JP2018084768A - Anti-reflection film and manufacturing method for anti-reflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-reflection film which offers superior flexibility, high alkali resistance, superior abrasion resistance, high transparency, and an anti-reflective property that is superior to light in the visible range, is less wavelength-dependent, and shows little variation associated with change in incident angle of light.SOLUTION: An anti-reflection film consists of at least four layers comprising a fine structure layer, an intermediate layer formed using a cross-liking resin, a hard coat layer, and a base material in order from a layer furthest from the base material in a thickness direction, the fine structure layer having a thickness of 50-200 nm and the intermediate layer having a thickness of 50-150 nm. The fine structure layer has a refractive index of 1-1.35, and a difference in refractive index between the hard coat layer and the base material is no greater than 0.3 in absolute terms. A value given by a formula (1) is in a range of 0.92 to 1.07, where nrepresents the refractive index of the fine structure layer, nrepresents a refractive index of the intermediate layer, and nrepresents a refractive index of the hard coat layer.SELECTED DRAWING: None

Description

  The present invention is excellent in flexibility, has high alkali resistance, excellent scratch resistance and high transparency, has excellent antireflection properties for light in the visible light region, has low wavelength dependency of antireflection properties, The present invention relates to an antireflection film in which the change in antireflection property due to the change in the incident angle of the film is small.

In a display device such as a liquid crystal display and an optical device such as a camera, an antireflection film is used to suppress a decrease in visibility due to reflected light from the outside. Conventionally, the following three types of antireflection films are known.
(I) A single-layer antireflection film that utilizes light interference and having a low refractive index (LR type).
(Ii) A multilayer antireflection film (AR type) that utilizes interference of light, but in which low refractive index layers and high refractive index layers are alternately laminated.
(Iii) A device that scatters light by a micro-scale large uneven structure (AG type).

  Among these, (i) has a problem that the antireflection property is insufficient.

  Regarding (ii), although the antireflection property for light of a specific wavelength is excellent, the reflection light is colored due to the large wavelength dependency of the antireflection property, and the change in the antireflection property is caused by the change in the incident angle of the light. There was a problem of being big. Furthermore, since it is necessary to laminate multiple layers, there is a problem that the mass productivity is inferior and the cost is high.

  With regard to (iii), there is a problem that it does not prevent reflection of light but scatters reflected light and is inferior in transparency and translucency.

  As an antireflection film using a principle different from these, an antireflection film has been proposed that uses a stamper to form a microscopic structure on the surface to reduce reflectivity (for example, Patent Documents). 1). In this antireflection film, the thickness of the fine structure layer is sufficiently larger than a quarter wavelength of light, and the average periodic pitch of the fine structure is smaller than about a half wavelength of light. High reflection resistance is imparted to light in the light region (380 to 780 nm) without causing light scattering. However, in this method, in order to obtain a practically sufficient antireflection property for light in the visible light region, the thickness of the microstructure layer needs to be larger than 200 nm, but the thickness of the microstructure layer is 200 nm. If larger, the strength of the microstructure of the antireflection film to be produced becomes insufficient, resulting in poor scratch resistance.

  In addition, as an antireflection film utilizing a fine structure, it consists of a dense layer and a silica airgel porous layer formed in order on the surface of the substrate, and the refractive index decreases in order from the substrate to the silica airgel porous layer. An antireflection film characterized by the above has been proposed (see, for example, Patent Document 2). In the antireflection film, the refractive index decreases in order from the base material to the silica airgel porous layer, so that the thickness of the fine structure layer is smaller than 200 nm, and a wide incident angle in a wide wavelength range. Excellent antireflection properties are imparted to the light beam. However, the antireflection film has a problem that the substrate is limited to an inorganic material such as glass because the microstructure layer is formed of silica aerogel and heat treatment at a high temperature is required. Further, since heat treatment for a long time is required, there is a problem that the mass productivity of the antireflection film is inferior and the cost is high. Furthermore, since the antireflection film to be produced has an inorganic silica airgel porous layer, there is a problem that when the antireflection film is bent, cracks (line defects and cracks) are likely to occur and flexibility is poor. there were.

  On the other hand, one of the main uses of the antireflection film is an antireflection film for a polarizing plate for display. This uses a film formed of an antireflection film on one main surface of a film such as triacetyl cellulose (TAC) as a protective film, and adheres the other main surface to the surface of a polyvinyl alcohol (PVA) film as a polarizing layer. It is something to be made. Conventionally, a method of saponifying the protective film by immersing it in an alkaline solution is known for the purpose of improving the adhesiveness when adhering to the PVA film. For this reason, it is desirable that the antireflection film used for the protective film has alkali resistance. However, since the antireflection film of Patent Document 2 has an inorganic silica airgel porous layer on its surface, it has a problem of poor alkali resistance and unsuitable for the application.

JP 2008-209540 A JP 2006-215542 A

  The present invention has been made in view of the above problems, and its object is to have excellent flexibility, high alkali resistance, excellent scratch resistance and high transparency, and antireflection property for light in the visible light region. An object of the present invention is to provide an antireflection film that is excellent in antireflection properties, has a small wavelength dependency of antireflection properties, and has a small change in antireflection properties due to a change in the incident angle of light.

  As a result of intensive studies to achieve the above object, the present inventors have at least four layers of a microstructure layer, an intermediate layer, a hard coat layer, and a substrate in order from a position far from the substrate in the film thickness direction. The present inventors have found that the above problem can be solved by a specific antireflection film, and have completed the present invention.

That is, the present invention is an antireflection film having at least four layers of a microstructure layer, an intermediate layer using a crosslinked resin, a hard coat layer, and a substrate in order from a position far from the substrate in the film thickness direction, The microstructure layer has a thickness of 50 to 200 nm, the intermediate layer has a thickness of 50 to 150 nm, the microstructure layer has a refractive index of 1 to 1.35, the hard coat layer and the base The absolute value of the difference in refractive index with the material is 0.3 or less, the refractive index of the microstructure layer is n _top , the refractive index of the intermediate layer is n _mid , and the refractive index of the hard coat layer is n _hc Then, the numerical value given by the following formula (1) is 0.92 to 1.07.

以下、本発明について詳細に説明する。

Hereinafter, the present invention will be described in detail.

  The antireflection film of the present invention has at least four layers of a fine structure layer, an intermediate layer using a cross-linked resin, a hard coat layer, and a substrate in order from a position far from the substrate in the film thickness direction. In the present invention, “microstructure” refers to a concavo-convex structure having a concavo-convex width smaller than the wavelength of light to be antireflected, and “microstructure layer” refers to a microstructural structure existing on the surface of the antireflection film. A layer from a convex part to a concave part is shown, for example, a layer indicated by reference numeral 10 in FIG. In the present invention, the “intermediate layer” refers to a layer adjacent to the microstructure layer, for example, a layer indicated by reference numeral 20 in FIG. In the present invention, the “hard coat layer” refers to a layer formed between the base material and the intermediate layer, for example, a layer indicated by reference numeral 30 in FIG. In the present invention, the “crosslinked resin” refers to a crosslinkable organic compound (hereinafter referred to as “crosslinkable resin”) caused by an external stimulus such as heat, light, active energy rays, or the progress of reaction over time. Represents a resin obtained by crosslinking.

  When the antireflection film of the present invention has a microstructure layer and an intermediate layer, the antireflection film has excellent antireflection properties. When the fine structure layer and the intermediate layer are not provided, the antireflection property is poor. In addition, the antireflection film of the present invention has a hard coat layer, so that the antireflection film has excellent scratch resistance. When the hard coat layer is not provided, the scratch resistance is poor. Furthermore, the antireflection film of the present invention has a base material, and the antireflection film has excellent scratch resistance by forming a microstructure layer, an intermediate layer and a hard coat layer on the base material. When the antireflection film is not formed on the substrate, the scratch resistance is poor.

  The antireflection film of the present invention is characterized in that the intermediate layer is made of a crosslinked resin. In the present invention, since the intermediate layer is made of a crosslinked resin, the antireflection film of the present invention is excellent in flexibility, alkali resistance, and scratch resistance. The antireflection film of the present invention is inferior in flexibility, alkali resistance, and scratch resistance when the intermediate layer is not made of a crosslinked resin.

  In the present invention, in the fine structure layer, the convex portion in the fine structure may be formed by a stamper or may be formed by particles (hereinafter, the particles forming the convex portions are referred to as “convex portion forming particles”. In addition, when the fine structure is formed by the convex portion forming particles, a region where the convex portion forming particles are buried in the intermediate layer (for example, a region indicated by reference numeral 21 in FIG. 1) is referred to as “convex portion forming particles. This is called the buried layer.) The material constituting the fine structure layer may contain a crosslinked resin.

  The present invention is characterized in that the intermediate layer and the hard coat layer have different refractive indexes. And since the interface from which a refractive index differs between the intermediate | middle layer and a hard-coat layer is formed, the obtained anti-reflective film has the outstanding anti-reflective property, It is characterized by the above-mentioned. About the material which comprises the said hard-coat layer, a crosslinked resin may be included. Here, when the hard coat layer contains a cross-linked resin, both the intermediate layer and the hard cord layer contain a cross-linked resin, but in the present invention, the cross-linked resins contained therein are different from each other, or When the cross-linked resin included in the intermediate layer and the hard coat layer is the same, the average value of the refractive index varies depending on the components other than the cross-linked resin.

  In the present invention, since it is more preferable to increase flexibility and alkali resistance, the microstructure of the microstructure layer is only a cross-linked resin (in the case where convex-formed particles are included, the portion other than the convex-formed particles is a cross-linked resin. It is preferable that fillers such as particles are dispersed in the crosslinked resin, and the crosslinked resin functions as a binder for connecting the fillers. Further, since it is more preferable to increase alkali resistance, when the filler such as the particles is dispersed in the crosslinked resin and the crosslinked resin functions as a binder, the particles are resin particles, or The particles are preferably inorganic particles, and the surface of the particles is preferably covered with a resin. Examples of the case where the particle is an inorganic particle and the surface of the particle is covered with a resin include, for example, a case where a core-shell type particle having a particle as a core and a resin as a shell is used, and the particle surface is crosslinked. For example, the surface of the particle is covered with the cross-linked resin by the reaction between the particle surface and the cross-linkable resin. Although there is no restriction | limiting in particular as a case where the said particle | grain surface can react with crosslinkable resin, For example, the case where the particle | grains are processed with the silane coupling agent is mentioned.

  In the present invention, since it is more preferable to increase the flexibility of the antireflection film, the intermediate layer is formed only of the crosslinked resin, or fillers such as particles are dispersed in the crosslinked resin, The crosslinked resin is preferably a binder that connects the fillers.

  In the present invention, since it is more preferable to increase the flexibility of the antireflection film, the hard coat layer is formed only of the crosslinked resin, or fillers such as particles are dispersed in the crosslinked resin. The crosslinked resin is preferably a binder that connects the fillers. In addition, since it is more suitable for enhancing the scratch resistance of the antireflection film, the cross-linked resin forming the hard coat layer is a cross-linked resin obtained by cross-linking a cross-linkable resin having a plurality of cross-linkable functional groups in the molecule. Is preferred.

  The film thickness of the fine structure layer is 50 to 200 nm. When the film thickness of the fine structure layer is in the above range, the antireflection film has excellent antireflection properties and scratch resistance. When the film thickness of the microstructure layer is less than 50 nm, the antireflection property is inferior, the wavelength dependency of the antireflection property is particularly large, and the change in the antireflection property due to the change in the incident angle of light becomes large. When the thickness of the fine structure layer exceeds 200 nm, the scratch resistance is poor. The film thickness of the fine structure layer is preferably 60 to 150 nm, more preferably 80 to 140 nm, and particularly preferably 90 to 130 nm because it is more suitable for enhancing the antireflection property. Most preferably, it is ˜120 nm. Further, since it is more suitable for enhancing the scratch resistance, the thickness of the fine structure layer is preferably 180 nm or less, more preferably 160 nm or less, particularly preferably 140 nm or less, and 120 nm or less. Most preferably. In the present invention, the film thickness of the fine structure layer indicates the distance in the film thickness direction from the top of the convex portion of the concavo-convex structure existing on the surface of the antireflection film to the bottom of the concave portion (for example, in FIGS. 1 and 2). In the scanning electron microscopic image of the cross section of the film H), the distance of 50 points or more can be measured and averaged.

  The intermediate layer has a thickness of 50 to 150 nm. When the thickness of the intermediate layer is in the above range, the antireflection film has excellent antireflection properties. When the thickness of the intermediate layer is less than 50 nm or exceeds 150 nm, the antireflection property is inferior. The thickness of the intermediate layer is preferably 60 to 130 nm, more preferably 60 to 120 nm, particularly preferably 70 to 110 nm, since it is more suitable for improving the antireflection property. Most preferably, it is 100 nm. The film thickness of the intermediate layer indicates the distance in the film thickness direction from the concave portion or flat portion adjacent to the convex portion to the hard coat layer in the scanning electron microscope image of the cross section of the antireflection film (for example, FIG. 1 and FIG. 2). The symbol T) can be obtained by measuring and averaging the distances of 50 points or more. When the intermediate layer has a convex-formed particle buried layer to be described later, the distance in the film thickness direction from the most microstructure layer side interface of the convex-formed particle buried layer to the interface with the hard coat layer is the film of the intermediate layer It is thick.

  Although there is no restriction | limiting in particular as the film thickness of the said hard-coat layer, Since it is more suitable for improving the abrasion resistance of an antireflection film, it is preferable that the film thickness of a hard-coat layer is 200 nm or more, and is 500 nm or more. More preferably, it is more preferably 1000 nm or more.

  The fine structure layer has a refractive index of 1-1.35. When the refractive index of the fine structure layer is within the above range, the antireflection film has excellent antireflection properties. When the refractive index of the microstructure layer exceeds 1.35, the antireflection property is inferior. The refractive index of the fine structure layer is preferably 1.05 to 1.3, more preferably 1.1 to 1.25, and more preferably 1.15 because it is more suitable for enhancing the antireflection property. Is particularly preferably ˜1.25, most preferably 1.18˜1.22. In the present invention, unless otherwise specified, “refractive index” indicates a value for sodium D line (wavelength 589 nm), and can be measured by an Abbe refractometer. In addition, when a plurality of components are included in each layer, the average value of the refractive index calculated from the Lorentz-Lorenz equation according to the volume fraction of each component is shown. In the present invention, the “refractive index of the fine structure layer” is an approximation (effective) that assumes that a space where no fine structure exists is filled with a substance having a refractive index of 1, and that it is a substantially uniform film. This indicates the refractive index obtained by medium approximation.

  Moreover, since it is more suitable for improving the antireflection property of the antireflection film, the refractive index of the intermediate layer is preferably in the range of 1.35 to 1.65, and is 1.35 to 1.6. Is more preferably 1.45 to 1.6, and most preferably 1.45 to 1.55.

  Furthermore, since it is more suitable for enhancing the scratch resistance of the antireflection film, the refractive index of the intermediate layer is preferably 1.4 or more, more preferably 1.45 or more, and 1.48 or more. Is particularly preferred, and most preferred is 1.5 or more. Here, examples of cases where the refractive index of the intermediate layer is less than 1.5, particularly less than 1.4, include a method of providing pores inside the intermediate layer and a method using a fluorine-based material having a low cohesive energy for the intermediate layer. It is done. In the present invention, the higher the refractive index of the intermediate layer, the lower the content of internal vacancies and fluorine material present in the intermediate layer. Therefore, the antireflection film is excellent in scratch resistance, and the solvent penetrates. Since it becomes difficult, it is excellent in alkali resistance. The content of the internal vacancies is preferably 50% or less in volume fraction, more preferably 30% or less, particularly preferably 10% or less, and no internal vacancies. Most preferred. The content of the fluorine material is preferably 80% or less, more preferably 50% or less, particularly preferably 30% or less in terms of volume fraction, and particularly preferably 30% or less. Most preferably it does not contain.

  In the present invention, the refractive index of the hard coat layer is preferably 1.4 to 2.0, since it is more suitable for enhancing the scratch resistance and antireflection properties of the antireflection film. It is further preferably 1.8, particularly preferably 1.5 to 1.75, and most preferably 1.55 to 1.7.

  In this invention, since it is more suitable to improve the antireflection property of an antireflection film, it is preferable that the refractive index of a base material is 1.45-1.9, and it is 1.45-1.8. Is more preferable, and it is especially preferable that it is 1.45-1.7.

  In the present invention, the absolute value of the difference in refractive index between the hard coat layer and the substrate is 0.3 or less. When the absolute value of the difference in refractive index between the hard coat layer and the substrate is in the above range, the antireflection film has excellent antireflection properties. At this time, the occurrence of interference fringes due to light interference can also be suppressed, so that the appearance of the antireflection film is excellent. When the absolute value of the difference in refractive index between the hard coat layer and the substrate exceeds 0.3, the antireflection film is inferior in antireflection properties. The absolute value of the difference in refractive index between the hard coat layer and the base material is preferably 0.2 or less, and more preferably 0.1 or less because it is more suitable for enhancing the antireflection property. Preferably, it is 0.05 or less, and most preferably 0.03 or less.

In the present invention, when the refractive index of the microstructure layer is n _top , the refractive index of the intermediate layer is n _mid , and the refractive index of the hard coat layer is n _hc , the numerical value given by the following formula (1) is 0 .92 to 1.07.

（１）式で与えられる数値が前記範囲にあることにより、本発明の反射防止膜は反射防止性に優れるものとなる。（１）式で与えられる数値が０．９２未満、又は、１．０７を超える場合、反射防止性に劣るものとなる。反射防止性を高めるのにより好適であることから、（１）式で与えられる数値が０．９４〜１．０５であることが好ましく、０．９６〜１．０３であることがさらに好ましく、０．９８〜１．０１であることが特に好ましい。

When the numerical value given by the formula (1) is in the above range, the antireflection film of the present invention has excellent antireflection properties. When the numerical value given by the formula (1) is less than 0.92 or exceeds 1.07, the antireflection property is inferior. Since it is more suitable for improving the antireflection property, the numerical value given by the formula (1) is preferably 0.94 to 1.05, more preferably 0.96 to 1.03, and 0 Particularly preferred is .98 to 1.01.

  In the present invention, since the transparency and antireflection properties of the antireflection film and the scratch resistance can be easily improved, the ratio of the height / particle diameter of the convex portion is 0.1 to 1.0, and the convex portion It is preferable that the ratio between the vertex distance / particle diameter is 1.05 to 5.0, the ratio of the height / particle diameter of the convex part is 0.5 to 0.95, and the distance between the vertexes of the convex part. It is more preferable that the ratio of particle diameter / particle diameter is 1.05 to 3.0, the ratio of height of protrusion / particle diameter is 0.6 to 0.9, and the distance between apexes of protrusion / grain The ratio of the diameters is particularly preferably 1.05 to 2.5, the ratio of the height / particle diameter of the protrusion is 0.7 to 0.85, and the distance between the vertices of the protrusion / the particle diameter Most preferably, the ratio is from 1.05 to 2.2. Here, in the present invention, the height of the convex portion refers to the average of the distances in the film thickness direction from the apex of the convex portion existing on the surface of the antireflection film to the bottom of the adjacent concave portion (for example, the symbol H in FIG. 1). ) In a scanning electron microscope image of the film cross section, the distance can be measured and averaged for 50 or more convex portions. In the present invention, when convexity-forming particles are used and each convexity is formed by a single particle, the height of the convexity matches the film thickness of the microstructure layer. Further, the distance between the vertices of the convex portions is the average of the distances in the in-plane direction (for example, symbol L in FIG. 1) from the vertex of the convex portion existing on the surface of the antireflection film to the vertex of the adjacent convex portion. The distance L for the convex portion is a value obtained by selecting four convex portions in order from the smallest distance L with respect to the convex portion, and averaging the distances L for the selected four convex portions. Show. The distance between the vertices of the convex portions can be calculated by measuring and averaging the distance L for 50 or more convex portions in the scanning electron microscope image of the film surface or cross section.

  In the present invention, since an antireflection film having more excellent antireflection properties can be obtained, it is preferable that the microstructure layer contains convexity-forming particles, and the particles are unevenly distributed on the surface of the antireflection film. Here, in the present invention, “is unevenly distributed” means that it is present more in a certain region than other regions, and “particles are unevenly distributed on the surface of the antireflection film”. This means that more particles are present on the surface of the antireflection film than inside the antireflection film. In addition, when the fine structure of the fine structure layer is formed by the protrusion-forming particles, the antireflection film is more excellent in mass productivity and scratch resistance, which is also preferable in this respect.

  In the present invention, it is more preferable that the microstructure layer contains convexity-forming particles having a particle size of 250 nm or less excluding hollow particles. When the particle diameter of the convex portion-forming particles is 250 nm or less, the antireflection film is excellent in transparency. Moreover, when the convex portion forming particles are particles other than the hollow particles, the deformation of the particles can be suppressed, and the scratch resistance of the antireflection film can be enhanced. Moreover, when the convex portion-forming particles are particles other than the hollow particles, the organic solvent resistance can be improved. Here, in the present invention, “hollow particles” refers to particles having pores therein. Since it is more suitable for enhancing the transparency of the antireflection film, the particle diameter of the convex-forming particles is more preferably 200 nm or less, particularly preferably 150 nm or less, and most preferably 130 nm or less. . In the present invention, the particle diameter of the particle is an average value of the above values measured for 50 or more particles by measuring the maximum diameter of each particle in a transmission electron microscope image.

  In the present invention, when the fine structure layer contains convex portion-forming particles, the convex portion-forming particles are fixed by the surface of the antireflection film, and the particles can be prevented from falling off, thereby obtaining an antireflection film having more excellent scratch resistance. Therefore, it is preferable that the convexity-forming particles are mainly arranged in a single layer. At this time, when the antireflection film is bent, the arrangement of the particles is not easily disturbed, and the flexibility of the antireflection film is further improved. Furthermore, since the convexity-forming particles are mainly arranged in a single layer, it is easy to remove dirt such as sebum adhering between the irregularities, and the antireflection film has excellent antifouling properties. . Here, in the present invention, “dropping of particles” means that particles present on the surface of the antireflection film are peeled off due to impact or scratches. In the present invention, the region where the particles have dropped is referred to as “defect”. In the present invention, when the size of the defect is visually recognizable (a region of about 1 μm or more), it is perceived as a flaw and causes a deterioration in the visual uniformity of the film. Moreover, even when the area where the particles have fallen is not larger than the visible size, the dropout of the particles causes a decrease in the transparency and antireflection property of the film. Further, in the present invention, “particles are mainly arranged in a single layer” means that the number of particles arranged in a single particle layer in the film thickness direction is the number of particles arranged in a microstructure layer. The ratio of the number of particles existing in the outermost layer occupies 50% or more. Further, since it is more preferable to suppress the drop-off of particles and to improve the scratch resistance of the antireflection film, the ratio of particles arranged in a single layer is more preferably 60% or more, and 75% or more. It is particularly preferable that it is 90% or more.

  In the present invention, it is preferable that the microstructure layer contains convex portion-forming particles and a binder, and the convex portion-forming particles form a chemical bond with the binder. Since the convexity-forming particles form a chemical bond with the binder, it is easy to suppress the dropout of the particles, and it is easy to improve the scratch resistance, which is preferable. Further, since the binder is a cross-linked resin and the convexity-forming particles form a chemical bond with the binder, the alkali resistance is easily improved even when the convexity-forming particles are inorganic particles, which is preferable. Here, in the present invention, the “binder” refers to a component excluding the filler in the case where fillers such as particles are present. For example, a fine structure layer is formed of convex-forming particles and a crosslinked resin. When the binder is present, the binder indicates a crosslinked resin. Moreover, it is not limited to this case, For example, when components other than a filler consist of mixtures, such as a crosslinkable resin and an additive, a binder shows these mixtures. Further, in the case where there is no filler such as particles, the binder simply indicates a component that forms a fine structure layer. Furthermore, also about an intermediate | middle layer and a hard-coat layer, a binder shows the same component as the above-mentioned.

  In the present invention, the microstructure layer contains convex part-forming particles and a binder, a part of the convex part-forming particles are embedded in the convex part-forming particle-embedded layer, and the refractive index of the convex part-forming particle-embedded layer and The absolute value of the difference in refractive index with a layer other than the convex-formed particle buried layer of the intermediate layer (for example, the layer indicated by reference numeral 22 in FIG. 1) is preferably 0.3 or less. The absolute value of the difference between the refractive index of the convex-formed particle-embedded layer and the refractive index of the intermediate layer other than the convex-formed particle-embedded layer is 0.3 or less. It is easy to increase and is preferable. In addition, since it is more suitable to enhance the antireflection property of the antireflection film, the absolute difference between the refractive index of the convex-formed particle buried layer and the refractive index of the intermediate layer other than the convex-formed particle buried layer The value is further preferably 0.2 or less, particularly preferably 0.1 or less, and most preferably 0.05 or less.

  In the present invention, when the fine structure layer contains convex part-forming particles and a binder, an antireflection film having more excellent scratch resistance can be obtained. Therefore, the particles and the binder have a liquid crosslinking structure derived from a meniscus shape. It is preferably formed between the particles or between the particles and an intermediate layer. Here, the “liquid cross-linking structure derived from the meniscus shape” refers to a liquid surface shape (for example, a shape indicated by reference numeral 3 in FIG. 3) formed on the solid surface by a capillary force (meniscus force). Show. This is formed by, for example, applying a liquid crosslinkable resin together with particles and then crosslinking the crosslinkable resin. In addition, when the liquid crosslinking structure derived from the meniscus shape is formed between the particles or between the particles and the intermediate layer, the contact area between the particles and the binder increases, and the particles are easily fixed firmly by the binder. An antireflection film having better scratch resistance can be obtained.

  In the present invention, since an antireflection film having more excellent scratch resistance is obtained, the intermediate layer contains internal particles and a binder, and has a non-smooth interface in the antireflection film due to the uneven shape derived from the internal particles. Is preferably formed. Here, in the present invention, “internal particles” means particles other than the convex portion forming particles among the particles contained in the antireflection film. Further, in the present invention, “a non-smooth interface is formed in the antireflection film” due to the uneven shape derived from the internal particles contained in the intermediate layer means that, for example, the antireflection film shown in FIG. In this case, when the layer indicated by reference numeral 22 is formed, the surface of the 22 layers is a non-smooth surface having irregularities due to internal particles, and by forming 21 layers thereon, the interface between the 21 layers and the 22 layers becomes A case where the surface is non-smooth. Since the interface between the 21 layer and the 22 layer is a non-smooth surface, the contact area between the 21 layer and the 22 layer is increased, and the layers are easily adhered to each other, and peeling between layers due to scratches and the like is easily suppressed. As a result, an antireflection film having better scratch resistance can be obtained. Moreover, it is not limited to such a case, When forming an antireflection film by multiple times of application | coating, it is preferable that the interface of each layer is a non-smooth surface. In the present invention, the “non-smooth surface” refers to a surface having an “average height Rc” defined by the surface roughness parameter of JIS B 0601 of 5 nm or more. Since it is suitable for enhancing the scratch resistance of the antireflection film, the average height Rc is more preferably 10 to 80 nm, the average height Rc is particularly preferably 15 to 50 nm, and the average height. Most preferably, Rc is 20-30 nm.

  The internal particles are preferably particles having a particle diameter smaller than that of the convexity-forming particles because they are suitable for enhancing the transparency of the antireflection film.

  The internal particles are preferably particles other than hollow particles because an antireflection film with more excellent alkali resistance can be obtained. In addition, when the internal particles are particles other than hollow particles, it is preferable in that the antireflection film can be improved in strength and elastic modulus, and an antireflection film having more excellent scratch resistance can be obtained. Furthermore, organic solvent resistance can be improved because the inner particles are particles other than hollow particles.

  In this invention, when an intermediate | middle layer contains an internal particle and a binder, it is preferable that the elasticity modulus of the said particle | grain is larger than the elasticity modulus of the said binder. When the intermediate layer contains internal particles and the elastic modulus of the internal particles is larger than the elastic modulus of the binder, the elastic modulus of the antireflection film is improved and a load is applied to the antireflection film. However, it is possible to easily suppress deformation of the antireflection film and to suppress peeling between the fine structure layer and the intermediate layer, thereby obtaining an antireflection film having better scratch resistance. In addition, when particles having an elastic modulus larger than the elastic modulus of the binder are contained, it is preferable in that the elastic modulus of the antireflection film is increased and the flexibility of the antireflection film is not impaired.

  Since the antireflection film of the present invention is suitable for enhancing the mass productivity of the antireflection film, a base material on which a hard coat layer is formed is used, and internal particles having a particle size of 5 to 100 nm are formed on the hard coat layer. A step of forming an intermediate layer by applying a coating liquid containing 01 to 65% by weight and a crosslinkable resin of 0.015 to 95% by weight, and a convex part having a particle size of 50 to 200 nm on the formed intermediate layer It is preferably manufactured by a manufacturing method including a step of forming a fine structure layer by applying a coating liquid containing 0.01 to 65% by weight of formed particles and 0.015 to 95% by weight of a crosslinkable resin.

  The base material used in the present invention is not particularly limited, and examples thereof include a resin base material, glass, ceramics, and the like, and in terms of shape, any shape such as a structure having a curved surface in addition to a film, a sheet, a plate, etc. Even a substrate can be used. Since it is suitable for enhancing the flexibility of the antireflection film, it is preferably a resin substrate or flexible glass, and since it is suitable for enhancing the alkali resistance of the antireflection film, the resin A substrate is preferred.

  Examples of resin base materials include cellulose resins such as triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose; polyester resins such as polyethylene terephthalate; polycarbonate resins; acrylic resins such as polymethyl methacrylate; polyurethane resins; Polysulfone resin; polyether sulfone; polyether ketone and the like.

  In order to improve the scratch resistance, adhesion, etc. on the surface of the base material, a coat layer such as an anchor coat layer, a polymer electrolyte layer, an antistatic layer, etc. may be formed. In order to improve the above, surface treatment such as UV ozone cleaning, plasma treatment, and corona treatment may be performed. Moreover, since it is suitable for suppressing light reflection, the difference in average refractive index between the coating layer such as the anchor coating layer and the polymer electrolyte layer formed on the substrate and the substrate is 0.10 or less. It is preferable that it is 0.05 or less.

  The crosslinkable resin used in the present invention (crosslinkable resin used in the microstructure layer, intermediate layer or hard coat layer) is not particularly limited as long as it is a crosslinkable resin, and examples thereof include an active energy ray crosslinkable resin and a heat crosslinkable resin. Is mentioned. Among these, an active energy ray crosslinkable resin is preferable because the obtained antireflection film has excellent scratch resistance. Here, in the present invention, “active energy rays” refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of the active energy ray crosslinkable resin include a crosslinkable group such as an acryl group, a methacryl group, an oxetane group, an alicyclic epoxy group, a glycidyl group, a vinyl ether group, a maleimide group, and an acrylamide group in the molecule. Compounds. Among them, a crosslinkable resin having an acrylic group or a methacrylic group is preferable because the obtained antireflection film is further excellent in scratch resistance.

  Examples of the crosslinkable resin having an acrylic group or a methacryl group include (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-hexyl (meth) acrylate, Monofunctional acrylates such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, p-methoxycyclohexyl (meth) acrylate; trimethylolpropane ethoxytriacrylate, trimethylolpropane propoxytriacrylate , Pentaerythritol ethoxytetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, poly Polyfunctional (meth) acrylates such as ethylene glycol diacrylate, polypropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated phenyl acrylate; U-4HA, U-6HA, U-6LPA, UA-5300H, UA-122P Urethane (meth) acrylate such as U-200PA, UA-7100 (2-15 functional urethane acrylate manufactured by Shin-Nakamura Chemical Co.); Epoxy (meth) acrylate such as EBECRYL600, EBECRYL860, EBECRYL373 (manufactured by Daicel Ornex); Polyester (meth) acrylates such as EBECRYL853 and EBECRYL1830 (manufactured by Daicel Ornex); polymers having an acryl group or a methacryl group in the side chain (for example, Shin-Nakamura Chemical Industry Co., Ltd. GH-1203 etc.); LINC-3A, LINC-182A (Kyoeisha Chemical Co., Ltd. 2-3 functional fluorine group-containing acrylate), 1,6-bis (acryloyloxy) hexane-containing fluorine Functional or polyfunctional (meth) acrylate; fluorinated polymer having acryl group or methacryl group in the side chain; polysilsesquioxane having (meth) acrylate group (for example, SQ series manufactured by Toagosei Co., Ltd.), (meth) Examples include (meth) acrylate group silicon compounds such as silane coupling agents having an acrylate group (for example, KBM, KBE series manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or as a mixture of a plurality of types of resins. Among them, since the obtained antireflection film becomes more excellent in scratch resistance, a crosslinkable resin having a plurality of (meth) acrylate groups in the molecule is preferable, and a tetrafunctional or higher functional (meth) acrylate is more preferable. Hexafunctional or higher functional (meth) acrylates are particularly preferred.

  There is no restriction | limiting in particular as a kind of convex part formation particle | grains and internal particle | grains used for this invention, For example, a silica particle, a polymethyl (meth) acrylate particle, a polystyrene particle etc. are mentioned. Particles other than hollow particles are preferred because they are suitable for suppressing deformation of the particles and improving scratch resistance. The silica particles are preferably surface-treated with a silane coupling agent because they are suitable for enhancing alkali resistance and scratch resistance, and surface treatment with a silane coupling agent having a reactive double bond. Are more preferable, and those that are surface-treated with a silane coupling agent having a vinyl group or a (meth) acryl group are particularly preferable, and are surface-treated with a silane coupling agent having a (meth) acryl group. Is most preferred. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and p-styryltrimethoxy. Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate , 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like.

  In the present invention, the binder may contain a silane coupling agent, a polymerization initiator, various additives, and the like as necessary in addition to the crosslinkable resin.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and p-styryltrimethoxy. Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate , 3-ureidopropyl trialkoxysilane, 3-mercaptopropyl methyl dimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate propyl triethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, and the like.

  Examples of the polymerization initiator include compounds that generate radicals by hydrogen abstraction such as benzophenone, benzyl, Michler ketone, thioxanthone, and anthraquinone; benzoin, dialkoxyacetophenone, acyloxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone And the like are compounds of the type that generate radicals by intramolecular splitting. Moreover, as a commercial item, IRUGACURE184, IRUGACURE651, IRUGACURE500, IRUGACURE907, DAROCUR1116, DAROCUR1173 (made by BASF), KY1203 (made by Shin-Etsu Chemical Co., Ltd.) etc. can be mentioned, for example. Further, tertiary amines such as methylamine, diethanolamine, N-methyldiethanolamine, and tributylamine may be used in combination in order to accelerate curing (crosslinking).

  Examples of the additive include a component for imparting slipperiness, imparting antifouling property, or increasing the elastic modulus. For example, BYK-UV3505, BYK-UV3500, BYK-UV3575, BYK-UV3570, BYK- UV3576, BYK-UV3535, BYK-UV3510, BYK-378, BYK-370, BYK-377, BYK-399, BYK-3550, BYK-3560, NANOBYK-3605, NANOBYK-3601, NANOBYK-3602, NANOBYK-3610, NANOBYK-3630, NANOBYK-3652, NANOBYK-3650, NANOBYK-3651, CERAFLOUR925, CERAFLOUR929, BYK-LP X 22699 (Bicchemy Japan) And adamantane derivatives (for example, Dia Purest series manufactured by Mitsubishi Gas Chemical Co., Inc.).

The antireflection film of the present invention is preferably formed by coating because it is suitable for increasing mass productivity and forming a liquid cross-linked structure derived from a meniscus shape. The coating liquid for the coating is not particularly limited. For example, a coating liquid obtained by diluting a composition containing the above-described components such as particles and a binder with a solvent is preferable. The solvent is not particularly limited, general formula ^{_{R 1 O- (C 2 H 4}} O) n -R 2 ( formula ^{(A)) (R 1,} R 2: H or C 1 -C 20 atoms It is preferable to contain a solvent represented by an alkyl group, acetyl group, vinyl group, acrylic group, methacryl group, n = 1 to 4), and R ¹ and R ² in the general formula (A) are alkyl groups. Is more preferable. Specifically, for example, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol diester Butyl ether, ethylene glycol diacetate, ethylene glycol vinyl ether, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether Diethylene glycol monohexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol monophenyl ether, diethylene glycol dibenzoate, diethylene glycol diacetate, diethylene glycol divinyl ether, Diethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol methyl ether methacrylate, triethylene glycol, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, Ethylene glycol monomethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol monopropyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monophenyl ether, triethylene glycol dibutyl ether, triethylene glycol diacetate, triethylene glycol vinyl ether, Triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol ethyl methyl ether, tetraethylene glycol monopropyl ether, tetra Examples include ethylene glycol monomethyl ether acetate, tetraethylene glycol monophenyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol diacetate, tetraethylene glycol vinyl ether, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate. When silica particles are used as the particles, a solvent having a diethylene glycol moiety is preferable in view of affinity with the silica particles, and diethylene glycol butyl methyl ether and diethylene glycol monohexyl ether are more preferable. The coating liquid used for this invention may also contain the diluent for the objectives, such as adjustment of a film thickness, as needed. As the diluent, an organic solvent in which particles can be dispersed and in which a binder is compatible can be used. Examples thereof include methanol, ethanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, and toluene.

  Since the antireflection film of the present invention is suitable for obtaining practically sufficient antireflection properties, the reflectance of light in the visible light region (380 to 780 nm) is preferably 1% or less, 0.6% More preferably, it is more preferably 0.4% or less.

  In the antireflection film of the present invention, the reflectance of light at a wavelength of 580 nm with high visibility is preferably 0.8% or less, more preferably 0.5% or less, and 0.4% or less. It is particularly preferable that it is 0.3% or less.

  Since the antireflection film of the present invention is suitable for obtaining an antireflection film having a small wavelength dependency of the antireflection property, it is suitable for incident light with an incident angle of 5 ° of the CIE standard light source D65 defined in JIS Z 8781-4. The absolute value of the a * value and the b * value is 4.0 or less when the color of the specularly reflected light is obtained from the L * value, a * value, and b * value of the CIE 1976 L * a * b * color space. Is more preferably 3.0 or less, particularly preferably 2.0 or less, and most preferably 1.0 or less.

  Since the antireflection film of the present invention is suitable for obtaining an antireflection film having a small change in antireflection property due to a change in the incident angle of light, the incident angle of light is 10 in the reflectance of light at a wavelength of 580 nm. The absolute value of the difference in reflectance between ° and 40 ° is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.

  Since the antireflection film of the present invention is suitable for enhancing transparency, the difference between the haze value defined in JIS K 7136 and the haze value of the base material alone is 1.0% or less. Preferably, it is 0.5% or less, more preferably 0.3% or less, and most preferably 0.1% or less.

  Since the antireflective film of the present invention is suitable for enhancing the translucency, when the antireflective film is formed on one surface of the substrate, the total light transmittance defined by JIS K 7361 is 90. % Or more, more preferably 92% or more, and particularly preferably 94% or more.

  Since the antireflection film of the present invention does not increase the scattering of light in the visible light region as compared with the case without the antireflection film, it prevents the reflection of external light without impairing the visibility of the display. Can do. Further, since the amount of transmitted light can be improved by the amount of preventing reflection, it can be used for improving the light capturing efficiency of the solar cell and the light extracting efficiency of the organic EL.

  According to the present invention, it has excellent flexibility, high alkali resistance, excellent scratch resistance and high transparency, excellent antireflection properties for light in the visible light region, and the wavelength dependency of antireflection properties is small. It is possible to provide an antireflection film in which the change in antireflection property due to the change in the incident angle of light is small.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to these. In the examples and comparative examples, commercially available samples were used for samples and the like not specifically described.
[Measurement of film thickness of microstructure layer]
The film thickness of the fine structure layer is adjacent to the top of the convex portion of the fine structure existing on the antireflection film surface in the antireflection film cross-sectional image measured using a scanning electron microscope (VE-9800 manufactured by Keyence Corporation). The distance in the film thickness direction to the bottom of the concave portion was calculated by measuring and averaging 50 or more convex portions.
[Measurement of refractive index of microstructure layer]
The refractive index of the fine structure layer is determined by observing the shape of the fine structure in the antireflection film surface and cross-sectional image measured using a scanning electron microscope (VE-9800 manufactured by Keyence Corporation), and refracting a region where no structure exists. The Lorentz-Lorenz equation (2) was calculated by an effective medium approximation that is regarded as a medium of rate 1.

（式中、ｎ_ｔｏｐは微細構造層の屈折率、ｎ_ｉは各成分の屈折率、ｆ_ｉは各成分の体積占有率をそれぞれ示す。）
［中間層の膜厚の測定］
中間層の膜厚は、走査型電子顕微鏡（キーエンス社製ＶＥ−９８００）を用いて測定した反射防止膜断面像において、反射防止膜表面に存在する微細構造の凹部の最底部から、ハードコート層までの膜厚方向の距離を、５０点以上の凹部について測定し、平均することで算出した。
［中間層の屈折率の測定］
微細構造層の屈折率は、屈折率が既知の基材上に中間層のみを形成した試料を作製し、裏面を黒マジックで塗り潰すことにより裏面反射を取り除いた後、中間層を形成した側の面のみの反射率を測定し、以下の（３）式を用いて算出した。

(In the formula, n _top is the refractive index of the fine structure layer, n _i is the refractive index of the components, f _i is the volume fraction of each component, respectively.)
[Measurement of intermediate layer thickness]
The film thickness of the intermediate layer is the hard coat layer from the bottom of the concave portion of the fine structure present on the surface of the antireflection film in the antireflection film cross-sectional image measured using a scanning electron microscope (VE-9800 manufactured by Keyence Corporation). The distance in the film thickness direction was measured for 50 or more recesses and averaged.
[Measurement of refractive index of intermediate layer]
The refractive index of the microstructure layer is the side on which the intermediate layer is formed after removing the back reflection by preparing a sample in which only the intermediate layer is formed on a substrate having a known refractive index, and painting the back surface with black magic. The reflectance of only the surface was measured and calculated using the following equation (3).

（式中、Ｒ_ｍｉｎは試料の極小反射率、ｎ_ｍｉｄは中間層の屈折率、ｎ_０は空気の屈折率、ｎ_ｓｕｂは基材の屈折率をそれぞれ示す。）
［ハードコート層の膜厚の測定］
ハードコート層の膜厚は、リニアゲージセンサー（小野測器製ＨＳ−３４１２）により試料の膜厚を測定し、基材にハードコート層を形成した試料の膜厚から、基材のみの膜厚を差し引くことにより算出した。
［ハードコート層の屈折率の測定］
ハードコート層の屈折率は、屈折率が既知の基材上にハードコート層を形成した試料を作製し、裏面を黒マジックで塗り潰すことにより裏面反射を取り除いた後、ハードコート層を形成した側の面のみの反射率を測定し、以下の（４）式を用いて算出した。

(In the formula, R _min represents the minimum reflectance of the sample, n _mid represents the refractive index of the intermediate layer, n ₀ represents the refractive index of air, and n _sub represents the refractive index of the substrate.)
[Measurement of film thickness of hard coat layer]
The film thickness of the hard coat layer was measured only with a linear gauge sensor (HS-3412 manufactured by Ono Sokki Co., Ltd.). Was calculated by subtracting.
[Measurement of refractive index of hard coat layer]
For the refractive index of the hard coat layer, a sample in which the hard coat layer was formed on a substrate having a known refractive index was prepared, and after the back surface reflection was removed by painting the back surface with black magic, the hard coat layer was formed. The reflectance of only the side surface was measured and calculated using the following equation (4).

（式中、Ｒ_ａｖｅは光の干渉がない場合の反射率、又は光の干渉により反射率に変動がある場合には可視光領域の反射率を平均して得られる反射率の平均値を示す。ｎ_ｈｃはハードコート層の屈折率、ｎ_０は空気の屈折率、ｎ_ｓｕｂは基材の屈折率をそれぞれ示す。）
［基材の屈折率の測定］
基材の屈折率は、裏面を黒マジックで塗り潰すことにより裏面反射を取り除いた後、基材の一方の面のみの反射率を測定し、以下の（５）式を用いて算出した。

(In the formula, R _ave represents the reflectance when there is no light interference or the average value of the reflectance obtained by averaging the reflectance in the visible light region when the reflectance varies due to light interference. N _hc is the refractive index of the hard coat layer, n ₀ is the refractive index of air, and n _sub is the refractive index of the substrate.)
[Measurement of refractive index of substrate]
The refractive index of the base material was calculated using the following equation (5) after measuring the reflectance of only one surface of the base material after removing the back surface reflection by painting the back surface with black magic.

（式中、Ｒは屈折率を求める波長における反射率で、ｎ_ｓｕｂは基材の屈折率、ｎ_０は空気の屈折率をそれぞれ示す。）
［走査型電子顕微鏡像の測定］
反射防止膜の表面及び断面の走査型電子顕微鏡像は、走査型電子顕微鏡（キーエンス社製ＶＥ−９８００）を用いて測定した。
［反射率の測定］
反射率の実測値は、角度可変絶対反射付属装置を内蔵する分光光度計（日立ハイテクサイエンス社製Ｕ−４１００）を用い、入射角１０°又は入射角４０°での反射率を測定した。反射率測定にあたっては裏面反射の影響を除くために、試料の裏面をマジックで黒く塗りつぶし、さらに裏面に黒色テープを貼り測定した。
［反射色相の算出］
反射色相は、角度可変絶対反射付属装置を内蔵する分光光度計（日立ハイテクサイエンス社製Ｕ−４１００）を用いて入射角５°の反射率を測定し、ＪＩＳ Ｚ ８７８１−４で規定されるＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間のａ＊値，ｂ＊値を算出することで求めた。
［ヘーズ値及び全光線透過率の測定］
ヘーズ値は日本電色工業製ＮＤＨ−５０００を用いて測定した。なお、用いた基材のヘーズ値はそれぞれ、ＴＡＣフィルム０．３％、ＰＥＴフィルム０．８％、ガラス基板０．２％であった。
［耐擦傷性の評価］
耐擦傷性はベンコット試験により評価した。ベンコット（旭化成社製Ｍ−３１１）の面積４ｃｍ^２の領域に荷重１００ｇをかけ、４ｃｍ／秒の速度で行い、試料上を１０往復させた。

(In the formula, R is the reflectance at the wavelength for _obtaining the refractive index, n _sub is the refractive index of the substrate, and n ₀ is the refractive index of air.)
[Measurement of scanning electron microscope images]
Scanning electron microscope images of the surface and cross section of the antireflection film were measured using a scanning electron microscope (VE-9800 manufactured by Keyence Corporation).
[Measurement of reflectance]
The reflectivity was measured at an incident angle of 10 ° or an incident angle of 40 ° using a spectrophotometer (U-4100 manufactured by Hitachi High-Tech Science Co., Ltd.) having a built-in variable angle absolute reflection accessory. In measuring the reflectance, in order to remove the influence of the back surface reflection, the back surface of the sample was painted black with a magic, and a black tape was further applied to the back surface.
[Calculation of reflection hue]
The reflection hue is determined by measuring the reflectivity at an incident angle of 5 ° using a spectrophotometer (U-4100 manufactured by Hitachi High-Tech Science Co., Ltd.) having a built-in variable angle absolute reflection accessory, and CIE1976L defined by JIS Z 8781-4. * A * b * Determined by calculating the a * value and b * value of the color space.
[Measurement of haze value and total light transmittance]
The haze value was measured using NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. In addition, the haze value of the used base material was TAC film 0.3%, PET film 0.8%, and glass substrate 0.2%, respectively.
[Evaluation of scratch resistance]
The scratch resistance was evaluated by a Bencott test. A load of 100 g was applied to an area of 4 cm ² in area of Bencot (M-311 manufactured by Asahi Kasei Co., Ltd.), and the sample was reciprocated 10 times at a speed of 4 cm / sec.

The scratch resistance was evaluated as follows.
(Double-circle): There is no flaw by a Bencott test.
○: Scratches are confirmed by the Bencott test.
X: The film was broken by the Bencott test.
[Evaluation of flexibility]
Flexibility was evaluated by winding the antireflection film together with a substrate around a roll having a diameter of 3 cm.
○: No influence on the film by wrapping around the roll is observed.
X: Cracking of the film caused by winding on a roll occurs.
[Evaluation of alkali resistance]
The alkali resistance was evaluated by immersing the antireflection film in a 0.1 mol / L sodium hydroxide aqueous solution for 1 hour.
◯: No influence on the film due to immersion in an alkaline aqueous solution is observed.
X: Destruction / peeling of the film by the alkaline aqueous solution occurs.
[Evaluation of organic solvent resistance]
The organic solvent resistance was evaluated by immersing the antireflection film in ethanol for 1 hour.
○: No influence on the film due to immersion in the solvent is observed.
[Evaluation of antifouling properties]
The antifouling property was evaluated from the adhesion and wiping property of the adhered fingerprint by attaching the fingerprint by tracing the antireflection film surface 10 times with a finger.
○: Fingerprints can be removed by washing with ethanol.
[Example 1]
(Hard coat layer formation)
100 g of a 70 wt% methyl ethyl ketone (MEK) solution of zirconia nanoparticles (Nippon Catalyst Zircostar ZP-153) and acrylate (Shin Nakamura Chemical A-TMM3LM-N, trifunctional / 4 functional = 57/43 wt% mixture, acrylate weight Of 20 wt% of the polymerization initiator IRUGACURE 184) was mixed at a weight ratio of zirconia nanoparticles / acrylate = 10/90. This mixed solution was diluted with methyl isobutyl ketone (MIBK) to prepare a coating solution having a concentration of 50 wt%. Triacetylcellulose (TAC) film (Fujifilm FUJITAC TD-80UL, film thickness 80 μm, refractive index 1.48) is bar-coated, dried with hot air at 60 ° C. for 5 minutes, and then irradiated with UV for 2 minutes (12 mW in air). / Cm2) to cure (crosslinking of the crosslinkable resin). The film thickness of the hard coat layer was 1.65 μm.
(Intermediate layer formation)
Using an aqueous dispersion of silica particles with a particle size of 65 nm (ST-YL, Nissan Chemical Co., Ltd., 40 wt%), 200 g of particles, 150 g of ethanol, 4 g of methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.), and 28 wt. 0.2 g of aqueous ammonia was added with stirring, and the mixture was reacted at 60 ° C. for 3 hours and cooled to room temperature. Thereafter, 56 g of pentaerythritol tetraacrylate (A-TMMT, tetrafunctional) manufactured by Shin-Nakamura Chemical Co., Ltd. and 150 g of methanol were added. The operation of distilling off the solvent with an evaporator, adding 500 g of methanol and distilling off the solvent again was repeated three times. After the distillation operation, a solution composition was prepared by adding 2.8 g of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR1173 manufactured by BASF) as a photoinitiator. MEK is added as a diluent to this solution composition to prepare a coating liquid composition having a composition concentration (amount of silica particles, pentaerythritol tetraacrylate, polymerization initiator, and silane coupling agent relative to the total solution amount) of 4 wt%. did. Also, instead of using pentaerythritol tetraacrylate and a polymerization initiator, a solution in which the whole amount is replaced with triacryloylheptadecafluorononenyl pentaerythritol (LINC-3A manufactured by Kyoeisha Chemical Co., Ltd.) or diethylene glycol butyl methyl ether is also prepared. Was prepared in the same manner as described above to prepare a coating solution composition having a composition concentration (silica particles, triacryloylheptadecafluorononenylpentaerythritol or diethylene glycol butylmethyl ether, and silane coupling agent) with respect to the total solution amount of 4 wt%. did.

By mixing the coating liquid composition, the weight ratio of silica particles / total acrylate / diethylene glycol butyl methyl ether = 4 / 4.5 / 1.5 and pentaerythritol tetraacrylate / trimethyl in the total acrylate A MEK solution having a composition concentration of 4 wt% was prepared with a composition of acryloylheptadecafluorononenylpentaerythritol = 2 / 2.5. This solution was spin-coated on a film on which a hard coat layer was formed at 1500 rpm for 10 seconds, dried with hot air at 110 ° C. for 5 minutes, and then cured by UV irradiation for 20 minutes in a nitrogen atmosphere (crosslinking of the crosslinkable resin).
(Fine structure layer formation)
Using an aqueous dispersion of silica particles having a particle size of 120 nm (MP-1040, 40 wt%, manufactured by Nissan Chemical Co., Ltd.), 200 g of particles, 150 g of ethanol, 4 g of methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), and 28 wt. 0.2 g of aqueous ammonia was added with stirring, and the mixture was reacted at 60 ° C. for 3 hours and cooled to room temperature. Thereafter, 56 g of dipentaerythritol hexaacrylate (A-DPH, hexafunctional) manufactured by Shin-Nakamura Chemical Co., Ltd. and 150 g of methanol were added. The operation of distilling off the solvent with an evaporator, adding 500 g of methanol and distilling off the solvent again was repeated three times. After the distillation operation, a solution composition was prepared by adding 2.8 g of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (IRUGACURE907 manufactured by BASF) as a polymerization initiator. MEK was added as a diluent to this solution composition, and a coating liquid composition having a composition concentration (amount of silica particles, dipentaerythritol hexaacrylate, a polymerization initiator, and a silane coupling agent) of 4 wt% was obtained. Prepared. Also, instead of using dipentaerythritol hexaacrylate and a polymerization initiator, a solution in which the whole amount was replaced with diethylene glycol butyl methyl ether was prepared, and the other components were prepared in the same manner as described above (composition concentration (silica particles, diethylene glycol butyl with respect to the total amount of solution)). Amount of methyl ether and silane coupling agent) A coating solution composition of 4 wt% was prepared.

  By mixing the above coating liquid composition, a MEK solution having a silica particle / acrylate / diethylene glycol butyl methyl ether = 4 / 1.5 / 6 by weight ratio and a composition concentration of 4 wt% is prepared. did. This solution was spin-coated on a film on which the intermediate layer had been formed at 3000 rpm for 10 seconds, dried with hot air at 110 ° C. for 5 minutes, and then cured by UV irradiation for 20 minutes in a nitrogen atmosphere (crosslinking of the crosslinkable resin).

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00.

  The produced antireflection film had a reflectance of 0.28% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.35 and the b * value was −0.62, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.12%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

  Table 1 shows the structure and characteristics of the produced antireflection film.

作製した反射防止膜表面の走査型電子顕微鏡像を図４に示す。凸部形成粒子が単層で配列している様子が観察された。また、作製した反射防止膜断面の走査型電子顕微鏡像を図５に示す。微細構造層、中間層、ハードコート層、基材の４層が存在している様子が観察された。
［実施例２］
基材としてポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡製コスモシャインＡ４１００、膜厚１００μｍ、屈折率１．６５）を用い、ハードコート層をジルコニアナノ粒子／アクリレート＝８０／２０の重量比で混合した塗工液を用いて形成した。また、中間層を形成する塗工液として、重量比でシリカ粒子／全アクリレート／ジエチレングリコールブチルメチルエーテル＝４／４．５／１．５であり、かつ、全アクリレート中のペンタエリスリトールテトラアクリレート／トリアクリロイルヘプタデカフルオロノネニルペンタエリスリトール＝４．５／０である組成物であって、組成物濃度４ｗｔ％のＭＥＫ溶液を用いた。その他は実施例１と同様にして反射防止膜を作製した。

A scanning electron microscope image of the surface of the produced antireflection film is shown in FIG. It was observed that the convex forming particles were arranged in a single layer. Further, FIG. 5 shows a scanning electron microscope image of the cross section of the produced antireflection film. It was observed that there were four layers, a microstructure layer, an intermediate layer, a hard coat layer, and a substrate.
[Example 2]
Coating in which a polyethylene terephthalate (PET) film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd., film thickness 100 μm, refractive index 1.65) is used as a base material, and a hard coat layer is mixed at a weight ratio of zirconia nanoparticles / acrylate = 80/20 Formed with liquid. In addition, as a coating solution for forming the intermediate layer, silica particles / total acrylate / diethylene glycol butyl methyl ether = 4 / 4.5 / 1.5 by weight ratio, and pentaerythritol tetraacrylate / trimethyl in the total acrylate A composition having acryloylheptadecafluorononenylpentaerythritol = 4.5 / 0 and a MEK solution having a composition concentration of 4 wt% was used. Otherwise, an antireflection film was produced in the same manner as in Example 1.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.10. The value of the formula (1) was 0.98.

  The produced antireflection film had a reflectance of 0.24% at a wavelength of 580 nm and was excellent in antireflection properties. Further, the a * value was 0.20 and the b * value was −0.51, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.15%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 3]
A flexible glass substrate (made by Corning, film thickness 70 μm, refractive index 1.52) is used as a base material, and silica particles / total acrylate / diethylene glycol butyl methyl ether by weight ratio is used as a coating liquid for forming an intermediate layer. = 4 / 4.5 / 1.5, and pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 1 / 3.5 in the total acrylate, the composition concentration A 4 wt% MEK solution was used. Otherwise, an antireflection film was produced in the same manner as in Example 1.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.03, The value of the formula (1) was 1.01.

  The produced antireflection film had a reflectance of 0.29% at a wavelength of 580 nm and was excellent in antireflection properties. Further, the a * value was 0.43 and the b * value was −0.57, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.16%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 4]
Instead of spin-coating the coating liquid at 1500 rpm for forming the intermediate layer, the coating liquid is spin-coated at 2800 rpm, and the coating liquid for forming the microstructure layer is silica particles / acrylate / diethylene glycol by weight ratio. Except that the composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / 2.5 / 6 was used in a weight ratio instead of using the composition of butyl methyl ether = 4 / 1.5 / 6 An antireflection film was produced in the same manner as in Example 1.

  The thickness of the microstructure layer of the produced antireflection film is 85 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00.

  The produced antireflection film had a reflectance of 0.35% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 1.25, the b * value was −1.85, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.49%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 5]
Instead of using an aqueous dispersion of silica particles with a particle size of 120 nm (MP-1040, 40 wt%, manufactured by Nissan Chemical Co., Ltd.) as a coating liquid for forming the microstructure layer, an aqueous dispersion of silica particles with a particle size of 150 nm (JGC) An anti-reflective coating was prepared in the same manner as in Example 1 except that a solution prepared using Catalytic Cataloid Special Products (40 wt%) was used.

  The thickness of the microstructure layer of the prepared antireflection film is 140 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00.

  The produced antireflection film had a reflectance of 0.24% at a wavelength of 580 nm and was excellent in antireflection properties. Further, the a * value was 0.25, the b * value was -1.92, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.11%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 6]
As the formation of the intermediate layer, an antireflection film was produced in the same manner as in Example 1 except that the coating liquid was spin-coated at 2500 rpm instead of spin-coating the coating liquid at 1500 rpm.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 65 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07. The value of the formula (1) was 1.00.

  The produced antireflection film had a reflectance of 0.22% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 2.25 and the b * value was −2.51, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.80%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 7]
As the formation of the intermediate layer, an antireflection film was produced in the same manner as in Example 1 except that the coating solution was spin-coated at 850 rpm instead of spin-coating the coating solution at 1500 rpm.

  The thickness of the microstructure layer of the produced antireflection film is 105 nm, the thickness of the intermediate layer is 115 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00.

  The produced antireflection film had a reflectance of 0.49% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 1.12 and the b * value was −0.98, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.96%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 8]
Instead of using a composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / 1.5 / 6 by weight ratio as a coating liquid for forming the fine structure layer, silica particles / acrylate / diethylene glycol butyl methyl by weight ratio An antireflection film was produced in the same manner as in Example 1 except that a composition of ether = 2 / 1.5 / 6 was used.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.08, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.05.

  The produced antireflection film had a reflectance of 0.29% at a wavelength of 580 nm and was excellent in antireflection properties. Further, the a * value was 0.35 and the b * value was −0.82, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.16%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 9]
Instead of using a composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / 1.5 / 6 by weight ratio as a coating liquid for forming the fine structure layer, silica particles / acrylate / diethylene glycol butyl methyl by weight ratio An antireflection film was produced in the same manner as in Example 1 except that a composition of ether = 5 / 1.5 / 6 was used.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.30, and the refractive index difference between the hard coat layer and the substrate is 0.07. The value of the formula (1) was 0.96.

  The produced antireflection film had a reflectance of 0.48% at a wavelength of 580 nm and was excellent in antireflection properties. Further, the a * value was 0.25 and the b * value was −0.64, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.31%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 10]
Instead of using a solution mixed at a weight ratio of zirconia nanoparticles / acrylate = 10/90 as a coating solution for forming a hard coat layer, silica particles having a particle diameter of 65 nm (surface treatment was applied in the same manner as in Example 1). ) / Total acrylate / diethylene glycol butyl methyl ether = 4 / 4.5 / 1.5, and pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol in all acrylates = 2.5 / 2 An antireflection film was produced in the same manner as in Example 1 except that a MEK solution having a composition concentration of 4 wt% was used.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.03, The value of the formula (1) was 1.03.

  The produced antireflection film had a reflectance of 0.15% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 1.52, the b * value was −1.45, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.29%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 11]
Instead of using a solution mixed at a weight ratio of zirconia nanoparticles / acrylate = 80/20, a solution mixed at a weight ratio of zirconia nanoparticles / acrylate = 90/10 is used as a coating liquid for forming a hard coat layer. Otherwise, an antireflection film was prepared in the same manner as in Example 2.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.20, The value of the formula (1) was 0.97.

  The produced antireflection film had a reflectance of 0.45% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 1.78 and the b * value was −1.13, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.46%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 12]
Instead of using a solution mixed at a weight ratio of zirconia nanoparticles / acrylate = 10/90 as a coating liquid for forming a hard coat layer, a solution mixed at a weight ratio of zirconia nanoparticles / acrylate = 80/20 is used. Otherwise, an antireflection film was produced in the same manner as in Example 1.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.27. The value of the formula (1) was 0.94.

  The produced antireflection film had a reflectance of 0.65% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.47 and the b * value was −0.61, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.26%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 13]
Instead of using a mixed solution of pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 4.5 / 0 in the total acrylate as the coating liquid for forming the intermediate layer, An antireflection film was produced in the same manner as in Example 2 except that a composition mixed in a weight ratio of pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 2 / 2.5 was used.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.10. The value of the formula (1) was 0.94.

  The produced antireflection film had a reflectance of 0.78% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.65 and the b * value was −0.88, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.44%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 14]
Instead of using a composition mixed in a weight ratio of pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 2 / 2.5 in the total acrylate as the coating liquid for forming the intermediate layer, An antireflective coating was prepared in the same manner as in Example 1 except that the composition mixed in a weight ratio of pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 4.5 / 0 was used.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.04.

The produced antireflection film had a reflectance of 0.21% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 1.45 and the b * value was -1.96, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.46%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.
[Example 15]
Instead of using a composition mixed in a weight ratio of pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 4.5 / 0 in the total acrylate as the coating liquid for forming the intermediate layer, An antireflective coating was prepared in the same manner as in Example 1 except that a composition mixed in a weight ratio of pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 0 / 4.5 was used.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 0.96.

  The produced antireflection film had a reflectance of 0.71% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was −1.46 and the b * value was 1.24, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.54%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 16]
An intermediate layer was formed by the following method, and an antireflection film was prepared in the same manner as in Example 2 except for the above.

  A 70 wt% methyl ethyl ketone (MEK) solution of zirconia nanoparticles (Nippon Shokubai Zircostar ZP-153) and an acrylate (Shin Nakamura Chemical Co., Ltd. A-TMM3LM-N, trifunctional / 4 functional = 57/43 wt% mixture, acrylate weight A 70 wt% MEK solution of 1/20 polymerization initiator IRUGACURE 184) was mixed at a weight ratio of zirconia nanoparticles / acrylate = 15/85. This solution was diluted with MEK to prepare a solution having a composition concentration of 4 wt%. This solution was spin-coated on a film on which a hard coat layer was formed at 1500 rpm for 10 seconds, dried with hot air at 110 ° C. for 5 minutes, and then cured by UV irradiation for 20 minutes in a nitrogen atmosphere (crosslinking of the crosslinkable resin).

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.10. The value of the formula (1) was 1.02.

  The produced antireflection film had a reflectance of 0.32% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.49 and the b * value was −1.53, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.33%, and the change in the antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 17]
In forming the microstructure layer, instead of using an aqueous dispersion of silica particles having a particle size of 120 nm (MP-1040, 40 wt% manufactured by Nissan Chemical Co., Ltd.), an isopropyl alcohol dispersion of hollow silica particles having a particle size of 60 nm (JGC) Example 1 except that a solution prepared using Catalytic Chemical's Thruria 4110, 20 wt%) was used, and instead of spin-coating this solution at 3000 rpm, this solution was spin-coated at 2200 rpm. Thus, an antireflection film was produced.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00. At this time, in the fine structure layer, particles having pores inside were arranged in multiple layers.

  The produced antireflection film had a reflectance of 0.25% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.35 and the b * value was −0.54, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.18%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 18]
An antireflection film was produced in the same manner as in Example 1 except that the intermediate layer was formed by the following method.

  Using an aqueous dispersion of silica particles with a particle size of 65 nm (ST-YL, Nissan Chemical Co., Ltd., 40 wt%), 200 g of particles, 150 g of ethanol, 4 g of methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.), and 28 wt. 0.2 g of aqueous ammonia was added with stirring, and the mixture was reacted at 60 ° C. for 3 hours and cooled to room temperature. Thereafter, 56 g of pentaerythritol tetraacrylate (A-TMMT, tetrafunctional) manufactured by Shin-Nakamura Chemical Co., Ltd. and 150 g of methanol were added. The operation of distilling off the solvent with an evaporator, adding 500 g of methanol and distilling off the solvent again was repeated three times. After the distillation operation, a solution composition was prepared by adding 2.8 g of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR1173 manufactured by BASF) as a polymerization initiator. MEK is added as a diluent to this solution composition to prepare a coating liquid composition having a composition concentration (amount of silica particles, pentaerythritol tetraacrylate, polymerization initiator, and silane coupling agent relative to the total solution amount) of 4 wt%. did. In addition, instead of using pentaerythritol tetraacrylate and a polymerization initiator, a solution in which the entire amount was replaced with diethylene glycol butyl methyl ether was also prepared, and the composition concentration (silica particles, diethylene glycol butyl methyl with respect to the total amount of the solution) was otherwise the same as described above. Amount of ether and silane coupling agent) A coating solution composition of 4 wt% was prepared. Further, instead of using an aqueous dispersion of silica particles having a particle diameter of 65 nm (ST-YL, Nissan Chemical Co., Ltd., 40 wt%), an isopropyl alcohol dispersion of hollow silica particles having a particle diameter of 60 nm (Thralia 4110, manufactured by JGC Catalysts & Chemicals, 20 wt%). ) And the coating liquid composition containing the same components except that the type of the particles is not silica particles having a particle size of 65 nm but hollow silica particles having a particle size of 60 nm by the same operation as described above. Prepared.

  By mixing the coating liquid composition, a composition having a weight ratio of silica particles / hollow silica particles = 80/20, silica particles / acrylate = 4/3, and acrylate / diethylene glycol butyl methyl ether = 1/1 An MEK solution having a composition concentration of 4 wt% was prepared. This solution was spin-coated on a film on which a hard coat layer was formed at 1500 rpm for 10 seconds, dried with hot air at 110 ° C. for 5 minutes, and then cured by UV irradiation for 20 minutes in a nitrogen atmosphere (crosslinking of the crosslinkable resin).

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00. At this time, the intermediate layer had pores.

  The produced antireflection film had a reflectance of 0.27% at a wavelength of 580 nm and was excellent in antireflection properties. Further, the a * value was 0.22 and the b * value was −0.57, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.11%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 19]
Instead of using a composition of silica particles / total acrylate / diethylene glycol butyl methyl ether = 4 / 4.5 / 1.5 by weight ratio as a coating solution for forming the intermediate layer, silica particles / acrylate / diethylene glycol by weight ratio An antireflection film was produced in the same manner as in Example 1 except that a composition of butyl methyl ether = 0/6 / 1.5 was used.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00. At this time, the interface between the fine structure layer and the intermediate layer was a smooth interface.

  The produced antireflection film had a reflectance of 0.29% at a wavelength of 580 nm and was excellent in antireflection properties. Further, the a * value was 0.43 and the b * value was −0.45, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.23%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 20]
Instead of using an aqueous dispersion of silica particles with a particle size of 120 m (MP-1040, 40 wt%, manufactured by Nissan Chemical Co., Ltd.) as a coating liquid for forming the fine structure layer, an aqueous dispersion of silica particles with a particle size of 65 m (Nissan) Example 1 with the exception that a solution prepared using ST-YL manufactured by Kagaku Co., Ltd. (40 wt%) was used and that this solution was spin-coated at 2200 rpm instead of being spin-coated at 3000 rpm. Similarly, an antireflection film was produced.

  The thickness of the microstructure layer of the prepared antireflection film is 105 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00. In the microstructure layer, the particles were arranged in multiple layers.

  The produced antireflection film had a reflectance of 0.25% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.21 and the b * value was −0.49, and the wavelength dependency of the antireflection property was small. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.18%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 21]
Instead of using an aqueous dispersion of silica particles with a particle size of 120 nm (MP-1040, 40 wt%, manufactured by Nissan Chemical Co., Ltd.) as a coating liquid for forming the microstructure layer, an aqueous dispersion of silica particles with a particle size of 180 nm (Nissan) Instead of using a composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / 1.5 / 6 by weight, using a solution prepared using MP-2040 (40 wt%, manufactured by Chemical Co., Ltd.) The ratio of silica particles / acrylate / diethylene glycol butyl methyl ether = 4/6/0 was used, and the carrier was cured by UV irradiation (crosslinking of the crosslinkable resin) for 20 minutes in a nitrogen atmosphere. 2 at a pressure of 13.3 Pa and an output of 30 A using a plasma surface treatment apparatus (PIB-20 manufactured by Vacuum Device Inc.) using air as gas. Except that was 30 seconds plasma etching (formation of the microstructure), thereby fabricating an antireflection film in the same manner as in Example 1.

  The thickness of the microstructure layer of the prepared antireflection film is 135 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00. At this time, the fine structure layer had the particles arranged in multiple layers.

  The produced antireflection film had a reflectance of 0.25% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.51 and the b * value was −0.47, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.14%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Example 22]
Instead of using a composition of silica particles / total acrylate / diethylene glycol butyl methyl ether = 4 / 4.5 / 1.5 by weight ratio as a coating liquid for forming the intermediate layer, silica particles / total acrylate / weight ratio The composition of diethylene glycol butyl methyl ether = 4 / 1.5 / 4.5 was used, and as a coating liquid for forming the fine structure layer, silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / Instead of using the 1.5 / 6 composition, the same procedure as in Example 1 was used except that a composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 5 / 0.5 / 6 was used in a weight ratio. An antireflection film was prepared.

  The thickness of the microstructure layer of the produced antireflection film is 120 nm, the thickness of the intermediate layer is 85 nm, the refractive index of the microstructure layer is 1.20, and the refractive index difference between the hard coat layer and the substrate is 0.07, The value of the formula (1) was 1.00. At this time, it did not have a convex part formation particle | grain buried layer.

  The produced antireflection film had a reflectance of 0.22% at a wavelength of 580 nm, and was excellent in antireflection properties. Further, the a * value was 0.31, the b * value was −0.78, and the wavelength dependency of the antireflection property was small. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 0.12%, and the change in antireflection property due to the change in the incident angle of light was small. The produced film was excellent in scratch resistance, flexibility, and alkali resistance.

Table 1 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 1]
Instead of using a solution of silica particles / total acrylate / diethylene glycol butyl methyl ether = 4 / 4.5 / 1.5 by weight ratio as a coating solution for forming the intermediate layer, silica particles / total acrylate / diethylene glycol by weight ratio An antireflection film was produced in the same manner as in Example 1 except that a solution of butyl methyl ether = 4/6/0 was used and a fine structure layer was not formed.

  The produced antireflection film had a reflectance of 3.20% at a wavelength of 580 nm, and was inferior in antireflection properties.

  Table 2 shows the structure and characteristics of the produced antireflection film.

［比較例２］
中間層の形成を行わず、ハードコート層の上に微細構造層を形成したことを除き、実施例１と同様にして反射防止膜を作製した。

[Comparative Example 2]
An antireflection film was produced in the same manner as in Example 1 except that the intermediate layer was not formed and a fine structure layer was formed on the hard coat layer.

  The produced antireflection film had an a * value of 5.25 and a b * value of 7.13, and the wavelength dependency of the antireflection property was large. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 1.11%, and the change in the antireflection property due to the change in the incident angle of light was large. Moreover, the haze difference with a base material was 1.12%, and it was inferior to transparency.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 3]
An antireflection film was produced in the same manner as in Example 1 except that the hard coat layer was not formed and an intermediate layer was formed on the substrate.

  The produced antireflection film had an a * value of 5.14 and a b * value of 7.39, and the wavelength dependency of the antireflection property was large. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 1.10%, and the change in the antireflection property due to the change in the incident angle of light was large. Moreover, it was inferior to abrasion resistance.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 4]
As the formation of the intermediate layer, instead of spin-coating the coating liquid at 1500 rpm, the coating liquid was spin-coated at 3500 rpm, and as the coating liquid for forming the microstructure layer, silica particles / acrylate / Instead of using a composition of diethylene glycol butyl methyl ether = 4 / 1.5 / 6, except that a composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / 3.5 / 6 by weight ratio was used, An antireflection film was produced in the same manner as in Example 1.

  The thickness of the microstructure layer of the produced antireflection film was 45 nm.

  The produced antireflection film had a reflectance of 2.12% at a wavelength of 580 nm, and was inferior in antireflection properties. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 2.20%, and the change in the antireflection property due to the change in the incident angle of light was large.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 5]
Instead of using an aqueous dispersion of silica particles having a particle size of 120 nm (MP-1040, 40 wt%, manufactured by Nissan Chemical Co., Ltd.) as a coating liquid for forming the fine structure layer, silica particles having a particle size of 300 nm (KE-made by Nippon Shokubai Co., Ltd.) P30) was used, and the composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / 1.5 / 6 was used as a coating solution for forming the microstructure layer by weight ratio. An antireflection film was produced in the same manner as in Example 1 except that a composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4/2/6 was used instead of using it.

  The thickness of the microstructure layer of the produced antireflection film was 250 nm.

  The produced antireflection film had a reflectance of 2.50% at a wavelength of 580 nm and was inferior in antireflection properties. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 2.65%, and the change in the antireflection property due to the change in the incident angle of light was large. Furthermore, the haze difference from the substrate was 3.56%, which was inferior in transparency. The produced film was inferior in scratch resistance.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 6]
An antireflection film was produced in the same manner as in Example 1 except that the coating liquid was spin-coated at 5500 rpm instead of spin-coating the coating liquid at 1500 rpm as the formation of the intermediate layer.

  The film thickness of the intermediate layer of the produced antireflection film was 40 nm.

  The produced antireflection film had an a * value of 4.95 and a b * value of 5.48, and the wavelength dependency of the antireflection property was large.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 7]
As the formation of the intermediate layer, an antireflection film was produced in the same manner as in Example 1 except that the coating liquid was spin-coated at 450 rpm instead of spin-coating the coating liquid at 1500 rpm.

  The film thickness of the intermediate layer of the produced antireflection film was 160 nm.

  The produced antireflection film had an a * value of 5.43 and a b * value of −6.42, and the wavelength dependency of the antireflection property was large. Furthermore, the difference in reflectance between the incident angles of 10 ° and 40 ° was 1.17%, and the change in the antireflection property due to the change in the incident angle of light was large.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 8]
Instead of using a composition of silica particles / acrylate / diethylene glycol butyl methyl ether = 4 / 1.5 / 6 by weight ratio as a coating liquid for forming the fine structure layer, silica particles / acrylate / diethylene glycol butyl methyl by weight ratio An antireflection film was produced in the same manner as in Example 1 except that a composition of ether = 6 / 0.5 / 6 was used.

  The refractive index of the microstructure layer of the produced antireflection film was 1.38.

  The produced antireflection film had a reflectance of 3.29% at a wavelength of 580 nm and was inferior in antireflection properties. Further, the a * value was 3.45 and the b * value was -2.15, and the wavelength dependency of the antireflection property was large. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 2.52%, and the change in the antireflection property due to the change in the incident angle of light was large.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 9]
Example 1 except that a composition of zirconia nanoparticles / acrylate = 90/10 was used instead of the composition of zirconia nanoparticles / acrylate = 10/90 as the coating liquid for forming the hard coat layer. An antireflection film was produced in the same manner as described above.

  The refractive index difference between the hard coat layer of the produced antireflection film and the substrate was 0.37.

  The produced antireflection film had a reflectance of 2.50% at a wavelength of 580 nm and was inferior in antireflection properties.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 10]
Instead of using a composition of pentaerythritol tetraacrylate / triacryloylheptadecafluorononenyl pentaerythritol = 4.5 / 0 in the total acrylate as a coating solution for forming the intermediate layer, pentaerythritol tetraacrylate in the total acrylate An antireflection film was produced in the same manner as in Example 2 except that a composition of /triacryloylheptadecafluorononenylpentaerythritol=0/4.5 was used.

  The value of the formula (1) of the manufactured antireflection film was 0.91.

  The produced antireflection film had a reflectance of 1.59% at a wavelength of 580 nm and was inferior in antireflection properties. Further, the a * value was 2.45 and the b * value was −6.17, and the wavelength dependency of the antireflection property was large.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 11]
An antireflection film was produced in the same manner as in Example 1 except that the intermediate layer was formed by the following method.

  A 70 wt% methyl ethyl ketone (MEK) solution of zirconia nanoparticles (Nippon Shokubai Zircostar ZP-153) and an acrylate (Shin Nakamura Chemical Co., Ltd. A-TMM3LM-N, trifunctional / 4 functional = 57/43 wt% mixture, acrylate weight A 70 wt% MEK solution (containing 1/20 polymerization initiator IRUGACURE 184) was mixed at a weight ratio of zirconia nanoparticles / acrylate = 20/80. This solution was diluted with MEK to prepare a solution having a composition concentration of 4 wt%. This solution was spin-coated on a film on which a hard coat layer was formed at 1500 rpm for 10 seconds, dried with hot air at 110 ° C. for 5 minutes, and then cured by UV irradiation for 20 minutes in a nitrogen atmosphere (crosslinking of the crosslinkable resin).

  The value of the formula (1) of the produced antireflection film was 1.09.

  The produced antireflection film had an a * value of 4.45 and a b * value of −7.39, and the wavelength dependency of the antireflection property was large. Further, the difference in reflectance between the incident angles of 10 ° and 40 ° was 1.27%, and the change in the antireflection property due to the change in the incident angle of light was large.

Table 2 shows the configuration and characteristics of the produced antireflection film.
[Comparative Example 12]
An antireflection film was produced in the same manner as in Example 1 except that the intermediate layer and the microstructure layer were formed by the following method.

  4 g of ethanol and 0.2 g of 0.01M hydrochloric acid were added to 5 g of tetraethoxysilane and stirred at 300 rpm for 1 hour at room temperature. This solution is concentrated by an evaporator, and an aqueous dispersion of silica particles having a particle size of 65 nm (ST-YL, Nissan Chemical Co., Ltd., 40 wt%), MEK, and diethylene glycol butyl methyl ether are added, and silica particles / tetraethoxysilane are added at a weight ratio. A MEK solution having a composition concentration of 5.8 wt% was prepared, which was a composition having / diethylene glycol butyl methyl ether = 4/9 / 1.5. This solution was spin-coated at 1500 rpm for 10 seconds on the film on which the hard coat layer was formed, and dried with hot air at 100 ° C. for 30 minutes.

  Centrifugation of an aqueous dispersion of silica particles having a particle size of 120 nm (MP-1040, 40 wt%, manufactured by Nissan Chemical Co., Ltd.) and replacing the dispersion medium with methanol, the particles were redispersed, and tetraethoxysilane, diethylene glycol butyl methyl ether , And MEK were added, and a MEK solution having a composition in which the weight ratio of particles / tetraethoxysilane / diethylene glycol butyl methyl ether = 4 / 1.5 / 6 and a composition concentration of 4 wt% was prepared. This solution was spin-coated at 3000 rpm for 10 seconds on the film on which the intermediate layer was formed, and dried with hot air at 100 ° C. for 30 minutes.

  The value of the formula (1) of the manufactured antireflection film was 1.00.

  The produced antireflection film did not contain a crosslinked resin, and was inferior in scratch resistance, flexibility, and alkali resistance.

  Table 2 shows the configuration and characteristics of the produced antireflection film.

  According to the present invention, it has excellent mass productivity, excellent scratch resistance, excellent scratch resistance and high transparency, excellent antireflection property for light in the visible light region, and the wavelength dependency of antireflection property. It is possible to provide an antireflection film that is small and has a small change in antireflection property due to a change in the incident angle of light. The antireflection film of the present invention is also applicable to a display with high visibility, a solar cell with high light capture efficiency, an organic EL with high light extraction efficiency, and the like.

Schematic diagram of the cross section showing the layer structure of the antireflection film of the present invention (with a convex-formed particle buried layer) Schematic diagram of the cross section showing the layer structure of the antireflection film of the present invention (without the convex-formed particle buried layer) Schematic diagram of cross section of antireflection film showing liquid cross-linking structure derived from meniscus shape Scanning electron microscope image of the antireflection film surface of Example 1 Scanning electron microscope image of cross section of antireflection film of Example 1

DESCRIPTION OF SYMBOLS 1 Particle | grain 2 Binder 3 Liquid cross-linking structure derived from meniscus shape 10 Fine structure layer 20 Intermediate layer 21 Convex-forming particle buried layer 22 Layer other than convex-formed particle buried layer 30 in intermediate layer 30 Hard coat layer 40 Base material 100 Reflection Prevention film H Film thickness of fine structure layer (height of convex part)
L Thickness between vertices of convex portions T Film thickness of intermediate layer t ₁ Film thickness of convex-formed particle buried layer t ₂ Film thickness of layers other than convex-formed particle buried layer in intermediate layer

Claims (7)

An antireflection film having at least four layers of a microstructure layer, an intermediate layer using a crosslinked resin, a hard coat layer, and a substrate in order from a position far from the substrate in the film thickness direction, the film of the microstructure layer The thickness is 50 to 200 nm, the thickness of the intermediate layer is 50 to 150 nm, the refractive index of the microstructure layer is 1 to 1.35, and the refractive index of the hard coat layer and the substrate is When the absolute value of the difference is 0.3 or less, the refractive index of the microstructure layer is n _top , the refractive index of the intermediate layer is n _mid , and the refractive index of the hard coat layer is n _hc , the following (1 A numerical value given by the formula is 0.92 to 1.07.

The antireflection film according to claim 1, wherein the intermediate layer contains internal particles and a binder, and a non-smooth interface is formed in the antireflection film due to the uneven shape derived from the internal particles. 3. The antireflection film according to claim 1, wherein the microstructure layer contains convexity-forming particles, and the intermediate layer contains internal particles having a smaller particle diameter than the convexity-forming particles. The antireflection film according to any one of claims 1 to 3, wherein the intermediate layer contains internal particles and a binder, and the intermediate layer does not have pores therein. The antireflection film according to any one of claims 1 to 4, wherein the intermediate layer contains internal particles and a binder, and the elastic modulus of the internal particles is larger than that of the binder. The base material is a resin film, the refractive index of the hard coat layer is 1.45 to 2.0, the refractive index of the intermediate layer is 1.45 to 1.6, and the microstructure layer has a particle size of 250 nm or less. The antireflection film according to any one of claims 1 to 5, further comprising a convex forming particle and a binder. Forming an intermediate layer by applying a coating liquid containing 0.01 to 65% by weight of internal particles having a particle diameter of 5 to 100 nm and 0.015 to 95% by weight of a crosslinkable resin on the hard coat layer, A fine structure layer is formed by applying a coating solution containing 0.01 to 65% by weight of convex-forming particles having a particle size of 50 to 200 nm and 0.015 to 95% by weight of a crosslinkable resin on the formed intermediate layer. The manufacturing method of the anti-reflective film in any one of Claims 1-6 including the process to form.

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