JP2019148805A - Anti-reflection film, polarizing plate, and image display device - Google Patents

Abstract

To provide an anti-reflection film which has a low reflectance and offers good steel wool resistance and stain resistance, and to provide a polarizing plate and image display device equipped with the same.SOLUTION: An anti-reflection film is provided, comprising a hard coat layer 12 provided on a transparent base material 11, and a low refractive index layer 14 provided on the hard coat layer 12, the low refractive index layer having a refractive index lower than that of the hard coat layer 12. The low refractive index layer 14 contains hollow silica fine particles having an average primary diameter of 65-85 nm, inclusive, a binder resin, and a surface modifier along a surface 14A, the surface modifier containing a silicon-containing compound and a fluorine-containing compound. The anti-reflection film 10 has a reflection Y-value less than 0.3% as measured from the low refractive index layer 14 side. When a steel wool resistance test is performed on the surface 14A of the low refractive index layer 14, the maximum load that does not leave a recognizable scratch on the surface 14 of the low refractive index layer 14 is 200 g/cm.SELECTED DRAWING: Figure 1

Description

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

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

  The antireflective film reflects light reflected at 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). The reflected light itself is reduced by canceling each other.

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

JP 2012-48195 A

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

  When hollow silica fine particles having an average primary particle size of 60 nm or less are used, it is necessary to contain a large amount of hollow silica fine particles in the low refractive index layer in order to realize a reflection Y value of 0.3% or less. However, if the hollow silica fine particles are contained in a large amount in the low refractive index layer, the steel wool resistance and anti-fouling properties are obtained when the surface of the low refractive index layer is subjected to a steel wool resistance test and a fingerprint antifouling evaluation test. There is a risk that the soiling will be extremely reduced.

  The present invention has been made to solve the above problems. That is, an object of the present invention is to provide an antireflection film capable of realizing a low reflectivity and having good steel wool resistance and antifouling properties, as well as a polarizing plate and an image display device provided with 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 that of the hard coat layer provided on the hard coat layer. An antireflection film comprising a refractive index layer, wherein the low refractive index layer is present on the surface of hollow silica fine particles having an average primary particle size of 65 nm to 85 nm, a binder resin, and at least the low refractive index layer. A surface modifier, the surface modifier includes 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%. Yes, when a steel wool test is performed in which the surface of the low refractive index layer is rubbed 10 times while applying 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 above-described antireflection film, and a polarizing element formed on a surface of the transparent base material 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-described antireflection film positioned closer to an observer than the display element, wherein the antireflection film is the low refractive index. An image display device is provided in which the surface of the rate layer is arranged so as to be a surface on the viewer side of the image display device.

  According to another aspect of the present invention, there is provided an image display device, comprising: a display element; and the above 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 to be a surface on the viewer side of the image display device.

According to the antireflection film of one embodiment of the present invention, the polarizing plate of another embodiment, and the image display device of another embodiment, 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 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 than when hollow silica fine particles having an average primary particle size of 60 nm or less are used. Further, 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 can be used in a smaller amount than when hollow silica fine particles having an average primary particle size of 60 nm or less are used, the low refractive index During the formation of the layer, the silicon-containing compound as a surface modifier is likely to precipitate (bleed out) on the surface of the low refractive index layer. For this reason, many silicon-containing compounds can be present on the surface of the low refractive index layer. Further, when 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 hollow silica fine particles in the low refractive index layer is larger than when hollow silica fine particles having an average primary particle size of 60 nm or less are used. Therefore, the amount of the binder resin in the low refractive index layer can be increased. For this reason, the hardness of the low refractive index layer can be increased. Therefore, when a steel wool test is performed in which the surface of the low refractive index layer is rubbed 10 times while applying 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 g / cm ^2. This can be done. Further, 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 can be used in a smaller amount than when hollow silica fine particles having an average primary particle size of 60 nm or less are used, the low refractive index The fluorine-containing compound as a surface modifier is likely to be deposited on the surface of the low refractive index layer during the formation of the layer. For this reason, since many fluorine-containing compounds can be made to exist on the surface of a low refractive index layer, antifouling property can be improved. Thereby, low reflectance can be realized and good steel wool resistance and antifouling properties can be obtained.

It is a schematic block diagram of the antireflection film concerning an embodiment. It is a schematic block diagram of the polarizing plate which concerns on embodiment. It is a schematic block diagram of the liquid crystal panel which is an example of the display panel which concerns on embodiment. It is a schematic block diagram of the liquid crystal display which is an example of the image display apparatus which concerns on embodiment.

  Hereinafter, an 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 this specification, “film” includes members called “sheets”, “plates” and the like. As a specific example, the “antireflection film” includes members called “antireflection sheet”, “antireflection plate” and the like. In the present specification, the “weight average molecular weight” is a value obtained by dissolving in a solvent such as tetrahydrofuran (THF) and converting to polystyrene by a conventionally known gel permeation chromatography (GPC) method. FIG. 1 is a schematic configuration diagram of an antireflection film according to this embodiment.

≪Antireflection 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. And a low refractive index layer 14 provided. The antireflection film 10 of the present embodiment includes the high refractive index layer 13, but does not need to include the high refractive index layer 13. However, it is preferable to provide the high refractive index layer 13 from the viewpoint of obtaining excellent scratch resistance and antifouling properties.

  In the antireflection film 10, the reflection Y value measured from the low refractive index layer 14 side is less than 0.3%. The reflection Y value is more preferably 0.15% or less, and still more preferably 0.1% or less, from the viewpoint of further suppressing 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. Receiving the reflected light in the specular reflection direction, measuring the reflectance in the wavelength range of 380 nm to 780 nm, and then calculating with software (for example, software built in the MPC 3100) that is converted as the brightness that humans perceive. Can do. In the present specification, “light having an incident angle of 5 degrees” means light inclined by 5 degrees with respect to the normal direction when the normal direction of the film surface of the antireflection film is 0 degrees. The “film surface” refers to a surface that coincides with the planar direction when the target antireflection film is viewed as a whole and globally. In addition, when measuring reflection Y value, in order to prevent the back surface reflection of an antireflection film, it is preferable to stick a black tape on the surface on the opposite side to the surface in which the hard-coat layer in a transparent base material is previously formed.

In the antireflection film 10, when a steel wool test in which the surface 14 A of the low refractive index layer 14 is rubbed 10 times while applying a load using steel wool, the surface 14 A of the low refractive index layer 14 is scratched. The maximum load 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 steel wool (product name “Bonstar”, manufactured by Nippon Steel Wool Co., Ltd.) 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, and more preferably 0.3% or less. The lower limit of the overall haze can be 0.2% or more. The haze value can be measured by a method based on 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 optical transparency. For example, a cellulose acylate substrate, a cycloolefin polymer substrate, a polycarbonate substrate, an acrylate polymer substrate, a polyester substrate, or a glass group is used. Materials.

  As a cellulose acylate base material, a cellulose triacetate base material and a cellulose diacetate base material are mentioned, for example. As a cycloolefin polymer base material, the base material which consists of polymers, such as a norbornene-type monomer and a monocyclic cycloolefin monomer, is mentioned, for example.

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

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

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

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

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

  In addition, as a triacetyl cellulose base material, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like may be used in combination with components other than acetic acid as a fatty acid forming an ester with cellulose. Good. Further, these triacetylcelluloses may be added with other additives such as other cellulose lower fatty acid esters such as diacetylcellulose, or plasticizers, ultraviolet absorbers, and lubricants as necessary.

  A cycloolefin polymer substrate is preferred from the standpoint of retardation and heat resistance, and a polyester substrate is preferred from the standpoint of mechanical properties and heat resistance.

  The thickness of the transparent substrate 11 is not particularly limited, but can be 5 μm or more and 100 μm or less. The lower limit of the thickness of the transparent substrate 11 is preferably 15 μm or more, more preferably 25 μm or more from the viewpoint of handling properties. . 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 higher in a pencil hardness test (4.9 N load) defined by JIS K5600-5-4 (1999). By setting the pencil hardness to “H” or higher, 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. The upper limit of the pencil hardness on the surface of the hard coat layer 12 is preferably about 4H from the viewpoint of adhesion to the high refractive index layer formed on the hard coat layer 12, toughness, and curling prevention.

  The film thickness of the hard coat layer 12 is preferably 1 μm or more and 10 μm or less. If the film thickness of the hard coat layer 12 is in this range, it is possible to obtain a desired hardness and to reduce the thickness of the hard coat layer. 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, using a scanning electron microscope image, the film thickness of three hard coat layers is measured in one image, and 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 curling while reducing the thickness of the hard coat layer, the film 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 within 0.10, more preferably within 0.06, from the viewpoint of suppressing the occurrence of interference fringes.

  The refractive index of the hard coat layer 12 is constant in the wavelength region of 380 nm to 780 nm, and the reflection spectrum measured by the spectrophotometer is fitted to the spectrum calculated from the thin film optical model using the Fresnel equation. Can be determined by In addition, the refractive index of the hard coat layer 12 may be obtained by measuring with an Abbe refractometer (NAR-4T manufactured by Atago Co., Ltd.) or an ellipsometer after forming a single layer. Further, as a method of measuring the refractive index after becoming the antireflection film 29, the hard coat layer 12 is scraped off with a cutter or the like to prepare a powder sample, and JIS K7142 (2008) B method (powder or granular) A Becke method (for a transparent material) (using a Cargill reagent having a known refractive index, placing the powdered sample on a glass slide, dropping the reagent on the sample, and immersing the sample in the reagent. Using a method in which the refractive index of the reagent is such that the bright line (Becke line) generated in 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, fine particles may be included.

<resin>
The resin includes a cured product (polymerized product, crosslinked product) of a curable resin precursor. The “curable resin precursor” in the present specification means a resin precursor in which the resin precursor has photocurability or thermosetting and becomes a resin by photocuring or thermosetting. The resin may contain a solvent-drying resin in addition to the cured product of the 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 light irradiation. Examples of the photopolymerizable functional group include ethylenic double bonds such as a (meth) acryloyl group, a vinyl group, and an allyl group. In the present specification, “(meth) acryloyl group” means both “acryloyl group” and “methacryloyl group”. Moreover, 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 properties 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. As the photocurable resin precursor, a combination of a photopolymerizable monomer and a photopolymerizable oligomer or photopolymerizable polymer is preferable.

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

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

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

(Photopolymerizable oligomer)
The photopolymerizable oligomer has a weight average molecular weight of 1000 or more and less than 10,000. The photopolymerizable oligomer is preferably a bifunctional or higher polyfunctional oligomer. Polyfunctional oligomers include polyester (meth) acrylate, urethane (meth) acrylate, polyester-urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, and isocyanurate (meth). Examples include acrylate and epoxy (meth) acrylate.

(Photopolymerizable polymer)
The photopolymerizable polymer has a weight average molecular weight of 10,000 or more, and the weight average molecular weight is preferably from 10,000 to 80,000, more preferably from 10,000 to 40,000. When the weight average molecular weight exceeds 80,000, the viscosity is high, so that the coating suitability is lowered, and the appearance of the obtained optical laminate 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. For example, 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 such as co-condensation resins, silicon resins, and polysiloxane resins.

  The solvent-drying resin is a resin that forms a film only by drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin. When the solvent-drying type resin is added, coating defects on the coating surface of the coating liquid can be effectively prevented when the hard coat layer 14 is formed. It does not specifically limit as solvent dry type resin, Generally, a thermoplastic resin can be used.

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

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

<Fine 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 (abbreviated as 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, polyethylene fine particles, and the like.

  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. Subsequently, in order to dry the film-form composition for hard-coat layers, it conveys to the heated zone, the composition for hard-coat layers is dried by various well-known methods, and a solvent is evaporated. Thereafter, the coating composition for hard coat layer is irradiated with light such as ultraviolet rays and / or heat is applied to cure (polymerize, crosslink) the curable resin precursor. The hard coat layer 12 is formed by curing.

  Examples of the method for applying the hard coat layer composition 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 the light for curing the hard coat layer composition, ultraviolet rays emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like can be used. Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

  You may add the said microparticles | fine-particles, the said thermoplastic resin, a solvent, and a polymerization initiator to the composition for hard-coat layers as needed. Furthermore, the hard coat layer composition includes conventionally known dispersants, surfactants and antistatic agents depending on purposes such as increasing the hardness of the hard coat layer, suppressing cure shrinkage, and controlling the refractive index. , Silane coupling agents, thickeners, anti-coloring agents, colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modification A quality agent, a lubricant, etc. may be added.

<solvent>
Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketones (acetone, methyl ethyl ketone (MEK), cyclohexanone. , Methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone, etc.), ethers (1,4-dioxane, dioxolane, 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 (dimethylsulfoxide etc.), amides (dimethylformamide, dimethylacetamide etc.), etc. A mixture thereof may be used.

<Leveling agent>
Although it does not specifically limit as a leveling agent, The non-polymerizable fluorine-containing compound which does not have a photopolymerizable functional group from a viewpoint which improves antifouling property so that it may mention later is preferable. Among the non-polymerizable fluorine-containing compounds, compounds having a weight average molecular weight of 30,000 to 40,000 are preferable. Examples of such commercially available non-polymerizable fluorine-containing compounds include F568 and F477 manufactured by DIC.

  The leveling agent content 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, the flatness of the surface of the hard coat layer can be sufficiently ensured.

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

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

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

  The content of the polymerization initiator in the 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 curing inhibition can be suppressed.

  Although it does not specifically limit as a content rate (solid content) of the raw material in the composition for hard-coat layers, Usually, 5 to 70 mass% is preferable, and it is more preferable to set it as 25 to 60 mass%. .

<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 difference in refractive index 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) (magnification is preferably 10,000 times or more). Specifically, using the image of the transmission electron microscope, the film thickness of the three high refractive index layers in one image is measured, 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 has a refractive index larger than that of the hard coat layer 12, but the high refractive index layer 13 is composed of, 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 constituting 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), and 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 constituting the high refractive index layer 13 is not particularly limited, and a thermoplastic resin can be used. From the viewpoint of increasing the surface hardness, a thermosetting resin precursor and / or a photocurable resin is used. What is hardened | cured material (polymerized material, crosslinked material), such as a precursor, is preferable, and what is hardened | cured material of a photocurable resin precursor is especially more preferable.

  Examples of the thermosetting resin precursor include precursors such as acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. When curing the thermosetting resin precursor, a curing agent may be used.

  Although it does not specifically limit as a photocurable resin precursor, A photopolymerizable monomer, an oligomer, and a polymer 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, and pentaerythritol tris. (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 include acrylates, compounds obtained by modifying these compounds with ethylene oxide, polyethylene oxide, and the like.

  In addition, these compounds may have a refractive index adjusted to be high by introducing an aromatic ring, a halogen atom other than fluorine, sulfur, nitrogen, phosphorus atoms, or the like. 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, spiroacetal resins, polybutadiene resins, polythiol polyene resins, etc. Can also be used. When polymerizing (crosslinking) the photocurable resin precursor, the polymerization initiator described in the column 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 for forming the hard coat layer 12. Specifically, first, a high refractive index layer composition 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 high refractive index layer composition preferably contains a leveling agent.

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

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

  Subsequently, in order to dry the coating-form composition for high refractive index layers, it conveys to the heated zone, the composition for high refractive index layers is dried by various well-known methods, and a solvent is evaporated. Then, the composition for a high refractive index layer is cured by irradiating the film-like composition for a high refractive index layer with light such as ultraviolet rays and / or applying heat to polymerize (crosslink) the curable resin precursor. Thus, 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, and may be 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 a fine uneven shape. The “surface of the antireflective film” means the surface opposite to the surface of the antireflective 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 This means the surface on the opposite side of 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) (magnification is preferably 10,000 times or more). Specifically, using the image of the transmission electron microscope, the film thickness of the low refractive index layer at three locations in one image is measured, and this is performed for five images, and the average value of the measured film thickness is calculated. .

  The low refractive index layer 14 includes 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 in JP-A-2005-099778.

<Hollow silica fine particles>
The hollow silica fine particles constituting the low refractive index layer 14 have an average primary particle size of 65 nm or more and 85 nm or less. The average primary particle size of the hollow silica fine particles can be obtained from an image of a cross-sectional electron microscope (preferably a transmission electron microscope such as TEM or STEM having a magnification of 50,000 times or more) using image processing software. it can. Further, by using an image of a cross-sectional electron microscope (preferably a transmission electron microscope such as TEM, STEM and the like having a magnification of 50,000 times or more) and taking the scale into consideration, the hollow silica fine particles are manually calculated by calculating the average value. The average primary particle size may be determined. In this case, ten hollow silica fine particles are selected from the larger hollow silica fine particles in one image, and this is performed for five images, and an average value is calculated from a total of 50 hollow silica fine particles. In addition, when the hollow silica fine particles exist alone, that is, before the hollow silica fine particles are incorporated into the low refractive index layer or the composition for the low refractive index layer, the average primary particle size of the hollow silica fine particles is determined by laser scattering. It can be measured by the method. The measurement result by the laser scattering method and the calculation result from the cross-sectional electron microscope image are almost equal. 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, a low reflectance is realized, and good steel wool resistance and This is because the antifouling property cannot be obtained, and when the average primary particle size of the hollow silica fine particles exceeds 85 nm, the void ratio of the hollow silica fine particles increases, so that the desired hardness may not be obtained, and the 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 clouded. This is because there is a risk of being caught by hollow silica fine particles protruding from the low refractive index layer and causing 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 in which the silane coupling agent is sprayed on the silica fine particles, or a wet method in which the silica fine particles are dispersed in a solvent and then reacted by adding the silane coupling agent. Etc.

<Binder resin>
Examples of the binder resin constituting the low refractive index layer 14 include the same binder resin as that constituting 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 that has a curability and becomes a fluororesin by curing. The curable fluororesin precursor preferably has a lower functional group equivalent than the crosslinkable fluorine-containing compound as the surface modifier. Here, “functional group equivalent” means a weight average molecular weight per polymerizable functional group.

  In addition, in the curable fluororesin precursor, it is preferable that the main chain contains more fluorine atoms than the side chain from the viewpoint of suppressing a decrease in hardness. On the other hand, in a crosslinkable fluorine-containing compound as a 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 antifouling properties.

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。 As a curable fluororesin precursor, the curable fluororesin precursor of following formula (1) is mentioned, for example.

In the formula, Rf ₁ represents a chain or cyclic (m + n) -valent fluorinated hydrocarbon group containing at least a carbon atom and a fluorine atom, and optionally containing an oxygen atom and / or a hydrogen atom. Rf ₂ independently represents a chain or cyclic divalent fluorinated hydrocarbon group that contains at least a carbon atom and a fluorine atom, and may contain 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 (provided that m + n ≧ 2).

The number of hydrogen atoms / 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 ) —), and a perfluoroethylmethylene group (—CF (CF ₂ CF ₃ ) —). Perfluoroethylene group (—CF ₂ CF ₂ —), perfluoropropylene group (—CF ₂ CF ₂ CF ₂ —) and the like. Among these, a perfluoroethylene group is preferable.

Q is preferably a radical, a cation, or a polycondensable group, and —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group, — (CH ₂ ) _x Si (OW) ₃ , — More preferably, it is (CH ₂ ) _y NCO or — (CH ₂ ) _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, x, y and z each represents an integer of 1 or more, 3 The number W may be different from each other. The substituent for the alkyl group in R ₀ may be any substituent, but is preferably a halogen atom. When n is 2 or more, the plurality of Q 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. More preferably, it is 37 mass% or more and 60 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 It is preferable that

  Although the specific example of the curable fluororesin precursor shown by the said Formula (1) is shown below, it is not limited to this.

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

In addition to the above formula (1), the curable fluororesin precursor is a curable fluororesin precursor represented by the following formulas (33) to (36) or a group represented by the following formula (37). Examples thereof include a curable fluororesin precursor having at least one selected segment.

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 constituting 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 spectrometer (XPS). The surface modifier may be present inside the low refractive index layer in addition to 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 detachment 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 cross-linked at the time of curing of the composition for a low refractive index layer, thereby cross-linking 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 crosslinkable silicon-containing compound containing no fluorine, and RS-55 is a crosslinkable silicon-containing compound containing fluorine.

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

  The blending ratio (by weight) of the total amount of the hollow silica fine particles and the curable resin precursor constituting the binder resin and the silicon-containing compound is preferably 95: 5 to 85:15. This range is preferred because if the proportion of the silicon-containing compound is less than the proportion of the above range, sufficient slipperiness may not be obtained, and the steel wool resistance may decrease, and the proportion of the silicon-containing compound It is because there exists a possibility of causing a coating nonuniformity when there is more than the ratio of the said range.

(Fluorine-containing compound)
From the viewpoint of suppressing detachment 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 at the time of curing the composition for the low refractive index layer, and 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, fluorine-containing compounds having a weight average molecular weight of 2,000 to 10,000 are preferable. By using a fluorine-containing compound having a weight average molecular weight of 2,000 to 10,000, the lift-up effect described later can be reliably obtained.

  Commercially available fluorine-containing compounds (crosslinkable fluorine-containing compounds) include, for example, Daikin Optool DAC, Kyoeisha Chemical Co., Ltd. LINC-3A-MI20 (triacryloylheptadecafluorononenyl pentaerythritol) and LINC-102A LINC series such as (1,2-diaacryloxymethylperfluorocyclohexane), Fluorolink series manufactured by Solvay Solexis, RS-71 manufactured by DIC, and the like.

  The blending ratio (by weight) of the total amount of the hollow silica fine particles and the curable resin precursor constituting the binder resin and the fluorine-containing compound is preferably 95: 5 to 85:15. This range is preferred because if the proportion of the fluorine-containing compound is less than the above range, sufficient antifouling property may not be obtained, and the proportion of the fluorine-containing compound is more than the above range. This is because if the amount is too large, the scratch resistance may be lowered 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 low refractive index layer composition 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.

  Subsequently, in order to dry the coating-form composition for low refractive index layers, it conveys to the heated zone, the composition for low refractive index layers is dried by various well-known methods, and a solvent is evaporated. Thereafter, the low refractive layer composition is cured by irradiating the film-like composition for the high refractive index layer with light such as ultraviolet rays and / or applying heat to polymerize (crosslink) the curable resin precursor. Thus, 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 described for the hard coat layer can be used.

According to this embodiment, since 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, the low reflectance of the antireflection film 10 can be realized. And good steel wool resistance and antifouling properties can be obtained. 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 smaller than that when hollow silica fine particles having an average primary particle size of 60 nm or less are used. It is possible to obtain an antireflection film having a reflection Y value of less than 0.3%. A 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 can be used in a smaller amount than when hollow silica fine particles having an average primary particle size of 60 nm or less are used, the low refractive index When the refractive index layer is formed, the silicon-containing compound is likely to precipitate (bleed out) on the surface of the low refractive index layer. For this reason, many silicon-containing compounds can be present on the surface of the low refractive index layer. Further, since the hollow silica fine particles have voids, the strength of the hollow silica fine particles is not so high. In addition, when a large amount of hollow silica fine particles are present in the low refractive index layer, the amount of the binder resin in the low refractive index layer is reduced. Accordingly, when a large amount of hollow silica fine particles are present in the low refractive index layer, the hardness of the low refractive index layer is lowered. In contrast, when hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used, hollow silica fine particles in the low refractive index layer are compared with the case where hollow silica fine particles having an average primary particle size of 60 nm or less are used. The amount of the binder resin in the low refractive index layer can be increased. For this reason, the hardness of the low refractive index layer can be increased. As a result, when a steel wool test is performed in which the surface of the low refractive index layer is rubbed 10 times while applying a load using # 0000 steel wool, the surface of the low refractive index layer is not damaged. The load can be 200 g / cm ² or more. A compound containing fluorine has a property of improving antifouling properties. 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 can be used in a smaller amount than when hollow silica fine particles having an average primary particle size of 60 nm or less are used, the low refractive index The fluorine-containing compound tends to precipitate on the surface of the low refractive index layer during the formation of the refractive index layer. For this reason, since many fluorine-containing compounds can be made to exist on the surface of a low refractive index layer, antifouling property can be improved. Thereby, low reflectance can be realized and good steel wool resistance and antifouling properties can be obtained.

  According to this embodiment, since the low refractive index layer 14 includes 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. Thereby, the antireflection effect similar to the antireflection film having a moth-eye structure can also 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 low refractive index layer composition contains a crosslinkable silicon-containing compound, the slipperiness is remarkably improved. Can do. The reason for this is not clear, but is presumed as follows. When a coating film of the composition for a low refractive index layer is formed on the high refractive index layer 13 in a state where the non-crosslinkable fluorine-containing compound is present in the hard coat layer 12 and / or the high refractive index layer 13, a low refractive index is obtained. By the solvent of the layer composition, the non-crosslinkable fluorine-containing compound in the hard coat layer 12 and / or the high refractive index layer 13 is eluted and enters the coating film of the low refractive index layer composition. And by the non-crosslinkable fluorine-containing compound in the coating film of the low refractive index layer composition, the crosslinkable silicon-containing compound in this coating film is pushed up to the vicinity of the surface of the coating film of the low refractive index layer composition ( Lift-up effect). Thereby, since a crosslinkable silicon-containing compound comes to deposit on the surface of this coating film, slipperiness can be remarkably improved. Although adding a large amount of a crosslinkable silicon-containing compound to the composition for a low refractive index layer is considered, adding a large amount of a crosslinkable silicon-containing compound to the composition for a low refractive index layer causes white turbidity in the low refractive index layer. Such a method cannot be taken because there is a risk of 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 silicon-containing compound, the non-crosslinkable fluorine-containing compound is precipitated on the surface of the low refractive index layer, resulting in slipperiness. However, 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, antifouling properties are obtained. Can be significantly improved. The reason for this is not clear, but is presumed as follows. When a coating film of the composition for a low refractive index layer is formed on the high refractive index layer 13 in a state where the non-crosslinkable fluorine-containing compound is present in the hard coat layer 12 and / or the high refractive index layer 13, a low refractive index is obtained. By the solvent of the layer composition, the non-crosslinkable fluorine-containing compound in the hard coat layer 12 and / or the high refractive index layer 13 is eluted and enters the coating film of the low refractive index layer composition. And by the non-crosslinkable fluorine-containing compound in the coating film of the low refractive index layer composition, the crosslinkable fluorine-containing compound in this coating film is pushed up to the vicinity of the surface of the coating film of the low refractive index layer composition ( Lift-up effect). Thereby, since a crosslinkable fluorine-containing compound comes to exist in the surface vicinity of this coating film, antifouling property can be improved notably. Although adding a large amount of a crosslinkable fluorine-containing compound to the composition for a low refractive index layer is considered, adding a large amount of a crosslinkable fluorine-containing compound to the composition for a low refractive index layer causes cloudiness in the low refractive index layer. Such a method cannot be taken because there is a risk of feeling. Further, when a non-crosslinkable fluorine-containing compound is added to the low refractive index layer composition 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, thereby preventing the contamination. Such a technique cannot be taken because the performance is lowered.

≪Polarizing plate≫
The antireflection film 10 can be used by being incorporated into a polarizing plate, for example. 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, an ethylene-vinyl acetate copolymer saponified film, which are dyed and stretched with iodine or the like. When the antireflection film 10 and the polarizing element 21 are laminated, it is preferable to saponify the light-transmitting substrate 11 in advance. By performing the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

≪LCD panel≫
The antireflection film 10 and the polarizing plate 20 can be used by being incorporated 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 has a protective film 31, such as a triacetyl cellulose film (TAC film), a polarizing element 32, a retardation film 33, a transparent film, from the light source side (backlight unit side) to 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 disposed closer to the viewer than the display element 25, and does not need to include the protective film 21 or 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. In the liquid crystal display element, a liquid crystal layer, an alignment film, an electrode layer, a color filter, and the like are disposed 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 being incorporated 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.

  An image display device 40 shown in FIG. 4 includes a backlight unit 41 and a liquid crystal panel 30 including an antireflection film 10 disposed on the viewer side of the backlight unit 41. A known backlight unit can be used as the backlight unit 41.

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

<Preparation of composition for hard coat layer>
First, each component was mix | blended so that it might become the composition shown below, and the composition for hard-coat layers was obtained.
(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): 4 parts by mass • Leveling agent (product) Name “F568” (manufactured by DIC): 0.1 part by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 120 parts by mass

<Preparation of composition for high refractive index layer>
Each component was mix | blended so that it might become a composition shown below, and the composition for high refractive index layers was obtained.
(Composition 1 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
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): 4 parts by mass • Leveling agent (product) Name “F568” (manufactured by DIC): 15 parts by mass (100% solid content conversion)
・ Methyl isobutyl ketone (MIBK): 16000 parts by mass

(Composition 2 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
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): 4 parts by mass • Leveling agent (product) Name “F568” (manufactured by DIC): 7.5 parts by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 16000 parts by mass

<Preparation of composition for low refractive index layer>
Each component was mix | blended so that it might become the composition shown below, and the composition for low refractive index layers was obtained.
(Composition 1 for low refractive index layer)
Hollow silica fine particles (average primary particle size 75 nm): 100 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): 80 parts by mass (100% solid content) Conversion 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.): 12 parts by mass Compound (product name “OPTOOL DAC”, manufactured by Daikin): 20 parts by mass (100% solid content 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 (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): 80 parts by mass (100% solid content) Conversion 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 Fluorine-containing compound (product name “OPTOOL DAC”, manufactured by Daikin): 22.5 parts by mass (100% solid content 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 (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): 80 parts by mass (100% solid content) Conversion 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 (100% solid content 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): 80 parts by mass (100% solid content) Conversion 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 (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 5 for low refractive index layer)
Hollow silica fine particles (average primary particle size 85 nm): 120 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): 80 parts by mass (100% solid content) Conversion 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.): 13.2 parts by mass 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 size 85 nm): 80 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): 80 parts by mass (100% solid content) Conversion 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.): 10.8 parts by mass Fluorine-containing compound (product name “OPTOOL DAC”, manufactured by Daikin): 18 parts by mass (100% solid content 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 (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): 80 parts by mass (100% solid content) Conversion 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 (100% solid content 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 (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): 80 parts by mass (100% solid content) Conversion 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.): 16.2 parts by mass 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 (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): 80 parts by mass (100% solid content) Conversion 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.): 18.6 parts by mass Silicon compound (product name “OPTOOL DAC”, manufactured by Daikin): 31 parts by mass (100% solid content 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 (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): 80 parts by mass (100% solid content) Conversion 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.): 21 parts by mass Crosslinkable fluorine-containing Compound (product name “OPTOOL DAC”, manufactured by Daikin): 35 parts by mass (converted to a solid content of 100%)
・ 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 (converted to solid content of 100%)
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): 80 parts by mass (100% solid content) Conversion 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.): 12.6 parts by mass Fluorine-containing compound (product name “OPTOOL DAC”, manufactured by Daikin): 21 parts by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 8000 parts by mass

<Example 1>
A 40 μm thick triacetylcellulose substrate (product name “KC4UAW”, manufactured by Konica Minolta Co., Ltd.) as a transparent substrate was prepared, and the hardcoat composition was applied to one side of the triacetylcellulose substrate, A film was formed. Next, 70 ° C. dry air was passed through the formed coating film at a flow rate of 0.2 m / s for 15 seconds, and then 70 ° C. dry air was passed through for 30 seconds at a flow rate of 10 m / s. By evaporating the solvent in the coating film and irradiating the ultraviolet light with an integrated light amount of 100 mJ / cm ² under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to cure the coating film, the refractive index is increased. A hard coat layer having a thickness of 1.52 and a thickness of 8 μm was formed. Next, the composition 1 for a high refractive index layer was applied on the hard coat layer to form a coating film. And after drying the formed coating film for 1 minute at 40 degreeC, under a nitrogen atmosphere (oxygen concentration 200 ppm or less), it hardens | cures by irradiating with an ultraviolet-ray with the integrated light quantity of 100 mJ / cm < ² >, and refractive index is 1. .63 and a high refractive index layer having a thickness of 150 nm were formed.
Subsequently, the composition 1 for low refractive index layers was apply | coated on the high refractive index layer, and the coating film was formed. And after drying the formed coating film for 1 minute at 40 degreeC, under a nitrogen atmosphere (oxygen concentration 200 ppm or less), it hardens | cures by irradiating with an ultraviolet-ray with the integrated light quantity of 100 mJ / cm < ² >, and refractive index is 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 constant in the wavelength region of 380 nm to 780 nm, and the reflection spectrum measured by the spectrophotometer is fitted with the spectrum calculated from the thin film optical model using the Fresnel equation. Determined 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 was formed using the low refractive index layer composition 2 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Example 2 was 1.31.

<Example 3>
In Example 3, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer was formed using the low refractive index layer composition 3 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Example 3 was 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 was formed using the high refractive index layer composition 2 instead of the high refractive index layer composition 1. Produced.

<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 was formed using the low refractive index layer composition 4 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Example 5 was 1.32.

<Example 6>
In Example 6, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer was formed using the low refractive index layer composition 5 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Example 6 was 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. Produced. The refractive index of the low refractive index layer of the antireflection film according to Example 7 was 1.32.

<Example 8>
In Example 8, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer was formed using the low refractive index layer composition 7 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Example 8 was 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 was formed using the low refractive index layer composition 8 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Comparative Example 1 was 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 was formed using the low refractive index layer composition 9 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Comparative Example 2 was 1.29.

<Comparative Example 3>
In Comparative Example 3, an antireflection film was prepared in the same manner as in Example 1 except that the low refractive index layer was formed using the low refractive index layer composition 10 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Comparative Example 3 was 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 was formed using the low refractive index layer composition 11 instead of the low refractive index layer composition 1. Produced. The refractive index of the low refractive index layer of the antireflection film according to Comparative Example 4 was 1.29.

<Measurement of reflection Y value>
About the antireflection film which concerns on an Example and a comparative example, the reflection Y value was measured using the spectrophotometer (MPC3100, Shimadzu Corporation make). 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 direction reflected by each film is received, and the wavelength of 380 nm to 780 nm. The reflectance of the range was measured, and then the reflection Y value was calculated by software (for example, software built in the MPC 3100) that was converted as lightness felt by human eyes. The reflection Y value was measured in a state where a black tape (manufactured by Teraoka Seisakusho) was attached to the surface (back surface) opposite to the surface on which the hard coat layer was formed in the triacetyl cellulose base material.

<Steel wool resistance test>
The surface of the low refractive index layer of the antireflective film according to the example and the comparative example was steel wool # 0000 (product name “Bonstar”, manufactured by Nippon Steel Wool Co., Ltd.), and a speed of 100 mm / second was applied while applying a load. And rubbed 10 times. Then, a black tape is applied to the surface of each triacetyl cellulose substrate opposite to the surface on which the hard coat layer is formed, and the presence or absence of scratches is confirmed by visual observation under a three-wavelength fluorescent lamp. The maximum load at the time of the steel wool resistance test in the antireflection film that was not applied was examined.

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

The results are shown in Table 1.

As shown in Table 1, in Comparative Examples 1 to 4, since the low refractive index layer does not contain hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, the reflection Y value of the antireflection film is 0. Even if it is less than 3%, the maximum load at which no scratch is confirmed on the surface of the low refractive index layer during the steel wool test is not 200 g / cm ² or more, or the antifouling property is poor. It was. On the other hand, in Examples 1-8, since the low refractive index layer contained hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, the reflection Y value of the antireflection film was less than 0.3%. The maximum load at which no scratch was confirmed on the surface of the low refractive index layer during the steel wool resistance test was 200 g / cm ² or more, and the antifouling property was also good.

DESCRIPTION OF SYMBOLS 10 ... Antireflection film 10A ... Surface 11 ... Transparent base material 12 ... Hard coat layer 13 ... High refractive index layer 14 ... Low refractive index layer 14A ... Surface 20 ... Polarizing element 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, and the hard coat layer An antireflection film provided between the low refractive index layer and a high refractive index layer having a higher refractive index than the hard coat layer,
The low refractive index layer includes 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 includes 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 comprises 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 test is performed in which the surface of the low refractive index layer is rubbed 10 times while applying 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 g / cm. ^An antireflection film that is 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. An antireflection film according to claim 1;
A polarizing plate comprising: a polarizing element formed on a surface opposite to a surface on which the hard coat layer of the transparent base material of the antireflection film 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 antireflection film is an image display device arranged such that the surface of the low refractive index layer is a surface on the viewer side of the image display device. 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 said polarizing plate is an image display apparatus arrange | positioned so that the said surface of the said low refractive index layer may turn into the observer side surface of the said image display apparatus.

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