for the high refractive index layer in a coating film with light such as ultraviolet rays and / or applying heat to polymerize (crosslink) the curable resin precursor. Then, the low refractive index layer 14 can be formed.

<solvent>
As the solvent used for the composition for the low refractive index layer, the same solvents as those mentioned for the hard coat layer can be used.

According to the present embodiment, since the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used as the hollow silica fine particles of the low refractive index layer 14, it is possible to realize the low reflectance of the antireflection film 10. It is possible to obtain good resistance to steel wool and stain resistance. That is, when the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used as the hollow silica fine particles of the low refractive index layer, the number is less than that when hollow silica fine particles having an average primary particle size of 60 nm or less are used. An antireflection film having a reflection Y value of less than 0.3% can be obtained. Further, the compound containing silicon has a property of improving slipperiness. On the other hand, since the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less in the low refractive index layer require a smaller amount as compared with the case of using hollow silica fine particles having an average primary particle size of 60 nm or less, a low refractive index is obtained. A silicon-containing compound is easily deposited (bleed out) on the surface of the low refractive index layer during formation of the refractive index layer. Therefore, a large amount of silicon-containing compound can be present on the surface of the low refractive index layer. Moreover, since the hollow silica fine particles have voids, the strength of the hollow silica fine particles is not so high. Further, if a large amount of hollow silica fine particles are present in the low refractive index layer, the amount of binder resin in the low refractive index layer will decrease. Therefore, if a large amount of hollow silica fine particles are present in the low refractive index layer, the hardness of the low refractive index layer will decrease. On the other hand, when the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used, the hollow silica fine particles in the low refractive index layer are larger than those when the hollow silica fine particles having an average primary particle size of 60 nm or less are used. Can be reduced, and the amount of binder resin in the low refractive index layer can be increased. Therefore, the hardness of the low refractive index layer can be increased. As a result, no scratches were observed on the surface of the low refractive index layer when a steel wool test was conducted in which the surface of the low refractive index layer was rubbed 10 times using # 0000 steel wool while applying a load. The load can be 200 g / cm ² or more. Further, the compound containing fluorine has a property of improving antifouling property. On the other hand, since the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less in the low refractive index layer require a smaller amount as compared with the case of using hollow silica fine particles having an average primary particle size of 60 nm or less, a low refractive index is obtained. A fluorine-containing compound is likely to be deposited on the surface of the low refractive index layer when the refractive index layer is formed. Therefore, a large amount of a fluorine-containing compound can be present on the surface of the low refractive index layer, so that the antifouling property can be improved. As a result, it is possible to realize a low reflectance and obtain good steel wool resistance and antifouling property.

  According to the present embodiment, since the low refractive index layer 14 contains hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, irregularities sufficiently smaller than the wavelength of visible light are formed on the surface of the low refractive index layer. can do. Accordingly, the same antireflection effect as that of the antireflection film having a moth-eye structure can be expected.

  When the hard coat layer 12 and / or the high refractive index layer 13 contains a non-crosslinkable fluorine-containing compound and the composition for a low refractive index layer contains a crosslinkable silicon-containing compound, the slip property is remarkably improved. You can The reason for this is not clear, but it is presumed as follows. When the coating film of the composition for a low refractive index layer is formed on the high refractive index layer 13 in the state where the non-crosslinkable fluorine-containing compound is present in the hard coat layer 12 and / or the high refractive index layer 13, the low refractive index The non-crosslinking fluorine-containing compound in the hard coat layer 12 and / or the high refractive index layer 13 is eluted by the solvent of the layer composition and enters the coating film of the low refractive index layer composition. Then, the non-crosslinkable fluorine-containing compound in the coating film of the low refractive index layer composition pushes up the crosslinkable silicon-containing compound in the coating film to the vicinity of the surface of the coating film of the low refractive index layer composition ( Lift-up effect). As a result, the crosslinkable silicon-containing compound is deposited on the surface of the coating film, so that the slipperiness can be remarkably improved. Although it is possible to add a large amount of the crosslinkable silicon-containing compound to the composition for the low refractive index layer, when a large amount of the crosslinkable silicon-containing compound is added to the composition for the low refractive index layer, the low refractive index layer becomes cloudy. Such a method cannot be adopted because it may cause a feeling. Further, when a non-crosslinkable fluorine-containing compound is added to the composition for low refractive index layer in addition to the crosslinkable silicon-containing compound, the non-crosslinkable fluorine-containing compound is deposited on the surface of the low refractive index layer, resulting in slipperiness. Therefore, such a method cannot be adopted.

  Similarly, when the hard coat layer 12 and / or the high refractive index layer 13 contains a non-crosslinkable fluorine-containing compound and the low refractive index layer composition contains a crosslinkable fluorine-containing compound, the antifouling property is Can be significantly improved. The reason for this is not clear, but it is presumed as follows. When the coating film of the composition for a low refractive index layer is formed on the high refractive index layer 13 in the state where the non-crosslinkable fluorine-containing compound is present in the hard coat layer 12 and / or the high refractive index layer 13, the low refractive index The non-crosslinking fluorine-containing compound in the hard coat layer 12 and / or the high refractive index layer 13 is eluted by the solvent of the layer composition and enters the coating film of the low refractive index layer composition. Then, the non-crosslinkable fluorine-containing compound in the coating film of the low refractive index layer composition pushes the crosslinkable fluorine-containing compound in the coating film up to near the surface of the coating film of the low refractive index layer composition ( Lift-up effect). This allows the crosslinkable fluorine-containing compound to be present near the surface of the coating film, so that the antifouling property can be remarkably improved. Although it is possible to add a large amount of the crosslinkable fluorine-containing compound to the composition for the low refractive index layer, when a large amount of the crosslinkable fluorine-containing compound is added to the composition for the low refractive index layer, the low refractive index layer becomes cloudy. Such a method cannot be adopted because it may cause a feeling. Further, when a non-crosslinkable fluorine-containing compound is added to the composition for a low refractive index layer in addition to the crosslinkable fluorine-containing compound, the non-crosslinkable fluorine-containing compound is deposited on the surface of the low refractive index layer to prevent stains. However, such a method cannot be adopted as well, since this reduces the quality.

≪Polarizer≫
The antireflection film 10 can be used, for example, by incorporating it in a polarizing plate. FIG. 2 is a schematic configuration diagram of a polarizing plate incorporating the antireflection film according to the present embodiment. As shown in FIG. 2, the polarizing plate 20 includes an antireflection film 10, a polarizing element 21, and a protective film 22. The polarizing element 21 is formed on the surface of the transparent substrate 11 opposite to the surface on which the hard coat layer 12 is formed. The protective film 22 is provided on the surface of the polarizing element 21 opposite to the surface on which the antireflection film 10 is provided. The protective film 22 may be a retardation film.

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

≪ LCD panel ≫
The antireflection film 10 and the polarizing plate 20 can be used by incorporating them in a display panel. FIG. 3 is a schematic configuration diagram of a liquid crystal panel which is an example of a display panel incorporating the antireflection film according to the present embodiment.

  The liquid crystal panel 30 shown in FIG. 3 is provided with a protective film 31, such as a triacetyl cellulose film (TAC film), a polarizing element 32, a retardation film 33, and a transparent film from the light source side (backlight unit side) toward the viewer side. The adhesive layer 34, the display element 35, the transparent adhesive layer 36, the retardation film 37, the polarizing element 21, and the antireflection film 10 are laminated in this order. The display panel 20 only needs to include the display element 25 and the antireflection film 29 arranged closer to the viewer than the display element 25, and may not include the protective film 21 and the like.

  The display element 25 is a liquid crystal display element. However, when the display panel is not a liquid crystal panel, for example, when the display panel is an organic EL panel, the display element is an organic EL display element. The liquid crystal display element is one in which a liquid crystal layer, an alignment film, an electrode layer, a color filter and the like are arranged between two glass substrates.

≪Image display device≫
The antireflection film 10, the polarizing plate 20, and the liquid crystal panel 30 can be used by incorporating them in an image display device. Examples of the image display device include a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, and electronic paper. Can be mentioned. FIG. 4 is a schematic configuration diagram of a liquid crystal display which is an example of an image display device incorporating the antireflection film according to the present embodiment.

  The image display device 40 shown in FIG. 4 includes a backlight unit 41 and a liquid crystal panel 30 provided with the antireflection film 10 and arranged on the viewer side of the backlight unit 41. As the backlight unit 41, a known backlight unit can be used.

  In order to explain the present invention in detail, examples will be given below, but the present invention is not limited to these descriptions. In addition, the following "solid content 100% conversion value" is a value when the solid content in the solvent diluted product is 100%. Further, the "average primary particle size" below is a value when the fine particles themselves are measured by a laser scattering method.

<Preparation of composition for hard coat layer>
First, each component was mixed so as to have the composition shown below to obtain a composition for a hard coat layer.
(Composition for hard coat layer)
Dipentaerythritol hexaacrylate (product name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan Co., Ltd.): 4 parts by mass ・ Leveling agent (product) Name "F568", manufactured by DIC): 0.1 part by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 120 parts by mass

<Preparation of composition for high refractive index layer>
Each component was mixed so as to have the composition shown below to obtain a composition for a high refractive index layer.
(Composition 1 for high refractive index layer)
・ Fine particles of antimony pentoxide (average primary particle size 20 nm): 400 parts by mass (solid content 100% conversion value)
Dipentaerythritol hexaacrylate (product name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan Co., Ltd.): 4 parts by mass ・ Leveling agent (product) Name "F568", manufactured by DIC): 15 parts by mass (solid content 100% conversion)
Methyl isobutyl ketone (MIBK): 16000 parts by mass

(Composition 2 for high refractive index layer)
・ Fine particles of antimony pentoxide (average primary particle size 20 nm): 400 parts by mass (solid content 100% conversion value)
Dipentaerythritol hexaacrylate (product name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan Co., Ltd.): 4 parts by mass ・ Leveling agent (product) Name "F568", manufactured by DIC): 7.5 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 16000 parts by mass

<Preparation of composition for low refractive index layer>
Each component was mixed so as to have the composition shown below to obtain a composition for a low refractive index layer.
(Composition 1 for low refractive index layer)
Hollow silica fine particles (average primary particle size 75 nm): 100 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan Ltd.): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 12 parts by mass-Contains crosslinkable fluorine Compound (Product name "OPTOOL DAC", manufactured by Daikin): 20 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 2 for low refractive index layer)
Hollow silica fine particles (average primary particle size 75 nm): 125 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 13.5 parts by mass-Crosslinkability Fluorine-containing compound (Product name "OPTOOL DAC", manufactured by Daikin): 22.5 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 3 for low refractive index layer)
Hollow silica fine particles (average primary particle size 75 nm): 150 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 15 parts by mass-Contains crosslinkable fluorine Compound (product name "OPTOOL DAC", manufactured by Daikin): 25 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 4 for low refractive index layer)
Hollow silica fine particles (average primary particle size 65 nm): 150 parts by mass (100% solid content conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 15 parts by mass-Contains crosslinkable fluorine Compound (product name "OPTOOL DAC", manufactured by Daikin): 25 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 5 for low refractive index layer)
Hollow silica fine particles (average primary particle diameter 85 nm): 120 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan Ltd.): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 13.2 parts by mass-Crosslinkability Fluorine-containing compound (Product name "OPTOOL DAC", manufactured by Daikin): 22 parts by mass (100% solid content conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 6 for low refractive index layer)
Hollow silica fine particles (average primary particle diameter 85 nm): 80 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan Ltd.): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 10.8 parts by mass-Crosslinkability Fluorine-containing compound (product name "OPTOOL DAC", manufactured by Daikin): 18 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 7 for low refractive index layer)
Hollow silica fine particles (average primary particle size 75 nm): 100 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "RS-55", manufactured by DIC): 12 parts by mass-Crosslinkable fluorine-containing compound (Product name "OPTOOL DAC", manufactured by Daikin): 20 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 8 for low refractive index layer)
Hollow silica fine particles (average primary particle size 60 nm): 170 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinking silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 16.2 parts by mass-Crosslinkability Fluorine-containing compound (Product name "OPTOOL DAC", manufactured by Daikin): 27 parts by mass (100% solid content conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 9 for low refractive index layer)
Hollow silica fine particles (average primary particle size 60 nm): 210 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", BASF Japan Ltd.): 4 parts by mass-Crosslinking silicon-containing compound (Product name "X22-164E", Shin-Etsu Chemical Co., Ltd.): 18.6 parts by mass-Crosslinkability Silicon compound (product name "OPTOOL DAC", manufactured by Daikin): 31 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 10 for low refractive index layer)
Hollow silica fine particles (average primary particle size 50 nm): 250 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", BASF Japan Ltd.): 4 parts by mass-Crosslinkable silicon-containing compound (Product name "X22-164E", Shin-Etsu Chemical Co., Ltd.): 21 parts by mass-Crosslinkable fluorine content Compound (Product name “OPTOOL DAC”, manufactured by Daikin): 35 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 11 for low refractive index layer)
Hollow silica fine particles (average primary particle size 90 nm): 110 parts by mass (solid content 100% conversion value)
-Pentaerythritol triacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass. Fluorine-containing polymer (product name "OPSTAR JN35", manufactured by JSR Co.): 80 parts by mass (solid content 100%). (Converted value)
-Polymerization initiator (Product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinking silicon-containing compound (Product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 12.6 parts by mass-Crosslinkability Fluorine-containing compound (product name "OPTOOL DAC", manufactured by Daikin): 21 parts by mass (solid content 100% conversion value)
Methyl isobutyl ketone (MIBK): 8000 parts by mass

<Example 1>
A 40 μm thick triacetyl cellulose substrate (product name “KC4UAW”, manufactured by Konica Minolta) as a transparent substrate is prepared, and the hard coat composition is applied to one surface of the triacetyl cellulose substrate and coated. A film was formed. Then, dry air at 70 ° C. was circulated for 15 seconds at a flow rate of 0.2 m / s, and then dry air at 70 ° C. was circulated for 30 seconds at a flow rate of 10 m / s to dry the formed coating film. By evaporating the solvent in the coating film and irradiating the coating film with ultraviolet rays in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) so that the integrated light amount becomes 100 mJ / cm ² , and thereby curing the coating film, A hard coat layer having a thickness of 1.52 and a film thickness of 8 μm was formed. Then, the composition 1 for a high refractive index layer was applied onto the hard coat layer to form a coating film. Then, after drying the formed coating film at 40 ° C. for 1 minute, the coating film was cured by being irradiated with ultraviolet rays in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) at an integrated light amount of 100 mJ / cm ² to have a refractive index of 1 And a high refractive index layer having a thickness of 150 nm was formed. Next, the composition 1 for low refractive index layer was applied onto the high refractive index layer to form a coating film. Then, after drying the formed coating film at 40 ° C. for 1 minute, the coating film was cured by being irradiated with ultraviolet rays in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) at an integrated light amount of 100 mJ / cm ² to have a refractive index of 1 And a low refractive index layer having a thickness of 100 nm was formed. Thereby, the antireflection film according to Example 1 was produced. The refractive index of each layer is fixed in the wavelength range of 380 nm to 780 nm, and the reflection spectrum measured by the spectrophotometer and the spectrum calculated from the optical model of the thin film using the Fresnel's equation are fitted. Sought by. The refractive indexes of the low refractive index layers and the like in the antireflection films according to Examples 2 to 8 and Comparative Examples 1 to 4 were also determined by the same method as in Example 1.

<Example 2>
In Example 2, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer composition 2 was used instead of the low refractive index layer composition 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Example 2 had a refractive index of 1.31.

<Example 3>
In Example 3, an antireflection film was prepared in the same manner as in Example 1, except that the composition 3 for low refractive index layer was used instead of the composition 1 for low refractive index layer to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Example 3 had a refractive index of 1.29.

<Example 4>
In Example 4, an antireflection film was prepared in the same manner as in Example 1 except that the high refractive index layer composition 2 was used in place of the high refractive index layer composition 1 to form the high refractive index layer. It was made.

<Example 5>
In Example 5, an antireflection film was prepared in the same manner as in Example 1, except that the low refractive index layer composition 4 was used instead of the low refractive index layer composition 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Example 5 had a refractive index of 1.32.

<Example 6>
In Example 6, an antireflection film was prepared in the same manner as in Example 1 except that the composition 5 for low refractive index layer was used in place of the composition 1 for low refractive index layer to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Example 6 had a refractive index of 1.29.

<Example 7>
In Example 7, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer composition 6 was used instead of the low refractive index layer composition 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Example 7 had a refractive index of 1.32.

<Example 8>
In Example 8, an antireflection film was prepared in the same manner as in Example 1 except that the composition for low refractive index layer 7 was used instead of the composition for low refractive index layer 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Example 8 had a refractive index of 1.32.

<Comparative Example 1>
In Comparative Example 1, an antireflection film was prepared in the same manner as in Example 1, except that the low refractive index layer composition 8 was used instead of the low refractive index layer composition 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Comparative Example 1 had a refractive index of 1.32.

<Comparative example 2>
In Comparative Example 2, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer composition 9 was used in place of the low refractive index layer composition 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Comparative Example 2 had a refractive index of 1.29.

<Comparative example 3>
In Comparative Example 3, an antireflection film was obtained in the same manner as in Example 1 except that the low refractive index layer composition 10 was used in place of the low refractive index layer composition 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Comparative Example 3 had a refractive index of 1.32.

<Comparative example 4>
In Comparative Example 4, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer composition 11 was used instead of the low refractive index layer composition 1 to form the low refractive index layer. It was made. The low refractive index layer of the antireflection film of Comparative Example 4 had a refractive index of 1.29.

<Reflection Y value measurement>
With respect to the antireflection films according to Examples and Comparative Examples, the reflection Y value was measured using a spectrophotometer (MPC3100, manufactured by Shimadzu Corporation). Specifically, light with an incident angle of 5 degrees is irradiated from the surface side of the low refractive index layer in each film, and the reflected light in the specular reflection direction reflected by each film is received to obtain a wavelength of 380 nm to 780 nm. The reflectance Y value was calculated with software (for example, software built in MPC3100) that measures the reflectance in the range and then converts it as the brightness that humans perceive. The reflection Y value was measured with a black tape (manufactured by Teraoka Seisakusho) attached to the surface (back surface) of the triacetyl cellulose substrate opposite to the surface on which the hard coat layer was formed.

<Steel wool test>
The surface of the low refractive index layers of the antireflection films according to the examples and the comparative examples was steel wool # 0000 (product name “Bonster”, manufactured by Nippon Steel Wool Co., Ltd.) and a speed of 100 mm / sec while applying a load. I rubbed it back and forth 10 times. Then, a black tape was attached to the surface of each triacetyl cellulose base material opposite to the surface on which the hard coat layer was formed, and the presence or absence of scratches was visually confirmed under a three-wavelength fluorescent lamp to confirm scratches. The maximum load during the steel wool resistance test for the antireflection film that was not tested was examined.

<Evaluation of antifouling property>
Antifouling evaluation for fingerprints After fingerprints were respectively attached to the surfaces of the low refractive index layers (the surface of the antireflection film) according to Examples and Comparative Examples, they were wiped off with Bemcot M-3 manufactured by Asahi Kasei Corporation, The ease of wiping was visually confirmed. The evaluation criteria are as follows.
⊚: Fingerprints were easily or relatively easily wiped off.
○: Fingerprints could be wiped off, but it was not easy.
X: The fingerprint could not be wiped off.

The results are shown in Table 1 below.

As shown in Table 1, in Comparative Examples 1 to 4, the low refractive index layer did not contain hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, so that the reflection Y value of the antireflection film was 0. Even if it is less than 0.3%, no scratch is confirmed on the surface of the low refractive index layer in the steel wool test, the maximum load is not 200 g / cm ² or more, or the stain resistance is poor. It was On the other hand, in Examples 1 to 8, the low refractive index layer contained hollow silica fine particles having an average primary particle diameter of 65 nm or more and 85 nm or less, so that the reflection Y value of the antireflection film was less than 0.3%. And the maximum load at which no scratch was observed on the surface of the low refractive index layer in the steel wool test was 200 g / cm ² or more, and the antifouling property was also good.

10 ... Antireflection film 10A ... Surface 11 ... Transparent substrate 12 ... Hard coat layer 13 ... High refractive index layer 14 ... Low refractive index layer 14A ... Surface 20 ... Polarizing plate 21 ... Polarizing element 30 ... Liquid crystal display panel 40 ... Image display apparatus

Claims (6)

A transparent substrate, a hard coat layer provided on the transparent substrate, a low refractive index layer provided on the hard coat layer and having a refractive index lower than that of the hard coat layer (however, a non-hollow reaction (Excluding a low refractive index layer containing fine silica particles) and a high refractive index layer provided between the hard coat layer and the low refractive index layer and having a higher refractive index than the hard coat layer. It is a prevention film,
The low refractive index layer contains hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, a binder resin, and at least a surface modifier present on the surface of the low refractive index layer,
The surface modifier contains a crosslinkable silicon-containing compound and a crosslinkable fluorine-containing compound,
The crosslinkable silicon-containing compound and / or the crosslinkable fluorine-containing compound is crosslinked with the binder resin,
The high refractive index layer contains a non-crosslinkable fluorine-containing compound,
The reflection Y value of the antireflection film measured from the low refractive index layer side is less than 0.3%,
When a steel wool resistance test was conducted on the surface of the low refractive index layer by rubbing 10 times with steel wool while applying a load, a maximum load of 200 g / cm at which no scratch was confirmed on the surface of the low refractive index layer was observed. ^An antireflection film having a thickness of ² or more.   The antireflection film according to claim 1, wherein the low refractive index layer has a refractive index of 1.20 or more and 1.32 or less.   The antireflection film according to claim 1, wherein the binder resin contains a fluororesin. The antireflection film according to claim 1,
A polarizing plate, comprising: a polarizing element formed on a surface of the antireflection film opposite to a surface of the transparent substrate on which the hard coat layer is formed. An image display device,
A display element,
The antireflection film according to claim 1, which is located closer to the viewer than the display element,
The image display device, wherein the antireflection film is arranged such that the surface of the low refractive index layer is the surface of the image display device on the observer side. An image display device,
A display element,
The polarizing plate according to claim 4 , which is located closer to the viewer than the display element,
The image display device, wherein the polarizing plate is arranged such that the surface of the low refractive index layer is the surface of the image display device on the observer side.

Images