Antiglare laminate, polarizing plate and image display device

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 comprising a first resin layer and a second resin layer in order from the substrate side and containing first particles having an average particle diameter of 0.5 μm or greater, where 70% or more of the first particles on a number basis are present across the first and second resin layers. The anti-glare laminate satisfies the following expression (1). 5<t1 / t2<15 ...(1), where t1 represents the average thickness of the first resin layer and t2 represents the average thickness of the second resin layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to an antiglare laminate, a polarizing plate, and an image display device. [Background technology]

[0002] Antiglare laminates are sometimes applied to the surfaces of image display devices such as televisions, notebook PCs, and desktop PC monitors to impart antiglare properties. Antiglare properties are the property of suppressing the reflection of lighting and people in the background.

[0003] An antiglare laminate has a basic structure including an antiglare layer having an uneven surface on a substrate. Antiglare laminates are often used as surface components for image display devices and the like, and therefore are frequently exposed to contact with human fingers, objects, and the like. For this reason, it is preferable that the antiglare laminate has a high pencil hardness.

[0004] In order to increase the pencil hardness of the antiglare laminate, a cured product of a curable resin composition is preferably used as the resin component of the antiglare layer (for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6840215 [Patent Document 2] International Publication No. WO2018 / 070426 Summary of the Invention [Problem to be solved by the invention]

[0006] Since the anti-glare laminates of Patent Documents 1 and 2 have a high hardness of the anti-glare layer, the pencil hardness is good. However, the anti-glare laminates of Patent Documents 1 and 2 may have insufficient flex resistance. Specifically, when the anti-glare laminates of Patent Documents 1 and 2 are applied to a foldable type image display device or a rollable type image display device, cracks may occur in the anti-glare laminates. The above-described flex resistance tended to deteriorate when an acrylic resin substrate was used as the substrate of the anti-glare laminate.

[0007] An object of the present disclosure is to provide an anti-glare laminate excellent in pencil hardness and flex resistance, and a polarizing plate and an image display device using the same. [Means for Solving the Problems]

[0008] The present disclosure provides the following anti-glare laminates, polarizing plates, and image display devices of [1] to [3]. [1] An anti-glare laminate having a resin layer on a substrate, The resin layer has a first resin layer and a second resin layer from the substrate side, The resin layer contains first particles having an average particle diameter of 0.5 μm or more, 70% or more of the first particles based on the number are present across the first resin layer and the second resin layer, An anti-glare laminate satisfying the following formula 1. 5.0 < t1 / t2 < 15.0 (Formula 1) [In Formula 1, t1 represents the average thickness of the first resin layer, and t2 represents the average thickness of the second resin layer. ] [2] A polarizing plate having a polarizer, a first transparent protection plate disposed on one side of the polarizer, and a second transparent protection plate disposed on the other side of the polarizer, wherein at least one of the first transparent protection plate and the second transparent protection plate is the anti-glare laminate according to [1]. [3] An image display device having the anti-glare laminate according to [1] on a display element. [Advantages of the Invention]

[0009] The antiglare laminate of the present disclosure can improve pencil hardness and flexural resistance. Since the polarizing plate and the image display device of the present disclosure have an antiglare laminate excellent in pencil hardness and flexural 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 3. [Figure 3] It is a cross-sectional view showing the antiglare laminate of Comparative Example 4. [Figure 4] It is a cross-sectional view showing an embodiment of the image display device of the present disclosure.

Embodiments 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 has a first resin layer and a second resin layer from the substrate side, The resin layer contains first particles having an average particle diameter of 0.5 μm or more, 70% or more of the first particles based on the number are present across the first resin layer and the second resin layer, It is an antiglare laminate that satisfies the following formula (1). 5.0 < t1 / t2 < 15.0 (Formula 1) [In Formula (1), t1 represents the average thickness of the first resin layer, and t2 represents the average thickness of the second resin layer.]

[0012] FIG. 1 is a cross-sectional view showing an embodiment of the antiglare laminate 100 of the present disclosure. The antiglare laminate 100 of FIG. 1 has a resin layer 20 on a substrate 10. The resin layer 20 of FIG. 1 has, from the substrate 10 side, a first resin layer 21 and a second resin layer 22. The resin layer 20 of FIG. 1 contains first particles 23 having an average particle diameter of 0.5 μm or more. The first particles 23 in FIG. 1 are present across the first resin layer 21 and the second resin layer 22. Note that Fig. 1 is a schematic cross-sectional view. That is, the scale of each layer constituting the antiglare laminate 100, the scale of each material, and the scale of the surface irregularities are schematic for ease of illustration and differ from the actual scale. Similarly, the other figures than Fig. 1 also differ from the actual scale.

[0013] <Base material> The substrate preferably has good light transmittance, smoothness, heat resistance, and mechanical strength. Examples of such substrates include resin substrates containing resins such as polyester, triacetyl cellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, acrylic resin, polycarbonate, polyurethane, and amorphous olefin (cycloolefin polymer: COP). The resin substrate may be a laminate of two or more resin substrates. The resin substrate is preferably subjected to a stretching treatment in order to improve mechanical strength and dimensional stability.

[0014] Among resin substrates, acrylic resin substrates are preferred because they have low hygroscopicity, which makes it easy to improve dimensional stability, and low optical anisotropy, which makes it easy to improve visibility. Furthermore, the acrylic resin substrate can easily form the first and second resin layers in a single coating by using a resin layer coating liquid with a predetermined composition and drying conditions. Because acrylic resin substrates are hard and brittle, forming a resin layer containing a cured product of a curable resin composition on the acrylic resin substrate may result in insufficient flex resistance. Even when a resin layer containing a cured product of a curable resin composition is formed on the acrylic resin substrate, the antiglare laminate of the present disclosure can easily suppress a decrease in flex resistance by having the first particles present at predetermined positions in the thickness direction of the resin layer and by satisfying Formula 1. In this specification, the acrylic resin means an acrylic resin and / or a methacrylic resin.

[0015] The acrylic resin contained in the acrylic resin substrate is not particularly limited, but is preferably, for example, one obtained by polymerizing one or more (meth)acrylic acid alkyl esters in combination, and more specifically, one obtained using methyl (meth)acrylate. Examples of acrylic resins include those described in JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, JP-A-2002-254544, and JP-A-2005-146084. Examples of acrylic resins that may be used include those having a ring structure, such as an acrylic resin having a lactone ring structure or an acrylic resin having an imide ring structure.

[0016] The acrylic resin preferably has a glass transition point (Tg) of 100°C or higher and 150°C or lower, more preferably 105°C or higher and 135°C or lower, and even more preferably 110°C or higher and 130°C or lower. When the glass transition point of the acrylic resin is 100°C or higher, it is possible to easily prevent the acrylic resin substrate from excessively dissolving when the resin layer is formed.When the glass transition point of the acrylic resin is 150°C or lower, it is possible to easily control the degree of dissolution of the acrylic resin substrate when the resin layer is formed.

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

[0018] The acrylic resin substrate can be produced, for example, by melt-extruding pellets made of humidity-conditioned acrylic resin, stretching the pellets in the machine direction while cooling them, and then stretching them in the transverse direction. In the melt extrusion step, a single screw, twin screws, or two or more screws can be used, and the rotation direction, rotation speed, and melt temperature of the screw can be set arbitrarily. Stretching is preferably carried out so that the film has a desired thickness after stretching. The stretching ratio is not limited, but is preferably 1.2 times or more and 4.5 times or less. The temperature and humidity during stretching can be determined as desired. A conventional 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 making the average thickness of the substrate 10 μm or more, the handleability of the antiglare laminate can be improved. 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 setting the average thickness of the substrate to 100 μm or less, the flex resistance of the antiglare laminate can be more easily improved.

[0020] The average thickness of the substrate mentioned above refers to the average thickness of the substrate when the antiglare laminate is completed. As will be described later, the average thickness of the substrate when the antiglare laminate is completed may be reduced from the initial average thickness of the substrate due to partial dissolution of the substrate by the resin layer coating liquid. For this reason, it is preferable that the initial average thickness of the substrate be greater than the average thickness of the substrate when the antiglare laminate is completed. The difference between the initial average thickness of the substrate and the average thickness of the substrate when the antiglare laminate is completed cannot be generalized because it varies depending on the thickness of the resin layer, the composition of the resin layer coating liquid, the drying conditions of the coating liquid, etc., but is preferably 0.1 μm to 10 μm, more preferably 1 μm to 5 μm.

[0021] The average thickness of the substrate can be calculated, for example, by averaging 20 arbitrary points selected from a cross-sectional photograph of the antiglare laminate taken with a scanning transmission electron microscope (STEM). The acceleration voltage of the STEM is preferably 10 kV to 30 kV, and the magnification of the STEM is preferably 1000x to 7000x. In order to measure the average thickness of the substrate, the thickness of the first resin layer, the thickness of the second resin layer, the position of the first particles in the thickness direction of the resin layer, the average inclination angle of the surface of the substrate facing the resin layer, the arithmetic mean height of the surface of the substrate facing the resin layer, etc., it is necessary to prepare a measurement sample in which the cross section of the antiglare laminate is exposed. The sample can be prepared, for example, by steps (A1) and (A2) described below. Note that if the interface is difficult to see due to insufficient contrast, the sample may be dyed with osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, or the like as a pretreatment.

[0022] In this specification, unless otherwise specified, the atmosphere in which various measurements and evaluations, and sampling for the measurements and evaluations, are carried out is a temperature of 23±5°C and a relative humidity of 40% to 65%. Furthermore, before carrying out the measurements, evaluations, and sampling, the antiglare laminate to be measured is exposed to the above atmosphere for 30 minutes or more.

[0023] The substrate preferably has an average inclination angle of 5.0 degrees or more and 15.0 degrees or less on the surface of the substrate facing the resin layer. By setting the average tilt angle to 5 degrees or more, it becomes easier to improve the flex resistance of the antiglare laminate. The reason for the improved flex resistance is thought to be that the adhesion between the substrate and the resin layer is good, so that interfacial peeling does not occur when the laminate is bent. By setting the average inclination angle to 15 degrees or less, it is possible to easily suppress an increase in internal haze. Furthermore, in the case of an embodiment in which a part of the substrate is dissolved in the coating liquid for the resin layer, by setting the average inclination angle to 15 degrees or less, it is possible to easily make the pencil hardness good. The reason why the pencil hardness can be easily made good in the above-mentioned embodiment is thought to be that the substrate components are not excessively eluted into the resin layer, so that the hardness of the resin layer is less likely to decrease. The average tilt angle of the substrate is more preferably 5.5 degrees or more, and even more preferably 6.0 degrees or more. The average tilt angle of the substrate is more preferably 14.0 degrees or less, and even more preferably 13.0 degrees or less.

[0024] The average tilt angle of the substrate and the arithmetic mean height of the substrate can be measured, for example, as follows. (1) A cross-sectional photograph of the antiglare laminate is taken with a scanning transmission electron microscope (STEM). The acceleration voltage of the STEM is preferably 10 kV to 30 kV, and the magnification of the STEM is preferably 5,000 times to 10,000 times. (2) From the image of the cross-sectional photograph, the ridge line of the interface between the substrate and the resin layer is obtained, and height data is acquired. Specifically, this is done as follows. The interface between the substrate and the resin layer corresponds to the surface of the substrate on the resin layer side. (a) The captured images were displayed using ImageJ (version 1.52a), an open-source, public domain image processing software. (b) The length per pixel is calculated from the scale displayed in the image. (c) Select “FreeHand Selections” and create an ROI that includes the interface. Adjust the Brightness to create a clear color difference at the interface. (d) Process-Smooth twice. (e) Set Image-Type to 8bit. (f) Select “Straight” to draw a line along the interface. (g) Install and run ABSnake, an ImageJ plugin. Set “Gradient threshold” to 10 and Draw color to Red. Leave other settings as default. (h) Visually check that the interface can be traced in red. If it is not, start again from (f). (i) Run Image-Adjust-Color Threshold. Set the threshold to separate Red from everything else. Specifically, set 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 set 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 trace line portion of the interface and the portion other than the trace line. (k) Save the binarized data as “Text Image” using File-Save As. (l) From the binarized data, the interface is converted into a sequence of height data points. (3) From the sequence of height data points, calculate the average slope angle and arithmetic mean height using the following procedure. (m) The center line of the height data is found using quadratic regression with the least squares method, and by subtracting it from the height data, the center line is converted to 0, with the upward direction being positive and the downward direction being negative. The direction of the center line is the x-axis, and the direction perpendicular to it (height direction) is the y-axis. (n) Using the length per pixel calculated in (b), convert the height data into length. (o) A Gaussian low-pass filter with a cutoff wavelength of 0.5 μm is applied. (p)tan -1 ((y i+1 -y i-1 ) / 2Δx)[y iThe average tilt angle is calculated by calculating the arithmetic mean of the absolute values ​​of the tilt angles of each point obtained by [where Δx is the height at the i-th point in the sequence of height data points, and Δx is the distance in the x-axis direction between adjacent points]. (q) The arithmetic mean height is determined by calculating the arithmetic mean of the absolute values ​​of the heights at each point.

[0025] The substrate preferably has an arithmetic mean height of the surface on the resin layer side of the substrate of 0.05 μm or more and 0.25 μm or less. By setting the arithmetic mean height to 0.05 μm or more, the flex resistance of the antiglare laminate can be improved. The reason for the improved flex resistance is thought to be that the adhesion between the substrate and the resin layer is improved, preventing interfacial peeling upon bending. By setting the arithmetic mean height to 0.25 μm or less, it is possible to easily suppress an increase in internal haze. Furthermore, in an embodiment in which a portion of the substrate is dissolved in the coating liquid for the resin layer, by setting the arithmetic mean height to 0.25 μm or less, it is possible to easily improve the pencil hardness. The reason why it is possible to easily improve the pencil hardness in the above-mentioned embodiment is thought to be that the substrate components are not excessively eluted into the resin layer, making it difficult for the hardness of the resin layer to decrease. The arithmetic mean height of the substrate is more preferably 0.07 μm or more, and even more preferably 0.09 μm or more, and more preferably 0.23 μm or less, and even more preferably 0.20 μm or less.

[0026] In order to set the average tilt angle and arithmetic mean height of the surface of the substrate on the resin layer side within the above-mentioned ranges, it is preferable to dissolve a part of the substrate in the coating liquid for the resin layer. However, when dissolving the substrate in the coating liquid for the resin layer, it is preferable to set the coating liquid for the resin layer to a predetermined composition and to set predetermined drying conditions. The predetermined composition and predetermined drying conditions will be described later.

[0027] The substrate may contain additives such as antioxidants, UV absorbers, light stabilizers, and plasticizers. To improve adhesion, the surface of the substrate may be subjected to a physical or chemical treatment such as corona discharge treatment, or an easy-adhesion layer may be formed.

[0028] <Resin layer> The resin layer is required to have a first resin layer and a second resin layer from the substrate side. Also, the first resin layer and the second resin layer are required to satisfy the following formula (1). 5.0 < t1 / t2 < 15.0 (Formula 1) [In Formula 1, t1 represents the average thickness of the first resin layer, and t2 represents the average thickness of the second resin layer.]

[0029] The first resin layer and the second resin layer can be formed, for example, by applying a coating liquid for a resin layer containing first particles, a resin-forming component, and a solvent onto a substrate, drying, and curing as necessary. The coating liquid for the resin layer may further contain inorganic fine particles and additives as necessary. In the above method, a region formed by the coating liquid for the resin layer dissolving a part of the substrate and mixing the components eluted from the substrate with the coating liquid for the resin layer becomes the first resin layer, and a region containing almost no components eluted from the substrate and mainly composed of the coating liquid for the resin layer becomes the second resin layer. That is, in the above method, the first resin layer and the second resin layer can be formed by one application using one coating liquid for the resin layer. In the above method, it is important to set the coating liquid for the resin layer to a predetermined composition and under predetermined drying conditions. The predetermined composition and predetermined drying conditions will be described later. The method of 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 coater, meniscus coater, flexographic printing, screen printing, and bead coater can be mentioned. When curing the resin layer coating liquid, 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. 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 Cockcroft-Waldt type, Van de Graaf type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type.

[0030] As a method for forming a two-layer resin layer, a method can be considered in which two resin layer coating liquids are prepared, a first resin layer is formed, and then a second resin layer is laminated, as in Comparative Examples 3 and 4 described below. However, if particles are added to the coating liquid for the first layer, it is difficult to improve the antiglare properties, and if particles are added to the coating liquid for the second layer, it is difficult to improve the flex resistance. Furthermore, when two resin layer coating liquids are used to form a two-layer resin layer, it is difficult to improve the adhesion between the first and second layers. For this reason, it is preferable to form the first resin layer and the second resin layer by one application using one resin layer coating liquid, as in the above-mentioned method.

[0031] When the resin layer is a single layer, the flex resistance or pencil hardness of the antiglare laminate cannot be improved. For example, when a single layer of a resin layer with high hardness is used, the flex resistance of the antiglare laminate cannot be improved. Furthermore, when a single layer of a resin layer with low hardness is used, the pencil hardness of the antiglare laminate cannot be improved. Furthermore, even if the resin layer has a first resin layer and a second resin layer, if Formula 1 is not satisfied, the flex resistance or pencil hardness of the antiglare laminate cannot be improved. Because the second resin layer is farther from the substrate than the first resin layer, the content of components eluted from the substrate is lower in the second resin layer than in the first resin layer. Therefore, the hardness of the second resin layer is likely to be higher than that of the first resin layer. A t1 / t2 ratio of 15.0 or greater means that the proportion of the thickness of the second resin layer, which has a higher hardness, is small. Therefore, when t1 / t2 is 15.0 or greater, the pencil hardness of the antiglare laminate cannot be improved. Furthermore, a t1 / t2 ratio of 5.0 or less means that the proportion of the thickness of the second resin layer, which has a higher hardness, is large. Therefore, when t1 / t2 is 5.0 or less, the flex resistance of the antiglare laminate cannot be improved.

[0032] The ratio t1 / t2 is preferably 5.5 or more, more preferably 6.0 or more, and is preferably 14.0 or less, more preferably 13.5 or less.

[0033] The thickness of the entire resin layer (in other words, the total thickness of the first resin layer and the second resin layer) is preferably 7.0 μm or more, more preferably 8.0 μm or more, and even more preferably 9.0 μm or more, and 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. The average thickness t1 of the first resin layer is preferably 5.0 μm or more, more preferably 7.0 μm or more, and even more preferably 8.5 μm or more, and is preferably 13.0 μm or less, more preferably 12.0 μm or less, and even more preferably 11.0 μm or less. By setting t1 to 5.0 μm or more, it is possible to easily improve flex resistance, and by setting t1 to 13.0 μm or less, it is possible to easily suppress a decrease in pencil hardness. The average thickness t1 of the second resin layer is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.7 μm or more, and is preferably 4.0 μm or less, more preferably 3.0 μm or less, and even more preferably 2.7 μm or less. By setting t2 to 0.3 μm or more, it is possible to easily improve the pencil hardness, and by setting t2 to 4.0 μm or less, it is possible to easily suppress a decrease in flex resistance.

[0034] The average thickness of the first resin layer and the average thickness of the second resin layer can be calculated by, for example, selecting 20 arbitrary points in a cross-sectional photograph of the antiglare laminate taken with a scanning transmission electron microscope (STEM) and averaging the thicknesses. The acceleration voltage of the STEM is preferably 10 kV to 30 kV, and the magnification of the STEM is preferably 1000x to 7000x.

[0035] The resin layer must contain first particles having an average particle size of 0.5 μm or more. If the resin layer does not contain the first particles, the antiglare laminate cannot be provided with antiglare properties.

[0036] In the resin layer, 70% or more of the first particles by number must be present across the first resin layer and the second resin layer. The presence of the first particles 23 straddling the first resin layer 21 and the second resin layer 22 means that the first particles 23 are present on both the first resin layer 21 side and the second resin layer 22 side in the thickness direction of the resin layer 20, as shown in Fig. 1. On the other hand, in Fig. 2, the first particles 23 are not present straddling the first resin layer 21 and the second resin layer 22, but are present on one side of the second resin layer 22. In Fig. 3, the first particles 23 are not present straddling the first resin layer 21 and the second resin layer 22, but are present on one side of the first resin layer 21. In this specification, "70% or more of the first particles, by number, existing across the first resin layer and the second resin layer" may be described as "the first particles satisfy the positional condition in the thickness direction." In this specification, "70% or more of the first particles, by number, not existing across the first resin layer and the second resin layer" may be described as "the first particles do not satisfy the positional condition in the thickness direction."

[0037] If the first particles do not satisfy the conditions for the position in the thickness direction, it is not possible to achieve good antiglare properties and bending resistance. If the first particles do not satisfy the thickness direction position condition, more than 30% of the first particles, by number, will be present in either the first resin layer or the second resin layer without straddling both. In this specification, first particles present in either the first resin layer or the second resin layer without straddling both will sometimes be referred to as "biased first particles." If a large number of biased first particles are present in the first resin layer, the first particles will make it difficult to form irregularities on the surface of the resin layer, thereby failing to improve antiglare properties. Furthermore, when the antiglare laminate is bent, peeling may occur at the interface between the first particles and the resin layer, which reduces flex resistance. Peeling at the interface between the first particles and the resin layer is more difficult to suppress when the resin layer is harder to harden. Therefore, if a large number of biased first particles are present in the second resin layer, flex resistance will not be improved.

[0038] The proportion of the first particles present on both the first resin layer side and the second resin layer side in the thickness direction of the resin layer is preferably 80% or more, and more preferably 90% or more, on a number basis.

[0039] The position where the first particles exist in the thickness direction of the resin layer can be determined, for example, from a cross-sectional photograph of the antiglare laminate imaged by a scanning transmission electron microscope (STEM). Further, the ratio based on the above-mentioned number criterion can be calculated from the cross-sectional photograph. In order to enhance the reliability of the numerical values, it is preferable to acquire a plurality of cross-sectional photographs, set the total number of the first particles to 50 or more, and then calculate the ratio based on the above-mentioned number criterion. Preferably, the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1000 times or more and 7000 times or less.

[0040] It is preferable that H1 indicating the indentation hardness at the center in the thickness direction of the first resin layer and H2 indicating the indentation hardness at the center in the thickness direction of the second resin layer satisfy the relationship of H1 < H2. By satisfying the relationship of H1 < H2, it is easy to improve the pencil hardness and bending resistance of the antiglare laminate.

[0041] Preferably, H1 and H2 satisfy 40 MPa < H2 - H1. By making H2 - H1 exceed 40 MPa, it is easy to improve the pencil hardness and bending resistance of the antiglare laminate. More preferably, H2 - H1 is 45 MPa or more, and even more preferably, it is 50 MPa or more. If H2 - H1 is too large, the bending resistance of the antiglare laminate may decrease because H2 is too large, or the pencil hardness of the antiglare laminate may easily decrease because H1 is too small. Therefore, preferably, H2 - H1 is 100 MPa or less, more preferably 90 MPa or less, and even more preferably 80 MPa or less. The value of H2 can be adjusted by the resin component constituting the coating liquid for the resin layer. Since the value of H1 is the value of a mixture of the resin component constituting the coating liquid for the resin layer and the component eluted from the base material, it can be adjusted by the above two components.

[0042] The lower limit of H1 is preferably 150 MPa or more, more preferably 160 MPa or more, and even more preferably 170 MPa or more, in order to facilitate achieving a good pencil hardness, and the upper limit is preferably 250 MPa or less, more preferably 240 MPa or less, and even more preferably 230 MPa or less, in order to facilitate suppressing a decrease in flex resistance. The lower limit of H2 is preferably 230 MPa or more, more preferably 240 MPa or more, and even more preferably 245 MPa or more, in order to facilitate achieving a good pencil hardness, and the upper limit is preferably 310 MPa or less, more preferably 290 MPa or less, and even more preferably 285 MPa or less, in order to facilitate suppressing a decrease in flex resistance.

[0043] -Indentation hardness measurement method- To measure H1 to H3, it is necessary to prepare a measurement sample in which the cross section of the layer to be measured is exposed. The sample can be prepared, for example, by the following steps (A1) and (A2).

[0044] (A1) The antiglare laminate is cut to a desired size to prepare a cut sample, and then the cut sample is embedded in a resin to prepare an embedded sample. The size of the cut sample is, for example, a strip of 10 mm length x 3 mm width. The resin used for embedding is preferably an epoxy resin. An embedded sample can be obtained, for example, by placing a cut sample in a silicon embedding plate, pouring in embedding resin, hardening the embedding resin, and then removing the cut sample and the embedding resin from the silicon embedding plate. In the case of the epoxy resin manufactured by Struers, as exemplified below, the aforementioned hardening step is preferably carried out by leaving it at room temperature for 12 hours. The embedded sample is in the shape of a block. The silicone embedding plate may be, for example, one manufactured by Dosaka EM Co., Ltd. The silicone embedding plate is also sometimes called a silicone capsule. The epoxy resin used for embedding may be, for example, a 10:1.2 mixture of "Epofix" (trade name) manufactured by Struers and "Epofix Hardener" (trade name) manufactured by the same company.

[0045] (A2) The block-shaped embedded sample is cut vertically to expose the cross section of the antiglare laminate, thereby preparing a sample for measuring indentation hardness. The shape of the sample for measuring indentation hardness is maintained as a block. The embedded sample is preferably cut so as to pass through the center of the cut sample. The embedded sample is preferably cut with a diamond knife. An example of an apparatus for cutting a block-shaped embedded sample is the Ultramicrotome EM UC7 manufactured by Leica Microsystems. When cutting a block-shaped embedded sample, it is preferable to first roughly cut it (coarse trimming) and then finally precisely trim it under the conditions of "SPEED: 1.00 mm / s" and "FEED: 70 nm." As described above, among the slices cut from the block-shaped embedded sample, slices 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 first resin layer, the average thickness of the second resin layer, the position of the first particles in the thickness direction of the resin layer, the average inclination angle of the surface of the substrate facing the resin layer, the arithmetic mean height of the surface of the substrate facing the resin layer, the particle diameter of the first particles, and the particle diameter of the inorganic microparticles.

[0046] H1 to H3 are measured by pressing a Berkovich indenter (material: diamond triangular pyramid) vertically into a predetermined position on the cut surface of the above-mentioned sample. The predetermined position is the center of the first resin layer in the thickness direction for measurement H1, the center of the second resin layer in the thickness direction for measurement H2, and the center of the substrate in the thickness direction for measurement H3. The center of the first resin layer in the thickness direction is preferably the center of the first resin layer in the thickness direction, but a deviation of 0.10 μm from the center is acceptable. Similarly, the center of the second resin layer in the thickness direction is preferably the center of the second resin layer in the thickness direction, but a deviation of 0.10 μm from the center is acceptable. Similarly, the center of the substrate in the thickness direction is preferably the center of the substrate in the thickness direction, but a deviation of 0.10 μm from the center is acceptable.

[0047] The indentation hardness is preferably measured under the following conditions. <Measurement conditions> Indenter used: Berkovich indenter (model number: TI-0039, manufactured by BRUKER) Push-in conditions: Load control method ·Maximum load: 50μN Load application time: 10 seconds (load change rate: 5 μN / sec) Hold time: 5 seconds ·Holding load: 50μN Load unloading time: 10 seconds (load change rate: -5μN / sec)

[0048] The indentation hardness can be calculated as follows. First, a load-displacement curve is created by continuously measuring the indentation depth h (nm) corresponding to the indentation load F (N). The maximum indentation load F is calculated by analyzing the created load-displacement curve. max (N) is the projected area A where the indenter is in contact with the layer to be measured. p (mm 2 ) is the indentation hardness H IT can be calculated (Equation 2 below). H IT =F max / A p (Formula 2) where A pis the contact projected area corrected for the indenter tip curvature by the Oliver-Pharr method using a standard sample of fused quartz (5-0098 manufactured by BRUKER). In this specification, H1 to H3 refer to the average values ​​of the measurements of 20 samples.

[0049] "The First Particle" The first particles have 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 shape on the surface of the resin layer, and good antiglare properties cannot be achieved.

[0050] 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, fluorine-based resin, and polyester-based 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 small specific gravity, making it easier for the first particles to satisfy the positional conditions in the thickness direction.

[0051] The content of the first particles is preferably at least 0.5 parts by mass, more preferably at least 1.0 parts by mass, and even more preferably at least 1.5 parts by mass, relative to 100 parts by mass of the resin component of the coating liquid for the resin layer, and is preferably at most 10.0 parts by mass, more preferably at most 5.0 parts by mass, and even more preferably at most 3.0 parts by mass. By setting the content of the first particles to 0.5 parts by mass or more, it is possible to easily improve antiglare properties, and by setting the content of the first particles to 10.0 parts by mass or less, it is possible to easily suppress a decrease in flex resistance.

[0052] The average particle size of the first particles is preferably 0.8 μm or more, and more preferably 1.0 μm or more. In order to make it easier for the first particles to satisfy the positional conditions in the thickness direction, the average particle size 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.

[0053] The average particle size of the first particles can be calculated, for example, by the following steps (B1) to (B3). (B1) A transmission observation image of the antiglare laminate is taken using an optical microscope, preferably at a magnification of 500 times or more and 2000 times or less. (B2) Randomly extract 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 sandwiched between the two lines. (B3) The same procedure is carried out five times on a separate observation image of the same sample, and the value obtained from the number average of the particle diameters of a total of 50 particles is regarded as the average particle diameter of the particles. However, when the first particles cannot be optically observed, the average particle size of the first particles is calculated according to the following (B4) to (B6). (B4) A section that is a cross section passing through the center of the first particle is prepared from the antiglare laminate using a microtome. The thickness of the section is preferably 60 nm to 100 nm. A plurality of sections are prepared consecutively for each first particle, and the section that has the maximum particle diameter calculated in step (B5) can be selected as the section that is a cross section passing through the center of the first particle. (B5) The obtained slice is observed under a scanning transmission electron microscope (STEM) to calculate the particle size. The method for calculating the particle size is the same as in (B2). The magnification is preferably 5,000 times or more and 20,000 times or less. (B6) The steps (B4) to (B5) are carried out on 20 particles, and the value obtained from the number average of the particle diameters of the 20 particles is set as the average particle diameter of the first particles.

[0054] It is preferable that D1, which indicates the average particle diameter of the first particles, and t2, which indicates the average thickness of the second resin layer, satisfy the relationship t2 < D1. By setting t2 < D1, it becomes easier to impart an uneven shape to the surface of the antiglare laminate by the first particles, and thus it becomes easier to improve the antiglare property. D1 - t2 is preferably 0.5 μm or more, and more preferably 0.7 μm or more.

[0055] If D1 - t2 is too large, the first particles may protrude from the surface of the second resin layer, which may reduce the flex resistance. Therefore, D1 - t2 is preferably 2.0 μm or less, more preferably 1.7 μm or less, and even more preferably 1.5 μm or less.

[0056] It is preferable that D1, which indicates the average particle diameter of the first particles, and t1, which indicates the average thickness of the first resin layer, satisfy the relationship D1 < t1. By setting D1 < t1, it becomes easier to improve the flex resistance more favorably. t1 - D1 is preferably 4.0 μm or more, more preferably 5.0 μm or more, and even more preferably 6.0 μm or more.

[0057] If t1 - D1 is too large, the thickness of the first resin layer with low hardness increases, which may reduce the pencil hardness. Therefore, t1 - D1 is preferably 10.0 μm or less, more preferably 9.0 μm or less, and even more preferably 8.5 μm or less.

[0058] 《Inorganic Fine Particles》 The resin layer may contain inorganic fine particles. By the resin layer containing inorganic fine particles with a relatively large specific gravity, it becomes difficult for the first particles to sink below the resin layer, so it becomes easier for the first particles to satisfy the conditions of the position in the thickness direction. Further, the inorganic fine particles can enhance the dispersibility of the first particles and easily suppress a decrease in flex resistance. In this specification, the inorganic fine particles mean inorganic particles having an average primary particle diameter of 200 nm or less. The average particle size of the inorganic fine particles is preferably 1 nm or more and 200 nm or less, more preferably 2 nm or more and 100 nm or less, and even more preferably 5 nm or more and 50 nm or less.

[0059] The average particle size of the inorganic fine particles can be calculated by the following steps (C1) to (C3). (C1) The cross section of the antiglare laminate is imaged by a TEM or STEM. The acceleration voltage of the TEM or STEM is preferably 10 kV or more and 30 kV or less, and the magnification is preferably 50,000 times or more and 300,000 times or less. (C2) Randomly extract 10 inorganic microparticles from the observed image, and calculate the particle diameter of each inorganic microparticle. 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 inorganic microparticle is sandwiched between the two lines. (C3) The same procedure is repeated five times on separate observation images of the same sample, and the value obtained from the number average of the particle diameters of a total of 50 particles is regarded as the average particle diameter of the inorganic fine particles.

[0060] Examples of inorganic fine particles include fine particles made of silica, alumina, zirconia, titania, etc. Among these, silica is preferred because it is easy to suppress the generation of internal haze.

[0061] The content of inorganic fine particles 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, relative to 100 parts by mass of the resin component of the coating liquid for the resin layer, and the upper limit is 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. By setting the content of inorganic fine particles to 0.1 parts by mass or more, the first particles can more easily satisfy the positional condition in the thickness direction. Also, by setting the content of inorganic fine particles to 5.0 parts by mass or less, the first particles can be prevented from floating excessively above the resin layer, so that the first particles can more easily satisfy the positional condition in the thickness direction.

[0062] <Resin component> The resin layer preferably contains a cured product of a curable resin composition as a resin component. When the resin layer contains a cured product of the curable resin composition, the pencil hardness of the antiglare laminate can be easily improved. The cured product of the curable resin composition is preferably contained in both the first resin layer and the second resin layer.

[0063] The proportion 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.

[0064] Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition and a cured product of an ionizing radiation curable resin composition. Among these, a cured product of an ionizing radiation curable resin composition is preferred, because it is easy to increase the pencil hardness and is easy to dissolve a substrate in the uncured composition state.

[0065] The thermosetting resin composition is a composition that contains at least a thermosetting resin and is a resin composition that is cured by heating. Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, etc. In the thermosetting resin composition, a curing agent is added to the curable resin as needed.

[0066] The 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 the ionizing radiation-curable functional group include ethylenically unsaturated bond 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 bond group is preferred. Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Usually, ultraviolet rays or electron beams are used, but other types of radiation such as electromagnetic waves (e.g., X-rays and gamma rays), and charged particle beams (e.g., alpha rays and ion beams) can also be used. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group, and the term "(meth)acrylate" refers to an acrylate or a methacrylate.

[0067] The ionizing radiation-curable compound may be a monofunctional compound having one ionizing radiation-curable functional group or a polyfunctional compound having two or more ionizing radiation-curable functional groups. Furthermore, the ionizing radiation-curable compound may be either a monomer or an oligomer. In order to dissolve a portion of the substrate, increase the pencil hardness, and facilitate suppression of cure 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 bond group as the ionizing radiation-curable functional group, and more preferably (meth)acrylate-based compounds. As the (meth)acrylate-based compound, compounds in which part of the molecular skeleton has been modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. can also be used. (a) Monofunctional ionizing radiation-curable monomer (b) Polyfunctional ionizing radiation-curable monomer (c) Polyfunctional ionizing radiation-curable oligomer

[0068] By including the monofunctional ionizing radiation-curable monomer (a) as the ionizing radiation-curable compound, it is possible to facilitate dissolution of a portion of the substrate and to facilitate compatibility of components eluted from the substrate with the components of the resin layer coating liquid. Furthermore, by including the monofunctional ionizing radiation-curable monomer (a), the viscosity of the resin layer coating liquid is reduced, facilitating convection of a mixture of the resin layer coating liquid and components eluted from the substrate. As a result, the thickness of the first resin layer is greater than that of the second resin layer, making it easier to achieve a t1 / t2 ratio of more than 5. However, if the amount of the monofunctional ionizing radiation-curable monomer (a) is too large, the substrate may be excessively dissolved, resulting in a decrease in the strength of the substrate and a decrease in the pencil hardness of the antiglare laminate. Also, if the amount of the monofunctional ionizing radiation-curable monomer (a) is too large, the convection described above may become intense, resulting in the thickness of the first resin layer being too large relative to the thickness of the second resin layer, and the ratio t1 / t2 may exceed 15. By including the polyfunctional ionizing radiation-curable monomer (b) as the ionizing radiation-curable compound, the pencil hardness of the antiglare laminate can be easily improved. However, if the amount of the polyfunctional ionizing radiation-curable monomer (b) is too large, the hardness of the resin layer may become too high, which may reduce the flex resistance of the antiglare laminate. By including the polyfunctional ionizing radiation-curable oligomer (c) as the ionizing radiation-curable compound, it is possible to easily suppress cure shrinkage while maintaining the pencil hardness of the antiglare laminate. However, if the amount of the polyfunctional ionizing radiation-curable oligomer (c) is too large, the pencil hardness of the antiglare laminate may decrease.

[0069] The amount of the monofunctional ionizing radiation-curable monomer (a) relative to the total amount of the ionizing radiation-curable compounds is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and even more preferably 17% by mass or more and 33% by mass or less. The amount of the polyfunctional ionizing radiation-curable monomer (b) relative to the total amount of the ionizing radiation-curable compounds 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) the polyfunctional ionizing radiation-curable oligomer relative to the total amount of the ionizing radiation-curable compounds is preferably 40% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 77% by mass or less, and even more preferably 55% by mass or more and 75% by mass or less.

[0070] Examples of the (a) monofunctional ionizing radiation-curable monomer 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, 2-hydroxypropyl(meth)acrylate, etc. Among these, monofunctional monomers having a hydroxyl group, such as 4-hydroxybutyl(meth)acrylate, are preferred because they tend to provide good adhesion to the substrate.

[0071] Among the (b) polyfunctional ionizing radiation-curable monomers, examples of bifunctional ionizing radiation-curable monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, 1,6-hexanediol diacrylate, etc. Examples of trifunctional or higher ionizing radiation-curable monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate, etc. The number of functional groups in the polyfunctional ionizing radiation-curable monomer (b) is preferably 3 or more and 5 or less, more preferably 3 or more and 4 or less, and even more preferably 3, in order to increase the pencil hardness while suppressing cure shrinkage.

[0072] Examples of the polyfunctional ionizing radiation-curable oligomer (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 reacting a polyhydric alcohol and an organic diisocyanate with a hydroxy (meth)acrylate. Preferred epoxy (meth)acrylates are (meth)acrylates obtained by reacting a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with (meth)acrylic acid; (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a polybasic acid and (meth)acrylic acid; and (meth)acrylates obtained by reacting a di- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a phenol and (meth)acrylic acid.

[0073] The number of functional groups in the polyfunctional ionizing radiation-curable oligomer (c) is preferably 4 or more and 8 or less, more preferably 5 or more and 7 or less, and even more preferably 6, in order to suppress cure shrinkage while maintaining pencil hardness. The weight average molecular weight of the polyfunctional ionizing radiation-curable oligomer (c) is preferably 1000 to 5000, more preferably 1100 to 3500, and even more preferably 1200 to 2000, in order to suppress cure shrinkage while maintaining pencil hardness. In this specification, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0074] When the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0075] Additives The coating liquid for the resin layer may contain additives such as a leveling agent, a refractive index adjuster, an antistatic agent, an antifouling agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a viscosity adjuster, and a thermal polymerization initiator, as necessary.

[0076] "solvent" The resin layer coating liquid preferably contains a solvent. It is preferable to select a solvent that can dissolve the substrate. However, if the substrate is dissolved excessively, the strength of the substrate will decrease, so it is preferable to select an appropriate solvent depending on the type of substrate. Furthermore, it is preferable to select a solvent taking into consideration not only the solubility of the substrate but also the evaporation rate specific to the solvent. This is because a solvent with a slow evaporation rate is likely to dissolve the substrate excessively. The evaporation rate of the solvent can also be controlled by the drying conditions. For example, increasing the drying temperature increases the evaporation rate of the solvent. In addition, increasing the drying air speed increases the evaporation rate of the solvent. From the above, it is preferable to select a solvent taking into consideration the solubility of the base material, evaporation rate, and drying conditions.

[0077] Examples of the solvent 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 in combination.

[0078] Acrylic resin substrates are easily dissolved in solvents. Therefore, when using an acrylic resin substrate as a substrate, it is preferable to use a solvent that has a fast evaporation rate inherent to the solvent as the main component. The main component means that the solvent accounts for 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 having a high evaporation rate means a solvent having an evaporation rate of 100 or more, where the evaporation rate of butyl acetate is set to 100. The evaporation rate of a solvent having a high evaporation rate is more preferably 120 or more and 300 or less, and even more preferably 140 or more and 220 or less. Examples of solvents with a fast evaporation rate include isopropyl alcohol (evaporation rate 150), methyl isobutyl ketone (evaporation rate 160), and toluene (evaporation rate 200).

[0079] Drying conditions When forming a resin layer from the resin layer coating liquid, it is preferable to control the drying conditions. Drying conditions can be controlled by the drying temperature and the air speed inside the dryer. The preferred ranges for the drying temperature and air speed vary depending on the composition of the resin layer coating liquid and cannot be generalized; however, the drying temperature is preferably 85°C or higher and 105°C or lower, and the drying air speed is preferably 5 m / s or higher and 20 m / s or lower. The drying time is preferably 30 seconds or higher and 90 seconds or lower. Among the drying conditions, the drying temperature is important. Lowering the drying temperature tends to decrease t1 / t2, while increasing the drying temperature tends to increase t1 / t2. In order to dissolve a portion of the substrate in the resin layer coating liquid and to fluidize a mixture of the components eluted from the substrate and the resin layer coating liquid to ensure the thickness of the first resin layer, it is preferable to irradiate the coating liquid with ionizing radiation after drying the coating liquid.

[0080] <Other layers> The antiglare laminate may have layers other than the substrate and the resin layer, such as an antireflection layer, an antifouling layer, and an antistatic layer.

[0081] <Optical properties, surface shape> The antiglare laminate preferably has a total light transmittance according to JIS K7361-1:1997 of 70% or more, more preferably 80% or more, and even more preferably 85% or more. When measuring the total light transmittance and the haze described later, the light incident surface is the substrate side.

[0082] The antiglare laminate preferably has a haze of 0.5% or more, more preferably 1.0% or more, and even more preferably 1.5% or more, as measured by JIS K7136:2000. By setting the haze to 0.5% or more, it is possible to easily achieve good antiglare properties. Furthermore, in order to easily prevent a decrease in image resolution, the antiglare laminate preferably has a haze of 20% or less, more preferably 10% or less, and even more preferably 5% or less.

[0083] To facilitate good antiglare properties, the antiglare laminate preferably has an arithmetic mean roughness Ra of 0.03 μm or more, more preferably 0.05 μm or more, on the surface of the resin layer side, as measured by JIS B0601:2001. Furthermore, to facilitate preventing a decrease in image resolution, the antiglare laminate preferably has an Ra of 0.12 μm or less, more preferably 0.10 μm or less, on the surface of the resin layer side. Ra refers to the value at a cutoff value of 0.8 mm.

[0084] <Size, shape, etc.> The antiglare laminate may be in the form of sheets cut to a predetermined size, or in the form of a roll obtained by winding a long sheet into a roll. The size of the sheets is not particularly limited, but the maximum diameter is approximately 2 inches to 500 inches. The "maximum diameter" refers to the maximum length when any two points on the antiglare laminate are connected. For example, if the antiglare laminate is rectangular, the diagonal of the rectangle is the maximum diameter. If the antiglare laminate is circular, the diameter of the circle is the maximum diameter. The width and length of the roll are not particularly limited, but generally, the width is about 500 mm to 3000 mm, and the length is about 500 m to 5000 m. The antiglare laminate in roll form can be cut into sheets according to the size of an image display device or the like. When cutting, it is preferable to remove the end portions of the roll, which have unstable physical properties. The shape of the sheet is not particularly limited, and may be, for example, a polygon such as a triangle, a rectangle, or a pentagon, a circle, or a random, indeterminate shape. More specifically, when the antiglare laminate is rectangular, the aspect ratio is not particularly limited as long as it does not cause any problems as a display screen. Examples include width:height = 1:1, 4:3, 16:10, 16:9, 2:1, 5:4, 11:8, etc.

[0085] [Polarizing plate] The polarizing plate of the present disclosure has a polarizer, a first transparent protective plate arranged on one side of the polarizer, and a second transparent protective plate arranged on the other side of the polarizer, and at least one of the first transparent protective plate and the second transparent protective plate is the antiglare laminate of the present disclosure described above.

[0086] A polarizing plate is used to impart anti-reflection properties by combining a polarizing plate with a λ / 4 retardation plate, for example. In this case, the λ / 4 retardation plate is disposed on the display element of the image display device, and the polarizing plate is disposed closer to the viewer than the λ / 4 retardation plate. When a polarizing plate is used for a liquid crystal display device, the polarizing plate is used to provide a liquid crystal shutter function. 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 perpendicular to each other. In this configuration, it is preferable to use the polarizing plate of the present disclosure as the upper polarizing plate.

[0087] <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 antiglare laminate of the present disclosure described above. In a preferred embodiment, of the first transparent protective plate and the second transparent protective plate, the transparent protective plate on the light exit side is the antiglare laminate of the present disclosure described above. The antiglare laminate is preferably arranged so that the surface of the antiglare laminate facing the substrate faces the polarizer.

[0088] When one of the first transparent protective plate and the second transparent protective plate is the antiglare laminate of the present disclosure, the other transparent protective plate is not particularly limited, but is preferably an optically isotropic transparent protective plate. In this specification, optical isotropy refers to an in-plane retardation of 20 nm or less, preferably 10 nm or less, and more preferably 5 nm or less. Acrylic films and triacetyl cellulose (TAC) films are easily imparted with optical isotropy.

[0089] <Polarizer> Examples of polarizers include sheet-type polarizers such as polyvinyl alcohol films, polyvinyl formal films, polyvinyl acetal films, and saponified ethylene-vinyl acetate copolymer films dyed with iodine or the like, and stretched, wire-grid polarizers made of a large number of parallel-arranged metal wires, coated polarizers coated with lyotropic liquid crystals or dichroic guest-host materials, and multilayer thin-film polarizers. These polarizers may be reflective polarizers that have the function of reflecting polarized light components that are not transmitted.

[0090] <Size, shape, etc.> Examples of the size and shape of the polarizing plate of the present disclosure include the size and shape of the antiglare laminate of the present disclosure described above.

[0091] [Image display device] The image display device of the present disclosure has the above-described antiglare laminate of the present disclosure on a display element.

[0092] Fig. 4 is a cross-sectional view showing an embodiment of an image display device 500 of the present disclosure. The image display device 500 of Fig. 4 has an antiglare laminate 100 of the present disclosure on a display element 200. In the image display device, the antiglare laminate is preferably arranged so that the substrate side faces the display element side.

[0093] Examples of the display element include a liquid crystal display element, an EL display element (organic EL display element, inorganic EL display element), a plasma display element, a display element using QD (Quantum Dot), an LED display element such as a mini LED or a micro LED display element, etc. These display elements may have a touch panel function inside the display element. Examples of the liquid crystal display mode of the liquid crystal display element include the IPS mode, VA mode, multi-domain mode, OCB mode, STN mode, and TSTN mode. When the display element is a liquid crystal display element, a backlight is required. The backlight is disposed on the side of the liquid crystal display element opposite to the side where the antiglare laminate is disposed.

[0094] The image display device of the present disclosure may be an image display device with a touch panel having a touch panel between a display element and the antiglare laminate. In this case, it is preferable that the antiglare laminate is disposed on the outermost surface of the image display device with a touch panel, and that the substrate side of the antiglare laminate is disposed so as to face the display element side.

[0095] 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 2 inches or more and 500 inches or less. The effective display area of ​​an image display device is the area in which an image can be displayed. For example, if the image display device has a housing that surrounds the display element, the area inside the housing is the effective image area. The maximum diameter of the effective image area is the maximum distance between any two points within the effective image area. For example, if the effective image area is rectangular, the maximum diameter is the diagonal of the rectangle. If the effective image area is circular, the maximum diameter is the diameter of the circle.

[0096] The image display device of the present disclosure is preferably a foldable type image display device or a rollable type image display device, since the antiglare laminate has excellent bending resistance. [Example]

[0097] Next, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to these examples. Note that "parts" and "%" are based on mass unless otherwise specified.

[0098] 1. Measurement and Evaluation The antiglare laminates of 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%. Before each measurement and evaluation, the sample was exposed to the atmosphere for 30 minutes or more before measurement and evaluation. The results are shown in Table 2. The antiglare laminate of Comparative Example 7 had a single-layer resin layer, and therefore the numerical value for the second resin layer in Table 2 is indicated by "-".

[0099] 1-1. Average thickness of the first resin layer and the second resin layer Samples of the antiglare laminates of Examples and Comparative Examples were prepared according to the description in the specification. Twenty randomly selected points were selected from the cross-sectional photographs of the samples taken with a scanning transmission electron microscope, and the average thicknesses t1 and t2 of the first and second resin layers were calculated from the average values.

[0100] 1-2. Position of the first particle Samples of the antiglare laminates of Examples and Comparative Examples were prepared in accordance with the description in the specification, with the cross sections exposed. The proportion by number of first particles present across the first resin layer and the second resin layer was calculated from cross-sectional photographs of the samples taken with a scanning transmission electron microscope. To calculate the proportion, multiple cross-sectional photographs were taken until the total number of first particles exceeded 50. Additionally, the proportion by number of first particles present only in the first resin layer and the proportion by number of first particles present only in the second resin layer were calculated.

[0101] 1-3. Average tilt angle of the surface on the resin layer side of the substrate, and arithmetic mean height of the surface on the resin layer side of the substrate Samples of the antiglare laminates of Examples and Comparative Examples were prepared in accordance with the description in the specification, with the cross sections exposed. From the cross-sectional photographs of the samples taken with a scanning transmission electron microscope, the average tilt angle of the surface of the substrate facing the resin layer and the arithmetic mean height of the surface of the substrate facing the resin layer were calculated in accordance with the description in the specification.

[0102] 1-4.Indentation hardness Samples with exposed cross sections of the antiglare laminates of Examples and Comparative Examples were prepared according to the description in the specification. Next, using a measuring device (Bruker, product number: TI950), the indentation hardness of the first resin layer of each sample at the center in the thickness direction and the indentation hardness of the second resin layer of each sample at the center in the thickness direction were measured according to the description in the specification. The average values ​​of the measurements for 20 samples were designated H1 and H2 for each Example and Comparative Example.

[0103] 1-5. Total light transmittance (Tt) and haze (Hz) The antiglare laminates of the examples and comparative examples were cut into 10 cm squares. The cut locations were selected randomly after visually checking for any abnormalities such as dust or scratches. Using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory), the total light transmittance of each sample according to JIS K7361-1:1997 and the haze according to JIS K7136:2000 were measured. To allow the light source to stabilize, the device was powered on and then left on for at least 15 minutes, and calibration was performed without placing anything in the entrance opening (where the measurement sample was placed), after which the measurement sample was placed in the entrance opening and measured. The light incident surface was set on the substrate side.

[0104] 1-6. Flexibility The antiglare 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 the diameter of the mandrel at which the antiglare laminate first cracked is shown in Table 2. A diameter of 5 mm or less is considered acceptable. When the antiglare laminate was wrapped around the mandrel, the substrate side was positioned on the mandrel side.

[0105] 1-7.Pencil hardness The antiglare laminates of the examples and comparative examples were cut into samples measuring 50 mm × 100 mm, and the pencil hardness of the upper surface of the resin layer of each sample 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 / sec. For the measurements, a pencil hardness tester (product number: NP-type pencil scratch coating hardness tester) manufactured by Toyo Seiki Seisakusho was used. Both ends of the cut sample were attached to the base of the pencil hardness tester using mending tape (3M, product number "810-3-18"). Five pencil hardness tests were conducted, and the hardness at which no appearance abnormalities such as scratches were observed in three or more tests was recorded as the pencil hardness value of each sample. For example, if five tests were conducted using a 2H pencil and no appearance abnormalities were observed in three tests, the pencil hardness of the antiglare laminate was 2H. Appearance abnormalities were checked for scratches and dents, excluding discoloration. A pencil hardness of 2H or higher was considered to be acceptable.

[0106] 1-8. Anti-glare property A black plate (Kuraray Co., Ltd., product name "Comoglass DFA2CG 502K (black) series," total light transmittance 0%, thickness 2 mm, refractive index 1.49) was laminated to the substrate side of the antiglare laminate of each of the examples and comparative examples (sample size: 10 cm length x 10 cm width). The samples were visually evaluated by 20 subjects in a bright room environment (illuminance on the first main surface of the sample was 500 lux to 1000 lux, lighting: Hf32 type straight tube three-wavelength daylight white fluorescent lamp) from a linear distance of 50 cm above the center of the first main surface to determine whether the antiglare performance was sufficient to prevent the observer from being bothered by their own reflection, according to the following criteria. The lighting position during evaluation was 2 m vertically above the horizontal stand. The subjects were healthy individuals in their 30s with visual acuity of 0.7 or better. A: More than 14 people answered "good" B: 7 to 13 people answered "good" C: 6 or fewer people answered good

[0107] 2. Preparation of antiglare laminate [Example 1] (Base material manufacturing) A copolymer of methyl methacrylate and methyl acrylate was kneaded at 260°C using a twin-screw extruder to obtain a pellet-shaped composition (glass transition temperature: 134°C). The obtained pellet-shaped 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 machine direction and transverse direction 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) The resin layer coating solution of Example 1 in Table 1 was applied to the acrylic resin substrate in an amount of 6.0 g / m by a Mayer bar coating method. 2 After applying the coating amount, the coating was dried for 60 seconds with hot air at a temperature of 100°C at a wind speed of 15 m / s. Then, the coating was dried in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, with an integrated light intensity of 100 mJ / cm. 2 The ionizing radiation curable resin composition of the resin layer coating solution was cured by irradiating with ultraviolet light so that the coating amount became equal to or greater than 1000 ppm, thereby forming a first resin layer and a second resin layer, thereby obtaining the antiglare laminate of Example 1. In this specification, the coating amount means the coating amount after drying.

[0108] [Examples 2 to 4], [Comparative Examples 1 to 2, 5 to 7] Antiglare laminates of Examples 2 to 4 and Comparative Examples 1, 2, and 5 to 7 were obtained in the same manner as in Example 1, except that the composition of the coating liquid for the resin layer, the coating amount of the coating liquid for the resin layer, and the drying conditions for the coating liquid for the resin layer were changed to the compositions and the like shown in Table 1. The antiglare laminate of Comparative Example 7 had a single-layer structure in which the resin layer was the first resin layer.

[0109] Comparative Example 3 The coating solution for the first resin layer of Comparative Example 3 in Table 1 was applied to the acrylic resin substrate in an amount of 6.0 g / m by a Mayer bar coating method. 2 After applying the coating amount, the coating was dried for 60 seconds with hot air at a temperature of 100°C at a wind speed of 15 m / s. Then, the coating was dried in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, with an integrated light dose of 50 mJ / cm. 2 The ionizing radiation curable resin composition of the first resin layer coating liquid was cured by irradiating with ultraviolet light so that the first resin layer was formed. Next, the coating liquid for the second resin layer of Comparative Example 3 in Table 1 was applied to the first resin layer by a Mayer bar coating method at a concentration of 2.0 g / m 2 After applying the coating amount, the coating was dried for 60 seconds with hot air at a temperature of 70°C at a wind speed of 15 m / s. Then, the coating was dried in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, with an integrated light dose of 100 mJ / cm. 2 The ionizing radiation curable resin composition of the second resin layer coating liquid was cured by irradiating with ultraviolet light so that the second resin layer coating liquid became 100%. Thus, a second resin layer was formed, and an antiglare laminate of Comparative Example 3 was obtained.

[0110] Comparative Example 4 An antiglare laminate of Comparative Example 4 was obtained in the same manner as in Comparative Example 3, except that the composition of the coating liquid for the first and second resin layers, the coating amount of the coating liquid for the first and second resin layers, and the drying conditions for the coating liquid for the first and second resin layers were changed to the compositions and the like shown in Table 1.

[0111] [Table 1]

[0112] In Table 1, the hexafunctional urethane acrylate oligomer represents a urethane acrylate oligomer manufactured by Mitsubishi Chemical Corporation (product name: Shikoh UV-7600B, weight average molecular weight: 1400), the difunctional acrylate monomer represents tetraethylene glycol diacrylate, the trifunctional acrylate monomer represents pentaerythritol triacrylate, the monofunctional acrylate monomer represents 4-hydroxybutyl acrylate, and the photopolymerization initiator represents the product name "Omnirad 184" manufactured by IGM Resins BV.

[0113] [Table 2]

[0114] From the results in Table 2, it can be confirmed that the antiglare laminates of the examples have good pencil hardness, flex resistance and antiglare properties. [Explanation of symbols]

[0115] 10: Base material 20: Resin layer 21: First resin layer 22: Second resin layer 23: First particle 100: Antiglare laminate 200: Display element 500: Image display device

Claims

1. An antiglare laminate having a resin layer on a substrate, the resin layer has, from the substrate side, a first resin layer and a second resin layer, the resin layer contains first particles having an average particle size of 0.5 μm or more, when the positions where the first particles are present in the thickness direction of the resin layer are confirmed from a cross-sectional photograph of the antiglare laminate taken with a scanning transmission electron microscope, 70% or more of the first particles are present across the first resin layer and the second resin layer, An antiglare laminate satisfying the following formula 1: 5.0<t1 / t2<15.0 (Formula 1) [In Formula 1, t1 represents the average thickness of the first resin layer, and t2 represents the average thickness of the second resin layer.]

2. 2. The antiglare laminate according to claim 1, wherein D1 representing an average particle diameter of the first particles and t2 representing an average thickness of the second resin layer satisfy the relationship t2<D1.

3. 3. The antiglare laminate according to claim 1, wherein D1 representing an average particle diameter of the first particles and t1 representing an average thickness of the first resin layer satisfy the relationship D1<t1.

4. 4. The antiglare laminate according to claim 1, wherein the first particles are organic particles.

5. 5. The antiglare laminate according to claim 1, wherein the surface of the substrate on the side of the resin layer has an average inclination angle of 5.0 degrees or more and 15.0 degrees or less.

6. 6. The antiglare laminate according to claim 1, wherein the surface of the substrate on the resin layer side has an arithmetic mean height of 0.05 μm or more and 0.25 μm or less.

7. The antiglare laminate according to any one of claims 1 to 6, wherein H1, which indicates the indentation hardness at the center in the thickness direction of the first resin layer, and H2, which indicates the indentation hardness at the center in the thickness direction of the second resin layer, satisfy the relationship H1 < H2.

8. The antiglare laminate according to claim 7, wherein 40 MPa<H2-H1.

9. The antiglare laminate according to claim 7, wherein 40 MPa<H2-H1≦100 MPa.

10. The antiglare laminate according to any one of claims 1 to 9, wherein the resin layer comprises a cured product of a curable resin composition.

11. An antiglare laminate as described in Claim 10, wherein the cured product of the curable resin composition is a cured product of an ionizing radiation curable resin composition.

12. The antiglare laminate according to any one of claims 1 to 11, wherein the substrate is an acrylic resin substrate.

13. An anti-glare laminate as described in Claim 12, wherein the glass transition point of the acrylic resin contained in the acrylic resin substrate is 100°C or higher and 150°C or lower.

14. An antiglare laminate described in any one of claims 1 to 13, wherein the first resin layer contains the same components as those contained in the substrate.

15. An antiglare laminate described in any one of claims 1 to 14, wherein the first resin layer contains the same resin as the resin contained in the second resin layer.

16. An antiglare laminate described in any one of claims 1 to 15, wherein the resin layer contains inorganic fine particles.

17. A polarizing plate having a polarizer, a first transparent protective plate arranged on one side of the polarizer, and a second transparent protective plate arranged 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 antiglare laminate according to any one of claims 1 to 16.

18. An image display device comprising the antiglare laminate according to any one of claims 1 to 16 on a display element.

19. 19. The image display device according to claim 18, which is a foldable type image display device or a rollable type image display device.

20. A method for producing an antiglare laminate having a resin layer on a substrate, comprising: a first step of applying a resin layer coating liquid, which includes first particles having an average particle size of 0.5 μm or more, a resin component, and a solvent, onto the substrate, and drying the coating liquid; a method for producing an antiglare laminate, wherein in the first step, a part of the substrate is dissolved in the coating liquid for a resin layer, and components of the dissolved substrate are eluted into the coating liquid for a resin layer, thereby forming a first resin layer in which the components eluted from the substrate and the coating liquid for a resin layer are mixed, and a second resin layer located on the opposite side of the first resin layer from the substrate, thereby obtaining the following antiglare laminate. <Antiglare laminate> An antiglare laminate having a resin layer on a substrate, the resin layer has, from the substrate side, a first resin layer and a second resin layer, the resin layer contains first particles having an average particle size of 0.5 μm or more, positions where the first particles are present in the thickness direction of the resin layer are confirmed from a cross-sectional photograph of the antiglare laminate taken with a scanning transmission electron microscope, and 70% or more of the first particles are present across the first resin layer and the second resin layer, An antiglare laminate satisfying the following formula 1: 5.0<t1 / t2<15.0 (Formula 1) [In Formula 1, t1 represents the average thickness of the first resin layer, and t2 represents the average thickness of the second resin layer.]

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