JP2019508753A - Antireflective film - Google Patents

Abstract

  The present invention comprises a hard coat layer; and a binder resin and a low refractive layer containing hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, the particles of the solid particles relative to the particle diameter of the hollow particles. A hard coat layer comprising an antireflective film having a diameter ratio of 0.26 to 0.55, a binder resin and organic or inorganic fine particles dispersed in the binder resin; and a hollow inorganic material dispersed in the binder resin and the binder resin A low refractive layer containing nanoparticles and solid inorganic nanoparticles; wherein the ratio of the average particle size of the solid particles to the average particle size of the hollow particles is 0.15 to 0.55, and the hard coat layer and 70 volumes in the whole solid inorganic nanoparticle within 50% of the total thickness of the low refractive layer from the interface between the low refractive layers There is more, regarding the anti-reflection film.

Description

Cross Reference to Related Applications This application is a Japanese Patent Application No. 10-2016-0089377 filed on July 14, 2016 and 10 Patent Applications Nos. 10-2017-0051842 filed on April 21, 2017. It claims the benefit and is included as a part of all the present disclosure disclosed in the document of the Korean patent application.

  The present invention relates to an antireflective film, more specifically, having low reflectance and high light transmittance, and capable of simultaneously achieving high scratch resistance and antifouling property, and having a clear screen of a display device. The invention relates to an antireflective film that can be enhanced.

  In general, an anti-reflection film is mounted on a flat display device such as a PDP or an LCD to minimize reflection of light incident from the outside.

  As a method for minimizing the reflection of light, a method of dispersing filler such as inorganic fine particles in resin and coating it on a base film to give unevenness (anti-glare: AG coating); on base film There is a method (anti-reflection: AR coating) of forming a plurality of layers having different refractive indexes and using light interference (AR coating) or a method of mixing them.

  Among them, in the case of the AG coating, the absolute amount of light reflected is at the same level as that of a common hard coat, but reducing the amount of light entering the eye using scattering of light through asperities Can provide a low reflection effect. However, since the above-mentioned AG coating reduces the sharpness of the screen due to surface irregularities, much research has been done on AR coatings recently.

  A film having a multilayer structure in which a hard coat layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film is commercialized as a film using the AR coating. However, the method of forming a large number of layers as described above has the disadvantage that the interlayer adhesion (interfacial adhesion) is weak and the scratch resistance is lowered by separately performing the step of forming each layer.

  Also, conventionally, in order to improve the scratch resistance of the low refractive layer contained in the antireflective film, the method of adding various particles of nanometer size (for example, particles of silica, alumina, zeolite, etc.) is mainly used. It was tried. However, when using the nanometer-sized particles as described above, there is a limit that it is difficult to simultaneously increase the scratch resistance while reducing the reflectance of the low refractive layer, and the nanometer-sized particles prevent the surface of the low refractive layer from having Contamination decreased greatly.

  As a result, many studies have been made to reduce the absolute reflection of incident light from the outside and improve the anti-scratch properties as well as the scratch resistance of the surface, but the degree of physical property improvement by this is insufficient .

  The present invention provides an antireflective film that has low reflectance and high light transmittance, can simultaneously achieve high scratch resistance and stain resistance, and can enhance the definition of the screen of a display device. Do.

  The present specification includes a hard coat layer; and a binder resin and a low refractive layer containing hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, wherein the solid particles relative to the average particle diameter of the hollow particles. The ratio of the average particle diameter of the entire solid inorganic nanoparticles within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer is 0.26 to 0.55. An antireflective film is provided, in which at least 70% by volume is present.

  In the present specification, a hard coat layer containing a binder resin and organic or inorganic fine particles dispersed in the binder resin; and a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin A refractive layer, wherein the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.15 to 0.55, and the low value from the interface between the hard coat layer and the low refractive layer An antireflective film is provided, wherein 70% or more by volume of the total solid inorganic nanoparticles is present within 50% of the total thickness of the refractive layer.

  Hereinafter, the antireflective film according to the specific implementation of the invention will be described in more detail.

  In the present specification, a photopolymerizable compound is generally referred to as a compound that causes a polymerization reaction when irradiated with light, for example, when irradiated with visible light or ultraviolet light.

  Moreover, a fluorine-containing compound means the compound in which the at least 1 or more fluorine element of compounds is contained.

  Furthermore, (meth) acrylic [(Meth) acrylic] is meant to include both acrylic (acrylic) and methacrylate (Methacryl).

  Moreover, a (co) polymer is a meaning including both a copolymer (co-polymer) and a homopolymer (homo-polymer).

  Furthermore, hollow silica particles are silica particles derived from a silicon compound or an organosilicon compound, and mean particles of a form in which a void space exists on the surface and / or inside of the silica particles. .

  According to one realization of the invention, it comprises a hardcoat layer; and a binder resin and a low refractive layer comprising hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, the average particle diameter of said hollow particles The ratio of the average particle diameter of the solid particles to that of the solid particles is 0.26 to 0.55, and the solid form within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer An antireflection film can be provided in which 70% by volume or more of the total amount of inorganic nanoparticles is present.

  The average particle diameter of the hollow particles and the average particle diameter of the solid particles are respectively determined by measuring the particle diameter of the hollow particles and the solid particles confirmed from the TEM photograph (for example, magnification of 25,000 times) of the antireflective film. , May be an average value obtained by calculation.

  The inventors proceeded with research on antireflective films, and the antireflective films comprising low refractive layers containing hollow particles and solid particles having the specific average particle size ratio described above have lower reflectivity and higher The invention has been completed by confirming through experiments that it has light transmittance and can simultaneously realize high scratch resistance and stain resistance.

  Although various factors affecting the distribution of the hollow particles and solid particles can be considered during the process of producing the low refractive layer, for example, the production conditions, the weight or density of the particles, etc. In the case of adjusting the difference in the average particle diameter of the particles of the above to the above ratio, it is possible to secure lower reflectance with the finally manufactured antireflective film and to realize improved scratch resistance and stain resistance. It was confirmed.

  More specifically, in the low refractive layer, the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.55 or less, or 0.15 to 0.55, or 0.26 to 0 .55, or 0.27 to 0.40, or 0.280 to 0.380, the hollow particles and the solid particles can exhibit different distribution and distribution modes in the low refractive index layer, For example, the positions where the hollow particles and the solid particles are mainly distributed may be different distances with respect to the interface between the hard coat layer and the low refractive layer.

  As described above, the regions where the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, so that the low refractive layer has an inherent internal structure and an arrangement aspect of components, resulting in lower reflection. You can have a rate. In addition, the surface characteristics of the low refractive layer are also different due to the difference in the region where the hollow particles and the solid particles are mainly distributed in the low refractive layer, thereby further improving the scratch resistance and the stain resistance. It can be realized.

  On the other hand, when the difference between the particle diameter of the hollow particles contained in the low refractive layer and the particle diameter of the solid particles is not so large, the hollow particles and the solid particles are mutually solidified or unevenly distributed or distributed depending on the kind of particles. Not only is it difficult to significantly reduce the reflectance of the antireflective film, but also it may be difficult to achieve the required scratch resistance and stain resistance.

  As described above, the display device can have the inherent effect of the antireflective film of the embodiment, such as low reflectance and high light transmittance, and high scratch resistance and stain resistance simultaneously. The characteristic that can enhance the definition of the screen is due to the ratio of the average particle size between the hollow particles and the solid particles described above.

  The solid inorganic nanoparticles refer to particles having a form in which no empty space exists.

  In addition, the hollow inorganic nanoparticles mean particles having a form in which an empty space exists on the surface and / or the inside.

  By satisfying the condition that the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles described above is 0.55 or less, the antireflective film has lower reflectance and high light transmittance, and While high scratch resistance and stain resistance can be achieved simultaneously, it has a predetermined average particle size to more easily adjust the properties of such antireflective films and to match the properties required in the application field. Hollow particles and solid particles can be used.

  For example, the average particle diameter of the hollow particles is 40 nm to 100 nm in order that the antireflective film has a lower reflectance and a higher light transmittance, and in order to improve and realize a high scratch resistance and an antifouling property. It may be within the range, and the average particle diameter of the solid particles may be within the range of 1 nm to 30 nm.

  When the average particle diameter of the hollow particles and the solid particles satisfies the above-described ratio and the above-described size range, the specific particle size range is not largely limited. However, in order to have a more uniform and improved quality of the antireflective film, the particle size of the hollow particles may be in the range of 10 nm to 200 nm, or 30 nm to 120 nm, or 38 nm to 80 nm. The particle size of the solid particles may be in the range of 0.1 nm to 100 nm, or 0.5 nm to 50 nm, or 2 nm to 25 nm.

  The diameters of the solid inorganic nanoparticles and the hollow inorganic nanoparticles can mean the longest diameter observed in the particle cross section.

  Meanwhile, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles is selected from the group consisting of hydroxy group, (meth) acrylate group, epoxide group, vinyl group (Vinyl), and thiol group (Thiol) on the surface. It can contain one or more reactive functional groups. By the solid inorganic nanoparticles and the hollow inorganic nanoparticles each having the above-mentioned reactive functional group on the surface, the low refractive layer can have a higher degree of crosslinking, thereby further improving Scratch resistance and stain resistance can be secured. Each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may have a hydroxyl group on the surface if there is no additional substituent.

  As described above, the antireflective film can include a hard coat layer; and a binder resin and a low refractive layer containing hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

  Specifically, in the antireflective film, solid inorganic nanoparticles may be distributed more than hollow inorganic nanoparticles near the interface between the hard coat layer and the low refractive layer.

  In the past, inorganic particles were added in excess to enhance the scratch resistance of the antireflective film, but there is a limit to enhancing the scratch resistance of the antireflective film, but rather the problem is that the reflectance and the antifouling property decrease. there were.

  On the other hand, when hollow inorganic nanoparticles and solid inorganic nanoparticles are distributed so as to be distinguishable from each other in the low refractive layer included in the antireflective film, they have low reflectance and high light transmittance and are high. Scratch resistance and stain resistance can be simultaneously achieved.

  Specifically, in the low refractive layer of the antireflective film, solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low refractive layer, and on the opposite surface side of the interface When the hollow inorganic nanoparticles are mainly distributed, lower reflectance can be achieved compared to the actual reflectance obtained using conventional inorganic particles, and the low refractive layer is greatly improved. Both scratch resistance and stain resistance can be realized.

  As described above, the low refractive layer includes a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, and is formed on one surface of the hard coat layer, but the solid inorganic 70% by volume or more of the total nanoparticles may be present within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.

  “70% by volume or more of the solid inorganic nanoparticles in the whole is present in a specific region” means that the solid inorganic nanoparticles are mostly present in the specific region in the cross section of the low refractive index layer Specifically, 70% by volume or more of the solid inorganic nanoparticles can be confirmed by measuring the volume of the solid inorganic nanoparticles as a whole, and also by transmission electron microscopy (TEM), etc. It is also possible to confirm by the photograph etc.

  Whether or not the hollow inorganic nanoparticles and solid inorganic nanoparticles are present in a specific region depends on whether the respective hollow inorganic nanoparticles or solid inorganic nanoparticles are present as particles in the specific region. And the particles existing over the boundary surface of the specific area are excluded.

  In addition, as described above, in the low refractive layer, hollow inorganic nanoparticles may be mainly distributed on the side opposite to the interface between the hard coat layer and the low refractive layer, specifically, 30% by volume, or 50% by volume or more, or 70% by volume or more of the hollow inorganic nanoparticles as a whole is more than the whole solid inorganic nanoparticles from the interface between the hard coat layer and the low refractive layer It can be located at a greater distance in the thickness direction of the low refractive layer.

  A region exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer (from the interface between the hard coat layer and the low refractive layer to a total thickness of the low refractive layer 30% by volume, or 50% by volume or more, or 70% by volume or more in the entire hollow inorganic nanoparticles in the region from the point exceeding 50% to the other surface of the low refractive layer facing the interface) It can.

  Also, 70% by volume or more of the solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. Furthermore, 70% by volume or more in the entire hollow inorganic nanoparticles may be present in the region of more than 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.

  Solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low refractive layer in the low refractive layer of the antireflective film, and hollow inorganic nanoparticles on the opposite surface side of the interface In the low refractive index layer, two or more portions or two or more layers having different refractive indices may be formed, thereby reducing the reflectance of the antireflective film.

  The specific distribution of the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the low refractive layer is determined by the average particle size between the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the specific manufacturing method described later. It is obtained by adjusting the ratio and adjusting the drying temperature of the photocurable resin composition for forming a low refractive layer containing the two types of nanoparticles.

  Solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low refractive layer in the low refractive layer of the antireflective film, and hollow inorganic nanoparticles on the opposite surface side of the interface In the case of mainly distributing, it is possible to realize a reflectance lower than the reflectance conventionally obtained using inorganic particles. Specifically, the antireflective film is 1.5% or less, or 1.0% or less, or 0.50 to 1.0%, 0.7% or less in the visible light wavelength band region of 380 nm to 780 nm. Or an average reflectance of 0.60% to 0.70%, or 0.62% to 0.67%.

  On the other hand, in the antireflection film of the embodiment, the low refractive layer includes a first layer containing 70% by volume or more of the solid inorganic nanoparticles, and 70 of the hollow inorganic nanoparticles. And a second layer containing at least% by volume, and the first layer may be located closer to the interface between the hard coat layer and the low refractive layer than the second layer.

  As described above, in the low refractive layer of the antireflective film, solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low refractive layer, and hollow on the opposite surface side of the interface That the primary inorganic nanoparticles are mainly distributed, but the regions where the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed form independent layers visually identified in the low refractive layer it can.

  Further, the first layer containing 70% by volume or more of the solid inorganic nanoparticles as a whole is within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. It can be located in More specifically, 70% by volume or more of the total solid inorganic nanoparticles is contained within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. There may be one layer.

  Furthermore, as described above, in the low refractive layer, hollow inorganic nanoparticles may be mainly distributed on the side opposite to the interface between the hard coat layer and the low refractive layer, specifically, 30% by volume or more, 50% by volume or more, or 70% by volume or more of the hollow inorganic nanoparticles as a whole is more from the interface between the hard coat layer and the low refractive layer than the solid inorganic nanoparticles as a whole The distance may be greater than the thickness direction of the low refractive layer. Thereby, as described above, the first layer may be located closer to the interface between the hard coat layer and the low refractive layer than the second layer.

  In addition, as described above, it is possible to visually confirm that each of the first layer and the second layer in the region in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed is present in the low refractive layer. It is. For example, it is possible to visually confirm that each of the first layer and the second layer exists in the low refractive layer by using a Transmission Electron Microscope or a Scanning Electron Microscope. In addition, the proportions of solid inorganic nanoparticles and hollow inorganic nanoparticles distributed in the first layer and the second layer in the low refractive layer can also be confirmed.

  On the other hand, each of the first layer containing 70% by volume or more in the whole solid inorganic nanoparticles and the second layer containing 70% by volume or more in the whole hollow inorganic nanoparticles are 1 Common optical properties can be shared within one layer, thereby defining one layer.

  More specifically, in each of the first layer and the second layer, the ellipticity of polarization measured by ellipsometry is optimized using the Cauchy model of the general formula 1 Sometimes, it has specific Cauchy parameters A, B and C, whereby the first and second layers can be distinguished from one another. In addition, the thickness of the first layer and the second layer can also be derived by fitting the ellipticity of polarization measured by the ellipsometry with the Cauchy model of the following general formula 1 Therefore, it becomes possible to define the first layer and the second layer in the low refractive layer.

  In the general formula 1, n (λ) is a refractive index at λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B and C are Cauchy parameters.

  On the other hand, the Cauchy parameters A, B and C derived when the ellipticity of polarization measured by the above-mentioned ellipsometry is fitted with the Cauchy model of the above-mentioned general formula 1 is 1 It may be an average value in two layers. Thus, when there is an interface between the first layer and the second layer, there may be an overlapping region of the Cauchy parameters A, B and C possessed by the first layer and the second layer. However, also in this case, depending on the region satisfying the average value of the Cauchy parameters A, B and C possessed by the first layer and the second layer, the thickness and position of the first layer and the second layer are It is identified.

For example, with respect to the first layer contained in the low refractive layer, the ellipticity of polarization measured by ellipsometry is optimized with the Cauchy model of the following general formula 1 (fitting) The following A, B, and C can satisfy the following conditions: 1.0 to 1.65, 0.0010 to 0.0350, 0 to 1 × 10 ⁻³ , and included in the low refractive layer A is 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511, and B is 0 to 0.005, with respect to the first layer. Or 0 to 0.00580, or 0 to 0.0053, and the condition of C is 0 to 1 × 10 ⁻³ , or 0 to 5.0 × 10 ⁻⁴ , or 0 to 4.1352 × 10 ⁻⁴ Can be satisfied.

In addition, with respect to the second layer contained in the low refractive layer, the ellipticity of polarization measured by ellipsometry is optimized with the Cauchy model of the general formula 1 (fitting) When A is 1.0 to 1.50, B is 0 to 0.007, C is 0 to 1 × 10 ^{-3 and} the low refractive index layer is included. A is 1.10 to 1.40, or 1.20 to 1.35, or 1.211 to 1.349, and B is 0 to 0.007, or 0 for the second layer. -0.00550, or 0 to 0.00513, and the C satisfies the condition of 0 to 1 × 10 ^-3 or 0 to 5.0 × 10 ^-4 or 0 to 4.8685 × 10 ^-4 can do.

  On the other hand, in the antireflection film of the embodiment described above, the first layer and the second layer included in the low refractive layer may have different ranges of refractive index.

  More specifically, the first layer included in the low refractive layer has a wavelength of 1.420 to 1.600, or 1.450 to 1.550, or 1.480 to 1.520, or 550 nm. It can have a refractive index of 491-1.511. In addition, the second layer included in the low refractive layer may have a refractive index of 1.200 to 1.410, or 1.210 to 1.400, or 1.211 to 1.375 at 550 nm. .

  The above-mentioned measurement of the refractive index can be carried out using a commonly known method, for example, at a wavelength of 380 nm to 1,000 nm for each of the first layer and the second layer contained in the low refractive layer. The determined elliptically polarized light and the Cauchy model can be used to calculate and determine the refractive index at 550 nm.

  On the other hand, the low refractive layer mentioned above is a photocurable coating composition comprising a photopolymerizable compound, a fluorine-containing compound containing a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles, and a photoinitiator. It can be manufactured.

  Thereby, the binder resin contained in the said low-refractive-index layer can contain the cross-linked (co) polymer between the (co) polymer of a photopolymerizable compound, and the fluorine-containing compound containing a photoreactive functional group.

  The photopolymerizable compound contained in the photocurable coating composition of the said implementation example can form the base material of the binder resin of the low-refractive-index layer manufactured. Specifically, the photopolymerizable compound can include a monomer or oligomer containing a (meth) acrylate or a vinyl group. More specifically, the photopolymerizable compound can include a monomer or oligomer containing one or more, or two or more, or three or more (meth) acrylates or vinyl groups.

  As a specific example of the monomer or oligomer containing said (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, tripentaerythritol hepta (meth) acrylate, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, trimethylolpropane trimethacrylate, ethylene glycol Dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate Or or a mixture of two or more of these or urethane-modified acrylate oligomer, epoxide acrylate oligomer, ether acrylate oligomers, dendritic acrylate oligomer or a mixture of two or more thereof. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.

  Specific examples of the monomer or oligomer containing a vinyl group include divinylbenzene, styrene, or paramethylstyrene.

  Although the content of the photopolymerizable compound in the photocurable coating composition is not largely limited, in consideration of mechanical properties and the like of the low refractive layer and the antireflective film to be finally produced, The content of the photopolymerizable compound in the solid content of the photocurable coating composition may be 5% by weight to 80% by weight. The solid content of the photocurable coating composition means only a solid component excluding a liquid component in the photocurable coating composition, for example, a component such as an organic solvent which is selectively included as described later. Do.

  On the other hand, the photopolymerizable compound may further contain a fluorine-based (meth) acrylate monomer or oligomer in addition to the above-mentioned monomer or oligomer. When it further includes the fluorine-based (meth) acrylate monomer or oligomer, the weight ratio of the fluorine-based (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group May be 0.1% to 10%.

  As a specific example of the said fluorine-type (meth) acrylate type monomer or oligomer, 1 or more types of compounds selected from the group which consists of following Chemical formula 1-5 are mentioned.

In Chemical Formula 1, R ¹ is a hydrogen group or an alkyl group having 1 to 6 carbon atoms, a is an integer of 0 to 7, and b is an integer of 1 to 3.

    In Chemical Formula 2, c is an integer of 1 to 10.

  In the chemical formula 3, d is an integer of 1 to 11.

  In the chemical formula 4, e is an integer of 1 to 5.

  In the chemical formula 5, f is an integer of 4 to 10.

  On the other hand, the low refractive layer includes a portion derived from the fluorine-containing compound containing the photoreactive functional group.

  The fluorine-containing compound containing the photoreactive functional group may contain or be substituted with one or more photoreactive functional groups, and the photoreactive functional group may be formed by irradiation of light, for example, A functional group capable of participating in a polymerization reaction by irradiation with visible light or ultraviolet light. The photoreactive functional group may include various functional groups known to be capable of participating in a polymerization reaction by light irradiation, and specific examples thereof include a (meth) acrylate group, an epoxide group, a vinyl group Or a thiol group (Thiol).

  Each of the fluorine-containing compounds containing a photoreactive functional group has a weight average molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000 (weight average molecular weight in terms of polystyrene measured by GPC method) be able to.

  When the weight average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too small, in the photocurable coating composition, the fluorine-containing compound can not be arranged uniformly and effectively on the surface and is finally manufactured. Located inside the low refractive layer, this reduces the antifouling properties of the surface of the low refractive layer and lowers the crosslink density of the low refractive layer, such as overall strength and scratch resistance Mechanical properties may be reduced.

  In addition, when the weight average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too high, the photocurable coating composition may have low compatibility with other components, whereby the final production is achieved. The haze of the low refractive layer may be high, the light transmission may be low, and the strength of the low refractive layer may also be low.

  Specifically, the fluorine-containing compound containing the photoreactive functional group is an aliphatic compound in which one or more photoreactive functional groups are substituted, and at least one carbon is substituted with one or more fluorines, or i) Aliphatic ring compounds; ii) heteroaliphatic compounds or hetero (substituted with one or more photoreactive functional groups, at least one hydrogen is substituted by fluorine, and one or more carbons is substituted by silicon) hetero) aliphatic ring compounds; iii) polydialkyl siloxane-based polymers in which one or more photoreactive functional groups are substituted and at least one silicon is substituted by one or more fluorines (for example, polydimethylsiloxane-based polymers) Iv) a polyether compound substituted by one or more photoreactive functional groups, wherein at least one hydrogen is substituted by fluorine, or i) to i) Mixtures of two or more of, or a copolymer thereof.

  The photocurable coating composition may include 20 to 300 parts by weight of the fluorine-containing compound including the photoreactive functional group with respect to 100 parts by weight of the photopolymerizable compound.

  In contrast to the photopolymerizable compound, when the fluorine-containing compound containing the photoreactive functional group is added in excess, the coating properties of the photocurable coating composition of the embodiment are lowered, or the photocurable coating composition Low refractive layers obtained from materials may not have sufficient durability or scratch resistance. In addition, when the amount of the fluorine-containing compound containing the photoreactive functional group is too small relative to the photopolymerizable compound, the low refractive layer obtained from the photocurable coating composition has sufficient antifouling property and scratch resistance It may not have mechanical properties such as elasticity.

  The fluorine-containing compound containing the photoreactive functional group may further contain silicon or a silicon compound. That is, the fluorine-containing compound containing the photoreactive functional group can selectively contain silicon or a silicon compound inside, and specifically, silicon in the fluorine-containing compound containing the photoreactive functional group The content of H may be 0.1% by weight to 20% by weight.

  The silicon contained in the fluorine-containing compound containing the photoreactive functional group can enhance the compatibility with the other components contained in the photocurable coating composition of the embodiment, whereby the final production is achieved. May function to prevent the generation of haze in the refractive layer to enhance transparency. On the other hand, when the content of silicon in the fluorine-containing compound containing the photoreactive functional group becomes excessively large, the phase between the other component contained in the photocurable coating composition and the fluorine-containing compound Solubility is rather reduced, which may result in the low refractive layer and the antireflective film finally manufactured not having sufficient light transmittance and antireflective performance, and also the surface antifouling property may be reduced. .

  The low refractive layer may include 100 parts by weight of the (co) polymer of the photopolymerizable compound, 10 to 400 parts by weight of the hollow inorganic nanoparticles, and 10 to 400 parts by weight of the solid inorganic nanoparticles. .

  When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive layer is too high, a phase between the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the process of producing the low refractive layer. Segregation may not be sufficient, but may be mixed to increase the reflectance, and surface irregularities may be generated excessively to reduce the stain resistance. In addition, when the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive layer is too small, the solid inorganic nano may be in a region near the interface between the hard coat layer and the low refractive layer. It may be difficult to locate many in the particles, and the reflectivity of the low refractive layer may be very high.

  The low refractive layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 nm, or 85 nm to 300 nm.

  On the other hand, as the hard coat layer, a generally known hard coat layer can be used without a great limitation.

  Examples of the hard coat layer include a hard coat layer containing a binder resin and organic or inorganic fine particles dispersed in the binder resin.

  The binder resin can include a photocurable resin. The photocurable resin contained in the hard coat layer is a polymer of a photocurable compound capable of causing a polymerization reaction when irradiated with light such as ultraviolet light, and may be a usual one in the art. . Specifically, the photocurable resin is a reactive acrylate oligomer group consisting of a urethane acrylate oligomer, an epoxide acrylate oligomer, a polyester acrylate, and a polyether acrylate; and dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, penta Erythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy triacrylate, 1,6-hexanediol diacrylate, propoxylated glycero triacrylate, tripropylene glycol diacrylate, And ethylene glycol diacrylate It may include one or more selected from potentially acrylate monomer group.

  The particle size of the organic or inorganic fine particle is not specifically limited. For example, the organic fine particle has a particle size of 1 to 10 μm, and the inorganic particle is 1 nm to 500 nm, or 1 nm to 300 nm Can have a particle size of The particle size of the organic or inorganic fine particles is defined by the volume average particle size.

  Moreover, although the specific example of the organic or inorganic fine particle contained in the said hard-coat film is not limited, For example, the said organic or inorganic fine particle consists of acrylic resin, a styrene resin, an epoxide resin, and nylon resin. It may be organic fine particles or inorganic fine particles consisting of silicon oxide, titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide.

  The binder resin of the hard coat layer may further contain a high molecular weight (co) polymer having a weight average molecular weight of 10,000 or more.

  The high molecular weight (co) polymer is at least one selected from the group consisting of cellulosic polymers, acrylic polymers, styrenic polymers, epoxide polymers, nylon polymers, urethane polymers, and polyolefin polymers. May be

  On the other hand, as another example of the hard coat film, a binder resin of a photocurable resin; and a hard coat film containing an antistatic agent dispersed in the binder resin can be mentioned.

  The photocurable resin contained in the hard coat layer is a polymer of a photocurable compound capable of causing a polymerization reaction when irradiated with light such as ultraviolet light, and may be a usual one in the art. . However, preferably, the photocurable compound may be a multifunctional (meth) acrylate monomer or oligomer, and in this case, the number of (meth) acrylate functional groups is 2 to 10, preferably Having 2 to 8 and more preferably 2 to 7 is advantageous in securing the physical properties of the hard coat layer. More preferably, the photocurable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hepta ( It is selected from the group consisting of meta) acrylate, tripentaerythritol hepta (meth) acrylate, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate Or more.

  The said antistatic agent is a quaternary ammonium salt compound; a pyridinium salt; a cationic compound having 1 to 3 amino groups; an anionic compound such as a sulfonate group, a sulfate group, a phosphate group or a phosphonate group Compound; Amphoteric compound such as amino acid type or amino sulfuric acid ester type compound; Nonionic compound such as imino alcohol type compound, glycerin type compound, polyethylene glycol type compound; Organometallic compound such as metal alkoxide compound containing tin or titanium etc. The metal chelate compound such as acetylacetonate salt of the organometallic compound; a reactant or a polymer of two or more of these compounds; and a mixture of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium bases in the molecule, and a low molecular weight type or a high molecular weight type can be used without limitation.

  In addition, conductive polymers and metal oxide fine particles can also be used as the antistatic agent. As the conductive polymer, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, conjugated polyaniline containing hetero atom, mixed conjugated poly (Phenylene vinylene), a conjugated double chain conjugated compound of a conjugated system having a plurality of conjugated chains in the molecule, and a conductive complex obtained by grafting or block copolymerizing conjugated polymer chains to a saturated polymer. Furthermore, examples of the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminum oxide, antimony-doped tin oxide, aluminum-doped zinc oxide and the like. .

  The hard coat film comprising the binder resin of the photocurable resin; and the antistatic agent dispersed in the binder resin further comprises one or more compounds selected from the group consisting of alkoxysilane oligomers and metal alkoxide oligomers. May be.

  The alkoxysilane compound may be a conventional one in the art, but preferably, it is tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyltriol. It may be one or more compounds selected from the group consisting of methoxysilane, glycidoxypropyltrimethoxysilane, and glycidoxypropyltriethoxysilane.

  Moreover, the said metal alkoxide type oligomer can be manufactured by the sol-gel reaction of the composition containing a metal alkoxide type compound and water. The sol-gel reaction can be carried out by a method according to the method for producing an alkoxysilane-based oligomer described above.

  However, since the metal alkoxide compound can rapidly react with water, the sol-gel reaction can be performed by a method of slowly dropping water after diluting the metal alkoxide compound in an organic solvent. At this time, it is preferable to adjust the molar ratio (based on metal ion) of the metal alkoxide compound to water within the range of 3 to 170 in consideration of the reaction efficiency and the like.

  Here, the metal alkoxide compound may be one or more compounds selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide and aluminum isopropoxide.

  Meanwhile, the hard coat layer may have a thickness of 0.1 μm to 100 μm.

  The substrate may further include a substrate bonded to the other surface of the hard coat layer. The specific type and thickness of the substrate are not particularly limited, and any substrate known to be used for the production of a low refractive layer or an antireflective film can be used without any particular limitation. For example, as the substrate, polycarbonate, cycloolefin polymer, polyester, triacetyl cellulose and the like can be mentioned.

  On the other hand, the low refractive layer may further contain a silane compound containing one or more reactive functional groups selected from the group consisting of vinyl groups and (meth) acrylate groups.

  The silane compound containing at least one reactive functional group selected from the group consisting of vinyl group and (meth) acrylate group has mechanical properties of the low refractive layer, for example It is possible to enhance the scratch resistance. At the same time, the scratch resistance further improved by the low refractive layer containing a silane compound having one or more reactive functional groups selected from the group consisting of vinyl and (meth) acrylate groups. It can be secured.

  In addition, the internal characteristics of the low refractive layer may be due to a silane functional group or a silicon atom contained in a silane compound containing one or more reactive functional groups selected from the group consisting of vinyl and (meth) acrylate groups. Can be improved. More specifically, lower average reflectance can be realized by uniformly distributing the silane functional group or the silicon atom contained in the silane compound inside the low refractive layer, and the silane function can be realized. The inorganic fine particles uniformly distributed in the inside of the low refractive layer due to groups or silicon atoms are uniformly bonded to the photopolymerizable compound, and the scratch resistance of the finally produced antireflective film can be improved.

  As described above, a chemistry in which a silane compound containing one or more reactive functional groups selected from the group consisting of vinyl and (meth) acrylate groups simultaneously contains the reactive functional group and the silicon atom. By having a structure, the internal properties of the low refractive layer can be optimized to lower the refractive index, whereby the low refractive layer can achieve low reflectivity and high transmissivity. At the same time, uniform crosslink density can be ensured to ensure better abrasion resistance or scratch resistance.

  Specifically, the silane-based compound containing one or more reactive functional groups selected from the group consisting of vinyl and (meth) acrylate groups is 100 to 1000 g / mol equivalent of the reactive functional group. Can be contained in

  When the content of the reactive functional group in the silane compound containing at least one reactive functional group selected from the group consisting of vinyl group and (meth) acrylate group is too small, the low refractive layer Resistance to scratching and mechanical properties may not be sufficiently improved.

  On the other hand, when the content of the reactive functional group in the silane compound containing at least one reactive functional group selected from the group consisting of vinyl group and (meth) acrylate group is too high, the low The homogeneity and the dispersibility of the inorganic fine particles may be reduced in the refractive layer, and the light transmittance of the low refractive layer may be reduced.

  The silane compound having at least one reactive functional group selected from the group consisting of vinyl and (meth) acrylate groups has a weight average molecular weight of 100 to 5,000, or 200 to 3,000 ( It can have a polystyrene equivalent weight average molecular weight measured by the GPC method.

  Specifically, the silane compound containing at least one reactive functional group selected from the group consisting of vinyl group and (meth) acrylate group is selected from the group consisting of vinyl group and (meth) acrylate group The organic functional group may include one or more selected reactive functional groups, one or more trialkoxysilane groups to which an alkylene group having 1 to 10 carbon atoms is bonded, and a urethane functional group. The trialkoxysilane group may be a functional group in which three alkoxy groups having 1 to 3 carbon atoms are substituted with a silicon compound.

  Although the specific chemical structure of the silane type compound which contains one or more types of 1 or more types of reactive functional groups selected from the group which consists of said vinyl group and a (meth) acrylate group is not limited, As the specific example And compounds of the following formulas 11 to 14:

In Formula 14, R ¹ is

And
X is any one of hydrogen, a monovalent residue derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxycarbonyl group having 1 to 4 carbon atoms And
Y is a single bond, -CO-, or -COO-,
R ² is a divalent residue derived from an aliphatic hydrocarbon having 1 to 20 carbon atoms, or one or more hydrogens of the divalent residue are substituted with a hydroxy group, a carboxyl group, or an epoxy group has been or is a divalent residue, or the bivalent one or more -CH residues 2 _- so that is not directly connected oxygen atom -O -, - CO-O - , - O-CO It is a bivalent residue substituted by-or -O-CO-O-,
A is any one of hydrogen and a monovalent residue derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, and B is a monovalent one derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms N is any one of the residues, and n is an integer of 0 to 2;

  As one example of the compound of Chemical Formula 14, a compound of Chemical Formula 15 may be mentioned.

In the chemical formula 15, R ₁ , R ₂ and R ₃ are each an alkoxy group having 1 to 3 carbon atoms or hydrogen, and X is a linear or branched alkylene group having 1 to 10 carbon atoms And R ₄ is an alkyl group of 1 to 3 carbon atoms or hydrogen.

  The low refractive layer is a silane type containing at least one reactive functional group selected from the group consisting of vinyl and (meth) acrylate groups relative to 100 parts by weight of the photopolymerizable compound contained in the low refractive layer. It can contain 2 to 40 parts by weight of the compound.

  When the content of the silane compound containing at least one or more reactive functional groups selected from the group consisting of vinyl group and (meth) acrylate group is too small, the low refractive layer, in contrast to the photopolymerizable compound. In some cases, it is difficult to secure sufficient scratch resistance. In addition, when the content of the silane compound having one or more reactive functional groups selected from the group consisting of vinyl group and (meth) acrylate group is too large in contrast to the photopolymerizable compound, the low The compatibility with other components contained in the refractive layer is largely reduced to generate haze in the low refractive layer or the antireflective film, or the transparency thereof may be reduced, and the scratch resistance may rather be reduced. is there.

  On the other hand, the antireflective film of the above-mentioned realization example comprises a photocurable compound or its (co) polymer, a fluorine-containing compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles. Applying a resin composition for forming a low refractive layer on the hard coat layer and drying it at a temperature of 35 ° C. to 100 ° C .; and photocuring the dried product of the resin composition. It can be provided by the manufacturing method.

  Specifically, the anti-reflection film provided by the method for producing the anti-reflection film has hollow inorganic nanoparticles and solid inorganic nanoparticles distributed so as to be distinguishable from each other in the low refractive layer, whereby low reflection is achieved. It is possible to simultaneously achieve high scratch resistance and stain resistance while having a high rate and high light transmittance.

  More specifically, the antireflective film is a hardcoat layer; and a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin and formed on one surface of the hardcoat layer. And 70% by volume or more of the total solid inorganic nanoparticles may be present within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.

  Further, 30% by volume or more in the whole hollow inorganic nanoparticles is further from the interface between the hard coat layer and the low refractive layer in the thickness direction of the low refractive layer than the whole solid inorganic nanoparticles. May be at distance.

  Furthermore, 70% by volume or more of the solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. In addition, 70% by volume or more of the hollow inorganic nanoparticles may be present in the region of more than 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.

  Furthermore, in the antireflective film provided by the method for producing the antireflective film, the low refractive layer is a first layer including 70% by weight or more of the entire solid inorganic nanoparticles, and the hollow layer And a second layer containing 70% by weight or more of the whole of the inorganic nanoparticles, wherein the first layer is between the hardcoat layer and the low refractive layer as compared to the second layer. It may be located closer to the interface.

  The low refractive layer includes a photocurable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and solid inorganic nanoparticles. The resin composition is applied onto the hard coat layer and formed by drying at a temperature of 35 ° C to 100 ° C, or 40 ° C to 80 ° C.

  If the temperature at which the resin composition for low refractive layer formation applied on the hard coat layer is dried is less than 35 ° C., the antifouling property of the low refractive layer to be formed may be greatly reduced. If the temperature for drying the resin composition for low refractive layer formation coated on the hard coat layer is over 100 ° C., the hollow inorganic nanoparticles and solid inorganic nano particles in the process of manufacturing the low refractive layer Not only does the phase separation between the particles occur sufficiently, and not only the scratch resistance and the stain resistance of the low refractive layer may be reduced, but also the reflectance may be very high.

By adjusting the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles together with the drying temperature in the process of drying the resin composition for forming a low refractive layer applied on the hard coat layer Low refractive layers having the above-mentioned characteristics can be formed. The solid inorganic nanoparticles may have a density higher than that of the hollow inorganic nanoparticles by 0.50 g / cm ³ or more, and the low density formed on the hard coat layer due to the difference of the density. In the refractive layer, the solid inorganic nanoparticles may be closer to the hard coat layer.

  On the other hand, the step of drying the low refractive layer forming resin composition applied on the hard coat layer is performed at a temperature of 35 ° C. to 100 ° C. for 10 seconds to 5 minutes, or 30 seconds to 4 minutes.

  If the drying time is too short, the phase separation between the solid inorganic nanoparticles and the hollow inorganic nanoparticles may not occur sufficiently. On the other hand, if the drying time is too long, the low refractive layer to be formed may corrode the hard coat layer.

  On the other hand, the low refractive layer includes a photocurable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles, and a light initiator. It can be produced from a curable coating composition.

  The low refractive layer is obtained by applying the photocurable coating composition on a predetermined substrate and photocuring the applied product. The specific type and thickness of the substrate are not particularly limited, and any substrate known to be used for the production of a low refractive layer or an antireflective film can be used without any particular limitation.

  The methods and apparatus usually used to apply the photocurable coating composition can be used without any particular limitation, for example, bar coating such as Meyer bar, gravure coating, 2 roll reverse coating, vacuum slot Die coating method, 2 roll coating method, etc. can be used.

  The low refractive layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 nm. Thereby, the thickness of the photocurable coating composition applied on the predetermined substrate may be about 1 nm to 300 nm, or 50 nm to 200 nm.

In the step of photocuring the photocurable coating composition, ultraviolet light or visible light having a wavelength of 200 to 400 nm can be irradiated, and the exposure dose at the time of irradiation is preferably 100 to 4,000 mJ / cm ² . The exposure time is also not particularly limited, and can be appropriately changed in accordance with the exposure apparatus to be used, the wavelength or exposure amount of the irradiation light beam.

  In addition, in the step of photocuring the photocurable coating composition, nitrogen purging and the like may be performed to apply nitrogen atmospheric conditions.

  The specific content of the photocurable compound, the hollow inorganic nanoparticles, the solid inorganic nanoparticles, and the fluorine-containing compound containing a photoreactive functional group includes the content described above with respect to the antireflective film of the one embodiment. .

  The hollow inorganic nanoparticles and the solid inorganic nanoparticles are each included in the composition in the form of colloid dispersed in a predetermined dispersion medium. The respective colloidal forms including the hollow inorganic nanoparticles and the solid inorganic nanoparticles may include an organic solvent as a dispersion medium.

  In consideration of the content range of each of the hollow inorganic nanoparticles and solid inorganic nanoparticles in the photocurable coating composition, the viscosity of the photocurable coating composition, and the like, the hollow inorganic nanoparticles and solid are described. The content of each of the fibrous inorganic nanoparticles in the colloid can be determined, for example, the solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the colloidal is 5 wt% to 60 wt%. It may be% by weight.

  Here, in the dispersion medium, as the organic solvent, alcohols such as methanol, isopropyl alcohol, ethylene glycol and butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide Amides such as dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and gamma butyrolactone; ethers such as tetrahydrofuran and 1,4-dioxane; or mixtures thereof.

  As the photopolymerization initiator, any compound known to be usable for a photocurable resin composition can be used without particular limitation. Specifically, benzophenone compounds, acetophenone compounds, biimidazole compounds A triazine compound, an oxime compound, or a mixture of two or more thereof can be used.

  The photopolymerization initiator may be used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the photopolymerizable compound. If the amount of the photopolymerization initiator is too small, uncured residual material may be generated in the photo-curing step of the photo-curable coating composition. When the amount of the photopolymerization initiator is too large, the unreacted initiator remains as an impurity, the crosslink density decreases, the mechanical properties of the produced film decrease, and the reflectance becomes very high. obtain.

  Meanwhile, the photocurable coating composition may further include an organic solvent.

  Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or a mixture of two or more thereof.

  Specific examples of such organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, i-butanol Or alcohols such as t-butanol; acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; ethers such as tetrahydrofuran or propylene glycol monomethyl ether; or a mixture of two or more of these Be

  The said organic solvent is added at the time of mixing each component contained in the said photocurable coating composition, or the said photocurable by adding the each component in the state disperse | distributed or mixed in the organic solvent Included in the coating composition. When the content of the organic solvent in the photocurable coating composition is too small, the flowability of the photocurable coating composition is reduced, and defects such as streaks are generated in the finally produced film. It may occur. In addition, when the organic solvent is added in excess, the solid content may be low, and the coating and film formation may not be sufficient, the physical properties and surface characteristics of the film may be deteriorated, and defects may occur in the drying and curing process. . Thus, the photocurable coating composition can include an organic solvent such that the concentration of the total solid content of the contained components is 1 wt% to 50 wt%, or 2 to 20 wt%.

  The hard coat layer can be used without particular limitation as long as the material is known to be usable for the antireflective film.

  Specifically, in the step of producing the antireflective film, a step of applying a polymer resin composition for forming a hard coat layer containing a photocurable compound or its (co) polymer or the like on a substrate and photocuring it. And the hard coat layer can be formed by the above steps.

  The components used to form the hardcoat layer are as described above for the antireflective film of the one implementation.

  Further, the polymer resin composition for forming a hard coat layer may further contain one or more compounds selected from the group consisting of alkoxysilane oligomers and metal alkoxide oligomers.

  The method and apparatus generally used for applying the polymer resin composition for forming a hard coat layer can be used without particular limitation, and for example, bar coating such as Meyer bar, gravure coating, 2 roll reverse coating A method, vacuum slot die coating method, 2 roll coating method, etc. can be used.

In the step of photocuring the polymer resin composition for forming a hard coat layer, ultraviolet light or visible light having a wavelength of 200 to 400 nm can be irradiated, and the exposure dose at the time of irradiation is 100 to 4,000 mJ / cm ² preferable. The exposure time is also not particularly limited, and can be appropriately changed in accordance with the exposure apparatus to be used, the wavelength or exposure amount of the irradiation light beam. Further, in the step of photocuring the polymer resin composition for forming a hard coat layer, nitrogen purging and the like can be performed in order to apply nitrogen atmospheric conditions.

  On the other hand, according to another embodiment of the present invention, a hard coat layer comprising a binder resin and organic or inorganic fine particles dispersed in the binder resin; a binder resin, hollow inorganic nanoparticles dispersed in the binder resin and a solid inorganic A low refractive layer containing nanoparticles, wherein the ratio of the average particle size of the solid particles to the average particle size of the hollow particles is 0.15 to 0.55, and between the hard coat layer and the low refractive layer The present invention provides an antireflective film in which 70% by volume or more of the total solid inorganic nanoparticles is present within 50% of the total thickness of the low refractive layer from the interface of

  The inventors proceeded with research on antireflective films, and the antireflective films comprising low refractive layers containing hollow particles and solid particles having the specific average particle size ratio described above have lower reflectivity and higher The invention was completed by experimentally confirming that it has a light transmittance and can simultaneously realize high scratch resistance and stain resistance.

  More specifically, in the low refractive layer, the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.55 or less, or 0.15 to 0.55, or 0.26 to 0 .55, or 0.27 to 0.40, or 0.280 to 0.380, the hollow particles and the solid particles can exhibit different distribution and distribution modes in the low refractive index layer, For example, the positions where the hollow particles and the solid particles are mainly distributed may be different distances with respect to the interface between the hard coat layer and the low refractive layer.

  As described above, the regions where the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, so that the low refractive layer has an inherent internal structure and an arrangement aspect of components, resulting in lower reflection. You can have a rate. In addition, the surface characteristics of the low refractive layer are also different due to the difference in the region where the hollow particles and the solid particles are mainly distributed in the low refractive layer, thereby further improving the scratch resistance and the stain resistance. It can be realized.

  Specific contents of the solid inorganic nanoparticles and the hollow inorganic nanoparticles include the contents described above in the antireflection film of one embodiment of the present invention.

  Solid inorganic nanoparticles are mainly distributed near the interface between the hard coat layer and the low refractive layer in the low refractive layer of the antireflective film, and hollow inorganic nanoparticles on the opposite surface side of the interface In the low refractive index layer, two or more portions or two or more layers having different refractive indices may be formed, thereby reducing the reflectance of the antireflective film.

  The specific distribution of the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the low refractive layer is determined by the average particle size between the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the specific manufacturing method described later. It is obtained by adjusting the ratio and adjusting the drying temperature of the photocurable resin composition for forming a low refractive layer containing the two types of nanoparticles.

  The low refractive layer includes a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, and is formed on one surface of the hard coat layer, and is contained in the entire solid inorganic nanoparticles. 70% by volume or more may exist within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.

  In addition, as described above, in the low refractive layer, hollow inorganic nanoparticles may be mainly distributed on the side opposite to the interface between the hard coat layer and the low refractive layer, specifically, 30% by volume, or 50% by volume or more, or 70% by volume or more of the hollow inorganic nanoparticles as a whole is more than the whole solid inorganic nanoparticles from the interface between the hard coat layer and the low refractive layer It can be located at a greater distance in the thickness direction of the low refractive layer.

  A region exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer (from the interface between the hard coat layer and the low refractive layer to a total thickness of the low refractive layer 30% by volume, or 50% by volume or more, or 70% by volume or more in the entire hollow inorganic nanoparticles in the region from the point exceeding 50% to the other surface of the low refractive layer facing the interface) It can.

  Also, 70% by volume or more of the solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. Furthermore, 70% by volume or more in the entire hollow inorganic nanoparticles may be present in the region of more than 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.

  The binder resin containing the said photocurable resin and the organic or inorganic fine particle disperse | distributed to this binder resin can be included.

  The organic fine particles may have a particle size of 1 to 10 μm, and the inorganic particles may have a particle size of 1 to 500 nm, or 1 to 300 nm.

  The contents relating to the binder resin of the hard coat layer and the organic or inorganic fine particles include the contents described above in relation to the antireflection film of one embodiment of the present invention.

  Further, except for the contents described above in the antireflection film of the other embodiment, more specific contents include the contents described above in relation to the antireflection film of one embodiment of the present invention.

  According to the present invention, it is possible to simultaneously realize high scratch resistance and anti-soiling property, having low reflectance and high light transmittance, and to improve the definition of the screen of a display device. And the manufacturing method of the said anti-reflective film can be provided.

7 shows a cross-sectional TEM image of the antireflection film of Example 1. 7 shows a cross-sectional TEM image of the antireflection film of Example 2. 7 shows a cross-sectional TEM image of the antireflection film of Example 3. 7 shows a cross-sectional TEM image of the antireflection film of Example 4. 7 shows a cross-sectional TEM image of the antireflection film of Example 5. 7 shows a cross-sectional TEM image of the antireflection film of Example 6. 7 is a cross-sectional TEM photograph of the antireflection film of Comparative Example 1; 7 is a cross-sectional TEM photograph of the antireflection film of Comparative Example 2;

  The invention is illustrated in more detail in the following examples. However, the following examples merely illustrate the present invention, and the contents of the present invention are not limited by the following examples.

<Production example>
Production example: Production of hard coat film A salt type antistatic hard coat solution (solid content 50% by weight, product name: LJD-1000) manufactured by KYOEISHA is coated on a triacetyl cellulose film with # 10 mayer bar, 1 at 90 ° C. After drying for a minute, UV light of 150 mJ / cm ² was irradiated to produce a hard coat film having a thickness of about 5 to 6 μm.

Examples 1 to 5: Production of Antireflection Film
Example 1
(1) Production of photocurable coating composition for producing a low refractive layer Hollow silica nanoparticles (diameter range: about 44 nm to 61 nm, product of JSC catalyst and chemicals) with respect to 100 parts by weight of pentaerythritol triacrylate (PETA) 281 parts by weight, solid silica nanoparticles (diameter range: about 12.7 nm to 17 nm) 63 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu company) 131 parts by weight, second fluorine-containing compound (RS-) 19 parts by weight of 537, DIC, and 31 parts by weight of an initiator (Irgacure 127, Ciba) were diluted in a methyl isobutyl ketone (MIBK) solvent to a solid concentration of 3% by weight.

(2) Production of Low Refractive Layer and Antireflection Film The obtained photocurable coating composition was coated on the hard coat film of the above production example to a thickness of about 110 to 120 nm with a # 4 mayer bar. The resultant was dried and cured at the temperature and time shown in Table 1 below to form a low refractive layer, and an antireflective film was manufactured. At the time of curing, the dried coating was irradiated with 252 mJ / cm ² of ultraviolet light under nitrogen purging.

  Then, using a transmission electron microscope (TEM), the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer is measured, and this is repeated 10 times. The average particle sizes of the hollow silica nanoparticles and the solid silica nanoparticles were determined [hollow silica nanoparticles average diameter: 55.9 nm, solid silica nanoparticles average diameter: 14.5 nm].

Example 2
(1) Preparation of photocurable coating composition for producing a low refractive layer Hollow silica nanoparticles (diameter range: about 42 nm to 66 nm, product of JSC catalyst and chemicals, based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA) 283 parts by weight, solid silica nanoparticles (diameter range: about 12 nm to 19 nm) 59 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu Co., Ltd.) 115 parts by weight, second fluorine-containing compound (RS-537) , DIC, 15.5 parts by weight, and 10 parts by weight of an initiator (Irgacure 127, Ciba) were diluted in MIBK (methyl isobutyl ketone) solvent to a solid concentration of 3% by weight.

(2) Production of Low Refractive Layer and Antireflection Film The obtained photocurable coating composition was coated on the hard coat film of the above production example to a thickness of about 110 to 120 nm with a # 4 mayer bar. The resultant was dried and cured at the temperature and time shown in Table 1 below to form a low refractive layer, and an antireflective film was manufactured. At the time of curing, the dried coating was irradiated with 252 mJ / cm ² of ultraviolet light under nitrogen purging.

  Then, using a transmission electron microscope (TEM), the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer is measured, and this is repeated 10 times. The average particle sizes of the hollow silica nanoparticles and solid silica nanoparticles were determined [hollow silica nanoparticles average diameter: 54.9 nm, solid silica nanoparticles average diameter: 14.5 nm].

Example 3
(1) Production of photocurable coating composition for producing a low refractive layer Hollow silica nanoparticles (diameter range: about 43 nm to 71 nm, product of JSC catalyst and chemicals) with respect to 100 parts by weight of pentaerythritol triacrylate (PETA) 281 parts by weight, solid silica nanoparticles (diameter range: about 13 nm to 16 nm) 63 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu Co., Ltd.) 111 parts by weight, second fluorine-containing compound (RS-537, 30 parts by weight of DIC, and 23 parts by weight of an initiator (Irgacure 127, Ciba) were diluted in a solvent of MIBK (methyl isobutyl ketone) to a solid concentration of 3% by weight.

(2) Production of Low Refractive Layer and Antireflection Film The obtained photocurable coating composition was coated on the hard coat film of the above production example to a thickness of about 110 to 120 nm with a # 4 mayer bar. The resultant was dried and cured at the temperature and time shown in Table 1 below to form a low refractive layer, and an antireflective film was manufactured. At the time of curing, the dried coating was irradiated with 252 mJ / cm ² of ultraviolet light under nitrogen purging.

  Then, using a transmission electron microscope (TEM), the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer is measured, and this is repeated 10 times. The average particle diameter of the hollow silica nanoparticles and the solid silica nanoparticles was determined [average diameter of hollow silica nanoparticles: 54.5 nm, average diameter of solid silica nanoparticles: 19.5 nm].

Example 4
(1) Preparation of photocurable coating composition for producing a low refractive index layer Hollow silica nanoparticles (diameter range: about 38 nm to 82 nm, product of JSC catalyst and chemicals, based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA) ) 264 parts by weight, solid silica nanoparticles (diameter range: about 15 nm to 19 nm) 60 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu company) 100 parts by weight, second fluorine-containing compound (RS-537) , DIC Corporation) and 30 parts by weight of an initiator (Irgacure 127, Ciba) were diluted in MIBK (methyl isobutyl ketone) solvent to a solid concentration of 3% by weight.

(2) Production of Low Refractive Layer and Antireflection Film The obtained photocurable coating composition was coated on the hard coat film of the above production example to a thickness of about 110 to 120 nm with a # 4 mayer bar. The resultant was dried and cured at the temperature and time shown in Table 1 below to form a low refractive layer, and an antireflective film was manufactured. At the time of curing, the dried coating was irradiated with 252 mJ / cm ² of ultraviolet light under nitrogen purging.

  Then, using a transmission electron microscope (TEM), the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer is measured, and this is repeated 10 times. The average particle sizes of the hollow silica nanoparticles and solid silica nanoparticles were determined [hollow silica nanoparticles average diameter: 55.4 nm, solid silica nanoparticles average diameter: 17.1 nm].

Example 5
(1) Production of photocurable coating composition for producing a low refractive layer Hollow silica nanoparticles (diameter range: about 43 nm to 81 nm, product of JSC catalyst and chemicals) with respect to 100 parts by weight of pentaerythritol triacrylate (PETA) 414 parts by weight, solid silica nanoparticles (diameter range: about 14 nm to 19 nm) 38 parts by weight, fluorine-containing compound (RS-537, DIC) 167 parts by weight, initiator (Irgacure 127, Ciba) 33 parts by weight, and 3 -110 parts by weight of methacryloxypropylmethyldimethoxysilane (molecular weight: 234.3) was diluted in a solvent of methyl isobutyl ketone (IBK) to a solid content concentration of 3.2% by weight.

(2) Production of Low Refractive Layer and Antireflection Film The obtained photocurable coating composition was coated on the hard coat film of the above production example to a thickness of about 110 to 120 nm with a # 4 mayer bar. The resultant was dried and cured at the temperature and time shown in Table 1 below to form a low refractive layer, and an antireflective film was manufactured. At the time of curing, the dried coating was irradiated with 252 mJ / cm ² of ultraviolet light under nitrogen purging.

  Then, using a transmission electron microscope (TEM), the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer is measured, and this is repeated 10 times. The average particle sizes of the hollow silica nanoparticles and the solid silica nanoparticles were determined [hollow silica nanoparticles average diameter: 55.5 nm, solid silica nanoparticles average diameter: 17.1 nm].

Example 6
(1) Production of hard coat layer (HD2) 30 g of pentaerythritol triacrylate, 2.5 g of high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000), 20 g of methyl ethyl ketone, and leveling agent (Tego wet 270) After uniformly mixing 0.5 g, 2 g of an acrylic-styrene copolymer (volume average particle diameter: 2 μm, manufacturing company: Sekisui Plastic) is added as fine particles having a refractive index of 1.525 to obtain a hard coat composition. Manufactured.

The hardcoat composition thus obtained was coated on a triacetylcellulose film at # 10 mayer bar and dried at 90 ° C. for 1 minute. The dried product was irradiated with UV light of 150 mJ / cm ² to produce a hard coat layer having a thickness of 5 μm.

(2) Preparation of Low Refractive Layer and Antireflection Film Hollow silica nanoparticles (diameter range: about 40 nm to 68 nm, product of JSC catalyst and chemicals) 283 parts by weight with respect to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) 59 parts by weight of solid silica nanoparticles (diameter range: about 14 nm to 17 nm), 115 parts by weight of a first fluorine-containing compound (X-71-1203M, ShinEtsu), a second fluorine-containing compound (RS-537, DIC) 15.5 parts by weight and 10 parts by weight of an initiator (Irgacure 127, Ciba) are diluted in MIBK (methyl isobutyl ketone) solvent to a solid content concentration of 3% by weight to form a photocurable coating for producing a low refractive layer The composition was manufactured.

The obtained photocurable coating composition for producing a low refractive layer is coated on the produced hard coat layer (HD2) to a thickness of about 110 to 120 nm under a # 4 mayer bar, and at 60 ° C. Drying and curing for 1 minute at temperature formed a low refractive layer to produce an antireflective film. At the time of curing, the dried coating was irradiated with 252 mJ / cm ² of ultraviolet light under nitrogen purging.

  Then, using a transmission electron microscope (TEM), the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer is measured, and this is repeated 10 times. The average particle diameter of the hollow silica nanoparticles and the solid silica nanoparticles was determined [average diameter of the hollow silica nanoparticles: 55.4 nm, average diameter of the solid silica nanoparticles: 14.7 nm].

Comparative Example: Production of Antireflection Film
Comparative Example 1
An antireflective film was manufactured in the same manner as Example 1, except that solid silica nanoparticles (diameter range: about 34 nm to 80 nm) were used.

  Using a transmission electron microscope (TEM), measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the low refractive layer formed as described above, and repeat 10 times to obtain the hollow The average particle sizes of the fibrous silica nanoparticles and the solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 54.6 nm, average diameter of solid silica nanoparticles: 53.2 nm].

Comparative example 2
An antireflective film was prepared in the same manner as Example 2, except that solid silica nanoparticles (diameter range: about 36 nm to 48 nm) were used.

  Using a transmission electron microscope (TEM), measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the low refractive layer formed as described above, and repeat 10 times to obtain the hollow The average particle sizes of the solid silica nanoparticles and the solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 54.5 nm, average diameter of solid silica nanoparticles: 41.1 nm].

<Experimental Example: Measurement of Physical Properties of Antireflection Film>
The experiments of the following items were carried out on the antireflective films obtained in the above Examples and Comparative Examples.

1. Measurement of Average Reflectance of Antireflection Film The average reflectance at which the antireflective films obtained in Examples and Comparative Examples appear in the visible light region (380 to 780 nm) was measured using a Solidspec 3700 (SHIMADZU) apparatus.

2. Measurement of antifouling property A straight line of 5 cm in length was drawn with a black name pen on the surface of the antireflective film obtained in Examples and Comparative Examples, and the number of times erased when rubbed with a dust-free cloth was confirmed. The antifouling properties were measured.
<Measure standard>
O: Less than 10 times at the time of extinction Δ: 11 times to 20 times of the erasure X: Over 20 times at the time of extinction

3. Measurement of Scratch Resistance A load was applied to the steel wool and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in Examples and Comparative Examples. The maximum load at which one or less scratch of 1 cm or less observed with the naked eye was observed was measured.

  As shown in Table 2 above, the ratio of the particle size of the solid particles to the particle size of the hollow particles contained in the low refractive index layers of the antireflective films of Examples 1 to 6 is 0.55 or less, It is confirmed that it exhibits a low reflectance of 0.70% or less in the visible light region and can simultaneously realize high scratch resistance and stain resistance.

  In addition, as shown in FIGS. 1 to 6, in the low refractive index layer of the antireflection film of Examples 1 to 4, the hollow inorganic nanoparticles and the solid inorganic nanoparticles are phase-separated, and the solid Inorganic nanoparticles are mostly present and concentrated on the interface side between the hard coat layer of the antireflective film and the low refractive layer, and the hollow inorganic nanoparticles are mostly present on the side far from the hard coat layer. The points that are concentrated are confirmed.

  As described in Table 2 above, in the low refractive layers of the antireflective films of Comparative Examples 1 and 2, the ratio of the particle size of solid particles to the particle size of hollow particles exceeds 0.55, and FIG. As shown in and 8, it is confirmed that hollow inorganic nanoparticles and solid inorganic nanoparticles are mixed without being phase separated.

  And as shown in the said Table 2, the point which shows low scratch resistance and antifouling property was confirmed with high reflectance, respectively.

Claims (25)

A hard coat layer; and a binder resin and a low refractive layer containing hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin;
The ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.26 to 0.55,
An antireflective film, wherein 70% by volume or more of the total solid inorganic nanoparticles is present within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.   In the region from the interface between the hard coat layer and the low refractive layer to the other surface of the low refractive layer opposite to the interface from a point exceeding 50% of the total thickness of the low refractive layer, the hollow inorganic nano The antireflective film according to claim 1, wherein 30% by volume or more of the total particles are present.   The antireflection film according to claim 1, wherein an average particle diameter of the hollow particles is within a range of 40 nm to 100 nm.   The antireflection film according to claim 1, wherein the particle diameter of the hollow particles is within the range of 10 nm to 200 nm.   The antireflection film according to claim 1, wherein an average particle diameter of the solid particles is within a range of 1 nm to 30 nm.   The antireflective film according to claim 1, wherein the particle size of the solid particles is within the range of 0.1 nm to 100 nm.   The antireflection film according to claim 1, wherein the antireflection film exhibits an average reflectance of 0.7% or less in a visible light wavelength band region of 380 nm to 780 nm.   The antireflective film according to claim 1, wherein solid inorganic nanoparticles are distributed more than hollow inorganic nanoparticles near the interface between the hard coat layer and the low refractive layer.   The reflection according to claim 1, wherein 70% by volume or more of the total solid inorganic nanoparticles is present within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. Prevention film.   At least 30% by volume in the whole hollow inorganic nanoparticles is at a distance farther from the interface between the hard coat layer and the low refractive layer than the whole solid inorganic nanoparticles in the thickness direction of the low refractive layer The antireflective film according to claim 1, which is present.   The antireflection according to claim 1, wherein 70% by volume or more of the total solid inorganic nanoparticles is present within 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. the film.   The volume ratio of 70% or more in the whole of the hollow inorganic nanoparticles is present in the region of more than 30% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer. Antireflective film. The low refractive layer includes a first layer containing 70% by volume or more of the solid inorganic nanoparticles and a second layer containing 70% by volume or more of the hollow inorganic nanoparticles. Including and
The antireflective film according to claim 1, wherein the first layer is located closer to the interface between the hard coat layer and the low refractive layer than the second layer.   Each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles is selected from the group consisting of hydroxy groups, (meth) acrylate groups, epoxide groups, vinyl groups (Vinyl), and thiol groups (Thiol) on the surface. The antireflective film according to claim 1, containing a species or more of reactive functional groups.   The binder resin contained in the low refractive layer includes a cross-linked (co) polymer between a (co) polymer of a photopolymerizable compound and a fluorine-containing compound containing a photoreactive functional group. Antireflective film.   The low refractive layer includes 100 parts by weight of the (co) polymer of the photopolymerizable compound, 10 to 400 parts by weight of the hollow inorganic nanoparticles, and 10 to 400 parts by weight of the solid inorganic nanoparticles. The antireflective film as described in 15.   The antireflective film according to claim 1, wherein the low refractive layer further comprises a silane compound containing one or more reactive functional groups selected from the group consisting of vinyl groups and (meth) acrylate groups. The silane compound containing at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group is any one of the compounds represented by the following chemical formulas 11 to 14, The antireflective film according to claim 17:
In Formula 14, R ¹ is
And
X is any one of hydrogen, a monovalent residue derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxycarbonyl group having 1 to 4 carbon atoms And
Y is a single bond, -CO-, or -COO-,
R ² is a divalent residue derived from an aliphatic hydrocarbon having 1 to 20 carbon atoms, or one or more hydrogens of the divalent residue are substituted with a hydroxy group, a carboxyl group, or an epoxy group has been or is a divalent residue, or the bivalent one or more -CH residues 2 _- so that is not directly connected oxygen atom -O -, - CO-O - , - O-CO It is a bivalent residue substituted by-or -O-CO-O-,
A is any one of hydrogen and a monovalent residue derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, and B is a monovalent one derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms N is any one of the residues, and n is an integer of 0 to 2;   The silane type compound which contains one or more types of one or more types of reactive functional groups selected from the group which consists of the said vinyl group and a (meth) acrylate group contains the said reactive functional group by 100-1,000 g / mol equivalent. The antireflective film according to claim 17.   The silane compound according to claim 17, wherein the silane compound containing one or more reactive functional groups selected from the group consisting of vinyl and (meth) acrylate groups has a weight average molecular weight of 100 to 5,000. Anti-reflection film.   The antireflection film according to claim 1, wherein the hard coat layer comprises a binder resin and organic or inorganic fine particles dispersed in the binder resin. The organic fine particles have a particle size of 1 to 10 μm,
22. The antireflective film of claim 21, wherein the inorganic particles have a particle size of 1 nm to 500 nm. A binder resin and a hard coat layer containing organic or inorganic fine particles dispersed in the binder resin; and a binder resin and a low refractive layer containing hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin;
The ratio of the average particle size of the solid particles to the average particle size of the hollow particles is 0.15 to 0.55,
An antireflective film, wherein 70% by volume or more of the total solid inorganic nanoparticles is present within 50% of the total thickness of the low refractive layer from the interface between the hard coat layer and the low refractive layer.   In the region from the interface between the hard coat layer and the low refractive layer to the other surface of the low refractive layer opposite to the interface from a point exceeding 50% of the total thickness of the low refractive layer, the hollow inorganic nano The antireflective film according to claim 23, wherein 30% by volume or more in the whole particles is present. The organic fine particles have a particle size of 1 to 10 μm,
24. The antireflective film of claim 23, wherein the inorganic particles have a particle size of 1 nm to 500 nm.