KR20240019772A - Anti-glare laminates, optical laminates, polarizers, and image display devices - Google Patents

Abstract

An anti-glare laminate with excellent pencil hardness and bending resistance is provided. An anti-glare laminate having a resin layer on a substrate, wherein the resin layer has a first resin layer and a second resin layer from the substrate side, and the resin layer contains first particles with an average particle diameter of 0.5 μm or more. An anti-glare laminate comprising, 70% or more of the number of the first particles is present across the first resin layer and the second resin layer, and satisfies the following equation 1. 5<t1/t2<15 (Equation 1) [In Equation 1, t1 represents the average thickness of the first resin layer, and t2 represents the average thickness of the second resin layer.]

Description

Anti-glare laminates, optical laminates, polarizers, and image display devices

The present disclosure relates to an anti-glare laminate, an optical laminate, a polarizing plate, and an image display device.

An anti-glare laminate may be provided on the surface of image display devices such as televisions, laptop PCs, and desktop PC monitors to provide anti-glare properties. Anti-glare is a property that suppresses reflections of backgrounds such as lighting and people.

Additionally, an optical laminate may be provided on the surface of the image display device to provide anti-fouling properties, anti-reflection properties, anti-glare properties, etc.

The anti-glare laminate has the basic structure of having an anti-glare layer with a concavo-convex surface on a base material. Since anti-glare laminates are often used as surface members for image display devices and the like, there are many opportunities for them to come into contact with human fingers or objects. For this reason, it is preferable that the anti-glare laminate has high pencil hardness.

An optical laminate consists of a basic structure having an optical function layer on a base material. Since optical laminates are often used as surface members for image display devices and the like, there are many opportunities for them to come into contact with human fingers, objects, etc. For this reason, it is preferable that the optical laminated body has good pencil hardness.

In order to increase the pencil hardness of an 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 and 2).

In order to improve the pencil hardness of the optical laminated body, the cured product of the curable resin composition is preferably used as the binder resin of the optical function layer.

The cured product of the curable resin composition tends to improve the pencil hardness of the optical laminate, but tends to have poor adhesion to the substrate. Patent Documents 3 and 4 propose an optical laminated body that uses a cured product of a curable resin composition as the binder resin of the optical function layer and has good adhesion.

Japanese Patent No. 6840215 Publication International Publication No. WO2018/070426 Japanese Patent Publication No. 2012-234163 Japanese Patent Publication No. 2015-188772

The anti-glare laminates of Patent Documents 1 and 2 have good pencil hardness because the anti-glare layer has a high hardness. However, the anti-glare laminates of Patent Documents 1 and 2 sometimes had insufficient bending resistance. Specifically, when the anti-glare laminate of Patent Documents 1 and 2 was applied to a foldable type image display device or a rollable type image display device, cracks sometimes occurred in the anti-glare laminate. The above-mentioned bending resistance tended to deteriorate when an acrylic resin substrate was used as the substrate of the anti-glare laminate.

The optical laminates of Patent Documents 3 to 4 have good initial adhesion. However, in the optical laminates of Patent Documents 3 to 4, there were cases where adhesion decreased over time or optical properties changed. Specifically, when a light resistance test by ultraviolet irradiation was conducted on the optical laminates of Patent Documents 3 to 4, there were cases where adhesion decreased or the clarity of the transmitted image changed.

The present disclosure aims to provide an anti-glare laminate excellent in pencil hardness and bending resistance, as well as a polarizing plate and an image display device using the same.

The object of this disclosure is to provide an optical laminate capable of suppressing a decrease in adhesion and a change in transmitted image clarity after a light resistance test, and a polarizing plate and an image display device using the same.

The present disclosure provides an anti-glare laminate, an optical laminate, a polarizing plate, and an image display device of the following [1] to [31].

[1] An anti-glare laminate having a resin layer on a base material,

The resin layer has a first resin layer and a second resin layer from the substrate side,

The resin layer contains first particles with an average particle diameter of 0.5 μm or more,

More than 70% of the number of the first particles is present across the first resin layer and the second resin layer,

An anti-glare laminate that satisfies the following formula 1.

5.0<t1/t2<15.0 (Equation 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] The anti-glare laminate according to [1], wherein D1, which represents the average particle diameter of the first particles, and t2, which represents the average thickness of the second resin layer, are in the relationship of t2 < D1.

[3] The anti-glare laminate according to [1] or [2], wherein D1, which represents the average particle diameter of the first particles, and t1, which represents the average thickness of the first resin layer, are in the relationship of D1 < t1.

[4] The anti-glare laminate according to any one of [1] to [3], wherein the first particles are organic particles.

[5] The anti-glare laminate according to any one of [1] to [4], wherein the average inclination angle of the surface of the base material on the resin layer side is 5.0 degrees or more and 15.0 degrees or less.

[6] The anti-glare laminate according to any one of [1] to [5], wherein the arithmetic mean height of the surface of the base material on the resin layer side is 0.05 μm or more and 0.25 μm or less.

[7] H1, which represents the indentation hardness in the middle of the thickness direction of the first resin layer, and H2, which represents the indentation hardness in the middle of the thickness direction of the second resin layer, are in the relationship of H1 < H2, [1] The anti-glare laminate according to any one of to [6].

[8] The anti-glare laminate according to [7], wherein 40 MPa < H2-H1.

[9] The anti-glare laminate according to [7], wherein 40 MPa < H2-H1 ≤ 100 MPa.

[10] The anti-glare laminate according to any one of [1] to [9], wherein the resin layer includes a cured product of a curable resin composition.

[11] The anti-glare laminate according to any one of [1] to [10], wherein the base material is an acrylic resin base material.

[12] It is an anti-glare laminate having a resin layer on a base material,

The resin layer contains first particles with an average particle diameter of 0.5 μm or more,

When the side of the substrate in the center of the thickness direction of the resin layer is defined as the first area, and the side opposite to the substrate in the center of the thickness direction of the resin layer is defined as the second area, 70 of the number standard of the first particles % or more is present in the second region,

An anti-glare laminate that satisfies the following condition 1A or condition 2A.

<Condition 1A>

The average inclination angle of the surface of the base material on the resin layer side is 5.0 degrees or more and 20.0 degrees or less.

<Condition 2A>

The arithmetic average height of the surface of the base material on the resin layer side is 0.10 μm or more and 0.40 μm or less.

[13] The anti-glare laminate according to [12], wherein D1, which represents the average particle diameter of the first particles, and t, which represents the average thickness of the resin layer, are in the relationship of 2.0 < t/D1 < 6.0.

[14] The anti-glare laminate according to [12] or [13], wherein the first particles are organic particles.

[15] The anti-glare laminate according to any one of [12] to [14], wherein the resin layer includes a cured product of a curable resin composition.

[16] The anti-glare laminate according to any one of [12] to [15], wherein the base material is an acrylic resin base material.

[17] It is an optical 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 first resin layer has a mutually independent region α1 and a region α2 surrounding the region α1, and the resin contained in the region α1 and the resin contained in the region α2 are different,

The second resin layer has a mutually independent region β1 and a region β2 surrounding the region β1, and the resin contained in the region β1 is different from the resin contained in the region β2,

An optical laminate satisfying the following condition 1B or condition 2B.

<Condition 1B>

θa1, which represents the average inclination angle of the surface of the substrate on the resin layer side, and θa2, which represents the average inclination angle of the surface of the first resin layer on the second resin layer side, have the relationship of θa2 < θa1.

<Condition 2B>

Pa1, which represents the arithmetic mean height of the surface of the substrate on the resin layer side, and Pa2, which represents the arithmetic average height of the surface of the first resin layer on the second resin layer side, are in the relationship of Pa2<Pa1.

[18] The optical laminate according to [17], wherein θa1 is 5.0 degrees or more and 20.0 degrees or less.

[19] The optical laminate according to [17] or [18], wherein θa2 is 10.0 degrees or less.

[20] The optical laminate according to [17], wherein Pa1 is 0.05 μm or more and 0.25 μm or less.

[21] The optical laminate according to [17] or [18], wherein the Pa2 is 0.15 μm or less.

[22] When the substrate side at the center of the thickness direction of the first resin layer is defined as the first region, and the second resin layer side at the center of the thickness direction of the first resin layer is defined as the second region, the region The optical laminate according to any one of [17] to [21], wherein 70% or more of α1 is present in the second region.

[23] The resin contained in the region α1 and the resin contained in the region β2 are substantially the same, and the resin contained in the region α2 and the resin contained in the region β1 are substantially the same, [17] to [22] ] The optical laminate according to any one of the above.

[24] The optical laminate according to any one of [17] to [23], wherein the resin layer contains first particles with an average particle diameter of 0.5 μm or more.

[25] The optical laminate according to [24], wherein the second resin layer contains the first particles.

[26] The optical laminate according to [24] or [25], wherein the first particles are organic particles.

[27] The optical laminate according to any one of [17] to [26], wherein the substrate is an acrylic resin substrate.

[28] The optical laminate according to any one of [17] to [27], wherein the resin layer contains a cured product of a curable resin composition.

[29] 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, among the first transparent protective plate and the second transparent protective plate. A polarizing plate, at least one of which is an anti-glare laminate or an optical laminate selected from the anti-glare laminates described in [1] to [16] and the optical laminates described in [17] to [28].

[30] An image having, on a display element, any anti-glare laminate or optical laminate selected from the anti-glare laminate described in [1] to [16] and the optical laminate described in [17] to [28]. display device.

[31] The image display device is a foldable type image display device or a rollable type image display device, and has an anti-glare laminate according to any one of [1] to [16] on the display element, The image display device described in [30].

The anti-glare laminate of the present disclosure can improve pencil hardness and bending resistance. Since the polarizing plate and image display device of the present disclosure have an anti-glare laminate excellent in pencil hardness and bending resistance, the degree of freedom in designing the polarizing plate and image display device can be increased.

The optical laminate, polarizing plate, and image display device of the present disclosure can suppress a decrease in adhesion and a change in transmitted image clarity after a light resistance test.

1 is a cross-sectional view showing one embodiment of an anti-glare laminate according to a first embodiment of the present disclosure.
Figure 2 is a cross-sectional view showing the anti-glare laminate of Comparative Examples 1-3.
Figure 3 is a cross-sectional view showing the anti-glare laminate of Comparative Examples 1-4.
Figure 4 is a cross-sectional view showing one embodiment of the image display device of the present disclosure.
Figure 5 is a cross-sectional view showing one embodiment of the anti-glare laminate of the second embodiment of the present disclosure.
Figure 6 is a cross-sectional view showing the anti-glare laminate of Comparative Example 2-2.
Figure 7 is a cross-sectional view showing one embodiment of the image display device of the present disclosure.
8 is a cross-sectional view showing one embodiment of the optical laminate of the present disclosure.
FIG. 9 is a diagram illustrating a method for calculating the position of region α1 in the thickness direction of the first resin layer of the optical laminate.
Fig. 10 is a cross-sectional view showing one embodiment of the image display device of the present disclosure.

Hereinafter, embodiments of the present disclosure will be described.

[Anti-glare laminate of first embodiment]

The anti-glare laminate of the first embodiment of the present disclosure has a resin layer on a base material,

The resin layer has a first resin layer and a second resin layer from the substrate side,

The resin layer contains first particles with an average particle diameter of 0.5 μm or more,

More than 70% of the number of the first particles is present across the first resin layer and the second resin layer,

It is an anti-glare laminate that satisfies the following formula 1.

5.0<t1/t2<15.0 (Equation 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.]

1 is a cross-sectional view showing one embodiment of an anti-glare laminate 100A of the first embodiment of the present disclosure.

The anti-glare laminate 100A in FIG. 1 has a resin layer 20A on a substrate 10. In addition, 20A of resin layers in FIG. 1 have 21A of first resin layers and 22A of second resin layers from the base material 10 side. Additionally, the resin layer 20A in FIG. 1 contains first particles 23A with an average particle diameter of 0.5 μm or more. Moreover, 23A of 1st particle|grains in FIG. 1 exist over 21 A of 1st resin layers and 22A of 2nd resin layers.

Additionally, Figure 1 is a schematic cross-sectional view. That is, the scale of each layer, the scale of each material, and the scale of surface irregularities constituting the anti-glare laminate 100A are modeled for ease of illustration and are different from the actual scale. Drawings other than Figure 1 are also different from the actual scale.

<Description>

As a base material, one having good light transparency, smoothness, heat resistance, and mechanical strength is preferable. Examples of such substrates include polyester, triacetylcellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethyl pentene, polyvinyl chloride, and polyvinyl acetal. , resin substrates containing resins such as polyether ketone, acrylic resin, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP). The resin substrate may be a bonding of two or more resin substrates.

The resin substrate is preferably stretched to improve mechanical strength and dimensional stability.

Among resin substrates, acrylic resin substrates are preferred because they have low hygroscopicity, so they tend to have good dimensional stability, and because they have low optical anisotropy, they tend to improve visibility. In addition, the acrylic resin substrate can easily form the first resin layer and the second resin layer in one application by using the coating liquid for the resin layer as a predetermined composition and under predetermined drying conditions.

Since the acrylic resin substrate is hard and easily broken, when a resin layer containing a cured product of a curable resin composition is formed on the acrylic resin substrate, bending resistance may become insufficient. The anti-glare laminate of the present disclosure is such that even when a resin layer containing a cured product of a curable resin composition is formed on an acrylic resin substrate, the first particles are present at a predetermined position in the thickness direction of the resin layer, and the formula: By satisfying 1, etc., it is possible to easily suppress the decline in bending resistance.

In this specification, acrylic resin means acrylic resin and/or methacrylic resin.

The acrylic resin contained in the acrylic resin base material is not particularly limited, but is preferably formed by polymerizing, for example, one type or a combination of two or more alkyl (meth)acrylate esters, and more specifically, methyl (meth)acrylate. It is preferable to obtain it using . In addition, as acrylic resin, Japanese Patent Laid-Open No. 2000-230016, Japanese Patent Laid-Open No. 2001-151814, Japanese Patent Laid-Open No. 2002-120326, Japanese Patent Laid-Open No. 2002-254544, and Japanese Patent Laid-Open No. Also included are those described in Publication No. 2005-146084, etc. As the acrylic resin, you may use an acrylic resin having a ring structure, such as an acrylic resin having a lactone ring structure or an acrylic resin having an imide ring structure.

The acrylic resin has a glass transition point (Tg) of preferably 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.

If the glass transition point of the acrylic resin is 100°C or higher, excessive dissolution of the acrylic resin base material can be easily suppressed when forming the resin layer. If the glass transition point of the acrylic resin is 150°C or lower, it is easy to control the degree to which the acrylic resin base material dissolves when forming the resin layer.

The acrylic resin substrate may contain a resin other than the acrylic resin, but the ratio of the acrylic resin to the total resin constituting the acrylic resin substrate is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass. It is more preferable that it is % or more.

The acrylic resin substrate can be manufactured, for example, by melt-extruding a pellet made of a humidity-controlled acrylic resin, stretching it in the longitudinal direction while cooling, and then stretching it in the transverse direction.

In the melt extrusion process, a single-axis, two-axis, 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 performed so that the desired thickness is achieved after stretching. In addition, the draw ratio is not limited, but is preferably 1.2 times or more and 4.5 times or less. The temperature and humidity during stretching are determined arbitrarily. The stretching method may be a general method.

The average thickness of the base material is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 35 μm or more. By setting the average thickness of the base material to 10 μm or more, the anti-glare laminate can be easily handled well.

The average thickness of the base material is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less. By setting the average thickness of the base material to 100 μm or less, the bending resistance of the anti-glare laminate can be easily improved.

Embodiments of suitable ranges of the average thickness of the base material include: 10 μm to 100 μm, 10 μm to 80 μm, 10 μm to 60 μm, 20 μm to 100 μm, 20 μm to 80 μm, and 20 μm or more. Examples include 60 μm or less, 35 μm or more and 100 μm or less, 35 μm or more and 80 μm or less, and 35 μm or more and 60 μm or less.

The above-mentioned average thickness of the substrate means the average thickness of the substrate upon completion of the anti-glare laminate. As will be described later, when part of the substrate is dissolved by the coating liquid for the resin layer, the average thickness of the substrate upon completion of the anti-glare laminate may decrease compared to the average thickness of the initial substrate. For this reason, it is preferable that the average thickness of the initial substrate is thicker than the average thickness of the substrate upon completion of the anti-glare laminate. The difference between the average thickness of the initial base material and the average thickness of the base material upon completion of the anti-glare laminate can not be said uniformly because 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. Although it is impossible, it is preferable that it is 0.1 ㎛ or more and 10 ㎛ or less, and it is more preferable that it is 1 ㎛ or more and 5 ㎛ or less.

The average thickness of the base material can be calculated, for example, by selecting 20 arbitrary points in a cross-sectional photograph of the anti-glare laminate taken with a scanning transmission electron microscope (STEM) and calculating the average value. It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

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 particle in the thickness direction of the resin layer, the average inclination angle of the surface on the resin layer side of the substrate, the resin layer side of the substrate In order to measure the arithmetic mean height of the surface, etc., it is necessary to produce a sample for measurement in which the cross section of the anti-glare laminate is exposed. The sample can be produced, for example, in steps (A1) to (A2) described later. Additionally, in cases where the interface is difficult to see due to lack of contrast, the sample may be dyed with osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, etc. as a pretreatment.

In this specification, unless otherwise specified, the atmosphere in which various measurements and evaluations and sampling for measurements and evaluations are performed are those measured at a temperature of 23 ± 5°C and a relative humidity of 40% to 65%. In addition, before carrying out measurement, evaluation and sampling, the target anti-glare laminate is exposed to the above atmosphere for 30 minutes or more. The above-mentioned atmosphere is a common atmosphere for the anti-glare laminate of the first embodiment, the anti-glare laminate of the second embodiment, and the optical laminate.

The base material preferably has an average inclination angle of the surface on the resin layer side of the base material of 5.0 degrees or more and 15.0 degrees or less.

By setting the average inclination angle to 5 degrees or more, the bending resistance of the anti-glare laminate can be easily improved. It is believed that the reason why the bending resistance is improved is because the adhesion between the base material and the resin layer is improved so that interfacial peeling does not occur during bending.

By setting the average inclination angle to 15 degrees or less, it is easy to suppress an increase in internal haze. In addition, in the case of the embodiment in which a part of the base material is dissolved by the coating liquid for the resin layer, the pencil hardness can be easily improved by setting the average inclination angle to 15 degrees or less. It is believed that the reason why pencil hardness can be easily improved in the above-described embodiment is because the base component does not elute excessively in the resin layer, making it difficult for the hardness of the resin layer to decrease.

The average inclination angle of the base material is more preferably 5.5 degrees or more, and even more preferably 6.0 degrees or more. The average inclination angle of the base material is more preferably 14.0 degrees or less, and even more preferably 13.0 degrees or less.

Embodiments of suitable ranges of the average inclination angle of the base material include: 5.0 degrees to 15.0 degrees, 5.0 degrees to 14.0 degrees, 5.0 degrees to 13.0 degrees, 5.5 degrees to 15.0 degrees, 5.5 degrees to 14.0 degrees, and 5.5 degrees or more. Examples include 13.0 degrees or less, 6.0 degrees or more and 15.0 degrees or less, 6.0 degrees or more and 14.0 degrees or less, and 6.0 degrees or more and 13.0 degrees or less.

The average inclination angle of the substrate and the arithmetic average height of the substrate can be measured, for example, as follows.

(1) A cross-sectional photograph of the anti-glare laminate is taken with a scanning transmission electron microscope (STEM). It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 5,000 times or more and 10,000 times or less.

(2) From the cross-sectional photographic image, the ridge line of the interface between the base material and the resin layer is acquired, and height data is acquired. Specifically, it is as follows (a) to (l). The interface between the substrate and the resin layer corresponds to the surface of the substrate on the resin layer side.

(a) The captured image is displayed using ImageJ (version 1.52a), an open source, public domain image processing software.

(b) The length per pixel is obtained from the scale display displayed in the image.

(c) Select "FreeHand Selections" to create an ROI to include the interface, and adjust the Brightness to make the color clearly different around the interface.

(d) Apply Process-Smooth twice.

(e) Set Image-Type to 8bit.

(f) Select “Straight” to draw a line along the interface.

(g) Introduce and run ABSnake, a plugin of ImageJ. Then set “Gradient threshold” to 10 and Draw color to Red. Leave other settings as default.

(h) Visually confirm that the interface is traced in red. In case of defect, repeat from (f).

(i) Run Image-Adjust-Color Threshold. Set a threshold to separate Red from others. Specifically, set the color space to RGB, check "Pass" for "Red", "Green", and "Blue", set the upper and lower limits of the range of Red to the maximum value (255), and set "Green" and "Blue" to the maximum value (255). The upper and lower limits of the range are set to the minimum value of 0.

(j) Execute Process-Binary-Make Binary to binarize the portion of the trace line at the interface and the portion other than the above trace line.

(k) Save the binary data as “Text Image” with File-Save As.

(l) From the binarized data, the interface is converted into a height data point string.

(3) From the height data point sequence, the average inclination angle and arithmetic average height are calculated in the following procedures (m) to (q).

(m) The center line of the height data is obtained by quadratic regression of the least squares method, and subtracted from the height data to transform the center line to 0 so that the upward direction is positive and the downward direction is negative. The direction of the center line is the x-axis, and the direction perpendicular to it (height direction) is the y-axis.

(n) Convert the height data to length using the length per pixel obtained in (b).

(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 _i is the height at the ith point of the height data point string, Δx is the distance in the x-axis direction of the neighboring point] The average inclination angle is obtained by calculating the arithmetic mean of the absolute value of the inclination angle of each point obtained by .

(q) The arithmetic mean height is obtained by calculating the arithmetic mean of the absolute value of the height of each point.

The base material preferably has an arithmetic average height of the surface on the resin layer side of the base material 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 bending resistance of the anti-glare laminate can be easily improved. It is believed that the reason why the bending resistance is improved is because the adhesion between the base material and the resin layer is improved so that interfacial peeling does not occur during bending.

By setting the arithmetic mean height to 0.25 μm or less, it is easy to suppress an increase in internal haze. In addition, in the case of the embodiment in which a part of the base material is dissolved by the coating liquid for the resin layer, the pencil hardness can be easily improved by setting the arithmetic mean height to 0.25 μm or less. It is believed that the reason why pencil hardness can be easily improved in the above-described embodiment is because the base component does not elute excessively in the resin layer, making it difficult for the hardness of the resin layer to decrease.

The arithmetic mean height of the base material is more preferably 0.07 μm or more, and even more preferably 0.09 μm or more. The arithmetic mean height of the base material is more preferably 0.23 μm or less, and even more preferably 0.20 μm or less.

Embodiments of suitable ranges of the arithmetic mean height of the substrate include: 0.05 μm to 0.25 μm, 0.05 μm to 0.23 μm, 0.05 μm to 0.20 μm, 0.07 μm to 0.25 μm, 0.07 μm to 0.23 μm, and 0.07 μm. Examples include 0.20 μm or less, 0.09 μm or more and 0.25 μm or less, 0.09 μm or more and 0.23 μm or less, and 0.09 μm or more and 0.20 μm or less.

In order to keep the average inclination angle and arithmetic mean height of the surface of the resin layer side of the substrate within the above-mentioned range, it is preferable to dissolve a part of the substrate in the coating liquid for the resin layer. However, when dissolving the base material into the coating liquid for the resin layer, it is preferable to use the coating liquid for the resin layer to have a prescribed composition and to set it to prescribed drying conditions. The predetermined composition and predetermined drying conditions will be described later.

The base material of the anti-glare laminate of the first and second embodiments, and the base material of the optical laminate may contain additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, and a plasticizer.

The surface of the base material of the anti-glare laminate of the first and second embodiments, and the surface of the base material of the optical laminate are subjected to physical treatment such as corona discharge treatment or chemical treatment to improve adhesion. Alternatively, an easy-adhesion layer may be formed.

<Resin layer>

The resin layer is required to have a first resin layer and a second resin layer from the base material side.

In addition, the first resin layer and the second resin layer are required to satisfy the following formula 1.

5.0<t1/t2<15.0 (Equation 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.]

The first resin layer and the second resin layer can be formed, for example, by applying a coating liquid for a resin layer containing the first particles, a resin component, and a solvent onto a substrate, drying it, and curing it as necessary. You can. The coating liquid for the resin layer may further contain inorganic fine particles and additives as needed.

In the case of the above method, the coating liquid for the resin layer dissolves a part of the substrate, and the area formed by mixing the components eluted from the substrate and the coating liquid for the resin layer becomes the first resin layer, and almost all of the components eluted from the substrate are formed. The area containing the resin layer coating liquid as the main component 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 essential to use the coating liquid for the resin layer to have a predetermined composition and to set it to 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 on the substrate is not particularly limited, and includes spin coat method, dipping method, spray method, die coat method, bar coat method, gravure coat method, roll coater method, and meniscus coater method. , general-purpose application methods such as flexographic printing, screen printing, and feed coater methods can be mentioned.

When curing the coating liquid for the resin layer, it is preferable to irradiate it with ionizing radiation such as ultraviolet rays 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. Additionally, as the wavelength of ultraviolet rays, a wavelength range of 190 nm to 380 nm is preferable. Specific examples of electron beam sources include various electron beam accelerators such as Cockcroft-Walton type, Vandergraaff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high-frequency type.

In addition, as a means of making the resin layer into two layers, as in Comparative Examples 1-3 and 1-4 described later, two coating liquids for the resin layer are prepared, and after forming the first resin layer, the second layer Means for laminating the resin layer are conceivable. However, when particles are included in the first-layer coating liquid, it is difficult to improve anti-glare properties, and when particles are included in the second-layer coating liquid, it is difficult to improve bending resistance. Additionally, in the method of forming two resin layers using two coating liquids for resin layers, it is difficult to achieve good 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 coating liquid for the resin layer, as in the method described above.

When the resin layer is a single layer, it is difficult to improve the bending resistance or pencil hardness of the anti-glare laminate. For example, in the case of a single layer of a resin layer with high hardness, it is difficult to improve the bending resistance of the anti-glare laminate. Additionally, in the case of a single layer of a low-hardness resin layer, it is difficult to improve the pencil hardness of the anti-glare laminate.

Moreover, even if the resin layer has a first resin layer and a second resin layer, if Formula 1 is not satisfied, the bending resistance or pencil hardness of the anti-glare laminate cannot be improved. Since the second resin layer is farther from the base material than the first resin layer, the content of components eluted from the base material is lower in the second resin layer than in the first resin layer. Therefore, the hardness of the second resin layer is likely to become higher than the hardness of the first resin layer. The fact that t1/t2 is 15.0 or more means that the ratio of the thickness of the second resin layer with high hardness is small. For this reason, when t1/t2 is 15.0 or more, the pencil hardness of the anti-glare laminate cannot be improved. In addition, t1/t2 of 5.0 or less means that the ratio of the thickness of the second resin layer with high hardness is large. For this reason, when t1/t2 is 5.0 or less, the bending resistance of the anti-glare laminate cannot be improved.

t1/t2 is preferably 5.5 or more, and more preferably 6.0 or more. Moreover, t1/t2 is preferably 14.0 or less, and more preferably 13.5 or less.

Embodiments of suitable ranges for t1/t2 include: 5.0 and less than 15.0, 5.0 and less than 14.0, more than 5.0 and 13.5 or less, 5.5 or more and less than 15.0, 5.5 or more and 14.0 or less, 5.5 or more and 13.5 or less, 6.0 or more and less than 15.0, and 6.0 or more and 14.0 or less. , 6.0 or more and 13.5 or less.

The lower limit of 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 still more preferably 9.0 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.

Embodiments of suitable ranges for the thickness of the entire resin layer include 7.0 μm to 15.0 μm, 7.0 μm to 14.0 μm, 7.0 μm to 13.0 μm, 8.0 μm to 15.0 μm, 8.0 μm to 14.0 μm, and 8.0 μm. Examples include 13.0 μm or less, 9.0 μm or more and 15.0 μm or less, 9.0 μm or more and 14.0 μm or less, and 9.0 μm or more and 13.0 μm or less.

The lower limit of the average thickness t1 of the first resin layer is preferably 5.0 μm or more, more preferably 7.0 μm or more, further preferably 8.5 μm or more, and the upper limit is preferably 13.0 μm or less and 12.0 μm or less. It is more preferable, and 11.0 μm or less is further preferable. By setting t1 to 5.0 μm or more, it is possible to easily improve bending resistance, and by setting t1 to 13.0 μm or less, it is possible to easily suppress a decrease in pencil hardness.

Embodiments of suitable ranges for t1 include: 5.0 μm to 13.0 μm, 5.0 μm to 12.0 μm, 5.0 μm to 11.0 μm, 7.0 μm to 13.0 μm, 7.0 μm to 12.0 μm, 7.0 μm to 11.0 μm. , 8.5 ㎛ or more and 13.0 ㎛ or less, 8.5 ㎛ or more and 12.0 ㎛ or less, and 8.5 ㎛ or more and 11.0 ㎛ or less.

The lower limit of the average thickness t2 of the second resin layer is preferably 0.3 μm or more, more preferably 0.5 μm or more, further preferably 0.7 μm or more, and the upper limit is preferably 4.0 μm or less and 3.0 μm or less. It is more preferable, and 2.7 μm or less is further preferable. By setting t2 to 0.3 μm or more, pencil hardness can be easily improved, and by setting t2 to 4.0 μm or less, it can be easily suppressed from a decrease in bending resistance.

Embodiments of suitable ranges for t2 include: 0.3 μm to 4.0 μm, 0.3 μm to 3.0 μm, 0.3 μm to 2.7 μm, 0.5 μm to 4.0 μm, 0.5 μm to 3.0 μm, 0.5 μm to 2.7 μm. , 0.7 μm or more and 4.0 μm or less, 0.7 μm or more and 3.0 μm or less, and 0.7 μm or more and 2.7 μm or less.

The average thickness of the first resin layer and the average thickness of the second resin layer are determined by selecting 20 arbitrary points from a cross-sectional photograph of an anti-glare laminate taken, for example, by a scanning transmission electron microscope (STEM). , can be calculated by the average value. It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

The resin layer is required to contain first particles with an average particle diameter of 0.5 μm or more.

If the resin layer does not contain the first particles, anti-glare properties cannot be imparted to the anti-glare laminate.

The resin layer requires that 70% or more of the number of first particles exist across the first resin layer and the second resin layer.

The fact that the first particles 23A span the first resin layer 21A and the second resin layer 22A means that, as shown in FIG. 1, in the thickness direction of the resin layer 20A, the first particles (23A) means that it exists on both sides of the 1st resin layer 21A side and the 2nd resin layer 22A side. On the other hand, in FIG. 2, the first particle 23A does not exist across the first resin layer 21A and the second resin layer 22A, but exists on one side of the second resin layer 22A. In FIG. 3, the first particles 23A do not exist across the first resin layer 21A and the second resin layer 22A, but exist on one side of the first resin layer 21A.

In this specification, "70% or more of the number standard of the first particles exists across the first resin layer and the second resin layer" means "the first particles satisfy the condition of the position in the thickness direction." There are cases where it is described as: In this specification, “70% or more of the number standard of the first particles does not exist across the first resin layer and the second resin layer” means “the first particles do not meet the condition of the position in the thickness direction.” There are cases where it is described as “not.”

If the first particles do not satisfy the conditions of the position in the thickness direction, anti-glare properties and bending resistance cannot be improved.

When the first particles do not satisfy the condition of the position in the thickness direction, more than 30% of the number standard of the first particles does not span the first resin layer and the second resin layer, and is in the first resin layer and the second resin layer. It exists in some of the strata. In this specification, the first particles that do not span the first resin layer and the second resin layer and exist in either the first resin layer or the second resin layer may be described as "biased first particles." . When the first resin layer contains a large number of biased first particles, it becomes difficult for the first particles to form irregularities on the surface of the resin layer, so anti-glare properties cannot be improved. Additionally, when the anti-glare laminate is bent, peeling may occur at the interface between the first particles and the resin layer, and this peeling causes the bending resistance to decrease. Peeling at the interface between the first particles and the resin layer is less likely to be suppressed when the hardness of the resin layer is harder. For this reason, when the second resin layer contains a large number of biased first particles, the bending resistance cannot be improved.

The proportion of the first particles present on both sides of the first resin layer and the second resin layer in the thickness direction of the resin layer is preferably 80% or more, and more preferably 90% or more, based on the number of particles.

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 anti-glare laminate taken with a scanning transmission electron microscope (STEM). Additionally, the ratio of the above-mentioned number standards can be calculated from the cross-sectional photograph. In addition, in order to increase the reliability of the numerical value, it is desirable to obtain a plurality of cross-sectional photographs, set the total number of first particles to 50 or more, and then calculate the ratio based on the above-mentioned number standards.

It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

It is preferable that H1, which represents the indentation hardness in the middle of the thickness direction of the first resin layer, and H2, which represents the indentation hardness in the middle of the thickness direction of the second resin layer, have the relationship of H1 < H2.

By satisfying the relationship H1<H2, it is easy to improve the pencil hardness and bending resistance of the anti-glare laminate.

It is preferable that H1 and H2 are 40 MPa < H2-H1. By setting H2-H1 to more than 40 MPa, it is easy to improve the pencil hardness and bending resistance of the anti-glare laminate. H2-H1 is more preferably 45 MPa or more, and even more preferably 50 MPa or more.

When H2-H1 is too large, the bending resistance of the anti-glare laminate tends to decrease because H2 is too large, or the pencil hardness of the anti-glare laminate tends to decrease when H1 is too small. For this reason, H2-H1 is preferably 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 depending on the resin component constituting the coating liquid for the resin layer. Since the value of H1 is the value of the 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.

Embodiments of suitable ranges for H2-H1 include: more than 40 MPa and less than 100 MPa, more than 40 MPa and less than 90 MPa, more than 40 MPa and less than 80 MPa, more than 45 MPa and less than 100 MPa, more than 45 MPa and less than 90 MPa, and more than 45 MPa and less than 80 MPa. Examples include MPa or less, 50 MPa or more and 100 MPa or less, 50 MPa or more and 90 MPa or less, and 50 MPa or more and 80 MPa or less.

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 easily improve pencil hardness, and the upper limit is to easily suppress the decline in bending resistance. For this reason, it is preferable that it is 250 MPa or less, more preferably 240 MPa or less, and even more preferably 230 MPa or less.

Embodiments of suitable ranges for H1 include: 150 MPa to 250 MPa, 150 MPa to 240 MPa, 150 MPa to 230 MPa, 160 MPa to 250 MPa, 160 MPa to 240 MPa, and 160 MPa to 230 MPa. , 170 MPa or more and 250 MPa or less, 170 MPa or more and 240 MPa or less, and 170 MPa or more and 230 MPa or less.

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 easily improve pencil hardness, and the upper limit is to easily suppress the decline in bending resistance. For this reason, it is preferable that it is 310 MPa or less, more preferably 290 MPa or less, and even more preferably 285 MPa or less.

Embodiments of suitable ranges for H2 include: 230 MPa to 310 MPa, 230 MPa to 290 MPa, 230 MPa to 285 MPa, 240 MPa to 310 MPa, 240 MPa to 290 MPa, and 240 MPa to 285 MPa. , 245 MPa or more and 310 MPa or less, 245 MPa or more and 290 MPa or less, and 245 MPa or more and 285 MPa or less.

-Method for measuring indentation hardness-

In order to measure H1 to H3, it is necessary to produce a measurement sample in which the cross section of the layer to be measured is exposed. The sample can be produced, for example, in the following steps (A1) to (A2).

(A1) A cut sample is produced by cutting the anti-glare laminate to an arbitrary size, and then an embedding sample is produced by embedding the cut sample in resin. The size of the cut sample is, for example, a strip of 10 mm in length x 3 mm in width. The resin for embedding is preferably an epoxy resin.

For the embedding sample, for example, after placing the cut sample in a silicone embedding plate, the embedding resin is introduced, and after curing the embedding resin, the cut sample and the embedding material surrounding it are cut from the silicone embedding plate. It can be obtained by taking out the resin. In the case of the epoxy resin manufactured by Struers Co., Ltd. exemplified below, the above-mentioned curing step is preferably performed by leaving the resin at room temperature for 12 hours. The shape of the embedded sample was block-shaped.

Examples of the silicone embedding plate include those manufactured by Tosaka EM. The silicone embedding plate is sometimes called a silicone capsule. The epoxy resin for embedding can be, for example, a mixture of "Epofix" under the trade name of Struers and "Hardener for Epofix" under the trade name of the same company at a ratio of 10:1.2.

(A2) The block-shaped embedded sample is cut vertically to produce a sample for measuring indentation hardness in which the cross section of the anti-glare laminate is exposed. The shape of the sample for measuring indentation hardness maintained a block shape. The embedded sample is preferably cut so as to pass through the center of the cut sample. Embedded samples are preferably cut with a diamond knife.

As a device for cutting the block-shaped embedded sample, for example, the brand name "Ultra Microtome EM UC7" manufactured by Leica Microsystems Inc. is available. When cutting a block-shaped embedded sample, it is desirable to first roughly cut it (rough trimming) and finally trim it precisely under the conditions of “SPEED: 1.00 mm/s” and “FEED: 70 nm.”

As described above, among the sections cut from the block-shaped embedding sample, the sections without defects such as holes and with a uniform thickness of 60 nm to 100 nm are the average thickness of the first resin layer and the second resin layer. Average thickness, position of the first particles in the thickness direction of the resin layer, average inclination angle of the surface on the resin layer side of the substrate, arithmetic average height of the surface on the resin layer side of the substrate, particle size of the first particles, particle size of the inorganic fine particles It can be used as a sample for measurement.

H1 to H3 are measured by vertically pressing a Berkovich indenter (material: diamond triangular pyramid) into a predetermined position on the cut surface of the sample described above.

The predetermined position is the middle of the thickness direction of the first resin layer in the measurement of H1, the middle of the thickness direction of the second resin layer in the measurement of H2, and the center of the thickness direction of the base material in the measurement of H3. The center of the thickness direction of the first resin layer is preferably the center of the thickness direction of the first resin layer, but a deviation of 0.10 μm from the center is acceptable. Similarly, it is preferable that the thickness direction of the second resin layer is at the center of the thickness direction of the second resin layer, but a deviation of 0.10 μm from the center is acceptable. Similarly, it is preferable that the thickness direction of the substrate is at the center of the thickness direction of the substrate, but a deviation of 0.10 μm from the center is acceptable.

Indentation hardness is preferably measured under the following conditions.

<Measurement conditions>

·Indenter used: Berkovich indenter (model number: TI-0039, manufactured by BRUKER)

·Press fitting conditions: load control method

·Maximum load: 50μN

·Load application time: 10 seconds (load change rate: 5μN/sec)

·Holding time: 5 seconds

·Holding load: 50μN

·Load unloading time: 10 seconds (load change rate: -5μN/sec)

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). By analyzing the created load-displacement curve, the indentation hardness H _IT can be calculated as the value obtained by dividing the maximum indentation load F _max (N) by the projected area A _p (mm2) where the indenter and the layer of the measurement object are in contact. (Equation 2 below).

H _IT =F _max /A _p (Equation 2)

Here, A _p is the projected contact area obtained by correcting the curvature of the indenter tip by the Oliver-Pharr method using a standard sample of fused quartz (5-0098 manufactured by BRUKER).

In this specification, H1 to H3 mean the average value of the measured values of 20 samples.

《First Particle》

The first particles are particles with an average particle diameter of 0.5 μm or more. When 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 anti-glare properties cannot be achieved.

As the first particle, polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine resin, and polyester. Organic particles formed from one or more types of resin such as system resin; Inorganic particles formed of one or more types of inorganic materials such as silica, alumina, zirconia, and titania; can be mentioned. Among these, organic particles are preferable because they are excellent in dispersion stability and have a relatively small specific gravity, so that the first particles can easily satisfy the condition of the position in the thickness direction.

The lower limit of the content of the first particles is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and even more preferably 1.5 parts by mass or more, with respect to 100 parts by mass of the resin component of the coating liquid for the resin layer. The upper limit is preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.

By setting the content of the first particles to 0.5 parts by mass or more, anti-glare properties can be easily improved. Additionally, 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 bending resistance.

Embodiments of suitable ranges for the content of the first particles relative to 100 parts by mass of the resin component are 0.5 parts by mass or more and 10.0 parts by mass or less, 0.5 parts by mass or more and 5.0 parts by mass or less, 0.5 parts by mass or more and 3.0 parts by mass or less, and 1.0 parts by mass. 10.0 parts by mass or less, 1.0 parts by mass or more but 5.0 parts by mass or less, 1.0 parts by mass or more but 3.0 parts by mass or less, 1.5 parts by mass or more but 10.0 parts by mass or less, 1.5 parts by mass or more but 5.0 parts by mass or less, 1.5 parts by mass or more 3.0 parts by mass The following can be mentioned.

The average particle diameter 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 condition of the position in the thickness direction, 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.

Embodiments of suitable ranges of the average particle diameter of the first particles include 0.8 μm to 3.0 μm, 0.8 μm to 2.7 μm, 0.8 μm to 2.5 μm, 1.0 μm to 3.0 μm, 1.0 μm to 2.7 μm, and 1.0 μm to 2.7 μm. Examples include ㎛ or more and 2.5 ㎛ or less.

The average particle diameter of the first particles can be calculated, for example, by the following operations (B1) to (B3).

(B1) A transmission observation image of the anti-glare laminate is captured using an optical microscope. The magnification is preferably 500 times or more and 2000 times or less.

(B2) Ten arbitrary particles are extracted from the observation image, and the particle diameter of each particle is calculated. The particle diameter is measured as the distance between straight lines in the combination of two straight lines that maximize the distance between the two straight lines when the cross section of the particle is placed between two arbitrary parallel straight lines.

(B3) The same operation is performed five times on the observation image of the same sample on another screen, and the value obtained from the number average of the particle diameters of a total of 50 particles is taken as the average particle diameter of the particles.

However, when the first particles cannot be observed optically, the average particle diameter of the first particles is calculated using the following (B4) to (B6).

(B4) From the anti-glare laminate, a section passing through the center of the first particle is produced using a microtome. The thickness of the section is preferably 60 nm to 100 nm. A plurality of sections are successively made for one first particle, and from each section, the section at which the particle diameter calculated through the operation (B5) is maximized is used as the section that passes through the center of the first particle. You can.

(B5) The obtained section is observed with a scanning transmission electron microscope (STEM) to calculate the particle size. The method for calculating the particle diameter is the same as (B2). The magnification is preferably 5,000 times or more and 20,000 times or less.

(B6) The operations (B4) to (B5) are performed on 20 particles, and the value obtained from the number average of the 20 particle diameters is taken as the average particle diameter of the first particles.

It is preferable that D1, which represents the average particle diameter of the first particles, and t2, which represents the average thickness of the second resin layer, have the relationship of t2<D1. By setting t2 < D1, the first particles can easily provide an uneven shape to the surface of the anti-glare laminate, making it easy to improve anti-glare properties.

D1-t2 is preferably 0.5 μm or more, and more preferably 0.7 μm or more.

If D1-t2 is too large, the bending resistance may decrease because the first particles protrude from the surface of the second resin layer. For this reason, 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.

Embodiments of suitable ranges for D1-t2 include: 0.5 μm to 2.0 μm, 0.5 μm to 1.7 μm, 0.5 μm to 1.5 μm, 0.7 μm to 2.0 μm, 0.7 μm to 1.7 μm, 0.7 μm to 1.5 μm. Examples include ㎛ or less.

It is preferable that D1, which represents the average particle diameter of the first particles, and t1, which represents the average thickness of the first resin layer, have the relationship of D1 < t1. By setting D1<t1, it is easy to improve bending resistance.

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.

If t1-D1 is too large, the thickness of the low-hardness first resin layer increases, and the pencil hardness may decrease. For this reason, 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.

Embodiments of suitable ranges for t1-D1 include: 5.0 μm to 10.0 μm, 5.0 μm to 9.0 μm, 5.0 μm to 8.5 μm, 6.0 μm to 10.0 μm, 6.0 μm to 9.0 μm, 6.0 μm to 8.5 μm. Examples include ㎛ or less.

《Inorganic particles》

The resin layer may contain inorganic fine particles. When the resin layer contains inorganic fine particles with a relatively large specific gravity, it becomes difficult for the first particles to sink below the resin layer, making it easy for the first particles to satisfy the condition of the position in the thickness direction. Additionally, the inorganic fine particles can increase the dispersibility of the first particles and make it easier to suppress a decrease in bending resistance.

In this specification, inorganic fine particles mean inorganic particles with an average primary particle diameter of 200 nm or less.

The average particle diameter 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.

The average particle diameter of the inorganic fine particles can be calculated by the following operations (C1) to (C3).

(C1) The cross section of the anti-glare laminate is imaged with TEM or STEM. It is desirable that the acceleration voltage of TEM or STEM be 10 kV or more and 30 kV or less, and the magnification should be 50,000 times or more and 300,000 times or less.

(C2) Ten arbitrary inorganic fine particles are extracted from the observation image, and the particle diameter of each inorganic fine particle is calculated. The particle diameter is measured as the distance between straight lines in the combination of two straight lines that maximize the distance between the two straight lines when the cross section of an inorganic fine particle is placed between two arbitrary parallel straight lines.

(C3) The same operation is performed five times on the observation image of the same sample on another screen, and the value obtained from the number average of the particle diameters of a total of 50 particles is taken as the average particle diameter of the inorganic fine particles.

Examples of inorganic fine particles include fine particles made of silica, alumina, zirconia, and titania. Among these, silica, which easily suppresses the generation of internal haze, is suitable.

The lower limit of the content of inorganic fine particles is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 0.7 part by mass or more, with respect to 100 parts by mass of the resin component of the coating liquid for the resin layer, and the upper limit is It is preferable that it is 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 the inorganic fine particles to 0.1 parts by mass or more, the first particles can easily satisfy the condition of the position in the thickness direction. In addition, by setting the content of the inorganic fine particles to 5.0 parts by mass or less, the first particles can be suppressed from excessively floating upwards of the resin layer, so the first particles can easily satisfy the condition of the position in the thickness direction. .

Embodiments of suitable ranges for the content of inorganic fine particles relative to 100 parts by mass of the resin component are 0.1 part by mass or more and 5.0 parts by mass or less, 0.1 parts by mass or more and 3.0 parts by mass or less, 0.1 parts by mass or more and 2.0 parts by mass or less, and 0.5 parts by mass. Not less than 5.0 parts by mass or less, not less than 0.5 parts by mass but not more than 3.0 parts by mass, not less than 0.5 parts by mass but not more than 2.0 parts by mass, not less than 0.7 parts by mass but not more than 5.0 parts by mass, not less than 0.7 parts by mass but not more than 3.0 parts by mass, not less than 0.7 parts by mass but not more than 2.0 parts by mass can be mentioned.

《Resin ingredients》

The resin layer preferably contains a cured product of the 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 anti-glare 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.

The ratio of the curable resin composition to the total amount of the resin component of the coating liquid for the resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass. Most desirable.

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 preferable, as it is easy to increase pencil hardness and is easy to dissolve the base material in the uncured state of the composition.

A thermosetting resin composition is a composition containing at least a thermosetting resin and is a resin composition that is cured by heating.

Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as needed.

An ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as an “ionizing radiation curable compound”). Examples of the ionizing radiation-curable functional group include ethylenically unsaturated bonding groups such as (meth)acryloyl group, vinyl group, and allyl group, and epoxy group and oxetanyl group. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bonding group is preferable.

Ionizing radiation means electromagnetic waves or charged particle beams that have energy quantum that can polymerize or cross-link molecules. Usually, ultraviolet rays or electron beams are used, but in addition, electromagnetic waves such as X-rays, γ-rays, and α-rays are used. , charged particle beams such as ion beams can also be used.

In this specification, (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. In addition, in this specification, (meth)acrylate refers to acrylate or methacrylate.

As the ionizing radiation curing compound, both a monofunctional ionizing radiation curing compound having one ionizing radiation curing functional group and a polyfunctional ionizing radiation curing compound having two or more ionizing radiation curing functional groups can be used. Additionally, as the ionizing radiation curable compound, both monomers and oligomers can be used.

In order to dissolve part of the base material, increase pencil hardness, and easily suppress curing shrinkage, it is preferable to use a mixture of the following (a) to (c) as an ionizing radiation curable compound. The following (a) to (c) are preferably compounds having an ethylenically unsaturated bond group as an ionizing radiation-curable functional group, and are more preferably (meth)acrylate-based compounds. (Meth)acrylate-based compounds can 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 monomer

(b) multifunctional ionizing radiation curable monomer

(c) multifunctional ionizing radiation curable oligomer

As an ionizing radiation curable compound, by containing the monofunctional ionizing radiation curable monomer of (a), a part of the substrate can be easily dissolved, and the components eluted from the substrate are made compatible with the components of the coating liquid for the resin layer. You can do it easily. In addition, by including the monofunctional ionizing radiation curable monomer (a), the viscosity of the resin layer coating liquid decreases, so that the mixture of the resin layer coating liquid and the component eluted from the base material becomes prone to convection. As a result, since the thickness of the first resin layer increases with respect to the thickness of the second resin layer, t1/t2 can easily be set to exceed 5.

However, if the amount of the monofunctional ionizing radiation curable monomer (a) is too large, the substrate may be excessively dissolved, which may lower the strength of the substrate or reduce the pencil hardness of the anti-glare laminate. Additionally, if the amount of the monofunctional ionizing radiation curable monomer (a) is too large, the above-mentioned convection becomes more intense, so the thickness of the first resin layer becomes too large relative to the thickness of the second resin layer, and t1/t2 becomes too large. There are cases where it exceeds 15.

By containing the polyfunctional ionizing radiation curable monomer of (b) as the ionizing radiation curable compound, the pencil hardness of the anti-glare 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 and the bending resistance of the anti-glare laminate may decrease.

By containing the polyfunctional ionizing radiation curable oligomer of (c) as the ionizing radiation curable compound, curing shrinkage can be easily suppressed while maintaining the pencil hardness of the anti-glare laminate. However, if the amount of the polyfunctional ionizing radiation curable oligomer (c) is too large, the pencil hardness of the anti-glare laminate may decrease.

The amount of the monofunctional ionizing radiation curable monomer (a) relative to the total amount of the ionizing radiation curable compound is preferably 10 mass% or more and 40 mass% or less, more preferably 15 mass% or more and 35 mass% or less, and 17 mass%. It is more preferable that it is % or more and 33 mass% or less.

The amount of the polyfunctional ionizing radiation curable monomer (b) relative to the total amount of the ionizing radiation curable compound is preferably 5 mass% or more and 20 mass% or less, more preferably 6 mass% or more and 15 mass% or less, and 7 mass%. It is more preferable that it is % or more and 13 mass% or less.

The amount of (c) polyfunctional ionizing radiation curable oligomer relative to the total amount of ionizing radiation curable compounds is preferably 40 mass% or more and 80 mass% or less, more preferably 50 mass% or more and 77 mass% or less, and 55 mass%. It is more preferable that it is 75 mass% or less.

Examples of the monofunctional ionizing radiation curable monomer of (a) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and 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. are mentioned. Among these, monofunctional monomers having a hydroxyl group, such as 4-hydroxybutyl (meth)acrylate, are preferable because they tend to improve adhesion to the substrate.

Among the polyfunctional ionizing radiation curable monomers of (b), examples of the bifunctional ionizing radiation curable monomer include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, and bisphenol A tetrapropoxy diacrylate. , 6-hexanediol diacrylate, etc. can be mentioned. 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. are mentioned.

The number of functional groups of the polyfunctional ionizing radiation curable monomer (b) is preferably 3 to 5, more preferably 3 to 4, and still more preferably 3 in order to increase pencil hardness and suppress cure shrinkage. do.

Examples of the multifunctional ionizing radiation curable oligomer of (c) include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. I can hear it.

Urethane (meth)acrylate is obtained, for example, by reaction of polyhydric alcohol and organic diisocyanate with hydroxy (meth)acrylate.

Preferred epoxy (meth)acrylates include trifunctional or higher aromatic epoxy resins, alicyclic epoxy resins, (meth)acrylates obtained by reacting an aliphatic epoxy resin, etc. with (meth)acrylic acid, bifunctional or higher aromatic epoxy resins, and cycloaliphatic epoxy resins. , (meth)acrylate obtained by reacting an aliphatic epoxy resin, etc. with a polybasic acid and (meth)acrylic acid, and (meth)acrylate obtained by reacting a bifunctional or more aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc., with phenols, and (meth)acrylic acid. ) It is acrylate.

The number of functional groups of the polyfunctional ionizing radiation curable oligomer (c) is preferably 4 to 8, more preferably 5 to 7, and still more preferably 6 in order to suppress curing shrinkage while maintaining pencil hardness. do.

The weight average molecular weight of the polyfunctional ionizing radiation curable oligomer (c) is preferably 1000 or more and 5000 or less, more preferably 1100 or more and 3500 or less, and 1200 or more and 2000 or less in order to suppress cure shrinkage while maintaining pencil hardness. It is more desirable.

In this specification, the weight average molecular weight is measured by GPC analysis and is the average molecular weight converted to standard polystyrene.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.

As the photopolymerization initiator, one or more types selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthone, etc. You can.

The photopolymerization accelerator is one that can speed up the curing speed by reducing polymerization inhibition by air during curing, for example, one or more types selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. can be mentioned.

"additive"

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

"menstruum"

It is preferable that the coating liquid for the resin layer contains a solvent.

As the solvent, it is preferable to select a solvent that can dissolve the substrate. However, if the substrate is excessively dissolved, the strength of the substrate decreases, so it is desirable to select an appropriate solvent depending on the type of substrate.

In addition, the solvent is preferably selected taking into account not only the solubility of the substrate but also the evaporation rate inherent to the solvent. This is because when the evaporation rate of the solvent is slow, it is easy to excessively dissolve the substrate. The rate at which the solvent evaporates can also be controlled by drying conditions. For example, if the drying temperature is increased, the rate at which the solvent evaporates becomes faster. Additionally, if the drying wind speed is increased, the rate at which the solvent evaporates becomes faster.

From the above, it is desirable to select the solvent taking into account the solubility of the substrate, evaporation rate, and drying conditions.

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 acetate; Sulfoxides such as dimethyl sulfoxide; Amides such as dimethylformamide and dimethylacetamide; etc. can be mentioned. One type of solvent may be used alone, or a mixture of two or more types may be used.

The acrylic resin substrate is easily soluble in solvents. For this reason, when using an acrylic resin substrate as a substrate, it is preferable that the main component is a solvent with a high evaporation rate inherent in the solvent. The main component means 50% by mass or more of the total amount of 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 with an evaporation rate of 100 or more when the evaporation rate of butyl acetate is 100. The evaporation rate of a solvent with 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 of 150), methyl isobutyl ketone (evaporation rate of 160), and toluene (evaporation rate of 200).

《Drying conditions》

When forming a resin layer from a coating liquid for a resin layer, it is desirable to control drying conditions.

Drying conditions can be controlled by drying temperature and wind speed in the dryer. The preferable ranges of drying temperature and wind speed cannot be stated uniformly because they vary depending on the composition of the coating liquid for the resin layer, but the drying temperature is preferably 85°C or more and 105°C or less, and the drying wind speed is 5 m/s or more and 20 m/s. The following is preferable. The drying time is preferably 30 seconds or more and 90 seconds or less. Among drying conditions, drying temperature is important. When the drying temperature is lowered, t1/t2 tends to decrease, and when the drying temperature is increased, t1/t2 tends to increase. In order to dissolve a part of the substrate with the coating liquid for the resin layer and to ensure the thickness of the first resin layer by flowing the mixture of the components eluted from the substrate and the coating liquid for the resin layer, irradiation of ionizing radiation is applied to the coating liquid. It is suitable to carry out after drying.

<Other floors>

The anti-glare laminate of the first embodiment and the second embodiment described later, and the optical laminate described later may have layers other than the base material and the resin layer. Other layers include an antireflection layer, an antifouling layer, and an antistatic layer.

<Optical properties, surface shape>

The anti-glare laminate of the first embodiment and the second embodiment described later, and the optical laminate described later preferably have a total light transmittance of 70% or more in accordance with JIS K7361-1:1997, and more preferably 80% or more, It is more preferable that it is 85% or more.

The light incident surface when measuring the total light transmittance and the haze described later is the substrate side.

The anti-glare laminate of the first embodiment and the second embodiment described later, and the optical laminate described later have a haze of JIS K7136:2000 of preferably 0.5% or more, more preferably 1.0% or more, and 1.5%. It is more desirable to have more than this. By setting the haze to 0.5% or more, anti-glare properties can be easily improved.

In addition, in order to easily suppress a decrease in image resolution, the anti-glare laminate of the first embodiment and the second embodiment described later, and the optical laminate described later preferably have a haze of 20% or less, and 10%. It is more preferable that it is less than 5%, and it is still more preferable that it is 5% or less.

Embodiments of suitable haze ranges for anti-glare laminates and optical laminates include 0.5% to 20%, 0.5% to 10%, 0.5% to 5%, 1.0% to 20%, and 1.0% to 10%. % or less, 1.0% or more and 5% or less, 1.5% or more and 20% or less, 1.5% or more and 10% or less, and 1.5% or more and 5% or less.

The anti-glare laminate of the first embodiment and the second embodiment described later, and the optical laminate described later have an arithmetic average roughness Ra of JIS B0601:2001 of the surface on the resin layer side in order to easily improve the anti-glare property. It is preferable that it is 0.03 ㎛ or more, and it is more preferable that it is 0.05 ㎛ or more. In addition, the anti-glare laminate of the first embodiment and the second embodiment described later, and the optical laminate described later have an Ra of the surface on the resin layer side of 0.12 μm or less in order to easily suppress a decrease in image resolution. It is preferable, and it is more preferable that it is 0.10㎛ or less. Ra means the value at a cutoff value of 0.8 mm.

Embodiments of suitable ranges of Ra of the surface on the resin layer side include 0.03 μm to 0.12 μm, 0.03 μm to 0.10 μm, 0.05 μm to 0.12 μm, and 0.05 μm to 0.10 μm.

<Size, shape, etc.>

The anti-glare laminate of the first embodiment and the second embodiment described later, and the optical laminate described later may be in the form of a sheet cut into a predetermined size, or may be in the form of a roll in which a long sheet is wound into a roll. . The size of the sheet leaf is not particularly limited, but its maximum diameter is approximately 2 inches or more and 500 inches or less. “Maximum diameter” refers to the maximum length when any two points of the anti-glare laminate or optical laminate are connected. For example, when the anti-glare laminate or the optical laminate is rectangular, the diagonal of the rectangle becomes the maximum diameter. When the anti-glare laminate or optical laminate is circular, the diameter of the circle becomes 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. An anti-glare laminate or optical laminate in the form of a roll can be used by cutting it into a sheet shape according to the size of an image display device or the like. When cutting, it is desirable to exclude the end of the roll where the physical properties are not stable.

The shape of the sheet is not particularly limited, and for example, it may be a polygon such as a triangle, square, or pentagon, may be circular, or may be a random irregular shape. More specifically, when the anti-glare laminate or optical laminate has a square shape, the aspect ratio is not particularly limited as long as there is no problem as a display screen. For example, width:height=1:1, 4:3, 16:10, 16:9, 2:1, 5:4, 11:8, etc.

[Anti-glare laminate of second embodiment]

The anti-glare laminate of the present disclosure has 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 side of the substrate in the center of the thickness direction of the resin layer is defined as the first area, and the side opposite to the substrate in the center of the thickness direction of the resin layer is defined as the second area, 70 of the number standard of the first particles % or more is present in the second region,

It satisfies Condition 1A or Condition 2A below.

<Condition 1A>

The average inclination angle of the surface of the base material on the resin layer side is 5.0 degrees or more and 20.0 degrees or less.

<Condition 2A>

The arithmetic average height of the surface of the base material on the resin layer side is 0.10 μm or more and 0.40 μm or less.

FIG. 5 is a cross-sectional view showing one embodiment of an anti-glare laminate 100B of the second embodiment of the present disclosure.

The anti-glare laminate 100B in FIG. 5 has a resin layer 20B on a base material 10. In addition, the resin layer 20B in FIG. 5 contains first particles 23B with an average particle diameter of 0.5 μm or more. In addition, the side opposite to the base material 10 from the center of the thickness direction of the resin layer 20B is called the first area 21B, and the side opposite to the base material 10 from the center of the thickness direction of the resin layer 20B is called the second area 22B. ), the first particle 23B in FIG. 5 exists in the second area 22B.

Additionally, Figure 5 is a schematic cross-sectional view. That is, the scale of each layer constituting the anti-glare laminate 100B, the scale of each material, and the scale of the surface irregularities are modeled for ease of illustration and are different from the actual scale. Drawings other than Figure 5 are also different from the actual scale.

<Description>

As a substrate, one having good light transparency, smoothness, heat resistance, and mechanical strength is preferable. Examples of such substrates include polyester, triacetylcellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethyl pentene, polyvinyl chloride, and polyvinyl acetal. , resin substrates containing resins such as polyether ketone, acrylic resin, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP). The resin substrate may be a bonding of two or more resin substrates.

The resin substrate is preferably stretched to improve mechanical strength and dimensional stability.

Among resin substrates, acrylic resin substrates are preferred because they have low hygroscopicity, so they tend to have good dimensional stability, and because they have low optical anisotropy, they tend to improve visibility. In addition, the acrylic resin substrate satisfies condition 1A and condition 2A by using the coating liquid for the resin layer as a predetermined composition and under predetermined drying conditions, and also satisfies the position of the first particle in the thickness direction. It can be done easily.

Since the acrylic resin substrate is hard and easily broken, when a resin layer containing a cured product of a curable resin composition is formed on the acrylic resin substrate, bending resistance may become insufficient. The anti-glare laminate of the present disclosure suppresses a decrease in bending resistance by satisfying Condition 1A or Condition 2A, etc., even when a resin layer containing a cured product of a curable resin composition is formed on an acrylic resin substrate. , it is easy to maintain pencil hardness.

Unless otherwise specified, the embodiment of the acrylic resin base of the second embodiment can be the same as the embodiment of the acrylic resin base of the first embodiment. For example, the embodiment of the glass transition point of the acrylic resin substrate of the second embodiment can be the same as the embodiment of the glass transition point of the acrylic resin substrate of the first embodiment.

The average thickness of the base material is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 35 μm or more. By setting the average thickness of the base material to 10 μm or more, the anti-glare laminate can be easily handled well.

The average thickness of the base material is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less. By setting the average thickness of the base material to 100 μm or less, the bending resistance of the anti-glare laminate can be easily improved.

Embodiments of suitable ranges of the average thickness of the base material include: 10 μm to 100 μm, 10 μm to 80 μm, 10 μm to 60 μm, 20 μm to 100 μm, 20 μm to 80 μm, and 20 μm or more. Examples include 60 μm or less, 35 μm or more and 100 μm or less, 35 μm or more and 80 μm or less, and 35 μm or more and 60 μm or less.

The above-mentioned average thickness of the substrate means the average thickness of the substrate upon completion of the anti-glare laminate. As will be described later, when part of the substrate is dissolved by the coating liquid for the resin layer, the average thickness of the substrate upon completion of the anti-glare laminate may decrease compared to the average thickness of the initial substrate. For this reason, it is preferable that the average thickness of the initial substrate is thicker than the average thickness of the substrate upon completion of the anti-glare laminate. The difference between the average thickness of the initial base material and the average thickness of the base material upon completion of the anti-glare laminate can not be said uniformly because 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. Although it is impossible, it is preferable that it is 0.1 ㎛ or more and 10 ㎛ or less, and it is more preferable that it is 1 ㎛ or more and 5 ㎛ or less.

The average thickness of the base material can be calculated, for example, by selecting 20 arbitrary points in a cross-sectional photograph of the anti-glare laminate taken with a scanning transmission electron microscope (STEM) and calculating the average value. It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

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 on the resin layer side of the substrate, the arithmetic average height of the surface on the resin layer side of the substrate, etc. To achieve this, it is necessary to produce a sample for measurement in which the cross section of the anti-glare laminate is exposed. The sample can be produced, for example, in the following steps (A1') to (A2'). Additionally, in cases where the interface is difficult to see due to lack of contrast, the sample may be dyed with osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, etc. as a pretreatment.

(A1') Process A1' is the same as process A1 of the first embodiment.

(A2') The block-shaped embedded sample is cut vertically to produce a sample for measurement in which the cross section of the anti-glare laminate is exposed. As a sample for measurement, a thin section cut from a block-shaped embedded sample is used (sample conditions for measurement will be described later). The embedded sample is preferably cut so as to pass through the center of the cut sample. Embedded samples are preferably cut with a diamond knife.

As a device for cutting the embedded sample, for example, the brand name "Ultra Microtome EM UC7" manufactured by Leica Microsystems. When cutting the embedded sample, it is desirable to initially roughly cut it (rough trimming) and finally trim it precisely under the conditions of “SPEED: 1.00 mm/s” and “FEED: 70 nm.”

Among the sections cut from the block-shaped embedding sample as described above, the sections without defects such as holes and with a uniform thickness of 60 nm to 100 nm are the average thickness of the base material, the thickness of the resin layer, and the thickness of the resin layer. It can be used as a sample for measuring the position of the first particle in the direction, the average inclination angle of the surface on the resin layer side of the substrate, the arithmetic average height of the surface on the resin layer side of the substrate, the particle diameter of the first particle, and the particle diameter of the inorganic fine particles. there is.

《Condition 1A, Condition 2A》

The anti-glare laminate of the second embodiment of the present disclosure is required to satisfy Condition 1A or Condition 2A below. The anti-glare laminate of the second embodiment of the present disclosure may satisfy at least one of Condition 1A and Condition 2A, but it is preferable to satisfy both.

<Condition 1A>

The average inclination angle of the surface of the base material on the resin layer side is 5.0 degrees or more and 20.0 degrees or less.

<Condition 2A>

The arithmetic average height of the surface of the base material on the resin layer side is 0.10 μm or more and 0.40 μm or less.

-Condition 1A-

When the average inclination angle of the substrate is less than 5.0 degrees, the adhesion between the substrate and the resin layer is insufficient and interfacial peeling occurs when the anti-glare laminate is bent, making it difficult to improve the bending resistance of the anti-glare laminate.

If the average inclination angle of the substrate exceeds 20.0 degrees, it means that the substrate components are excessively eluted into the resin layer. For this reason, if the average inclination angle of the base material exceeds 20.0 degrees, it is difficult to improve the pencil hardness of the anti-glare laminate. Additionally, if the average inclination angle of the substrate exceeds 20.0 degrees, the internal haze increases and the resolution tends to decrease.

The average inclination angle of the base material 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 base material is preferably 19.5 degrees or less, more preferably 19.0 degrees or less, and even more preferably 18.5 degrees or less.

Embodiments of suitable ranges of the average inclination angle of the base material include: 5.0 degrees to 20.0 degrees, 5.0 degrees to 19.5 degrees, 5.0 degrees to 19.0 degrees, 5.0 degrees to 18.5 degrees, 6.0 degrees to 20.0 degrees, and 6.0 degrees or more. 19.5 degrees or less, 6.0 degrees or more but 19.0 degrees or less, 6.0 degrees or more but 18.5 degrees or less, 8.0 degrees or more but 20.0 degrees or less, 8.0 degrees or more but 19.5 degrees or less, 8.0 degrees and more but 18.5 degrees or less, 8.0 degrees and more but 18.5 degrees and less, 10.0 degrees and more 20.0 degrees degrees or less, 10.0 degrees or more and 19.5 degrees or less, 10.0 degrees or more and 19.0 degrees or less, and 10.0 degrees or more and 18.5 degrees or less.

The average inclination angle of the base material and the arithmetic mean height of the base material can be measured, for example, by the same method as in the first embodiment.

-Condition 2A-

When the arithmetic mean height of the substrate is less than 0.10 μm, the adhesion between the substrate and the resin layer is insufficient and interfacial peeling occurs when the anti-glare laminate is bent, making it difficult to improve the bending resistance of the anti-glare laminate. .

If the arithmetic average height of the substrate exceeds 0.40 μm, it means that the substrate components are excessively eluted into the resin layer. For this reason, if the arithmetic mean height of the base material exceeds 0.40 μm, it is difficult to improve the pencil hardness of the anti-glare laminate. Additionally, when the arithmetic mean height of the substrate exceeds 0.40 μm, the internal haze increases, which tends to reduce resolution.

The arithmetic mean height of the base material is preferably 0.15 μm or more, and more preferably 0.20 μm or more. The arithmetic mean height of the base material is more preferably 0.38 μm or less, and even more preferably 0.36 μm or less.

Embodiments of suitable ranges of the arithmetic mean height of the substrate include: 0.10 μm to 0.40 μm, 0.10 μm to 0.38 μm, 0.10 μm to 0.36 μm, 0.15 μm to 0.40 μm, 0.15 μm to 0.38 μm, and 0.15 μm. Examples include 0.36 μm or less, 0.20 μm or more and 0.40 μm or less, 0.20 μm or more and 0.38 μm or less, and 0.20 μm or more and 0.36 μm or less.

In order to keep the average inclination angle and arithmetic mean height of the surface of the resin layer side of the substrate within the above-mentioned range, it is preferable to dissolve a part of the substrate in the coating liquid for the resin layer. However, when dissolving the base material into the coating liquid for the resin layer, it is preferable to use the coating liquid for the resin layer to have a prescribed composition and to set it to prescribed drying conditions. The predetermined composition and predetermined drying conditions will be described later.

<Resin layer>

The resin layer is required to contain first particles with an average particle diameter of 0.5 μm or more.

If the resin layer does not contain the first particles, anti-glare properties cannot be imparted to the anti-glare laminate.

In the anti-glare laminate of the present disclosure, when the side of the substrate in the center of the thickness direction of the resin layer is defined as the first region, and the side opposite to the substrate in the center of the thickness direction of the resin layer is defined as the second region, the first particles More than 70% of the number standard is required to be in the second area.

Referring to FIGS. 5 and 6, the first particle 23B in FIG. 5 exists in the second area 22B, and the first particle 23B in FIG. 6 exists in the first area 21B.

In the second embodiment, the resin layer is preferably a single layer.

If more than 70% of the number of first particles does not exist in the second area, then 30% or more of the number of first particles exists in the first area.

Since the first particles present in the first region make it difficult to give the surface of the resin layer an uneven shape, it is difficult to improve anti-glare properties as in Comparative Example 2-2 described later.

As in Comparative Example 2-1 described later, when the absolute value of the content of the first particles is large, the anti-glare property can be improved even if 70% or more of the number of the first particles is not present in the second region. However, in this case, since the interface between the first particles and the resin layer increases, which causes a decrease in bending resistance, the bending resistance of the anti-glare laminate cannot be improved.

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

In this specification, the position where the first particles exist in the thickness direction of the resin layer is determined by the methods (1) to (5) below.

(1) A cross-sectional photograph of the anti-glare laminate is taken using a scanning transmission electron microscope (STEM). It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

(2) Based on the cross-sectional photograph, calculate the average X1 of the elevation of the ridges on the surface on the substrate side of the resin layer and the average X2 of the elevation of the ridges on the surface on the opposite side to the substrate of the resin layer (symbol and X2).

(3) The middle of the elevations of X1 and X2 is defined as the center M in the thickness direction of the resin layer (see symbol M in FIG. 5).

(4) Based on the cross-sectional photograph, the first particles present in the first region on the side of the substrate from the center of the thickness direction of the resin layer, and the second region on the side opposite to the substrate from the center of the thickness direction of the resin layer. The number of first particles present is counted. The number of first particles existing in both the first region and the second region across the center of the thickness direction of the resin layer is assigned to each region according to the area ratio of each region. For example, for the first particle whose area ratio of the first region is 40% and the area ratio of the second region is 60%, 0.4 particles are allocated to the first region and 0.6 particles are allocated to the second region.

(5) In order to increase the reliability of the numerical value, a plurality of cross-sectional photographs are acquired, the total number of first particles is set to 50 or more, and then the ratio of the number of first particles present in the first area and the second area is calculated. Calculate

The resin layer can be formed, for example, by applying a coating liquid for a resin layer containing the first particles, a resin component, and a solvent onto a substrate, drying it, and curing it as necessary. The coating liquid for the resin layer may further contain inorganic fine particles and additives as needed.

In the case of the above method, the coating liquid for the resin layer dissolves a part of the substrate, thereby roughening the surface of the resin layer side of the substrate. The components eluted from the base material are mixed with the coating liquid for the resin layer and become constituents of the resin layer.

In the above method, it is essential to use the coating liquid for the resin layer to have a predetermined composition and to set it to 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 on the substrate is not particularly limited, and includes spin coat method, dipping method, spray method, die coat method, bar coat method, gravure coat method, roll coater method, and meniscus coater method. , general-purpose application methods such as flexographic printing, screen printing, and feed coater methods can be mentioned.

When curing the coating liquid for the resin layer, it is preferable to irradiate it with ionizing radiation such as ultraviolet rays 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. Additionally, as the wavelength of ultraviolet rays, a wavelength range of 190 nm to 380 nm is preferable. Specific examples of electron beam sources include various electron beam accelerators such as Cockcroft-Walton type, Vandergraaff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high-frequency type.

The lower limit of the average thickness of the resin layer is preferably 6.0 μm or more, more preferably 7.0 μm or more, more preferably 8.0 μm or more, and the upper limit is preferably 15.0 μm or less, and more preferably 14.0 μm or less. , 13.0㎛ or less is more preferable.

By setting the average thickness of the resin layer to 6.0 μm or more, pencil hardness can be easily improved. By setting the average thickness of the resin layer to 15.0 μm or less, it is possible to easily suppress a decrease in bending resistance.

Embodiments of suitable ranges of the average thickness of the resin layer include 6.0 μm to 15.0 μm, 6.0 μm to 14.0 μm, 6.0 μm to 13.0 μm, 7.0 μm to 15.0 μm, 7.0 μm to 14.0 μm, and 7.0 μm. Examples include 13.0 μm or less, 8.0 μm or more and 15.0 μm or less, 8.0 μm or more and 14.0 μm or less, and 8.0 μm or more and 13.0 μm or less.

The average thickness of the resin layer can be calculated, for example, by selecting 20 arbitrary points in a cross-sectional photograph of an anti-glare laminate captured with a scanning transmission electron microscope (STEM) and calculating the average value. It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

《First Particle》

The first particles are particles with an average particle diameter of 0.5 μm or more. When 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 anti-glare properties cannot be achieved.

As the first particle, polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine resin, and polyester. Organic particles formed from one or more types of resin such as system resin; Inorganic particles formed of one or more types of inorganic materials such as silica, alumina, zirconia, and titania; can be mentioned. Among these, organic particles are preferable because they are excellent in dispersion stability and have a relatively small specific gravity, so that the first particles can easily satisfy the condition of the position in the thickness direction.

The lower limit of the content of the first particles is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and even more preferably 1.5 parts by mass or more, with respect to 100 parts by mass of the resin component of the coating liquid for the resin layer. The upper limit is preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.

By setting the content of the first particles to 0.5 parts by mass or more, anti-glare properties can be easily improved. Additionally, 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 bending resistance.

Embodiments of suitable ranges for the content of the first particles relative to 100 parts by mass of the resin component are 0.5 parts by mass or more and 10.0 parts by mass or less, 0.5 parts by mass or more and 5.0 parts by mass or less, 0.5 parts by mass or more and 3.0 parts by mass or less, and 1.0 parts by mass. 10.0 parts by mass or less, 1.0 parts by mass or more but 5.0 parts by mass or less, 1.0 parts by mass or more but 3.0 parts by mass or less, 1.5 parts by mass or more but 10.0 parts by mass or less, 1.5 parts by mass or more but 5.0 parts by mass or less, 1.5 parts by mass or more 3.0 parts by mass The following can be mentioned.

The average particle diameter 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 condition of the position in the thickness direction, 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.

Embodiments of suitable ranges of the average particle diameter of the first particles include 0.8 μm to 3.0 μm, 0.8 μm to 2.7 μm, 0.8 μm to 2.5 μm, 1.0 μm to 3.0 μm, 1.0 μm to 2.7 μm, and 1.0 μm to 2.7 μm. Examples include ㎛ or more and 2.5 ㎛ or less.

The average particle diameter of the first particles can be calculated, for example, by the same method as in the first embodiment.

It is preferable that D1, which represents the average particle diameter of the first particles, and t, which represents the average thickness of the resin layer, have a relationship of 2.0<t/D1<6.0.

By setting t/D1 to less than 6.0, the first particles can easily provide an uneven shape to the surface of the anti-glare laminate, making it easy to improve anti-glare properties. By setting t/D1 to more than 2.0, it is possible to easily suppress a decrease in bending resistance due to the first particles protruding from the surface of the resin layer.

The lower limit of t/D1 is more preferably 2.5 or more, more preferably 3.5 or more, and the upper limit is more preferably 5.0 or less, and still more preferably 4.5 or less.

Embodiments of suitable ranges for t/D1 include: 2.0 and less than 6.0, 2.0 and 5.0 or less, 2.0 and 4.5 or less, 2.5 or more and less than 6.0, 2.5 or more and 5.0 or less, 2.5 or more and 4.5 or less, 3.5 or more and less than 6.0, and 3.5 or more and 5.0 or less. , 3.5 or more and 4.5 or less.

The lower limit of t-D1 is preferably 2.0 μm or more, more preferably 3.0 μm or more, and still more preferably 4.0 μm or more in order to easily suppress a decrease in bending resistance, and the upper limit is for good anti-glare properties. In order to make it easy to do, it is preferably 10 μm or less, more preferably 8.0 μm or less, and even more preferably 7.0 μm or less.

Embodiments of suitable ranges for t-D1 include: 2.0 μm to 10 μm, 2.0 μm to 8.0 μm, 2.0 μm to 7.0 μm, 3.0 μm to 10 μm, 3.0 μm to 8.0 μm, and 3.0 μm to 7.0 μm. Examples include ㎛ or less, 4.0 ㎛ or more and 10 ㎛ or less, 4.0 ㎛ or more and 8.0 ㎛ or less, and 4.0 ㎛ or more and 7.0 ㎛ or less.

《Inorganic particles》

The resin layer may contain inorganic fine particles. When the resin layer contains inorganic fine particles with a relatively large specific gravity, it becomes difficult for the first particles to sink below the resin layer, making it easy for the first particles to satisfy the condition of the position in the thickness direction. Additionally, the inorganic fine particles can increase the dispersibility of the first particles and make it easier to suppress a decrease in bending resistance.

The embodiment of the average particle diameter and type of the inorganic fine particles of the second embodiment can be the same as the embodiment of the average particle diameter and type of the inorganic fine particles of the first embodiment.

The lower limit of the content of inorganic fine particles is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 0.7 part by mass or more, with respect to 100 parts by mass of the resin component of the coating liquid for the resin layer, and the upper limit is It is preferable that it is 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 the inorganic fine particles to 0.1 parts by mass or more, the first particles can easily satisfy the condition of the position in the thickness direction. In addition, by setting the content of the inorganic fine particles to 5.0 parts by mass or less, the first particles can be prevented from floating excessively above the resin layer, making it easy to suppress a decrease in bending resistance.

Embodiments of suitable ranges for the content of inorganic fine particles relative to 100 parts by mass of the resin component are 0.1 part by mass or more and 5.0 parts by mass or less, 0.1 parts by mass or more and 3.0 parts by mass or less, 0.1 parts by mass or more and 2.0 parts by mass or less, and 0.5 parts by mass. Not less than 5.0 parts by mass or less, not less than 0.5 parts by mass but not more than 3.0 parts by mass, not less than 0.5 parts by mass but not more than 2.0 parts by mass, not less than 0.7 parts by mass but not more than 5.0 parts by mass, not less than 0.7 parts by mass but not more than 3.0 parts by mass, not less than 0.7 parts by mass but not more than 2.0 parts by mass can be mentioned.

《Resin ingredients》

The resin layer preferably contains a cured product of the 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 anti-glare laminate can be easily improved.

The ratio of the curable resin composition to the total amount of the resin component of the coating liquid for the resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass. Most desirable.

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 preferable, as it is easy to increase pencil hardness and is easy to dissolve the base material in the uncured state of the composition.

The embodiment of the thermosetting resin composition of the second embodiment can be the same as the embodiment of the thermosetting resin composition of the first embodiment.

An ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as an “ionizing radiation curable compound”). Examples of the ionizing radiation-curable functional group include ethylenically unsaturated bonding groups such as (meth)acryloyl group, vinyl group, and allyl group, and epoxy group and oxetanyl group. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bonding group is preferable.

Ionizing radiation means electromagnetic waves or charged particle beams that have energy quantum that can polymerize or cross-link molecules. Usually, ultraviolet rays or electron beams are used, but in addition, electromagnetic waves such as X-rays, γ-rays, and α-rays are used. , charged particle beams such as ion beams can also be used.

In this specification, (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. In addition, in this specification, (meth)acrylate refers to acrylate or methacrylate.

As the ionizing radiation curing compound, both a monofunctional ionizing radiation curing compound having one ionizing radiation curing functional group and a polyfunctional ionizing radiation curing compound having two or more ionizing radiation curing functional groups can be used. Additionally, as the ionizing radiation curable compound, both monomers and oligomers can be used.

In order to dissolve part of the base material, increase pencil hardness, and easily suppress curing shrinkage, it is preferable to use a mixture of the following (a) to (c) as an ionizing radiation curable compound. The following (a) to (c) are preferably compounds having an ethylenically unsaturated bond group as an ionizing radiation-curable functional group, and are more preferably (meth)acrylate-based compounds. (Meth)acrylate-based compounds can 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 monomer

(b) multifunctional ionizing radiation curable monomer

(c) multifunctional ionizing radiation curable oligomer

As an ionizing radiation curable compound, by containing the monofunctional ionizing radiation curable monomer of (a), a part of the substrate can be easily dissolved, and therefore it is possible to easily satisfy condition 1A or condition 2A. In addition, by including the monofunctional ionizing radiation curable monomer of (a), the components eluted from the substrate can be easily made compatible with the components of the coating liquid for the resin layer, making it easy to improve the physical properties of the resin layer. You can.

However, if the amount of the monofunctional ionizing radiation curable monomer (a) is too large, the substrate may be excessively dissolved, which may lower the strength of the substrate or reduce the pencil hardness of the anti-glare laminate.

By containing the polyfunctional ionizing radiation curable monomer of (b) as the ionizing radiation curable compound, the pencil hardness of the anti-glare 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 and the bending resistance of the anti-glare laminate may decrease.

By containing the polyfunctional ionizing radiation curable oligomer of (c) as the ionizing radiation curable compound, curing shrinkage can be easily suppressed while maintaining the pencil hardness of the anti-glare laminate. However, if the amount of the polyfunctional ionizing radiation curable oligomer (c) is too large, the pencil hardness of the anti-glare laminate may decrease.

The amount of the monofunctional ionizing radiation curable monomer (a) relative to the total amount of the ionizing radiation curable compound is preferably 10 mass% or more and 40 mass% or less, more preferably 13 mass% or more and 30 mass% or less, and 15 mass%. It is more preferable that it is % or more and 25 mass% or less.

The amount of the polyfunctional ionizing radiation curable monomer (b) relative to the total amount of the ionizing radiation curable compound is preferably 5 mass% or more and 20 mass% or less, more preferably 6 mass% or more and 15 mass% or less, and 7 mass%. It is more preferable that it is % or more and 13 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 mass% or more and 85 mass% or less, more preferably 60 mass% or more and 80 mass% or less, and 65 mass%. It is more preferable that it is 75 mass% or less.

The embodiment of the monofunctional ionizing radiation curable monomer of (a), the polyfunctional ionizing radiation curable monomer of (b), and the polyfunctional ionizing radiation curable oligomer of (c) of the second embodiment is the first embodiment. The monofunctional ionizing radiation curable monomer of (a), the polyfunctional ionizing radiation curable monomer of (b), and the polyfunctional ionizing radiation curable oligomer of (c) can be used in the same embodiment.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator, similar to the first embodiment.

As in the first embodiment, the coating liquid for the resin layer may contain additives as needed.

"menstruum"

It is preferable that the coating liquid for the resin layer contains a solvent.

As the solvent, it is preferable to select a solvent that can dissolve the base material. However, if the substrate is excessively dissolved, the strength of the substrate decreases, so it is desirable to select an appropriate solvent depending on the type of substrate. Among the three components of the Hansen solubility parameter, the solvent preferably contains a solvent in which δp, which is a polar component, is 7.0 (J/cm 3 ) ^0.5 or more and 10.0 (J/cm 3 ) ^0.5 or less. When δp is 7.0 (J/cm 3 ) ^0.5 or more, the base material can be easily dissolved, and when it is 10.0 (J/cm 3 ) ^0.5 or less, it can be prevented from dissolving too much. The values of δp [(J/cm3) ^0.5 ] for 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, the solvent is preferably selected taking into account not only the solubility of the substrate but also the evaporation rate inherent to the solvent. This is because when the evaporation rate of the solvent is slow, it is easy to excessively dissolve the substrate. The rate at which the solvent evaporates can also be controlled by drying conditions. For example, if the drying temperature is increased, the rate at which the solvent evaporates becomes faster. Additionally, if the drying wind speed is increased, the rate at which the solvent evaporates becomes faster.

From the above, it is desirable to select the solvent taking into account the solubility of the substrate, evaporation rate, and drying conditions.

The embodiment of the type of solvent in the second embodiment can be the same as the embodiment of the type of solvent in the first embodiment.

The acrylic resin substrate is easily soluble in solvents. For this reason, when using an acrylic resin substrate as a substrate, it is preferable that the main component is a solvent with a high evaporation rate inherent in the solvent. The main component means 50% by mass or more of the total amount of 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 with an evaporation rate of 100 or more when the evaporation rate of butyl acetate is 100. The evaporation rate of a solvent with a high evaporation rate is more preferably 120 or more and 450 or less, and even more preferably 140 or more and 400 or less.

Solvents with a fast evaporation rate include, for example, isopropyl alcohol (evaporation rate 150), methyl isobutyl ketone (evaporation rate 160), toluene (evaporation rate 200), and methyl ethyl ketone (evaporation rate 370).

Additionally, the solvent preferably contains a solvent with a small molecular weight and high polarity. The highly polar solvent is preferably one in which δp of the Hansen solubility parameter is in the above-mentioned range. By containing a solvent with a small molecular weight, high polarity, and the above-mentioned evaporation rate, it is possible to easily dissolve the acrylic resin substrate appropriately. Examples of such solvents include methyl ethyl ketone.

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 1A or condition 2A.

《Drying conditions》

When forming a resin layer from a coating liquid for a resin layer, it is desirable to control drying conditions.

In addition, in the anti-glare laminate of the present disclosure, it is preferable to dry the coating liquid for the resin layer in two steps. Specifically, it is preferable that the first stage of drying weakens the drying intensity, and that the second stage of drying increases the drying intensity. During drying with low intensity in the first stage, dissolution of the substrate progresses, and a mixture of the components eluted from the substrate and the components of the coating liquid for the resin layer is formed, and the convection time of the mixture is determined by Since it can be made longer, it is easy to satisfy the condition of the position of the first particle in the thickness direction. Additionally, by weakening the intensity of the first-stage drying, the components eluted from the substrate and the components of the coating liquid for the resin layer become easier to mix, making it easier to form the resin layer into a single layer. Additionally, by carrying out intensive drying in the second step, excessive dissolution of the substrate can be suppressed, making it easy to suppress the average inclination angle of the substrate and the arithmetic mean height of the substrate from becoming too large.

Drying conditions can be controlled by drying temperature and wind speed in the dryer. The preferable ranges of drying temperature and wind speed cannot be stated uniformly because they vary depending on the composition of the coating liquid for the resin layer, but the following conditions are preferable.

<First stage drying>

The drying temperature is preferably 65°C or higher and 85°C or lower, and the drying wind speed is preferably 0.5 m/s or higher and 2 m/s or lower. The drying time is preferably 20 seconds or more and 40 seconds or less.

<2nd stage drying>

The drying temperature is preferably 65°C or higher and 85°C or lower, and the drying wind speed is preferably 15 m/s or higher and 25 m/s or lower. The drying time is preferably 20 seconds or more and 40 seconds or less.

In order to dissolve a part of the substrate with the coating liquid for the resin layer and to facilitate sufficient mixing of the components eluted from the substrate and the coating liquid for the resin layer, irradiation of ionizing radiation is preferably performed after drying the coating liquid.

[Optical laminate]

The optical 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 first resin layer has a mutually independent region α1 and a region α2 surrounding the region α1, and the resin contained in the region α1 and the resin contained in the region α2 are different,

The second resin layer has a mutually independent region β1 and a region β2 surrounding the region β1, and the resin contained in the region β1 is different from the resin contained in the region β2,

It satisfies Condition 1B or Condition 2B below.

<Condition 1B>

θa1, which represents the average inclination angle of the surface of the substrate on the resin layer side, and θa2, which represents the average inclination angle of the surface of the first resin layer on the second resin layer side, have the relationship of θa2 < θa1.

<Condition 2B>

Pa1, which represents the arithmetic mean height of the surface of the substrate on the resin layer side, and Pa2, which represents the arithmetic average height of the surface of the first resin layer on the second resin layer side, are in the relationship of Pa2<Pa1.

FIG. 8 is a cross-sectional view showing one embodiment of an optical laminate 100C of the present disclosure.

The optical laminated body 100C of FIG. 8 has a resin layer 20C on the base material 10. Moreover, 20C of resin layers in FIG. 8 have 21C of 1st resin layers and 22C of 2nd resin layers from the base material 10 side.

In addition, the first resin layer 21C in FIG. 8 has a mutually independent region α1 and a region α2 surrounding the region α1. In addition, the second resin layer 22C in FIG. 8 has a mutually independent region β1 and a region β2 surrounding the region β1. In this specification, a structure having a mutually independent region n1 and a region n2 surrounding the region n1, such as the first resin layer and the second resin layer in FIG. 8, may be referred to as a "sea-island structure."

Additionally, Figure 8 is a schematic cross-sectional view. That is, the scale of each layer constituting the optical laminate 100C, the scale of each material, and the scale of the surface irregularities are modeled for ease of illustration and are different from the actual scale. Drawings other than Figure 8 are also different from the actual scale.

<Description>

As a substrate, one having good light transparency, smoothness, heat resistance, and mechanical strength is preferable. Examples of such substrates include polyester, triacetylcellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethyl pentene, polyvinyl chloride, and polyvinyl acetal. , resin substrates containing resins such as polyether ketone, acrylic resin, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP). The resin substrate may be a bonding of two or more resin substrates.

The resin substrate is preferably stretched to improve mechanical strength and dimensional stability.

Among resin substrates, acrylic resin substrates are preferable because they have low hygroscopicity, so they tend to have good dimensional stability, and because they have low optical anisotropy, they tend to improve visibility. In addition, the acrylic resin substrate satisfies Condition 1B and or Condition 2B by making the coating liquid for the resin layer a predetermined composition and further setting it under predetermined drying conditions, and further, the first resin layer and the second resin layer are It is easy to do with the chart structure.

Since the acrylic resin substrate is hard and fragile, it is difficult to achieve good adhesion when another layer is formed on the acrylic resin substrate. In particular, when a hard resin layer such as a resin layer containing a cured product of a curable resin composition is formed on an acrylic resin substrate, the adhesion between the substrate and the resin layer tends to become insufficient. The optical laminate of the present disclosure satisfies Condition 1B or Condition 2B even if a resin layer containing a cured product of a curable resin composition is formed on an acrylic resin substrate, and the resin layer has a sea-island structure, etc. A decrease in adhesion can be suppressed, and changes in image clarity can be easily suppressed.

In this specification, acrylic resin means acrylic resin and/or methacrylic resin.

Unless otherwise specified, the embodiment of the acrylic resin base of the optical laminate can be the same as the embodiment of the acrylic resin base of the first embodiment. For example, the embodiment of the glass transition point of the acrylic resin base of the optical laminate can be the same as the embodiment of the glass transition point of the acrylic resin base of the first embodiment.

Resins such as acrylic resin contained in the resin substrate preferably have a weight average molecular weight of 10,000 to 500,000, and more preferably 50,000 to 300,000. By setting the weight average molecular weight of the resin within the above range, it is possible to easily control Condition 1B, Condition 2B, and the above sea-island structure.

The average thickness of the base material is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 35 μm or more. By setting the average thickness of the base material to 10 μm or more, the handling of the optical laminate can be easily improved.

The average thickness of the base material is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less. By setting the average thickness of the base material to 100 μm or less, the bending resistance of the optical laminate can be easily improved.

Embodiments of suitable ranges of the average thickness of the base material include: 10 μm to 100 μm, 10 μm to 80 μm, 10 μm to 60 μm, 20 μm to 100 μm, 20 μm to 80 μm, and 20 μm or more. Examples include 60 μm or less, 35 μm or more and 100 μm or less, 35 μm or more and 80 μm or less, and 35 μm or more and 60 μm or less.

The above-mentioned average thickness of the substrate means the average thickness of the substrate upon completion of the optical laminate. As will be described later, when a part of the substrate is dissolved by the coating liquid for the resin layer, the average thickness of the substrate upon completion of the optical laminate may decrease compared to the average thickness of the initial substrate. For this reason, it is preferable that the average thickness of the initial substrate is thicker than the average thickness of the substrate upon completion of the optical laminate. The difference between the average thickness of the initial substrate and the average thickness of the substrate upon completion of the optical laminate cannot be stated uniformly because 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. Although there is none, it is preferable that it is 0.1 ㎛ or more and 10 ㎛ or less, and it is more preferable that it is 1 ㎛ or more and 5 ㎛ or less.

The average thickness of the base material can be calculated, for example, by selecting 20 arbitrary points in a cross-sectional photograph of the optical laminate taken with a scanning transmission electron microscope (STEM) and calculating the average value. It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

Average thickness of the base material, thickness of the first resin layer, thickness of the second resin layer, position of area α1 in the thickness direction of the first resin layer, position of the first particle in the thickness direction of the resin layer, θa1, In order to measure θa2, Pa1, Pa2, etc., it is necessary to produce a measurement sample in which the cross section of the optical laminate is exposed. The sample can be produced, for example, in the following processes (A1'') to (A2''). Additionally, in cases where the interface is difficult to see due to lack of contrast, the sample may be dyed with osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, etc. as a pretreatment.

(A1'') Process A1'' is the same as process A1 of the first embodiment.

(A2'') The block-shaped embedded sample is cut vertically to produce a sample for measurement in which the cross section of the optical laminate is exposed. As a sample for measurement, a thin section cut from a block-shaped embedded sample is used (sample conditions for measurement will be described later). The embedded sample is preferably cut so as to pass through the center of the cut sample. Embedded samples are preferably cut with a diamond knife.

As a device for cutting the embedded sample, for example, the brand name "Ultra Microtome EM UC7" manufactured by Leica Microsystems. When cutting the embedded sample, it is desirable to initially roughly cut it (rough trimming) and finally trim it precisely under the conditions of “SPEED: 1.00 mm/s” and “FEED: 70 nm.”

Among the sections cut from the block-shaped embedding sample as described above, the sections without defects such as holes and with a uniform thickness of 60 nm to 100 nm are the average thickness of the base material, the thickness of the first resin layer, and the second Thickness of the resin layer, position of area α1 in the thickness direction of the first resin layer, position of the first particle in the thickness direction of the resin layer, θa1, θa2, Pa1, Pa2, particle size of the first particle, inorganic fine particles It can be used as a sample for measuring the particle diameter.

<Resin layer>

The resin layer is required to have a first resin layer and a second resin layer from the base material side. By having a 1st resin layer and a 2nd resin layer as a resin layer, a fall in pencil hardness can be easily suppressed while improving adhesiveness.

When the resin layer is a single layer, it is difficult to improve the bending resistance or pencil hardness of the optical laminate. For example, in the case of a single layer of a resin layer with high hardness, it is difficult to improve the bending resistance of the optical laminate. Additionally, in the case of a single layer of a resin layer with low hardness, it is difficult to improve the pencil hardness of the optical laminate.

The first resin layer and the second resin layer can be formed, for example, by applying a coating liquid for a resin layer containing a resin component and a solvent onto a base material, drying it, and curing it as necessary. The coating liquid for the resin layer may further contain first particles, inorganic fine particles, and additives as needed.

In the case of the above method, for example, the coating liquid for the resin layer dissolves a part of the substrate, the resin component eluted from the substrate is used as the main component, and the first water is formed by a region containing a small amount of the resin component of the coating liquid for the resin layer. The content of the resin component eluted from the substrate when forming the stratum is small, and the second resin layer can be formed by the region containing the resin component of the coating liquid for the resin layer as the main component. 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 addition, the second resin layer formed by the above method can easily improve pencil hardness because the content of the resin component eluted from the base material is small.

In the above method, it is essential to use the coating liquid for the resin layer to have a predetermined composition and to set it to 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 on the substrate is not particularly limited, and includes spin coat method, dipping method, spray method, die coat method, bar coat method, gravure coat method, roll coater method, and meniscus coater method. , general-purpose application methods such as flexographic printing, screen printing, and feed coater methods can be mentioned.

When curing the coating liquid for the resin layer, it is preferable to irradiate it with ionizing radiation such as ultraviolet rays 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. Additionally, as the wavelength of ultraviolet rays, a wavelength range of 190 nm to 380 nm is preferable. Specific examples of electron beam sources include various electron beam accelerators such as Cockcroft-Walton type, Vandergraaff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high-frequency type.

The first resin layer has a mutually independent region α1 and a region α2 surrounding the region α1, and the resin contained in the region α1 and the resin contained in the region α2 are required to be different. In addition, the second resin layer is required to have a mutually independent region β1 and a region β2 surrounding the region β1, and that the resin contained in the region β1 and the resin contained in the region β2 are different.

When the first resin layer has the region α1 and the region α2, and the second resin layer has the region β1 and the region β2, the adhesion after the light resistance test can be easily improved.

The fact that the resin contained in region α1 and the resin contained in region α2 are different means that at least one of the composition and molecular weight of the resins is different. It is preferable that the resin contained in area α1 and the resin contained in area α2 have different resin compositions. Examples of different resin compositions include a case where region α1 and region α2 contain different types of resin, and a case where area α1 and area α2 contain the same type of resin but the mixing ratio of the resins is different.

The fact that the resin contained in region β1 and the resin contained in region β2 are different means that at least one of the composition and molecular weight of the resins is different. It is preferable that the resin contained in region β1 and the resin contained in region β2 have different resin compositions. Examples of different resin compositions include a case where region β1 and region β2 contain different types of resin, and a case where area β1 and area β2 contain the same type of resin but the mixing ratio of the resins is different.

In this specification, the resins of region α1, region α2, region β1, and region β2 mean so-called binder resins. For this reason, particles such as the first particles described later do not refer to the resins of area α1, area α2, area β1, and area β2.

If the ratio of area α1 is large, hardness tends to become insufficient, and if the ratio of area α2 is large, adhesion tends to deteriorate. For this reason, the area ratio between area α1 and area α2 is preferably 1:99 to 10:90, and more preferably 2:98 to 5:95.

If the ratio of area β1 is large, hardness tends to become insufficient, and if the ratio of area β2 is large, adhesion tends to deteriorate. For this reason, the area ratio between region β1 and region β2 is preferably 5:95 to 50:50, and more preferably 10:90 to 40:60.

The area ratio can be calculated from a cross-sectional photograph of the optical laminate captured with a scanning transmission electron microscope (STEM). In order to increase the reliability of the numerical value, a plurality of cross-sectional photographs are acquired, and the total number of areas α1 or area β1 is set to 50 or more before calculating the area ratio.

In the first resin layer and the second resin layer, it is preferable that the resin contained in area α1 and the resin contained in area β2 are substantially the same, and the resin contained in area α2 and the resin contained in area β1 are preferably substantially the same. The same is preferred. By providing the above structure, it is possible to easily improve the adhesion after the light resistance test. The reason why the adhesion after the light resistance test can be easily improved by the above configuration is that the affinity between the first resin layer and the second resin layer increases, so that even in a harsh environment such as a light resistance test, the first resin layer and the second resin layer can be easily improved. 2 It is thought that this is because the adhesiveness of the interface between the resin layers becomes less likely to decrease.

In order to make it easy to configure the first resin layer to have the region α1 and the region α2, and to make it easy to configure the second resin layer to have the region β1 and the region β2, the coating liquid for the resin layer includes It is desirable to lower the compatibility between components or to lower the compatibility between components contained in the coating liquid for the resin layer and components eluted from the substrate.

By lowering the compatibility as described above, it is thought that it is possible to make it easier to form the first resin layer and the second resin layer in the optical laminate of the present disclosure according to the ideas (1) to (4) below.

(1) When the coating liquid for the resin layer is applied on the substrate, part of the substrate dissolves.

(2) With the resin component eluted from the base material as the main component, a region containing a small amount of the resin component of the coating liquid for the resin layer becomes the first resin layer, the content of the resin component eluted from the base material is small, and the area for the resin layer is The area containing the resin component of the coating liquid as the main component becomes the second resin layer.

(3) Because the compatibility is low, in the case of (2) above, the resin component of the coating liquid for the resin layer contained in a small amount in the first resin layer forms region α1, and the resin component eluted from the substrate forms region α2. do.

(4) Because the compatibility is low, in the case of (2) above, the resin component eluted from the substrate contained in a small amount in the second resin layer forms region β1, and the resin component of the coating liquid for the resin layer forms region β2. do.

When the base material side at the center of the thickness direction of the first resin layer is defined as the first region, and the second resin layer side at the center of the thickness direction of the first resin layer is defined as the second region, more than 70% of the area α1 is defined as the second region. It is desirable to exist in area 2. By having the above structure, it is possible to easily improve the adhesion after the light resistance test.

The proportion of area α1 present in the second area is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more, based on the number.

In this specification, the position where region α1 exists in the thickness direction of the first resin layer is determined by the methods (1) to (5) below.

(1) A cross-sectional photograph of the optical laminate is taken using a scanning transmission electron microscope (STEM). It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

(2) Based on the cross-sectional photograph, calculate the average X1 of the elevation of the ridges of the surface on the substrate side of the first resin layer and the average X2 of the elevation of the ridges of the surface on the second resin layer side of the first resin layer (Figure (see signs X1 and X2 in 9).

(3) The middle of the elevations of X1 and X2 is defined as the center M in the thickness direction of the first resin layer (see symbol M in FIG. 9).

(4) Based on the cross-sectional photograph, region α1 exists in the first region on the substrate side from the center of the thickness direction of the first resin layer, and the region α1 exists on the second resin layer side from the center of the thickness direction of the first resin layer. Count the number of areas α1 existing in area 2. The number of regions α1 existing on both sides of the first region and the second region across the center of the thickness direction of the first resin layer is assigned to the first region and the second region according to the area ratio of the region α1. For example, for area α1, where the area ratio existing in the first area is 40% and the area ratio existing in the second area is 60%, 0.4 areas are allocated to the first area and 0.6 areas are allocated to the second area. do.

(5) In order to increase the reliability of the numerical value, a plurality of cross-sectional photographs are acquired, the total number of regions α1 is set to 50 or more, and then the ratio based on the number of regions α1 existing in the first region and the second region is calculated. .

The lower limit of 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 4.0 μm or more, more preferably 5.0 μm or more, and still more preferably 6.0 μm or more, The upper limit is preferably 15.0 μm or less, more preferably 12.0 μm or less, and even more preferably 10.0 μm or less.

Embodiments of suitable ranges for the thickness of the entire resin layer include 4.0 μm to 15.0 μm, 4.0 μm to 12.0 μm, 4.0 μm to 10.0 μm, 5.0 μm to 15.0 μm, 5.0 μm to 12.0 μm, and 5.0 μm. Examples include 10.0 μm or less, 6.0 μm or more and 15.0 μm or less, 6.0 μm or more and 12.0 μm or less, and 6.0 μm or more and 10.0 μm or less.

The lower limit of the average thickness t1 of the first resin layer is preferably 3.0 μm or more, more preferably 4.0 μm or more, further preferably 4.5 μm or more, and the upper limit is preferably 10.0 μm or less and 8.0 μm or less. It is more preferable, and 7.0 μm or less is further preferable. By setting t1 to 3.0 μm or more, it is possible to easily improve adhesion and bending resistance, and by setting t1 to 10.0 μm or less, it is possible to easily suppress a decrease in pencil hardness.

Embodiments of suitable ranges for t1 include: 3.0 μm to 10.0 μm, 3.0 μm to 8.0 μm, 3.0 μm to 7.0 μm, 4.0 μm to 10.0 μm, 4.0 μm to 8.0 μm, 4.0 μm to 7.0 μm. , 4.5 μm or more and 10.0 μm or less, 4.5 μm or more and 8.0 μm or less, and 4.5 μm or more and 7.0 μm or less.

The lower limit of the average thickness t2 of the second resin layer is preferably 0.3 μm or more, more preferably 0.5 μm or more, still more preferably 1.0 μm or more, and the upper limit is preferably 4.0 μm or less and 3.0 μm or less. It is more preferable, and 2.7 μm or less is further preferable. By setting t2 to 0.3 μm or more, pencil hardness can be easily improved, and by setting t2 to 4.0 μm or less, it can be easily suppressed from a decrease in bending resistance.

Embodiments of suitable ranges for t2 include: 0.3 μm to 4.0 μm, 0.3 μm to 3.0 μm, 0.3 μm to 2.7 μm, 0.5 μm to 4.0 μm, 0.5 μm to 3.0 μm, 0.5 μm to 2.7 μm. , 1.0 μm or more and 4.0 μm or less, 1.0 μm or more and 3.0 μm or less, and 1.0 μm or more and 2.7 μm or less.

In order to easily suppress a decrease in adhesion and bending resistance, t1/t2 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Moreover, in order to make it easy to improve pencil hardness, t1/t2 is preferably 10.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less.

Embodiments of suitable ranges for t1/t2 are 1.5 to 10.0 or less, 1.5 to 5.0 or less, 1.5 to 3.0 or less, 1.8 to 10.0 or less, 1.8 to 5.0 or less, 1.8 to 3.0 or less, 2.0 to 10.0, 2.0 to 5.0 or less. , 2.0 or more and 3.0 or less.

The average thickness of the first resin layer and the average thickness of the second resin layer are selected from, for example, 20 arbitrary points in a cross-sectional photograph of an optical laminated body imaged with a scanning transmission electron microscope (STEM), It can be calculated by the average value. It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

《Resin ingredients》

The resin layer preferably contains a cured product of the 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 optical laminated body can be easily improved.

The ratio of the curable resin composition to the total amount of the resin component of the coating liquid for the resin layer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass. Most desirable.

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 preferable, as it is easy to increase pencil hardness and is easy to dissolve the base material in the uncured state of the composition.

The embodiment of the thermosetting resin composition of the optical laminate can be the same as the embodiment of the thermosetting resin composition of the anti-glare laminate of the first embodiment.

An ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as an “ionizing radiation curable compound”). Examples of the ionizing radiation-curable functional group include ethylenically unsaturated bonding groups such as (meth)acryloyl group, vinyl group, and allyl group, and epoxy group and oxetanyl group. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bonding group is preferable.

Ionizing radiation means electromagnetic waves or charged particle beams that have energy quantum that can polymerize or cross-link molecules. Usually, ultraviolet rays or electron beams are used, but in addition, electromagnetic waves such as X-rays, γ-rays, and α-rays are used. , charged particle beams such as ion beams can also be used.

In this specification, (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. In addition, in this specification, (meth)acrylate refers to acrylate or methacrylate.

As the ionizing radiation curing compound, both a monofunctional ionizing radiation curing compound having one ionizing radiation curing functional group and a polyfunctional ionizing radiation curing compound having two or more ionizing radiation curing functional groups can be used. Additionally, as the ionizing radiation curable compound, both monomers and oligomers can be used. In addition, since the monofunctional ionizing radiation curable monomer tends to have good compatibility with other resin components, it tends to be difficult to form a sea-island structure in the first resin layer and the second resin layer. When using monofunctional ionizing radiation curable monomers, attention must be paid to the above-mentioned properties.

In order to dissolve part of the substrate, form a sea-island structure in the first resin layer and the second resin layer, increase pencil hardness, and easily suppress cure shrinkage, as an ionizing radiation curable compound, It is preferable to use a mixture of (a) to (c) below. The following (a) to (c) are preferably compounds having an ethylenically unsaturated bond group as an ionizing radiation-curable functional group, and are more preferably (meth)acrylate-based compounds. (Meth)acrylate-based compounds can 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) Bifunctional ionizing radiation curable monomer

(b) Trifunctional or higher ionizing radiation curable monomer

(c) multifunctional ionizing radiation curable oligomer

By containing the bifunctional ionizing radiation curable monomer of (a) as an ionizing radiation curable compound, a part of the substrate can be easily dissolved, and therefore θa1 or Pa1 can be easily increased. However, if the amount of the bifunctional ionizing radiation curable monomer (a) is too large, the strength of the substrate may decrease or the pencil hardness of the optical laminate may decrease due to excessive dissolution of the substrate.

As the ionizing radiation curable compound, the pencil hardness of the optical layered product can be easily improved by containing the trifunctional or higher ionizing radiation curable monomer of (b). However, if the amount of the trifunctional or higher ionizing radiation curable monomer (b) is too large, the hardness of the resin layer may become too high and the bending resistance of the optical laminate may decrease.

By containing the polyfunctional ionizing radiation curable oligomer of (c) as the ionizing radiation curable compound, cure shrinkage can be easily suppressed while maintaining the pencil hardness of the optical laminate. However, if the amount of the polyfunctional ionizing radiation curable oligomer (c) is too large, the pencil hardness of the optical laminated body may decrease.

The amount of the bifunctional ionizing radiation curable monomer (a) relative to the total amount of the ionizing radiation curable compound is preferably 10 mass% or more and 40 mass% or less, more preferably 13 mass% or more and 30 mass% or less, and 15 mass%. It is more preferable that it is % or more and 25 mass% or less.

The amount of the trifunctional or higher ionizing radiation curable monomer of (b) relative to the total amount of the ionizing radiation curable compound is preferably 25% by mass or more and 55% by mass or less, more preferably 30% by mass or more and 50% by mass or less, and 35% by mass. It is more preferable that it is % or more and 45 mass% or less.

The amount of (c) polyfunctional ionizing radiation curable oligomer relative to the total amount of ionizing radiation curable compounds is preferably 25 mass% or more and 55 mass% or less, more preferably 30 mass% or more and 50 mass% or less, and 35 mass%. It is more preferable that it is 45 mass% or less.

An embodiment of the monofunctional ionizing radiation curable monomer of (a), the polyfunctional ionizing radiation curable monomer of (b), and the polyfunctional ionizing radiation curable oligomer of (c) of the optical laminate is the first embodiment. An embodiment similar to the embodiment of the anti-glare laminate of the monofunctional ionizing radiation curable monomer of (a), the polyfunctional ionizing radiation curable monomer of (b), and the polyfunctional ionizing radiation curable oligomer of (c). can do.

When the ionizing radiation curable compound is an ultraviolet curable compound, similarly to the first embodiment, the ionizing radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.

《First Particle》

In order to easily improve anti-glare properties, the resin layer preferably contains first particles having an average particle diameter of 0.5 μm or more. In order to easily improve anti-glare properties, it is more preferable that the second resin layer contains the first particles.

In order to easily improve anti-glare properties, it is preferable that 70% or more of the first particles are present on the second resin layer side. The above ratio is preferably 80% or more, and more preferably 90% or more.

The position where the first particle exists in the thickness direction of the resin layer can be determined, for example, from a cross-sectional photograph of the optical laminated body imaged with a scanning transmission electron microscope (STEM). Additionally, the ratio of the above-mentioned number standards can be calculated from the cross-sectional photograph. In addition, in order to increase the reliability of the numerical value, it is desirable to obtain a plurality of cross-sectional photographs, set the total number of first particles to 50 or more, and then calculate the ratio based on the above-mentioned number standards.

In addition, across the first resin layer and the second resin layer, the number of the first particles existing in both the first resin layer and the second resin layer is assigned to each layer according to the area ratio of each layer. For example, for the first particles whose area ratio existing in the first resin layer is 40% and the area ratio existing in the second resin layer is 60%, 0.4 are allocated to the first resin layer, and the number of the first particles present in the second resin layer is 0.4. Allocate 0.6 to the stratum.

It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 1,000 times or more and 7,000 times or less.

As the first particle, polymethyl methacrylate, polyacrylic-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine resin, and polyester. Organic particles formed from one or more types of resin such as system resin; Inorganic particles formed of one or more types of inorganic materials such as silica, alumina, zirconia, and titania; can be mentioned. Among these, organic particles are preferable because they are excellent in dispersion stability and have a relatively small specific gravity, making it easy to position the first particles in the second resin layer.

The lower limit of the content of the first particles is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and still more preferably 1.3 parts by mass or more, with respect to 100 parts by mass of the resin component of the coating liquid for the resin layer. The upper limit is preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.

By setting the content of the first particles to 0.5 parts by mass or more, anti-glare properties can be easily improved. Additionally, 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 bending resistance.

Embodiments of suitable ranges for the content of the first particles relative to 100 parts by mass of the resin component are 0.5 parts by mass or more and 10.0 parts by mass or less, 0.5 parts by mass or more and 5.0 parts by mass or less, 0.5 parts by mass or more and 3.0 parts by mass or less, and 1.0 parts by mass. 10.0 parts by mass or less, 1.0 parts by mass or more but 5.0 parts by mass or less, 1.0 parts by mass or more but 3.0 parts by mass or less, 1.3 parts by mass or more and 10.0 parts by mass or less, 1.3 parts by mass or more but 5.0 parts by mass or less, 1.3 parts by mass or more 3.0 parts by mass The following can be mentioned.

It can be easily suppressed.

In order to easily improve anti-glare properties, the average particle diameter of the first particles is preferably 0.8 μm or more, and more preferably 1.0 μm or more.

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 in order to easily suppress a decrease in bending resistance.

Embodiments of suitable ranges of the average particle diameter of the first particles include 0.8 μm to 3.0 μm, 0.8 μm to 2.7 μm, 0.8 μm to 2.5 μm, 1.0 μm to 3.0 μm, 1.0 μm to 2.7 μm, and 1.0 μm to 2.7 μm. Examples include ㎛ or more and 2.5 ㎛ or less.

The average particle diameter of the first particles can be calculated, for example, by a method similar to that of the anti-glare laminate of the first embodiment.

As for D1, which represents the average particle diameter of the first particles, and t2, which represents the average thickness of the second resin layer, t2-D1 is preferably -0.5 μm or more, and is preferably 2.0 μm or less.

When t2-D1 is -0.5 µm or more, the first particles can easily provide an uneven shape to the surface of the optical laminate, making it easy to improve anti-glare properties. t2-D1 is more preferably 0 μm or more, and even more preferably 0.1 μm or more.

When t2-D1 is 2.0 μm or less, it is difficult for the first particles to protrude from the surface of the second resin layer, making it easy to improve scratch resistance. t2-D1 is more preferably 1.5 μm or less, and even more preferably 0.8 μm or less.

Embodiments of suitable ranges for t2-D1 include -0.5 μm to 2.0 μm, -0.5 μm to 1.5 μm, -0.5 μm to 0.8 μm, 0 μm to 2.0 μm, 0 μm to 1.5 μm, 0 Examples include ㎛ or more and 0.8 ㎛ or less, 0.1 ㎛ or more and 2.0 ㎛ or less, 0.1 ㎛ or more and 1.5 ㎛ or less, and 0.1 ㎛ or more and 0.8 ㎛ or less.

《Inorganic particles》

The resin layer may contain inorganic fine particles. When the resin layer contains inorganic fine particles with a relatively large specific gravity, it becomes difficult for the first particles to sink below the resin layer, making it easy to position the first particles in the second resin layer. Additionally, the inorganic fine particles can increase the dispersibility of the first particles and make it easier to suppress a decrease in bending resistance.

The embodiment of the average particle diameter and type of the inorganic fine particles of the optical laminate can be the same as the embodiment of the average particle diameter and type of the inorganic fine particles of the anti-glare laminate of the first embodiment.

The lower limit of the content of inorganic fine particles is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 0.7 part by mass or more, with respect to 100 parts by mass of the resin component of the coating liquid for the resin layer, and the upper limit is It is preferable that it is 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 the inorganic fine particles to 0.1 mass part or more, it is possible to easily position the first particles in the second resin layer. In addition, by setting the content of the inorganic fine particles to 5.0 parts by mass or less, the first particles can be prevented from floating excessively above the resin layer, making it easy to suppress a decrease in bending resistance.

Embodiments of suitable ranges for the content of inorganic fine particles relative to 100 parts by mass of the resin component are 0.1 part by mass or more and 5.0 parts by mass or less, 0.1 parts by mass or more and 3.0 parts by mass or less, 0.1 parts by mass or more and 2.0 parts by mass or less, and 0.5 parts by mass. Not less than 5.0 parts by mass or less, not less than 0.5 parts by mass but not more than 3.0 parts by mass, not less than 0.5 parts by mass but not more than 2.0 parts by mass, not less than 0.7 parts by mass but not more than 5.0 parts by mass, not less than 0.7 parts by mass but not more than 3.0 parts by mass, not less than 0.7 parts by mass but not more than 2.0 parts by mass can be mentioned.

As in the first embodiment, the coating liquid for the resin layer may contain additives as needed.

"menstruum"

It is preferable that the coating liquid for the resin layer contains a solvent.

As the solvent, it is preferable to select a solvent that can dissolve the base material. As a solvent, the more easily a solvent that dissolves the substrate is used, the easier it is for the values of θa1 and Pa1 to become larger. However, if the substrate is excessively dissolved, the strength of the substrate decreases, so it is desirable to select an appropriate solvent depending on the type of substrate.

In addition, the solvent is preferably selected taking into account not only the solubility of the substrate but also the evaporation rate inherent to the solvent. The rate at which the solvent evaporates can also be controlled by drying conditions. For example, if the drying temperature is increased, the rate at which the solvent evaporates becomes faster. Additionally, if the drying wind speed is increased, the rate at which the solvent evaporates becomes faster.

If drying of the solvent is slow, dissolution of the substrate progresses and θa1 and Pa1 tend to increase. Additionally, if drying of the solvent is slow and the temperature during drying is high, the movement of the resin component between the first and second resin layers increases, and θa2 and Pa2 tend to increase.

From the above, it is desirable to select the solvent taking into account the solubility of the substrate, evaporation rate, and drying conditions.

The embodiment of the type of solvent for the optical laminate can be the same as the embodiment of the type of solvent for the anti-glare laminate of the first embodiment.

The acrylic resin substrate is easily soluble in solvents. For this reason, when using an acrylic resin substrate as the substrate, it is preferable that the solvent contains a solvent with an inherent high evaporation rate.

In this specification, a solvent with a fast evaporation rate means a solvent with an evaporation rate of 100 or more when the evaporation rate of butyl acetate is 100. Additionally, in this specification, a solvent with a slow evaporation rate means a solvent with an evaporation rate of less than 100 when the evaporation rate of butyl acetate is set to 100.

The evaporation rate of a solvent with a high evaporation rate is more preferably 120 or more and 450 or less, and even more preferably 140 or more and 400 or less.

Solvents with a fast evaporation rate include, for example, isopropyl alcohol (evaporation rate 150), methyl isobutyl ketone (evaporation rate 160), toluene (evaporation rate 200), and methyl ethyl ketone (evaporation rate 370).

The solvent with a high evaporation rate is preferably 75% by mass or more and 85% by mass or less of the total amount of the solvent.

In addition, in order to easily form a sea-island structure in the first resin layer and the second resin layer, it is preferable that the solvent contains a solvent that has a slow evaporation rate inherent in the solvent, has high polarity, and has a large molecular weight. A solvent having the above-mentioned properties increases the viscosity of the coating liquid, making it easier for the coating liquid to become gel-like. For this reason, a solvent having the above-mentioned characteristics can easily reduce the compatibility of the coating liquid, and thus can easily form a sea-island structure. Examples of solvents having the above-mentioned properties include cyclohexanone and diacetone alcohol.

The solvent that has a slow evaporation rate, is highly polar, and has a large molecular weight is preferably 15% by mass or more and 25% by mass or less of the total amount of the solvent.

《Drying conditions》

When forming a resin layer from a coating liquid for a resin layer, it is desirable to control drying conditions.

In addition, in the optical laminate of the present disclosure, it is preferable to dry the coating liquid for the resin layer in two steps. Specifically, it is desirable to reduce the drying wind speed in the first stage of drying, and to increase the drying wind speed in the second stage of drying. During the first stage of drying, a first resin layer is formed by a region containing the resin component eluted from the substrate as the main component and a small amount of the resin component of the coating liquid for the resin layer, and the resin eluted from the substrate further. The second resin layer can be formed by a region containing a small amount of the component and containing the resin component of the coating liquid for the resin layer as a main component. Additionally, by increasing the drying temperature in the first stage, the resin component can be easily moved, making it easier to form a sea-island structure.

Also, by carrying out the second stage of drying, excessive dissolution of the base material can be suppressed, making it easy to suppress θa1 and Pa1 from becoming too large.

In addition, in the first-stage drying and the second-stage drying, it is desirable to control the drying time. The longer drying time for drying the coating liquid for the resin layer means that the time until the resin component of the coating liquid for the resin layer is irradiated with ionizing radiation becomes longer. In other words, the longer drying time for drying the coating liquid for the resin layer means that the resin component of the coating liquid for the resin layer is maintained in an uncured and fluid state for a long time. For this reason, when the drying time for drying the coating liquid for the resin layer becomes longer, the movement of the resin component becomes severe between the layers of the first resin layer and the second resin layer, and θa2 and Pa2 tend to increase, so that conditions 1B and It becomes difficult to satisfy condition 2B.

Drying conditions can be controlled by drying temperature and wind speed in the dryer. The preferable ranges of drying temperature and wind speed cannot be stated uniformly because they vary depending on the composition of the coating liquid for the resin layer, but the following conditions are preferable.

<First stage drying>

The drying temperature is preferably 75°C or higher and 95°C or lower, and the drying wind speed is preferably 1 m/s or higher and 10 m/s or lower. The drying time is preferably 20 seconds or more and 40 seconds or less.

<2nd stage drying>

The drying temperature is preferably 75°C or higher and 95°C or lower, and the drying wind speed is preferably 15 m/s or higher and 30 m/s or lower. The drying time is preferably 20 seconds or more and 40 seconds or less.

In order to dissolve a part of the substrate with the coating liquid for the resin layer and to facilitate sufficient mixing of the components eluted from the substrate and the coating liquid for the resin layer, irradiation of ionizing radiation is preferably performed after drying the coating liquid.

<Condition 1B, Condition 2B>

The optical laminate of the present disclosure is required to satisfy the following condition 1B or condition 2B. The optical laminate of the present disclosure may satisfy at least one of Condition 1B and Condition 2B, but it is preferable to satisfy both.

<Condition 1B>

θa1, which represents the average inclination angle of the surface of the substrate on the resin layer side, and θa2, which represents the average inclination angle of the surface of the first resin layer on the second resin layer side, have the relationship of θa2 < θa1.

<Condition 2B>

Pa1, which represents the arithmetic mean height of the surface of the substrate on the resin layer side, and Pa2, which represents the arithmetic average height of the surface of the first resin layer on the second resin layer side, are in the relationship of Pa2<Pa1.

-Condition 1B-

When the relationship θa2<θa1 is not satisfied, if θa1 is small, it is difficult to achieve good initial adhesion, or if θa2 is large, it is difficult to suppress the change in the clarity of the transmitted image after the light fastness test.

It is believed that the reason why the clarity of the transmitted image changes before and after the light fastness test is because the difference in refractive index at the interface between the first and second resin layers changes before and after the light fastness test. In the optical laminate of the present disclosure, not only the interface between the first resin layer and the second resin layer but also the interface between the base material and the first resin layer exists. Substrates (particularly acrylic resin substrates) are relatively unlikely to be denatured by light resistance tests. On the other hand, the resin component of the coating liquid for the resin layer is relatively easy to be denatured by the light resistance test. For this reason, the refractive index of the second resin layer with a low content of the resin component of the base material tends to change before and after the light resistance test. On the other hand, the refractive index of the base material and the first resin layer containing a large amount of the resin component of the base material becomes difficult to change before and after the light resistance test. For this reason, when θa2 is large and the relationship θa2 < θa1 is not satisfied, it is thought that it is difficult to suppress the change in the clarity of the transmitted image after the light fastness test.

-Condition 2B-

When the relationship of Pa2<Pa1 is not satisfied, if Pa1 is small, it is difficult to achieve good initial adhesion, or if Pa2 is large, it is difficult to suppress the change in the clarity of the transmitted image after the light fastness test.

When Pa2 is large and the relationship Pa2<Pa1 is not satisfied, the reason why it is difficult to suppress the change in transmitted image clarity after the light fastness test can be considered the same as that of condition 1B.

In order to easily improve initial adhesion, θa1 is preferably 5.0 degrees or more, more preferably 8.0 degrees or more, and even more preferably 10.0 degrees or more. In order to easily improve pencil hardness, θa1 is preferably 20.0 degrees or less, more preferably 18.0 degrees or less, and even more preferably 17.0 degrees or less.

Embodiments of suitable ranges for θa1 include: 5.0 degrees to 20.0 degrees, 5.0 degrees to 18.0 degrees, 5.0 degrees to 17.0 degrees, 8.0 degrees to 20.0 degrees, 8.0 degrees to 18.0 degrees, 8.0 degrees to 17.0 degrees. , 10.0 degrees or more and 20.0 degrees or less, 10.0 degrees or more and 18.0 degrees or less, and 10.0 degrees or more and 17.0 degrees or less.

θa2 is preferably 10.0 degrees or less, more preferably 8.0 degrees or less, more preferably 6.0 degrees or less, and even more preferably 4.0 degrees or less in order to easily suppress changes in transmitted image clarity after the light fastness test. do.

In order to easily improve adhesion, θa2 is preferably greater than 0 degrees, more preferably 1.0 degrees or more, and still more preferably 2.0 degrees or more.

Embodiments of suitable ranges for θa2 include: 0 degrees and 10.0 degrees or less, 0 degrees and 8.0 degrees or less, 0 degrees and 6.0 degrees or less, 0 degrees and 4.0 degrees or less, 1.0 degrees or more and 10.0 degrees or less, 1.0 degrees or more and 8.0 degrees or less. , 1.0 degrees or more and 6.0 degrees or less, 1.0 degrees or more and 4.0 degrees or less, 2.0 degrees or more and 10.0 degrees or less, 2.0 degrees or more and 8.0 degrees or less, 2.0 degrees or more and 6.0 degrees or less, and 2.0 degrees or more and 4.0 degrees or less.

In order to easily improve initial adhesion, Pa1 is preferably 0.05 μm or more, more preferably 0.07 μm or more, and still more preferably 0.10 μm or more. In order to easily improve pencil hardness, Pa1 is preferably 0.25 μm or less, more preferably 0.23 μm or less, and still more preferably 0.20 μm or less.

Embodiments of suitable ranges for Pa1 include: 0.05 μm to 0.25 μm, 0.05 μm to 0.23 μm, 0.05 μm to 0.20 μm, 0.07 μm to 0.25 μm, 0.07 μm to 0.23 μm, 0.07 μm to 0.20 μm. , 0.10 μm or more and 0.25 μm or less, 0.10 μm or more and 0.23 μm or less, and 0.10 μm or more and 0.20 μm or less.

Pa2 is preferably 0.15 μm or less, more preferably 0.13 μm or less, more preferably 0.10 μm or less, and even more preferably 0.06 μm or less in order to easily suppress changes in transmitted image clarity after the light resistance test. do.

In order to easily improve adhesion, Pa2 is preferably 0.02 μm or more, more preferably 0.04 μm or more, and still more preferably 0.05 μm or more.

Embodiments of suitable ranges for Pa2 include: 0.02 μm to 0.15 μm, 0.02 μm to 0.13 μm, 0.02 μm to 0.10 μm, 0.04 μm to 0.15 μm, 0.04 μm to 0.13 μm, 0.04 μm to 0.10 μm. , 0.05 μm or more and 0.15 μm or less, 0.05 μm or more and 0.13 μm or less, and 0.05 μm or more and 0.10 μm or less.

θa1 and θa2, and Pa1 and Pa2 can be measured, for example, as follows.

(1) A cross-sectional photograph of the optical laminate is taken with a scanning transmission electron microscope (STEM). It is desirable that the acceleration voltage of the STEM is 10 kV or more and 30 kV or less, and the magnification of the STEM is 5,000 times or more and 10,000 times or less.

(2) From the image of the cross-sectional photograph, the ridge line at the interface between the base material and the resin layer and the ridge line at the interface between the first resin layer and the second resin layer are acquired, and height data is acquired. Specifically, the steps are the same as (a) to (l) of the first embodiment. The interface between the substrate and the resin layer corresponds to the surface of the substrate on the resin layer side. The interface between the first resin layer and the second resin layer corresponds to the surface on the second resin layer side of the first resin layer.

(3) From the height data point string, the average inclination angle and arithmetic average height are calculated using the procedures (m) to (q) of the first embodiment.

In this specification, θa1 and θa2, and Pa1 and Pa2 mean the average value of the measured values of 20 samples.

In order to set θa1 and θa2 and Pa1 and Pa2 in the above range, as described above, a part of the base material must be dissolved in the resin layer coating liquid, the composition of the resin layer coating liquid must be appropriately prepared, and the resin layer It is important to keep the drying conditions of the coating liquid within an appropriate range.

[Polarizer]

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, the first transparent protective plate and the second transparent protective plate. At least one of the transparent protective plates is selected from the anti-glare laminate of the first embodiment of the present disclosure described above, the anti-glare laminate of the second embodiment of the present disclosure described above, and the optical laminate of the present disclosure described above. It is an anti-glare laminate or an optical laminate.

A polarizing plate is used to provide antireflection properties, for example, by combining a polarizing plate and a λ/4 retardation plate. In this case, a λ/4 retardation plate is disposed on the display element of the image display device, and a polarizing plate is disposed on the viewer side rather 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 the function of a liquid crystal shutter. In this case, the liquid crystal display device is arranged in the order of the lower polarizer, the liquid crystal display element, and the upper polarizer, and the absorption axis of the polarizer of the lower polarizer is arranged so that the absorption axis of the polarizer of the upper polarizer is orthogonal. In the above configuration, it is preferable to use the polarizing plate of the present disclosure as the upper polarizing plate.

<Transparent protective plate>

The polarizing plate of the present disclosure includes at least one of the first transparent protective plate and the second transparent protective plate, the anti-glare laminate of the first embodiment of the present disclosure described above, the anti-glare laminate of the second embodiment of the present disclosure described above, and any anti-glare laminate or optical laminate selected from the optical laminate of the present disclosure described above. In a preferred embodiment, among the first transparent protective plate and the second transparent protective plate, the transparent protective plate on the light emission side is the anti-glare laminate of the first embodiment of the present disclosure described above and the anti-glare laminate of the second embodiment of the present disclosure described above. This embodiment is an anti-glare laminate or an optical laminate selected from the anti-glare laminate and the optical laminate of the present disclosure described above. The anti-glare laminate and the optical laminate are preferably arranged so that the surface on the substrate side is on the polarizer side.

One of the first transparent protective plate and the second transparent protective plate is the anti-glare laminate of the first embodiment of the present disclosure described above, the anti-glare laminate of the second embodiment of the present disclosure described above, and the optics of the present disclosure described above. In the case of any anti-glare laminate or optical laminate selected from the laminate, the other transparent protective plate is not particularly limited, but an optically isotropic transparent protective plate is preferable.

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 triacetylcellulose (TAC) films tend to provide optical isotropy.

<Polarizer>

As a polarizer, for example, a sheet-shaped polarizer such as a polyvinyl alcohol film dyed with iodine or the like and stretched, a polyvinyl formal film, a polyvinyl acetal film, or an ethylene-vinyl acetate copolymer saponified film, and a plurality of metal wires arranged in parallel. Examples include a wire grid polarizer made of a polarizer, an applied polarizer coated with lyotropic liquid crystal or dichroic guest-host material, and a multilayer thin film polarizer. These polarizers may be reflective polarizers that have a function of reflecting polarized light components that do not transmit.

<Size, shape, etc.>

The embodiment of the size and shape of the polarizing plate of the present disclosure can be the same as the embodiment of the size and shape of the anti-glare laminate of the present disclosure or the optical laminate of the present disclosure described above.

[Image display device]

The image display device of the present disclosure includes, on a display element, the anti-glare laminate of the above-described first embodiment of the present disclosure, the anti-glare laminate of the second embodiment of the present disclosure described above, and the optical laminate of the above-described present disclosure. It has any anti-glare laminate or optical laminate selected from the group.

4, 7, and 10 are cross-sectional views showing an embodiment of the image display device 500 of the present disclosure. The image display device 500 in FIG. 4 has the anti-glare laminate 100A of the first embodiment of the present disclosure on the display element 200. The image display device 500 in FIG. 7 has an anti-glare laminate 100B of the second embodiment of the present disclosure on the display element 200. The image display device 500 in FIG. 10 has the optical laminate 100C of the present disclosure on the display element 200. In an image display device, the anti-glare laminate or optical laminate is preferably arranged so that the substrate side faces the display element side.

Examples of display elements include liquid crystal display elements; EL display elements (organic EL display elements, inorganic EL display elements); Plasma display element; Display device using QD (Quantum dot); LED display devices such as mini LED and micro LED display devices; etc. can be mentioned. These display elements may have a touch panel function inside the display element.

Examples of the liquid crystal display method of the liquid crystal display element include IPS method, VA method, multi-domain method, OCB method, STN method, and TSTN method. When the display element is a liquid crystal display element, a backlight is required. The backlight is disposed on the side opposite to the side on which the anti-glare laminate or optical laminate of the liquid crystal display element is disposed.

Additionally, the image display device of the present disclosure may be an image display device with a touch panel that has a touch panel between the display element and the anti-glare laminate. In this case, it is preferable to arrange the anti-glare laminate or optical laminate on the outermost surface of the image display device with a touch panel, and arrange the anti-glare laminate or optical laminate so that the base material side faces the display element side. do.

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 an area where an image can be displayed. For example, when the image display device has a housing surrounding the display element, the inner area of the housing becomes the effective image area.

The maximum diameter of the effective image area refers to the maximum length when any two points in the effective image area are connected. For example, if the effective image area is rectangular, the diagonal of the rectangle becomes the maximum diameter. Additionally, when the effective image area is circular, the diameter of the circle becomes the maximum diameter.

The anti-glare laminate of the first embodiment of the present disclosure and the anti-glare laminate of the second embodiment of the present disclosure are excellent in bending resistance. For this reason, the image display device having the anti-glare laminate of the first embodiment of the present disclosure or the anti-glare laminate of the second embodiment of the present disclosure on the display element is a foldable type image display device or a rollable type. It is preferable that it is a type of image display device.

Example

Next, the present disclosure will be described in more detail by way of examples, but the present disclosure is in no way limited by these examples. Additionally, “part” and “%” are based on mass unless otherwise specified.

<Examples of the anti-glare laminate of the first embodiment>

1. Measurement and evaluation

As follows, the anti-glare laminates of Examples and Comparative Examples were measured and evaluated. Additionally, the atmosphere during each measurement and evaluation was set at 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 and then measurement and evaluation were performed. The results are shown in Table 2. In the anti-glare laminate of Comparative Example 1-7, since the resin layer had a single-layer structure, in Table 2, the numerical value for the second resin layer was expressed as "-".

1-1. Average thickness of the first resin layer and the second resin layer

In accordance with the description in the main text of the specification, samples with exposed cross sections of the anti-glare laminates of Examples and Comparative Examples were produced. Twenty points are selected at random from the cross-sectional photograph of the sample taken with a scanning transmission electron microscope, and the average value is t1, which is the average thickness of the first resin layer, and t2, which is the average thickness of the second resin layer. was calculated.

1-2. Position of first particle

In accordance with the description in the main text of the specification, samples with exposed cross sections of the anti-glare laminates of Examples and Comparative Examples were produced. From a cross-sectional photograph of the sample taken with a scanning transmission electron microscope, the ratio based on the number of first particles present across the first and second resin layers was calculated. In calculating the ratio, multiple cross-sectional photographs were acquired until the total number of first particles exceeded 50. In addition, the ratio based on the number of first particles present only in the first resin layer and the ratio based on the number of first particles present only in the second resin layer were calculated.

1-3. Average inclination angle of the surface on the resin layer side of the substrate, arithmetic average height of the surface on the resin layer side of the substrate

In accordance with the description in the main text of the specification, samples with exposed cross sections of the anti-glare laminates of Examples and Comparative Examples were produced. From the cross-sectional photograph of the sample 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 according to the description in the main text of the specification. .

1-4. Indentation hardness

In accordance with the description in the main text of the specification, samples with exposed cross sections of the anti-glare laminates of Examples and Comparative Examples were produced. Next, using a measuring device (Bruker Co., Ltd., product number: TI950), in accordance with the description in the main text of the specification, the indentation hardness at the center of the thickness direction of the first resin layer of the sample and the second resin layer of the sample were measured. The indentation hardness in the middle of the thickness direction was measured. The average value of the measured values of 20 samples was taken as H1 and H2 for each example and comparative example.

1-5. Total light transmittance (Tt) and haze (Hz)

The anti-glare laminates of Examples and Comparative Examples were cut into 10 cm squares. The cutting location was selected from a random location after visually confirming that there were no abnormalities such as dust or scratches. Using a haze meter (HM-150, manufactured by Murakami Shikisai Kijutsu Kenkyujo Co., Ltd.), the total light transmittance of JIS K7361-1:1997 and the haze of JIS K7136:2000 of each sample were measured.

In addition, to ensure that the light source is stable, turn on the power switch of the device in advance, wait at least 15 minutes, perform calibration without setting anything in the inlet opening (the location where the measurement sample is installed), and then set the measurement sample in the inlet opening. It was measured. The light incident surface was on the substrate side.

1-6. bending resistance

For the anti-glare laminates of Examples and Comparative Examples, a bending resistance test was performed 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 where a crack first occurred in the anti-glare laminate is shown in Table 2. A diameter of 5 mm or less is the passing level. When winding the anti-glare laminate onto a mandrel, the substrate side was positioned on the mandrel side.

1-7. pencil hardness

Samples were produced by cutting the anti-glare laminates of Examples and Comparative Examples to a size of 50 mm x 100 mm. Based on JIS K5600-5-4:1999, the pencil hardness of the upper surface of the resin layer of the sample was measured under the conditions of a load of 500 g and a speed of 1.4 mm/sec.

For the measurement, a Toyo Seiki Seisakusho pencil hardness tester (product number: NP type pencil scratching coating hardness tester) was used. Using mending tape (3M, product number “810-3-18”), both ends of the cut sample were joined to the base of the pencil hardness tester. Five pencil hardness tests were performed, and the hardness when no external abnormalities such as flaws were observed three or more times was taken as the pencil hardness value of each sample. For example, five tests are performed using a 2H pencil, and if no visual abnormalities occur three times, the pencil hardness of the anti-glare laminate is 2H. Regarding external abnormalities, discoloration was not included, and flaws and dents were checked. Pencil hardness of 2H or higher is the passing level.

1-8. Bang Hyeon-seong

On the base material side of the anti-glare laminate of Examples and Comparative Examples, a black board (Curare, brand name "Como") was applied through a transparent adhesive layer (Panacline) with a thickness of 25 ㎛, brand name "Panacrine PD-S1", refractive index 1.49). A sample was produced by bonding glass DFA2CG 502K (black), total light transmittance 0%, thickness 2 mm, refractive index 1.49) (sample size: 10 cm long x 10 cm wide). The sample is placed in a bright room environment (illuminance on the first main surface of the sample is 500 lux or more and 1000 lux or less. Illumination: Hf32 type straight three-wave length day white fluorescent lamp) at a straight line distance from the center of the first main surface of the sample 50 cm above the eye. In view of this, 20 subjects evaluated whether or not anti-glare properties were obtained to the extent that the observer's own reflection was not a concern, based on the following criteria. The location of the lighting during evaluation is at a height of 2 m vertically above the horizontal bar. The subjects were healthy people in their 30s with a visual acuity of 0.7 or higher.

A: More than 14 people answered ‘good’

B: 7 to 13 people answered ‘good’

C: Less than 6 people answered ‘good’

2. Production of anti-glare laminate

[Example 1-1]

(Manufacture of base material)

A copolymer of methyl methacrylate and methyl acrylate was kneaded at 260°C using a twin-screw extruder to obtain a pellet-like composition (glass transition point: 134°C). The obtained pellet-like composition was melt-extruded using a T die (T die temperature: 260°C) and discharged onto a cooling roll at 130°C. Next, biaxial stretching was sequentially performed at a stretching temperature of 145°C in the longitudinal and transverse directions at a stretching ratio of 1.5. After that, it was cooled, and an acrylic resin base material with a thickness of 40 μm was obtained.

(Formation of resin layer)

On the acrylic resin substrate, the coating liquid for the resin layer of Example 1-1 in Table 1 was applied at a coating amount of 6.0 g/m2 by the Meyerbar coating method, and then applied with warm air at a wind speed of 15 m/s and a temperature of 100°C. It was dried for 60 seconds. Next, in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, the ionizing radiation curable resin composition of the resin layer coating liquid is cured by irradiating ultraviolet rays so that the accumulated light amount is 100 mJ/cm2, thereby forming a first resin layer and a second resin layer. , the anti-glare laminate of Example 1-1 was obtained. In this specification, the application amount means the application amount after drying.

[Examples 1-2 to 1-4], [Comparative Examples 1-1 to 1-2, 1-5 to 1-7]

Except that the composition of the coating liquid for the resin layer, the application amount of the coating liquid for the resin layer, and the drying conditions of the coating liquid for the resin layer were changed to the compositions shown in Table 1, the same procedure as Example 1-1 was performed. Example 1 Anti-glare laminates of -2 to 1-4 and Comparative Examples 1-1 to 1-2 and 1-5 to 1-7 were obtained. In addition, in the anti-glare laminate of Comparative Example 1-7, the resin layer had a single-layer structure of the first resin layer.

[Comparative Example 1-3]

On the acrylic resin substrate, the first layer resin layer coating liquid of Comparative Example 1-3 in Table 1 was applied at a coating amount of 6.0 g/m2 by the Meyerbar coating method, and then applied at a wind speed of 15 m/s and a temperature of 100. It was dried for 60 seconds with warm air at ℃. Next, in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, the ionizing radiation curable resin composition of the first-layer resin layer coating liquid was cured by irradiating ultraviolet rays so that the accumulated light amount was 50 mJ/cm 2 to form a first resin layer.

Next, the second resin layer coating liquid of Comparative Example 1-3 in Table 1 was applied on the first resin layer at a coating amount of 2.0 g/m2 by the Meyerbar coating method, and then applied at a wind speed of 15 m/s, It was dried for 60 seconds with warm air at a temperature of 70 degrees. Next, in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, the ionizing radiation curable resin composition of the second-layer resin layer coating liquid is cured by irradiating ultraviolet rays so that the accumulated light amount is 100 mJ/cm2, and a second resin layer is formed for comparison. The anti-glare laminate of Example 1-3 was obtained.

[Comparative Example 1-4]

The composition of the coating liquid for the 1st and 2nd layer resin layers, the application amount of the coating liquid for the 1st and 2nd layer resin layers, the drying conditions of the coating liquid for the 1st and 2nd layer resin layers, the compositions shown in Table 1, etc. Except for the change, the anti-glare laminate of Comparative Example 1-4 was obtained in the same manner as in Comparative Example 1-3.

In Table 1, the hexafunctional urethane acrylate oligomer represents Mitsubishi Chemical's urethane acrylate oligomer (Product name: Cico UV-7600B, weight average molecular weight: 1400), and the bifunctional acrylate monomer represents tetraethylene glycol diacrylate. The trifunctional acrylate monomer represents pentaerythritol triacrylate, the monofunctional acrylate monomer represents 4-hydroxybutylacrylate, and the photopolymerization initiator represents the product name "Omnirad 184" manufactured by IGM Resins B.V. .

From the results in Table 2, it can be confirmed that the anti-glare laminate of the examples of the first embodiment has good pencil hardness, bending resistance, and anti-glare properties.

<Examples of anti-glare laminate of the second embodiment>

3. Measurement and evaluation

As follows, the anti-glare laminates of Examples and Comparative Examples were measured and evaluated. Additionally, the atmosphere during each measurement and evaluation was set at 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 and then measurement and evaluation were performed. The results are shown in Table 4.

3-1. Average inclination angle of the surface on the resin layer side of the substrate, arithmetic average height of the surface on the resin layer side of the substrate

In accordance with the description in the main text of the specification, samples with exposed cross sections of the anti-glare laminates of Examples and Comparative Examples were produced. From the cross-sectional photograph of the sample 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 according to the description in the main text of the specification. .

3-2. Position of first particle

In accordance with the description in the main text of the specification, samples with exposed cross sections of the anti-glare laminates of Examples and Comparative Examples were produced. From a cross-sectional photograph of the sample taken with a scanning transmission electron microscope, the ratio based on the number of first particles present in the second region was calculated. In calculating the ratio, multiple cross-sectional photographs were acquired until the total number of first particles exceeded 50.

3-3. Average thickness of resin layer

In accordance with the description in the main text of the specification, samples with exposed cross sections of the anti-glare laminates of Examples and Comparative Examples were produced. Twenty points were selected at random from the cross-sectional photograph of the sample taken with a scanning transmission electron microscope, and t, which was the average thickness of the resin layer, was calculated from the average value.

3-4. Total light transmittance (Tt) and haze (Hz)

The total light transmittance and haze of the anti-glare laminates of Examples and Comparative Examples were measured by the same method as in 1-5 above.

3-5. bending resistance

A bending resistance test using the cylindrical mandrel method was conducted on the anti-glare laminates of Examples and Comparative Examples in the same manner as in 1-6 above.

3-6. pencil hardness

The pencil hardness of the upper surface of the resin layer of the anti-glare laminates of Examples and Comparative Examples was measured by the same method as in 1-7 above.

3-7. Bang Hyeon-seong

The anti-glare properties of the anti-glare laminates of Examples and Comparative Examples were evaluated by the same method as in 1-8 above.

4. Fabrication of anti-glare laminate

[Example 2-1]

(Manufacture of base material)

A copolymer of methyl methacrylate and methyl acrylate was kneaded at 260°C using a twin-screw extruder to obtain a pellet-like composition (glass transition point: 134°C). The obtained pellet-like composition was melt-extruded using a T die (T die temperature: 260°C) and discharged onto a cooling roll at 130°C. Next, biaxial stretching was sequentially performed at a stretching temperature of 145°C in the longitudinal and transverse directions at a stretching ratio of 1.5. After that, it was cooled, and an acrylic resin base material with a thickness of 40 μm was obtained.

(Formation of resin layer)

On the acrylic resin substrate, the coating liquid for the resin layer of Example 2-1 in Table 3 was applied at a coating amount of 6.0 g/m2 by the Meyerbar coating method, and then applied with warm air at a wind speed of 1 m/s and a temperature of 70°C. was dried for 30 seconds, and the first stage of drying was performed. Additionally, the coating liquid was dried for 30 seconds with warm air at a wind speed of 20 m/s and a temperature of 70°C, and the second stage of drying was performed. Next, in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, the ionizing radiation curable resin composition of the resin layer coating liquid is cured by irradiating ultraviolet rays so that the accumulated light amount is 100 mJ/cm2, and a resin layer is formed. Example 2-1 An anti-glare laminate was obtained. In this specification, the application amount means the application amount after drying.

[Examples 2-2 to 2-4], [Comparative Examples 2-1 to 2-4]

Except that the composition of the coating liquid for the resin layer, the application amount of the coating liquid for the resin layer, and the drying conditions of the coating liquid for the resin layer were changed to the compositions shown in Table 3, Example 2 was carried out in the same manner as in Example 2-1. Anti-glare laminates of -2 to 2-4 and Comparative Examples 2-1 to 2-4 were obtained.

In Table 3, the hexafunctional urethane acrylate oligomer represents Mitsubishi Chemical's urethane acrylate oligomer (brand name: Cico UV-7600B, weight average molecular weight: 1400), and the difunctional acrylate monomer represents tetraethylene glycol diacrylate. , the trifunctional acrylate monomer represents pentaerythritol triacrylate, the four-functional acrylate monomer represents pentaerythritol tetraacrylate, and the monofunctional acrylate monomer represents 4-hydroxybutyl acrylate. , the photopolymerization initiator represents the brand name “Omnirad 184” manufactured by IGM Resins B.V.

From the results in Table 4, it can be confirmed that the anti-glare laminate of the examples has good pencil hardness, bending resistance, and anti-glare properties.

On the other hand, in the anti-glare laminates of Comparative Examples 2-1 and 2-2, 70% or more of the first particles were not present in the second region. In the anti-glare laminate of Comparative Example 2-1, more than 70% of the number of first particles does not exist in the second region, but since the content of the first particles is large, the anti-glare property is at a passing level. However, since the anti-glare laminate of Comparative Example 2-1 has a large content of the first particles, the interface between the first particles and the resin layer, which causes a decrease in bending resistance, increases, thereby reducing the anti-glare laminate. The decline in flexibility could not be suppressed. In the anti-glare laminate of Comparative Example 2-2, 70% or more of the number of first particles was not present in the second region and the content of the first particles was not large, so the anti-glare property could not be improved. . In the anti-glare laminates of Comparative Examples 2-1 and 2-2, the reason that more than 70% of the number of first particles does not exist in the second region is because the intensity of initial drying is strong, which causes convection of the coating liquid. Since the solvent was volatilized before sufficient generation occurred, it was thought that it was difficult for the first particles to rise above the resin layer due to convection.

The optical laminate of Comparative Example 2-3 has a large average tilt angle of the substrate and a large arithmetic average height of the substrate. That is, in the optical laminated body of Comparative Example 2-3, the hardness of the resin layer decreased due to a large amount of the substrate component being eluted into the resin layer, and the pencil hardness could not be improved. Since the optical laminate of Comparative Example 2-3 had a large proportion of monofunctional monomers, it is believed that the average inclination angle of the substrate and the arithmetic mean height of the substrate increased as a result of excessive elution of the substrate.

In the optical laminate of Comparative Example 2-4, since the average inclination angle and the arithmetic mean height of the substrate were small, the adhesion between the substrate and the resin layer deteriorated, and the decrease in bending resistance could not be suppressed. Since the optical laminate of Comparative Example 2-4 does not contain a monofunctional monomer and does not contain highly polar methyl ethyl ketone, dissolution of the substrate does not proceed, and the average inclination angle of the substrate and the arithmetic mean of the substrate I think the height has become smaller. In addition, the optical laminated body of Comparative Example 2-2 also does not contain a monofunctional monomer and does not contain highly polar methyl ethyl ketone, but the optical laminated body of Comparative Example 2-2 contains a bifunctional monomer with a small number of functional groups. Because it contains a large amount, it is believed that the base material was dissolved.

<Examples of optical laminates>

5. Measurement and evaluation

The optical laminates of Examples and Comparative Examples were measured and evaluated as follows. Additionally, the atmosphere during each measurement and evaluation was set at 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 and then measurement and evaluation were performed. The results are shown in Table 6.

5-1. Presence or absence of region α1 and region β1, proportion of region α1 present in the second region

In accordance with the description in the main text of the specification, samples with exposed cross sections of the optical laminates of Examples and Comparative Examples were produced. From a cross-sectional photograph of the sample taken with a scanning transmission electron microscope, the presence or absence of region α1 and region β1 was confirmed. Additionally, the area ratio between region α1 and region α2 and the area ratio between region β1 and region β2 were calculated. The existence of an independent region α1 in the first resin layer 21, the resin contained in the region α1 and the resin contained in the region α2 are different, the existence of an independent region β1 in the second resin layer 22, a region The difference between the resin contained in β1 and the resin contained in area β2 can be determined by the difference in brightness of the photograph.

Additionally, the ratio based on the number of regions α existing in the second region was calculated. In calculating the ratio, multiple cross-sectional photographs were acquired until the total number of areas α exceeded 50.

5-2. θa1 and θa2, and Pa1 and Pa2

In accordance with the description in the main text of the specification, samples with exposed cross sections of the optical laminates of Examples and Comparative Examples were produced. From the cross-sectional photograph of the sample taken with a scanning transmission electron microscope, θa1 and θa2, and Pa1 and Pa2 were calculated according to the description in the main text of the specification.

5-3. Average thickness of the first resin layer and the second resin layer

In accordance with the description in the main text of the specification, samples with exposed cross sections of the optical laminates of Examples and Comparative Examples were produced. Twenty points were selected at random from the cross-sectional photograph of the sample taken with a scanning transmission electron microscope, and the average thickness t1 of the first resin layer and t2, which was the average thickness of the second resin layer, were calculated from the average value. .

5-4. Total light transmittance (Tt) and haze (Hz)

The optical laminates of Examples and Comparative Examples were cut into 10 cm squares. The cutting location was selected from a random location after visually confirming that there were no abnormalities such as dust or scratches. Using a haze meter (HM-150, manufactured by Murakami Shikisai Kijutsu Kenkyujo Co., Ltd.), the total light transmittance of JIS K7361-1:1997 and the haze of JIS K7136:2000 of each sample were measured.

In addition, to ensure that the light source is stable, turn on the power switch of the device in advance, wait at least 15 minutes, perform calibration without setting anything in the inlet opening (the location where the measurement sample is installed), and then set the measurement sample in the inlet opening. It was measured. The light incident surface was on the substrate side.

5-5. Adhesion

The adhesion of the optical laminates of Examples and Comparative Examples was evaluated by the following method.

Additionally, the adhesion of the optical laminates of Examples and Comparative Examples was evaluated after the following light resistance test was performed.

The sample for evaluation was cross-cut into a checkerboard pattern with a total of 100 cells, 10 vertical and 10 horizontal. The cut interval was 1 mm. At the time of cutting, the cutter blade was inserted from the second resin layer side, and crosscut was performed so that the cutter blade reached the upper part of the base material.

An adhesive tape (manufactured by Nichiban Corporation, product name “Cellophane Tape (registered trademark)”) was attached to the surface of the crosscut sample, and the crosscut method specified in JIS K 5600-5-6:1999 was applied. A peel test was performed. From the results of the peel test, adhesion was evaluated according to the following evaluation criteria.

<Evaluation criteria>

A: The crosscut portion where peeling can be observed in the grid pattern is less than 5%.

B: The crosscut portion where peeling can be confirmed in the grid pattern is 5% or more and less than 15%.

C: The crosscut portion where peeling can be observed in the grid pattern is 15% or more.

<Light fastness test>

Conducted in an ultraviolet carbon arc lamp light fastness and weather resistance tester compliant with JIS B7751 (product name “FAL-AU·B” manufactured by Suga Shikenki, light source: ultraviolet carbon arc lamp, irradiance: 500 W/m2, black panel temperature: 63°C) The optical laminates of Examples and Comparative Examples were installed with the resin layer side facing the light source, and a test was conducted for 200 hours.

5-6. Transmitted image clarity (Transmitted image clarity of JIS K7374:2007)

Transmitted image clarity of the optical laminates of Examples and Comparative Examples was measured. The light incident surface was on the substrate side. The measuring device used was a filiformity measuring device (brand name: ICM-1T) manufactured by Suga Shikenki Co., Ltd. Table 6 shows the total of the transmitted image sharpness of the widths of the four optical combs (unit: “%”). Four comb widths were used: 0.125 mm, 0.5 mm, 1.0 mm, and 2.0 mm.

Additionally, for the optical laminates of Examples and Comparative Examples after the light resistance test, the transmitted image clarity was measured in the same manner as above. Table 6 shows the total of the transmitted image sharpness of the widths of the four optical combs (unit: “%”).

Table 6 shows the difference in transmitted image clarity before and after the light fastness test (unit: “%”). The difference of 10.0% or less is the passing level, and among the passing levels, it is more preferable that the difference is 5.0% or less.

5-7. Bang Hyeon-seong

On the base material side of the optical laminate of the examples and comparative examples, a black plate (Curaless, product name "Comoglass") was applied through a transparent adhesive layer with a thickness of 25 μm (Panacline PD-S1, brand name, refractive index 1.49). A sample was produced by bonding "DFA2CG 502K (black) system", total light transmittance 0%, thickness 2 mm, refractive index 1.49) (sample size: 20 cm long x 30 cm wide). The sample is placed in a bright room environment (illuminance on the first main surface of the sample is 500 lux or more and 1000 lux or less. Illumination: Hf32 type straight three-wave length day white fluorescent lamp) at a straight line distance from the center of the first main surface of the sample 50 cm above the eye. In view of this, 20 subjects evaluated whether or not anti-glare properties were obtained to the extent that the observer's own reflection was not a concern, based on the following criteria. The location of the lighting during evaluation is at a height of 2 m vertically above the horizontal bar. The subjects were healthy people in their 30s with a visual acuity of 0.7 or higher.

A: More than 14 people answered ‘good’

B: 7 to 13 people answered ‘good’

C: Less than 6 people answered ‘good’

6. Fabrication of optical laminate

[Example 3-1]

(Manufacture of base material)

A copolymer of methyl methacrylate and methyl acrylate was kneaded at 260°C using a twin-screw extruder to obtain a pellet-like composition (glass transition point: 134°C). The obtained pellet-like composition was melt-extruded using a T die (T die temperature: 260°C) and discharged onto a cooling roll at 130°C. Next, biaxial stretching was sequentially performed at a stretching temperature of 145°C in the longitudinal and transverse directions at a stretching ratio of 1.5. After that, it was cooled, and an acrylic resin base material with a thickness of 40 μm was obtained.

(Formation of resin layer)

On the acrylic resin substrate, the coating liquid for the resin layer of Example 3-1 in Table 5 was applied at a coating amount of 6.0 g/m2 by the Meyerbar coating method, and then applied with warm air at a wind speed of 5 m/s and a temperature of 90°C. was dried for 30 seconds, and the first stage of drying was performed. Additionally, the coating liquid was dried for 30 seconds with warm air at a wind speed of 20 m/s and a temperature of 90°C, and the second stage of drying was performed. Next, in a nitrogen atmosphere with an oxygen concentration of 200 ppm or less, the ionizing radiation curable resin composition of the resin layer coating liquid is cured by irradiating ultraviolet rays so that the accumulated light amount is 100 mJ/cm2, thereby forming a first resin layer and a second resin layer. , the optical laminate of Example 3-1 was obtained. In this specification, the application amount means the application amount after drying.

[Examples 3-2 to 3-4], [Comparative Examples 3-1 to 3-3]

Example 3 was carried out in the same manner as in Example 3-1, except that the composition of the resin layer coating liquid, the application amount of the resin layer coating liquid, and the drying conditions of the resin layer coating liquid were changed to the compositions shown in Table 5. Optical laminates of -2 to 3-4 and Comparative Examples 3-1 to 3-3 were obtained.

In Table 5, the hexafunctional urethane acrylate oligomer represents Mitsubishi Chemical's urethane acrylate oligomer (brand name: Cico UV-7600B, weight average molecular weight: 1400), and the difunctional acrylate monomer represents tetraethylene glycol diacrylate. The trifunctional acrylate monomer represents pentaerythritol triacrylate, the monofunctional acrylate monomer represents 4-hydroxybutylacrylate, and the photopolymerization initiator represents the product name "Omnirad 184" manufactured by IGM Resins B.V. .

From the results in Table 6, it can be confirmed that the optical laminate of the example can suppress the decrease in adhesion and the change in transmitted image clarity after the light resistance test.

On the other hand, in the optical laminate of Comparative Example 3-1, the first resin layer does not have region α1. For this reason, the optical laminated body of Comparative Example 3-1 was unable to improve the affinity between the first resin layer and the second resin layer, and the adhesion after the light resistance test fell. In Comparative Example 3-1, since the coating liquid for the resin layer contained a monofunctional monomer and thus had good compatibility, it was thought that it was difficult to form a sea-island structure and region α1 was not formed.

In the optical laminate of Comparative Example 3-2, θa1 and Pa1 were large and did not satisfy both conditions 1B and 2B. For this reason, the optical laminated body of Comparative Example 3-2 had a sharp change in transmitted image clarity after the light resistance test. The reason why Comparative Example 3-2 does not satisfy Condition 1B and Condition 2B is that the drying time is long, the movement of the resin component becomes severe between the layers of the first resin layer and the second resin layer, and θa2 and Pa2 become large. I think it's because of this.

The optical laminate of Comparative Example 3-3 had small θa1 and Pa1 and did not satisfy both conditions 1B and 2B. For this reason, the optical laminated body of Comparative Example 3-3 was unable to achieve good adhesion after the light resistance test. In addition, the optical laminate of Comparative Example 3-3 had insufficient adhesion before the light resistance test. It is believed that the reason why Comparative Example 3-3 does not satisfy Conditions 1B and 2B is because the coating liquid for the resin layer does not contain a bifunctional monomer.

10: Description
20A: Resin layer
21A: first resin layer
22A: second resin layer
23A: first particle
20B: Resin layer
21B: Area 1
22B: Second area
23B: first particle
20C: Resin layer
21C: first resin layer
22C: second resin layer
100A: Anti-glare laminate
100B: Anti-glare laminate
100C: Optical Laminate
200: display element
500: Image display device

Claims (31)

It is an anti-glare laminate having a resin layer on a base material,
The resin layer has a first resin layer and a second resin layer from the substrate side,
The resin layer contains first particles with an average particle diameter of 0.5 μm or more,
More than 70% of the number of the first particles is present across the first resin layer and the second resin layer,
An anti-glare laminate that satisfies the following formula 1.
5.0<t1/t2<15.0 (Equation 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.] According to paragraph 1,
An anti-glare laminate in which D1, which represents the average particle diameter of the first particles, and t2, which represents the average thickness of the second resin layer, have the relationship of t2 < D1. According to paragraph 1,
An anti-glare laminate in which D1, which represents the average particle diameter of the first particles, and t1, which represents the average thickness of the first resin layer, are in the relationship of D1 < t1. According to paragraph 1,
An anti-glare laminate wherein the first particles are organic particles. According to paragraph 1,
An anti-glare laminate wherein the average inclination angle of the surface of the base material on the resin layer side is 5.0 degrees or more and 15.0 degrees or less. According to paragraph 1,
An anti-glare laminate wherein the arithmetic mean height of the surface of the base material on the resin layer side is 0.05 μm or more and 0.25 μm or less. According to paragraph 1,
An anti-glare laminate wherein H1, which represents the indentation hardness in the middle of the thickness direction of the first resin layer, and H2, which represents the indentation hardness in the middle of the thickness direction of the second resin layer, are in the relationship of H1 < H2. In clause 7,
Anti-glare laminate with 40MPa<H2-H1. In clause 7,
Anti-glare laminate with 40MPa<H2-H1≤100MPa. According to paragraph 1,
An anti-glare laminate wherein the resin layer contains a cured product of a curable resin composition. According to paragraph 1,
An anti-glare laminate wherein the substrate is an acrylic resin substrate. It is an anti-glare laminate having a resin layer on a base material,
The resin layer contains first particles with an average particle diameter of 0.5 μm or more,
When the side of the substrate in the center of the thickness direction of the resin layer is defined as the first area, and the side opposite to the substrate in the center of the thickness direction of the resin layer is defined as the second area, 70 of the number standard of the first particles % or more is present in the second region,
An anti-glare laminate that satisfies the following condition 1A or condition 2A.
<Condition 1A>
The average inclination angle of the surface of the base material on the resin layer side is 5.0 degrees or more and 20.0 degrees or less.
<Condition 2A>
The arithmetic average height of the surface of the base material on the resin layer side is 0.10 μm or more and 0.40 μm or less. According to clause 12,
An anti-glare laminate in which D1, which represents the average particle diameter of the first particles, and t, which represents the average thickness of the resin layer, are in the relationship of 2.0<t/D1<6.0. According to clause 12,
An anti-glare laminate wherein the first particles are organic particles. According to clause 12,
An anti-glare laminate wherein the resin layer contains a cured product of a curable resin composition. According to clause 12,
An anti-glare laminate wherein the substrate is an acrylic resin substrate. It is an optical 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 first resin layer has a mutually independent region α1 and a region α2 surrounding the region α1, and the resin contained in the region α1 and the resin contained in the region α2 are different,
The second resin layer has a mutually independent region β1 and a region β2 surrounding the region β1, and the resin contained in the region β1 is different from the resin contained in the region β2,
An optical laminate satisfying the following condition 1B or condition 2B.
<Condition 1B>
θa1, which represents the average inclination angle of the surface of the substrate on the resin layer side, and θa2, which represents the average inclination angle of the surface of the first resin layer on the second resin layer side, have the relationship of θa2 < θa1.
<Condition 2B>
Pa1, which represents the arithmetic mean height of the surface of the substrate on the resin layer side, and Pa2, which represents the arithmetic average height of the surface of the first resin layer on the second resin layer side, are in the relationship of Pa2<Pa1. According to clause 17,
An optical laminate wherein the θa1 is 5.0 degrees or more and 20.0 degrees or less. According to clause 17,
An optical laminate wherein the θa2 is 10.0 degrees or less. According to clause 17,
An optical laminate wherein the Pa1 is 0.05 μm or more and 0.25 μm or less. According to clause 17,
An optical laminate wherein the Pa2 is 0.15 μm or less. According to clause 17,
When the substrate side at the center of the thickness direction of the first resin layer is defined as the first area, and the second resin layer side at the center of the thickness direction of the first resin layer is defined as the second area, 70% of the area α1 % or more is present in the second region. According to clause 17,
An optical laminate in which the resin contained in the region α1 and the resin contained in the region β2 are substantially the same, and the resin contained in the region α2 and the resin contained in the region β1 are substantially the same. According to clause 17,
An optical laminate in which the resin layer contains first particles with an average particle diameter of 0.5 μm or more. According to clause 24,
An optical layered body in which the second resin layer contains the first particles. According to clause 24,
An optical laminate wherein the first particles are organic particles. According to clause 17,
An optical laminate, wherein the substrate is an acrylic resin substrate. According to clause 17,
An optical laminate in which the resin layer contains a cured product of a curable resin composition. 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, and at least one of the first transparent protective plate and the second transparent protective plate is , an anti-glare laminate according to claim 1, an anti-glare laminate according to claim 12, and an optical laminate according to claim 17. An image display device comprising, on a display element, one selected from the anti-glare laminate according to claim 1, the anti-glare laminate according to claim 12, and the optical laminate according to claim 17. According to clause 30,
The image display device is a foldable type image display device or a rollable type image display device, and has the anti-glare laminate according to claim 1 or the anti-glare laminate according to claim 12 on the display element. , image display device.