Anti-reflective components, polarizing plates, image display devices, anti-reflective items

Abstract

The present invention provides an anti-reflective component with low reflectivity and improved scratch resistance, and an image display device having the anti-reflective component. The anti-reflective member 100 of the present invention has a low refractive index layer 130 on a transparent substrate 110. The low refractive index layer 130 includes an adhesive resin and silicon dioxide particles 132 and 134. The ratio of Si element attributed to the silicon dioxide particles obtained by X-ray photoelectron spectroscopy analysis of the surface area of ​​the low refractive index layer 130 is 10.0 atomic% or more and 18.0 atomic% or less, and the ratio of C element when the ratio of Si element is converted to 100 atomic% is 180 atomic% or more and 500 atomic% or less.

Description

[Technical Field]

[0001] This invention relates to an anti-reflective component, a polarizing plate having the same, an image display device, and an anti-reflective article. [Previous Technology]

[0002] It is known that in display devices such as liquid crystal display devices, organic EL display devices, and micro LED display devices, as well as display cases, anti-reflective components are provided on the surface of the device to improve visibility. In recent years, in addition to televisions, touch panel image display devices such as car navigation displays, tablets, and smartphones, which are operated by users directly touching the screen, are becoming increasingly popular, and anti-reflective components are also provided in these devices.

[0003] Methods for manufacturing antireflective components include those involving the deposition of inorganic thin films with different refractive indices onto a hard coating on a transparent substrate using dry film deposition methods such as sputtering, or the coating of a resin containing microparticles onto a hard coating to form an antireflective layer. Generally, antireflective components formed with resin layers have the following advantages over those formed with inorganic thin films: less variation in tilt reflection hue, superior chemical stability (especially alkali resistance), and are more economical. On the other hand, antireflective components formed with resin layers have poorer mechanical properties such as scratch resistance compared to those formed with inorganic thin films, and tend to have higher reflectivity.

[0004] For this type of problem, for example, in Patent Documents 1 and 2, the low refractive index layer contains hollow inorganic nanoparticles such as silicon dioxide and solid inorganic nanoparticles. Furthermore, the solid inorganic nanoparticles are concentrated on the interface side with the hard coating, and the hollow inorganic nanoparticles are concentrated on the side opposite to that interface. In this way, both high scratch resistance and low reflectivity are achieved.

[0005] Patent document 3 discloses the following situation: by setting the reactive silica microparticles in the low refractive index layer to be concentrated at the interface on the hard coating side and / or at the interface on the opposite side of the hard coating layer, and by densely filling the low refractive index layer with hollow silica microparticles, the surface hardness (scratch resistance) is improved.

[0006] Patent Document 4 discloses the following: an antireflective film is formed on an optical substrate, wherein hollow silicon dioxide microparticles and fine silicon dioxide particles are dispersed in an adhesive mainly composed of reactive silanes. (Prior Art Documents, Patent Documents)

[0007] Patent Document 1: Japanese Patent Publication No. 2018-533068; Patent Document 2: Japanese Patent Publication No. 2018-533762; Patent Document 3: Japanese Patent No. 6011527; Patent Document 4: Japanese Patent Application Publication No. 2007-078711 [Summary of the Invention]

[0008] [Problem to be Solved by the Invention] However, even with the addition of silica microparticles to the low refractive index layer as described in the aforementioned patent literature, the anti-reflective component with a resin layer still has limitations in its resistance to steel wool, and its scratch resistance is inferior to that of inorganic thin films formed by known dry film deposition methods such as sputtering. Furthermore, the problem is particularly evident in the following situation: if an anti-reflective component with a resin layer is used in a touch panel type image display device, scratches will appear on the surface simply from the user's finger operation.

[0009] Furthermore, when an antireflective film is formed using an adhesive composed of reactive silanes, as in Patent Document 4, the problem is that sufficient scratch resistance cannot be obtained.

[0010] In view of the above-mentioned problems, the present invention aims to provide an anti-reflective component with lower reflectivity and improved scratch resistance, an anti-reflective component, a polarizing plate having the same, an image display device, and an anti-reflective article. [Technical means to solve the problems]

[0011] The inventors have discovered that even when scratches are not visible due to friction between the resin layer surface and fine solid matter (such as sand) or oil, scratches can still be formed on the resin layer surface by friction with an oily substance containing solid matter. This is equivalent to a user operating a touch panel image display device with fingers that are coated with oils contained in cosmetics and food, as well as sand contained in the atmosphere.

[0012] The inventors conducted research and found that the aforementioned scratches are mainly caused by the loss or detachment of some of the hollow silica particles contained in the low refractive index layer. The reason for this is believed to be the relatively large unevenness of the hollow silica particles formed on the surface of the low refractive index layer. Specifically, if the surface of the low refractive index layer is rubbed with an oily finger containing solids such as sand, the oil acts as an adhesive. With the solid components adhering to the finger, the finger moves across the surface of the low refractive index layer. At this time, it is easy for a portion of the solid (e.g., the finer part of the sand) to enter the concave portion of the low refractive index layer surface, and for the solid that has entered the concave portion to leave the concave portion along with the finger, passing over the convex portion (hollow silica particles). It is believed that a greater force is applied to the convex portion (hollow silica particles) at this time, thus damaging or detaching the hollow silica particles. Furthermore, it is believed that the resin itself located in the concave portion is also damaged by friction from the solid material, or that the damage makes it easier for the hollow silicon dioxide particles to detach. Therefore, the inventors have diligently researched methods to solve the above problems, and have obtained an anti-reflective component with excellent surface resistance, such as a smooth low-refractive-index layer surface, low reflectivity, and thus high scratch resistance, thereby completing the present invention.

[0013] In order to solve the above-mentioned problems, the present invention provides the following [1] to

[11] . [1] An anti-reflection member having a low refractive index layer on a transparent substrate, the low refractive index layer comprising an adhesive resin and silicon dioxide particles, wherein the ratio of Si element attributable to the silicon dioxide particles obtained by X-ray photoelectron spectroscopy analysis of the surface region of the low refractive index layer is 10.0 atomic% or more and 18.0 atomic% or less, and the ratio of C element when the ratio of Si element is converted to 100 atomic% is 180 atomic% or more and 500 atomic% or less. [2] The anti-reflection member of [1] wherein the silicon dioxide particles are hollow silicon dioxide particles and non-hollow silicon dioxide particles. [3] The anti-reflection member of [2] wherein the ratio of the average particle size of the non-hollow silicon dioxide particles to the average particle size of the hollow silicon dioxide particles is 0.29 or less. [4] An antireflective member as described in [2] or [3], wherein the average particle size of the hollow silica particles is 50 nm or more and 100 nm or less, and the average particle size of the non-hollow silica particles is 5 nm or more and 20 nm or less. [5] An antireflective member as described in any one of [2] to [4], wherein the surfaces of the hollow silica particles and the non-hollow silica particles are coated with a silane coupling agent. [6] An antireflective member as described in [1], wherein the surface region of the low refractive index layer substantially does not contain fluorine atoms. [7] An antireflective member as described in any one of [1] to [6], wherein the indentation hardness of the low refractive index layer obtained by nanoindentation is 480 MPa or more. [8] An antireflective member as described in any one of [1] to [7], wherein the recovery rate of the low refractive index layer obtained by nanoindentation is 80% or more. [9] An anti-reflective member of any one of [1] to [8], wherein when the maximum height roughness of the surface of the low refractive index layer is defined as Rz and the arithmetic mean roughness of the surface of the low refractive index layer is defined as Ra, Rz / Ra is 22.0 or less.

[10] A polarizing plate having a transparent protective plate, a polarizer and a transparent protective plate in sequence, wherein at least one of the two transparent protective plates is an anti-reflective member of any one of [1] to [9].

[11] An image display device having an anti-reflective member of any one of [1] to [9] on a display element.

[12] An anti-reflective article having an anti-reflective member of any one of [1] to [9] on a component. [Effects of the Invention]

[0014] According to the present invention, an anti-reflective component having low reflectivity and excellent surface resistance such as scratch resistance can be obtained.

Implementation Method

[0016] Hereinafter, the anti-reflective member of the present invention will be described in detail. Furthermore, the numerical range of "AA to BB" in this specification refers to "AA or higher and BB or lower".

[0017] [Anti-reflective component] The anti-reflective component of the present invention comprises a low-refractive-index layer on a transparent substrate. This low-refractive-index layer includes an adhesive resin and silicon dioxide particles. The ratio of Si element attributed to the silicon dioxide particles, obtained by X-ray photoelectron spectroscopy analysis of the surface region of the low-refractive-index layer, is 10.0 atomic% or more and 18.0 atomic% or less. Furthermore, the ratio of C element, when converted to 100 atomic% of Si, is 180 atomic% or more and 500 atomic% or less. Preferably, the silicon dioxide particles include both hollow silicon dioxide particles and non-hollow silicon dioxide particles.

[0018] FIG1 is a schematic cross-sectional view illustrating one embodiment of the anti-reflective member of the present invention. The anti-reflective member 100 of FIG1 is formed by sequentially depositing a hard coating layer 120 and a low refractive index layer 130 on one surface of a transparent substrate 110. The low refractive index layer 130 contains hollow silicon dioxide particles 132 and non-hollow silicon dioxide particles 134 as silicon dioxide particles.

[0019] FIG2 is a schematic cross-sectional view illustrating another embodiment of the anti-reflective member of the present invention. The anti-reflective member 200 of FIG2 has a high refractive index layer 140 between the hard coating layer 120 and the low refractive index layer 130. The high refractive index layer 140 contains inorganic microparticles 142 having a high refractive index.

[0020] [Physical Properties of the Anti-reflective Component] <Optical Properties> The apparent reflectance Y value of the anti-reflective component of the present invention, measured at a light incident angle of 5 degrees from the side having the low refractive index layer, is preferably 1.0% or less, and more preferably 0.5% or less. In this specification, the apparent reflectance Y value refers to the apparent reflectance Y value of the CIE 1931 standard colorimetric system. The apparent reflectance Y value can be calculated using a spectrophotometer (e.g., manufactured by Shimadzu Corporation; trade name "UV-3600plus"). Generally, the apparent reflectance Y value of an anti-reflective component formed with 4 or 5 layers by sputtering (hereinafter referred to as "dry anti-reflective component") is 0.5% or less. The anti-reflective component of the present invention exhibits a low reflectance to the same extent as the dry anti-reflective component. Furthermore, the change in apparent reflectance of the anti-reflective component of the present invention when the light incident angle is increased is less than that of the dry anti-reflective component. That is, the change in hue of the tilted reflection is relatively small.

[0021] The total light transmittance of the anti-reflective component of the present invention, according to JIS K7361-1:1997, is preferably 50% or more, more preferably 80% or more, and even more preferably 90% or more. The total light transmittance and the following haze can be measured, for example, by a haze meter (product number: HM-150) manufactured by Murakami Color Technology Research Institute.

[0022] The haze of the anti-reflective member of the present invention, according to JIS K7136:2000, is preferably 1.0% or less, more preferably 0.5% or less, and even more preferably 0.2% or less. Furthermore, when providing anti-glare properties, it is not limited to this. When clarity of transmission or contrast is important, the haze is preferably less than 5.0%, and when anti-glare properties are important, the haze is preferably 5% to 50%.

[0023] <Elemental Analysis of the Surface Region of the Low Refractive Index Layer> If the surface of the low refractive index layer of the antireflective component of the present invention is analyzed by X-ray photoelectron spectrometry (hereinafter referred to as "XPS"), at least C, O, and Si elements are detected. The Si element originates from silicon dioxide particles (inorganic components) and organic components such as silane coupling agents or leveling agents. The C element originates from adhesive resin, surface treatment agents for silicon dioxide particles (silane coupling agents), and additives. However, considering the content within the low refractive index layer, the C element can be considered to be substantially derived from the adhesive resin.

[0024] The ratio of Si element attributed to silicon dioxide particles in the surface region of the low-refractive-index layer of the present invention, as obtained by XPS analysis, is 10.0 atomic% or more and 18.0 atomic% or less, and the ratio of C element when the Si element ratio is converted to 100 atomic% is 180 atomic% or more and 500 atomic% or less. Furthermore, the term "surface region" in the present invention refers to the region within the area detected by X-ray photoelectron spectroscopy, and the area in the low-refractive-index layer with a surface depth of 10 nm or less on the side opposite to the hard coating. The "ratio of C element when the Si element ratio is converted to 100 atomic%" can be calculated by "C / Si × 100 (%)". Hereinafter, the "ratio of C element when the Si element ratio is converted to 100 atomic%" may be abbreviated as "C / Si". Furthermore, the Si studied in this invention refers to the inorganic Si element belonging to silicon dioxide particles. Therefore, unless otherwise specified, Si also refers to the inorganic Si element.

[0025] The aforementioned C / Si ratio in the surface region of the low-refractive-index layer reflects the distribution of non-hollow silica particles and hollow silica particles in the thickness direction of the low-refractive-index layer. When silica particles are concentrated on the side of the low-refractive-index layer opposite to the surface (hard coating side), the ratio of Si element attributable to silica particles in the surface region is lower, and the ratio of C element is relatively higher. The same tendency exists when silica particles are embedded in the adhesive resin and are almost absent from the surface of the low-refractive-index layer. When silica particles (especially hollow silica particles) are not covered by the adhesive resin and are exposed on the surface of the low-refractive-index layer, the ratio of Si element attributable to silica particles becomes higher, and the ratio of C element becomes relatively lower.

[0026] The ratio of Si element attributed to silicon dioxide particles in the surface region of the low-refractive-index layer reflects the presence of non-hollow and hollow silicon dioxide particles in that surface region. Even if hollow silicon dioxide is more abundant in the surface region of the low-refractive-index layer, its cavities do not significantly contribute to increasing the ratio of Si element attributed to silicon dioxide particles. However, when non-hollow silicon dioxide is more abundant in the surface region, the ratio of Si element attributed to silicon dioxide particles becomes higher. Ideally, the ratio of Si element attributed to silicon dioxide particles in the surface region of the low-refractive-index layer should be 10.0 atomic% or higher, provided that silicon dioxide particles are present in sufficient quantities. In particular, a ratio of 13.0 atomic% or higher of Si element attributed to silicon dioxide particles results in a high concentration of non-hollow silicon dioxide particles on the surface side, thereby improving scratch resistance. On the other hand, when the percentage of Si belonging to silicon dioxide particles exceeds 18.0 atomic%, not only are non-hollow silicon dioxide particles present, but also hollow silicon dioxide particles are more abundant in the surface area and exposed, thus causing a decrease in scratch resistance as described below. Furthermore, for silicon dioxide particles to exist in a sufficient amount in the surface area of ​​the low-refractive-index layer, the C / Si ratio must be 500 atomic% or less. If the C / Si ratio exceeds 500 atomic%, the silicon dioxide particles are embedded in the adhesive resin, resulting in excessive adhesive resin in the surface area, thus failing to achieve sufficient scratch resistance. On the other hand, if the C / Si ratio is less than 180 atomic%, the amount of silicon dioxide particles present on the surface increases, especially the hollow silicon dioxide particles not covered by the adhesive resin, which are exposed on the surface, causing a decrease in scratch resistance. Considering both scratch resistance and sufficient coverage, the C / Si ratio is preferably 200 atomic% or more, and more preferably 250 atomic% or more. Furthermore, the C / Si ratio is preferably below 400 atomic percent, and more preferably below 350 atomic percent.

[0027] By setting the ratio of C to Si elements in the surface region of the low refractive index layer within the aforementioned range, a state can be achieved where hollow silica particles are coated with an appropriate amount of adhesive resin, and a sufficient amount of non-hollow silica particles exist between the hollow silica particles. This results in an anti-reflective component with excellent surface resistance, such as a smoother surface of the low refractive index layer, low reflectivity, and high scratch resistance.

[0028] Furthermore, when a low-refractive-index layer is formed using reactive silanes as an adhesive material, as in Patent Document 4, the C / Si ratio becomes very small. That is, the C / Si ratio differs between a low-refractive-index layer using reactive silanes as an adhesive material and a low-refractive-index layer using resin as an adhesive material. In the case of a low-refractive-index layer using reactive silanes as an adhesive material, scratch resistance deteriorates due to the influence of the adhesive composition. Therefore, by setting the C / Si ratio in the surface region of the low-refractive-index layer to 180 atomic% or more and 500 atomic% or less, an anti-reflective component with superior surface resistance, such as high scratch resistance, can be obtained.

[0029] Furthermore, there exists a situation where, even if the coating liquid used to form the low refractive index layer does not contain fluorine-containing compounds such as fluorine-based leveling agents, fluorine is still detected on the surface of the low refractive index layer after formation. This is because the hard coating layer that forms the base layer of the low refractive index layer, and the lower layers such as the high refractive index layer described below, contain fluorine-based leveling agents, which diffuse and transfer to the surface of the low refractive index layer during its formation. In the antireflective member of the present invention, it is preferable that even if the lower layer contains fluorine-based leveling agents (fluorine-containing compounds), F elements are not detected by XPS. That is, it is preferable that the surface area of ​​the aforementioned low refractive index layer does not substantially contain fluorine atoms. If fluorine-containing compounds are present in the surface area, the following situations may occur due to processing conditions: scratches are easily generated on the adhesive resin itself, and hollow silicon dioxide particles are easily detached. That is, in this situation, if the low-refractive-index layer contains fluorine-containing compounds, it becomes a cause of reduced scratch resistance. The reason is presumably that since fluorine-containing compounds are inherently softer, the hardness of the adhesive resin itself is reduced. By displaying the aforementioned elemental ratios in the low-refractive-index layer, compared to the adhesive resin containing a high concentration of silicon dioxide particles, it is easy to achieve a state where the diffusion of fluorine-containing compounds is suppressed and the surface area is substantially free of fluorine atoms. Furthermore, in this specification, "substantially free of fluorine atoms" means that the ratio of fluorine elements in the surface area is 0.5 atomic% or less, preferably 0.1 atomic% or less.

[0030] The anti-reflective component of the present invention also achieves a higher gas barrier effect (water vapor penetration rate, oxygen penetration rate) by using the surface area of ​​the low refractive index layer with the above-mentioned element ratio.

[0031] <Dispersion State of Silicon Dioxide Particles> To achieve the above-mentioned elemental ratios, the low-refractive-index layer of the anti-reflective member of the present invention preferably has hollow silicon dioxide particles and non-hollow silicon dioxide particles uniformly dispersed. The term "uniformly dispersed" in the present invention means that the hollow silicon dioxide particles and non-hollow silicon dioxide particles are not only uniformly dispersed in the surface region of the low-refractive-index layer but also uniformly dispersed in the thickness direction of the low-refractive-index layer when viewed in cross-section. That is, preferably, when XPS analysis is performed in the thickness direction of the low-refractive-index layer, the ratio of Si element attributed to silicon dioxide particles and the C / Si ratio satisfy the above-mentioned range at different locations in the thickness direction. For example, preferably, when the thickness of the low-refractive-index layer is divided into three equal parts and sequentially defined as a first region, a second region, and a third region from the transparent substrate side, the ratio of Si element attributed to silicon dioxide particles and the C / Si ratio satisfy the above-mentioned range for any location within the first region and any location within the second region.

[0032] Figure 3 is a cross-sectional image of the low-refractive-index layer in the anti-reflective member of Embodiment 1 of the present invention, obtained by transmission electron microscopy (TEM). In the low-refractive-index layer of the present invention, non-hollow silica particles (solid silica particles) are present not only at the interface between the low-refractive-index layer and the hard coating layer, but also in large quantities along with the adhesive resin on the surface of the low-refractive-index layer (the side opposite to the hard coating layer). Multiple hollow silica particles are arranged in the thickness direction. Based on the image in Figure 3, it is considered that the non-hollow silica particles are uniformly dispersed in the thickness direction of the low-refractive-index layer. Furthermore, it can be confirmed that the amount of hollow silica particles protruding from the surface of the low-refractive-index layer is small and is covered by the adhesive resin.

[0033] Figures 4 and 5 show cross-sectional images of an example of a low-refractive-index layer with poor particle dispersion. Figure 4 is a cross-sectional image obtained by observing the low-refractive-index layer in the anti-reflective component of Comparative Example 2 using a transmission electron microscope. In Figure 4, it can be confirmed that non-hollow silica particles (solid silica particles) are densely concentrated at the interface between the low-refractive-index layer and the hard coating layer. Furthermore, it can be confirmed that hollow silica particles protrude significantly from the surface of the low-refractive-index layer and are exposed without being covered by the adhesive resin. Figure 5 is a cross-sectional image obtained by observing the low-refractive-index layer in the anti-reflective component of Comparative Example 5 using a scanning electron microscope (SEM). In Figure 5, it can be confirmed that non-hollow silica particles (solid silica particles) are densely concentrated on the surface of the low-refractive-index layer.

[0034] The cross-sectional images in Figures 3 and 4 were obtained using an electron microscope H-7650 manufactured by Hitachi High-Technologies under conditions of 10 μA emission current, 100 keV accelerating voltage, and 20 V filament voltage. The cross-sectional image in Figure 5 was obtained using an electron microscope S-4800 manufactured by Hitachi High-Technologies under conditions of 10 μA emission current and 30 keV accelerating voltage.

[0035] <Abrasion Resistance> The low-refractive-index layer of the anti-reflective component of the present invention exhibits excellent abrasion resistance, including both steel wool resistance and oil stain resistance. Generally, pencil hardness is known as an indicator of the abrasion resistance of the surface of optical components such as anti-reflective components. However, pencil hardness evaluates the resistance of a harder material to stress contact under near-point load. On the other hand, under repeated friction or long-term use, minute scratches often occur due to the stable application of surface loads. It is more appropriate to evaluate the resistance to such scratches using indicators different from pencil hardness, namely steel wool resistance and oil stain resistance.

[0036] In this invention, the steel wool durability test is conducted by applying a load under the following conditions, rubbing the surface of the low-refractive-index layer with steel wool, and then changing the angle between the light-emitting part and the object while observing the test. The maximum load is set so that no scratches on the low-refractive-index layer can be observed with the naked eye (0 scratches). The observation is conducted under fluorescent lamps (illuminance: 200-2000 Lx; for example, a 3-wavelength fluorescent lamp manufactured by Panasonic Corporation; model: FHF32EX-NH) and LED lighting (illuminance: 100-8000 Lx; for example, manufactured by Ohm Electric Corporation; model: LPL-48N), with the distance between the light-emitting part and the object set to 10 cm to 300 cm. The contact area between the steel wool and the object (the surface of the low-refractive-index layer) is set to within the range of 0.5 to 1.5 cm². The shape of the surface of the steel wool in contact with the object can be circular, triangular, polygonal, etc., preferably circular. During the test, the steel wool was moved at the same location with a single-pass distance of 30 mm or more (a single-round travel distance of 60 mm or more). The single-pass travel distance was appropriately set according to the size of the device using the anti-reflective component. <Test Conditions> Steel wool: Manufactured by Nihon Steel Wool Co., Ltd.; Product name: BONSTAR; Product number: #0000; Moving speed: 100 mm / s; Number of rounds: 10

[0037] The steel wool toughness of the low-refractive-index layer of the anti-reflective member of the present invention is preferably 750 g / cm² or more under fluorescent light, more preferably 900 g / cm² or more, further preferably 1000 g / cm² or more, and even more preferably 1200 g / cm² or more. Furthermore, the steel wool toughness of the low-refractive-index layer is preferably 450 g / cm² or more under LED light, more preferably 500 g / cm² or more, further preferably 600 g / cm² or more, and even more preferably 700 g / cm² or more. The steel wool toughness of the anti-reflective member manufactured by the conventional wet process is 700 g / cm² or less under fluorescent light and 200 g / cm² or less under LED light (minimum inspection load). In the case of commercially available dry anti-reflective components (where a fluorine-based coating is deposited on a 5-layer sputtered film with SiO2 as the outermost layer), the steel wool resistance is approximately 1500 g / cm² under fluorescent light and less than 200 g / cm² under LED light (minimum inspection load). That is, the anti-reflective component of the present invention has higher steel wool resistance than anti-reflective components manufactured by conventional wet methods, and achieves steel wool resistance comparable to that of dry anti-reflective components in fluorescent light evaluation. Furthermore, the anti-reflective component of the present invention exhibits superior steel wool resistance compared to dry anti-reflective components in LED light evaluation.

[0038] In the low-refractive-index layer of the anti-reflective member of the present invention, the amount of hollow silica particles exposed to the surface is small, and they are covered by adhesive resin. Furthermore, it is believed that because non-hollow silica particles exist at a high concentration in the adhesive resin in the surface area, the hardness of the adhesive resin itself increases. Also, because the non-hollow silica particles are uniformly dispersed in the adhesive resin, uneven shrinkage during resin hardening is suppressed, resulting in a smoother surface. Therefore, it can be inferred that when the surface of the low-refractive-index layer of the present invention is rubbed with steel wool, damage or detachment of the hollow silica particles and damage to the adhesive resin itself can be suppressed.

[0039] The so-called oil dust resistance test is a test that determines the rubbing marks left when a mixture of AC dust and olive oil specified in ISO 12103-1 is absorbed into a cloth or wiping cloth and rubbed against the surface of an object. The AC dust can be fine (A2), coarse (A4), or a mixture of fine (A2) and coarse (A4). In this invention, oil dust resistance is defined as the maximum load under which no scratches (0 scratches) are visible to the naked eye after rubbing the surface of a low-refractive-index layer with a cloth or wiping cloth infused with the mixture, while a load is applied under the following conditions. Observations are conducted under fluorescent lamps (illuminance: 200–2000 Lx) and LEDs (illuminance: 100–8000 Lx), with the distance between the light-emitting part and the object set to 10 cm–300 cm. The oil and dust resistance test is conducted by attaching a cloth or wiping cloth to the end of a metal component, allowing the mixture to penetrate, and then moving the cloth or wiping cloth in contact with the object. The shape of the contact surface between the end of the metal component and the object (the low-refractive-index layer surface) can be triangular, polygonal, circular, etc., but square is preferred. Furthermore, the area of ​​the contact surface is preferably in the range of 0.5–1.5 cm². During the test, the cloth or wiping cloth is moved at least 30 mm in the same location, with a single reciprocating motion of at least 60 mm. The single-journey distance is appropriately set according to the size of the anti-reflective component being used. <Test Conditions> Moving speed: 100 mm / s Number of reciprocating motions: 10 times

[0040] The oil dust resistance of the low refractive index layer of the antireflective member of the present invention is preferably 700 g / cm² or more under fluorescent light, more preferably 750 g / cm² or more, further preferably 800 g / cm² or more, and even more preferably 1200 g / cm² or more. The oil dust resistance of the low refractive index layer of the antireflective member of the present invention is preferably 400 g / cm² or more under LED light, more preferably 450 g / cm² or more, further preferably 500 g / cm² or more, and even more preferably 900 g / cm² or more. In antireflective members manufactured by conventional wet methods, the oil dust resistance is approximately 200 g / cm² under fluorescent light and less than 100 g / cm² (minimum inspection load) under LED light. In the case of commercially available dry antireflective components (where a fluorine-based coating is deposited on a 5-layer sputtered film with SiO2 as the outermost layer), the oil dust resistance under fluorescent light is 1500 g / cm², while under LED light, the oil dust resistance is 100 g / cm² or less (minimum test load). That is, the antireflective component of the present invention exhibits superior oil dust resistance under both fluorescent and LED light evaluations compared to antireflective components manufactured using conventional wet methods. Furthermore, the antireflective component of the present invention demonstrates oil dust resistance comparable to conventional dry antireflective components under fluorescent light, and furthermore, exhibits superior oil dust resistance compared to conventional dry antireflective components under LED light evaluation.

[0041] <Surface Roughness> To obtain excellent surface resistance, the low refractive index layer in this invention preferably has a smooth surface. The maximum height roughness Rz only needs to be 110 nm or less, preferably 100 nm or less, and even more preferably 90 nm or less. Furthermore, a smoother surface can obtain even better surface resistance, so it is preferably 70 nm or less, and even more preferably 60 nm or less. Also, Rz / Ra (Ra is the arithmetic mean roughness) is preferably 22.0 or less, even more preferably 18.0 or less, even more preferably 16.0 or less, and even more preferably 12.0 or less. In this invention, Ra and Rz are roughness parameters described in the SPM-9600 Scanning Probe Microscope Upgrade Kit Operation Manual (SPM-9600 February 2016; pp. 194-195) as a three-dimensional roughness parameter. Ra and Rz are defined as follows. (Arithmetic Mean Roughness Ra) The roughness curve is obtained by selecting only a reference length (L) along its mean line, taking the X-axis along the mean line direction of this selected portion and the Y-axis along the longitudinal expansion direction, and representing the roughness curve as y = f(x). [Number 1] (Maximum Height Roughness Rz) The maximum height roughness Rz is the value obtained by selecting only a reference length along the mean line direction of the roughness curve and measuring the interval between the mountain top and valley bottom lines of this selected portion along the longitudinal expansion direction of the roughness curve.

[0042] A smaller Rz refers to a smaller convexity caused by hollow silica particles in a micro-region. Furthermore, a smaller Rz / Ra refers to a uniform unevenness caused by silica particles in a micro-region without any significant elevation difference relative to the average unevenness. Moreover, in this invention, the value of Ra is not particularly limited; Ra only needs to be 15 nm or less, and further, 12 nm or less. Furthermore, to obtain better surface resistance, it is preferably 10 nm or less, and more preferably 6.5 nm or less. By displaying the above elemental ratios in a low-refractive-index layer, a sufficient amount of non-hollow silica particles can be present in the adhesive between the hollow silica particles, and the hollow silica particles exist in the surface region in a state where they do not protrude from the surface and are coated with adhesive resin, thereby suppressing uneven shrinkage of the low-refractive-index layer. Therefore, the above-mentioned ranges of Rz and Rz / Ra are easily satisfied. The surface Rz of a low-refractive-index layer can increase to around 90–110 nm depending on the processing conditions of the low-refractive-index layer. In this case, when Rz / Ra is within the above range, it is easier to obtain better surface resistance.

[0043] By using the aforementioned ranges for Rz and Rz / Ra on the surface of the low-refractive-index layer, the resistance encountered by the solid material when crossing the protrusions on the surface of the low-refractive-index layer (caused by the hollow silica particles present near the surface) can be reduced. Therefore, it is believed that even when rubbing is performed while a load is applied by AC dust accompanied by oil, the solid material moves smoothly on the surface of the low-refractive-index layer. Furthermore, it is believed that the hardness of the recesses themselves is also increased. As a result, it can be inferred that damage or detachment of the hollow silica particles can be prevented, as well as damage to the adhesive resin itself can be prevented.

[0044] On the other hand, if the Rz and Rz / Ra values ​​on the surface of the low refractive index layer are too small, there is a risk of adhesion during the manufacturing process. Therefore, Rz is preferably 30 nm or more, and more preferably 70 nm or more. Furthermore, Rz / Ra is preferably 3.0 or more, and more preferably 5.0 or more.

[0045] <Indentation Hardness, Recovery Rate> The indentation hardness of the low-refractive-index layer in this invention, measured by nano-indentation, is preferably 480 MPa or higher. Furthermore, the recovery rate of the low-refractive-index layer in this invention, measured by nano-indentation, is preferably 80% or higher. By satisfying the above ranges for both indentation hardness and recovery rate, a low-refractive-index layer with excellent steel wool resistance and oil dust resistance can be obtained.

[0046] The indentation hardness and recovery rate are affected by the layer on the lower side (transparent substrate side) of the lower refractive index layer. In this invention, a hard coating layer is provided on the layer below the low refractive index layer, and a high refractive index layer is provided between the low refractive index layer and the hard coating layer, thereby improving the indentation hardness and recovery rate.

[0047] Considering the resistance to steel wool and oil dust, the indentation hardness is preferably 500 MPa or higher, more preferably 550 MPa or higher, and even more preferably 600 MPa or higher and 650 MPa or higher. Furthermore, the indentation hardness is preferably 1000 MPa or lower, more preferably 950 MPa or lower, even more preferably 900 MPa or lower, and particularly preferably 800 MPa or lower.

[0048] If the resistance of steel wool and oil dust is taken into consideration, the recovery rate is preferably above 82%, more preferably above 83%, and even more preferably above 85%.

[0049] Furthermore, the product of indentation hardness and recovery rate ([indentation hardness] × [recovery rate] ÷ 100) is an indicator of the scratch resistance of the low refractive index layer. That is, the larger the product of indentation hardness and recovery rate, the better the scratch resistance of the low refractive index layer. In this invention, this product is preferably 380 MPa or more, more preferably 410 MPa or more, and even more preferably 460 MPa or more. Furthermore, this product is preferably 1000 MPa or less, more preferably 950 MPa or less, and even more preferably 900 MPa or less.

[0050] The "indentation hardness" in this invention is a value measured and analyzed using a surface film property testing machine (Triboindenter TI950; manufactured by HYSITRON) via nanoindentation. The measurement is performed by pressing a Berkovich indenter (material: diamond triangular pyramid) into the surface of the low-refractive-index layer under the following conditions. During measurement, the unevenness of the low-refractive-index surface is observed under a microscope, and the flattest possible area without any particular defects is selected as the measurement point.

[0051] <Indentation Hardness Measurement Conditions> ・Indenter used: Triangular cone indenter (Model: TI-0039; manufactured by HYSITRON) ・Indentation conditions: Displacement control method ・Maximum indentation depth: 30 nm ・Load application time: 3 seconds (speed: 10 nm / sec) ・Holding time: 5 seconds ・Load unloading time: 3 seconds (speed: 10 nm / sec)

[0052] The "recovery rate" in this invention is a value obtained by analyzing the load-displacement curve measured using a surface film property testing machine (Triboindenter TI950; manufactured by HYSITRON) via nanoindentation. The load-displacement curve is measured by pressing a Berkovich indenter (material: diamond triangular pyramid) into the surface of the low-refractive-index layer under the following conditions. During measurement, the unevenness of the low-refractive-index surface is observed under a microscope, and the flattest possible area without any particular defects is selected as the measurement point. <Load-displacement curve measurement conditions> • Indenter used: Triangular pyramid indenter (model: TI-0039; manufactured by HYSITRON) • Indentation conditions: Load control mode • Maximum load: 30 μN • Load application time: 3 seconds (speed: 10 μN / sec) • Holding time: 5 seconds • Load unloading time: 3 seconds (speed: 10 μN / sec)

[0053] Based on the obtained load-displacement curve data, calculate the total deformation workload Wtotal and the elastic deformation workload Welast. The total deformation workload Wtotal is expressed by the following formula: Wtotal = Welast + Wplast Wplast: Plastic deformation workload. Based on Wtotal and Welast, calculate the recovery rate (elastic recovery rate) using the following formula: Recovery rate [%] = (Welast / Wtotal) × 100

[0054] Unless otherwise specified, the optical properties, elemental ratios, surface roughness, indentation hardness, and recovery rate in this specification refer to the average value of the measured values ​​at 14 of the 16 locations, excluding the minimum and maximum values. In this specification, the 16 measurement locations are preferably defined as follows: 16 locations are the intersections of lines drawn in the longitudinal and transverse directions that divide the area 0.5 cm from the outer edge of the sample into a blank area. For example, when the sample is quadrilateral, it is preferable to define the area 0.5 cm from the outer edge of the quadrilateral into a blank area, and to measure the 16 locations at the intersections of dashed lines that divide the area in the longitudinal and transverse directions into five equal parts. The parameters are then calculated using the average value of these locations. Furthermore, when the sample being measured is a shape other than a quadrilateral such as a circle, ellipse, triangle, or pentagon, it is preferable to draw a quadrilateral inscribed in such a shape and measure 16 parts of the quadrilateral using the method described above.

[0055] Unless otherwise specified, the optical properties, surface roughness, indentation hardness, and recovery rate described in this specification are set as values ​​measured at a temperature of 23±5℃ and a relative humidity of 40-65%. Furthermore, it is assumed that the sample is exposed to the aforementioned environment for at least 30 minutes before each measurement and evaluation begins. For elemental analysis, it is also assumed that the sample is exposed to the aforementioned environment for at least 30 minutes before the measurement begins.

[0056] Hereinafter, the conditions for obtaining the anti-reflective member of the present invention will be described. [Transparent substrate] The transparent substrate is a support of a hard coating and a low refractive index layer. The transparent substrate preferably has high light transmittance. Specifically, it is preferably one with a total light transmittance of 90% or more according to JIS K7361-1:1997.

[0057] Examples of transparent substrates include plastics and glass. In terms of being lightweight and easy to manufacture, transparent substrates are preferably made of plastics.

[0058] The plastic substrate may be formed from one or more of the following: polyolefin resins such as polyethylene and polypropylene; ethylene resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; acrylic resins such as poly(methyl methacrylate) and poly(ethyl methacrylate); styrene resins such as polystyrene; polyamide resins such as nylon 6 or nylon 66; cellulose resins such as triacetyl cellulose; polycarbonate resins; polyimide resins; and cyclic olefin resins obtained from cyclic olefins such as norcamphene and dicyclopentadiene.

[0059] There is no particular limitation on the thickness of the plastic substrate. From an operability point of view, the thickness of the plastic substrate is preferably 10 to 500 μm, more preferably 20 to 400 μm, and even more preferably 50 to 300 μm. The plastic substrate may also be a plate with a thickness exceeding 500 μm. In cases requiring flexibility, such as foldable applications, the thickness of the plastic substrate is preferably 10 to 40 μm to make the anti-reflective component thinner. Furthermore, when glass is used in parts on which the anti-reflective component is mounted, the thickness of the plastic substrate is preferably 40 to 100 μm from the viewpoint of preventing glass from scattering.

[0060] [Low Refractive Index Layer] The low refractive index layer is a layer having a lower refractive index than the transparent substrate. Furthermore, when an anti-reflective component has been installed in an image display device, the low refractive index layer is located on the side opposite to the display element (e.g., a liquid crystal display element, an EL display element). The low refractive index layer comprises an adhesive resin, hollow silica particles, and non-hollow silica particles.

[0061] <Adhesive Resin> The adhesive resin includes a cured product of a curable resin composition such as a thermosetting resin composition or a free radiation curable resin composition. From the viewpoint of scratch resistance, a cured product of a curable resin composition is preferred. Furthermore, examples of curable resin compositions include thermosetting resin compositions and free radiation curable resin compositions; from the viewpoint of scratch resistance, a free radiation curable resin composition is preferred. That is, as an adhesive resin, a cured product containing a free radiation curable resin composition is most preferably preferred.

[0062] The thermosetting resin composition is a composition comprising at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of thermosetting resins include acrylic resins, polyurethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and polysiloxane resins. For the thermosetting resin composition, a curing agent is added to these curing resins as needed.

[0063] The ionizing radiation curable resin composition is a composition comprising a compound having a ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). Examples of ionizing radiation curable functional groups include vinyl unsaturated groups such as (meth)acrylyl, vinyl, and allyl, as well as epoxy and oxocyclobutyl groups. The ionizing radiation curable compound preferably has two or more ionizing radiation curable functional groups. The ionizing radiation curable compound is preferably a compound having vinyl unsaturated groups. Among these, (meth)acrylate compounds having (meth)acrylyl are more preferably (meth)acrylate compounds. Hereinafter, (meth)acrylate compounds having four or more vinyl unsaturated groups are referred to as "multifunctional (meth)acrylate compounds". Furthermore, (meth)acrylate compounds having two to three vinyl unsaturated groups are referred to as "low-functional (meth)acrylate compounds".

[0064] As a (meth)acrylate compound, either a monomer or an oligomer can be used. In particular, from the viewpoint of easily smoothing the uneven shape of the surface of the low-refractive-index layer by suppressing uneven shrinkage during curing, the ionizing radiation curing compound is preferably a low-functionality (meth)acrylate compound. Furthermore, the proportion of the low-functionality (meth)acrylate compound in the ionizing radiation curing compound is preferably 60% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass. Furthermore, from the viewpoint of easily smoothing the uneven shape of the surface of the low-refractive-index layer by suppressing uneven shrinkage during curing, the low-functionality (meth)acrylate compound is preferably a (meth)acrylate compound having two vinyl unsaturated bonding groups. When the free radiation curing compound contains a large amount of polyfunctional (meth)acrylate compounds, as described below, the unevenness of the surface of the low refractive index layer can be easily smoothed by appropriately adjusting the type of solvent and drying conditions.

[0065] Examples of difunctional (meth)acrylate compounds include isocyanurate dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polybutylene glycol dimethacrylate, and other polyalkylene glycol dimethacrylates, bisphenol A tetraethoxydimethacrylate, bisphenol A tetrapropoxydimethacrylate, and 1,6-hexanediol dimethacrylate. Examples of trifunctional (meth)acrylate compounds include trimethylolpropane trimethacrylate, neopentyltetroxide trimethacrylate, and isocyanurate-modified trimethacrylate. Examples of polyfunctional (meth)acrylate compounds with four or more functions include neopentyltetroxide tetramethacrylate, dinepentyltetroxide hexamethacrylate, and dinepentyltetroxide tetramethacrylate. These (meth)acrylate compounds may also be obtained by modification in the following manner.

[0066] Furthermore, examples of (meth)acrylate oligomers include methacrylic acid esters, epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, and other acrylate polymers. Methacrylic acid esters are obtained, for example, by reacting a polyol and an organic diisocyanate with a hydroxyl ester of (meth)acrylate. Preferably, epoxy (meth)acrylates are (meth)acrylates obtained by reacting a trifunctional or higher aromatic epoxy resin, alicyclic epoxy resin, or aliphatic epoxy resin with (meth)acrylate; (meth)acrylates obtained by reacting a difunctional or higher aromatic epoxy resin, alicyclic epoxy resin, or aliphatic epoxy resin with a polybasic acid and (meth)acrylate; and (meth)acrylates obtained by reacting a difunctional or higher aromatic epoxy resin, alicyclic epoxy resin, or aliphatic epoxy resin with a phenol and (meth)acrylate.

[0067] Furthermore, from the viewpoint of suppressing uneven shrinkage caused by crosslinking, the aforementioned (meth)acrylate compounds may also be those in which a portion of the molecular backbone is modified. For example, compounds obtained by modification with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl groups, cyclic alkyl groups, aromatic groups, bisphenols, etc., may also be used. In particular, from the viewpoint of easily improving affinity with silicon dioxide particles and suppressing particle aggregation and setting the C / Si ratio within the aforementioned range, the aforementioned (meth)acrylate compounds are preferably obtained by modification with ethylene oxide, propylene oxide, or other alkyl oxides. The ratio of alkyl oxide-modified (meth)acrylate compounds in the ionizing radiation-curing compound is preferably 60% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass. Furthermore, the epoxide-modified (meth)acrylate compounds are preferably low-functional (meth)acrylate compounds, and more preferably (meth)acrylate compounds having two vinyl unsaturated bonding groups.

[0068] Examples of (meth)acrylate compounds having two vinyl unsaturated groups obtained by epoxide modification include bisphenol F epoxide-modified di(meth)acrylate, bisphenol A epoxide-modified di(meth)acrylate, isocyanurate epoxide-modified di(meth)acrylate, and polyalkylene glycol di(meth)acrylate, with polyalkylene glycol di(meth)acrylate being preferred. The average repeating unit of the alkylene glycol di(meth)acrylate is preferably 3 to 5. Furthermore, the alkylene glycol di(meth)acrylate is preferably composed of ethylene glycol and / or polyethylene glycol. Examples of (meth)acrylate compounds having three vinyl unsaturated groups obtained by epoxide modification include trimethylolpropane epoxide-modified tri(meth)acrylate and isocyanurate epoxide-modified tri(meth)acrylate. The above-mentioned free radiation curing resins can be used alone or in combination of two or more.

[0069] When the ionizing radiation curing resin is an ultraviolet curing resin, the anti-glare layer forming coating liquid preferably contains additives such as photopolymerization initiators or photopolymerization accelerators. As a photopolymerization initiator, one or more can be selected from acetophenone, benzophenone, α-hydroxyalkyl phenyl ketone, milchnerone, benzoin, benzodiazepine dimethyl ketal, benzoylbenzoate, α-acryloxime ester, α-aminealkyl phenyl ketone, thioxanone, etc. Furthermore, the photopolymerization accelerator is one that can reduce polymerization hindrance caused by air during curing and accelerate the curing speed; for example, one or more can be selected from p-dimethylaminobenzoate isoamyl ester, p-dimethylaminobenzoate ethyl ester, etc.

[0070] The adhesive resin may further contain additives such as antistatic agents, antioxidants, surfactants, dispersants, and ultraviolet absorbers. For the curable resin composition forming the adhesive resin, there are no particular limitations on the additives, but it is preferable to include a polysiloxane leveling agent (polysiloxane compound). By including this polysiloxane leveling agent, the surface of the low-refractive-index layer can be made smoother. Furthermore, the sliding properties and antifouling properties (fingerprint wiping properties, larger contact angle relative to pure water and hexadecane) of the low-refractive-index layer surface can be improved. Moreover, depending on the processing conditions, fluorinated leveling agents, or mixtures of fluorinated and polysiloxane leveling agents, or a system combining multiple types of fluorinated and polysiloxane leveling agents may also be used.

[0071] However, considering the scratch resistance (resistance to steel wool and oil dust) of the low refractive index layer, it is preferable not to add fluorinated oligomers and / or monomers with free radiation-curing functional groups to the curing resin composition forming the adhesive resin (especially in cases requiring high-speed mass production). Furthermore, there is a possibility of generating hydrofluoric acid during combustion, such as when the product is discarded; therefore, it is particularly preferable that the additive does not contain fluorinated leveling agents (fluorinated compounds). Fluorinated leveling agents are used when there is poor compatibility between polysiloxane leveling agents and adhesive resins.

[0072] <Silica Particles> In this invention, the low refractive index layer preferably comprises hollow silica particles and non-hollow silica particles. Hollow silica particles refer to particles having an outer shell made of silica, the particles enclosed by this outer shell having cavities containing air. Hollow silica particles are particles whose refractive index is reduced proportionally to the gas occupancy rate compared to the original refractive index of silica due to the inclusion of air. Non-hollow silica particles are particles that are not hollow like hollow silica particles. Non-hollow silica particles are, for example, solid silica particles. The shape of both hollow and non-hollow silica particles is not particularly limited; they can be true spheres, ellipsoids of revolution, or polyhedral shapes that approximate spheres, etc. Among these, considering scratch resistance, a true sphere, a rotational ellipsoid, or a nearly spherical shape is preferred.

[0073] Hollow silica particles, by containing air, reduce the overall refractive index of the low-refractive-index layer. By using larger-sized hollow silica particles with an increased air ratio, the refractive index of the low-refractive-index layer can be further reduced. On the other hand, hollow silica particles tend to have poor mechanical strength. In particular, when using larger-sized hollow silica particles with an increased air ratio, the scratch resistance of the low-refractive-index layer tends to decrease. Non-hollow silica particles, by being dispersed in the adhesive resin, improve the scratch resistance of the low-refractive-index layer.

[0074] To ensure that hollow silica particles and non-hollow silica particles exist at a high concentration in the adhesive resin and that the particles are uniformly dispersed in the resin along the film thickness direction, it is preferable to set the average particle size of the hollow silica particles and the average particle size of the non-hollow silica particles in a manner where the hollow silica particles approach each other and the non-hollow particles enter between the hollow silica particles. Specifically, the ratio of the average particle size of the non-hollow silica particles to the average particle size of the hollow silica particles is preferably 0.29 or less, more preferably 0.20 or less. Furthermore, this average particle size ratio is preferably 0.05 or more. Considering optical properties and mechanical strength, the average particle size of the hollow silica particles is preferably 50 nm or more and 100 nm or less, more preferably 60 nm or more and 80 nm or less. Furthermore, to prevent the aggregation of non-hollow silica particles and to consider dispersibility, the average particle size of the non-hollow silica particles is preferably 5 nm or more and 20 nm or less, and more preferably 10 nm or more and 15 nm or less.

[0075] Furthermore, the “average particle size” in this invention can be calculated by the following operations (1) to (3). (1) Take a cross-section of the anti-reflective component containing the particles by TEM or STEM. Preferably, the accelerating voltage of TEM or STEM is set to 10 kV to 30 kV, and the magnification is set to 50,000 to 300,000 times. (2) Select any 10 particles from the observed image and calculate the particle size of each particle. The particle size is determined as the distance between the two straight lines in the combination of two straight lines, which is the largest distance between the two straight lines when the cross-section of the particle is sandwiched between any two parallel straight lines. (3) Perform the same operation 5 times in the observed images of different images of the same sample, and take the average value obtained from the total of 50 quantities as the average particle size.

[0076] Hollow silica particles and non-hollow silica particles are preferably coated with a silane coupling agent. More preferably, a silane coupling agent having (meth)acrylic or epoxy groups is used. By subjecting the silica particles to surface treatment with a silane coupling agent, the affinity between the silica particles and the adhesive resin is increased, thereby reducing the likelihood of silica particle aggregation. Therefore, the dispersion of the silica particles becomes more uniform.

[0077] As silane coupling agents, examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyl... 3-Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Ethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane Oxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane, etc. Preferably, one or more selected from 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane are used.

[0078] The higher the content of hollow silica particles, the higher the filling rate of hollow silica particles relative to the adhesive resin, thereby reducing the refractive index of the low-refractive-index layer. On the other hand, if the content of hollow silica particles relative to the adhesive resin is too high, the number of hollow silica particles exposed from the adhesive resin increases, and the amount of adhesive resin binding between the particles decreases. Therefore, the hollow silica particles are easily damaged or detached, resulting in a tendency for a decrease in the mechanical strength of the low-refractive-index layer, such as its scratch resistance. Therefore, the content of hollow silica particles is preferably 100 parts by mass or more relative to 100 parts by mass of the adhesive resin, and more preferably 150 parts by mass or more. Furthermore, the content of hollow silica particles relative to 100 parts by mass of the adhesive resin is preferably 400 parts by mass or less, and more preferably 300 parts by mass or less.

[0079] If the content of non-hollow silica particles is low, there may be a situation where the presence of non-hollow silica particles on the surface of the low refractive index layer does not affect the increase in hardness. Furthermore, if the content of non-hollow silica particles is high, the effect of uneven shrinkage caused by the polymerization of the adhesive resin can be reduced, thus reducing the unevenness on the surface of the low refractive index layer after the resin hardens. On the other hand, if the content of non-hollow silica particles is excessive, the non-hollow silica will agglomerate, resulting in uneven shrinkage of the adhesive resin and increased surface unevenness. The content of non-hollow silica particles is preferably 90 parts by mass or more relative to 100 parts by mass of the adhesive resin, more preferably 100 parts by mass or more. Furthermore, the content of non-hollow silica particles is preferably 200 parts by mass or less relative to 100 parts by mass of the adhesive resin, more preferably 150 parts by mass or less.

[0080] By containing hollow silica particles and non-hollow silica particles relative to the adhesive resin at the above ratio, even if fluorinated compounds such as fluorinated leveling agents are present in the hard coating or high refractive index layer, no fluorinated compounds can be detected on the surface of the low refractive index layer. It is speculated that this is because the silica particles are uniformly dispersed in the adhesive resin at a high concentration, and the silica particles hinder the diffusion of the fluorinated leveling agents.

[0081] Furthermore, by adding hollow silica particles and non-hollow silica particles to the adhesive resin in the above ratio, the gas barrier properties of the anti-reflective component itself can be improved. This is presumably because the silica particles are uniformly dispersed with a high filling rate, hindering the penetration of gases, etc. Also, there are cases where cosmetics such as sunscreens and hand creams contain low-molecular-weight polymers with low volatility. By improving the barrier properties of the low-refractive-index layer, the penetration of low-molecular-weight polymers into the interior of the low-refractive-index layer can be suppressed. Therefore, adverse conditions (such as abnormal appearance) caused by the long-term retention of low-molecular-weight polymers within the low-refractive-index layer can be suppressed.

[0082] The thickness of the low-refractive-index layer is not particularly limited as long as it is 50 nm or more (above the average particle size of hollow silicon dioxide), preferably 80–120 nm, more preferably 85–110 nm, and even more preferably 90–105 nm. The refractive index of the low-refractive-index layer is preferably 1.40 or less, more preferably 1.35 or less. By setting the refractive index of the low-refractive-index layer to 1.40 or less, the high reflectivity of the surface of the low-refractive-index layer can be suppressed, and visibility can be easily improved. The lower limit of the refractive index of the low-refractive-index layer is about 1.10. Furthermore, in this specification, the refractive index refers to the refractive index at a wavelength of 589.3 nm.

[0083] [Hard Coating] When the transparent substrate is made of plastic, it is preferable to provide a hard coating between the low refractive index layer and the transparent substrate. By providing the hard coating, the indentation hardness and recovery rate can be improved. The hard coating comprises a cured product of a curable resin composition such as a thermosetting resin composition or a free radiation curable resin composition. As the curable resin, the same curable resin used for the low refractive index layer can be used.

[0084] When the ionizing radiation curing compound is an ultraviolet curing compound, the ionizing radiation curing composition preferably contains additives such as a photopolymerization initiator or a photopolymerization accelerator. The same materials used for the low-refractive-index layer can be used as the photopolymerization initiator and photopolymerization accelerator.

[0085] Preferably, the hard coating layer further includes a leveling agent as an additive. By adding a leveling agent, a coating film serving as the hard coating layer can be uniformly formed. As a leveling agent, fluorinated leveling agents, polysiloxane leveling agents, fluorinated-polysiloxane leveling agents, and mixtures thereof can be used. In this invention, even if the hard coating layer contains a fluorinated leveling agent, the diffusion of the fluorinated leveling agent can be hindered by the silica particles of the low-refractive-index layer, thereby easily suppressing the transfer of the fluorinated leveling agent to the surface of the low-refractive-index layer. Furthermore, the hard coating layer may also contain additives such as antistatic agents, antioxidants, surfactants, dispersants, and ultraviolet absorbers.

[0086] The thickness of the hard coating is preferably 0.1 to 100 μm, more preferably 0.5 to 20 μm, and even more preferably 1 to 10 μm. By setting the thickness of the hard coating within the above range, scratch resistance can be easily improved and cracking during processing such as cutting can be suppressed.

[0087] The refractive index of the hard coating is preferably adjusted within the range of 1.45 or higher and 1.70 or lower. Furthermore, when the antireflective component has a high refractive index layer, the refractive index of the hard coating is preferably lower than that of the high refractive index layer, more preferably 1.50 to 1.65, and even more preferably 1.55 to 1.60. If the refractive index of the hard coating is within this range, the hard coating functions as a medium refractive index layer, and the interference effect can be generated by the three layers—the hard coating (medium refractive index layer), the high refractive index layer, and the low refractive index layer—thereby further reducing reflectivity. Furthermore, when there are other layers (light-transmitting substrate, or other layers constituting the resin layer) between the hard coating and the substrate, from the viewpoint of suppressing interference stripes, it is preferable to reduce the difference between the refractive index of the other layer and the refractive index of the hard coating. In this specification, the refractive index can be calculated, for example, by fitting the reflectance spectrum measured using a reflectance spectrophotometer with the reflectance spectrum calculated based on an optical model of a multilayer thin film using Fresnel coefficients.

[0088] As a means of imparting the function of a medium refractive index layer to the hard coating, methods such as incorporating a resin with a higher refractive index into the hard coating coating liquid and incorporating particles with a higher refractive index can be listed. As a resin with a higher refractive index, examples include those obtained by introducing groups containing sulfur, phosphorus, bromine, or aromatic rings into the aforementioned thermosetting resin or ionized radiation-curing compound. As for particles with a higher refractive index, examples include those identical to the high refractive index particles used in the high refractive index layer described below.

[0089] [High Refractive Index Layer] The high refractive index layer is a layer with a higher refractive index than a hard coating. It contains high refractive index particles and adhesive resin.

[0090] The high refractive index layer comprises a cured form of a curable resin composition, such as a thermosetting resin composition or a free radiation curable resin composition, as an adhesive resin. The curable resin composition may be the same as that exemplified in the low refractive index layer, but a free radiation curable resin composition is preferred.

[0091] When the ionizing radiation curing compound is an ultraviolet curing compound, the ionizing radiation curing composition preferably contains additives such as a photopolymerization initiator or a photopolymerization accelerator. The same materials used for the low-refractive-index layer can be used as the photopolymerization initiator and photopolymerization accelerator.

[0092] Preferably, the high refractive index layer further includes a leveling agent as an additive. By adding a leveling agent, a coating film serving as the high refractive index layer can be uniformly formed. As a leveling agent, fluorinated leveling agents, polysiloxane leveling agents, fluorinated-polysiloxane leveling agents, and mixtures thereof can be used. In this invention, even if a fluorinated leveling agent is contained in the high refractive index layer, the diffusion of the fluorinated leveling agent can be hindered by the silica particles of the low refractive index layer, thereby easily suppressing the transfer of the fluorinated leveling agent to the surface of the low refractive index layer. Furthermore, the high refractive index layer may also contain additives such as antistatic agents, antioxidants, surfactants, dispersants, and ultraviolet absorbers.

[0093] Examples of high refractive index particles include antimony pentoxide, zinc oxide, titanium oxide, cerium oxide, tin-doped indium oxide, antimony-doped tin oxide, yttrium oxide, and zirconium oxide. The average particle size of the high refractive index particles is preferably 5 nm or more and 200 nm or less, more preferably 5 nm or more and 100 nm or less, and even more preferably 10 nm or more and 80 nm or less.

[0094] From the viewpoint of balancing the high refractive index of the coating film and the strength of the coating film, the content of high refractive index particles is preferably 100 parts by mass or more and 2,500 parts by mass or less relative to 100 parts by mass of adhesive resin, more preferably 300 parts by mass or more and 2,200 parts by mass or less, and even more preferably 500 parts by mass or more and 2,000 parts by mass or less.

[0095] In particular, by setting a high-refractive-index layer in which high-hardness particles such as zirconium oxide, antimony pentoxide, and titanium oxide are dispersed at a high concentration as high-refractive-index particles in the adhesive resin, the indentation hardness and recovery rate of the low-refractive-index layer can be improved. If improving the indentation hardness and recovery rate of the low-refractive-index layer is desired, the content of high-refractive-index particles is preferably 1000 parts by mass or more and 2000 parts by mass or less, more preferably 1500 parts by mass or more and 2000 parts by mass or less.

[0096] The refractive index of the high refractive index layer is preferably 1.55 or higher and 1.85 or lower, more preferably 1.56 or higher and 1.75 or lower. Furthermore, the thickness of the high refractive index layer is preferably 200 nm or lower, more preferably 50 nm or higher and 180 nm or lower.

[0097] [Manufacturing Method of Anti-reflective Component] The hard coating layer, low refractive index layer, and high refractive index layer of the anti-reflective component of the present invention can be formed by a wet method of coating a coating liquid containing the components constituting each layer onto a transparent substrate, drying, and curing, or by a transfer method of forming each layer on the substrate using a wet method. The coating liquid contains a solvent, solid components constituting each layer, and additives such as polymerization initiators.

[0098] In the case of wet forming, firstly, a low-refractive-index layer forming liquid is coated onto a transparent substrate and dried and hardened to form a low-refractive-index layer. In the case of a hard coating layer, a hard coating layer forming liquid is coated onto a transparent substrate and dried and hardened to form a hard coating layer; then, a low-refractive-index layer is formed in the same manner as above. In the case of both a hard coating layer and a high-refractive-index layer, a high-refractive-index layer forming liquid is coated onto the hard coating layer and dried and hardened to form both a hard coating layer and a high-refractive-index layer; then, a low-refractive-index layer is formed in the same manner as above. Alternatively, the hard coating layer and the high-refractive-index layer can be in a semi-hardened state (not fully hardened) and fully hardened during the formation of the low-refractive-index layer.

[0099] For coating solutions forming low refractive index layers, solvents are typically used to adjust viscosity or to dissolve or disperse the components. Examples of solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dialkyl, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), carbon halides (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), acetic acid cellosolves, sulfoxides (dimethyl sulfoxide, etc.), glycol ethers (1-methoxy-2-propyl acetate, etc.), acetamides (dimethylformamide, dimethylacetamide, etc.), and mixtures thereof.

[0100] When the solvent evaporates too quickly, the solvent convection is intense during the drying of the coating liquid used to form the low refractive index layer. Therefore, even if the silicon dioxide particles in the coating liquid are uniformly dispersed, the intense convection of the solvent during drying can easily disrupt the uniform dispersion. Therefore, it is preferable to include solvents with a slower evaporation rate. Specifically, it is preferable to include solvents with a relative evaporation rate (the relative evaporation rate when the evaporation rate of butyl acetate is set to 100) of 70 or less, and more preferably solvents with a relative evaporation rate of 30 to 60. Furthermore, solvents with a relative evaporation rate of 70 or less are preferably 10 to 50% by mass of all solvents, and more preferably 20 to 40% by mass. Examples of the relative evaporation rates of solvents with slower evaporation rates are: isobutanol 64, 1-butanol 47, 1-methoxy-2-propyl acetate 44, ethyl cellosolve 38, and cyclohexanone 32. Furthermore, the residual solvent components (solvents other than those with slow evaporation rates) are preferably those with excellent resin solubility. Also, the residual solvent components are preferably those with a relative evaporation rate of 100 or higher.

[0101] Furthermore, in order to suppress solvent convection during drying and improve the dispersion of silicon dioxide particles, the drying temperature during the formation of the low refractive index layer should preferably be as low as possible. The drying temperature can be appropriately set taking into account the type of solvent, the dispersion of silicon dioxide particles, production speed, etc.

[0102] As a means of hardening each layer, methods such as irradiation with ultraviolet light or electron beams or curing by heat can be used. Considering factors such as productivity, curing by ionizing radiation is preferred.

[0103] [Size, shape, etc. of the anti-reflective component] The anti-reflective component can be cut into a blade shape of a specific size, or it can be rolled into a cylinder shape by rolling a long strip into a cylinder shape. Furthermore, there is no particular limitation on the size of the blade, with a maximum diameter of approximately 2 to 500 inches. The term "maximum diameter" refers to the maximum length when connecting any two points of the anti-reflective component. For example, when the anti-reflective component is rectangular, the diagonal of that area becomes the maximum diameter. Similarly, when the anti-reflective component is circular, the diameter becomes the maximum diameter. There is no particular limitation on the width and length of the cylinder shape; generally, the width is 500 to 3000 mm, and the length is approximately 100 to 5000 m. The cylinder-shaped anti-reflective component can be cut into a blade shape according to the size of the image display device, etc. When cutting, it is preferable to exclude the cylinder end, which has unstable physical properties. Furthermore, the shape of the leaf is not particularly limited; for example, it can be polygonal (triangle, quadrilateral, pentagon, etc.) or circular, or it can be a random, indefinite shape. More specifically, when the anti-reflective component is quadrilateral, the aspect ratio is not particularly limited as long as it does not pose a problem for the display screen. For example, aspect ratios such as 1:1, 4:3, 16:10, 16:9, and 2:1 can be listed.

[0104] [Polarizing plate] The polarizing plate of the present invention has a transparent protective plate, a polarizer and a transparent protective plate in sequence, wherein at least one of the two transparent protective plates is the anti-reflection member.

[0105] When only one of the two transparent protective plates is used as the anti-reflective member, the other transparent protective plate may be the same as that exemplified with the transparent substrate described above.

[0106] Examples of polarizers include sheet-type polarizers such as polyvinyl alcohol films dyed and stretched with iodine or the like, polyvinyl alcohol formal films, polyvinyl alcohol acetal films, and ethylene-vinyl acetate copolymer saponified films; wire grid polarizers composed of multiple parallel metal lines; coated polarizers coated with lyotropic liquid crystals or dichroic host-guest materials; and multilayer thin-film polarizers. Furthermore, these polarizers can also be reflective polarizers that have the function of reflecting non-transmittable polarizing components.

[0107] [Image Display Device] The image display device of the present invention is formed by having the above-mentioned anti-reflective member on a display element. In this case, the anti-reflective member is arranged such that a transparent substrate is located on the display element side and a low refractive index layer is located on the user side of the image display device. The display element and the anti-reflective member are preferably laminated together with an adhesive layer as a barrier. Examples of display elements include liquid crystal display elements, EL display elements, plasma display elements, and electronic paper elements.

[0108] The image display device of the present invention has the above-mentioned anti-reflection component, which has extremely low reflectivity and excellent visibility, and not only has excellent steel wool resistance but also excellent oil and dust resistance.

[0109] [Anti-reflective article] The anti-reflective article of the present invention is formed by having the above-mentioned anti-reflective member on a component. In this case, the anti-reflective member is arranged such that the transparent substrate is located on the component side and the low refractive index layer is located on the user side of the article. The component and the anti-reflective member are preferably laminated together with an adhesive layer as a barrier.

[0110] Examples of components include dashboards, clocks, display cases, shop windows, and windows. That is, examples of articles of the present invention include dashboards, clocks, display cases, shop windows, and windows arranged with the release layer of the low-reflection component facing forward. Furthermore, the components can be transparent or opaque, and the color tone is not particularly limited. Examples

[0111] Hereinafter, embodiments and comparative examples will be provided to specifically describe the present invention. Furthermore, the present invention is not limited to the forms described in the embodiments.

[0112] 1. Evaluation and Measurement The antireflective components obtained in the Examples and Comparative Examples were subjected to the following measurements and evaluations. The results are shown in Tables 1 and 2. Furthermore, unless otherwise specified, and unless the tests were conducted under specific conditions, the environment for each measurement and evaluation was set at a temperature of 23±5°C and a relative humidity of 40-65%. Before each measurement and evaluation, the sample was exposed to the above environment for more than 30 minutes before the measurement and evaluation were performed.

[0113] 1-1. Reflectivity (Visual Reflectivity Y-value) A sample (5 cm × 5 cm) was prepared by bonding a black plate (manufactured by Kuraray Co., Ltd.; trade name: Comaglas DFA2CG 502K (black) series; thickness 2 mm) to the transparent substrate side of the antireflective component of the examples and comparative examples, with a 25 μm thick transparent adhesive layer (manufactured by Panac Co., Ltd.; trade name: Panaclean PD-S1) as a buffer. With the vertical direction relative to the surface of the low refractive index layer of the antireflective component set to 0 degrees, light was incident on the sample from a direction of 5 degrees, and the reflectivity (visual reflectivity Y-value) of the sample was measured based on the unidirectional reflection of the incident light. Regarding reflectance, the value representing perceived reflectance was determined using a spectrophotometer (manufactured by Shimadzu Corporation; product name: UV-2450) under conditions of a 2-degree field of view, C light source, and a wavelength range of 380–780 nm. The value was then calculated using software that converts the reflectance to the level of human visual perception (UVPC color measurement version 3.12 built into the device). For each sample, the average reflectance of 14 locations was taken as the reflectance of that sample.

[0114] 1-2. XPS Analysis of Test Sheets Cut from Anti-reflective Components of Examples and Comparative Examples. Using an X-ray photoelectron spectrometer, the X-ray photoelectron spectra of the C1s, O1s, Si2p, and F1s orbitals on the low-refractive-index layer surface of each test sheet were measured under the conditions described below. Peak separation was performed on each X-ray photoelectron spectrum to determine the ratios of C, O, F, and Si elements. Furthermore, based on the X-ray photoelectron spectra of the Si2p orbitals, peak separation was performed between the inorganic component (silicon dioxide) and the organic component (polysiloxane) to determine the ratio of Si element belonging to silicon dioxide particles (hollow silicon dioxide particles and non-hollow silicon dioxide particles) ("Inorganic Si" in the table). Measurements were performed on each sample at 14 locations, and analysis was conducted with a sample number n=2. The average of these measurements was used as the elemental ratios for each example and comparative example. Furthermore, based on the obtained elemental ratios, the ratio of Si element attributed to silicon dioxide particles, as calculated above, was converted to 100 atomic percent (C / Si). Moreover, in Tables 1 and 2, elements other than Si element derived from inorganic components (inorganic Si element), C element, and F element were designated as "Other Elements," and the total ratios of these elements were recorded. <Measurement> Apparatus: Kratos AXIS-NOVA X-ray source: AlKα X-ray output: 150 W Emission current: 10 mA Accelerating voltage: 15 kV Measurement area: 300 × 700 μm

[0115] 1-3. Surface Roughness: Using an Atomic Force Microscope (AFM) SPM-9600 manufactured by Shimadzu Corporation, in the online (measurement) mode of the SFM manager software, the surface shape of the low refractive index layer was measured using the samples of the examples and comparative examples prepared in the measurement of 1-1. The measurement conditions are shown below. Subsequently, in the offline (resolution) mode, tilt correction processing was performed to obtain a tonal image with height 0 nm set to black and height 100 nm and above set to white. Furthermore, the lowest point within the measurement range was set to "height 0 nm". The obtained AFM image was analyzed to obtain the Rz (maximum height roughness) and Ra (arithmetic mean roughness) of each sample. The average values ​​of Rz and Rz / Ra at 14 locations were evaluated for each sample. <AFM Measurement Conditions> Measurement Mode: Phase Scan Range: 5 μm × 5 μm Scan Speed: 0.8–1 Hz Pixel Count: 512 × 512 Cantilever Used: Nanoworld NCHR (Resonant Frequency: 320 kHz; Spring Constant: 42 N / m) <AFM Resolution Conditions> Tilt Correction: Linear Fitting

[0116] 1-4. Steel Wool Resistance Test: The antireflective component evaluated in 1-1 was bonded to the base of a vibration abrasion testing machine (manufactured by Tester Sangyo Co., Ltd.; trade name "AB-301") with the low refractive index layer as the upper surface. Steel Wool #0000 (manufactured by Nihon Steel Wool Co., Ltd.; trade name "BONSTAR B-204") was placed in contact with the surface of the low refractive index layer and moved at a speed of 100 mm / s, with a reciprocating distance of 200 mm per cycle (100 mm per single pass), while a load was applied and the steel Wool was moved back and forth 10 times. The contact area between the steel Wool and the low refractive index layer was set to 1 cm2. Furthermore, unless otherwise specified, the test environment was set to a temperature of 23±1℃ and a relative humidity of 50±5%. The aforementioned BONSTAR B-204 has business dimensions of approximately 390 mm in width, approximately 75 mm in length, and approximately 110 mm in thickness. A suitable amount of steel wool was torn off (if cut, the cross-section of the steel wool fibers would protrude, so it was not cut with a knife), and uniformly rolled until there were no unusual steel wool protrusions. Furthermore, it was set that when a load of 1000 g was applied, the thickness of the steel wool was 20 mm with a contact area of ​​1 cm². Subsequently, the number of scratches on each antireflective component was evaluated by visual inspection under fluorescent light (Panasonic Inc. 3-wavelength fluorescent lamp; model: FHF32EX-NH; illuminance on the sample: 800–1200 Lx; observation distance: 30 cm) and under LED lighting (GENTOS Inc. LED lamp; model: TX-850Re; illuminance on the sample: 4000–6000 Lx; observation distance: 30 cm). Steel wool durability is expressed as the maximum load (g / cm²) per unit area when no scratches (0) are observed after the test. For both the examples and comparative examples, tests were conducted with n=2, and the average value was taken as the steel wool resistance of each example and comparative example.

[0117] 1-5. Preparation of Oil Dust Resistance Test: A test solution was prepared by mixing AC dust (ISO12103-1, A2 (fine)) and olive oil (CAS No. 8001-25-0) in a 1:1 (weight ratio). A wiping cloth (manufactured by AS ONE Co., Ltd.; trade name "ASPURE PROPREA II") was folded into 8 layers and securely attached to the front end of a rod-shaped metal component (the end face of the rod is a 1 cm × 1 cm square) using rubber bands. The side of the rod-shaped metal component with the wiping cloth attached was immersed in the above test solution. For the wiping cloth, 5 g of the above test solution was evenly distributed on the end face to obtain a rod-shaped metal component for wiping. The anti-reflective components of the examples and comparative examples were attached to the test stage with a low refractive index layer as the upper surface. The weights were mounted on the aforementioned rod-shaped metal component used for wiping, with the wiping cloth side of the rod-shaped metal component in contact with the surface of the low-refractive-index layer. The weights were moved at a speed of 100 mm / s, with a single reciprocating movement distance of 200 mm (100 mm per pass), and the weights were moved back and forth 10 times. The contact area between the wiping cloth and the low-refractive-index layer was approximately 1 cm², roughly equal to the area of ​​the end face of the rod-shaped metal component. Furthermore, unless otherwise specified, the test environment was set to a temperature of 23 ± 1 °C and a relative humidity of 50 ± 5%. Subsequently, the antireflective components of the embodiments and comparative examples were evaluated by visual observation under fluorescent light (3-wavelength fluorescent lamp manufactured by Panasonic Corporation; model: FHF32EX-NH; illuminance on the sample: 800-1200 Lx; observation distance: 30 cm) and LED lighting (LED lamp manufactured by GENTOS Corporation; model: TX-850Re; illuminance on the sample: 4000-6000 Lx; observation distance: 30 cm) to assess the number of scratches. The load was defined as the weight of a weight, and the maximum load per unit area (g / cm2) when no scratches were observed after the test represented the oil dust resistance. For the embodiments and comparative examples, tests were conducted with n=2, and the average of these tests was used as the oil dust resistance of each embodiment and comparative example.

[0118] 1-6. Anti-fouling property (fingerprint wiping property) A fingertip was pressed against the low-refractive-index layer surface of the anti-reflective member of the embodiment and comparative example to allow fingerprints to adhere. Subsequently, a non-woven fabric (manufactured by Asahi Kasei Corporation; trade name: BEMCOT) was used to wipe away the adhered fingerprints, and the number of times the fingerprint disappeared was evaluated. "A" was defined as fingerprints disappearing after 3 or fewer wipes, "B" was defined as fingerprints disappearing after 4 to 7 wipes, and "C" was defined as fingerprints remaining visible even after 7 wipes.

[0119] 1-7. Indentation Hardness: For the low-refractive-index layers of the anti-reflective components of Examples 1, 6, 8 and Comparative Examples 1, 3-4, load-displacement curves were measured using a TriboIndenter TI950 manufactured by Hysitron under the following conditions. The indentation hardness was obtained from the obtained load-displacement curves using the analytical software (TRIBOSCAN) attached to the device. Measurements were performed on 16 locations for each sample, and analysis was conducted with a sample number n=2. The average of the obtained values ​​was taken as the indentation hardness of each example and comparative example.

[0120] <Indentation Hardness Measurement Conditions> ・Indenter used: Triangular cone indenter (TI-0039) ・Indentation conditions: Displacement control method ・Maximum indentation depth: 30 nm ・Load application time: 3 seconds (speed: 10 nm / sec) ・Holding time: 5 seconds ・Load unloading time: 3 seconds (speed: 10 nm / sec) ・Indentation speed: 10 nm / sec

[0121] 1-8. Resilience Rate: For the low-refractive-index layers of the anti-reflective components of Examples 1, 6, 8 and Comparative Examples 1, 3-4, load-displacement curves were measured using a TriboIndenter TI950 manufactured by Hysitron under the following conditions. The resilience rate was calculated based on the obtained load-displacement curves. Measurements were performed on 16 locations for each sample, and analysis was conducted with a sample size n=2. The average of the obtained values ​​was taken as the resilience rate for each example and comparative example.

[0122] <Recovery Rate Measurement Conditions> ・Indenter used: Triangular cone indenter (TI-0039) ・Indentation conditions: Load control mode ・Maximum load: 30 μN ・Load application time: 3 seconds (speed: 10 μN / sec) ・Holding time: 5 seconds ・Load unloading time: 3 seconds (speed: 10 μN / sec)

[0123] 2. Preparation of Coating Liquid The following coating liquid for forming a hard coating is prepared. <Coating Liquid for Forming a Hard Coating 1> ・Composition containing UV-curable acrylate (manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD PET-30"; solid content 100%) 22 parts by weight ・Composition containing UV-curable acrylate (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.; trade name "New Frontier R-1403MB"; solid content 80%) 17 parts by weight ・Fluorine leveling agent (manufactured by DIC Co., Ltd.; trade name "MEGAFAC F-568") 1 part by weight ・Photopolymerization initiator (manufactured by IGM Resins Co., Ltd.; trade name "Omnirad184") 1 part by weight ・Methyl isobutyl ketone 15 parts by weight ・Methyl ethyl ketone 44 parts by weight

[0124] <Coating Liquid 2 for Hard Coating Formation> ・Reactive silica microparticles (“Z7837” manufactured by JSR Corporation; solid content 50%; product containing 60% reactive silica microparticles) 10 parts by weight ・Acrylic amine ester (“UV1700B” manufactured by Mitsubishi Chemical Corporation) 5.7 parts by weight ・Photopolymerization initiator (manufactured by IGM Resins; trade name “Omnirad184”) 1 part by weight ・Fluorine leveling agent (manufactured by DIC Corporation; trade name “MEGAFAC F-568”) 1 part by weight ・Methyl ethyl ketone 3.3 parts by weight ・Methyl isobutyl ketone 2.3 parts by weight

[0125] Prepare a coating solution for forming a high refractive index layer with the following formulation. <Coating Solution 1 for Forming a High Refractive Index Layer>・PETA (manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD PET-30"; 100% solids content) 0.15 parts by weight・High refractive index particles (manufactured by Nippon Shokubai Co., Ltd.; trade name "ZIRCOSTAR"; 70% solids content) 4.5 parts by weight・Fluorine leveling agent (manufactured by DIC Co., Ltd.; trade name "MEGAFAC F251") 0.01 parts by weight・Photopolymerization initiator (manufactured by IGM Resins Co., Ltd.; trade name "Omnirad 127") 0.14 parts by weight・Methyl isobutyl ketone 47.6 parts by weight・Propylene glycol monomethyl ether 47.6 parts by weight

[0126] <Coating Solution 2 for High Refractive Index Layer Formation> ・PETA (manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD PET-30"; 100% solids content) 0.68 parts by weight ・High refractive index particles (manufactured by Nippon Kayaku Co., Ltd.; trade name "ELCOM V-4564" (containing antimony pentoxide particles); 40.5% solids content) 6.71 parts by weight ・Fluorine leveling agent (manufactured by DIC Co., Ltd.; trade name "MEGAFAC F251") 2.03 parts by weight ・Photopolymerization initiator (manufactured by IGM Resins Co., Ltd.; trade name "Omnirad127") 0.05 parts by weight ・Methyl isobutyl ketone 46.3 parts by weight ・Propylene glycol monomethyl ether 44.23 parts by weight

[0127] <Coating Solution 3 for High Refractive Index Layer Formation>・Ethanol dispersion of ITO microparticles (solid content 20.5 wt%) 20 parts by mass・PETA (manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD PET-30"; solid content 100%) 1 part by mass・ITO dispersing agent (phosphate ester based) 0.1 parts by mass・Photopolymerization initiator (manufactured by IGM Resins Co., Ltd.; trade name "Omnirad184") 0.2 parts by mass・Ethanol (the amount added is adjusted to achieve a solid content concentration of 4% by mass)

[0128] Prepare a coating liquid for forming a low refractive index layer according to the following formulation. <Coating liquid for forming a low refractive index layer 1> Use the following as hollow silica particles and non-hollow silica particles. Tables 1 and 2 show the mixing amount (solid composition) of hollow silica particles and non-hollow silica particles (solid silica particles) when the adhesive resin (solid composition) is set to 100 parts by mass. (1) Hollow silica particles are surface treated with a dispersion of 20% by mass of solid composition and a silane coupling agent with methacrylic group; average particle size 75 nm (2) Non-hollow silica particles are surface treated with a dispersion of 40% by mass of solid silica particles and a silane coupling agent with methacrylic group; average particle size 7 nm or 12.5 nm

[0129] The following are used as adhesive resins. Tables 1 and 2 show the ratio of solid components. (3) Adhesive resins • TEGDA: Polyethylene glycol (n≒4) diacrylate (difunctional acrylate); manufactured by Toa Synthetic Co., Ltd.; trade name "M-240" • PETA: Neopentyl tertetrol (tri / tetra) acrylate; manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD PET-30" • DPHA: Dinepentyl tertetrol (hexa / penta) acrylate; manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD DPHA" • Fluorinated compounds: Fluorinated compounds containing silane units having (meth)acrylic groups, reactive silane units, and perfluoropolyether groups; solid component 20% by mass%; solvent: methyl isobutyl ketone; manufactured by Shin-Etsu Chemical Co., Ltd.; trade name "X-71-1203M"

[0130] The following are used as photopolymerization initiators and leveling agents. Tables 1 and 2 show the ratio of solid components when the adhesive resin (solid component) is set to 100 parts by weight. (4) Photopolymerization initiator: IGM Resins, Inc.; trade name "Omnirad127" 4.3 parts by weight (5) Leveling agent (a) Polysiloxane (Si-1) leveling agent: Shin-Etsu Chemical Co., Ltd.; trade name "KP-420" 13 parts by weight (b) Fluorine leveling agent 1 (F-1): Shin-Etsu Chemical Co., Ltd.; trade name "X-71-1203M" 13 parts by weight (c) Fluorine leveling agent 2 (F-2): DIC Co., Ltd.; trade name "MEGAFAC RS-81" 5 parts by weight

[0131] In Examples 1-8 and Comparative Examples 1-2, methyl isobutyl ketone and 1-methoxy-2-propyl acetate were used as solvents. The mixing ratio was set to methyl isobutyl ketone / 1-methoxy-2-propyl acetate = 68 / 32 (mass ratio). The amount of mixed solvent was set to 14,867 parts by mass relative to 100 parts by mass of adhesive resin (solid component). In Comparative Examples 3-4, methyl isobutyl ketone and 2-methoxy-1-methylethyl acetate were used as solvents. The mixing ratio was set to methyl isobutyl ketone / 2-methoxy-1-methylethyl acetate = 89 / 11 (mass ratio). The amount of mixed solvent was set to 8,667 parts by mass relative to 100 parts by mass of adhesive resin (solid component).

[0132] <Coating liquid 2 for forming low refractive index layer> The following are used as hollow silica particles and non-hollow silica particles. Table 2 shows the mixing amount (solid composition) of hollow silica particles and non-hollow silica particles (solid silica particles) when the adhesive resin (solid composition) is set to 100 parts by mass. (1) Hollow silica particles are surface treated with a dispersion of 20% by mass of solid composition and a silane coupling agent with methacrylic group; average particle size 55 nm (2) Non-hollow silica particles are surface treated with a dispersion of 30% by mass of solid silica particles and a silane coupling agent with methacrylic group; average particle size 12.5 nm

[0133] The following are used as adhesive resins. Table 2 shows the ratio of solid components. (3) Adhesive resins: ・PETA: Neopentyl tert-(tri / tetra) acrylate; manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD PET-30" ・DPHA: Dinepentyl tert-(hexa / pent) acrylate; manufactured by Nippon Kayaku Co., Ltd.; trade name "KAYARAD DPHA"

[0134] The following are used as photopolymerization initiators and leveling agents. Table 2 shows the ratio of solid components when the adhesive resin (solid component) is set to 100 parts by weight. (4) Photopolymerization initiator: IGM Resins, Inc.; trade name "Omnirad127" 10 parts by weight (5) Leveling agent (a) Polysiloxane (Si-2) leveling agent: Shin-Etsu Chemical Co., Ltd.; trade name "X-22-164E" 10 parts by weight

[0135] Methyl isobutyl ketone and propylene glycol monomethyl ether are used as solvents. The mixing ratio is set to methyl isobutyl ketone / propylene glycol monomethyl ether = 60 / 40 (mass ratio). The amount of mixed solvent is set to 5,000 parts by mass relative to 100 parts by mass of adhesive resin (solid component).

[0136] <Coating solution for forming low refractive index layer 3> The following are used as hollow silica particles and non-hollow silica particles. Table 2 shows the mixing amount (solid composition) of hollow silica particles and non-hollow silica particles (solid silica particles) when the film composition (solid composition) is set to 100 parts by mass. (1) Hollow silica particle solid composition 20% by mass isopropanol dispersion; refractive index 1.30; average particle size 60 nm (2) Non-hollow silica particle spherical silica sol (solid silica particles); surface treated with 25% by mass isopropanol dispersion and silane coupling agent with methacrylic acid group; average particle size 10.5 nm

[0137] (3) The following reactive silane is used as the raw material for the membrane component (SiO2): • 3-Methylpropenyloxypropyltrimethoxysilane

[0138] The following are used as photopolymerization initiators. Table 2 shows the ratio of solids content when the film composition (solids content) is set to 100 parts by weight. (4) Photopolymerization initiator manufactured by IGM Resins; trade name "Omnirad369" 8.9 parts by weight

[0139] The coating solution 3 for forming a low refractive index layer is prepared by the following steps. First, a silica particle dispersion, a non-hollow silica particle dispersion, and isopropanol are mixed in a ratio of 20 / 8 / 25 (mass ratio) to obtain a silica particle dispersion. A reactive silane (3-methacryloxypropyltrimethoxysilane) is added dropwise to the silica particle dispersion and mixed. The mixing ratio is set as reactive silane:silica particle dispersion = 100:1432 (mass ratio). While stirring the mixture, a 0.4 M nitric acid aqueous solution is added dropwise to hydrolyze the reactive silane. The above-mentioned photopolymerization initiator and solvent (isopropanol) are added dropwise to the hydrolyzed mixture and mixed to obtain the coating solution 3 for forming a low refractive index layer (solid content concentration 3.5% by mass).

[0140] (Examples 1, 4-7, Comparative Examples 1-2) The hard coating forming liquid 1 of the above formulation was applied to an acrylic film (refractive index 1.50) with a thickness of 80 μm, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (100 mJ / cm²) to form a hard coating (dry thickness 10 μm). The high refractive index layer forming liquid 1 of the above formulation was applied to the hard coating, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (100 mJ / cm²) to form a high refractive index layer (dry thickness 150 nm). The low refractive index layer forming liquid 1 of the formulations shown in Tables 1 and 2 was applied to the high refractive index layer, and then dried at 60°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (200 mJ / cm2) was performed to form a low refractive index layer (dry thickness 100 nm), thereby obtaining the anti-reflection components of Examples 1, 4-7 and Comparative Examples 1-2.

[0141] (Example 2) The drying conditions after applying the coating liquid 1 for forming a low refractive index layer were set to 50°C for 1 minute. Otherwise, each layer was formed under the same conditions as in Example 1 to obtain the anti-reflection component of Example 2.

[0142] (Example 3) The drying conditions after applying the coating liquid 1 for forming a low refractive index layer were set to 100°C for 1 minute. Otherwise, each layer was formed under the same conditions as in Example 1 to obtain the anti-reflection component of Example 3.

[0143] (Example 8) No high refractive index layer is formed. Otherwise, each layer is formed under the same conditions as in Example 1 to obtain the anti-reflection member of Example 8.

[0144] (Comparative Example 3) The hard coating forming liquid 1 of the above formulation was applied to an acrylic film (refractive index 1.50) with a thickness of 80 μm, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (100 mJ / cm²) to form a hard coating (dry thickness 10 μm). The high refractive index layer forming liquid 2 of the above formulation was applied to the hard coating, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (100 mJ / cm²) to form a high refractive index layer (dry thickness 150 nm). The low refractive index layer forming liquid 1 of the formulation shown in Table 2 was applied to the high refractive index layer, and then dried at 60°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (200 mJ / cm²) to form a low refractive index layer (dry thickness 100 nm), thus obtaining the antireflective component of Comparative Example 3.

[0145] (Comparative Example 4) No high refractive index layer is formed. Otherwise, each layer is formed under the same conditions as in Comparative Example 3, and the anti-reflection member of Comparative Example 4 is obtained.

[0146] (Comparative Example 5) The hard coating forming liquid 2 of the above formulation was applied to an acrylic film (refractive index 1.50) with a thickness of 80 μm, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (50 mJ / cm²) to form a hard coating (dry thickness 12 μm). The low refractive index layer forming liquid 2 of the above formulation was applied to the hard coating, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (200 mJ / cm²) to form a high refractive index layer (dry thickness 100 nm). The low refractive index layer forming liquid 2 of the above formulation was applied to the high refractive index layer, and then dried at 60°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (200 mJ / cm²) to form a low refractive index layer (dry thickness 100 nm), thus obtaining the antireflective component of Comparative Example 5.

[0147] (Comparative Example 6) The hard coating forming liquid 1 of the above formulation was applied to an acrylic film (refractive index 1.50) with a thickness of 80 μm, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (100 mJ / cm²) to form a hard coating (dry thickness 10 μm). The high refractive index layer forming liquid 3 of the above formulation was applied to the hard coating, and then dried at 70°C for 2 minutes to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (100 mJ / cm²) to form a high refractive index layer (dry thickness 100 nm). The low refractive index layer forming liquid 3 of the above formulation was applied to the high refractive index layer, and then dried at 60°C for 1 minute to evaporate the solvent. Subsequently, it was irradiated with ultraviolet light (200 mJ / cm²) to form a low refractive index layer (dry thickness 105 nm). Subsequently, a 0.1 wt% solution was obtained by diluting "OPTOOL DSX-E (trademark registered)" manufactured by Daikin Industries, Ltd. with "Demnum Solvent SOL-1" manufactured by Daikin Industries, Ltd. The solution was coated onto a low refractive index layer using a rod coater and heated at 120°C for 1 minute to form a coating layer with a thickness of approximately 2 nm, thereby obtaining the antireflective component of Comparative Example 6.

[0148] (Comparative Example 7) As Comparative Example 7, a commercially available Apple-manufactured MacBook Pro (15-inch; 2016 model) was disassembled, and the anti-reflective component was removed. The surface of the anti-reflective component (the user-side surface) was appropriately cut / trimmed to the evaluation / measurement dimensions, and evaluations and measurements were performed as described in 1-2 to 1-6.

[0149] [Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Low refractive index layer adhesive resin composition TEGDA TEGDA TEGDA TEGDA TEGDA TEGDA PETA TEGDA PETA TEGDA Blending amount (parts by mass) 100 100 100 100 100 80 20 60 40 100 Hollow silicon dioxide particles Blending amount (parts by mass) 200 200 200 200 200 200 200 200 Particle size (nm) 75 75 75 75 75 75 75 75 Solid silicon dioxide particles Blending amount (parts by mass) 117 117 117 117 117 117 117 117 Particle size (nm) 12.5 12.5 12.5 7 12.5 12.5 12.5 12.5 Particle size ratio 0.17 0.17 0.17 0.09 0.17 0.17 0.17 0.17 Low refractive index layer leveling agent Si series Si series Si series Si series F-series -1 Si series Si series Si series Drying temperature of low refractive index layer (°C) 60 50 100 60 60 60 60 60 Refractive index Low refractive index layer 1.33 1.33 1.33 1.33 1.33 1.33 1.33 1.33 High refractive index layer 1.65 1.65 1.65 1.65 1.65 1.65 1.65 - Hard coating 1.57 1.57 1.57 1.57 1.57 1.57 1.57 1.57 Reflectance (visual reflectance Y value) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.5 Element ratio Inorganic Si (atomic%) 13.5 16.8 11.1 11.4 10.8 10.9 10.3 14.7 C (atomic%) 41.2 34.2 40.7 39.9 39.8 40.1 41.0 34.1 F (atomic%) (Not detected) (Not detected) (Not detected) (Not detected) 30.8 (Not detected) (Not detected) (Not detected) Other (atomic%) 45.3 49.0 48.2 48.7 18.6 49.0 48.7 51.2 C / Si (%) 305.2 203.6 366.7 350.0 368.5 367.9 398.1 232.0 Surface roughness Rz (nm) 50.47 49.80 61.92 62.38 59.81 66.24 67.98 50.01 Ra (nm) 6.03 6.12 6.21 6.66 6.12 6.23 6.38 6.19 Rz / Ra 8.38 8.14 9.97 9.37 9.77 10.63 10.66 8.08 Steel wire toughness (g / cm) 2 ) Under fluorescent light 1500 1500 1200 1200 1000 900 800 1500 LED 1000 1000 900 900 700 600 500 1000 Oil dust resistance (g / cm) 2 ) Under fluorescent lights 1500 1500 1200 1200 800 750 700 1500 LED 1000 1000 900 900 500 450 400 1000 Stain resistance A A A A A A A A Nano indentation hardness (MPa) 699.7 - - - - 790.3 - 481.4 Response rate (%) 85.6 - - - - 82.9 - 83.2

[0150] [Table 2] Table 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Low refractive index layer adhesive resin composition PETA DPHA PETA DPHA PETA Fluorine compounds PETA Fluorine compounds PETA DPHA 3-Methylpropenoxypropyltrimethoxysilane - Blending amount (parts by mass) 50 50 50 50 70 30 30 70 50 50 100 - Hollow silicon dioxide particles Blending amount (parts by mass) 200 200 135 130 160 108 - Particle size (nm) 75 75 75 75 55 60 - Solid silicon dioxide particles Blending amount (parts by mass) 117 117 10 10 30 54 - Particle size (nm) 12.5 12.5 12.5 12.5 12.5 10.5 - Particle size ratio 0.17 0.17 0.17 0.17 0.23 0.18 - Low refractive index layer leveling agent Si series F-series -1 F-series -2 F-series -2 Si-series-2 - Drying temperature of low refractive index layer (°C) 60 60 60 60 25→70 60 - Refractive index Low refractive index layer 1.33 1.33 1.33 1.33 1.38 1.38 - High refractive index layer 1.65 1.65 1.65 - - 1.65 - Hard coating 1.57 1.57 1.57 1.57 1.50 1.53 - Reflectance (visual reflectance Y value) 0.3 0.3 0.3 0.5 1.4 0.4 - Element ratio Inorganic Si (atomic%) 9.3 8.2 5.7 5.3 - - 14.8 C (atomic%) 42.1 32.7 36.4 39.5 - - 20.4 F (atomic%) (Not detected) 31.3 33.4 32.1 - - 36.6 Other (atomic%) 48.6 27.8 24.5 23.1 - - 28.2 C / Si (%) 452.7 398.8 638.6 745.3 - - 137.8 Surface roughness Rz (nm) 67.19 65.06 67.70 84.87 - - 64.80 Ra (nm) 6.02 6.02 4.75 6.59 - - 8.57 Rz / Ra 11.17 10.82 14.26 12.88 - - 7.56 Steel wool toughness (g / cm) 2 ) Under fluorescent lights 600 500 300 300 200 500 1500 LED ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 ≤200 Oil dust resistance (g / cm) 2 ) Under fluorescent lights 600 500 200 200 ≤200 ≤200 1500 LED ≤100 ≤100 ≤100 ≤100 ≤100 ≤100 ≤100 Stain resistance A A A A B A A Nano indentation hardness (MPa) 843.8 - 476.9 392.6 - - - Response rate (%) 83.7 - 77.5 71.9 - - -

[0151] According to the results in Table 1, it can be confirmed that the anti-reflective components of Examples 1 to 8, where the Si element ratio is 10.0 atomic% or more and 18.0 atomic% or less, and the C element ratio (C / Si) when the Si element ratio is converted to 100 atomic% is 180 atomic% or more and 500 atomic% or less, exhibit good scratch resistance, such as steel wool resistance and oil dust resistance. As shown in Figure 3, the anti-reflective component of Example 1 is composed of hollow silicon dioxide particles and non-hollow silicon dioxide particles uniformly dispersed in a low refractive index layer.

[0152] In contrast, as shown in Table 2, the antireflective components of Comparative Examples 1 to 7 all have Si element ratios and C / Si ratios that do not meet the above-mentioned ranges, and their scratch resistance, such as steel wool resistance and oil dust resistance, is poor. In the antireflective component of Comparative Example 2 shown in Figure 4, it is believed that because the hollow silicon dioxide particles are exposed on the surface of the low refractive index layer, steel wool or oil dust can easily enter through the gaps between the hollow silicon dioxide particles, thus reducing scratch resistance. Furthermore, in the antireflective component of Comparative Example 5 shown in Figure 5, it is believed that because the non-hollow silicon dioxide particles are exposed on the surface of the low refractive index layer, the non-hollow silicon dioxide particles can easily detach from the film due to scratches, thus reducing scratch resistance.

[0153] Furthermore, although not shown in the table, the anti-reflective components obtained by changing the adhesive composition of the low refractive index layer in Examples 1 to 8 (e.g., a mixture of di-trimethylolpropane tetraacrylate / trimethylolpropane PO modified (n≒2)triacrylate = 23 / 77, etc.) and adjusting the type of solvent and drying temperature to make the ratio of Si and C / Si within the above range also have the same scratch resistance.

[0154] (Examples 9-12) Using the same anti-reflective component as in Example 1, and changing the test environment as described in Table 3, the steel wool resistance test and oil dust resistance test were performed. Other test conditions were set to be the same as those described in 1-4 and 1-5.

[0155] [Table 3] Table 3 Example 1 Example 9 Example 10 Example 11 Example 12 Test environment Temperature (°C) 23±1 16±1 16±1 30±1 30±1 Relative humidity (%) 50±5 30±5 70±5 30±5 70±5 Steel wool toughness (g / cm) 2 ) Under fluorescent lights 1500 1500 1500 1500 1500 LED 1000 1000 1000 1000 1000 Oil dust resistance (g / cm) 2 ) Under fluorescent lights 1500 1500 1500 1500 1500 LED 1000 1000 1000 1000 1000

[0156] Temperatures of 16–30°C and relative humidity of 30–70% are equivalent to the typical operating environment of an image display device equipped with an anti-reflective component. According to the results in Table 3, the anti-reflective component of the present invention exhibits almost no change in steel wool resistance and oil dust resistance even under different operating environments. [Simplified Explanation of the Diagram]

[0015] [Figure 1] is a schematic cross-sectional view illustrating one embodiment of the anti-reflective member of the present invention. [Figure 2] is a schematic cross-sectional view illustrating another embodiment of the anti-reflective member of the present invention. [Figure 3] is a cross-sectional image of the low refractive index layer in Example 1. [Figure 4] is a cross-sectional image of the low refractive index layer in Comparative Example 2. [Figure 5] is a cross-sectional image of the low refractive index layer in Comparative Example 5.

Claims

1. An anti-reflective member comprising a low-refractive-index layer on a transparent substrate, the low-refractive-index layer comprising an adhesive resin, hollow silica particles, and non-hollow silica particles, wherein the average particle size of the hollow silica particles is 50 nm or more and 100 nm or less, the average particle size of the non-hollow silica particles is 5 nm or more and 20 nm or less, the thickness of the low-refractive-index layer is 80 to 120 nm, and X-ray photoelectron spectroscopy analysis shows that the surface depth of the low-refractive-index layer on the side opposite to the transparent substrate is 10 nm. In a region within nm, the ratio of Si to all elements belonging to the aforementioned silicon dioxide particles is 10.0 atomic% or more and 18.0 atomic% or less, the ratio of F to all elements is 0.5 atomic% or less, and the ratio of C to 100 atomic% of the aforementioned Si element is 180 atomic% or more and 500 atomic% or less. When the thickness of the aforementioned low refractive index layer is divided into three equal parts and sequentially defined as a first region, a second region, and a third region from the transparent substrate side, for any part in the aforementioned first region and any part in the aforementioned second region, the following conditions are met: the ratio of Si to all elements belonging to the aforementioned silicon dioxide particles is 10.0 atomic% or more and 18.0 atomic% or less, and the ratio of C to 100 atomic% of the aforementioned Si element is 180 atomic% or more and 500 atomic% or less.

2. As in claim 1, the anti-reflective component, wherein, When the maximum height roughness of the surface of the aforementioned low refractive index layer is defined as Rz, and the arithmetic mean roughness of the surface of the aforementioned low refractive index layer is defined as Ra, Rz is less than 110 nm, Ra is less than 15 nm, and Rz / Ra is less than 22.

0.

3. As in claim 1 or 2, the anti-reflective component, wherein, The ratio of the average particle size of the aforementioned non-hollow silicon dioxide particles to the average particle size of the aforementioned hollow silicon dioxide particles is less than 0.

29.

4. As in claim 1 or 2, the anti-reflective component, wherein, The surfaces of the aforementioned hollow silica particles and the aforementioned non-hollow silica particles are coated with a silane coupling agent.

5. For the anti-reflective member of claim 1 or 2, the indentation hardness of the low refractive index layer obtained by nanoindentation is 480 MPa or higher.

6. For the antireflective member of claim 1 or 2, the recovery rate of the aforementioned low refractive index layer obtained by nanoindentation is 80% or more.

7. As in claim 2, the anti-reflective component, wherein, Rz / Ra is below 10.

66.

8. A polarizing plate having, in sequence, a transparent protective plate, a polarizer and a transparent protective plate, wherein at least one of the two transparent protective plates is an anti-reflection member of any one of claims 1 to 7.

9. An image display device comprising having an anti-reflective member of any one of claims 1 to 7 on a display element.

10. An anti-reflective article comprising having an anti-reflective component of any one of claims 1 to 7 on a component.

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