Anti-glare laminate, polarizing plate, image display device, and method for manufacturing an anti-glare laminate

Abstract

To provide an anti-glare laminate with superior pencil hardness and bending resistance.SOLUTION: An anti-glare laminate comprising a resin layer on a substrate is provided, the resin layer containing first particles having an average particle diameter of 0.5 μm or greater. When a region of the resin layer on the substrate side with respect to the center in a thickness direction is defined as a first region and a region on a side opposite the substrate side with respect to the center in the thickness direction as a second region, 70% or more of the first particles on a number basis are present in the second region. The anti-glare laminate satisfies the following conditions 1 and 2. <Condition 1> a resin layer-side surface of the substrate has an average slope angle of 5.0 to 20.0 degrees, inclusive; <condition 2> the resin layer-side surface of the substrate has an arithmetic average height of 0.10 to 0.40 μm, inclusive.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to an anti-glare laminate, a polarizing plate, and an image display device. [Background technology]

[0002] The surfaces of image display devices such as televisions, laptops, and desktop PC monitors may be fitted with anti-glare laminates to provide anti-glare properties. Anti-glare properties refer to the characteristic of suppressing reflections of lighting and backgrounds such as people.

[0003] Anti-glare laminates have a basic structure consisting of an anti-glare layer with an uneven surface on a substrate. Since anti-glare laminates are often used as surface components for image display devices and the like, they are frequently in contact with people's fingers and other objects. For this reason, it is preferable that anti-glare laminates have high pencil hardness.

[0004] To increase the pencil hardness of the anti-glare laminate, a cured product of a curable resin composition is preferably used as the resin component of the anti-glare layer (for example, Patent Documents 1-2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 6840215 [Patent Document 2] International Publication Number WO2018 / 070426 [Overview of the project] [Problems that the invention aims to solve]

[0006] The anti-glare laminates described in Patent Documents 1 and 2 exhibit good pencil hardness due to the high hardness of the anti-glare layer. However, the anti-glare laminates described in Patent Documents 1 and 2 sometimes had insufficient bending resistance. Specifically, when the anti-glare laminates described in Patent Documents 1 and 2 were applied to foldable or rollable image display devices, cracks sometimes occurred in the anti-glare laminate. The aforementioned bending resistance tended to worsen when an acrylic resin substrate was used as the base material for the anti-glare laminate.

[0007] The object of this disclosure is to provide an anti-glare laminate with excellent pencil hardness and flexibility, as well as a polarizing plate and an image display device using the same. [Means for solving the problem]

[0008] This disclosure provides the following anti-glare laminates, polarizing plates, and image display devices [1] to [3]. [1] An anti-glare laminate having a resin layer on a substrate, The resin layer contains first particles with an average particle diameter of 0.5 μm or more. When the area on the substrate side of the center of the resin layer in the thickness direction is defined as the first region, and the area on the opposite side of the substrate from the center of the resin layer in the thickness direction is defined as the second region, 70% or more of the first particle count criterion is present in the second region. An anti-glare laminate that satisfies either condition 1 or condition 2 below. <Condition 1> The average inclination angle of the surface of the substrate on the resin layer side is 5.0 degrees or more and 20.0 degrees or less. <Condition 2> The arithmetic mean height of the resin layer side surface of the substrate is 0.10 μm or more and 0.40 μm or less. [2] A polarizing plate having a polarizer, a first transparent protective plate disposed on one side of the polarizer, and a second transparent protective plate disposed on the other side of the polarizer, wherein at least one of the first transparent protective plate and the second transparent protective plate is the anti-glare laminate described in [1]. [3] An image display device having the anti-glare laminate described in [1] on a display element. [Effects of the Invention]

[0009] The antiglare laminate of the present disclosure can improve the pencil hardness and bending resistance. Since the polarizing plate and the image display device of the present disclosure have an antiglare laminate excellent in pencil hardness and bending resistance, the degree of freedom in the design of the polarizing plate and the image display device can be increased.

Brief Description of the Drawings

[0010] [Figure 1] It is a cross-sectional view showing an embodiment of the antiglare laminate of the present disclosure. [Figure 2] It is a cross-sectional view showing the antiglare laminate of Comparative Example 2. [Figure 3] It is a cross-sectional view showing an embodiment of the image display device of the present disclosure.

Modes for Carrying Out the Invention

[0011] Hereinafter, embodiments of the present disclosure will be described. [Antiglare Laminate] The antiglare laminate of the present disclosure has a resin layer on a substrate, the resin layer contains first particles having an average particle diameter of 0.5 μm or more, when the side closer to the substrate than the center in the thickness direction of the resin layer is defined as the first region and the side opposite to the substrate than the center in the thickness direction of the resin layer is defined as the second region, 70% or more of the first particles in terms of the number are present in the second region, and satisfies the following Condition 1 or Condition 2. <Condition 1> The average inclination angle of the surface of the substrate on the resin layer side is 5.0 degrees or more and 20.0 degrees or less. <Condition 2> The arithmetic mean height of the surface of the substrate on the resin layer side is 0.10 μm or more and 0.40 μm or less.

[0012] FIG. 1 is a cross-sectional view showing an embodiment of the antiglare laminate 100 of the present disclosure. The anti-glare laminate 100 in Figure 1 has a resin layer 20 on a substrate 10. The resin layer 20 in Figure 1 contains first particles 23 with an average particle diameter of 0.5 μm or more. Furthermore, when the area on the substrate 10 side from the center of the resin layer 20 in the thickness direction is defined as the first region 21, and the area on the opposite side from the substrate 10 from the center of the resin layer 20 in the thickness direction is defined as the second region 22, the first particles 23 in Figure 1 are located in the second region 22. Note that Figure 1 is a schematic cross-sectional view. That is, the scales of each layer constituting the anti-glare laminate 100, the scales of each material, and the scales of the surface irregularities are schematic for ease of illustration and differ from the actual scales. Similarly, the other figures also differ from the actual scales.

[0013] <Base material> The substrate is preferably one that has good light transmittance, smoothness, heat resistance, and mechanical strength. Examples of such substrates include resin substrates containing resins such as polyester, triacetylcellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyetherketone, acrylic resin, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP). The resin substrate may be formed by laminating two or more resin substrates together. The resin substrate is preferably stretched to improve its mechanical strength and dimensional stability.

[0014] Among resin substrates, acrylic resin substrates are preferred because they have low hygroscopicity, making it easy to achieve good dimensional stability, and low optical anisotropy, making it easy to achieve good visibility. Furthermore, by using an acrylic resin substrate with a predetermined composition for the resin layer coating liquid and predetermined drying conditions, it is possible to satisfy condition 1 and or condition 2, and to easily satisfy the position of the first particles in the thickness direction. Because acrylic resin substrates are hard and brittle, forming a resin layer containing a cured product of a curable resin composition on an acrylic resin substrate may result in insufficient flexibility. The anti-glare laminate of this disclosure, even when forming a resin layer containing a cured product of a curable resin composition on an acrylic resin substrate, can suppress the decrease in flexibility and maintain pencil hardness by satisfying condition 1 or condition 2, etc. In this specification, acrylic resin means acrylic resin and / or methacrylic resin.

[0015] The acrylic resin contained in the acrylic resin substrate is not particularly limited, but for example, one obtained by polymerizing one or more alkyl (meth)acrylates is preferred, and more specifically, one obtained using methyl (meth)acrylate is preferred. Examples of acrylic resins include those described in Japanese Patent Publication No. 2000-230016, Japanese Patent Publication No. 2001-151814, Japanese Patent Publication No. 2002-120326, Japanese Patent Publication No. 2002-254544, Japanese Patent Publication No. 2005-146084, etc. As the acrylic resin, one having a ring structure such as an acrylic resin having a lactone ring structure or an acrylic resin having an imide ring structure may be used.

[0016] The acrylic resin preferably has a glass transition temperature (Tg) of 100°C to 150°C, more preferably 105°C to 135°C, and even more preferably 110°C to 130°C. If the glass transition temperature of the acrylic resin is 100°C or higher, it becomes easier to suppress excessive melting of the acrylic resin substrate when forming the resin layer. If the glass transition temperature of the acrylic resin is 150°C or lower, it becomes easier to control the degree to which the acrylic resin substrate melts when forming the resin layer.

[0017] The acrylic resin substrate may contain resins other than acrylic resin, but it is preferable that the proportion of acrylic resin to the total resin constituting the acrylic resin substrate is 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0018] Acrylic resin substrates can be manufactured, for example, by melt-extruding pellets made of humidified acrylic resin, then stretching them longitudinally while cooling, and subsequently stretching them transversely. In the melt extrusion process, single-screw, double-screw, or double-screw or more-screw devices can be used, and the direction of screw rotation, rotation speed, and melting temperature can be set arbitrarily. Stretching should preferably be performed to achieve the desired thickness after stretching. While the stretching ratio is not limited, a ratio of 1.2 to 4.5 is preferred. The temperature and humidity during stretching can be determined arbitrarily. A general stretching method may be used.

[0019] The average thickness of the substrate is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 35 μm or more. By setting the average thickness of the substrate to 10 μm or more, it is possible to improve the handling properties of the anti-glare laminate. The average thickness of the substrate is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 60 μm or less. By making the average thickness of the substrate 100 μm or less, it is easier to improve the flexibility of the anti-glare laminate.

[0020] The average thickness of the substrate mentioned above refers to the average thickness of the substrate at the time the anti-glare laminate is completed. As will be described later, the average thickness of the substrate at the time the anti-glare laminate is completed may decrease from the initial average thickness of the substrate due to the dissolution of a portion of the substrate by the coating liquid for the resin layer. For this reason, it is preferable that the initial average thickness of the substrate be thicker than the average thickness of the substrate at the time the anti-glare laminate is completed. The difference between the initial average thickness of the substrate and the average thickness of the substrate at the time the anti-glare laminate is completed cannot be generalized as it varies depending on the thickness of the resin layer, the composition of the coating liquid for the resin layer, the drying conditions of the coating liquid, etc., but it is preferably 0.1 μm or more and 10 μm or less, and more preferably 1 μm or more and 5 μm or less.

[0021] The average thickness of the substrate can be calculated, for example, by selecting 20 arbitrary points from a cross-sectional image of the anti-glare laminate taken with a scanning transmission electron microscope (STEM) and taking the average value. It is preferable that the STEM acceleration voltage be between 10kV and 30kV, and the STEM magnification be between 1000x and 7000x. To measure the average thickness of the substrate, the thickness of the resin layer, the position of the first particle in the thickness direction of the resin layer, the average inclination angle of the surface of the substrate on the resin layer side, and the arithmetic mean height of the surface of the substrate on the resin layer side, it is necessary to prepare a sample for measurement in which the cross-section of the anti-glare laminate is exposed. The sample can be prepared, for example, by the following steps (A1) to (A2). If the interface etc. is difficult to see due to insufficient contrast, the sample may be stained with osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, etc., as a pretreatment.

[0022] (A1) After preparing cut samples by cutting the anti-glare laminate to any size, embedded samples are prepared by embedding the cut samples in resin. The size of the cut samples is, for example, a strip of 10 mm in length and 3 mm in width. Epoxy resin is preferred for embedding. An embedded sample can be obtained, for example, by placing a cut sample in a silicone embedding plate, pouring in embedding resin, and then, after the embedding resin has hardened, removing the cut sample and the embedding resin surrounding it from the silicone embedding plate. In the case of the epoxy resin manufactured by Storuas, as exemplified below, the hardening process described above is preferably carried out by leaving it at room temperature for 12 hours. The shape of the embedded sample is block-like. Silicone embedding plates can be found, for example, those manufactured by Dosaka EM Co., Ltd. Silicone embedding plates are sometimes also called silicone capsules. For embedding, epoxy resin can be used, for example, a mixture of "Epofix" (product name) and "Epofix Hardener" (product name) manufactured by Storuas Co., Ltd., in a ratio of 10:1.2.

[0023] (A2) A sample for measurement is prepared by vertically cutting a block-shaped embedded sample, exposing the cross-section of the anti-glare laminate. The thin section cut from the block-shaped embedded sample is used as the sample for measurement (the conditions for the measurement sample will be described later). It is preferable to cut the embedded sample so that it passes through the center of the cut sample. It is preferable to cut the embedded sample with a diamond knife. One example of a device used to cut embedded samples is the "Ultramicrotome EM UC7" manufactured by Leica Microsystems. When cutting embedded samples, it is preferable to first roughly cut them (coarse trimming) and then finally trim them precisely under the conditions of "SPEED: 1.00 mm / s" and "FEED: 70 nm". As described above, sections cut from a block-shaped embedded sample that are free of defects such as holes and have a uniform thickness of 60 nm to 100 nm can be used as samples for measuring the average thickness of the substrate, the thickness of the resin layer, the position of the first particle in the thickness direction of the resin layer, the average inclination angle of the surface of the substrate on the resin layer side, the arithmetic mean height of the surface of the substrate on the resin layer side, the particle diameter of the first particle, and the particle diameter of inorganic fine particles.

[0024] In this specification, unless otherwise specified, the atmosphere in which various measurements and evaluations, as well as sampling for measurements and evaluations, are carried out shall be a temperature of 23±5°C and a relative humidity of 40% to 65%. Furthermore, before carrying out measurements, evaluations, and samplings, the target anti-glare laminate shall be exposed to the aforementioned atmosphere for 30 minutes or more.

[0025] Condition 1, Condition 2 The anti-glare laminate of this disclosure must satisfy either condition 1 or condition 2 below. The anti-glare laminate of this disclosure only needs to satisfy at least one of condition 1 and condition 2, but it is preferable that it satisfies both. <Condition 1> The average inclination angle of the surface of the substrate on the resin layer side is 5.0 degrees or more and 20.0 degrees or less. <Condition 2> The arithmetic mean height of the resin layer side surface of the substrate is 0.10 μm or more and 0.40 μm or less.

[0026] -Condition 1- If the average tilt angle of the substrate is less than 5.0 degrees, the adhesion between the substrate and the resin layer will be insufficient, causing interfacial delamination when the anti-glare laminate is bent, making it impossible to improve the bending resistance of the anti-glare laminate. If the average tilt angle of the substrate exceeds 20.0 degrees, it means that substrate components will excessively dissolve into the resin layer. Therefore, if the average tilt angle of the substrate exceeds 20.0 degrees, it will be impossible to achieve good pencil hardness in the anti-glare laminate. In addition, if the average tilt angle of the substrate exceeds 20.0 degrees, internal haze will increase, which will easily lead to a decrease in resolution. The average inclination angle of the substrate is preferably 6.0 degrees or more, more preferably 8.0 degrees or more, and even more preferably 10.0 degrees or more. The average inclination angle of the substrate is preferably 19.5 degrees or less, more preferably 19.0 degrees or less, and even more preferably 18.5 degrees or less.

[0027] The average inclination angle and the arithmetic mean height of the substrate can be measured, for example, as follows: (1) A cross-sectional image of the anti-glare laminate is taken using a scanning transmission electron microscope (STEM). Preferably, the acceleration voltage of the STEM is 10kV to 30kV, and the magnification of the STEM is 5000x to 10000x. (2) From the cross-sectional image, obtain the edge of the interface between the substrate and the resin layer, and obtain the height data. Specifically, do the following: The interface between the substrate and the resin layer corresponds to the surface of the substrate on the resin layer side. (a) Display the captured images using ImageJ (version 1.52a), an open-source, public-domain image processing software. (b) Determine the length per pixel from the scale displayed in the image. (c) Select “FreeHand Selections” to create an ROI that includes the interface, and adjust the Brightness so that the colors are clearly different on either side of the interface. (d) Run Process-Smooth twice. (e) Set Image-Type to 8bit. (f) Select “Straight” and draw a line along the interface. (g) Install and run the ABSnake plugin for ImageJ. Set the "Gradient threshold" to 10 and the Draw color to Red. Leave all other settings at their default values. (h) Visually confirm that the interface can be traced with Red. If it is not, start again from (f). (i) Run Image-Adjust-Color Threshold. Set the threshold to separate Red from the others. Specifically, set the Color space to RGB, check "Pass" for "Red," "Green," and "Blue," set the upper and lower limits of the Red range to the maximum value (255), and the upper and lower limits of the Green and Blue ranges to the minimum value (0). (j) Execute Process-Binary-Make Binary to binarize the interface into the trace line portion and the portion other than the trace line portion. (k) Save the binarized data as "Text Image" using File-Save As. (l) Convert the binarized data into a sequence of height data points for the interface. (3) From the height data point sequence, calculate the average slope angle and arithmetic mean height using the following procedure. (m) The center line of the height data is found using the least squares method of quadratic regression, and subtracted from the height data to transform the data so that the center line is 0, the upward direction is positive, and the downward direction is negative. The direction of the center line is defined as the x-axis, and the direction perpendicular to it (height direction) is defined as the y-axis. (n) Using the length per pixel obtained in (b), convert the height data into length. (o) Apply a Gaussian low-pass filter with a cutoff wavelength of 0.5 μm. (p)tan -1 ((y i+1 -y i-1 ) / 2Δx)[yi The average slope angle is calculated by determining the arithmetic mean of the absolute values ​​of the slope angles of each point, which are obtained by [where Δx is the height at the i-th point in the height data point sequence, and Δx is the distance in the x-axis direction between adjacent points]. (q) Calculate the arithmetic mean height by calculating the arithmetic mean of the absolute values ​​of the heights of each point.

[0028] -Condition 2- If the arithmetic mean height of the substrate is less than 0.10 μm, the adhesion between the substrate and the resin layer is insufficient, causing interfacial delamination when the anti-glare laminate is bent, making it impossible to achieve good bending resistance of the anti-glare laminate. If the arithmetic mean height of the substrate exceeds 0.40 μm, it means that substrate components will excessively dissolve into the resin layer. Therefore, if the arithmetic mean height of the substrate exceeds 0.40 μm, it will be difficult to achieve good pencil hardness in the anti-glare laminate. In addition, if the arithmetic mean height of the substrate exceeds 0.40 μm, the internal haze will increase, which will easily lead to a decrease in resolution. The arithmetic mean height of the substrate is preferably 0.15 μm or more, and more preferably 0.20 μm or more. The arithmetic mean height of the substrate is more preferably 0.38 μm or less, and even more preferably 0.36 μm or less.

[0029] In order to set the average inclination angle and arithmetic mean height of the resin layer surface of the substrate within the range described above, it is preferable to dissolve a portion of the substrate with the resin layer coating solution. However, when dissolving the substrate with the resin layer coating solution, it is preferable to use a resin layer coating solution with a predetermined composition and predetermined drying conditions. The predetermined composition and predetermined drying conditions will be described later.

[0030] The base material may contain additives such as antioxidants, UV absorbers, light stabilizers, and plasticizers. The surface of the substrate may be subjected to physical or chemical treatments, such as corona discharge treatment, or a readily adhesive layer may be formed to improve adhesion.

[0031] <Resin layer> The resin layer must contain first particles with an average particle diameter of 0.5 μm or more. If the resin layer does not contain the first particle, it is not possible to impart anti-glare properties to the anti-glare laminate.

[0032] The anti-glare laminate of this disclosure requires that, when the area on the substrate side from the center in the thickness direction of the resin layer is defined as the first region and the area on the opposite side of the substrate from the center in the thickness direction of the resin layer is defined as the second region, at least 70% of the number of particles in the first region are present in the second region. Referring to Figures 1 and 2, the first particle 23 in Figure 1 is located in the second region 22, and the first particle 23 in Figure 2 is located in the first region 21.

[0033] If more than 70% of the first particle count criterion is not present in the second region, then more than 30% of the first particle count criterion is present in the first region. The first particles present in the first region make it difficult to create an uneven surface on the resin layer, and therefore, it is difficult to achieve good anti-glare properties, as in Comparative Example 2 described later. As shown in Comparative Example 1 below, if the absolute value of the content of the first particles is large, good anti-glare properties can be achieved even if 70% or more of the first particles are not present in the second region. However, in this case, the interface between the first particles and the resin layer increases, which causes a decrease in flexibility, and therefore the flexibility of the anti-glare laminate cannot be improved.

[0034] The proportion of the first particles present in the second region is preferably 75% or more, and more preferably 80% or more, based on the number of particles.

[0035] In this specification, the position of the first particle in the thickness direction of the resin layer shall be determined by the following methods (1) to (5). (1) A cross-sectional image of the anti-glare laminate is taken using a scanning transmission electron microscope (STEM). Preferably, the acceleration voltage of the STEM is 10kV to 30kV, and the magnification of the STEM is 1000x to 7000x. (2) Based on the cross-sectional photograph, calculate the average elevation X1 of the ridges on the substrate side of the resin layer and the average elevation X2 of the ridges on the opposite side of the substrate of the resin layer (see symbols X1 and X2 in Figure 1). (3) The midpoint between the elevations of X1 and X2 is defined as the center M in the thickness direction of the resin layer (see symbol M in Figure 1). (4) Based on the cross-sectional photograph, the number of first particles present in the first region on the substrate side from the center of the resin layer in the thickness direction, and the number of first particles present in the second region on the opposite side from the substrate from the center of the resin layer in the thickness direction are counted. For first particles present in both the first and second regions, straddling the center of the resin layer in the thickness direction, the number of particles is allocated to each region according to the area ratio of each region. For example, if the area ratio of the first region is 40% and the area ratio of the second region is 60%, then 0.4 particles are allocated to the first region and 0.6 particles are allocated to the second region. (5) To improve the reliability of the numerical values, multiple cross-sectional images are taken, and the total number of first particles is set to 50 or more, and the ratio of first particles based on the number of first particles present in the first and second regions is calculated.

[0036] The resin layer can be formed, for example, by applying a coating solution for the resin layer, which contains first particles, a resin component, and a solvent, onto a substrate, drying it, and curing it as needed. The coating solution for the resin layer may further contain inorganic fine particles and additives as needed. In the above method, the coating solution for the resin layer dissolves a portion of the substrate, creating an uneven surface on the resin layer side of the substrate. The components leached from the substrate mix with the coating solution for the resin layer and become constituent components of the resin layer. In the above method, it is essential to use a coating solution for the resin layer with a predetermined composition and predetermined drying conditions. The predetermined composition and predetermined drying conditions will be described later. The method for applying the coating liquid for the resin layer onto the substrate is not particularly limited, and general coating methods such as spin coating, dip coating, spray coating, die coating, bar coating, gravure coating, roll coating, meniscus coating, flexographic printing, screen printing, and speed coating are examples of such methods. When curing the coating liquid for the resin layer, it is preferable to irradiate it with ionizing radiation such as ultraviolet light and electron beams. Specific examples of ultraviolet light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamps. Furthermore, the wavelength of the ultraviolet light is preferably in the range of 190 nm to 380 nm. Specific examples of electron beam sources include various electron beam accelerators such as Cockcroftwald type, Van de Graft type, resonant transformer type, insulated core transformer type, linear type, Dynamitron type, and high-frequency type.

[0037] The average thickness of the resin layer is preferably 6.0 μm or more at the lower limit, more preferably 7.0 μm or more, and even more preferably 8.0 μm or more. The upper limit is preferably 15.0 μm or less, more preferably 14.0 μm or less, and even more preferably 13.0 μm or less. By setting the average thickness of the resin layer to 6.0 μm or more, it is easier to achieve good pencil hardness. By setting the average thickness of the resin layer to 15.0 μm or less, it is easier to suppress the decrease in bending resistance.

[0038] The average thickness of the resin layer can be calculated, for example, by selecting 20 arbitrary points from a cross-sectional image of the anti-glare laminate taken with a scanning transmission electron microscope (STEM) and taking the average value. It is preferable that the STEM acceleration voltage be between 10kV and 30kV, and the STEM magnification be between 1000x and 7000x.

[0039] 《The First Particle》 The first type of particle is one with an average particle diameter of 0.5 μm or more. If the average particle diameter is less than 0.5 μm, it is difficult to form an uneven surface on the resin layer, and good anti-glare properties cannot be achieved.

[0040] Examples of the first particles include organic particles formed from one or more resins such as polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, and polyester resin; and inorganic particles formed from one or more inorganic materials such as silica, alumina, zirconia, and titania. Among these, organic particles are preferred because they have excellent dispersion stability and a relatively low specific gravity, making it easier for the first particles to satisfy the positional conditions in the thickness direction.

[0041] The content of the first particles is preferably at a lower limit of 0.5 parts by mass or more, more preferably at 1.0 part by mass or more, and even more preferably at 1.5 parts by mass or more, with respect to 100 parts by mass or less, more preferably at 5.0 parts by mass or less, and even more preferably at 3.0 parts by mass or less, with respect to 100 parts by mass or less, and even more preferably at 3.0 parts by mass or less. By setting the content of the first particle to 0.5 parts by mass or more, it is easier to improve the anti-glare properties. Furthermore, by setting the content of the first particle to 10.0 parts by mass or less, it is easier to suppress the decrease in flexibility.

[0042] The average particle diameter of the first particles is preferably 0.8 μm or larger, and more preferably 1.0 μm or larger. To facilitate the satisfying of the positional conditions in the thickness direction for the first particles, the average particle diameter of the first particles is preferably 3.0 μm or less, more preferably 2.7 μm or less, and even more preferably 2.5 μm or less.

[0043] The average particle size of the first particle can be calculated, for example, by the following steps (B1) to (B3). (B1) Observe a transmission image of the anti-glare laminate using an optical microscope. A magnification of 500x to 2000x is preferred. (B2) Extract any 10 particles from the observation image and calculate the particle diameter of each particle. The particle diameter is measured as the distance between two straight lines in a combination of two straight lines such that the distance between the two straight lines is maximized when the cross-section of the particle is sandwiched by any two parallel straight lines. (B3) Perform the same operation 5 times on the observation images of different screens of the same sample, and use the value obtained from the number average of the particle diameters of a total of 50 particles as the average particle diameter of the particles. However, when the first particle cannot be observed optically, calculate the average particle diameter of the first particle according to the following (B4) to (B6). (B4) Prepare a section that is a cross-section passing through the center of the first particle from the antiglare laminate using a microtome. The thickness of the section is preferably 60 nm to 100 nm. For each first particle, prepare a plurality of consecutive sections, and the section with the maximum particle diameter calculated by the operation of (B5) from each section can be set as the section that is a cross-section passing through the center of the first particle. (B5) Observe the obtained section with a scanning transmission electron microscope (STEM) to calculate the particle diameter. The method for calculating the particle diameter is the same as that in (B2). The magnification is preferably 5000 times or more and 20000 times or less. (B6) Perform the operations of (B4) to (B5) on 20 particles, and use the value obtained from the number average of the particle diameters of 20 particles as the average particle diameter of the first particle.

[0044] It is preferable that D1 indicating the average particle diameter of the first particle and t indicating the average thickness of the resin layer have a relationship of 2.0 < t / D1 < 6.0. By setting t / D1 less than 6.0, it is easy to impart an uneven shape to the surface of the antiglare laminate by the first particle, so that the antiglare property can be easily improved. By setting t / D1 greater than 2.0, it is easy to suppress the decrease in the flexural resistance due to the protrusion of the first particle from the surface of the resin layer. For t / D1, the lower limit is more preferably 2.5 or more, further preferably 3.5 or more, and the upper limit is more preferably 5.0 or less, further preferably 4.5 or less.

[0045] The lower limit of t-D1 is preferably 2.0 μm or more, more preferably 3.0 μm or more, and even more preferably 4.0 μm or more, in order to help suppress the decrease in flexibility. The upper limit is preferably 10 μm or less, more preferably 8.0 μm or less, and even more preferably 7.0 μm or less, in order to help improve anti-glare properties.

[0046] 《Inorganic fine particles》 The resin layer may contain inorganic fine particles. By including inorganic fine particles with a relatively high specific gravity in the resin layer, the first particles are less likely to sink to the bottom of the resin layer, making it easier for the first particles to satisfy the positional condition in the thickness direction. In addition, the inorganic fine particles can improve the dispersibility of the first particles, making it easier to suppress the decrease in flexibility. In this specification, inorganic fine particles mean inorganic particles with an average primary particle diameter of 200 nm or less. The average particle size of the inorganic fine particles is preferably 1 nm to 200 nm, more preferably 2 nm to 100 nm, and even more preferably 5 nm to 50 nm.

[0047] The average particle size of inorganic microparticles can be calculated by the following steps (C1) to (C3). (C1) The cross-section of the anti-glare laminate is imaged using TEM or STEM. Preferably, the acceleration voltage of the TEM or STEM is 10kV to 30kV, and the magnification is 50,000x to 300,000x. (C2) Ten arbitrary inorganic microparticles are extracted from the observation image, and the particle diameter of each inorganic microparticle is calculated. The particle diameter is measured as the distance between two arbitrary parallel lines that maximize the distance between the two lines when the cross-section of the inorganic microparticle is sandwiched between them. (C3) Perform the same procedure five times on observation images of the same sample on different screens, and the average particle size of the inorganic microparticles is taken from the number average of the particle sizes of a total of 50 particles.

[0048] Examples of inorganic fine particles include those made of silica, alumina, zirconia, and titania. Among these, silica is preferred because it is easier to suppress the generation of internal haze.

[0049] The inorganic fine particle content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.7 parts by mass or more, per 100 parts by mass of the resin component of the coating liquid for the resin layer, at the lower limit, and preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less, per 100 parts by mass of the resin component of the coating liquid for the resin layer. By setting the inorganic fine particle content to 0.1 parts by mass or more, the first particles can more easily satisfy the positional condition in the thickness direction. Furthermore, by setting the inorganic fine particle content to 5.0 parts by mass or less, it is possible to suppress the first particles from floating excessively above the resin layer, thereby making it easier to suppress a decrease in flexibility.

[0050] Resin components The resin layer preferably contains a cured product of a curable resin composition as a resin component. Including a cured product of a curable resin composition in the resin layer makes it easier to improve the pencil hardness of the anti-glare laminate.

[0051] The ratio of the curable resin composition to the total amount of resin components in the coating liquid for the resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass.

[0052] Examples of cured products of curable resin compositions include cured products of thermosetting resin compositions and cured products of ionizing radiation-curable resin compositions. Among these, cured products of ionizing radiation-curable resin compositions are preferred because they easily achieve high pencil hardness and readily dissolve the substrate in their uncured state.

[0053] 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.

[0054] 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. As the ionizing radiation-curable compound, a compound having an ethylenically unsaturated bonding group is preferred. Ionizing radiation refers to electromagnetic waves or charged particle beams that possess energy quanta capable of polymerizing or bridging molecules. While ultraviolet rays or electron beams are commonly used, other electromagnetic waves such as X-rays and gamma rays, as well as charged particle beams such as alpha rays and ion beams, can also be used. In this specification, (meth)acryloyl group refers to either an acryloyl group or a metacloyl group. Also, in this specification, (meth)acrylate refers to either an acrylate or a methacrylate.

[0055] As the ionizing radiation-curable compound, either a monofunctional ionizing radiation-curable compound having one ionizing radiation-curable functional group or a polyfunctional ionizing radiation-curable compound having two or more ionizing radiation-curable functional groups can be used. Furthermore, as the ionizing radiation-curable compound, either monomers or oligomers can be used. In order to dissolve a portion of the substrate, increase the pencil hardness, and easily suppress curing shrinkage, it is preferable to use a mixture of the following (a) to (c) as the ionizing radiation-curable compound. The following (a) to (c) are preferably compounds having an ethylenically unsaturated bonding group as the ionizing radiation-curable functional group, and more preferably (meth)acrylate compounds. The (meth)acrylate compounds may also be those in which part of the molecular skeleton has been modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. (a) Monofunctional ionizing radiation-curable monomers (b) Polyfunctional ionizing radiation-curable monomers (c) Polyfunctional ionizing radiation-hardening oligomer

[0056] By including the monofunctional ionizing radiation-curable monomer (a) as the ionizing radiation-curable compound, it is possible to make it easier to dissolve a portion of the substrate, thereby making it easier to satisfy condition 1 or condition 2. Furthermore, by including the monofunctional ionizing radiation-curable monomer (a), it is possible to make the components eluted from the substrate more compatible with the components of the coating solution for the resin layer, thereby making it easier to improve the physical properties of the resin layer. However, if the amount of monofunctional ionizing radiation-curable monomer in (a) is too large, it may excessively dissolve the substrate, which may reduce the strength of the substrate or decrease the pencil hardness of the anti-glare laminate. By including the polyfunctional ionizing radiation-curable monomer of (b) as the ionizing radiation-curable compound, it is possible to improve the pencil hardness of the anti-glare laminate. However, if the amount of the polyfunctional ionizing radiation-curable monomer of (b) is too high, the hardness of the resin layer may become too high, which may reduce the flexibility of the anti-glare laminate. By including the polyfunctional ionizing radiation-curable oligomer of (c) as the ionizing radiation-curable compound, it is possible to suppress curing shrinkage while maintaining the pencil hardness of the anti-glare laminate. However, if the amount of the polyfunctional ionizing radiation-curable oligomer of (c) is too large, the pencil hardness of the anti-glare laminate may decrease.

[0057] The amount of the monofunctional ionizing radiation-curable monomer of (a) relative to the total amount of the ionizing radiation-curable compound is preferably 10% by mass or more and 40% by mass or less, more preferably 13% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 25% by mass or less. The amount of the polyfunctional ionizing radiation-curable monomer of (b) relative to the total amount of the ionizing radiation-curable compound is preferably 5% by mass or more and 20% by mass or less, more preferably 6% by mass or more and 15% by mass or less, and even more preferably 7% by mass or more and 13% by mass or less. The amount of (c) polyfunctional ionizing radiation-curable oligomer relative to the total amount of ionizing radiation-curable compounds is preferably 50% by mass or more and 85% by mass or less, more preferably 60% by mass or more and 80% by mass or less, and even more preferably 65% ​​by mass or more and 75% by mass or less.

[0058] Examples of monofunctional ionizing radiation-curable monomers in (a) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Among these, monofunctional monomers having a hydroxyl group, such as 4-hydroxybutyl (meth)acrylate, are preferred because they easily provide good adhesion to the substrate.

[0059] (b) Among the polyfunctional ionizing radiation-curable monomers, examples of bifunctional ionizing radiation-curable monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of ionizing radiation-curable monomers with three or more functions include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate. The number of functional groups in the polyfunctional ionizing radiation-curable monomer of (b) is preferably 3 to 5, more preferably 3 to 4, and even more preferably 3, in order to increase pencil hardness while suppressing curing shrinkage.

[0060] Examples of polyfunctional ionizing radiation-curable oligomers in (c) 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. 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.

[0061] The number of functional groups in the polyfunctional ionizing radiation-curable oligomer of (c) is preferably 4 to 8, more preferably 5 to 7, and even more preferably 6, in order to suppress curing shrinkage while maintaining pencil hardness. The weight-average molecular weight of the polyfunctional ionizing radiation-curable oligomer of (c) is preferably 1000 to 5000, more preferably 1100 to 3500, and even more preferably 1200 to 2000, in order to suppress curing shrinkage while maintaining pencil hardness. In this specification, weight-average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

[0062] 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. Examples of photopolymerization initiators include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, etc. Photopolymerization accelerators are those that can reduce polymerization inhibition by air during curing and accelerate the curing speed, and examples include one or more selected from p-dimethylaminobenzoate isoamyl ester, p-dimethylaminobenzoate ethyl ester, etc.

[0063] Additives The coating liquid for the resin layer may contain additives such as leveling agents, refractive index modifiers, antistatic agents, antifouling agents, ultraviolet absorbers, light stabilizers, antioxidants, viscosity modifiers, and thermal polymerization initiators, as needed.

[0064] "solvent" The coating liquid for the resin layer preferably contains a solvent. As the solvent, it is preferable to select a solvent that can dissolve the base material. However, if the base material is excessively dissolved, the strength of the base material will decrease. Therefore, it is preferable to select an appropriate solvent according to the type of the base material. Among the three components of the Hansen solubility parameter, the solvent preferably contains a solvent whose polar component δp is 7.0 (J / cm 3 ) 0.5 or more and 10.0 (J / cm 3 ). 0.5 By δp being 7.0 (J / cm 3 ) 0.5 or more, it is possible to easily dissolve the base material, and by being 10.0 (J / cm 3 ) 0.5 or less, it is possible to prevent excessive dissolution. The values of δp [(J / cm 3 ) 0.5 of toluene, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK) are as follows. ([Toluene: 1.4, IPA: 6.1, MEK: 9.0, MIBK: 6.1]) In addition, it is preferable to select the solvent in consideration of not only the solubility of the base material but also the evaporation rate inherent to the solvent. This is because when the evaporation rate of the solvent is slow, the base material is likely to be excessively dissolved. The rate at which the solvent evaporates can also be controlled by the drying conditions. For example, if the drying temperature is increased, the rate at which the solvent evaporates will increase. Also, if the drying wind speed is increased, the rate at which the solvent evaporates will increase. From the above, it is preferable to select the solvent in consideration of the solubility of the base material, the evaporation rate, and the drying conditions.

[0065] Examples of solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated carbons such as dichloromethane and dichloroethane; esters such as methyl acetate, ethyl acetate, and butyl acetate; alcohols such as isopropanol, butanol, and cyclohexanol; cellosolves such as methyl cellosolve and ethyl cellosolve; glycol ethers such as propylene glycol monomethyl ether acetate; cellosolve acetates; sulfoxides such as dimethyl sulfoxide; and amides such as dimethylformamide and dimethylacetamide. The solvent may be used alone or as a mixture of two or more.

[0066] Acrylic resin substrates are readily soluble in solvents. Therefore, when using an acrylic resin substrate as the base material, it is preferable to use a solvent with a fast evaporation rate inherent to the solvent as the main component. The main component means that it constitutes 50% by mass or more of the total amount of the solvent, preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass. In this specification, a solvent with a fast evaporation rate means a solvent whose evaporation rate is 100 or higher, with the evaporation rate of butyl acetate set to 100. The evaporation rate of a solvent with a fast evaporation rate is more preferably 120 to 450, and even more preferably 140 to 400. Examples of solvents with a fast evaporation rate include isopropyl alcohol (evaporation rate 150), methyl isobutyl ketone (evaporation rate 160), toluene (evaporation rate 200), and methyl ethyl ketone (evaporation rate 370).

[0067] Furthermore, the solvent preferably contains a solvent with a low molecular weight and high polarity. The highly polar solvent is preferably one whose Hansen solubility parameter δp is within the range described above. By including a solvent with a low molecular weight, high polarity, and the evaporation rate described above, the acrylic resin substrate can be properly dissolved. Methyl ethyl ketone is an example of such a solvent. The amount of methyl ethyl ketone is preferably 20% by mass or more and 40% by mass or less of the total amount of solvent, in order to easily satisfy condition 1 or condition 2.

[0068] Drying conditions When forming a resin layer from a coating liquid for resin layers, it is preferable to control the drying conditions. Furthermore, the anti-glare laminate of this disclosure is preferably dried in two stages using the resin coating liquid. Specifically, it is preferable to use a weaker drying intensity in the first stage and a stronger drying intensity in the second stage. During the first stage of weak drying, the substrate dissolves, a mixture is formed of components eluted from the substrate and components of the resin coating liquid, and the convection time of the mixture can be extended, making it easier to satisfy the conditions for the position of the first particles in the thickness direction. Also, by using a weaker drying intensity in the first stage, the components eluted from the substrate and components of the resin coating liquid mix more easily, making it easier to form a single resin layer. Then, by performing a strong drying in the second stage, excessive dissolution of the substrate can be suppressed, making it easier to prevent the average tilt angle and arithmetic mean height of the substrate from becoming too large.

[0069] Drying conditions can be controlled by the drying temperature and the airflow velocity inside the dryer. The preferred range for drying temperature and airflow velocity varies depending on the composition of the coating liquid for the resin layer and cannot be stated definitively, but the following conditions are preferable. <First stage of drying> The drying temperature is preferably between 65°C and 85°C, and the drying air velocity is preferably between 0.5 m / s and 2 m / s. The drying time is preferably between 20 seconds and 40 seconds. <Second stage of drying> The drying temperature is preferably between 65°C and 85°C, and the drying air velocity is preferably between 15 m / s and 25 m / s. The drying time is preferably between 20 seconds and 40 seconds.

[0070] In order to dissolve a portion of the substrate with the resin coating solution and to facilitate thorough mixing of the components eluted from the substrate with the resin coating solution, it is preferable to irradiate with ionizing radiation after the coating solution has dried.

[0071] <Other layers> The anti-glare laminate may have layers other than the base material and the resin layer. Examples of other layers include an anti-reflective layer, an anti-fouling layer, and an anti-static layer.

[0072] <Optical properties, surface shape> The anti-glare laminate preferably has a total light transmittance of 70% or more, more preferably 80% or more, and even more preferably 85% or more, according to JIS K7361-1:1997. When measuring total light transmittance and the haze described later, the light incident surface shall be the substrate side.

[0073] The anti-glare laminate preferably has a haze of 0.5% or more, more preferably 1.0% or more, and even more preferably 1.5% or more, according to JIS K7136:2000. By setting the haze to 0.5% or more, it is easier to improve the anti-glare properties. Furthermore, in order to make it easier to suppress the decrease in image resolution, the anti-glare laminate preferably has a haze of 20% or less, more preferably 10% or less, and even more preferably 5% or less.

[0074] To facilitate good anti-glare properties, the arithmetic mean roughness Ra of the resin layer surface of the anti-glare laminate is preferably 0.03 μm or more, and more preferably 0.05 μm or more, according to JIS B0601:2001. Furthermore, to facilitate suppression of image resolution degradation, the Ra of the resin layer surface of the anti-glare laminate is preferably 0.12 μm or less, and more preferably 0.10 μm or less. Ra refers to the value at a cutoff value of 0.8 mm.

[0075] <Size, shape, etc.> The anti-glare laminate 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 should be between 2 inches and 500 inches. "Maximum diameter" refers to the maximum length when connecting any two points on the anti-glare laminate. For example, if the anti-glare laminate is rectangular, the diagonal of the rectangle will be the maximum diameter. If the anti-glare laminate is circular, the diameter of the circle will be the maximum diameter. The width and length of the roll are not particularly limited, but generally, the width is 500 mm to 3000 mm and the length is 500 m to 5000 m. The anti-glare laminate 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. The shape of the sheet is not particularly limited; for example, it may be a polygon such as a triangle, square, or pentagon, or it may be circular, or it may be a random, irregular shape. More specifically, if the anti-glare laminate is rectangular, the aspect ratio is not particularly limited as long as it does not cause problems as a display screen. Examples include width:height = 1:1, 4:3, 16:10, 16:9, 2:1, 5:4, 11:8, etc.

[0076] [Polarizing plate] The polarizing plate of the present disclosure is a polarizing plate having a polarizer, a first transparent protective plate disposed on one side of the polarizer, and a second transparent protective plate disposed on the other side of the polarizer, wherein at least one of the first transparent protective plate and the second transparent protective plate is the anti-glare laminate of the present disclosure described above.

[0077] Polarizing plates are used, for example, to provide anti-reflective properties by combining them with λ / 4 phase difference plates. In this case, the λ / 4 phase difference plate is placed on the display element of an image display device, and the polarizing plate is placed on the viewer side of the λ / 4 phase difference plate. When a polarizing plate is used for a liquid crystal display device, the polarizing plate is used to provide the function of a liquid crystal shutter. In this case, the liquid crystal display device is arranged in the order of a lower polarizing plate, a liquid crystal display element, and an upper polarizing plate, and the absorption axis of the polarizer of the lower polarizing plate and the absorption axis of the polarizer of the upper polarizing plate are arranged orthogonally. In the above configuration, it is preferable to use the polarizing plate of this disclosure as the upper polarizing plate.

[0078] <Transparent protection plate> In the polarizing plate of the present disclosure, at least one of the first transparent protective plate and the second transparent protective plate is the anti-glare laminate of the present disclosure described above. A preferred embodiment is one in which the light-emitting transparent protective plate of the first and second transparent protective plates is the anti-glare laminate of the present disclosure described above. It is preferable that the anti-glare laminate is arranged such that the substrate-side surface of the anti-glare laminate faces the polarizer side.

[0079] If one of the first transparent protective plate and the second transparent protective plate is the anti-glare laminate of the present disclosure described above, the other transparent protective plate is not particularly limited, but an optically isotropic transparent protective plate is preferred. In this specification, optical isotropy refers to a plane phase difference of 20 nm or less, preferably 10 nm or less, and more preferably 5 nm or less. Acrylic films and triacetylcellulose (TAC) films are easily given optical isotropy.

[0080] <Polarizer> 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 do not transmit through them.

[0081] <Size, shape, etc.> Embodiments of the size and shape of the polarizing plate of this disclosure include the embodiments of the size and shape of the anti-glare laminate of this disclosure described above.

[0082] [Image display device] The image display device of this disclosure has the anti-glare laminate of this disclosure described above on a display element.

[0083] Figure 3 is a cross-sectional view showing an embodiment of the image display device 500 of the present disclosure. The image display device 500 in Figure 3 has an anti-glare laminate 100 of the present disclosure on a display element 200. Within the image display device, it is preferable to arrange the anti-glare laminate so that the substrate side faces the display element side.

[0084] Examples of display elements include liquid crystal display elements; EL display elements (organic EL display elements, inorganic EL display elements); plasma display elements; display elements using QD (Quantum Dot); LED display elements such as mini-LEDs and micro-LEDs; and others. These display elements may also have a touch panel function inside. Examples of liquid crystal display methods for liquid crystal display elements include IPS, VA, multi-domain, OCB, STN, and TSTN methods. When the display element is a liquid crystal display element, a backlight is required. The backlight is positioned on the side opposite to the side where the anti-glare laminate of the liquid crystal display element is located.

[0085] Furthermore, the image display device of this disclosure may also be an image display device with a touch panel, having a touch panel between the display element and the anti-glare laminate. In this case, it is preferable to place the anti-glare laminate on the outermost surface of the image display device with a touch panel, and to position the substrate side of the anti-glare laminate facing the display element side.

[0086] The size of the image display device is not particularly limited, but it is preferable that the maximum diameter of the effective display area is between 2 inches and 500 inches. The effective display area of ​​an image display device is the area in which an image can be displayed. For example, if an image display device has a housing that surrounds the display element, the area inside the housing becomes the effective image area. The maximum diameter of the effective image area is defined as the maximum length between any two points within the effective image area. For example, if the effective image area is rectangular, the diagonal of the rectangle is the maximum diameter. If the effective image area is circular, the diameter of the circle is the maximum diameter.

[0087] The image display device disclosed herein is preferably a foldable type or a rollable type because the anti-glare laminate has excellent flexibility. [Examples]

[0088] Next, the present disclosure will be described in more detail by examples, but the present disclosure is not limited in any way by these examples. Unless otherwise specified, "parts" and "%" refer to mass.

[0089] 1. Measurement and Evaluation The anti-glare laminates of the examples and comparative examples were measured and evaluated as follows. The atmosphere during each measurement and evaluation was a temperature of 23±5°C and a relative humidity of 40% to 65%. In addition, before starting each measurement and evaluation, the target sample was exposed to the above atmosphere for 30 minutes or more. The results are shown in Table 2.

[0090] 1-1. Average inclination angle of the resin layer side surface of the substrate, and arithmetic mean height of the resin layer side surface of the substrate. In accordance with the description in the specification, samples were prepared in which the cross-sections of the anti-glare laminates of the examples and comparative examples were exposed. From the cross-sectional images of the samples taken with a scanning transmission electron microscope, the average inclination angle of the surface on the resin layer side of the substrate and the arithmetic mean height of the surface on the resin layer side of the substrate were calculated in accordance with the description in the specification.

[0091] 1-2. Position of the first particle In accordance with the description in the specification, samples of the anti-glare laminates of the examples and comparative examples were prepared with exposed cross-sections. From the cross-sectional images of the samples taken with a scanning transmission electron microscope, the proportion of the first particles present in the second region was calculated based on their number. In calculating the proportion, multiple cross-sectional images were taken until the total number of first particles exceeded 50.

[0092] 1-3. Average thickness of the resin layer In accordance with the description in the specification, samples of the anti-glare laminates of the examples and comparative examples with exposed cross-sections were prepared. Twenty arbitrary points were selected from the cross-sectional photographs of the samples taken with a scanning transmission electron microscope, and the average thickness t of the resin layer was calculated from the average value of these points.

[0093] 1-4. Total light transmittance (Tt) and haze (Hz) The anti-glare laminates of the examples and comparative examples were cut into 10 cm squares. The cutting locations were selected randomly after visually confirming that there were no abnormalities such as dust or scratches. The total light transmittance according to JIS K7361-1:1997 and the haze according to JIS K7136:2000 were measured for each sample using a haze meter (HM-150, manufactured by Murakami Color Technology Laboratory). To ensure the light source stabilized, the device's power switch was turned ON and waited for at least 15 minutes. Calibration was performed with nothing in the inlet opening (where the measurement sample is placed), and then the measurement sample was placed in the inlet opening and measurements were taken. The light incidence surface was the substrate side.

[0094] 1-5. Flexibility The anti-glare laminates of the examples and comparative examples were subjected to a bending resistance test using the cylindrical mandrel method specified in JIS K5600-5-1:1999. The diameter of the mandrel was gradually reduced, and Table 2 shows the diameter of the mandrel at which the anti-glare laminate first cracked. A diameter of 5 mm or less is considered acceptable. When wrapping the anti-glare laminate around the mandrel, the base material side was made to face the mandrel side.

[0095] 1-6.Pencil hardness Samples of the anti-glare laminates of the examples and comparative examples were prepared by cutting them to a size of 50 mm x 100 mm. The pencil hardness of the upper surface of the resin layer of the samples was measured in accordance with JIS K5600-5-4:1999 under conditions of a load of 500 g and a speed of 1.4 mm / second. For the measurements, a pencil hardness tester (model number: NP type pencil scratch coating hardness tester) manufactured by Toyo Seiki Seisakusho was used. Using mending tape (3M, model number "810-3-18"), both ends of the cut sample were attached to the base of the pencil hardness tester. Five pencil hardness tests were performed, and the hardness at which no scratches or other appearance abnormalities were observed in three or more tests was taken as the pencil hardness value for each sample. For example, if a 2H pencil was used and no appearance abnormalities occurred in three out of five tests, the pencil hardness of the anti-glare laminate was considered to be 2H. Appearance abnormalities were checked for scratches and dents, but discoloration was not included. A pencil hardness of 2H or higher is considered an acceptable level.

[0096] 1-7. Anti-glare property Samples were prepared by laminating a black plate (Kuraray Co., Ltd., product name "Comoglass DFA2CG 502K (black) series", total light transmittance 0%, thickness 2 mm, refractive index 1.49) to the substrate side of the anti-glare laminates of the examples and comparative examples (sample size: 10 cm x 10 cm). The samples were then examined by 20 subjects under bright room conditions (illuminance on the first main surface of the sample was between 500 lux and 1000 lux; lighting: Hf32 type straight tube tri-wavelength daylight white fluorescent lamp) from a straight-line distance of 50 cm above the center of the first main surface of the sample, to determine whether sufficient anti-glare properties were achieved, such that the observer's own reflection was not noticeable, according to the following criteria. The position of the lighting during evaluation was 2 m vertically above the horizontal table. The subjects were healthy individuals in their 30s with a visual acuity of 0.7 or better. A: More than 14 people answered "good". B: 7 to 13 people answered "good" C: Six or fewer people answered "good".

[0097] 2. Fabrication of anti-glare laminates [Example 1] (Manufacturing of base materials) A copolymer of methyl methacrylate and methyl acrylate was kneaded at 260°C using a twin-screw extruder to obtain a pelletized composition (glass transition temperature: 134°C). The obtained pelletized composition was melt-extruded using a T-die (T-die temperature: 260°C) and discharged onto a cooling roll at 130°C. Next, it was sequentially biaxially stretched in the longitudinal and transverse directions at a stretching ratio of 1.5 times at a stretching temperature of 145°C. After cooling, an acrylic resin substrate with a thickness of 40 μm was obtained. (Formation of resin layer) On the aforementioned acrylic resin substrate, the resin layer coating solution of Example 1 in Table 1 was applied using the Meyer bar coating method at a rate of 6.0 g / m². 2After applying the coating solution, the first stage of drying was performed by drying it with hot air at a wind speed of 1 m / s and a temperature of 70°C for 30 seconds. Furthermore, the second stage of drying was performed by drying the coating solution with hot air at a wind speed of 20 m / s and a temperature of 70°C for 30 seconds. Subsequently, under a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, the cumulative light intensity was 100 mJ / cm². 2 By irradiating with ultraviolet light in such a manner, the ionizing radiation-curable resin composition of the resin layer coating liquid was cured, forming a resin layer and obtaining the anti-glare laminate of Example 1. In this specification, the coating amount refers to the coating amount after drying.

[0098] [Examples 2-4], [Comparative Examples 1-4] Except for changing the composition of the coating solution for the resin layer, the amount of coating solution applied, and the drying conditions for the coating solution for the resin layer as described in Table 1, anti-glare laminates of Examples 2 to 4 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1.

[0099] [Table 1]

[0100] In Table 1, the hexafunctional urethane acrylate oligomer is Mitsubishi Chemical's urethane acrylate oligomer (product name: Shiko UV-7600B, weight-average molecular weight: 1400), the bifunctional acrylate monomer is tetraethylene glycol diacrylate, the trifunctional acrylate monomer is pentaerythritol triacrylate, the tetrafunctional acrylate monomer is pentaerythritol tetraacrylate, the monofunctional acrylate monomer is 4-hydroxybutyl acrylate, and the photopolymerization initiator is IGM Resins BV's product name "Omnirad 184".

[0101] [Table 2]

[0102] The results in Table 2 confirm that the anti-glare laminates of the examples exhibit good pencil hardness, flexibility, and anti-glare properties. On the other hand, in the anti-glare laminates of Comparative Examples 1 and 2, more than 70% of the first particles are absent from the second region. In the anti-glare laminate of Comparative Example 1, more than 70% of the first particles are absent from the second region, but because the content of the first particles is high, the anti-glare performance is at an acceptable level. However, because the anti-glare laminate of Comparative Example 1 has a high content of the first particles, the interface between the first particles and the resin layer increases, which causes a decrease in flexibility, and thus the decrease in flexibility of the anti-glare laminate could not be suppressed. In the anti-glare laminate of Comparative Example 2, more than 70% of the first particles are absent from the second region, and the content of the first particles is not high, so good anti-glare performance could not be achieved. In the anti-glare laminates of Comparative Examples 1 and 2, the reason why more than 70% of the first particle count is not present in the second region is thought to be that the strong initial drying intensity caused the solvent to evaporate before sufficient convection of the coating liquid occurred, making it difficult for the first particles to float to the top of the resin layer due to convection. The optical laminate of Comparative Example 3 has a large average tilt angle and arithmetic mean height of the substrate. In other words, in the optical laminate of Comparative Example 3, a large amount of substrate components eluted into the resin layer, which reduced the hardness of the resin layer and prevented it from achieving a good pencil hardness. It is thought that the optical laminate of Comparative Example 3 had a large proportion of monofunctional monomers, which led to excessive elution of the substrate, resulting in a large average tilt angle and arithmetic mean height of the substrate. The optical laminate of Comparative Example 4 had a small average tilt angle and arithmetic mean height of the substrate, which resulted in poor adhesion between the substrate and the resin layer, and thus the reduction in flexibility could not be suppressed. It is thought that the optical laminate of Comparative Example 4 did not contain monofunctional monomers and did not contain highly polar methyl ethyl ketones, so the dissolution of the substrate did not progress, resulting in a small average tilt angle and arithmetic mean height of the substrate. Although the optical laminate of Comparative Example 2 also did not contain monofunctional monomers and did not contain highly polar methyl ethyl ketones, it is thought that the optical laminate of Comparative Example 2 contained a large amount of difunctional monomers with a small number of functional groups, which is thought to have dissolved the substrate. [Explanation of symbols]

[0103] 10: Base material 20: Resin layer 21:First area 22:Second area 23: The first particle 100: Anti-glare laminate 200: Display element 500: Image display device

Claims

1. An anti-glare laminate having a resin layer on a substrate, The aforementioned substrate is an acrylic resin substrate, The resin layer contains first particles with an average particle diameter of 0.5 μm or more. When the area on the substrate side of the center of the resin layer in the thickness direction is defined as the first region, and the area on the opposite side of the substrate from the center of the resin layer in the thickness direction is defined as the second region, then 70% or more of the first particle count criterion is present in the second region. An anti-glare laminate that satisfies either condition 1 or condition 2 below. <Condition 1> The average inclination angle of the surface of the substrate on the resin layer side is 5.0 degrees or more and 20.0 degrees or less. <Condition 2> The arithmetic mean height of the resin layer side surface of the substrate is 0.10 μm or more and 0.40 μm or less.

2. The anti-glare laminate according to claim 1, wherein D1, which represents the average particle diameter of the first particles, and t, which represents the average thickness of the resin layer, satisfy the relationship 2.0 < t / D1 < 6.

0.

3. The anti-glare laminate according to claim 1 or 2, wherein the first particles are organic particles.

4. The anti-glare laminate according to any one of claims 1 to 3, wherein the resin layer comprises a cured product of a curable resin composition.

5. The anti-glare laminate according to claim 4, wherein the cured product of the curable resin composition is a cured product of an ionizing radiation-curable resin composition.

6. The anti-glare laminate according to any one of claims 1 to 5, wherein the glass transition temperature of the acrylic resin contained in the acrylic resin substrate is 100°C or more and 150°C or less.

7. The anti-glare laminate according to any one of claims 1 to 6, wherein the resin layer contains the same acrylic resin as the acrylic resin contained in the acrylic resin substrate.

8. A polarizing plate having a polarizer, a first transparent protective plate disposed on one side of the polarizer, and a second transparent protective plate disposed on the other side of the polarizer, wherein at least one of the first transparent protective plate and the second transparent protective plate is an anti-glare laminate according to any one of claims 1 to 7.

9. An image display device having an anti-glare laminate according to any one of claims 1 to 7 on a display element.

10. The image display device according to claim 9, which is a foldable type image display device or a rollable type image display device.

11. A method for manufacturing an anti-glare laminate having a resin layer on a substrate, The aforementioned substrate is an acrylic resin substrate, The process includes a first step of applying and drying a resin layer coating solution containing first particles with an average particle size of 0.5 μm or more, a resin component, and a solvent onto the acrylic resin substrate. A method for manufacturing an anti-glare laminate, wherein in the first step, a portion of the acrylic resin substrate is dissolved by the coating liquid for the resin layer, and the dissolved components of the acrylic resin substrate become part of the components constituting the resin layer, thereby obtaining the anti-glare laminate described below. <Anti-glare laminate> Having a resin layer on an acrylic resin substrate, The resin layer contains first particles with an average particle diameter of 0.5 μm or more. When the area on the substrate side of the center of the resin layer in the thickness direction is defined as the first region, and the area on the opposite side of the substrate from the center of the resin layer in the thickness direction is defined as the second region, then 70% or more of the first particle count criterion is present in the second region. An anti-glare laminate that satisfies either condition 1 or condition 2 below. <Condition 1> The average inclination angle of the surface of the substrate on the resin layer side is 5.0 degrees or more and 20.0 degrees or less. <Condition 2> The arithmetic mean height of the resin layer side surface of the substrate is 0.10 μm or more and 0.40 μm or less.

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