Anti-reflective member, and polarizing plate, image display device, and anti-reflective article equipped therewith.

Abstract

To provide an antireflection member having low reflectance and improved excoriation resistance, and an image display device including the antireflection member.SOLUTION: An antireflection member 100 includes a low reflective index layer 130 on a transparent base material 110. The low refractive index layer 130 contains a binder resin and silica particles 132 and 134. The ratio of a Si element attributed to the silica particles obtained by analyzing the surface region of the low refractive index layer 130 by X-ray photoelectron spectroscopy is 10.0 atomic% or more and 18.0 atomic% or less, and when the ratio of the Si element is converted to 100 atomic%, the ratio of the C element is 180 atomic% or more and 500 atomic% or less.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to an anti-reflective member, and to a polarizing plate, an image display device, and an anti-reflective article equipped therewith. [Background technology]

[0002] In display devices such as liquid crystal displays, organic EL displays, and micro-LED displays, as well as in showcases, it is known that anti-reflective materials are provided on the surface of the device to improve visibility. In recent years, in addition to televisions, touch-panel image display devices that users operate by directly touching the screen with their hands, such as in-car displays for car navigation systems, tablets, and smartphones, have become widespread, and anti-reflective materials are also provided on these devices.

[0003] Methods for manufacturing anti-reflective materials include laminating inorganic thin films with different refractive indices as anti-reflective layers on a hard coat layer provided on a transparent substrate by dry deposition methods such as sputtering, and forming an anti-reflective layer by coating a hard coat layer with a resin containing fine particles. Generally, anti-reflective materials with a resin layer have advantages over those with an inorganic thin film, such as smaller changes in oblique reflection hue, superior chemical stability (especially alkali resistance), and lower cost. On the other hand, anti-reflective materials with a resin layer tend to have inferior mechanical properties such as scratch resistance and higher reflectivity compared to those with an inorganic thin film.

[0004] To address these challenges, for example, Patent Documents 1 and 2 describe incorporating hollow inorganic nanoparticles such as silica and solid inorganic nanoparticles into a low refractive index layer. Furthermore, the solid inorganic nanoparticles are unevenly distributed on the interface side with the hard coat, while the hollow inorganic nanoparticles are unevenly distributed on the opposite side of the interface. This achieves both high scratch resistance and low reflectivity.

[0005] In Patent Document 3, it is disclosed that by causing reactive silica fine particles in a low refractive index layer to be unevenly distributed at the interface on the hard coat layer side and / or the interface on the side opposite to the hard coat layer and making the hollow silica fine particles densely packed in the low refractive index layer, the surface hardness (scratch resistance) can be improved.

[0006] In Patent Document 4, it is disclosed that an antireflection film in which hollow silica fine particles and fine silica particles are dispersed in a binder mainly composed of reactive silanes is formed on an optical substrate.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Disclosure of the Invention

Problems to be Solved by the Invention

[0008] [[ID=​​​​​​ In view of the above-mentioned problems, the present invention aims to provide an anti-reflective member having low reflectivity and improved scratch resistance, an anti-reflective member, and a polarizing plate, an image display device, and an anti-reflective article equipped therewith. [Means for solving the problem]

[0011] The inventors have discovered that even if scratches are not visible when rubbing the surface of a resin layer with only fine solid matter (e.g., sand) or only oil, scratches can be made on the resin layer surface when rubbing it with an object containing solid matter and oil. This is equivalent to, for example, a user operating a touch-panel image display device with fingers that have oil contained in cosmetics and food products, as well as sand contained in the atmosphere, on them.

[0012] As a result of the inventors' investigation, they found that the aforementioned scratches mainly occur when a portion of the hollow silica particles contained in the low refractive index layer is chipped or when the hollow silica particles fall off. The cause of this is thought to be the large irregularities caused by the hollow silica particles formed on the surface of the low refractive index layer. In other words, when the surface of the low refractive index layer is rubbed with a finger that has oil containing solid matter such as sand attached to it, the oil acts as a binder, and the solid matter remains attached to the finger as the finger moves across the surface of the low refractive index layer. At this time, it is easy for a portion of the solid matter (for example, a sharp part of the sand) to get stuck in the depressions of the surface of the low refractive index layer, and for the solid matter that has gotten stuck in the depressions to pass through the depressions with the finger and go over the protrusions (hollow silica particles). It is thought that a large force is applied to the protrusions (hollow silica particles) at this time, causing the hollow silica particles to be damaged or fall off. Furthermore, it is thought that the resin itself located in the depressions is also scratched by friction from the solid matter, and that the damage makes the hollow silica particles more likely to fall off. Therefore, the inventors diligently researched methods to solve the above problems and were able to obtain an anti-reflective member with a smooth surface, low reflectivity, and excellent surface resistance such as high scratch resistance, thus completing the present invention.

[0013] To solve the above problems, the present invention provides the following [1] to

[12] . [1] An anti-reflective member comprising a low refractive index layer on a transparent substrate, wherein the low refractive index layer comprises a binder resin and silica particles, and the ratio of Si elements belonging to the silica particles, obtained by analyzing the surface region of the low refractive index layer by X-ray photoelectron spectroscopy, is 10.0 atomic% or more and 18.0 atomic% or less, and the ratio of C elements when the ratio of Si elements is converted to 100 atomic% is 180 atomic% or more and 500 atomic% or less. [2] The anti-reflective member according to [1], wherein the silica particles are hollow silica particles and non-hollow silica particles. [3] The anti-reflective member according to [2], wherein the ratio of the average particle diameter of the non-hollow silica particles to the average particle diameter of the hollow silica particles is 0.29 or less. [4] The anti-reflective member according to [2] or [3], wherein the average particle diameter of the hollow silica particles is 50 nm or more and 100 nm or less, and the average particle diameter of the non-hollow silica particles is 5 nm or more and 20 nm or less. [5] The anti-reflective member according to 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] The anti-reflective member according to [1], wherein the surface region of the low refractive index layer substantially does not contain fluorine atoms. [7] The anti-reflective member according to any one of [1] to [6], wherein the indentation hardness of the low refractive index layer by nanoindentation method is 480 MPa or more. [8] The anti-reflective member according to any one of [1] to [7], wherein the restoration rate of the low refractive index layer by nanoindentation is 80% or more. [9] The anti-reflective member according to 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 this order, wherein at least one of the two transparent protective plates is an anti-reflective member as described in any one of items [1] to [9].

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

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

[0014] According to the present invention, an anti-reflective member can be obtained that has a low reflectivity and excellent surface resistance, such as scratch resistance. [Brief explanation of the drawing]

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

[0016] The anti-reflective member of the present invention will be described in detail below. In this specification, the numerical range "AA~BB" means "AA or higher and BB or lower".

[0017] [Anti-reflective material] The anti-reflective member of the present invention is an anti-reflective member comprising a low refractive index layer on a transparent substrate, wherein the low refractive index layer comprises a binder resin and silica particles, and the ratio of Si elements belonging to the silica particles, obtained by analyzing the surface region of the low refractive index layer by X-ray photoelectron spectroscopy, is 10.0 atomic% or more and 18.0 atomic% or less, and the ratio of C elements when the ratio of Si elements is converted to 100 atomic% is 180 atomic% or more and 500 atomic% or less. The above silica particles preferably include hollow silica particles and non-hollow silica particles.

[0018] Figure 1 is a schematic cross-sectional view illustrating one embodiment of the anti-reflective member of the present invention. The anti-reflective member 100 in Figure 1 is constructed by laminating a hard coat layer 120 and a low refractive index layer 130 in that order on one surface of a transparent substrate 110. The low refractive index layer 130 contains hollow silica particles 132 and non-hollow silica particles 134 as silica particles.

[0019] Figure 2 is a schematic cross-sectional view illustrating another embodiment of the anti-reflective member of the present invention. The anti-reflective member 200 in Figure 2 has a high refractive index layer 140 between a hard coat layer 120 and a low refractive index layer 130. The high refractive index layer 140 contains inorganic fine particles 142 having a high refractive index.

[0020] [Physical properties of anti-reflective materials] <Optical properties> The anti-reflective member of the present invention preferably has a luminous reflectance Y value of 1.0% or less, and more preferably 0.5% or less, measured at a light incidence angle of 5 degrees from the side having the low refractive index layer. In this specification, the luminous reflectance Y value refers to the luminous reflectance Y value of the CIE1931 standard color system. The luminous reflectance Y value can be calculated using a spectrophotometer (for example, a Shimadzu Corporation product, "UV-3600plus"). Generally, the luminous reflectance Y value of an anti-reflective material (hereinafter referred to as "dry anti-reflective material") formed by sputtering a 4 or 5-layer film is 0.5% or less. The anti-reflective material of the present invention exhibits a low reflectance comparable to that of a dry anti-reflective material. Furthermore, the anti-reflective member of the present invention exhibits a smaller change in luminous reflectance when the angle of incident light is increased compared to the dry anti-reflective member. In other words, the change in oblique reflection hue is smaller.

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

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

[0023] <Elemental analysis of the surface region of the low refractive index layer> When the surface of the low refractive index layer of the anti-reflective member of the present invention is analyzed by X-ray photoelectron spectroscopy (hereinafter simply referred to as "XPS"), at least C, O, and Si elements are detected. The Si element originates from silica particles (inorganic component) and organic components such as silane coupling agents and leveling agents. The C element originates from the binder resin, the surface treatment agent for the silica particles (silane coupling agent), and additives. However, considering the content within the low refractive index layer, the C element can be considered to originate substantially from the binder resin.

[0024] Analysis by XPS revealed that the surface region of the low refractive index layer of the present invention has a Si element ratio attributable to silica particles of 10.0 atomic% to 18.0 atomic%, and the C element ratio, when the Si element ratio is converted to 100 atomic%, is 180 atomic% to 500 atomic%. In this invention, the "surface region" refers to the area within the detection range by X-ray photoelectron spectroscopy, and represents the region from the side opposite the hard coat layer of the low refractive index layer to a depth of 10 nm. The ratio of C element when the ratio of Si element is converted to 100 atomic percent can be calculated as "C / Si × 100 (%)". Hereafter, the ratio of C element when the ratio of Si element is converted to 100 atomic percent may be abbreviated as "C / Si". Furthermore, since the Si considered in this invention is the inorganic Si element belonging to silica particles, unless otherwise specified, Si refers to the inorganic Si element.

[0025] The 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 unevenly distributed on the side opposite the surface of the low refractive index layer (the hard coat layer side), the proportion of Si element attributed to the silica particles in the surface region is low, and the proportion of C element is relatively high. A similar trend is observed when silica particles are embedded in the binder resin and hardly present on the surface of the low refractive index layer. When silica particles (especially hollow silica particles) are exposed on the surface of the low refractive index layer without being covered by the binder resin, the proportion of Si element attributed to the silica particles increases, and the proportion of C element decreases relatively.

[0026] The ratio of Si elements belonging to silica particles in the surface region of the low refractive index layer reflects the presence of non-hollow silica particles and hollow silica particles in that surface region. Even if hollow silica is abundant in the surface region of the low refractive index layer, it does not significantly contribute to increasing the ratio of Si elements belonging to silica particles because it is hollow. However, if non-hollow silica is abundant in the surface region, the ratio of Si elements belonging to silica particles increases. When a sufficient amount of silica particles is present in the surface region of the low refractive index layer, the ratio of Si elements belonging to silica particles in the surface region of the low refractive index layer satisfies 10.0 atomic percent or more. In particular, a ratio of Si elements belonging to silica particles of 13.0 atomic percent or more is preferable because it results in a high concentration of non-hollow silica particles on the surface side, improving scratch resistance. On the other hand, if the ratio of Si elements belonging to silica particles exceeds 18.0 atomic percent, not only non-hollow silica but also hollow silica particles become abundant in the surface region and are exposed on the surface, which causes a decrease in scratch resistance as described later. Furthermore, the presence of a sufficient amount of silica particles in the surface region of the low refractive index layer ensures that the C / Si ratio is 500 atomic% or less. If the C / Si ratio exceeds 500 atomic%, the silica particles become embedded in the binder resin, resulting in an excess of binder resin in the surface region and insufficient scratch resistance. On the other hand, if the C / Si ratio is less than 180 atomic%, the amount of silica particles present on the surface increases, and hollow silica particles not covered by the binder resin become exposed on the surface, causing a decrease in scratch resistance. Considering 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 400 atomic% or less, and more preferably 350 atomic% or less.

[0027] By setting the ratio of C element and Si element in the surface region of the low refractive index layer within the above range, it is possible to coat the hollow silica particles with an appropriate amount of binder resin while ensuring that a sufficient amount of non-hollow silica particles are present in the gaps between the hollow silica particles. This makes it possible to obtain an anti-reflective material that has a smoother surface on the low refractive index layer, low reflectivity, and excellent surface resistance such as high scratch resistance.

[0028] Furthermore, as shown in Patent Document 4, when a low refractive index layer is formed using reactive silanes as a binder material, the C / Si ratio becomes very small. In other words, the C / Si ratio differs between a low refractive index layer using reactive silanes as a binder material and a low refractive index layer using resin as a binder material. In the case of a low refractive index layer using reactive silanes as a binder material, scratch resistance and other properties deteriorate due to the influence of the binder component. Therefore, it can be said that 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 member with excellent surface resistance, such as high scratch resistance, can be obtained.

[0029] Furthermore, even if the coating solution for forming the low refractive index layer does not contain fluorine-containing compounds such as fluorine-based leveling agents, fluorine may be detected on the surface of the formed low refractive index layer. This is because fluorine-based leveling agents are contained in the hard coat layer that forms the base layer of the low refractive index layer, and in the layers below such as the high refractive index layer described later. During the formation of the low refractive index layer, the fluorine-based leveling agent diffuses through the low refractive index layer and migrates to the surface of the low refractive index layer. In the anti-reflective member of the present invention, it is preferable that even if a fluorine-based leveling agent (fluorine-containing compound) is included in the lower layer, element F is not detected by XPS. In other words, it is preferable that the surface region of the low refractive index layer substantially does not contain fluorine atoms. If a fluorine-containing compound is present in the surface region, scratches may easily occur in the binder resin itself, and hollow silica particles may easily fall off, depending on the processing conditions. That is, in such cases, the presence of a fluorine-containing compound in the low refractive index layer causes a decrease in scratch resistance. This is presumed to be because the fluorine-containing compound itself is soft, which reduces the hardness of the binder resin itself. By having the low refractive index layer exhibit the above elemental ratio and containing silica particles at a high concentration relative to the binder resin, the diffusion of the fluorine-containing compound can be suppressed, making it easier to achieve a state in which the surface region substantially does not contain fluorine atoms. In this specification, "substantially does not contain fluorine atoms" means that the ratio of element F in the surface region is 0.5 atomic% or less, more preferably 0.1 atomic% or less.

[0030] The anti-reflective member of the present invention also exhibits the effect of having high gas barrier properties (water vapor permeability, oxygen gas permeability) due to the above-mentioned elemental ratio in the surface region of the low refractive index layer.

[0031] <Dispersion state of silica particles> To achieve the elemental ratios described above, it is preferable that hollow silica particles and non-hollow silica particles are uniformly dispersed in the low refractive index layer of the anti-reflective member of the present invention. In the present invention, "uniformly dispersed" means that the hollow silica particles and non-hollow silica 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, when XPS analysis is performed in the thickness direction of the low refractive index layer, it is preferable that the ratio of Si elements and C / Si attributed to the silica particles satisfy the above-mentioned range at different locations in the thickness direction. For example, when the thickness of the low refractive index layer is divided into three equal parts and defined as the first region, second region, and third region in order from the transparent substrate side, it is preferable that the ratio of Si elements attributed to the silica particles and C / Si satisfy the above-mentioned range at 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 Example 1 of the present invention, observed using a transmission electron microscope (TEM). In the low refractive index layer of the present invention, non-hollow silica particles (solid silica particles) are present in large quantities along with the binder resin not only at the interface between the low refractive index layer and the hard coat layer, but also on the surface of the low refractive index layer (the side opposite the hard coat layer). Multiple hollow silica particles are arranged in the thickness direction. From the image in Figure 3, it can be 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 protrusion from the surface of the low refractive index layer of the hollow silica particles is small and that they are coated with the binder 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 of the low refractive index layer in the anti-reflective material of Comparative Example 2, observed using a transmission electron microscope. In Figure 4, it can be seen that non-hollow silica particles (solid silica particles) are densely concentrated and unevenly distributed at the interface between the low refractive index layer and the hard coat layer. Furthermore, it can be seen that the hollow silica particles protrude significantly from the surface of the low refractive index layer and are exposed without being covered by the binder resin. Figure 5 is a cross-sectional image of the low refractive index layer of the anti-reflective material of Comparative Example 5, observed using a scanning electron microscope (SEM). In Figure 5, it can be seen that non-hollow silica particles (solid silica particles) are densely and unevenly distributed on the surface of the low refractive index layer.

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

[0035] <Scratch resistance> The low refractive index layer of the anti-reflective member of the present invention exhibits excellent scratch resistance, including resistance to steel wool and oil dust. Generally, pencil hardness is known as an index to represent the scratch resistance of the surface of optical components such as anti-reflective materials. However, pencil hardness evaluates resistance when a hard material comes into contact with a stress close to a point load. On the other hand, repeated friction and prolonged use cause many minute scratches due to the gentle application of surface load. It is appropriate to evaluate resistance to such scratches using steel wool resistance and oil dust resistance, which are different indices from pencil hardness.

[0036] In this invention, steel wool resistance is defined as the maximum load at which no scratches are visible to the naked eye (zero scratches) after rubbing the surface of the low refractive index layer with steel wool while applying a load under the following conditions, and observing while changing the angle between the light-emitting part and the object. Observations are performed under fluorescent lamps (illuminance: 200-2000 Lx, for example, Panasonic Corporation's 3-wavelength fluorescent lamp, model number: FHF32EX-NH) and LED lighting (illuminance: 100-8000 Lx, for example, Ohm Electric Co., Ltd., model number: LPL-48N), with the distance from the light-emitting part to the object being 10 cm to 300 cm. The contact area of ​​the steel wool with the object (low refractive index layer surface) is 0.5 to 1.5 cm².2 It shall be within the range. The shape of the surface where the steel wool contacts the object can be circular, triangular, polygonal, etc., but a circular shape is preferred. In the test, the steel wool is moved at a one-way moving distance of 30 mm or more (a moving distance of 60 mm or more in one round trip) at the same location. The one-way moving distance is appropriately set according to the size of the device to which the antireflection member is applied. <Test Conditions> Steel wool: Manufactured by Nippon Steel Wool Co., Ltd., product name: Bonster, product number: #0000 Moving speed: 100 mm / second Number of reciprocations: 10 times

[0037] The steel wool resistance of the low refractive index layer of the antireflection member of the present invention is preferably 750 g / cm or more under a fluorescent lamp, 2 more preferably 900 g / cm or more, 2 even more preferably 1000 g / cm or more, 2 still more preferably 1200 g / cm or more, 2 and particularly preferably 1200 g / cm or more. Also, the steel wool resistance of the low refractive index layer is preferably 450 g / cm or more under an LED, 2 more preferably 500 g / cm or more, 2 even more preferably 600 g / cm or more, 2 still more preferably 600 g / cm or more, 2 and particularly preferably 700 g / cm or more. The steel wool resistance of the antireflection member manufactured by the conventional wet method is 700 g / cm or less under a fluorescent lamp, 2 200 g / cm or less (minimum inspection load) under an LED, 2 (Minimum inspection load) or less. In the case of a commercially available dry antireflection member (a fluorine-based coating film is laminated on a 5-layer sputtered film with SiO2 as the outermost layer), the steel wool resistance is about 1500 g / cm under a fluorescent lamp, 2 but 200 g / cm or less under an LED, 2It is below the (minimum inspection load). In other words, the anti-reflective member of the present invention has higher steel wool resistance than anti-reflective members manufactured by the conventional wet method, and in evaluation under fluorescent lighting, it can achieve excellent steel wool resistance equivalent to that of dry anti-reflective members. Furthermore, the anti-reflective member of the present invention has better steel wool resistance than dry anti-reflective members in evaluation under LED lighting.

[0038] In the anti-reflective member of the present invention, the low refractive index layer has a small amount of hollow silica particles exposed on the surface and is coated with a binder resin. Furthermore, because non-hollow silica particles are present at a high concentration in the binder resin in the surface region, the hardness of the binder resin itself is increased, and because the non-hollow silica particles are uniformly dispersed in the binder resin, it is thought that uneven shrinkage during resin curing is suppressed, resulting in a smoother surface. For this reason, it can be inferred that when the low refractive index layer of the present invention is rubbed with steel wool, damage to or shedding of hollow silica particles and damage to the binder resin itself can be suppressed.

[0039] The oil dust resistance test is a test in which a cloth or rag is soaked with a mixture of AC dust and olive oil as specified in ISO 12103-1, and the surface of the object is rubbed with the mixture to determine the resulting abrasion marks. As the AC dust, Fine (A2), Coarse (A4), or a mixture of Fine (A2) and Coarse (A4) can be used. In this invention, oil dust resistance is defined as the maximum load at which no scratches are observed on the low refractive index layer (zero scratches) after rubbing the surface of the low refractive index layer with a cloth or rag soaked in the mixture while applying a load under the following conditions. Observations are performed under fluorescent lamps (illuminance: 200~2000 Lx) and LEDs (illuminance: 100~8000 Lx), with a distance of 10 cm to 300 cm from the light source to the object. The oil dust resistance test is performed by attaching a cloth or rag to the end of a metal component, soaking it in the mixed liquid, and then moving the cloth or rag in contact with the object. The shape of the contact surface between the end of the metal component and the object (low refractive index layer surface) can be a triangle, polygon, circle, etc., but a square is preferred. The contact surface area is 0.5 to 1.5 cm². 2 It is preferable that the range is within this range. In the test, the cloth or rag is moved at the same location for a distance of 30 mm or more, and for a round trip distance of 60 mm or more. The one-way travel distance is set appropriately depending on the size of the device to which the anti-reflective material is applied. <Test Conditions> Traveling speed: 100mm / sec Number of round trips: 10

[0040] The low refractive index layer of the anti-reflective member of the present invention has an oil dust resistance of 700 g / cm³ under fluorescent light. 2 Preferably, it is 750 g / cm³ or more. 2 It is more preferable that it be greater than or equal to 800 g / cm³. 2 It is even more preferable that the amount be greater than or equal to 1200 g / cm³. 2 The above is particularly preferable. The low refractive index layer of the anti-reflective member in the present invention has an oil dust resistance of 400 g / cm³ under LED lighting. 2 Preferably, it is 450 g / cm³ or more. 2 It is more preferable that it be greater than or equal to 500 g / cm³. 2 It is even more preferable that the amount be greater than or equal to 900 g / cm³. 2 It is especially preferable that the above conditions are met. In anti-reflective materials manufactured using the conventional wet method, the oil dust resistance is 200 g / cm³ under fluorescent lighting. 2 Approximately 100g / cm² under LED lighting. 2 It is below the (minimum inspection load). In the case of commercially available dry anti-reflective material (a fluorine-based coating film laminated on a 5-layer sputtered film with an outermost layer of SiO2), the oil dust resistance evaluated under fluorescent light is 1500 g / cm². 2 On the other hand, the oil dust resistance when evaluated under LED light was 100 g / cm³. 2It is below the (minimum inspection load). In other words, the anti-reflective material of the present invention has superior oil dust performance compared to conventional anti-reflective material manufactured by the wet method, both in evaluation under fluorescent lights and LEDs. Furthermore, the anti-reflective material of the present invention has excellent oil dust resistance equivalent to that of conventional dry anti-reflective material under fluorescent lights, and furthermore, in evaluation under LEDs, it has superior oil dust resistance compared to conventional dry anti-reflective material.

[0041] <Surface roughness> In the present invention, the low refractive index layer is preferably a smooth surface in order to obtain excellent surface resistance. The maximum height roughness Rz should be 110 nm or less, preferably 100 nm or less, and more preferably 90 nm or less. Furthermore, a smoother surface is preferable to obtain even better surface resistance, so it is preferable to be 70 nm or less, and more preferably 60 nm or less. In addition, Rz / Ra (where Ra is the arithmetic mean roughness) is preferably 22.0 or less, more preferably 18.0 or less, even more preferably 16.0 or less, and even more preferably 12.0 or less. In the present invention, Ra and Rz are three-dimensional extensions of the two-dimensional roughness parameters described in the Scanning Probe Microscope SPM-9600 Upgrade Kit Instruction Manual (SPM-9600 February 2016, pp. 194-195). Ra and Rz are defined as follows. (Arithmetic mean roughness Ra) When a reference length (L) is extracted from the roughness curve in the direction of its mean line, and the X-axis is drawn in the direction of the mean line of this extracted portion and the Y-axis in the direction of the vertical scaling, and the roughness curve is represented as y=f(x), it can be calculated using the following formula.

number

[0042] A small Rz value means that the protrusions caused by hollow silica particles in the micro-region are small. Furthermore, a small Rz / Ra ratio means that the unevenness caused by silica particles in the micro-region is uniform and does not have protruding irregularities relative to the average elevation difference of the unevenness. In this invention, the value of Ra is not particularly limited, but Ra should be 15 nm or less, and more preferably 12 nm or less. Moreover, to obtain even better surface resistance, it is preferable to have Ra of 10 nm or less, and more preferably 6.5 nm or less. By exhibiting the above elemental ratios in the low refractive index layer, a sufficient amount of non-hollow silica particles are present in the binder between the hollow silica particles, and the hollow silica particles can exist in the surface region coated with the binder resin without protruding to the surface, thereby suppressing uneven shrinkage of the low refractive index layer. This makes it easier to satisfy the above ranges of Rz and Rz / Ra. The Rz of the surface of the low refractive index layer may increase to approximately 90-110 nm depending on the processing conditions of the low refractive index layer. In that case, if the Rz / Ra is within the above range, it is easier to obtain desirable surface resistance.

[0043] Because the Rz and Rz / Ra of the low refractive index layer surface are within the above range, the resistance when solid objects overcome the protrusions on the low refractive index layer surface (caused by hollow silica particles present near the surface) can be reduced. Therefore, even when rubbed with AC dust containing oil under load, the solid objects are thought to move smoothly across the low refractive index layer surface. Furthermore, the hardness of the recesses themselves is also thought to have increased. As a result, it can be inferred that damage and detachment of the hollow silica particles are prevented, and damage to the binder resin itself is also prevented.

[0044] On the other hand, if the Rz and Rz / Ra on the surface of the low refractive index layer are too small, blocking may occur during the manufacturing process. For this reason, Rz is preferably 30 nm or higher, and more preferably 70 nm or higher. Furthermore, Rz / Ra is preferably 3.0 or higher, and more preferably 5.0 or higher.

[0045] <Indentation hardness, recovery rate> In the present invention, the low refractive index layer preferably has an indentation hardness of 480 MPa or higher, as measured by nanoindentation. Furthermore, the low refractive index layer preferably has a recovery rate of 80% or higher, as measured by nanoindentation. By satisfying the above ranges for indentation hardness and recovery rate, a low refractive index layer with excellent resistance to both steel wool and oil dust can be obtained.

[0046] Indentation hardness and recovery rate are influenced by the layers below the low refractive index layer (on the transparent substrate side). In this invention, by providing a hard coat layer below the low refractive index layer, and further providing a high refractive index layer between the low refractive index layer and the hard coat layer, the indentation hardness and recovery rate can be improved.

[0047] Considering steel wool resistance and oil dust resistance, 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] Considering steel wool resistance and oil dust resistance, the recovery rate is preferably 82% or higher, more preferably 83% or higher, and even more preferably 85% or higher.

[0049] Furthermore, the product of indentation hardness and recovery rate ([indentation hardness] × [recovery rate] ÷ 100) serves as 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 the present invention, this product is preferably 380 MPa or more, more preferably 410 MPa or more, and even more preferably 460 MPa or more. Also, this product is preferably 1000 MPa or less, more preferably 950 MPa or less, and even more preferably 900 MPa or less.

[0050] In this invention, "indentation hardness" refers to a value measured and analyzed using a surface film property tester (Triboindenter TI950, manufactured by HYSITRON) by the nanoindentation method. The measurement is performed by pressing a Berkovich indenter (material: diamond triangular pyramidal) into the surface of the low refractive index layer under the following conditions. For the measurement, the surface irregularities of the low refractive index layer are 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: Berkovich indenter (model number: TI-0039, manufactured by HYSITRON) • Pushing conditions: Displacement control method • Maximum indentation depth: 30nm • Load application time: 3 seconds (speed: 10 nm / sec) • Holding time: 5 seconds • Load unloading time: 3 seconds (speed: 10 nm / sec)

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

[0053] From the acquired load-displacement curve data, the total deformation work W total , and the work of elastic deformation W elast Calculate the total deformation work W. total It can be expressed by the following formula. W total =W elast +W plast W plast : Work done by plastic deformation W total and W elast Therefore, the recovery rate (elastic recovery rate) is calculated using the following formula. Recovery rate [%] = (W elast / W total ) × 100

[0054] In this specification, optical properties, elemental ratios, surface roughness, indentation hardness, and recovery rates refer to the average values ​​of 14 measurements, excluding the minimum and maximum values ​​of 16 measurements, unless otherwise specified. In this specification, it is preferable that the 16 measurement points described above be measured at 16 points where lines are drawn to divide the area inside the outer edge of the measurement sample into five equal parts vertically and horizontally, with a margin of 0.5 cm from the outer edge of the measurement sample. For example, if the measurement sample is a rectangle, it is preferable to measure at 16 points where dotted lines are drawn to divide the area inside the margin of the rectangle into five equal parts vertically and horizontally, with a margin of 0.5 cm from the outer edge of the rectangle, and calculate the parameter using the average value. If the measurement sample is a shape other than a rectangle, such as a circle, ellipse, triangle, or pentagon, it is preferable to draw a rectangle inscribed in this shape and perform 16 measurements on the rectangle using the method described above.

[0055] In this specification, optical properties, surface roughness, indentation hardness, and recovery rate shall be values ​​measured at a temperature of 23±5°C and a relative humidity of 40-65%, unless otherwise specified. Furthermore, before commencing each measurement and evaluation, the target sample shall be exposed to the above atmosphere for at least 30 minutes. For elemental analysis, the target sample shall also be exposed to the above atmosphere for at least 30 minutes before commencing the measurement.

[0056] The following describes the conditions for obtaining the anti-reflective member of the present invention. [Transparent base material] The transparent substrate serves as a support for the hard coat layer and the low refractive index layer. The transparent substrate is preferably one with high light transmittance. Specifically, it is preferable to have a total light transmittance of 90% or more, in accordance with JIS K7361-1:1997.

[0057] Examples of transparent substrates include plastics and glass. Plastic is more preferable as the transparent substrate because it is lightweight and easy to manufacture.

[0058] The plastic substrate can be formed from one or more of the following: polyolefin resins such as polyethylene and polypropylene; vinyl 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(meth)acrylate and poly(meth)acrylate; styrene resins such as polystyrene; polyamide resins such as nylon 6 or nylon 66; cellulose resins such as triacetylcellulose; resins such as polycarbonate; polyimide resins; and cycloolefin resins obtained from cycloolefins such as norbornene and dicyclopentadiene.

[0059] The thickness of the plastic substrate is not particularly limited. From the viewpoint of ease of handling, 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 be in the form of a plate with a thickness exceeding 500 μm. When flexibility is required, such as for foldable applications, the thickness of the plastic substrate is preferably 10 to 40 μm in order to thin the anti-reflective member. Furthermore, if glass is used in the part to which the anti-reflective member is attached, the thickness of the plastic substrate is preferably 40 to 100 μm from the viewpoint of preventing glass from shattering.

[0060] [Low refractive index layer] The low refractive index layer is a layer with a lower refractive index than the transparent substrate. Furthermore, when the anti-reflective material is incorporated into an image display device, the low refractive index layer is located on the opposite side from the display elements (e.g., liquid crystal display elements, EL display elements). The low refractive index layer comprises a binder resin, hollow silica particles, and non-hollow silica particles.

[0061] <Binder resin> The binder resin includes cured products of curable resin compositions such as thermosetting resin compositions or ionizing radiation-curable resin compositions. Among these, cured products of curable resin compositions are preferred from the viewpoint of scratch resistance. Examples of curable resin compositions include thermosetting resin compositions and ionizing radiation-curable resin compositions, with ionizing radiation-curable resin compositions being preferred from the viewpoint of scratch resistance. In other words, it is optimal for the binder resin to include cured products of ionizing radiation-curable resin compositions.

[0062] A thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that hardens upon heating. Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea-melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. A curing agent is added to these thermosetting resin compositions as needed.

[0063] An ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as "ionizing radiation-curable compound"). Examples of ionizing radiation-curable functional groups include ethylenically unsaturated bonding groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, as well as epoxy groups and oxetanyl groups. It is preferable that the ionizing radiation-curable compound has two or more ionizing radiation-curable functional groups. As ionizing radiation-curable compounds, compounds having an ethylenically unsaturated bonding group are preferred. Among these, (meth)acrylate compounds having a (meth)acryloyl group are more preferred. Hereinafter, (meth)acrylate compounds having four or more ethylenically unsaturated bonding groups will be referred to as "polyfunctional (meth)acrylate compounds." Conversely, (meth)acrylate compounds having two to three ethylenically unsaturated bonding groups will be referred to as "low-functional (meth)acrylate compounds."

[0064] As the (meth)acrylate compound, either monomers or oligomers can be used. In particular, from the viewpoint of suppressing uneven shrinkage during curing and making it easier to smooth the uneven surface of the low refractive index layer, it is even more preferable that the ionizing radiation-curable compound contains a low-functional (meth)acrylate compound. Furthermore, the proportion of the low-functional (meth)acrylate compound in the ionizing radiation-curable compound is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass. Furthermore, from the viewpoint of suppressing uneven shrinkage during curing and making it easier to smooth the uneven surface of the low refractive index layer, it is preferable that the low-functional (meth)acrylate compound is a (meth)acrylate compound having two ethylenically unsaturated bonding groups. Even when the ionizing radiation-curable compound contains a large amount of polyfunctional (meth)acrylate compounds, the uneven surface shape of the low refractive index layer can be easily smoothed by appropriately adjusting the type of solvent and drying conditions, as described later.

[0065] Among (meth)acrylate compounds, examples of difunctional (meth)acrylate compounds include isocyanuric acid di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, polyalkylene glycol di(meth)acrylate such as polybutylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate. Examples of polyfunctional (meth)acrylate compounds with four or more functions include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol tetra(meth)acrylate. These (meth)acrylate compounds may be modified as described later.

[0066] Furthermore, examples of (meth)acrylate oligomers include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. Urethane (meth)acrylates can be obtained, for example, by the reaction of polyhydric alcohols and organic diisocyanates with hydroxy(meth)acrylates. Furthermore, preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting trifunctional or higher aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with (meth)acrylic acid; (meth)acrylates obtained by reacting bifunctional or higher aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with polybasic acids and (meth)acrylic acid; and (meth)acrylates obtained by reacting bifunctional or higher aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with phenols and (meth)acrylic acid.

[0067] Furthermore, the above (meth)acrylate compounds may have a modified molecular skeleton from the viewpoint of suppressing uneven shrinkage due to crosslinking. For example, compounds modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc., can also be used. In particular, from the viewpoint of increasing affinity with silica particles to suppress particle aggregation and making it easier to bring the C / Si ratio within the above range, the above (meth)acrylate compounds are preferably modified with alkylene oxides such as ethylene oxide and propylene oxide. The proportion of alkylene oxide-modified (meth)acrylate compounds in the ionizing radiation-curable compound is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass. Furthermore, the alkylene oxide-modified (meth)acrylate compound is preferably a low-functional (meth)acrylate compound, and more preferably a (meth)acrylate compound having two ethylenically unsaturated bonding groups.

[0068] Examples of (meth)acrylate compounds having two ethylenically unsaturated bonding groups modified by alkylene oxide include bisphenol F alkylene oxide-modified di(meth)acrylate, bisphenol A alkylene oxide-modified di(meth)acrylate, isocyanuric acid alkylene oxide-modified di(meth)acrylate, and polyalkylene glycol di(meth)acrylate, with polyalkylene glycol di(meth)acrylate being preferred. The average repeating units of the alkylene glycol contained in polyalkylene glycol di(meth)acrylate are preferably 3 to 5. Furthermore, the alkylene glycol contained in polyalkylene glycol di(meth)acrylate is preferably ethylene glycol and / or polyethylene glycol. Examples of (meth)acrylate compounds having three ethylenically unsaturated bonding groups after being modified with alkylene oxide include trimethylolpropane alkylene oxide-modified tri(meth)acrylate and isocyanuric acid alkylene oxide-modified tri(meth)acrylate. The above-mentioned ionizing radiation-curable resins can be used individually or in combination of two or more types.

[0069] When the ionizing radiation-curable resin is an ultraviolet-curable resin, the anti-glare layer forming coating solution preferably contains additives such as photopolymerization initiators and photopolymerization accelerators. Examples of photopolymerization initiators include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, α-aminoalkylphenone, thioxanthones, etc. Furthermore, photopolymerization accelerators can reduce polymerization inhibition by air during curing and accelerate the curing speed. Examples include one or more selected from p-dimethylaminobenzoate isoamyl ester, p-dimethylaminobenzoate ethyl ester, etc.

[0070] The binder resin may further contain additives such as antistatic agents, antioxidants, surfactants, dispersants, and ultraviolet absorbers. The curable resin composition forming the binder resin may contain, but is not particularly limited, a silicone-based leveling agent (silicone compound) as an additive. The inclusion of the silicone-based leveling agent makes the surface of the low refractive index layer smoother. Furthermore, it improves the slipperiness and antifouling properties (fingerprint wiping ability, large contact angle with pure water and hexadecane) of the low refractive index layer surface. Depending on the processing conditions, a fluorine-based leveling agent, a mixture of fluorine-based and silicone-based leveling agents, or a mixture of multiple fluorine- and silicone-based leveling agents can also be used.

[0071] However, considering the scratch resistance (steel wool resistance and oil dust resistance) of the low refractive index layer, it may be preferable that fluorine-containing compounds such as fluorine-containing oligomers and / or monomers having ionizing radiation-curable functional groups are not added to the curable resin composition that forms the binder resin (especially when high-speed mass production processing is required). Also, since hydrofluoric acid may be generated when the product is burned, such as when it is disposed of, it is particularly preferable that the additive does not contain fluorine-based leveling agents (fluorine-containing compounds). Fluorine-based leveling agents may be used when the compatibility between the silicone-based leveling agent and the binder resin is poor.

[0072] <Silica particles> In the present invention, the low refractive index layer preferably contains hollow silica particles and non-hollow silica particles. Hollow silica particles are particles that have an outer shell made of silica, with a hollow interior surrounded by this outer shell, containing air within that cavity. Because hollow silica particles contain air, their refractive index decreases in proportion to the gas occupancy rate compared to the original refractive index of silica. Non-hollow silica particles are particles that do not have a hollow interior like hollow silica particles. Examples of non-hollow silica particles include solid silica particles. The shape of the hollow silica particles and non-hollow silica particles is not particularly limited and may be spherical, ellipsoidal, or approximately spherical, such as a polyhedron that can approximate a sphere. Among these, a spherical, ellipsoidal, or approximately spherical shape is preferred when considering scratch resistance.

[0073] Hollow silica particles, because they contain air, play a role in lowering the overall refractive index of the low refractive index layer. By using hollow silica particles with a larger particle size and a higher air content, the refractive index of the low refractive index layer can be further reduced. On the other hand, hollow silica particles tend to have inferior mechanical strength. In particular, when using hollow silica particles with a larger particle size and a higher air content, the scratch resistance of the low refractive index layer tends to decrease. Non-hollow silica particles, when dispersed in the binder resin, play a role in improving the scratch resistance of the low refractive index layer.

[0074] To ensure that hollow silica particles and non-hollow silica particles are present in a binder resin at high concentrations and that the particles are uniformly dispersed in the film thickness direction within the resin, it is preferable to set the average particle diameters of the hollow silica particles and non-hollow silica particles so that the hollow silica particles are close together and that non-hollow particles can fit between the hollow silica particles. Specifically, the ratio of the average particle diameter of non-hollow silica particles to the average particle diameter of hollow silica particles is preferably 0.29 or less, and more preferably 0.20 or less. Furthermore, the ratio of the average particle diameters is preferably 0.05 or more. Considering optical properties and mechanical strength, the average particle diameter of hollow silica particles is preferably 50 nm to 100 nm, and more preferably 60 nm to 80 nm. Furthermore, considering dispersibility while preventing aggregation of non-hollow silica particles, the average particle diameter of non-hollow silica particles is preferably 5 nm to 20 nm, and more preferably 10 nm to 15 nm.

[0075] In this invention, the "average particle diameter" can be calculated by the following steps (1) to (3). (1) The cross-section of the anti-reflective material containing particles is imaged using TEM or STEM. The acceleration voltage of the TEM or STEM is preferably 10kV to 30kV, and the magnification is preferably 50,000 to 300,000 times. (2) Extract any 10 particles from the observed image and calculate the particle diameter of each particle. The particle diameter is measured as the distance between two parallel lines that maximizes the distance between the two lines when the cross-section of the particle is enclosed by those two lines. (3) Perform the same procedure five times on observation images of the same sample on different screens, and the average value obtained from the number average of a total of 50 particles is taken as the average particle diameter.

[0076] It is preferable that the hollow silica particles and non-hollow silica particles have their surfaces coated with a silane coupling agent. It is more preferable to use a silane coupling agent having (meth)acryloyl groups or epoxy groups. By surface-treating silica particles with a silane coupling agent, the affinity between the silica particles and the binder resin is improved, making aggregation of the silica particles less likely. As a result, the dispersion of silica particles becomes more uniform.

[0077] Examples of silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-di Examples include methyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. In particular, it is preferable to use one or more selected from 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.

[0078] As the content of hollow silica particles increases, the packing density of hollow silica particles in the binder resin increases, and the refractive index of the low refractive index layer decreases. On the other hand, if the content of hollow silica particles in the binder resin is too high, the number of hollow silica particles exposed from the binder resin increases, and the amount of binder resin binding the particles together decreases. As a result, the hollow silica particles become more susceptible to damage and detachment, and the mechanical strength, such as scratch resistance, of the low refractive index layer tends to decrease. For this reason, the content of hollow silica particles is preferably 100 parts by mass or more, and more preferably 150 parts by mass or more, per 100 parts by mass of binder resin. Furthermore, the content of hollow silica particles is preferably 400 parts by mass or less, and more preferably 300 parts by mass or less, per 100 parts by mass of binder resin.

[0079] If the content of non-hollow silica particles is low, their presence on the surface of the low refractive index layer may not affect the hardness increase. Conversely, if a large amount of non-hollow silica particles are included, the effect of uneven shrinkage due to the polymerization of the binder resin can be reduced, and the irregularities that occur on the surface of the low refractive index layer after resin curing can be reduced. On the other hand, if the content of non-hollow silica particles is too high, the non-hollow silica will aggregate, causing uneven shrinkage of the binder resin and increasing surface irregularities. The content of non-hollow silica particles is preferably 90 parts by mass or more, and more preferably 100 parts by mass or more, per 100 parts by mass of binder resin. Furthermore, the content of non-hollow silica particles is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less, per 100 parts by mass of binder resin.

[0080] By incorporating hollow silica particles and non-hollow silica particles into the binder resin in the above proportions, even if fluorine-containing compounds such as fluorine-based leveling agents are present in the hard coat layer or high refractive index layer, these fluorine-containing compounds are not detected on the surface of the low refractive index layer. This is presumed to be because the high concentration and uniform dispersion of silica particles in the binder resin inhibits the diffusion of the fluorine-based leveling agent.

[0081] Furthermore, by adding hollow silica particles and non-hollow silica particles to the binder resin in the above proportions, the gas barrier properties of the anti-reflective material itself can be improved. This is presumed to be because the silica particles are uniformly dispersed with a high filling rate, thereby inhibiting the permeation of gases and the like. Furthermore, cosmetics such as sunscreens and hand creams may contain low-molecular-weight polymers with low volatility. By improving the barrier properties of the low-refractive-index layer, it is possible to suppress the penetration of low-molecular-weight polymers into the low-refractive-index layer. This makes it possible to suppress problems (e.g., abnormal appearance) caused by the long-term persistence of low-molecular-weight polymers within the low-refractive-index layer.

[0082] The thickness of the low refractive index layer is not particularly limited as long as it is 50 nm or more (greater than or equal to the average particle diameter of hollow silica), but it is preferably 80 to 120 nm, more preferably 85 to 110 nm, and even more preferably 90 to 105 nm. The refractive index of the low refractive index layer is preferably 1.40 or less, and more preferably 1.35 or less. By setting the refractive index of the low refractive index layer to 1.40 or less, it is possible to suppress the high reflectivity of the surface of the low refractive index layer and improve visibility. The lower limit of the refractive index of the low refractive index layer is about 1.10. In this specification, the refractive index refers to the refractive index at a wavelength of 589.3 nm.

[0083] [Hard court layer] When the transparent substrate is made of plastic, it is preferable to provide a hard coat layer between the low refractive index layer and the transparent substrate. By providing a hard coat layer, the indentation hardness and recovery rate mentioned above can be improved. The hard coat layer includes a cured product of a curable resin composition, such as a thermosetting resin composition or an ionizing radiation-curable resin composition. The curable resin can be the same as that used for low refractive index layers.

[0084] When the ionizing radiation-curable compound is an ultraviolet-curable compound, the ionizing radiation-curable composition preferably contains additives such as photopolymerization initiators and photopolymerization accelerators. The same photopolymerization initiators and accelerators used for low-refractive-index layers can be used.

[0085] Preferably, the hard coat layer further contains a leveling agent as an additive. By adding a leveling agent, a uniform coating film that forms the hard coat layer can be formed. As the leveling agent, fluorine-based leveling agents, silicone-based leveling agents, fluorine-silicone-based leveling agents, or mixtures thereof can be used. In the present invention, even if a fluorine-based leveling agent is contained in the hard coat layer, the diffusion of the fluorine-based leveling agent is inhibited by the silica particles in the low refractive index layer, making it easier to suppress the migration of the fluorine-based leveling agent to the surface of the low refractive index layer. Furthermore, the hard coat layer may also contain additives such as antistatic agents, antioxidants, surfactants, dispersants, and ultraviolet absorbers.

[0086] The thickness of the hard coat layer 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 coat layer within the above range, it is possible to improve scratch resistance while suppressing the occurrence of cracks during processing such as cutting.

[0087] The refractive index of the hard coat layer is preferably adjusted within the range of 1.45 to 1.70. Furthermore, if the anti-reflective member has a high refractive index layer as described later, it is preferable that the refractive index of the hard coat layer be 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 coat layer is within this range, the hard coat layer acts as a medium refractive index layer, and interference between the three layers—the hard coat layer (medium refractive index layer), the high refractive index layer, and the low refractive index layer—becomes possible, thereby further reducing the reflectivity. Furthermore, if there is another layer (a light-transmitting substrate or another layer constituting the resin layer) between the hard coat layer and the adherend, it is preferable to reduce the difference between the refractive index of the other layer and the refractive index of the hard coat layer from the viewpoint of suppressing interference fringes. In this specification, the refractive index can be calculated, for example, by fitting a reflection spectrum measured by a reflectance photometer with a reflection spectrum calculated from an optical model of a multilayer thin film using Fresnel coefficients.

[0088] Means for imparting the role of a medium refractive index layer to the hard coat layer include blending a resin with a high refractive index into the hard coat layer coating liquid and blending particles with a high refractive index. Examples of resins with a high refractive index include those obtained by introducing groups containing sulfur, phosphorus, or bromine, or aromatic rings, into the thermosetting resins or ionizing radiation-curable compounds mentioned above. Examples of particles with a high refractive index include those similar to the high refractive index particles used in the high refractive index layer described later.

[0089] [High refractive index layer] The high refractive index layer is a layer having a higher refractive index than the hard coat layer. It contains high refractive index particles and a binder resin.

[0090] The high refractive index layer contains a cured product of a curable resin composition, such as a thermosetting resin composition or an ionizing radiation-curable resin composition, as a binder resin. The curable resin composition can be the same as that exemplified for the low refractive index layer, and an ionizing radiation-curable resin composition is preferred.

[0091] When the ionizing radiation-curable compound is an ultraviolet-curable compound, the ionizing radiation-curable composition preferably contains additives such as photopolymerization initiators and photopolymerization accelerators. The same photopolymerization initiators and accelerators used for low-refractive-index layers can be used.

[0092] The high refractive index layer preferably further contains a leveling agent as an additive. By adding a leveling agent, a coating film that forms a high refractive index layer can be uniformly formed. As the leveling agent, fluorine-based leveling agents, silicone-based leveling agents, fluorine-silicone-based leveling agents, or mixtures thereof can be used. In this invention, even if a fluorine-based leveling agent is contained in the high refractive index layer, the diffusion of the fluorine-based leveling agent is inhibited by the silica particles in the low refractive index layer, making it easier to suppress the migration of the fluorine-based 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 diameter of the high refractive index particles is preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and even more preferably 10 nm to 80 nm.

[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 2500 parts by mass or less, more preferably 300 parts by mass or more and 2200 parts by mass or less, and even more preferably 500 parts by mass or more and 2000 parts by mass or less, per 100 parts by mass of binder resin.

[0095] In particular, by providing a high refractive index layer in which high-hardness particles such as zirconium oxide, antimony pentoxide, and titanium oxide are dispersed at high concentrations in the binder resin, the indentation hardness and recovery rate of the low refractive index layer can be improved. Considering the improvement of the indentation hardness and recovery rate of the low refractive index layer, the content of high refractive index particles is preferably 1,000 parts by mass or more and 2,000 parts by mass or less, and more preferably 1,500 parts by mass or more and 2,000 parts by mass or less.

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

[0097] [Method for manufacturing anti-reflective material] The hard coat layer, low refractive index layer, and high refractive index layer of the anti-reflective member of the present invention can be formed by a wet method, in which a coating liquid containing the components constituting each layer is applied to a transparent substrate, dried, and cured, and by a transfer method, in which each layer formed on the substrate by the wet method is transferred. The coating liquid contains a solvent, solid components constituting each layer, and additives such as polymerization initiators.

[0098] When forming by the wet method, first, a coating solution for forming a low refractive index layer is applied to a transparent substrate, and then dried and cured to form the low refractive index layer. When a hard coat layer is to be provided, a coating solution for forming a hard coat layer is applied to a transparent substrate, and then dried and cured to form the hard coat layer, after which the low refractive index layer is formed in the same manner as above. When a hard coat layer and a high refractive index layer are to be provided, a coating solution for forming a high refractive index layer is applied to the hard coat layer, and then dried and cured to form the hard coat layer and the high refractive index layer, after which the low refractive index layer is formed in the same manner as above. Note that the hard coat layer and the high refractive index layer may be in a semi-cured state (not completely cured) and fully cured during the formation of the low refractive index layer.

[0099] Low refractive index layer-forming coating solutions typically use solvents to adjust viscosity or to dissolve or disperse each component. Examples of solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethyl sulfoxide, etc.), glycol ethers (1-methoxy-2-propyl acetate, etc.), amides (dimethylformamide, dimethylacetamide, etc.), and mixtures thereof.

[0100] If the solvent evaporates too quickly, the solvent will convect violently during the drying of the coating solution for forming a low refractive index layer. As a result, even if the silica particles in the coating solution are uniformly dispersed, the violent convection of the solvent during drying can easily disrupt the uniform dispersion. For this reason, it is preferable to include a solvent with a slow evaporation rate. Specifically, it is preferable to include a solvent with a relative evaporation rate (relative evaporation rate when the evaporation rate of n-butyl acetate is set to 100) of 70 or less, and more preferably a solvent with a relative evaporation rate of 30 to 60. Furthermore, the solvent with a relative evaporation rate of 70 or less is preferably 10 to 50% by mass of the total solvent, and more preferably 20 to 40% by mass. Examples of the relative evaporation rates of solvents with slow evaporation rates include isobutyl alcohol at 64, 1-butanol at 47, 1-methoxy-2-propyl acetate at 44, ethyl cellosolve at 38, and cyclohexanone at 32. Furthermore, the solvent residue (solvents other than those with a slow evaporation rate) is preferably one that has excellent resin solubility. In addition, the solvent residue is preferably one with a relative evaporation rate of 100 or higher.

[0101] Furthermore, in order to suppress solvent convection during drying and improve the dispersibility of silica particles, it is preferable to keep the drying temperature as low as possible when forming the low refractive index layer. The drying temperature can be set appropriately considering the type of solvent, the dispersibility of silica particles, the production rate, etc.

[0102] Methods for curing each layer include irradiation with ionizing radiation such as ultraviolet light or electron beams, or curing by heating. Considering productivity and other factors, curing by ionizing radiation is preferable.

[0103] [Size, shape, etc. of anti-reflective material] The anti-reflective material may be in the form of a single sheet cut to a predetermined size, or in the form of a roll formed by winding a long sheet into a roll. The size of the sheet is not particularly limited, but the maximum diameter is approximately 2 to 500 inches. "Maximum diameter" refers to the maximum length when connecting any two points on the anti-reflective material. For example, if the anti-reflective material is rectangular, the diagonal of that region is the maximum diameter. If the anti-reflective material is circular, the diameter is the maximum diameter. The width and length of the roll are not particularly limited, but generally, the width is about 500 to 3000 mm and the length is about 100 to 5000 m. The anti-reflective material in roll form can be cut into individual sheets to match the size of an image display device or the like. When cutting, it is preferable to remove the roll ends where the physical properties are unstable. Furthermore, the shape of the sheet is not particularly limited; for example, it may be a polygon (triangle, quadrilateral, pentagon, etc.), a circle, or a random, irregular shape. More specifically, if the anti-reflective material is rectangular, the aspect ratio is not particularly limited as long as it does not pose a problem as a display screen. Examples include width:height = 1:1, 4:3, 16:10, 16:9, 2:1, etc.

[0104] [Polarizing plate] The polarizing plate of the present invention is a polarizing plate having a transparent protective plate, a polarizer, and a transparent protective plate in that order, wherein at least one of the two transparent protective plates is the anti-reflective member described above.

[0105] If only one of the two transparent protective plates is made of the anti-reflective material described above, the other transparent protective plate can be, for example, the same material as exemplified in the transparent substrate described above.

[0106] Examples of polarizers include sheet-type polarizers such as polyvinyl alcohol film, polyvinyl formal film, polyvinyl acetal film, and ethylene-vinyl acetate copolymer saponified film dyed with iodine or the like and stretched; wire grid-type polarizers consisting of numerous parallel metal wires; coated polarizers coated with lyotropic liquid crystal or dichroic guest-host materials; and multilayer thin-film polarizers. These polarizers may also be reflective polarizers that have the function of reflecting polarization components that are not transmitted.

[0107] [Image display device] The image display device of the present invention has the above-described anti-reflective member on a display element. In this case, the anti-reflective member is arranged such that the transparent substrate is located on the display element side and the low refractive index layer is located on the user side of the image display device. Preferably, the display element and the anti-reflective member are laminated with an adhesive layer in between. Examples of display elements include liquid crystal display elements, EL display elements, plasma display elements, and electronic paper elements.

[0108] By incorporating the above-mentioned anti-reflective member, the image display device of the present invention exhibits extremely low reflectivity and excellent visibility, as well as superior resistance not only to steel wool but also to oil dust.

[0109] [Anti-reflective article] The anti-reflective article of the present invention comprises an 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. Preferably, the component and the anti-reflective member are laminated with an adhesive layer in between.

[0110] Examples of components include instrument panels, clocks, showcases, display windows, and windows. Specifically, the articles of the present invention include instrument panels, clocks, showcases, display windows, and windows in which the release layer of the low-reflectance component is arranged to face the surface. The component may be transparent or opaque, and its color is not particularly limited. [Examples]

[0111] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the embodiments described in the examples.

[0112] 1. Evaluation and Measurement The anti-reflective materials obtained in the examples and comparative examples were subjected to the following measurements and evaluations. The results are shown in Tables 1 and 2. Unless otherwise specified, and unless the tests were conducted under specific environmental conditions, the atmosphere during each measurement and evaluation was 23±5°C and 40-65% relative humidity. Before starting each measurement and evaluation, the target sample was exposed to the aforementioned atmosphere for at least 30 minutes.

[0113] 1-1. Reflectance (Visual reflectance Y value) Samples (5cm x 5cm) were prepared by laminating a black plate (Kuraray Co., Ltd., product name: Comoglass DFA2CG 502K (black), 2mm thick) to the transparent substrate side of the anti-reflective members of the examples and comparative examples via a 25μm thick transparent adhesive layer (Panac Co., Ltd., product name: Panaclean PD-S1). With the direction perpendicular to the surface of the low refractive index layer of the anti-reflective material set to 0 degrees, light was incident on the sample from a direction of 5 degrees, and the reflectance of the sample (visible reflectance Y value) was measured based on the specular reflection of the incident light. The reflectance was measured using a spectrophotometer (Shimadzu Corporation, product name: UV-2450) under the conditions of a field of view of 2 degrees, a C light source, and a wavelength range of 380-780 nm. Subsequently, the value representing the luminous reflectance, calculated using software (UVPC color measurement version 3.12 built into the device) that converts it to brightness as perceived by the human eye, was determined as the reflectance. For each sample, the average of the reflectances measured at 14 locations was taken as the reflectance for that sample.

[0114] 1-2.XPS analysis Measurement pieces were cut from the anti-reflective materials of the 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 surface of the low refractive index layer of each measurement piece 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, the inorganic component (silica) and the organic component (silicone) were separated from the X-ray photoelectron spectrum of the Si2p orbital to determine the ratio of Si elements belonging to silica particles (hollow silica particles and non-hollow silica particles) (inorganic Si in the table). Measurements were performed at 14 locations for each sample, and further analysis was performed with n=2 samples. The average was used as the elemental ratio for each example and comparative example. In addition, the ratio of C element (C / Si) was calculated from the obtained elemental ratios, when the ratio of Si elements belonging to silica particles determined above was converted to 100 atomic percent. Tables 1 and 2 show the total elemental ratios of elements other than inorganic components such as oxygen (O), silicon (Si), carbon (C), and phosphorus (F), categorized as "other elements." <Measurement> Equipment: Kratos AXIS-NOVA X-ray source: AlKα X-ray output: 150W Emission current: 10mA Acceleration voltage: 15kV Measurement area: 300×700μm

[0115] 1-3. Surface roughness Using the Atomic Force Microscope (AFM) SPM-9600 manufactured by Shimadzu Corporation, the shape of the low refractive index layer surface was measured using the samples of the examples and comparative examples prepared in the measurement of 1-1 in the On-Line (measurement) mode in the SPM Manager software. The measurement conditions are shown below. Then, using the Off-Line (analysis) mode, tilt correction processing was performed to obtain a grayscale image when the height: 0 nm was black and the height: 100 nm or more was white. Note that the lowest point within the measurement range was defined as "height 0 nm". The obtained AFM images were 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 for each sample were evaluated. <AFM Measurement Conditions> Measurement Mode: Phase Scanning Range: 5 μm × 5 μm Scanning Speed: 0.8 - 1 Hz Number of Pixels: 512 × 512 Cantilever Used: NCHR manufactured by Nanoworld (Resonance Frequency: 320 kHz, Spring Constant 42 N / m) <AFM Analysis Conditions> Tilt Correction: Line Fit

[0116] 1-4. Steel Wool Resistance Test The antireflection member evaluated in 1-1 was bonded to the base of a wear testing machine for academic societies (manufactured by Tester Sangyo Co., Ltd., product name "AB-3**01") with the low refractive index layer on the upper surface. Steel wool #0000 (manufactured by Nippon Steel Wool Co., Ltd., product name "Bons**ter B-204") was set and brought into contact with the surface of the low refractive index layer, and the steel wool was reciprocated 10 times while applying a load at a moving speed of 100 mm / second and a moving distance of 200 mm in one reciprocation (one-way moving distance of 100 mm). The contact area between the steel wool and the low refractive index layer was 1 cm 2The test environment was set to a temperature of 23±1℃ and a relative humidity of 50±5% unless otherwise specified. The Bonstar B-204 mentioned above is a commercial size with dimensions of approximately 390mm in width, 75mm in height, and 110mm in thickness. A suitable amount was torn off from this (do not cut with a blade as this would cause the cross-section of the steel wool fibers to protrude), and it was rolled up uniformly until there were no distinctive protruding steel wool parts. When a load of 1000g was applied, the contact area was 1cm². 2 Set the thickness of the steel wool to 20mm at that time. Subsequently, each anti-reflective material was visually inspected under fluorescent lighting (Panasonic Corporation 3-wavelength fluorescent lamp, model number: FHF32EX-NH, illuminance on the sample: 800-1200 Lx, observation distance: 30 cm) and under LED lighting (Gentos Corporation LED light, model number: TX-850Re, illuminance on the sample: 4000-6000 Lx, observation distance: 30 cm), and the number of scratches was evaluated. Steel wool resistance was evaluated by the maximum load per unit area (g / cm²) when no scratches were observed after the test (0 scratches). 2 The results were expressed as follows. For each example and comparative example, tests were conducted with n=2, and the average was taken as the steel wool resistance for each example and comparative example.

[0117] 1-5. 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. Eight layers of cloth (manufactured by AS ONE Corporation, product name "Azpure Proplea II") were folded and securely attached to the tip of a rod-shaped metal component (the end face of the rod was a 1cm x 1cm square) using a rubber band. The side of the rod-shaped metal component with the cloth attached was immersed in the above-mentioned test solution, and 5g of the test solution was evenly absorbed into the end face of the cloth to obtain a rod-shaped metal component for abrasion. The anti-reflective members of the examples and comparative examples were attached to a test stand with the low refractive index layer facing upwards. A weight was attached to the aforementioned rod-shaped metal member for abrasion, and the cloth side of the rod-shaped metal member was brought into contact with the surface of the low refractive index layer. The weight was moved back and forth 10 times at a moving speed of 100 mm / second, with a travel distance of 200 mm per reciprocal (100 mm one way). The contact area between the cloth and the low refractive index layer was approximately 1 cm², which is roughly equal to the area of ​​the end face of the rod-shaped metal member. 2 The test environment was set to a temperature of 23±1℃ and a relative humidity of 50±5%, unless otherwise specified. Subsequently, the anti-reflective materials of the examples and comparative examples were observed visually under fluorescent lighting (Panasonic Corporation 3-wavelength fluorescent lamp, model number: FHF32EX-NH, illuminance on the sample: 800-1200 Lx, observation distance: 30 cm) and under LED lighting (Gentos Corporation LED light, model number: TX-850Re, illuminance on the sample: 4000-6000 Lx, observation distance: 30 cm), and the number of scratches was evaluated. The load was defined as the weight of a weight, and the oil dust resistance was evaluated by the maximum load per unit area (g / cm²) when no scratches were observed after the test (0 scratches). 2 The results were expressed as follows. For each example and comparative example, tests were conducted with n=2, and the average was taken as the oil dust resistance of each example and comparative example.

[0118] 1-6. Stain resistance (fingerprint wiping ability) Fingerprints were applied to the low refractive index layer surface of the anti-reflective materials in the examples and comparative examples by pressing the pad of a finger against it. Then, the applied fingerprints were wiped off using a nonwoven fabric (manufactured by Asahi Kasei Corporation, product name: Bencotton), and the number of times until the fingerprints disappeared was evaluated. Materials in which the fingerprints disappeared after 3 wipes were classified as "A", materials in which the fingerprints disappeared after 4 to 7 wipes were classified as "B", and materials in which the fingerprints were still visible after 7 wipes were classified as "C".

[0119] 1-7. Indentation hardness For the low refractive index layers of the anti-reflective materials in Examples 1, 6, and 8 and Comparative Examples 1, 3, and 4, load-displacement curves were measured using a Hysitron TriboIndenter TI950 under the following conditions. The indentation hardness was obtained from the obtained load-displacement curves using the analysis software (TRIBOSCAN) included with the instrument. Measurements were taken at 16 locations for each sample, and further analysis was performed with n=2 samples. The average of the obtained values ​​was taken as the indentation hardness for each example and comparative example.

[0120] <Indentation hardness measurement conditions> • Indenter used: Berkovich indenter (TI-0039) • Pushing conditions: Displacement control method • Maximum indentation depth: 30nm • Load application time: 3 seconds (speed: 10 nm / sec) • Holding time: 5 seconds • Load unloading time: 3 seconds (speed: 10 nm / sec) • Push speed: 10nm / sec

[0121] 1-8. Recovery Rate For the low refractive index layers of the anti-reflective materials in Examples 1, 6, and 8 and Comparative Examples 1, 3, and 4, load-displacement curves were measured using a Hysitron TriboIndenter TI950 under the following conditions. The recovery rate was calculated from the obtained load-displacement curves. Measurements were taken at 16 locations for each sample, and further analysis was performed with n=2 samples. The average of the obtained values ​​was taken as the recovery rate for each example and comparative example.

[0122] <Recovery Rate Measurement Conditions> • Indenter used: Berkovich indenter (TI-0039) • Indentation conditions: Load control method ·Maximum load: 30μN • 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 the coating solution A hard coat layer forming solution was prepared according to the following formulation. <Coating liquid for forming a hard coat layer 1> • UV-curable acrylate-containing composition (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30", solids content 100%) 22 parts by mass • UV-curable acrylate-containing composition (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "New Frontier R-1403MB", solids content 80%) 17 parts by mass • Fluorine-based leveling agent (manufactured by DIC Corporation, product name "Megafac F-568") 1 part by mass ·Photopolymerization initiator (manufactured by IGM Resins, product name "Omnirad184") 1 part by mass • 15 parts by mass of methyl isobutyl ketone • Methyl ethyl ketone 44 parts by mass

[0124] <Coating solution for forming a hard coat layer 2> ·Reactive silica fine particles (manufactured by JSR Corporation, "Z7837", product containing 50% solids and 60% reactive silica fine particles) 10 parts by mass • Urethane acrylate (manufactured by Mitsubishi Chemical Corporation, "UV1700B") 5.7 parts by mass ·Photopolymerization initiator (manufactured by IGM Resins, product name "Omnirad184") 1 part by mass • Fluorine-based leveling agent (manufactured by DIC Corporation, product name "Megafac F-568") 1 part by mass • Methyl ethyl ketone 3.3 parts by mass • Methyl isobutyl ketone 2.3 parts by mass

[0125] A coating solution for forming a high refractive index layer was prepared according to the following formulation. <Coating solution for forming a high refractive index layer 1> • PETA (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30", solids content 100%) 0.15 parts by mass • High refractive index particles (manufactured by Nippon Shokubai Co., Ltd., product name "Zircostar", solid content 70%) 4.5 parts by mass • Fluorine-based leveling agent (manufactured by DIC Corporation, product name "Megafac F251") 0.01 parts by mass • Photopolymerization initiator (manufactured by IGM Resins, trade name "Omnirad127") 0.14 parts by mass • Methyl isobutyl ketone 47.6 parts by mass • Propylene glycol monomethyl ether 47.6 parts by mass

[0126] <Coating solution for forming a high refractive index layer 2> • PETA (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30", solids content 100%) 0.68 parts by mass • High refractive index particles (manufactured by JGC Catalysts & Chemicals Co., Ltd., product name "ELCOM V-4564" (contains antimony pentoxide particles), solid content 40.5%) 6.71 parts by mass • Fluorine-based leveling agent (manufactured by DIC Corporation, product name "Megafac F251") 2.03 parts by mass • Photopolymerization initiator (manufactured by IGM Resins, trade name "Omnirad127") 0.05 parts by mass Methyl isobutyl ketone 46.3 parts by mass • Propylene glycol monomethyl ether 44.23 parts by mass

[0127] <Coating solution for forming a high refractive index layer 3> • Ethanol dispersion of ITO fine particles (solid content 20.5 wt%) 20 parts by mass • PETA (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30", solids content 100%) 1 part by mass • ITO dispersing agent (phosphate ester type) 0.1 parts by mass ·Photopolymerization initiator (manufactured by IGM Resins, product name "Omnirad184") 0.2 parts by mass • Ethanol (adjust the amount added so that the solid content concentration is 4% by mass)

[0128] A coating solution for forming a low refractive index layer was prepared according to the following formulation. <Coating solution for forming a low refractive index layer 1> The following hollow silica particles and non-hollow silica particles were used. Tables 1 and 2 show the blending amounts (solid content) of hollow silica particles and non-hollow silica particles (solid silica particles) in parts by mass, when the binder resin (solid content) is 100 parts by mass. (1) Hollow silica particles A dispersion with a solid content of 20% by mass, surface-treated with a silane coupling agent having a methacryloyl group, with an average particle size of 75 nm. (2) Non-hollow silica particles A dispersion of solid silica particles with a solid content of 40% by mass, surface-treated with a silane coupling agent having a methacryloyl group, with an average particle size of 7 nm or 12.5 nm.

[0129] The following binder resins were used. Tables 1 and 2 show the percentage of solids. (3) Binder resin TEGDA: Polyethylene glycol (n≒4) diacrylate (bifunctional acrylate), manufactured by Toagosei Co., Ltd., product name "M-240" • PETA: Pentaerythritol (tri / tetra)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30" • DPHA: Dipentaerythritol (hexa / penta)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA" • Fluorine-containing compound: A fluorine-containing compound having a (meth)acryloyl group, a reactive silane unit, and a silane unit having a perfluoropolyether group, solids content 20% by mass, solvent: methyl isobutyl ketone, manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-71-1203M"

[0130] The following were used as photopolymerization initiators and leveling agents. Tables 1 and 2 show the percentage of solids when the binder resin (solids) is 100 parts by mass. (4) Photopolymerization initiator Manufactured by IGM Resins, product name “Omnirad127” 4.3 parts by mass (5) Leveling agent (a) Silicone-based (Si-1) leveling agent: Manufactured by Shin-Etsu Chemical Co., Ltd., product name "KP-420", 13 parts by mass (b) Fluorine-based leveling agent 1 (F-1): Manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-71-1203M", 13 parts by mass (c) Fluorine-based leveling agent 2 (F-2): Manufactured by DIC Corporation, product name "Megafac RS-81", 5 parts by mass

[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 methyl isobutyl ketone / 1-methoxy-2-propyl acetate = 68 / 32 (mass ratio). The amount of mixed solvent was 14,867 parts by mass per 100 parts by mass of binder resin (solids). In Comparative Examples 3 and 4, methyl isobutyl ketone and 2-methoxy-1-methyl ethyl acetate were used as solvents. The mixing ratio was methyl isobutyl ketone / 2-methoxy-1-methyl ethyl acetate = 89 / 11 (mass ratio). For every 100 parts by mass of binder resin (solids), the amount of mixed solvent was 8,667 parts by mass.

[0132] <Coating solution for forming a low refractive index layer 2> The following hollow silica particles and non-hollow silica particles were used. Table 2 shows the amount (solid content) of hollow silica particles and non-hollow silica particles (solid silica particles) in parts by mass, when the binder resin (solid content) is 100 parts by mass. (1) Hollow silica particles A dispersion with a solid content of 20% by mass, surface-treated with a silane coupling agent containing methacryloyl groups, and with an average particle size of 55 nm. (2) Non-hollow silica particles A dispersion of solid silica particles with a solid content of 30% by mass, surface-treated with a silane coupling agent containing methacryloyl groups, and with an average particle size of 12.5 nm.

[0133] The following binder resins were used. Table 2 shows the percentage of solids. (3) Binder resin • PETA: Pentaerythritol (tri / tetra)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30" • DPHA: Dipentaerythritol (hexa / penta)acrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA"

[0134] The following were used as photopolymerization initiators and leveling agents. Table 2 shows the percentage of solids when the binder resin (solids) is 100 parts by mass. (4) Photopolymerization initiator Manufactured by IGM Resins, product name “Omnirad127” 10 parts by mass (5) Leveling agent (a) Silicone-based (Si-2) leveling agent: 10 parts by mass of "X-22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.

[0135] Methyl isobutyl ketone and propylene glycol monomethyl ether were used as solvents. The mixing ratio was methyl isobutyl ketone / propylene glycol monomethyl ether = 60 / 40 (mass ratio). For every 100 parts by mass of binder resin (solids), the amount of mixed solvent was 5,000 parts by mass.

[0136] <Coating solution for forming a low refractive index layer 3> The following hollow silica particles and non-hollow silica particles were used. Table 2 shows the amount (solid content) of hollow silica particles and non-hollow silica particles (solid silica particles) in parts by mass, with the film component (solid content) being 100 parts by mass. (1) Hollow silica particles Isopropyl alcohol dispersion with 20% solid content by mass, refractive index 1.30, average particle size 60 nm (2) Non-hollow silica particles Spherical silica sol (solid silica particles), isopropyl alcohol dispersion with a solid content of 25% by mass, surface treated with a silane coupling agent having a methacryloyl group, average particle size 10.5 nm.

[0137] (3) Membrane components The following reactive silanes were used as raw materials for the film component (SiO2). • 3-Methacryloxypropyltrimethoxysilane

[0138] The following photopolymerization initiators were used. Table 2 shows the percentage of solid content when the film component (solid content) is set to 100 parts by mass. (4) Photopolymerization initiator Manufactured by IGM Resins, product name “Omnirad369” 8.9 parts by mass

[0139] The coating solution 3 for forming a low refractive index layer was prepared by the following process. First, a dispersion of hollow silica particles, a dispersion of non-hollow silica particles, and isopropyl alcohol were mixed in a ratio of 20 / 8 / 25 (by mass) to obtain a silica particle dispersion. A reactive silane (3-methacryloxypropyltrimethoxysilane) was added dropwise to this silica particle dispersion and mixed. The mixing ratio was reactive silane:silica particle dispersion = 100:1432 (mass ratio). A 0.4 M aqueous nitric acid solution was added dropwise to the mixture while stirring to hydrolyze the reactive silane. The above photopolymerization initiator and solvent (isopropyl alcohol) were added to the hydrolyzed mixture and mixed to obtain 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) A hard coat layer forming solution 1 with the above formulation was applied to an 80 μm thick acrylic film (refractive index 1.50), and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (100 mJ / cm²) was performed. 2 A hard coat layer (dry thickness 10 μm) was formed. The high refractive index layer-forming coating solution 1 according to the above formulation was applied onto the hard coat layer, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (100 mJ / cm²) was performed. 2 A high refractive index layer was formed (dry thickness 150 nm). A coating solution 1 for forming a low refractive index layer, with 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. 2 A low refractive index layer (dry thickness 100 nm) was formed, and anti-reflective members of Examples 1, 4 to 7 and Comparative Examples 1 to 2 were obtained.

[0141] (Example 2) Except for the drying conditions after applying the low refractive index layer forming coating liquid 1 being 50°C for 1 minute, each layer was formed under the same conditions as in Example 1 to obtain the anti-reflective member of Example 2.

[0142] (Example 3) Except for the drying conditions after applying the low refractive index layer forming coating liquid 1 being 100°C for 1 minute, each layer was formed under the same conditions as in Example 1 to obtain the anti-reflective member of Example 3.

[0143] (Example 8) Except for not forming a high refractive index layer, each layer was formed under the same conditions as in Example 1 to obtain the anti-reflective member of Example 8.

[0144] (Comparative Example 3) A hard coat layer forming solution 1 with the above formulation was applied to an 80 μm thick acrylic film (refractive index 1.50), and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (100 mJ / cm²) was performed. 2 A hard coat layer (dry thickness 10 μm) was formed. The high refractive index layer-forming coating solution 2 described above was applied to the hard coat layer, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (100 mJ / cm²) was performed. 2 A high refractive index layer was formed (dry thickness 150 nm). A coating solution 1 for forming a low refractive index layer, as 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). 2 A low refractive index layer (dry thickness 100 nm) was formed, and the anti-reflective member of Comparative Example 3 was obtained.

[0145] (Comparative Example 4) Each layer was formed under the same conditions as in Comparative Example 3, except that a high refractive index layer was not formed, to obtain the anti-reflective member of Comparative Example 4.

[0146] (Comparative Example 5) The hard coat layer forming solution 2, according to the above formulation, was applied to an 80 μm thick acrylic film (refractive index 1.50), and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (50 mJ / cm²) was performed. 2 A hard coat layer (dry thickness 12 μm) was formed. The low refractive index layer-forming coating solution 2 described above was applied to the hard coat layer, and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (200 mJ / cm²) was performed. 2 ) and a high refractive index layer was formed (dry thickness 100 nm). The coating solution 2 for forming the low refractive index layer according to 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, ultraviolet irradiation (200 mJ / cm²) was performed. 2 A low refractive index layer (dry thickness 100 nm) was formed, and the anti-reflective member of Comparative Example 5 was obtained.

[0147] (Comparative Example 6) A hard coat layer forming solution 1 according to the above formulation was applied to an 80 μm thick acrylic film (refractive index 1.50), and then dried at 70°C for 1 minute to evaporate the solvent. Subsequently, ultraviolet irradiation (100 mJ / cm²) was performed. 2 A hard coat layer (dry thickness 10 μm) was formed. The high refractive index layer-forming coating solution 3 of the above formulation was applied onto the hard coat layer, and then dried at 70°C for 2 minutes to evaporate the solvent. Subsequently, ultraviolet irradiation (100 mJ / cm²) was performed. 2 A high refractive index layer was formed (dry thickness 100 nm). The coating solution 3 for forming the low refractive index layer according to 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, ultraviolet irradiation (200 mJ / cm²) was performed. 2 A low refractive index layer (dry thickness 105 nm) was formed. Next, a 0.1 wt% solution was obtained by diluting Daikin Industries, Ltd.'s "Optoul DSX-E (trademark registered)" with Daikin Industries, Ltd.'s "Demnam Solvent SOL-1". This solution was applied onto a low refractive index layer using a bar coater and heated at 120°C for 1 minute to form a coating layer with a thickness of approximately 2 nm, thereby obtaining the anti-reflective member of Comparative Example 6.

[0148] (Comparative Example 7) As Comparative Example 7, a commercially available Apple MacBook Pro (15-inch, 2016 model) was disassembled, and the anti-reflective material was removed. The surface of the anti-reflective material (the side facing the user) was cut to the appropriate evaluation / measurement size, and evaluations and measurements 1-2 to 1-6 were performed.

[0149] [Table 1]

[0150] [Table 2]

[0151] From the results in Table 1, it can be confirmed that the anti-reflective members of Examples 1 to 8, in which the ratio of Si element is 10.0 atomic% to 18.0 atomic%, and the ratio of C element (C / Si) when the ratio of Si element is converted to 100 atomic%, is 180 atomic% to 500 atomic%, exhibit good scratch resistance, such as resistance to steel wool and oil dust. As shown in Figure 3, the anti-reflective member of Example 1 had hollow silica particles and non-hollow silica particles uniformly dispersed in the low refractive index layer.

[0152] In contrast, as shown in Table 2, the anti-reflective materials of Comparative Examples 1 to 7 all failed to satisfy the above ranges for the ratio of Si elements and C / Si, resulting in poor scratch resistance, such as resistance to steel wool and oil dust. In the anti-reflective material of Comparative Example 2 shown in Figure 4, hollow silica particles are exposed on the surface within the low refractive index layer, making it easier for steel wool and oil dust to enter through the gaps between the hollow silica particles, which is thought to have resulted in poor scratch resistance. Furthermore, in the anti-reflective material of Comparative Example 5 shown in Figure 5, non-hollow silica particles are exposed on the surface within the low refractive index layer, making it easier for the non-hollow silica particles to detach from the film due to scratches, which is thought to have resulted in poor scratch resistance.

[0153] Although not shown in the table, by changing the binder composition of the low refractive index layers in Examples 1-8 (for example, ditrimethylolpropanetetraacrylate / trimethylolpropanePO-modified (n≒2) triacrylate = 23 / 77 mixture, etc.), and by adjusting the type of solvent and drying temperature, anti-reflective members with a Si element ratio and C / Si within the above range also exhibited equivalent scratch resistance.

[0154] (Examples 9-12) Using the same anti-reflective material as in Example 1, steel wool resistance tests and oil dust resistance tests were conducted under the same conditions as described in Table 3. Other test conditions were the same as those described in 1-4 and 1-5.

[0155] [Table 3]

[0156] A temperature of 16-30°C and a relative humidity of 30-70% correspond to the typical operating environment for image display devices equipped with anti-reflective materials. From the results in Table 3, it can be seen that the anti-reflective material of the present invention exhibits almost no change in steel wool resistance and oil dust resistance even under different operating environments. [Explanation of Symbols]

[0157] 100,200 Anti-reflective material 110 Transparent base material 120 Hard Court Layer 130 Low refractive index layer 132 Hollow silica particles 134 Non-hollow silica particles 140 High refractive index layer 142 High refractive index particles

Claims

1. An anti-reflective member comprising a low refractive index layer on a transparent substrate, The low refractive index layer comprises a binder resin, hollow silica particles, and non-hollow silica particles. The average particle diameter of the hollow silica particles is 50 nm or more and 100 nm or less, and the average particle diameter of the non-hollow silica particles is 5 nm or more and 20 nm or less. By analyzing the region of the low refractive index layer from the surface opposite to the transparent substrate to a depth of 10 nm using X-ray photoelectron spectroscopy, it is determined that the ratio of Si elements to all elements is 10.0 atomic% or more and 18.0 atomic% or less, and the ratio of C elements when the Si element ratio is converted to 100 atomic% is 180 atomic% or more and 500 atomic% or less. When the thickness of the low refractive index layer is divided into three equal parts, and these are defined as the first region, the second region, and the third region in order from the transparent substrate side, the ratio of Si element to the total elements attributable to the silica particles 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. The refractive index of the low refractive index layer is 1.10 or more and 1.40 or less. An anti-reflective member in which, 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 10.66 or less.

2. The anti-reflective member according to claim 1, wherein the ratio of element F to all elements obtained by analysis by X-ray photoelectron spectroscopy in a region of the low refractive index layer from the surface opposite to the transparent substrate to a depth of 10 nm is 0.5 atomic% or less.

3. The anti-reflective member according to claim 1 or 2, wherein Rz is 110 nm or less and Ra is 15 nm or less.

4. The anti-reflective member according to any one of claims 1 to 3, wherein the ratio of the average particle diameter of the non-hollow silica particles to the average particle diameter of the hollow silica particles is 0.29 or less.

5. The anti-reflective member according to any one of claims 1 to 4, wherein the surfaces of the hollow silica particles and the non-hollow silica particles are coated with a silane coupling agent.

6. The anti-reflective member according to any one of claims 1 to 5, wherein the indentation hardness of the low refractive index layer by the nanoindentation method is 480 MPa or more.

7. The anti-reflective member according to any one of claims 1 to 6, wherein the restoration rate of the low refractive index layer by nanoindentation is 80% or more.

8. The anti-reflective member according to claim 1, wherein the binder resin comprises a cured product of polyalkylene glycol di(meth)acrylate.

9. A polarizing plate having a transparent protective plate, a polarizer, and a transparent protective plate in this order, wherein at least one of the two transparent protective plates is an anti-reflective member according to any one of claims 1 to 8.

10. An image display device having an anti-reflective member according to any one of claims 1 to 8 on a display element.

11. An anti-reflective article having an anti-reflective member according to any one of claims 1 to 8 on a component.

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