TW201518765A - Anti-glare film - Google Patents

Abstract

The present invention provides an anti-glare film, which has an excellent anti-glaring property at a wild observation angel even in low haze, and capable of suppressing the occurrence of whitening and glaring while provided in a picture display device. Provided is a anti-glare film comprising a transparent support body and a finely uneven surface formed thereon, which has a root-mean-square roughness within a specific rouge when being determined at a specific cut-off length, for example the root-mean-square roughness Rq(0.08) determined at a specific cut-off length of 0.08 mm being 0.01 [mu]m or more and 0.05 [mu]m or less. A ration of a luminous reflectance RSCI determined by injecting a regular reflection light and a luminous reflectance RSCE determined by expecting the regular reflection light RSCI/RSCE is, 0.1 or less.

Description

Anti-glare film

The present invention relates to a film excellent in anti-glare.

An image display device such as a liquid crystal display, a plasma display panel, a cathode ray tube (CRT) display, or an organic electroluminescence (EL) display is used to prevent deterioration of the visibility due to external light on the display surface thereof. An anti-glare film is disposed on the display surface.

As an anti-glare film, a transparent film having a surface uneven shape is mainly studied. Such an anti-glare film exhibits anti-glare property by scattering the external light by the surface uneven shape and reducing the reflection by (outer light-scattering light). However, when the external light scatters light, the display surface of the image display device may all become white, or the turbid color may be displayed, that is, so-called "discoloration" occurs. Further, the pixels of the image display device may interfere with the surface unevenness of the anti-glare film, and a luminance distribution may occur, which makes it difficult to recognize, and so-called "glare" occurs. In view of the above, it is desirable to ensure excellent anti-glare properties in the anti-glare film, and to prevent the occurrence of "whitening" and "glare".

As such an anti-glare film, for example, Patent Document 1 discloses an anti-glare film which is an anti-glare film which does not cause glare when it is disposed on a high-definition image display device, and also sufficiently prevents whitening from occurring. a fine surface uneven shape is formed on the material, and an average length PSm of an arbitrary cross-sectional curve of the surface uneven shape is 12 μm or less, and a ratio Pa/PSm of an arithmetic mean height Pa to an average length PSm of the cross-sectional curve is 0.005 or more and 0.012 or less. The ratio of the surface of the uneven shape having an inclination angle of 2° or less is 50% or less, and the ratio of the surface having the inclination angle of 6° or less is 90% or more.

Anti-glare film disclosed in Patent Document 1, due to any cross-section The average length PSm of the wire is extremely small, and the glare can be effectively suppressed by eliminating the surface unevenness shape having a period of around 50 μm which is prone to glare. However, in the anti-glare film disclosed in Patent Document 1, if the haze is to be further reduced (if a low haze is to be formed), the anti-glare property is observed when the display surface of the image display device in which the anti-glare film is disposed is observed from an oblique direction. Reduced situation. Therefore, in the anti-glare film disclosed in Patent Document 1, there is still room for improvement in the point of preventing the glare of the wide viewing angle.

Prior technical literature Patent literature

Patent Document 1; JP-A-2007-187952

An object of the present invention is to provide an anti-glare film which can sufficiently suppress the occurrence of whitening and glare when disposed in an image display device even when the low haze has good anti-glare properties at a wide viewing angle.

In order to solve the above problems, the inventors focused on reviewing As a result, the present invention has thus been completed. That is, the present invention is

(1) an anti-glare film comprising a transparent support and an anti-glare layer having a fine uneven surface formed thereon; characterized in that the total haze is 0.1% or more and 3% or less; and the surface haze is 0.1% or more 2 % or less; when measured by a cut length of 0.08 mm, the root mean square roughness Rq (0.08) is 0.01 μm or more and 0.05 μm or less; and when the cut length is 0.25 mm, the root mean square roughness Rq (0.25) is measured. When the measurement is performed at a cutting length of 0.8 mm, the root mean square roughness Rq (0.8) is 0.07 μm or more and 0.12 μm or less; and when the cutting length is 2.5 mm, the square root is measured. The root roughness Rq (2.5) is 0.08 μm or more and 0.15 μm or less; the ratio of the visual reflectance R _SCI measured by the specular reflection light entering method to the apparent reflectance R _SCE measured by the specular reflection light removal method R _SCE /R _SCI is 0.1 or less. Further, in the present invention, the anti-glare films of the following (2) to (4) are preferred.

(2) The anti-glare film according to the above (1), wherein the average length Sm (0.25) when measured at a cut length of 0.25 mm is 90 μm or more and 160 μm or less; and the average length Sm when measured at a cut length of 0.8 mm ( 0.8) is 100 μm or more and 300 μm or less; and the average length Sm (2.5) when measured by cutting the length of 2.5 mm is 200 μm or more and 400 μm or less.

(3) In the antiglare film according to (1) or (2) above, the width of the dark portion and the bright portion is used. The transmittance of the five kinds of optical combs of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, respectively, measured a sharpness and a Tc of 375% or more; the widths of the dark portion and the bright portion were 0.25 mm and 0.5 mm, respectively. Four kinds of optical combs of 1.0mm and 2.0mm, the reflection sharpness and Rc(45) measured by the incident angle of light of 45° are 180% or less; the widths of the dark portion and the bright portion are 0.25 mm, 0.5 mm, and 1.0, respectively. Four types of optical combs of mm and 2.0 mm have a reflection sharpness and Rc (60) of 240% or less as measured by an incident angle of light of 60°.

(4) The anti-glare film according to any one of (1) to (3), wherein the visual reflectance R _SCE measured by the specular reflection light removal method is 0.5% or less.

According to the present invention, it is possible to provide an antiglare film which has excellent antiglare properties even at a low viewing angle even at a low viewing angle, and can sufficiently suppress the occurrence of whitening and glare when disposed in an image display device.

12 ‧ ‧ integral ball

13‧‧‧Light source

14‧‧‧Density reflectance measurement samples for anti-glare film

15‧‧‧Light trap

40‧‧‧Mold base for mold

41‧‧‧ Surface of the substrate for the mold after the first plating step and the polishing step (plating)

46‧‧‧ First surface relief shape formed by the first etching process

47‧‧‧ Surface relief shape shape passivated by the second etching process

50‧‧‧Photosensitive resin film

60‧‧‧ mask

70‧‧‧The surface irregularities after chrome plating are shaped passivated surfaces

71‧‧‧Chromium plating

80‧‧‧Send the wheel

81‧‧‧Transparent support

83‧‧‧ coated area

86‧‧‧Active energy line irradiation device

87‧‧‧Roll-shaped mould

88, 89‧‧‧Clamping roller

90‧‧‧ film winding device

Fig. 1 is a schematic view of an optical system for measuring a visual reflectance R _SCI .

Figure 2 is a schematic diagram of an optical system for determining the visual reflectance R _SCE .

Fig. 3 (a) to (e) are views showing a preferred example of a method of manufacturing a mold (first half).

Fig. 4 (a) to (d) are schematic views showing a preferred example of the method of manufacturing the mold (the latter half).

Fig. 5 is a schematic view showing a preferred example of a manufacturing apparatus used in the method for producing an anti-glare film of the present invention.

Fig. 6 is a view showing a preferred method of producing the antiglare film of the present invention, and a preferred preliminary hardening step.

Fig. 7 is a schematic view showing a unit cell for glare evaluation.

Fig. 8 is a schematic view showing a glare evaluation device.

Fig. 9 is a view showing a part of the pattern A used in the first to third embodiments and the comparative example 1.

Fig. 10 is a view showing a part of a figure B used in Comparative Example 2.

Figure 11 is a graph showing the power spectrum Γ(f) of the graphs A and B obtained by discrete Fourier transform.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings, and the dimensions and the like of the drawings are of any size for ease of viewing.

The anti-glare film of the present invention is characterized in that the root mean square roughness Rq at the time of measurement of the specified cut length is in the above range, and the reflectance R _SCI and the specular reflected light measured by the regular reflection light entering method are respectively The ratio R _SCE /R _SCI of the visual reflectance R _SCE measured by the removal method is 0.1 or less.

First, the method for obtaining the root mean square roughness Rq, the visual reflectance R _SCI, and the visual reflectance R _SCE will be described with respect to the antiglare film of the present invention.

[root mean square roughness Rq]

The anti-glare film of the present invention has a root mean square roughness Rq (0.08) when the fine uneven surface of the anti-glare layer is measured by cutting lengths of 0.08 mm, 0.25 mm, 0.8 mm, and 2.5 mm. Rq (0.25), Rq (0.8), and Rq (2.5) are each 0.01 μm or more and 0.05 μm or less, 0.05 μm or more and 0.1 μm or less, 0.07 μm or more and 0.12 μm or less, and 0.08 μm or more and 0.15 μm or less. The Rq (0.08), Rq (0.25), Rq (0.8), and Rq (2.5) are set as follows, and can be measured by the method according to JIS B 0601.

Rq (0.08): cut length 0.08mm, evaluation length 0.4mm

Rq (0.25): cut length 0.25mm, evaluation length 1.25mm

Rq (0.8): cut length 0.8mm, evaluation length 4mm

Rq (2.5): cut length 2.5mm, evaluation length 12.5mm

The root mean square roughness measured by the specified cutting length is a cross-sectional curve obtained by the measurement method defined by the above JIS, and a long-wavelength component having a predetermined cutting length or more is used as a high-frequency filter. The obtained roughness curve was blocked and the surface roughness was determined. Therefore, the root mean square roughness measured when the cutting length is 0.8 mm refers to a roughness curve when the surface unevenness having a wavelength of 0.08 mm or more is removed from the cross-sectional curve, and the root mean square roughness is obtained. The surface unevenness shape having a wavelength of 1/2 of 0.04 mm or less of the cut length was mainly evaluated. Similarly, the root mean square roughness measured when the cutting length is 0.25 mm, 0.8 mm, or 2.5 mm means that the surface unevenness having a wavelength of 0.25 mm or more, 0.8 mm or more, or 2.5 mm or more is removed from the cross-sectional curve. The roughness curve at the shape, the root mean square roughness obtained, the main evaluation A surface uneven shape having a wavelength of 0.125 mm or less, 0.4 mm or less, or 1.25 mm or less of 1/2 of the cut length.

The large Rq (0.08) means that the anti-glare film of the present invention has The surface uneven shape of the antiglare layer is often a surface uneven shape having a wavelength of 0.04 mm or less. Similarly, when the Rq (0.25) is large, the anti-glare layer is often a surface uneven shape having a wavelength of 0.04 mm or more and 0.125 mm or less. The Rq (0.8) is large, and the number is mostly 0.125 mm or more and 0.4 mm or less. The surface unevenness of the wavelength is large, and Rq (2.5) is large, and is a surface uneven shape having a wavelength of 0.4 mm or more and 1.25 mm or less. When Rq (0.08) is less than 0.01 μm, the surface irregularities of a short period having a wavelength of 0.04 mm or less are extremely small, that is, an antiglare film having an antiglare layer formed only by a long period of surface unevenness, and the surface texture is changed. Crude. When Rq (0.08) is more than 0.05 μm, the image display device having such an anti-glare film is likely to be whitened because it has an anti-glare layer having a strong scattering due to a surface uneven shape having a short period of 0.04 mm or less. . The anti-glare film of the present invention has Rq (0.08) in the above range, and preferably 0.02 μm or more and 0.04 μm or less.

When Rq (0.25) is less than 0.05 μm, it becomes a wave An anti-glare film having an anti-glare layer having a surface unevenness of 0.04 mm or more and 0.125 mm or less, and an image display device including the anti-glare film, which has an anti-glare property when viewed from the front surface (about 0 to 10°) Become insufficient. When Rq (0.25) exceeds 0.1 μm, the surface unevenness of the wavelength of 0.04 mm or more and 0.125 mm or less increases. The surface unevenness shape of such a wavelength region is particularly strong in glare, and an image display device having such an anti-glare film is liable to cause glare. Light. The Rq (0.25) of the antiglare film of the present invention is in the above range, and is preferably 0.06 μm or more and 0.08 μm or less.

When Rq (0.8) is less than 0.07 μm, it becomes a wavelength An anti-glare layer having a surface unevenness of 0.125 mm or more and 0.4 mm or less, and an image display device having such an anti-glare film, the anti-glare property is insufficient when viewed from an oblique direction (about 10 to 30 degrees) . When Rq (0.8) exceeds 0.12 μm, the uneven shape having a wavelength of 0.125 mm or more and 0.4 mm or less becomes too large, and an image display device which is likely to be whitened is obtained. The anti-glare film of the present invention has Rq (0.8) in the above range, preferably 0.08 μm or more and 0.10 μm or less.

When Rq (2.5) is less than 0.08 μm, it becomes a wavelength An anti-glare layer having a small unevenness of 0.4 mm or more and 1.25 mm or less, and an image display device including such an anti-glare film has insufficient anti-glare property when viewed from an oblique direction (30° or more). When Rq (2.5) exceeds 0.15 μm, the long-period uneven shape having a wavelength of 0.4 mm or more and 1.25 mm or less becomes too large, and the surface texture of the anti-glare film becomes thick. The Rq (2.5) of the antiglare film of the present invention has the above range, and is preferably 0.09 μm or more and 0.11 μm or less.

[Visual reflectance R _SCI and visual reflectance R _SCE ]

Fig. 1 is a schematic view showing an optical system for measuring a visual reflectance R _SCI by a specular reflection light entering method, and Fig. 2 is a schematic view showing an optical system for measuring a visual reflectance R _SCE by a specular reflection light removing method. In the first and second figures, an optical system of a diffused illumination system is shown. The diffusion illumination method is a method of measuring the uniform illumination of the sample from all directions by using an integrating sphere or the like. In the first and second figures, the integrating sphere 12 (a white paint such as barium sulfate which is almost completely diffused and reflected by light is applied and coated). Inside the ball). The light emitted from the light source 13 is diffused inside the integrating sphere 12 and reflected on the surface of the measurement sample 14. In the second light-receiving portion, a light trap 15 is provided at a position of the integrating sphere 12 in the specular reflection direction (in the first drawing, a jig having a conical hollow is attached, and light entering a conical hollow is formed. The light is absorbed in the cavity and becomes a mechanism that cannot be returned to the integrating sphere 12, and the light in the direction of the normal reflection of the light receiving portion becomes a surface on which the measurement sample cannot be obtained.

The optical system that does not use the light trap shown in Fig. 1 is called a specular light entering mode (SCI mode). On the other hand, the optical system using the light trap shown in Fig. 2 is called a specular reflected light removal mode (SCE mode). The reflectance spectrum of the sample measured from the two modes, the visual reflectance calculated according to the method described in JIS Z 8722, the visual reflectance R _SCI measured by the specular reflected light entering method, and the visual reflectance measured by the specular reflected light removal method. Rate R _SCE .

When the ratio R _SCE /R _SCI of the apparent reflectance R _SCI measured by the specular reflection light entering method and the reflectance R _SCE measured by the specular reflected light removal method exceeds 0.1, the surface of the anti-glare film is used toward the use environment. The reflected light in the user direction of the ambient light becomes strong, and as a result, the image display device having such an anti-glare film is whitened. Further, in the image display device, there is a tendency that the contrast of the bright portion is lowered. It is more preferably 0.08 or less than R _SCE /R _SCI , and more preferably 0.06 or less. Further, the visual reflectance R _SCE measured by the specular reflection light removal method is preferably 0.5% or less, more preferably 0.4% or less, and even more preferably 0.3% or less.

[Total haze, surface haze]

The anti-glare film of the present invention has a total haze of 0.1% or more and 3% or less for vertical incident light in order to exhibit anti-glare property and prevent whitening, and surface fogging. The degree is in the range of 0.1% or more and 2% or less. The total haze of the anti-glare film can be measured by a method according to JIS K7136. An image display device in which an anti-glare film having a total haze or a surface haze of less than 0.1% is disposed is inferior because it does not exhibit sufficient anti-glare properties. Further, in the anti-glare film when the total haze exceeds 3% or when the surface haze exceeds 2%, the image display device in which the anti-glare film is disposed is less likely to be whitened, which is not preferable. Moreover, such an image display device has a lack of contrast in its comparison.

Internal haze obtained by subtracting the surface haze from the total haze The lower one is better. An image display device in which the anti-glare film having an internal haze of more than 2.5% is disposed, and the contrast tends to decrease.

[Specific length Sm when specifying cut length measurement]

In the antiglare film of the present invention, the surface roughness of the antiglare layer is determined by the root mean square roughness at the time of specifying the cutting length, and the average length of the predetermined cutting length is as follows. The range is better. Specifically, the average length Sm (0.25) when the cutting length is 0.25 mm is 90 μm or more and 160 μm or less, and the cutting length is 0.8 mm. The average length Sm (0.8) when measured is 100 μm or more and 300 μm or less, and the cutting length is 2.5 mm. The average length Sm (2.5) at the time of measurement is preferably 200 μm or more and 400 μm or less.

An anti-glare film having an Sm (0.25) of less than 90 μm is an anti-glare layer having a large surface unevenness shape in the vicinity of 50 μm, and an image display device in which such an anti-glare layer is disposed is likely to cause glare. An anti-glare film having an Sm (0.25) of more than 160 μm is an anti-glare layer having a long period of surface unevenness, and the surface texture may become thick. Anti-glare with Sm (0.8) less than 100μm The film is provided with an anti-glare layer having a surface unevenness of 100 to 200 μm in which the anti-glare property is observed from an oblique direction (about 10 to 30°), and an image display device in which such an anti-glare layer is disposed. The anti-glare property when viewed from an oblique direction is lowered. An anti-glare film having an Sm (0.8) of more than 300 μm is an anti-glare layer having a long period of surface unevenness, and the surface texture may become thick. An anti-glare film having an Sm (2.5) of less than 200 μm is provided with an anti-glare layer having a surface unevenness of 200 to 300 μm in an anti-glare property when viewed from an oblique direction (30° or more). The image display device of the layer may have an anti-glare property when viewed from an oblique direction (30° or more). An anti-glare film having an Sm (2.5) of more than 400 μm is an anti-glare layer having a long period of surface irregularities, and the surface texture may become thick.

[Through the sharpness Tc, the reflection sharpness Rc (45) and the opposite Shooting brightness Rc(60)]

The antiglare film of the present invention preferably has a transmittance of 375% or more, which is obtained by the following measurement conditions. The sharpness and Tc are calculated according to the method of JIS K7105 using the optical comb of a predetermined width, and the image sharpness is measured and the sum is calculated. Specifically, five kinds of optical combs having a width ratio of a dark portion to a bright portion of 1:1 and a width of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm are used, and the sharpness is measured, and the sum is obtained. As Tc. An anti-glare film having a Tc of less than 375% is apt to be glare when disposed in a higher-definition image display device. The upper limit of Tc is selected to be in the range of 500% or less of the maximum value. However, when the Tc is too high, an image display device which is likely to have an anti-glare property from the front is easily obtained, and is preferably, for example, 450% or less.

The anti-glare film of the invention is measured by incident light at an incident angle of 45° The predetermined reflection brightness Rc (45) is preferably 180% or less. The reflection sharpness Rc (45) is the same as the above Tc, and is measured by the method of JIS K7105, and four kinds of optical combs having widths of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm are used among the five kinds of optical combs. , respectively, the brightness is determined, and the sum is taken as Rc (45). When Rc (45) is 180% or less, the image display device in which such an anti-glare film is disposed is preferable because it has better anti-glare property when viewed from the front side and the oblique direction. The lower limit of Rc (45) is not particularly limited, but is preferably 80% or more in order to suppress whitening and glare.

The anti-glare film of the invention is measured by incident light at an incident angle of 60° The predetermined reflection brightness Rc (60) is preferably 240% or less. The reflection sharpness Rc (60) was measured in accordance with the method of JIS K7105, except that the incident angle was changed, in the same manner as the reflection sharpness Rc (45). When the Rc (60) is 240% or less, the image display device in which such an anti-glare film is disposed is preferable because it has better anti-glare property when viewed from an oblique direction. The lower limit of Rc (60) is not particularly limited, but is preferably 150% or more in order to satisfactorily suppress the occurrence of whitening glare.

[Method for Producing Antiglare Film of the Present Invention]

The anti-glare film of the present invention is produced, for example, in the following manner. In the first method, a fine uneven-concave-forming mold formed on the surface of the surface of the predetermined pattern is prepared, and the shape of the uneven surface of the mold is transferred to the transparent support, and the transparent support having the shape of the uneven surface is transferred. The method of peeling from the mold. In the second method, a composition containing fine particles, a resin (adhesive), and a solvent, and such fine particles are dispersed in a resin solution, and the composition is applied onto a transparent support, and dried as needed to form a coating. Membrane A method of hardening a coating film containing fine particles. In the second method, the coating film thickness and the aggregation state of the fine particles are adjusted by the composition of the composition, the drying conditions of the coating film, and the like so that the fine particles are exposed on the surface of the coating film, and irregular irregularities are formed on the surface. On a transparent support. From the viewpoint of production stability and production reproducibility of the antiglare film, it is preferred to produce the antiglare film of the present invention by the first method.

Here, a preferred first method as a method of producing the antiglare film of the present invention will be described in detail.

In order to form an anti-glare layer having a surface unevenness having the above-described characteristics with high precision, it is important to prepare a fine uneven-concave forming mold (hereinafter simply referred to as "mold"). More specifically, the surface uneven shape (hereinafter referred to as "mold uneven surface") of the mold is formed according to a specified pattern, which is a graph obtained by determining the intensity of the one-dimensional power spectrum against the spatial frequency. the spatial frequency than 0.05μm ^-1 0.015μm ^-1 or less, having a minimum value are preferred. Here, the "pattern" refers to image data of a fine uneven surface of an anti-glare layer which is formed by an anti-glare film, a mask having a light-transmitting portion and a light-shielding portion, and the like, and is simply referred to as "pattern" hereinafter.

First, a method of setting the pattern of the fine uneven surface of the antiglare layer to form the antiglare film of the present invention will be described.

For example, the way in which the two-dimensional power spectrum of the graphic is represented when the graphic is image data is obtained. First, after the image data is converted into two-tone binary image data, the hue is represented by a two-dimensional function g(x, y). The obtained two-dimensional function g(x, y) is Fourier transformed into the following formula (1), and the two-dimensional function G(f _x , f _y ) is calculated, as shown in the following formula (2), and the obtained two-dimensional function G The absolute value of (f _x , f _y ) is squared to obtain a two-dimensional power spectrum f(f _x , f _y ). Here, x and y represent rectangular coordinates in the plane of the image data. Further, f _x and f _y represent frequencies in the x direction and the y direction, respectively, and have a dimension of the reciprocal of the length.

In the formula (1), π is a pi, and i is an imaginary unit.

The two-dimensional power spectrum f(f _x , f _y ) represents the spatial frequency distribution of the figure. In general, since the antiglare film can be obtained isotropic, the pattern for producing the antiglare film of the present invention is also isotropic. Therefore, the two-dimensional function Γ(f _x , f _y ) representing the two-dimensional power spectrum of the figure can be expressed as a dimensional function Γ(f) depending only on the distance f from the origin (0, 0). The one-dimensional function Γ(f) represents a one-dimensional power spectrum of the graph. Next, a method of obtaining the one-dimensional function Γ(f) from the two-dimensional function Γ(f _x , f _y ) will be described. First, the two-dimensional function Γ(f _x , f _y ) of the height two-dimensional power spectrum is expressed as a polar coordinate as in equation (3).

Here, θ is the declination in the Fourier space. The one-dimensional function Γ(f) can be obtained by calculating the rotation average of the two-dimensional function Γ(fcos θ , fsins θ ) represented by the polar coordinates as in the equation (4).

In order to obtain a good accuracy the antiglare film of the present invention, a one-dimensional power spectrum pattern Γ (f), the spatial frequency of more than 0.05μm ^-1 0.015μm ^-1 or less, preferably those having a minimum value.

When obtaining the two-dimensional power spectrum of a figure, the two-dimensional color The function g(x, y) is usually obtained as a discrete function. In this case, the two-dimensional power spectrum can be calculated by discrete complex leaf transformation. The one-dimensional power spectrum of the graph is obtained by the two-dimensional power spectrum of the graph.

Moreover, in order to make the obtained surface uneven shape For a uniform continuous surface, the average of the two-dimensional function g(x, y) is 30% to 70% of the difference between the maximum value of the two-dimensional function g(x, y) and the minimum value of the two-dimensional function g(x, y) % is better. When the concave-convex surface of the mold is manufactured by the lithography method, the two-dimensional function g(x, y) becomes the aperture ratio of the pattern. When the concave and convex surface of the mold is manufactured by the lithography method, the aperture ratio of the pattern is first defined here. The aperture ratio when the photoresist used in the lithography method is a positive photoresist refers to the exposure of the entire surface area of the coating film when the image data is drawn on the coating film of the positive photoresist. The ratio of the area. On the other hand, the aperture ratio when the photoresist used in the lithography method is a negative photoresist refers to the entire surface of the coating film when the image data is drawn on the coating film of the positive photoresist. The ratio of areas, areas that are not exposed. The lithography method is an aperture ratio at the time of exposure, and refers to a ratio of a light-transmitting portion of a photomask having a light-transmitting portion and a light-shielding portion.

The antiglare film of the present invention, a one-dimensional power spectrum pattern Γ (f) in the spatial frequency 0.015μm ^-1 less than 0.05μm ^-1 having a minimum value, for producing a desired mold, may be used in accordance with the first mold Manufactured by the method.

In order to produce a one-dimensional power spectrum pattern having a minimum spatial frequency of 0.015 μm ^-1 or more and 0.05 μm ^-1 or less, the dots are arranged irregularly, and the similarly generated images are generated in advance by the created graphics, random numbers, or computer generated. The number determines a shaded pattern (prepared pattern) having an irregular brightness distribution from which components of a specific spatial frequency range are removed. The components in the specific spatial frequency range are removed, and the preliminary pattern is passed through a band pass filter.

In order to manufacture a surface having a defined pattern The anti-glare film of the anti-glare layer of the uneven shape is produced by transferring a surface uneven shape formed by the predetermined pattern to a mold having a concave-convex surface of the mold for the transparent support. The first method of using such a mold is characterized in that embossing of the antiglare layer on the transparent support is performed.

As the aforementioned imprint method, for example, a photocurable resin is used. Photoimprint method, hot stamping using thermoplastic resin, and the like. Among them, from the viewpoint of productivity, photo imprinting is preferred.

Photoimprinting on a transparent support (transparent support) A method of forming a photocurable resin layer and laminating the photocurable resin on the uneven surface of the mold of the mold, and transferring the shape of the uneven surface of the mold to the photocurable resin layer. Specifically, the photocurable resin is applied onto the transparent support, and the formed photocurable resin layer is irradiated with light from the side of the transparent support in a state of being in close contact with the uneven surface of the mold (this light system can be used for photocurability) In the case where the resin is cured, the photocurable resin (photocurable resin contained in the photocurable resin layer) is cured, and then the transparent support having the cured photocurable resin layer is peeled off from the mold. The anti-glare film obtained by such a manufacturing method has an anti-glare layer which is a photocurable resin layer after hardening. Furthermore, as a photocurable resin, from the viewpoint of ease of manufacture, When the ultraviolet curable resin is used, when the ultraviolet curable resin is used, ultraviolet light is used (imprinting method using an ultraviolet curable resin as a photocurable resin, hereinafter referred to as "UV imprint method"). In order to manufacture an anti-glare film integrated with a polarizing film, a polarizing film is used as a transparent support, and the imprint method described here may be performed by a polarizing film instead of a transparent support.

Kind of ultraviolet curable resin used in UV imprinting There is no particular limitation, and those which are commercially available may be used depending on the type of transparent support to be used and the type of ultraviolet rays. Such an ultraviolet curable resin includes a concept of a monomer (polyfunctional monomer), an oligomer, a polymer, and a mixture thereof which are photopolymerized by ultraviolet irradiation. Further, depending on the type of the ultraviolet curable resin, it is preferably used by combining the selected photoinitiators, and a resin which can be cured by using visible light having a longer wavelength than ultraviolet rays can be used. Preferred examples of the ultraviolet curable resin and the like are described later.

As a transparent support used in UV imprinting, for example Glass, plastic film, etc. can be used. As the plastic film, it can be used as long as it has moderate transparency and mechanical strength. Specifically, for example, cellulose acetate resin such as TAC (triethyl fluorenyl cellulose); acrylic resin; polycarbonate resin; polyester resin such as polyethylene terephthalate; A transparent resin film made of a polyolefin resin such as polypropylene. The transparent resin film may be a solvent cast film or an extruded film.

The thickness of the transparent support is, for example, 10 to 500 μm. It is preferably 10 to 100 μm, more preferably 10 to 60 μm. Transparent support When the thickness is within this range, an anti-glare film having sufficient mechanical strength tends to be obtained, and an image display device including the anti-glare film is more likely to cause glare.

On the other hand, the hot stamping method is formed by a thermoplastic resin. The formed transparent resin film is heated, and in a softened state, the uneven surface of the mold is pressed, and the surface uneven shape of the uneven surface of the mold is transferred to the transparent resin film. The transparent resin film used in the hot stamping method may be substantially transparent, and specifically, for example, an example of a transparent resin film used in the UV imprint method.

Next, the mold used in the manufacture of the imprint method will be described. The method.

Regarding the manufacturing method of the mold, the forming surface of the mold is The range of the surface unevenness formed by the predetermined pattern can be transferred to the transparent support (the anti-glare layer capable of forming the surface uneven shape formed by the predetermined pattern), and is not particularly limited, and is preferably used with high precision. Further, the antiglare layer having the surface unevenness is excellent in reproducibility, and the lithography method is preferable. Furthermore, the lithography method includes [1] a first plating step, [2] a polishing step, [3] a photosensitive resin film forming step, [4] an exposure step, a [5] developing step, and [6] The first etching step, the [7] photosensitive resin film peeling step, the [8] second etching step, and the [9] second plating step are preferred.

Figure 3 shows the manufacturing method of the mold (first half) A schematic diagram of a preferred embodiment. Figure 3 is a schematic view showing the cross section of the mold of each step. Hereinafter, each step of the method for producing a mold for producing an anti-glare film according to the present invention will be described in detail with reference to FIG.

[1] First plating step

First, a substrate (a substrate for a mold) used for mold production is prepared, and copper plating is applied to the surface of the substrate for the mold. In this way, by performing copper plating on the surface of the substrate for a mold, the adhesion and gloss of the chromium plating in the second plating step to be described later can be improved. Since the copper plating has high coating property and strong smoothing effect, it can fill the fine unevenness of the substrate for the mold, the whisker, and the like to form a flat and shiny surface. Therefore, in such a manner, copper plating is performed on the surface of the substrate for a mold, and in the second plating step to be described later, even if chrome plating is performed, it is possible to solve the chrome plating which is considered to be caused by the fine unevenness and the silk which are present on the substrate. The surface is rough and the coating of copper plating is high, which can reduce the occurrence of fine cracks. Therefore, even if the surface unevenness shape (fine uneven surface shape) of the predetermined pattern is formed on the molding surface of the base material for the mold, the influence of the surface of the base (substrate for the mold) such as fine unevenness, whisker, and crack can be sufficiently prevented. The resulting misplacement.

Copper used for copper plating in the first plating step, An alloy containing copper as a main component (copper alloy) can also be used as the pure metal of copper. Therefore, the "copper" used in copper plating is a concept including copper and a copper alloy. The copper plating may be electrolytic plating or electroless plating, but the copper plating in the first plating step is preferably electrolytic plating. Further, the preferred plating layer in the first plating step may be composed not only of a copper plating layer but also a plating layer composed of a copper plating layer and a metal other than copper.

Plating by copper plating on the surface of the substrate for a mold When the layer is too thin, since the influence of the surface of the substrate (fine irregularities, whiskers, cracks, etc.) cannot be completely excluded, the thickness thereof is preferably 50 μm or more. Coating thickness The limit is not limited, and when the cost is considered, it is preferably about 500 μm or less.

The substrate for the mold is a substrate composed of a metal material. good. Further, from the viewpoint of cost, aluminum, iron, or the like is preferable as the material of the metal material. Further, from the viewpoint of the convenience of the treatment of the substrate for a mold, a substrate composed of lightweight aluminum is particularly preferable as a substrate for a mold. Further, the aluminum and iron referred to herein are not necessarily pure metals, and may be an alloy mainly composed of aluminum or iron.

The shape of the substrate for the mold, as long as it is in accordance with the present invention The method for producing the glare film may be a suitable shape. Specifically, it can be selected from a flat substrate, a cylindrical substrate, a cylindrical (roller shape) substrate, or the like. When the antiglare film of the present invention is continuously produced, the mold is preferably in the shape of a roller. Such a mold can be manufactured from a substrate for a roll-shaped mold.

[2] Grinding step

Next, in the polishing step, the surface (plating layer) of the copper-plated mold base material subjected to the first plating step is polished. In the method for producing a mold used in the method for producing an anti-glare film of the present invention, it is preferred that the surface of the substrate for a mold is polished to a state close to the mirror surface. In order to form a desired precision, a commercially available product of a flat substrate or a roll-shaped base material used as a base material for a mold is often subjected to machining such as cutting or polishing, whereby fineness remains on the surface of the base material for the mold. Tool traces. Therefore, even if a plating layer (preferably copper plating) is formed by the first plating step, the above-described processing marks remain. Further, even if the copper plating in the first plating step is performed, the surface of the substrate for a mold may not be completely smooth. that is, In the substrate for a mold in which the surface of such a deep processing mark or the like remains, even if the steps [3] to [9] described later are carried out, the surface unevenness of the surface of the obtained mold may be the surface uneven shape according to the specified pattern. Different, or contain irregularities from processing marks and the like. When an anti-glare film is produced using a mold in which the influence of a processing mark or the like is left, the optical characteristics such as the anti-glare property for the purpose cannot be sufficiently exhibited, and an unexpected influence may be caused.

The grinding method applied in the grinding step is not limited The polishing method is selected depending on the shape and properties of the substrate for the mold to be polished. Specific examples of the polishing method applicable to the polishing step include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. Among these, as the mechanical polishing method, any of an ultrafine processing method, a lapping method, a fluid polishing method, and a buffing polishing method can be used. Further, in the polishing step, the surface of the substrate for the mold can be mirror-finished by mirror-cutting using a cutting tool. In the material/shape of the cutting tool in this case, a hard edge, a CBN blade, a ceramic blade, a diamond blade, or the like can be used depending on the type of the material (metal material) of the substrate for the mold, and the diamond blade is used from the viewpoint of processing accuracy. Preferably. The surface roughness after polishing is expressed by the center line average roughness Ra according to JIS B0601, and is preferably 0.1 μm or less, more preferably 0.05 μm or less. If the center line average roughness Ra after grinding is more than 0.1 μm, the influence of such surface roughness may remain on the uneven surface of the mold of the finally obtained mold. Further, the lower limit of the center line average roughness Ra is not particularly limited. Therefore, the lower limit can be determined from the viewpoints of the processing time (polishing time) of the polishing step and the processing cost.

[3] Photosensitive resin film forming step

Next, a photosensitive resin film forming step will be described with reference to Fig. 3 .

In the photosensitive resin film forming step, by the above research The surface 41 of the substrate 40 for mirror polishing obtained by the grinding step is applied to a solution (photosensitive resin solution) in which a photosensitive resin is dissolved in a solvent, and a photosensitive resin film (photoresist) is formed by heating/drying. membrane). Fig. 3 is a view schematically showing a state in which the photosensitive resin film 5 is formed on the surface 41 of the mold substrate 40 (Fig. 3(b)).

As the photosensitive resin, conventionally known photosensitive light can be used. As the resin, it is also possible to directly use the commercially available one as a photoresist or to refine the latter by filtration or the like as needed. For example, as a negative photosensitive resin having a photosensitive portion hardening property, a monomer, a prepolymer, a double azide which is used for a (meth) acrylate having an acryl fluorenyl group or a methacryl fluorenyl group in a molecule can be used. A mixture with a diene rubber, a polyvinyl alcohol cinnamate compound, or the like. Further, as the positive photosensitive resin having a property of dissolving the photosensitive portion by development and leaving only the photosensitive portion, a phenol resin, a novolak, or the like can be used. Such a positive or negative photosensitive resin can be easily obtained from the market in terms of positive photoresist and negative photoresist. Further, the photosensitive resin solution may be blended with various additives such as a sensitizer, a development accelerator, an adhesion modifier, and a coatability improver, as needed, and such additives may be mixed with a commercially available photoresist. It can also be used as a photosensitive resin solution.

In order to apply the photosensitive resin solution to the mold base On the surface 41 of the material 40, a most suitable solvent is selected on the smoother photosensitive resin film, and a photosensitive resin solution obtained by dissolving/diluting the photosensitive resin in such a solvent is preferable. Such a solvent, and then based on the photosensitive tree The type of fat and its solubility selection. Specifically, it is selected, for example, from a cellosolve solvent, a propylene glycol solvent, an ester solvent, an alcohol solvent, a ketone solvent, a highly polar solvent, or the like. When a commercially available photoresist is used, an optimum photoresist is selected depending on the kind of the solvent contained in the photoresist or an appropriate preliminary test, and it is used as a photosensitive resin solution.

Coating the surface of the mold substrate with a mirror-polished surface Method for resin solution, from meniscus coating, fountain coating, dip coating, spin coating, roller coating, bar coating, air knife coating, blade coating, shower coating, ring coating A conventional method is selected depending on the shape of the substrate for the mold and the like. The thickness of the photosensitive resin film after application is preferably in the range of 1 to 10 μm after drying, and more preferably in the range of 6 to 9 μm.

[4] Exposure step

Next, the exposure step is a step of exposing the photosensitive resin film 50 formed in the photosensitive resin film forming step and transferring the intended pattern to the photosensitive resin film 50. The light source used in the exposure step may be appropriately selected as long as it conforms to the photosensitive wavelength, sensitivity, and the like of the photosensitive resin contained in the photosensitive resin film. For example, a g-line (wavelength: 436 nm) and an h-line (wavelength) of a high-pressure mercury lamp can be used. : 405 nm) or i line (wavelength: 365 nm), semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, etc.), YAG laser (wavelength: 1064 nm), KrF excimer laser (wavelength: 248 nm), ArF Molecular laser (wavelength: 193 nm), F2 excimer laser (wavelength: 157 nm), and the like. The exposure method is a method in which the photomask corresponding to the target is used for exposure, or a drawing method. Furthermore, it has been described graphic purposes, the one-dimensional power spectrum is expressed as the intensity of view of spatial frequencies, based on the spatial frequency of more than 0.05μm ^-1 0.015μm ^-1 or less, those having a minimum value.

In the mold manufacturing method, for better accuracy terrain The surface irregularities of the mold are formed, and the intended pattern is preferably exposed on the photosensitive resin film in a state of precise control. In order to expose in such a state, the image of the destination is made into image data on the computer, and the laser light emitted from the laser light controlled by the computer is drawn on the photosensitive resin film according to the graphic of the image data. (laser depiction) is preferred. For laser drawing, a general-purpose laser drawing device such as a printing plate can be used. As a commercial item of such a laser drawing device, for example, Laser Stream FX (manufactured by Think Laboratory) or the like.

Fig. 3(c) is a view schematically showing the photosensitive resin film 50 The state of the shape exposure. When the photosensitive resin film 50 contains a negative photosensitive resin (for example, when a negative photoresist is used as the photosensitive resin solution), the exposed region 51 receives the energy of exposure and performs a crosslinking reaction of the photosensitive resin, which will be described later. The solubility of the developing solution is lowered. Therefore, in the developing step, the unexposed area 52 is dissolved by the image forming liquid, and only the exposed area 51 remains on the surface of the substrate to become the mask 60. On the other hand, when the photosensitive resin film 50 contains a positive photosensitive resin (for example, when a positive photoresist is used as the photosensitive resin solution), exposure energy is received in the exposed region 51, and the bonding of the photosensitive resin is cut. It becomes easily soluble in the developing liquid mentioned later. Therefore, the exposed region 51 in the developing step is dissolved by the image forming liquid, and only the unexposed region 52 remains on the surface of the substrate to become the mask 60.

[5] imaging step

In the developing step, the photosensitive resin film 50 contains a negative photosensitive tree In the case of fat, the unexposed area 52 is dissolved by the developing solution, and the exposed region 51 remains on the substrate for the mold to form the mask 60. On the other hand, when the photosensitive resin film 50 contains a positive photosensitive resin, only the exposed region 51 is dissolved by the image forming liquid, and the unexposed region 52 remains on the substrate for the mold to form the mask 60. In the first etching step, the photosensitive resin film remaining on the substrate for a mold is used as a substrate for the mold for the photosensitive resin film in the first etching step, and functions as a mask in the first etching step to be described later.

The imaging solution used in the imaging step can be used from the past The person who knows is suitable for the type of photosensitive resin to be used. For example, the developing solution is an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or ammonia; a primary amine such as ethylamine or n-propylamine; a second-grade amine such as an amine or di-n-butylamine; a tertiary amine such as triethylamine or methyldiethylamine; an alcohol amine such as dimethylethanolamine or triethanolamine; tetramethylammonium hydroxide and hydrogen a four-stage ammonium compound such as tetraethylammonium chloride or trimethylhydroxyethylammonium hydroxide; an alkaline aqueous solution such as a cyclic amine such as pyrrole or piperidine; or an organic solvent such as xylene or toluene.

The imaging method of the developing step is not particularly limited, and Dip development, spray imaging, brush imaging, ultrasonic imaging, etc.

In Figure 3 (d), it is schematically indicated that the negative type is used as the photosensitive The resin is in a state after the development step. In the third diagram (d), the unexposed region 52 is dissolved by the image forming liquid, and only the exposed region 51 remains on the surface of the substrate, and the photosensitive resin film in this region serves as the mask 60. In the third drawing (e), a state in which a positive type is used as a photosensitive resin and a developing step is performed is schematically shown. The exposed area 51 in Fig. 3(e) is dissolved by the imaging liquid, only The unexposed area 52 remains on the surface of the substrate, and the photosensitive resin film in this area serves as the mask 60.

[6] First etching step

In the first etching step, a photosensitive resin film remaining on the surface of the substrate for a mold after the above-described developing step is used as a mask, and an etching step of a plating layer mainly in a region without a mask is formed on the surface of the substrate for a mold.

Figure 4 is a schematic representation of the second half of the manufacturing method of the mold. A preferred embodiment of the portion. In the fourth etching step (a), the first etching step mainly shows the state in which the plating layer in the region where no mask is etched. The plating layer on the lower portion of the mask 60 is applied to the mask 60 by the photosensitive resin film, and is not etched, but etching is performed while etching from the region 45 where the mask is not provided. Therefore, in the vicinity of the region having the mask 60 and the boundary without the mask region 45, the plating of the lower portion of the mask 60 is also etched. Thus, in the vicinity of the region having the mask 60 and the boundary without the mask region 45, the plating of the lower portion of the mask 60 is also etched, which is referred to as side etching.

In the etching treatment (first etching treatment) in the first etching step, a ferric chloride (FeCl ₃ ) solution, a copper chloride (CuCl ₂ ) solution, an alkali etching solution (Cu(NH ₃ ) ₄ Cl ₂ ), or the like is usually used. The etching liquid and the surface of the substrate for the mold are mainly made by etching a plating layer (metal surface) in a region where the mask 60 is not covered. As the etching treatment, a strong acid such as hydrochloric acid or sulfuric acid may be used as the etching liquid, and when the plating layer is formed by electrolytic plating, the etching treatment may be performed by reverse electrolytic etching which gives a potential opposite to that at the time of electrolytic plating. When the etching treatment is performed, the surface of the substrate for a mold has a concave-convex shape, and the type of the constituent material (metal material) of the substrate for the mold, the type of the plating layer, the type of the photosensitive resin film, and the type of etching treatment in the first etching step. The difference is not uniform, and when the etching amount is 10 μm or less, the surface of the substrate for the mold which is in contact with the etching liquid is etched in approximately the same direction. The amount of etching referred to herein means the thickness of the plating layer which is etched and removed.

The etching amount of the first etching step is preferably from 1 to 10 μm, more preferably from 2 to 5 μm. When the etching amount exceeds 10 μm, the difference in the unevenness of the surface unevenness formed on the surface of the mold is large. As a result, when using the mold for manufacturing the antiglare film, sometimes more than R _SCE / R _SCI than 0.1. Therefore, the etching amount in the first etching step is set to 10 μm or less, and it is preferable to manufacture a mold through a procedure described later, and an anti-glare film which can sufficiently prevent whitening can be obtained by using the mold to produce an anti-glare film. On the other hand, when the etching amount is less than 1 μm, the surface irregularities are hardly formed in the mold, and since the mold has a nearly flat surface, even if the mold is used to manufacture an anti-glare film, such an anti-glare film has almost no surface. The anti-glare film is not able to obtain a sufficient anti-glare property. Further, the first etching treatment in the first etching step may be performed by one etching treatment or may be performed by two or more etching treatments. Here, when the etching treatment is carried out in two or more steps, the total etching amount of the etching treatment of two or more times is preferably 1 to 10 μm.

[7] Photosensitive resin film peeling step

Next, in the photosensitive resin film peeling step, the first etching step acts as the mask 60, and the step of removing the photosensitive resin film remaining on the substrate for the mold is performed, and by this step, the substrate remaining on the mold is completely removed. The photosensitive resin film is preferable. In the photosensitive resin film peeling step, it is preferred to use a release liquid to dissolve the photosensitive resin film. As a stripping solution, it can be used as a developing solution. The indicator is changed by changing its concentration, pH, and the like. Alternatively, in the same manner as the developing solution used in the developing step, the developing step may change the temperature, the immersion time, or the like, or may peel off the photosensitive resin film. In the photosensitive resin film peeling step, the contact method (peeling method) of the peeling liquid and the substrate for a mold is not particularly limited, and immersion peeling, spray peeling, brush peeling, ultrasonic peeling, or the like can be used.

Figure 4(b) is a schematic representation showing the peeling by a photosensitive resin film In the step of dissolving, the first etching step is completely removed using the photosensitive resin film as the mask 60. The first surface uneven shape 46 is formed on the surface of the substrate for a mold by the mask 60 obtained by the photosensitive resin film and the etching treatment.

[8] Second etching step

The second etching step is a step of passivating the first surface uneven shape 46 formed by the first etching step by an etching treatment (second etching treatment). By the second etching process, the portion of the first surface uneven shape 46 formed by the first etching process is steeply steeped (hereinafter, in the surface uneven shape, the portion whose surface is steeply inclined is passivated. "Shape passivation"). In the fourth etching process, the first surface uneven shape 46 of the mold base material 40 is passivated by the second etching treatment, and the portion having a steep surface inclination is passivated, and the second surface unevenness having the surface inclination and gentleness is formed. The state of shape 47. As described above, the mold obtained by the second etching treatment has an effect of further improving the optical characteristics of the anti-glare film of the present invention produced by using the mold.

In the second etching treatment in the second etching step, etching treatment using the same etching liquid as in the first etching step or reverse electricity may be used. De-etching. The degree of passivation of the shape after the second etching treatment (the degree of disappearance of the portion where the surface unevenness of the surface after the first etching step is steep) is due to the material of the substrate for the mold, the means for the second etching treatment, and the first etching. The size and depth of the unevenness of the surface unevenness obtained in the step are not uniform, but the largest factor in controlling the passivation (degree of shape passivation) is the etching amount of the second etching treatment. The etching amount here is also the same as that in the first etching step, and indicates the thickness of the substrate which is removed by the second etching treatment. When the etching amount of the second etching treatment is small, the effect of passivating the shape of the surface unevenness obtained by the first etching step becomes insufficient. Therefore, the anti-glare film produced by using a mold having insufficient shape passivation may sometimes be whitened. On the other hand, when the etching amount of the second etching treatment is too large, the unevenness of the surface unevenness formed by the first etching step is almost eliminated, and becomes a mold having a nearly flat surface. The antiglare film produced by using such a mold having an almost flat surface becomes insufficient in antiglare property. Therefore, the etching amount of the second etching treatment is preferably in the range of 1 to 50 μm, more preferably in the range of 4 to 20 μm, and still more preferably in the range of 13 to 18 μm. The second etching treatment can be performed by one etching process as in the first etching step, or can be performed by two or more etching processes. Here, when the etching treatment is carried out in two or more steps, the total etching amount of the etching treatment of two or more times is preferably from 1 to 50 μm.

[9] 2nd plating step

The final stage of the mold production is based on the substrate for the mold which has been subjected to the above steps [6] and [7], and is preferably plated on the surface of the substrate for the mold which has undergone the steps [6] to [8]. It is preferably the second chrome plating described later. Plating step. By performing the second plating step, the surface uneven shape 47 of the mold base material is further passivated, and the surface of the mold can be protected by the plating. In the fourth surface (not shown), the chrome plating layer 71 is formed on the second surface uneven shape 47 formed by the second etching process, and the surface uneven shape shape is passivated (surface 70).

The plating layer formed by the second plating step is preferably chrome plated in that it has gloss, high hardness, small friction coefficient, and good release property. In chrome plating, it is called so-called gloss chrome plating, chrome plating for decoration, etc., and chrome plating which exhibits good gloss is particularly preferable. Chromium plating is usually carried out by electrolysis, but as a plating bath, an aqueous solution containing anhydrous chromic acid (CrO ₃ ) and a small amount of sulfuric acid is used as a plating solution. The thickness of the chrome plating can be controlled by adjusting the current density and the electrolysis time.

The plating of the second plating step is preferably performed in such a manner. A mold for producing an anti-glare film of the present invention can be obtained by chrome plating. The surface unevenness shape of the surface of the substrate for a mold after the second etching treatment can be passivated by chrome plating, and a mold having a high surface hardness can be obtained. The most important factor in controlling the degree of passivation at this time is the thickness of the chrome plating. If the thickness is small, the degree of passivation of the shape becomes insufficient, and when the thickness of the chrome plating layer is too thick, the productivity is deteriorated, and a projection-like plating defect called a nodule occurs, which is an anti-invention of the present invention. The mold for glare film manufacturing is not good. The thickness of the chrome plating layer is preferably in the range of 1 to 20 μm, more preferably in the range of 3 to 15 μm, and even more preferably in the range of 3 to 6 μm.

The chrome plating formed by the second plating step forms the Vickers The (Vickers) hardness is preferably 800 or more, and more preferably 1,000 or more. chromium When the Vickers hardness of the plating layer is less than 800, when the antiglare film is produced using a mold, the durability of the mold tends to be lowered.

Hereinafter, the anti-glare as a manufacturing method of the present invention will be described. The method for film is preferably the aforementioned imprint method. As described above, the UV imprint method is particularly preferable as a photoimprint method, and an imprint method using an active energy ray-curable resin is specifically described herein.

In order to continuously manufacture the anti-glare film of the present invention, when the anti-glare film of the present invention is produced by photoimprinting, it is preferred to include the following step: [P1] a coating step on a transparent support for continuous conveyance Applying a coating liquid containing an active energy ray-curable resin to form a coating layer; [P2] a final curing step which is applied to the surface of the coating layer and is pressed against the surface of the mold from the side of the transparent support The active energy line is illuminated. Further, when the antiglare film of the present invention is produced by photoimprinting, it is more preferred to include a [P3] preliminary hardening step after the coating step [P1], before the curing step [P2], and after coating. Both ends of the layer in the width direction are irradiated with active energy rays.

Hereinafter, each step will be described in detail with reference to the drawings. Fig. 5 is a schematic view showing a preferred example of a manufacturing apparatus used in the method for producing an anti-glare film of the present invention. The arrow in Fig. 5 indicates the conveying direction of the film or the direction of rotation of the roller.

[P1] coating step

In the coating step, a coating liquid containing an active energy ray-curable resin is applied onto a transparent support to form a coating layer. The coating step, as shown in Fig. 5, is applied to the transparent support 81 which is successively discharged from the delivery roller 80 in the coating area. 83 A coating liquid containing an active energy ray-curable resin was applied.

Coating of the coating liquid toward the transparent support 81, for example, It is carried out by a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, an air knife coating method, an anastomosis coating method, a slit coating method, or the like.

(transparent support)

The transparent support 81 may be any one that transmits light, and for example, glass, a plastic film, or the like can be used. As the plastic film, it is sufficient as long as it has moderate transparency and mechanical strength. Specifically, any of the transparent supports that have been used as the UV imprint method can be used, and in order to continuously manufacture the anti-glare film of the present invention by photoimprint, it is possible to select moderate flexibility. By.

Improved coating properties of coating liquid, transparent support and For the purpose of improving the adhesion of the coating layer, various surface treatments can be performed on the surface (coating layer side surface) of the transparent support 81. As the surface treatment, for example, corona discharge treatment, arc discharge treatment, acid surface treatment, alkali surface treatment, ultraviolet irradiation treatment, and the like. Further, on the transparent support 81, for example, another layer such as an undercoat layer may be formed, and a coating liquid may be applied to the other layer.

Moreover, as an anti-glare film of the present invention, it is manufactured and biased. When the optical film is formed integrally, in order to improve the adhesion between the transparent support and the polarizing film, the surface of the transparent support (the surface opposite to the coating layer) is preferably hydrophilized by various surface treatments. This surface treatment can also be carried out after the production of the anti-glare film.

(coating liquid)

The coating liquid contains an active energy ray-curable resin, and usually further contains a photopolymerization initiator (radical polymerization initiator). Light transmissive as needed Various additives such as a solvent such as a microparticle or an organic solvent, a leveling agent, a dispersing agent, a charging inhibitor, an antifouling agent, and a surfactant.

(1) Active energy ray-curable resin

As the active energy ray-curable resin, for example, a polyfunctional (meth) acrylate compound can be preferably used. The polyfunctional (meth) acrylate compound is a compound having at least two (meth) acryloxy groups in the molecule. Specific examples of the polyfunctional (meth) acrylate compound include, for example, an esterified product of a polyvalent alcohol and (meth)acrylic acid, a urethane (meth) acrylate compound, and a polyester (meth) acrylate. A polyfunctional polymerizable compound containing two or more (meth)acrylonium groups, such as a compound or an epoxy (meth) acrylate compound.

As a polyvalent alcohol, such as ethylene glycol, diethylene glycol, three Ethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, 2-B a divalent alcohol of 1,3-1,3-hexanediol, 2,2'-thiodiethanol, 1,4-cyclohexanedimethanol; trimethylolpropane, glycerol, pentaerythritol, diglycerol, An alcohol having a divalent or higher valence of dipentaerythritol or ditrimethylolpropane.

As an esterified product of a polyvalent alcohol and (meth)acrylic acid, specific For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylic acid Ester, trimethylolpropane tri(meth) acrylate, trimethylolethane tri(meth) acrylate, tetramethylol methane tri(meth) acrylate, 1,6-hexanediol (meth) acrylate, tetramethylol methane tetra (meth) acrylate, Pentaglycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

As a metal urethane (meth) acrylate compound The substance is, for example, an ethyl carbamate reaction product of an organic isocyanate having a plurality of isocyanate groups in one molecule and a (meth)acrylic acid derivative having a hydroxyl group. As an organic isocyanate having a plurality of isocyanate groups in one molecule, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolyl diisocyanate, stilbene diisocyanate, diphenylmethane diisocyanate, xylyl An organic isocyanate having two isocyanate groups in one molecule such as diisocyanate or dicyclohexylmethane diisocyanate, the organic isocyanate being modified with isocyanate, modified with an adduct, and modified with a biuret An organic isocyanate having three isocyanate groups in one molecule. As a (meth)acrylic acid derivative having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (methyl) 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, pentaerythritol triacrylate.

Preferred as a polyester (meth) acrylate compound A polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth)acrylic acid. The hydroxyl group-containing polyester which is preferably used is a hydroxyl group-containing polyester obtained by esterification reaction of a polyvalent alcohol with a carboxylic acid, a compound having a plurality of carboxyl groups, and/or an anhydride thereof. As a polyvalent alcohol, for example, with the aforementioned compound The same. Further, in addition to the polyvalent alcohol, as the phenol, for example, bisphenol A or the like. As a compound having a plurality of carboxyl groups and/or anhydrate thereof, for example, maleic acid, phthalic acid, fumaric acid, methylene succinic acid, adipic acid, terephthalic acid, butene Diacid anhydride, phthalic anhydride, trimellitic acid, cyclohexane dicarboxylic anhydride, and the like.

In the above polyfunctional (meth) acrylate compound, hexanediol di(meth) acrylate or neopentyl glycol diol is preferred from the viewpoint of improvement in strength of the cured product and easiness of obtaining the cured product. Methyl) acrylate, diethylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, An ester compound such as dipentaerythritol hexa(meth)acrylate; an adduct of hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate; isophorone diisocyanate and 2-hydroxyl (meth)acrylate An adduct of ethyl ester; an adduct of tolyl diisocyanate and 2-hydroxyethyl (meth)acrylate; an adduct-modified isophorone diisocyanate and 2-hydroxyethyl (meth)acrylate An adduct; and an adduct of a biuret-modified isophorone diisocyanate and 2-hydroxyethyl (meth)acrylate. Further, these polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more kinds.

The active energy ray-curable resin may contain a monofunctional (meth) acrylate compound in addition to the above-described polyfunctional (meth) acrylate compound. As the monofunctional (meth) acrylate compound, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (methyl) 3rd butyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxy (meth) acrylate Butyl ester, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-ethylene Pyrrolidone, tetrahydrofuranyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, ethyl methacrylate , benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, (A) Phenyl oxyacrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide (meth) acrylate, nonyl phenol (meth) acrylate, ethylene oxide modified (A Acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, 2-(methyl) propylene oxiranyl ethyl-2-hydroxyl A (meth) acrylate such as propyl phthalate, methylaminoethyl bis(meth)acrylate or methoxytriethylene glycol (meth) acrylate. These compounds may be used alone or in combination of two or more.

Further, the active energy ray-curable resin may contain a polymerizable oligomer. The hardness of the cured product can be adjusted by containing a polymerizable oligomer. The polymerizable oligomer is, for example, the aforementioned polyfunctional (meth) acrylate compound, that is, an esterified product of a polyvalent alcohol and (meth)acrylic acid, an ethyl urethane (meth) acrylate compound, and a polyester (A) An oligomer of a dimer, a trimer or the like of an acrylate compound or an epoxy (meth) acrylate.

As another polymerizable oligomer, for example, a urethane (meth)acrylic acid obtained by reacting a polyisocyanate having at least one isocyanate group in the molecule with a polyvalent alcohol having at least one (meth) propylene decyloxy group Ester oligomer. As a polyisocyanate, such as hexamethylene diisocyanate, a polymer of isophorone diisocyanate, tolyl diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, as a polyvalent alcohol having at least one (meth) propylene decyloxy group, such as a polyvalent alcohol a hydroxyl group-containing (meth) acrylate obtained by esterification reaction with (meth)acrylic acid, as a polyvalent alcohol such as 1,3-butanediol, 1,4-butanediol, 1,6-hexane Alcohol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like. The polyvalent alcohol having at least one (meth) acryloxy group is a part of an alcoholic hydroxyl group of a polyvalent alcohol and is esterified with (meth) acrylate, and the alcoholic hydroxy group remains in the molecule.

Further, as an example of another polymerizable oligomer, for example, A polyester (meth) acrylate oligomer obtained by reacting a compound having a plurality of carboxy groups and/or an anhydride thereof with a polyvalent alcohol having at least one (meth) acryloxy group. The polyester (meth) acrylate which is a compound having a plural carboxy group and/or an anhydride thereof, for example, the above-mentioned polyfunctional (meth) acrylate compound is described in the same manner. Further, the polyvalent alcohol having at least one (meth) acryloxy group, for example, the above-described urethane (meth) acrylate oligomer is described in the same manner.

In addition to the above polymerizable oligomers, as an amine group Examples of the acid ethyl ester (meth) acrylate oligomer, for example, a hydroxyl group-containing polyester, a hydroxyl group-containing polyether or a hydroxyl group-containing (meth) acrylate hydroxyl group, are reacted with an isocyanate. The hydroxyl group-containing polyester which is preferably used is a hydroxyl group-containing polyester obtained by esterification reaction of a polyvalent alcohol with a carboxylic acid, a compound having a plurality of carboxyl groups, and/or an anhydride thereof. As much The polyester (meth) acrylate of a polyvalent (meth) acrylate compound is described in the same manner as the phenolic acid, the compound having a plurality of carboxy groups, and/or an anhydride thereof. The hydroxyl group-containing polyether which is preferably used is a hydroxyl group-containing polyether obtained by adding one or more kinds of alkylene oxide and/or ε-caprolactone to a polyvalent alcohol. The polyvalent alcohol may be the same as the above hydroxyl group-containing polyester. The hydroxyl group-containing (meth) acrylate which is preferably used is, for example, the same as the urethane (meth) acrylate of the polymerizable oligomer. The isocyanate is preferably a compound having one or more isocyanate groups in the molecule, and particularly preferably a divalent isocyanate compound such as tolyl diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.

The polymerizable oligomer compounds may be separately or 2 More than one kind.

(2) Photopolymerization initiator

The photopolymerization initiator can be appropriately selected depending on the kind of active energy ray applied to the production of the antiglare film of the present invention. Further, when an electron beam is used as the active energy ray, a coating liquid containing no photopolymerization initiator may be used in the production of the antiglare film of the present invention.

As the photopolymerization initiator, for example, an acetophenone system can be used. Photopolymerization initiator, benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, triazine-based photopolymerization initiator, oxadiazole Oxadiazole) is a photopolymerization initiator. Further, as the photopolymerization initiator, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5 can be used. , 5'-tetraphenyl-1,2'-bisimidazole, 10-butyl-2-chloroacridone, 2-ethyl hydrazine, Benzoyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, and the like. The amount of the photopolymerization initiator to be used is usually 0.5 to 20 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the active energy ray-curable resin.

The coating liquid is used to improve the coating of the transparent support It may also contain a solvent such as an organic solvent. Examples of the organic solvent include aliphatic hydrocarbons such as hexane, cyclohexane, and octane; aromatic hydrocarbons such as toluene and xylene; and alcohols such as ethanol, 1-propanol, isopropanol, 1-butanol, and cyclohexanol. Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, isobutyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , glycol ethers such as diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; esterified glycol ethers such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate; Cellosolve such as oxyethanol, 2-ethoxyethanol, 2-butoxyethanol; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy) Base) Ethyl alcohol, carbitol such as 2-(2-butoxyethoxy)ethanol, etc., and is selected for use in consideration of viscosity. These solvents may be used singly or in combination of plural kinds as needed. After coating, the above organic solvent must be evaporated. Therefore, the boiling point is desirably in the range of 60 ° C to 160 ° C. Further, the saturated vapor pressure at 20 ° C is preferably from 0.1 kPa to 20 kPa.

When the coating liquid contains a solvent, after the above coating step, Before the first hardening step, it is preferred to provide a drying step of evaporating the solvent for drying. Drying is performed, for example, in the example shown in Fig. 5, and the transparent support 81 having the coating layer is passed through the inside of the drying zone 84. The drying temperature is appropriately selected depending on the type of solvent to be used and the transparent support. Generally 20 The range of °C to 120 °C, but is not limited to this range. Moreover, the temperature of each drying oven can be varied when there are multiple drying ovens. The thickness of the coating layer after drying is preferably from 1 to 30 μm.

Thereby, the product of the transparent support and the coating layer is formed Layer body.

[P2] hardening step

This step is performed on the surface of the coating layer, and the coating layer is hardened by irradiating the active energy ray from the transparent support side in a state where the concave-convex surface (forming surface) of the mold having the desired surface unevenness is pressed. The step of forming a hardened resin layer on the transparent support. Thereby, while the coating layer is hardened, the surface uneven shape of the uneven surface of the mold is transferred to the surface of the coating layer. The mold used here is a roller shape, and is a one manufactured by using a roller-shaped mold base material in the mold manufacturing method already described.

This step, for example, as shown in Fig. 5, for example, by coating The layered body having the coating layer in the region 83 (the dry region 84 during the drying process, the preliminary hardening step to be described later, and the irradiation of the active energy ray irradiation device 86) is used in the transparent layer. The active energy ray irradiation device 86 such as the ultraviolet irradiation device on the side of the support 81 is irradiated with the active energy ray.

First, the coating layer of the laminate in the hardening step The surface is pressed by a pressing device such as a grip roller 88, and the roller 87-shaped mold 87 is pressed. In this state, the active energy ray irradiation device 86 is used, and the active energy ray is irradiated from the side of the transparent support 81 to harden the coating layer 82. . Here, "curing a coating layer" means that the active energy ray included in the coating layer is hard. The resin receives the energy of the active energy ray and produces a hardening reaction. The use of the grip roller is effective in preventing air bubbles from being mixed between the coating layer of the laminate and the mold. The active energy ray irradiation device can use one machine or a plurality of machines.

After the active energy ray is irradiated, the laminated system is on the exit side The pinch roller 89 is a fulcrum and is peeled off from the die 87. The obtained transparent support and the cured coating layer are used as an antiglare layer, and the antiglare film of the present invention can be obtained. The resulting anti-glare film is typically taken up by a film take-up device 90. In this case, for the purpose of protecting the antiglare layer, a protective film made of polyethylene terephthalate or polyethylene is bonded to the surface of the antiglare layer via an adhesive layer having removability. Take it on one side. Here, although the mold to be used is described as a roller shape, a mold other than the shape of the roller may be used. Further, after being peeled off from the mold, additional active energy ray irradiation can be performed.

The active energy line used in this step is included in The type of the active energy ray-curable resin of the coating liquid can be appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays, etc., but among these, ultraviolet rays and electron beams are preferable. From the viewpoint of simple handling, high energy can be obtained, and ultraviolet rays are particularly preferable (as described above, as a photoimprint method, preferably a UV imprint method).

As a light source of ultraviolet rays, for example, low pressure mercury can be used. Lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, electrodeless lamp, metal halide lamp, xenon arc lamp, etc. Further, an ArF excimer laser, a KrF excimer laser, an excimer lamp, or synchrotron radiation may be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a xenon arc lamp, a metal halide lamp or the like is preferably used.

Moreover, as an electronic line, for example from Cockroft-Waltons Electrons having energy of 50 to 1000 keV, preferably 100 to 300 keV, emitted by various electron accelerators of the type, Van de Graaff type, resonant transformer type, insulating core transformation type, linear type, Dynamitron type, high frequency type, etc. line.

When the active energy ray is ultraviolet ray, the cumulative amount of UVA of the ultraviolet ray is preferably 100 mJ/cm ² or more and 3,000 mJ/cm ² or less, more preferably 200 mJ/cm ² or more and 2000 mJ/cm ² or less. Further, the transparent support absorbs ultraviolet rays on the short-wavelength side, and the cumulative light amount of UVV (395 to 445 nm) of ultraviolet rays is preferably 100 mJ/cm ² or more and 3000 mJ/cm ² or less, more preferably 200 mJ/cm ² or more and 2000 mJ. /cm ² or less. When the amount of accumulated light is less than 100 mJ/cm ² , the hardening of the coating layer is insufficient, the hardness of the obtained antiglare layer is lowered, and the uncured resin adheres to the guide roller or the like, which tends to cause contamination of the step. When the cumulative amount of light exceeds 3,000 mJ/cm ² , the heat radiated from the ultraviolet irradiation device may cause shrinkage of the transparent support and wrinkles.

[P3] preliminary hardening step

This step is a step of irradiating the active energy rays to the both end portions in the width direction of the transparent support of the coating layer before the hardening step, and preliminarily hardening the both end portions. Fig. 6 is a schematic view showing a preliminary hardening step. In Fig. 6, the end portion 82b of the coating layer in the width direction (direction perpendicular to the conveying direction) is a region from the specified width of the end portion including the coating layer.

In the preliminary hardening step, by hardening the end region in advance Further, in the end region, the adhesion to the transparent support 81 is further improved, and the step after the hardening step can be prevented, and a part of the cured resin peels off and the step is contaminated. The end region 82b is an end portion of the coating layer 82, for example, a region of 5 mm or more and 50 mm or less.

Irradiating the active energy line with the end region of the coating layer, Referring to Fig. 4 and Fig. 5, for example, for the transparent support 81 having the coating layer 82 passing through the application region 83 (the drying region 84 when dried), the opposite ends respectively provided on the side of the coating layer 82 are used. The active energy ray irradiation device 85 such as an ultraviolet ray irradiation device in the vicinity of the portion is irradiated with an active energy ray. The active energy ray irradiation device 85 may be provided on the transparent support 81 side as long as it can illuminate the end region 82b of the coating layer 82 with an active energy ray.

The type of active energy ray and the light source are the same as the formal hardening step. When the active energy ray is ultraviolet ray, the cumulative amount of UVA of the ultraviolet ray is preferably 10 mJ/cm ² or more and 400 mJ/cm ² or less, more preferably 50 mJ/cm ² or more and 400 mJ/cm ² or less. By the irradiation of 50 mJ/cm ² or more, the deformation of the main hardening step can be effectively prevented. In addition, when the curing reaction exceeds 400 mJ/cm ² , the boundary between the cured portion and the uncured portion is caused by the difference in film thickness and internal stress, and resin peeling may occur.

As described above, the preferred embodiment of the first method for producing the antiglare film of the present invention is mainly described, and the antiglare film of the present invention can also be produced by the second method. In the second method, as described above, the resin solution in which the fine particles are dispersed is applied onto the transparent support, and the fine particles are exposed on the surface of the coating film to form irregular irregularities on the transparent support. In this case, the adjustment is performed. The particle diameter (average particle diameter) of the fine particles to be used may be the film thickness of the coating film or the dispersion state of the fine particles. In particular, the particle size of the fine particles is increased, and the film thickness of the coating film is adjusted to be larger than the particle diameter, whereby scattered light due to fine particles can be reduced, and the ratio R _SCE /R _SCI and the regular reflection light can be reduced. The visual reflectance R _SCE measured by the method. Further, even if the composition and manufacturing conditions of the coating liquid are adjusted so that the fine particles are aggregated to some extent, the ratio R _SCE /R _SCI and the apparent reflectance R _SCE can be reduced.

[Use of Anti-glare Film of the Present Invention]

The anti-glare film of the present invention obtained as described above can be used for an image display device or the like, and is usually used as an identification-side protective film of the identification-side polarizing plate, and is bonded to a polarizing film (that is, disposed on an image display device). surface). Further, as described above, when a polarizing film is used as the transparent support, an anti-glare film of a polarizing film-integrated type can be obtained, and such a polarizing film-integrated anti-glare film can also be used in an image display device. The image display device including the anti-glare film of the present invention has sufficient anti-glare properties at a wide viewing angle, and can well prevent whitening and glare.

Example

Hereinafter, the present invention will be described in more detail by way of examples. In the example, "%" and "parts" of the content to the amount of use are shown, and unless otherwise specified, the basis is based on the weight.

The evaluation method of the mold or the anti-glare film of the following examples is as follows.

[1] Determination of surface shape of anti-glare film

(surface roughness parameter of fine uneven surface)

The surface roughness parameter of the anti-glare film was measured by a surface roughness measuring machine Surftest SJ-301 manufactured by Mitutoyo according to the method of JIS B001. In order to prevent the measurement sample from being warped, the surface opposite to the anti-glare layer of the measurement sample was bonded to the glass substrate using an optically transparent adhesive, and measurement was performed.

[2] Determination of optical properties of anti-glare film

(haze)

The total haze of the anti-glare film is an optically transparent adhesive for the anti-glare film, and the surface opposite to the anti-glare layer of the measurement sample is bonded to the glass substrate, and the anti-glare film is bonded to the glass substrate. The light was incident from the side of the glass substrate, and the measurement was carried out by using a haze meter "HM-150" manufactured by Murakami Color Research Laboratory according to the method of JIS K7136. The surface haze is obtained by determining the internal haze of the anti-glare film according to the following formula: surface haze = total haze - the internal haze is obtained by subtracting the internal haze from the total haze. The internal haze was measured on the antiglare layer of the measurement sample after the measurement of the total haze, and the triethylenesulfonated cellulose film having a haze of almost 0 was attached thereto using glycerin, and then measured in the same manner as the total haze.

(through vividness)

The transmission clarity of the anti-glare film was measured by the image sharpness measuring device "ICM-1DP" manufactured by Suga Tester Co., Ltd. according to the method of JIS K7105. In this case, in order to prevent the sample from being warped, the surface opposite to the anti-glare layer of the measurement sample is bonded to the glass substrate using an optically transparent adhesive. After that, the assay is provided. In this state, light was incident from the glass substrate side, and measurement was performed. Here, the measured values are five optical combs each having a width of a dark portion and a bright portion of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, which are the total values of the respective measured values.

(reflection sharpness measured at an incident angle of light of 45°)

The reflection sharpness of the anti-glare film was measured by the image sharpness measuring device "ICM-1DP" manufactured by Suga Tester Co., Ltd. according to the method of JIS K7105. In order to prevent the sample from being warped, an optically transparent adhesive was used, and the surface opposite to the antiglare layer of the measurement sample was bonded to a black acrylic substrate, and measurement was performed. In this state, light was incident at 45° from the side of the anti-glare layer, and measurement was performed. Here, the measured values are four optical combs each having a width of a dark portion and a bright portion of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, which are the total values of the respective measured values.

(reflection sharpness measured at an incident angle of light of 60°)

The reflection sharpness of the anti-glare film was measured by the image sharpness measuring device "ICM-1DP" manufactured by Suga Tester Co., Ltd. according to the method of JIS K7105. At this time, in order to prevent the sample from being warped, an optically transparent adhesive was used, and the surface opposite to the antiglare layer of the measurement sample was bonded to the black acrylic substrate, and measurement was performed. In this state, light was incident from the side of the anti-glare layer at 60°, and measurement was performed. Here, the measured values are four optical combs each having a width of a dark portion and a bright portion of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, which are the total values of the respective measured values.

(Visual reflectance R _SCI and visual reflectance R _SCE )

The spectroscopic reflectance R _SCI measured by the specular reflection light entering method and the visual reflectance R _SCE measured by the specular reflection light removal method were measured using a spectrophotometer CM2002 (Konica Minolta Sensing System). The reflection from the side opposite to the antiglare layer of the measurement sample was removed. In order to prevent the measurement sample from being warped, an optically transparent adhesive was used, and the surface opposite to the antiglare layer of the measurement sample was attached to a black acrylic plate to provide a measurement.

[3] Evaluation of anti-glare performance of anti-glare film

(visual evaluation of reflection and whitening)

In order to prevent reflection from the back surface of the anti-glare film, the anti-glare film is bonded to the black acrylic plate on the surface opposite to the anti-glare layer of the measurement sample, and visually viewed from the side of the anti-glare layer in the room where the fluorescent lamp is lit. Observation was carried out to visually evaluate the degree of reflection of the fluorescent lamp and the degree of whitening. With respect to the reflection, the degree of reflection when the antiglare film was observed from the front and the degree of reflection when observed from the inclination of 30° were evaluated. The reflection and whitening were evaluated based on the following criteria using three stages of 1 to 3, respectively.

Reflection 1: no reflections observed

2: A little reflection was observed

3: Obviously observed

Albino 1: no whitening observed

2: A little whitening was observed

3: Obviously observed whitening

(evaluation of glare)

The glare was evaluated in the following order. That is, first, a mask having a pattern of unit cells shown in a plan view of Fig. 7 is prepared. In the figure, the unit cell 100 is attached to a transparent substrate to form a key shape having a line width of 10 μm. In the chrome-shielding pattern 101, the portion where the chrome-shielding pattern 101 is not formed becomes the opening portion 102. Here, since the size of the unit cell used is 211 μm × 70 μm (vertical × horizontal in the drawing), the size of the opening is 201 μm × 60 μm (vertical × horizontal in the figure). The unit cells shown in the figure are arranged in a plurality of vertical and horizontal directions to form a photomask.

Thus, as shown in the cross-sectional view of Fig. 8, the mask The chrome-shielding pattern 111 of 113 is placed upward, placed in the light box 115, and the anti-glare film is attached to the sample of the glass plate 117 with the anti-glare layer as the surface of the anti-glare film, and placed on the reticle 113. In the light box 115, a light source 116 is disposed. In this state, the degree of glare was evaluated in a seven-stage sensory state by visual observation from a position 119 at a sample distance of about 30 cm. Level 1 is a state in which glare is completely unrecognizable, level 7 is a state in which severe glare is observed, and level 4 is a state in which a slight glare is observed.

(comparative evaluation)

The polarizing plates on both sides of the front and back sides were peeled off from a commercially available liquid crystal television ("KDL-32EX550" manufactured by SONY Co., Ltd.). In place of the original polarizing plates, the back side and the surface side are each adhered to a polarizing plate "SRDB831E" made by Sumitomo Chemical Co., Ltd., and the absorption axis thereof is aligned with the absorption axis of the original polarizing plate, respectively. The anti-glare film shown in each of the following examples was bonded to the polarizing plate on the display surface side via an adhesive so that the uneven surface became a surface. The liquid crystal television thus obtained was started in a dark room, and the brightness of the black display state and the white display state was measured using a TOPCON (Brightness) brightness meter "BM5A" type, and the contrast was calculated. Here, contrast refers to the ratio of the brightness of the white display state to the brightness of the black display state. As a result, the contrast ratio measured by the anti-glare film in the bonded state is the ratio of the contrast measured in the state in which the anti-glare film is not attached. Said.

[4] Evaluation of the pattern used in the manufacture of anti-glare film

The created graphic data is set to two-tone binary image data, and the color tone is represented by a two-dimensional discrete function g(x, y). The horizontal resolution Δx and Δy of the discrete function g(x, y) are both 2 μm. The obtained two-dimensional function g(x, y) is subjected to discrete Fourier transform to obtain a two-dimensional function G(f _x , f _y ). To square the absolute value of the two-dimensional function G(f _x ,f _y ), calculate the two-dimensional function 二维(f _x ,f _y ) of the two-dimensional power spectrum, and calculate the power spectrum of one of the functions of the distance f from the origin. One-dimensional function Γ(f).

<Example 1>

(Production of mold for manufacturing anti-glare film)

A copper ballard plated person was prepared on the surface of an aluminum roller (JIS A6063) having a diameter of 300 mm. The copper Balad plating is composed of a copper plating layer/a thin silver plating layer/a surface copper plating layer, and the thickness of the entire plating layer is set to be about 200 μm. The copper plating surface is mirror-polished, and a photosensitive resin is applied onto the surface of the copper plating to be polished, and dried to form a photosensitive resin film. Then, the pattern in which the pattern A shown in Fig. 9 is repeatedly arranged is exposed on the photosensitive resin film by laser light to be developed. Exposure and development by laser light were carried out using Laser Stream FX (manufactured by Think Laboratory). As the photosensitive resin film, those containing a positive photosensitive resin are used. Here, the pattern A is formed from a pattern having an irregular luminance distribution by a complex Gaussian function type band pass filter, the aperture ratio is 45.0%, and the one-dimensional power spectrum has a minimum value at a frequency of 0.0195 μm ^-1 . Graphics.

Then, the first etching treatment is performed with a copper chloride solution. at this time The etching amount was set to 4 μm. After the first etching treatment, the photosensitive resin film was removed from the roller, and the second etching treatment was performed again with the copper chloride solution. The etching amount at this time was set to 13 μm. Then, chrome plating was performed to prepare a mold A. At this time, the thickness of the chromium plating was set to 3 μm.

(production of anti-glare film)

Each of the following components was dissolved in ethyl acetate at a solid concentration of 60% to prepare an ultraviolet curable resin composition A which can form a film having a refractive index of 1.53 after curing.

Pentaerythritol triacrylate 60 parts

Polyfunctional urethane acrylate 40 parts

(Reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate)

Diphenyl (2,4,6-trimethoxy benzhydryl) phosphine oxide 5 parts

The ultraviolet curable resin composition A was applied onto a triacetonitrile cellulose (TAC) film having a thickness of 60 μm, and the thickness of the applied coating layer after drying was 5 μm, and dried in a dryer set at 60 ° C. 3 minutes. The dried film was placed on the mold surface of the previously obtained mold A (surface having the surface uneven shape) by a rubber roller so that the dried coating layer became the mold side, and the film was adhered. In this state, light from a high pressure mercury lamp having a strength of 20 mW/cm ^{2 was} irradiated from the TAC film side so that the amount of converted h-line light became 200 mJ/cm ² , and the coating layer was cured to produce an antiglare film. Then, the obtained antiglare film was peeled off from the mold, and a transparent antiglare film A having an antiglare layer on the TAC film was produced.

<Example 2>

A mold B was produced in the same manner as in the mold A of Example 1, except that the amount of etching in the first etching treatment was changed to 3 μm, and an anti-glare film was produced in the same manner as in Example 1 except that the mold B was used instead of the mold A. This anti-glare film is set as the anti-glare film B.

<Example 3>

An anti-glare film was produced in the same manner as in Example 1 except that the mold C was used instead of the mold A except that the etching amount of the first etching treatment was set to 5 μm. This anti-glare film is set as the anti-glare film C.

<Comparative Example 1>

A mold D was produced in the same manner as in the production of the mold A of Example 1, except that the mold A was used instead of the mold A, and an anti-glare film was produced in the same manner as in Example 1 except that the etching amount of the first etching treatment was set to 6 μm. This anti-glare film is set as the anti-glare film D.

<Comparative Example 2>

The pattern in which the pattern B shown in Fig. 10 is repeatedly arranged is exposed by laser light on the photosensitive resin film, the etching amount of the first etching treatment is set to 5 μm, and the etching amount of the second etching treatment is set to 13 μm, and chromium plating is performed. A mold E was produced in the same manner as in the production of the mold A of Example 1, except that the mold E was used instead of the mold A, and an anti-glare film was produced in the same manner as in Example 1. This anti-glare film is set as the anti-glare film E. Here, the pattern B is formed from a pattern having an irregular luminance distribution by a complex Gaussian function type band pass filter, the aperture ratio is 45.0%, and the one-dimensional power spectrum of the pattern is at a frequency of 0.015 μm ^-1 or more. A pattern having a minimum value of 0.05 μm ^-1 or less.

<Comparative Example 3>

The surface of a 300 mm diameter aluminum roller (JIS A5056) was mirror-polished, and the chrome-plated beads TZ-SX-17 (Tongcao (the chrome-plated beads) were placed on the ground aluminum surface using an impact device (manufactured by Fujitsu Fujia Co., Ltd.). by Tosoh) (shares), average particle diameter: 20μm) for an impact with an impact pressure of 0.1MPa (gauge pressure, hereinafter the same), the beads used in an amount 8g / cm ² (surface area of the roller used in an amount per 1cm ^2, the same applies hereinafter) , the surface of the aluminum roller is provided with irregularities. The obtained aluminum roller with irregularities was subjected to electroless nickel plating to prepare a mold F. At this time, the thickness of electroless nickel plating was set to 15 μm. An anti-glare film was produced in the same manner as in Example 1 except that the mold A was used instead of the mold A. This anti-glare film is set as the anti-glare film F.

<Comparative Example 4>

Prepared on the surface of a 200 mm diameter aluminum roller (JIS A5056) to perform copper ballard plating. The copper ballard plating is composed of a copper plating layer/thin silver plating layer/surface copper plating layer, and the entire plating layer has a thickness of about 200 μm. The copper-plated surface was mirror-polished, and the zirconia bead TZ-SX-17 (made by Tosoh) was produced on the polished surface by using an impact device (manufactured by Seiko Co., Ltd.). average particle diameter: 20μm) with an impact pressure of 0.05MPa (gauge pressure, hereinafter the same), the beads used in an amount 6g / cm ² for shock imparting irregularities on the aluminum surface of the roll. The obtained copper-plated aluminum roller with irregularities was subjected to chromium plating to prepare a mold G. At this time, the thickness of the chromium plating was set to 6 μm. An anti-glare film was produced in the same manner as in Example 1 except that the mold A was used instead of the mold A. This anti-glare film is set as the anti-glare film G.

[One-dimensional work of the graphics used in the manufacture of each mold Rate spectrum

Fig. 11 is a view corresponding to a power spectrum Γ(f) obtained by discrete Fourier transform of the patterns A and B used for the production of the antiglare films A to E (Examples 1 to 3 and Comparative Examples 1 and 2).

〔Evaluation results〕

The results of the evaluation of the above antiglare film in the above examples and comparative examples are shown in Table 1.

The anti-glare films A to C (Examples 1 to 3) satisfying the requirements of the present invention, although low in haze, have excellent anti-glare properties, sufficient whitening and glare even if the viewing angle is front or oblique. The inhibitory effect. On the other hand, the anti-glare film D (Comparative Example 1) produced whitening. The anti-glare film E (Comparative Example 2) had insufficient anti-glare property when viewed from an oblique direction. The anti-glare film F (Comparative Example 3) is susceptible to glare. Anti-glare film G (Comparative Example 4) is from oblique direction Insufficient anti-glare properties during observation.

Industrial utilization possibility

The anti-glare film of the present invention can be used for an image display device such as a liquid crystal display.

12 ‧ ‧ integral ball

13‧‧‧Light source

14‧‧‧Density reflectance measurement samples for anti-glare film

Claims (4)

An anti-glare film comprising a transparent support and an anti-glare layer having a fine uneven surface formed thereon; the anti-glare film is characterized by a total haze of 0.1% or more and 3% or less; and a surface haze of 0.1% or more and 2% or less; the root mean square roughness Rq (0.08) when the cutting length is 0.08 mm is 0.01 μm or more and 0.05 μm or less; and the root mean square roughness Rq when the cutting length is 0.25 mm. (0.25) is 0.05 μm or more and 0.1 μm or less; the root mean square roughness Rq (0.8) when measuring with a cut length of 0.8 mm is 0.07 μm or more and 0.12 μm or less; and the mean square when the cut length is 2.5 mm The root roughness Rq (2.5) is 0.08 μm or more and 0.15 μm or less; the ratio of the visual reflectance R _SCI measured by the specular reflection light entering method to the apparent reflectance R _SCE measured by the specular reflection light removal method R _SCE /R _SCI is 0.1 or less. The anti-glare film according to the first aspect of the invention, wherein the average length Sm (0.25) when the measurement is performed at a cut length of 0.25 mm is 90 μm or more and 160 μm or less; and the average length Sm when the cut length is 0.8 mm. (0.8) is 100 μm or more and 300 μm or less; and the average length Sm (2.5) when measured by cutting the length of 2.5 mm is 200 μm or more and 400 μm or less. An anti-glare film as described in claim 1 or 2, wherein The transparency and the Tc of the five kinds of optical combs with the width of the dark portion and the bright portion are 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, respectively, and the Tc is 375% or more; the widths of the dark portion and the bright portion are respectively Four kinds of optical combs of 0.25mm, 0.5mm, 1.0mm and 2.0mm, the reflection sharpness and Rc(45) measured by the incident angle of light of 45° are 180% or less; the widths of the dark portion and the bright portion are respectively Four kinds of optical combs of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm have a reflection sharpness and Rc (60) of 240% or less as measured by an incident angle of light of 60°. The anti-glare film according to any one of the items 1 to 3, wherein the specular reflectance R _SCE measured by the specular reflection light removal method is 0.5% or less.