TW201534989A - Anti-glare film - Google Patents

Abstract

This invention provides an anti-glare film which exhibits excellent anti-glare characteristics over a wide viewing angle even in a low haze condition, and is capable of sufficiently suppressing the occurrence of fading and glaring when used in an image display device. The anti-glare device of this invention has a transparent supporting member and an anti-glare layer formed thereon, the anti-glare layer having fine relieves on the surface thereof, a total haze of 0.1% or more to 3% or less, a surface haze of 0.1% or more to 2% or less. The anti-glare film has a ratio of reflection rate R(30) to reflection rate R(40) of 0.00001 or higher to 0.0025 or lower, the reflection rate R (30) denotes a reflection rate of reflection light reflected at a reflection angle of 30 DEG with respect to an incident light which is incident at an incident angle of 30 DEG, and the reflection rate R(40) denotes a reflection rate of reflection light reflected at a reflection angle of 40 DEG with respect to an incident light which is incident at an incident angle of 30 DEG; the film also has a ratio of intensity of the power spectrum of a complex amplitude at two specific special frequencies within a predetermined range, the complex amplitude being calculated from the elevation of the surface relieves and a refraction rate of the anti-glare layer.

Description

Anti-glare film

The present invention relates to an antiglare film excellent in antiglare property.

Image display devices such as liquid crystal displays and plasma display panels, Brown tube (Cathode ray tube: CRT) displays, and organic electroluminescence (EL) displays are designed to avoid the glare of external light on the display surface. Since the deterioration occurs, an anti-glare film is disposed on the display surface.

As for the anti-glare film, a transparent film having a surface uneven shape is mainly reviewed. The anti-glare film reduces external reflection light (external scattered light) by surface unevenness to reduce reflection glare to exhibit anti-glare property. However, when the external scattered light is strong, the display surface of the image display device may be whitened or the display may become a turbid color, that is, a so-called "whitening" occurs. Further, the surface of the image display device and the surface of the anti-glare film are uneven, and a bright portion of the cloth is generated and is difficult to see, that is, so-called "glare" occurs. From the above, it is expected that the anti-glare film ensures excellent anti-glare properties and sufficiently prevents the occurrence of "whitening" or "glare".

In the anti-glare film, for example, Patent Document 1 discloses an anti-glare film which is not disposed when placed on a high-definition image display device. An anti-glare film which is glare-proof and sufficiently prevents the occurrence of whitening, has a fine surface uneven shape formed on a transparent substrate, and an average length PSm in an arbitrary cross-sectional curve of the surface uneven shape is 12 μm or less. The ratio Pa/PSm of the arithmetic mean height Pa to the average length PSm is 0.005 or more and 0.012 or less, and the surface unevenness is a ratio of a surface having an inclination angle of 2 or less of 50% or less and a ratio of the surface having the inclination angle of 6 or less is 90. More than %.

The anti-glare film disclosed in Patent Document 1 can effectively suppress the glare by eliminating the surface unevenness having a period of about 50 μm which is likely to cause glare, by minimizing the average length PSm in an arbitrary cross-sectional curve. However, if the anti-glare film disclosed in Patent Document 1 is intended to have a smaller haze (if it is desired to have a low haze), the anti-glare may be observed when the display surface of the image display device in which the anti-glare film is disposed is obliquely observed. Sex will decrease. Therefore, the anti-glare film disclosed in Patent Document 1 still needs to be improved in terms of the anti-glare property of a wide viewing angle.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-187952

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

The present inventors conducted an in-depth review in order to solve the above problems, and as a result, completed the present invention. That is, the present invention provides the following.

An anti-glare film comprising a transparent support and an anti-glare layer having a fine surface uneven shape formed thereon, wherein the total haze is 0.1% or more and 3% or less, and the surface haze is 0.1% or more. 2% or less, for the light incident at an incident angle of 30°, the ratio R(40)/R(30) of the reflectance R(30) of the reflection angle of 30° to the reflectance R(40) of the reflection angle of 40° is 0.00001 or more and 0.0025 or less, the power spectrum of the composite amplitude obtained by the power spectrum algorithm described below satisfies any of the following conditions (1) to (3).

(1) The ratio of the spatial frequency of the power spectrum of 0.002 μm ^{-1 to} the intensity H (0.002) and the spatial frequency of the power spectrum of 0.01 μm ^{-1 to} the intensity H (0.01) H (0.01) / H (0.002) is 0.02 or more 0.6 or less; (2) the spatial frequency power spectrum of the intensity of H 0.002μm ^-1 (0.002), and spatial frequency power spectrum of the intensity H (0.02) ratio of 0.02μm ^-1 H (0.02) / H (0.002 ) 0.005 less than 0.05; and (3) the spatial frequency power spectrum of the intensity of H 0.002μm ^-1 (0.002), and spatial frequency power spectrum of the intensity H (0.04) ratio of 0.04μm ^-1 H (0.04) / H (0.002 ) is 0.0005 or more and 0.01 or less.

<Power Spectrum Algorithm>

(A) determining the virtual plane from the average of the elevations of the aforementioned surface relief shapes (B) determining a lowest elevation point including the lowest point of the surface relief shape and parallel to the virtual plane of the average surface, and a highest elevation point including the surface relief shape, and parallel to the average surface The highest elevation surface of the virtual plane; (C) the plane wave having a wavelength of 550 nm emitted from the highest elevation plane from the main normal direction perpendicular to the minimum elevation plane, and the elevation and anti-glare from the surface relief shape are obtained. The refractive index of the layer calculates the power spectrum of the composite amplitude at the composite amplitude of the aforementioned highest elevation surface.

Further, in the anti-glare film of the present invention, it is preferable to use the penetration clarity measured by five types of optical combs 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, respectively. And Tc is 375% or more, and the sum of the reflection resolutions measured by the light incident angle of 45° is used for the four types of optical combs having the widths of the dark portion and the bright portion of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm, respectively. ) is 180% or less, and the sum of the reflection resolutions measured by the light incident angle of 60° using four kinds of optical combs of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm in the dark portion and the bright portion, respectively, Rc (60) It is 240% or less.

According to the present invention, it is possible to provide an anti-glare film which has sufficient anti-glare property even at a wide viewing angle even when it has a low haze, and can sufficiently suppress the occurrence of whitening and glare when disposed in an image display device.

1‧‧‧Anti-glare film

2‧‧‧Micro bumps

3‧‧‧film projection surface

5‧‧‧Main normal direction

10‧‧‧Anti-glare film

11‧‧‧ incident angle of light (30°)

12‧‧‧Reflected light at a regular reflection angle (30°)

15‧‧‧Reflecting angle of reflection angle θ

20‧‧‧ normal

40‧‧‧Mold base for mold

41‧‧‧The surface of the substrate for the mold is plated

45‧‧‧Unmasked area

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

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

50‧‧‧Photosensitive resin film

51‧‧‧ exposed areas

52‧‧‧Unexposed areas

60‧‧‧ mask

70‧‧‧ Surface embossed surface after chrome plating

71‧‧‧chrome plating

80‧‧‧Send rolls

81‧‧‧ Transparent support

82‧‧‧ Coating layer

82b‧‧‧End area

83‧‧‧ Coating area

84‧‧‧Drying area

86‧‧‧Active energy line irradiation device

87‧‧‧Roll mold

88, 89‧‧‧ pinch roller

90‧‧‧ Film winding device

101‧‧‧ Transparent support

102‧‧‧Anti-glare layer

103‧‧‧ Lowest elevation surface

104‧‧‧highest elevation

110‧‧‧Anti-glare film

111‧‧‧Chromium shade pattern

113‧‧‧Photomask

115‧‧‧Lightbox

116‧‧‧Light source

117‧‧‧ glass plate

119‧‧‧Approximately 30cm from the sample

Θ‧‧‧incident angle, reflection angle

Fig. 1 is a view for simply explaining the reflectance of the anti-glare film at each angle when light is incident from the side of the anti-glare layer at an incident angle of 30°.

Fig. 2 is a view for simply explaining the elevation of the surface uneven shape of the antiglare film.

Fig. 3 is a view for simply explaining the relationship between the elevation of the surface uneven shape of the anti-glare film and the coordinates (x, y).

Fig. 4 is a view for simply explaining the relationship between the elevation h(x, y) of the surface unevenness of the anti-glare film and the elevation reference surface and the highest elevation surface.

Fig. 5 is a view showing a state in which the surface unevenness of the surface of the anti-glare film is dispersibly obtained.

Fig. 6 is a view showing a state in which a one-dimensional power spectrum is calculated from a two-dimensional power spectrum of a composite amplitude calculated from the elevation of the surface concavo-convex shape obtained as a discrete function.

Fig. 7 is a graph showing the one-dimensional power spectrum H(f) of the composite amplitude calculated from the elevation of the surface uneven shape of the anti-glare film for the spatial frequency f.

Fig. 8 (a) to (e) are schematic views showing a preferred example of the method of manufacturing the mold (first half).

Fig. 9 (a) to (d) are schematic views showing a preferred example of the method of manufacturing the mold (the latter half).

Fig. 10 is a view showing a preferred example of a manufacturing apparatus used in the method for producing an anti-glare film of the present invention.

Fig. 11 is a schematic view showing a suitable preliminary hardening step in the method for producing an antiglare film of the present invention.

Figure 12 is a schematic diagram of a unit cell for glare evaluation.

Figure 13 is a schematic diagram of a glare evaluation device.

Fig. 14 is a view showing a part of the pattern A used in Examples 1 to 3 and Comparative Example 1.

Fig. 15 is a view showing a part of the pattern B used in the fourth embodiment.

Fig. 16 is a view showing a part of the pattern C used in the fifth embodiment.

Fig. 17 is a view showing a part of the pattern D used in Comparative Example 2.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings, and the dimensions and the like shown in the drawings are arbitrarily set for convenience of viewing.

The anti-glare film of the present invention is a ratio of a reflectance R (30) of a reflection angle of 30° and a reflectance R (40) of a reflection angle of 40° to a light incident at an incident angle of 30° R(40)/R. (30) of 0.00001 or less than 0.0025, by the improved spatial power spectrum obtained from the power spectrum of the frequency intensity 0.002μm ^-1, the spatial frequency of 0.01μm ^-1, 0.02μm ^-1, and the intensity of 0.04μm ^-1 The ratio is the aforementioned range.

First, regarding the antiglare film of the present invention, a method for determining the power spectrum of the reflectance ratio R(40)/R(30) and the composite amplitude will be described.

[reflectance ratio]

Explain how to calculate the reflectance ratio R(40)/R(30).

Fig. 1 is a schematic view (perspective view) for explaining the reflectance at each angle when light is incident at an incident angle of 30° from the side of the antiglare layer of the antiglare film of the present invention, schematically showing Light from the side of the anti-glare layer of the anti-glare film 10 Injection direction and reflection direction. In this figure, the incident light 11 incident on the anti-glare layer side of the anti-glare film 10 from the normal line 20 at an angle of 30° causes the reflection angle to be 30°, that is, the reflected light in the regular reflection direction 12 The reflectance (that is, the regular reflectance) is set to R (30). Further, the reflected light having an arbitrary reflection angle θ is indicated by reference numeral 15 , and the directions 12 and 15 of the reflected light when the reflectance is measured are in the surface 30 including the direction 11 of the incident light and the normal line 20 . Further, the reflectance in the direction of the reflection angle of 40° is set to R (40).

When the reflectance of the anti-glare film is measured, it is necessary to accurately measure the reflectance of 0.001% or less. Therefore, it is effective to use a detector having a wide dynamic range, and such a commercially available optical power meter or the like can be applied. An orifice was provided in front of the detector of the optical power meter, and the measurement was performed using a goniophotometer whose angle of the anti-glare film was 2°. The incident light at this time can use visible light of 380 to 780 nm. The light source for measurement is a collimator using light emitted from a light source such as a halogen lamp, and a parallel light having a monochromatic light source such as a laser may be used. When the reflectance is obtained for the transparent anti-glare film having a smooth back surface, the reflection from the back surface of the anti-glare film affects the measured value, and such influence must be avoided. Therefore, when the reflectance is measured, the smooth surface of the anti-glare film to be measured is adhered to the black acrylic resin sheet by the adhesive, or by using a liquid such as water or glycerin. With its optical contact, it is possible to measure only the reflectance of the outermost surface of the anti-glare film.

In the anti-glare film of the present invention, when the light is incident at an incident angle of 30°, the reflectance in the direction of the reflection angle of 30°, that is, the reflectance in the direction of the reflection angle of the positive reflectance R (30) of 40°. The ratio (40)/R(30) of (40) is 0.00001 or more and 0.0025 or less. The configuration has a ratio R(40)/R(30) lower than 0.00001 The image display device of the anti-glare film is insufficient in anti-glare property. On the other hand, an image display device in which an anti-glare film having a ratio of R (40) / R (30) higher than 0.0025 is disposed is liable to be whitened. In order to obtain an image display device having excellent anti-glare properties and sufficiently preventing the occurrence of whitening, the ratio R(40)/R(30) of the anti-glare film is preferably 0.00005 or more and 0.001 or less.

[Power spectrum of composite amplitude]

The power spectrum of the composite amplitude calculated from the elevation of the surface uneven shape of the anti-glare film and the refractive index of the anti-glare layer will be described. Fig. 2 is a cross-sectional view schematically showing an anti-glare film of the present invention. As shown in FIG. 2, the one-sided 様 (anti-glare film 1) of the anti-glare film of the present invention has a transparent support 101 and an anti-glare layer 102 formed thereon, and the anti-glare layer 102 is provided on the transparent support 101. The opposite side has a surface uneven shape of the fine unevenness 2.

Here, the "elevation of the surface uneven shape" as used in the present invention means the main normal direction 5 of the anti-glare film of the present invention at any point P on the surface uneven shape and the lowest elevation surface (the normal of the aforementioned lowest elevation surface) The straight line distance of the direction). The height of any point on the virtual minimum surface height is 0 μm, and is the reference for determining the elevation of an arbitrary point on the surface uneven shape. In FIG. 2, the lowest elevation surface 103 is indicated.

Actually, the anti-glare film is schematically shown in Fig. 3, and has an anti-glare layer having a fine surface uneven shape on a two-dimensional plane. Therefore, the elevation of the surface concavo-convex shape is as shown in Fig. 3. When the rectangular coordinate in the film plane is represented by (x, y), it can be expressed as a two-dimensional function h(x, y) of the coordinate (x, y).

The elevation of the surface concavo-convex shape can be obtained by three-dimensional information on the surface shape measured by a device such as a conjugate focal length microscope, an interference microscope, or an atomic force microscope (AFM). The horizontal resolution required for the measuring machine is preferably 5 μm or less, more preferably 2 μm or less, and the vertical resolution required for the measuring machine is preferably 0.1 μm or less, more preferably 0.01 μm or less. A non-contact three-dimensional surface shape/roughness measuring machine suitable for the measurement includes a New View 5000 series (manufactured by Zygo Corporation), a three-dimensional microscope PLμ 2300 (manufactured by Sensofar Co., Ltd.), and the like. The resolution of the power spectrum for measuring the area height is required to be 0.002 μm ^-1 or less, so it is preferably at least 500 μm × 500 μm, more preferably 750 μm × 750 μm or more.

Fig. 4 is a view schematically showing the relationship between the elevation h(x, y) of the surface uneven shape, the lowest elevation surface 103, and the highest elevation surface 104. Here, the elevation of the highest elevation surface 104 is set to H _max (μm). Moreover, this fourth figure shows a cross-sectional structure including a point at which the elevation of the anti-glare film is the highest and a point at which the elevation is the lowest.

The optical path length d(x, y) between the lowest elevation surface 103 of the coordinate (x, y) and the highest elevation surface 104 can be expressed by the equation (1) using the two-dimensional function h(x, y) of the elevation. .

d ( x , y )= n _AG h ( x , y )+ n _air [ h _max - h ( x , y )]...(1)

Here, n _AG is the refractive index of the antiglare layer, and n _air is the refractive index of air. Further, if the refractive index n _{air of air is} approximately 1, the formula (1) can be expressed by the formula (2).

d ( x , y )=( n _AG -1) h ( x , y )+ h _max (2)

Next, a plane wave of a single wavelength λ propagating in the main normal direction 5 (perpendicular to the main normal direction of the lowest elevation plane) is incident from the transparent support side (the lowest elevation surface 103 side) toward the anti-glare layer side (the highest When the elevation surface 104 side is emitted, the composite amplitude of the plane wave will be described. The composite amplitude refers to the portion of the fluctuation that does not include the time factor when expressed as a composite. The amplitude of a plane wave of a single wavelength λ can generally be represented by a combination of the following formula (3).

Here, in the formula (3), A is the maximum amplitude of the plane wave, π is the pi, i is the imaginary unit, z is the coordinate of the z-axis direction (the main normal direction 5) (the optical path length from the origin), ω For angular frequency, t is time, Is the initial phase.

The term that does not depend on time in equation (3) is the composite amplitude. Therefore, for the composite amplitude in the coordinates (x, y) of the highest elevation surface 104 of the plane wave represented by the equation (3) (x, y), which is a term that does not depend on the time of the equation (3), can be expressed by the equation (4) in which z is substituted into the optical path length d (x, y) or less.

Furthermore, in equation (4), the maximum amplitude A and initial phase of the plane wave In the present invention, which is not dependent on the coordinates (x, y) and the distribution of the surface unevenness of the coordinates (x, y), since it is constant, the following is A=1 and =0. Also, if substituting the above formula (2), the composite amplitude (x, y) can be expressed by the following formula (5). Further, in the present invention, λ = 550 nm is used as a reference.

Next, a method of determining the power spectrum of the composite amplitude will be described. First, from the two-dimensional function expressed by equation (5) (x, y), the two-dimensional function Ψ(f _x , f _y ) is obtained by the two-dimensional Fourier transform defined by the equation (6).

Here, f _x and f _y are frequencies in the x direction and the y direction, respectively, and have a reciprocal dimension of length. Can be obtained by the two-dimensional function Ψ (f _x, f _y) of the absolute value squared, obtaining a two-dimensional power spectrum H (f _x, f _y) by the formula (7).

H ( f _x , f _y )=|Ψ( f _x , f _y )| ² (1)

The two-dimensional power spectrum H(f _x , f _y ) represents a spatial frequency distribution of the composite amplitude calculated from the elevation of the surface uneven shape of the anti-glare film. Since the anti-glare film is isotropic, the two-dimensional function H(f _x , f _y ) representing the two-dimensional power spectrum of the composite amplitude can be obtained by relying on the distance function f from the origin (0, 0). )To represent. Next, a method of obtaining a one-dimensional function H(f) from the two-dimensional function H(f _x , f _y ) is disclosed. First, the two-dimensional function H(f _x , f _y ) of the two-dimensional power spectrum of the composite amplitude is represented by a polar coordinate according to the equation (8).

H ( f _x , f _y )= H ( f cos θ, f sin θ)... (8)

Here, the angle in the θ-system Fourier space. The one-dimensional function H(f) can be obtained by calculating the rotation average of the two-dimensional function H (fcos θ, fsin θ) expressed by the polar coordinates according to the equation (9). One dimensional function H(f) is obtained from the rotational average of the two-dimensional function H(f _x , f _y ) of the two-dimensional power spectrum of the composite amplitude, hereinafter also referred to as the one-dimensional power spectrum H(f).

One-dimensional power based composite amplitude characteristics of the antiglare film of the present invention is calculated from the elevation of the surface irregularities of the spectrum H (f) of the spatial frequency intensity 0.002μm H (0.002) ^-1 in the spatial frequency 0.01μm ^-1 The ratio of the intensity H (0.01) to the ratio H (0.01) / H (0.002), the intensity H (0.002) and the spatial frequency 0.02 μm ^-1 of the intensity H (0.02) H (0.02) / H (0.002), And the ratio H (0.04) / H (0.002) of the intensity H (0.002) and the intensity H (0.04) in the spatial frequency of 0.04 μm ^-1 is within the above specific range.

Hereinafter, the two-dimensional power spectrum for calculating the composite amplitude calculated from the elevation of the surface uneven shape of the anti-glare film will be further specifically described. method. The three-dimensional information of the surface shape actually measured by the above-described conjugate focal length microscope, interference microscope, atomic force microscope, or the like is a value of general dispersion, that is, an elevation corresponding to a plurality of measurement points. Fig. 5 is a view showing a state in which the discreteness is obtained as a function of the function h(x, y) indicating the elevation. As shown in Fig. 5, the right-angled coordinates in the plane of the film are represented by (x, y), and on the film projection surface 3, the line divided by Δx in the x-axis direction and the y-axis are indicated by broken lines. In the actual measurement, the elevation of the surface unevenness is obtained as the discrete elevation value of each area Δx × Δy divided by the broken lines on the film projection surface 3 in the actual measurement.

The value of the obtained elevation is determined by the measurement range and Δx and Δy. As shown in Fig. 5, the measurement range in the x-axis direction is X = M Δx, and the measurement range in the y-axis direction is taken as Y = When N Δy, the number of the obtained elevation values is M × N.

As shown in Fig. 5, the coordinates of the eye point A on the film projection surface 3 are (m Δx, n Δy) [here, m is 0 or more and M-1 or less, and n is 0 or more and N-1 or less. When the angle P corresponding to the film surface on the eye point A is expressed as h (m Δx, n Δy).

Here, the measurement intervals Δx and Δy depend on the horizontal resolution of the measuring device, and in order to evaluate the surface unevenness with good precision, it is preferable that both Δx and Δy are 5 μm or less, and more preferably 2 μm or less. Further, the measurement ranges X and Y are preferably 500 μm or more, and more preferably 750 μm or more, as described above.

In such an actual measurement, the function indicating the elevation of the surface concavo-convex shape obtains a discrete function h(x, y) having M × N values. Therefore, the composite amplitude ψ(x, y) obtained from the two-dimensional function h(x, y) of the surface concavo-convex shape by the equation (5) is also obtained as a discrete function, whereby the composite amplitude ψ(x, y) is obtained. The two-dimensional function Ψ(f _x , f _y ) obtained by the two-dimensional Fourier transform is also obtained as a discrete function by the method of equation (10) by the discrete Fourier transform calculated by the discreteness of equation (6).

Here, j in the formula (10) is an integer of -M/2 or more and M/2 or less, and k is an integer of -N/2 or more and N/2 or less. Further, Δf _x and Δf _y are frequency intervals in the x direction and the y direction, respectively, and are defined by the equations (11) and (12).

The two-dimensional power spectrum H(f _x , f _y ) is obtained by the square of the absolute value of the discrete function Ψ(f _x , f _y ) obtained by the equation (10), as shown in the equation (13). .

The two-dimensional power spectrum H(f _x , f _y ) obtained as a discrete function also represents the spatial frequency distribution of the composite amplitude calculated from the elevation of the surface concavo-convex shape of the anti-glare film. Moreover, since the anti-glare film is isotropic, the two-dimensional discrete function H(f _x , f _y ) indicating the two-dimensional power spectrum of the composite amplitude may also depend only on one of the distances f from the origin (0, 0). The dimensional discrete function H(f) is represented. When the one-dimensional discrete function H(f) is obtained from the two-dimensional discrete function H(f _x , f _y ), the rotation average may be calculated in the same manner as in the equation (9). The discrete rotation average of the two-dimensional discrete function H(f _x , f _y ) can be calculated by equation (14). The power function algorithm calculates one of the power spectrums represented by the one-dimensional discrete function H(f).

Here, in the case of M≧N, 1 is an integer of 0 or more and N/2 or less, and when M<N, 1 is an integer of 0 or more and M/2 or less. Further, Δf is the interval between the distances from the origin, and Δf = (Δf _x + Δf _y )/2. Further, θ(x) is a Heaviside function defined by the formula (15), and the distance from the origin in the f _jk system (j, k) is calculated by the equation (16).

The calculation shown in the equation (14) will be explained with reference to Fig. 6. The function Θ(f _jk -(1-1/2) Δf) is 0 when f _{jk is} less than (1-1/2) Δf, and is 1 when (1-1/2) Δf or more. The function Θ(f _jk -(1+1/2) Δf) is 0 when f _{jk is} less than (1+1/2) Δf, and is 1 when (1+1/2) Δf or more. Therefore, Θ(f _jk -(1-1/2)Δf)-Θ(f _jk -(1+1/2)Δf) of the formula (14) is only (1-1/2) at f _jk When Δf or more and less than (1-1/2) Δf, it becomes 1 and otherwise becomes 0. Here, in the frequency space, f _jk is the distance from the origin O (f _x =0, f _y =0), and therefore, the denominator of the equation (14) calculates the distance f _jk from the origin O as ( 1-1/2) The number of points (the black dots in Fig. 6) of Δf or more and less than (1 + 1/2) Δf. Further, the molecular system of the formula (14) calculates H (f) at a point where the distance f _jk from the origin O is (1-1/2) Δf or more and does not reach (1 + 1/2) Δf. The total value of _x , f _y ) (the total value of H(f _x , f _y ) in the black dot in Fig. 6).

In general, the one-dimensional power spectrum obtained by the aforementioned method contains noise in the measurement. Here, in order to obtain the one-dimensional power spectrum, in order to remove the influence of the noise, it is preferable to measure the elevation of the surface unevenness shape at the plurality of portions on the anti-glare film, and to obtain the elevation of the surface irregularities of the respective surfaces. The average of the one-dimensional power spectrum is used as the one-dimensional power spectrum H(f). The number of the measurement points of the surface unevenness on the anti-glare film is preferably 3 or more, more preferably 5 or more.

Figure 7 is a graph showing the H(f) of the one-dimensional power spectrum of the composite amplitude calculated from the elevation of the surface relief shape thus obtained. The one-dimensional power spectrum H(f) of Fig. 7 is obtained by averaging one-dimensional power spectra obtained from the elevations of the surface irregularities at five different points on the anti-glare film.

Wherein the antiglare film of the present invention the composite amplitude calculated by the elevation of the surface irregularities of the one-dimensional power spectrum H (f) of the spatial frequency intensity 0.002μm H (0.002) ^-1 in the spatial frequency 0.01μm ^-1 The ratio of the intensity H (0.01) to H (0.01) / H (0.002) is 0.02 or more and 0.6 or less, and the ratio of the intensity H (0.002) to the intensity H (0.02) of the spatial frequency of 0.02 μm ^-1 is H (0.02) / H ( 0.002) is 0.005 or more and 0.05 or less, and the ratio H (0.04) / H (0.002) of the intensity H (0.02) of the intensity H (0.002) and the spatial frequency of 0.04 μm ^-1 is 0.0005 or more and 0.01 or less. Here, since the one-dimensional power spectrum H(f) is obtained as a discrete function, in order to obtain the intensity H(f ₁ ) in the specific spatial frequency f ₁ , interpolation is performed in the manner shown in the equation (17). And the calculation can be.

In the anti-glare film of the present invention, when the intensity ratio in the specific spatial frequency is set to a predetermined range, the effect of whitening and glare is favorably prevented by the synergistic effect of the haze and the reflectance ratio described later. Excellent anti-glare properties. In order to further exhibit this effect, the ratio of H (0.01) / H (0.002) is preferably 0.02 or more and 0.6 or less, and more preferably 0.03 or more and 0.3 or less. Similarly, the ratio of H (0.02) / H (0.002) is preferably 0.005 or more and 0.05 or less, more preferably 0.007 or more and 0.04 or less, and more preferably 0.005 or more and 0.9 or more of H (0.04) / H (0.002). It is more preferably 0.001 or more and 0.005 or less.

When the ratio H (0.01) / H (0.002) is lower than the above range, it contributes to the periodicity of about 100 μm (corresponding to a spatial frequency of 0.01 μm ^-1 ) for the antiglare effect when the antiglare film is observed at an inclination of 30 or more. The optical fluctuation becomes small, and the anti-glare property becomes insufficient. When the ratio H (0.01) / H (0.002) is higher than the above range, the periodic optical fluctuation of about 100 μm becomes excessively large, and the surface unevenness of the antiglare film becomes rough, and the haze tends to increase, which is not preferable.

When the ratio H(0.02)/H(0.002) is lower than the above range, it is about 50 μm (corresponding to a spatial frequency of 0.02 μm ^-1 ) which is useful for observing the antiglare film from the inclination (10° to 30°). The periodic optical fluctuations become smaller, and the anti-glare property becomes insufficient. When the ratio H (0.02) / H (0.002) is higher than the above range, the periodic optical fluctuation of about 50 μm becomes excessively large, and glare is generated.

When the ratio H(0.04)/H(0.002) is lower than the above range, it is about 25 μm (corresponding to a spatial frequency of 0.04 μm ^-1 ) which is useful for observing the antiglare effect from the front surface (0° to 10°). The periodic optical variation is small, and the anti-glare property is insufficient. When H (0.04) / H (0.002) is higher than the above range, scattering due to optical fluctuation of a short period of about 25 μm becomes strong, and whitening easily occurs.

[Total haze, surface haze]

The anti-glare film of the present invention has an anti-glare property and prevents whitening. Therefore, the total haze of the normal incident light is in the range of 0.1% or more and 3% or less, and the surface haze 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 the method shown in JIS K7136. An image display device equipped with an anti-glare film having a total haze or a surface haze of less than 0.1% is not preferable because sufficient anti-glare property is not exhibited. Further, when the total haze is higher than 3% or the surface haze is higher than 2%, the anti-glare film is not preferable because the image display device in which the anti-glare film is disposed is whitened. Moreover, the image display device is also There is a bad situation in which the contrast becomes insufficient.

The internal haze obtained by subtracting the surface haze from the total haze is preferably as low as possible. An image display device equipped with an anti-glare film having an internal haze of more than 2.5% has a tendency to be lowered in contrast.

[Transmission resolution Tc, reflection resolution Rc (45), and reflection resolution Rc (60)]

The antiglare film of the present invention is preferably one in which the sum of penetration sharpness Tc obtained by the following measurement conditions is 375% or more. The sum of the penetration sharpness Tc is calculated by measuring the image sharpness in accordance with the method of JIS K 7105 and using an optical comb of a predetermined width, and calculating the total. Specifically, five types 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 to measure image sharpness, and the total is obtained as Tc. When the anti-glare film having a Tc of less than 375% is disposed in a higher-definition image display device, glare sometimes becomes apt to occur. The upper limit of Tc is selected from the range of 500% or less of the maximum value. However, if the Tc is too high, an image display device which is easily degraded from the front side is obtained, and is preferably, for example, 450% or less.

The anti-glare film of the present invention preferably has a reflection resolution Rc (45) measured by incident light having an incident angle of 45° of 180% or less. The reflection sharpness Rc (45) is the same as the above Tc, and is measured by the method according to JIS K 7105. Four types of the optical combs are 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. The optical comb measures the image sharpness separately, and finds the total as Rc (45). When Rc (45) is 180% or less, the image display device in which the anti-glare film is disposed is anti-glare from the front and the oblique view. Sex is better, so it is better. The lower limit of Rc (45) is not particularly limited, but is preferably 80% or more in order to satisfactorily suppress the occurrence of whitening and glare.

The anti-glare film of the present invention preferably has a reflection resolution Rc (60) of 240% or less as measured by incident light having an incident angle of 60°. The reflection sharpness Rc (60) is measured by a method according to JIS K 7105 in the same manner as the reflection sharpness Rc (45) except that the incident angle is changed. When Rc (60) is 240% or less, the image display device in which the anti-glare film is disposed is preferable because the anti-glare property at the time of oblique observation is further improved. The lower limit of Rc (60) is not particularly limited, but is preferably 150% or more in order to suppress whitening and glare more satisfactorily.

[Method for manufacturing anti-glare film]

The antiglare film of the present invention is produced, for example, in the following manner. In the first method, a mold for forming a fine unevenness having a surface unevenness shape according to a predetermined pattern is formed, 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 the body from the mold. In the second method, a composition containing fine particles, a resin (binder) and a solvent, and the fine particles are dispersed in a resin solution, and the composition is applied onto a transparent support, and dried as needed to make A method of hardening a formed coating film (a coating film containing fine particles). In the second method, the coating film thickness and the fine particle aggregation state are adjusted by the composition of the composition and the drying conditions of the coating film, etc., so that the fine particles are exposed on the surface of the coating film, and the transparent support is formed on the transparent support. Bump. 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 for producing an anti-glare film of the present invention will be described in detail.

In order to form the antiglare layer having the surface unevenness shape as described above with good precision, it is important to prepare a fine unevenness forming mold (hereinafter sometimes simply referred to as "mold"). More specifically, the surface uneven shape of the mold (hereinafter sometimes referred to as "mold uneven surface") is formed according to a predetermined pattern, which is preferably a spatial frequency of a one-dimensional power spectrum of 0.002 μm ^-1 The strength Γ(0.002) and the spatial frequency 0.01μm ^-1 intensity Γ(0.01) ratio Γ(0.01)/Γ(0.002) is 1.5 or more and 6 or less; the spatial frequency is 0.002μm ^-1 strength Γ(0.002) and space frequency intensity Γ (0.02) ratio of 0.02μm ^-1 Γ (0.02) / Γ (0.002 ) of 5 or less than 0.3; spatial frequency intensity of the Γ 0.002μm ^-1 (0.002) and the spatial frequency of the intensity Γ 0.04μm ^-1 The ratio Γ(0.04)/Γ(0.002) of (0.04) is 3 or more and 13 or less. Here, the "pattern" means image data for forming a surface uneven shape of the antiglare layer of the antiglare film, a mask having a light transmitting portion and a light shielding portion, and the like, and may be simply referred to as a "pattern" hereinafter.

First, a method of determining a pattern for forming a surface uneven shape of an antiglare layer of the antiglare film of the present invention will be described.

A method of obtaining a two-dimensional power spectrum of a pattern is disclosed, for example, when the pattern is image data. First, after converting the image data into binary image data of 2 gradients, the gradient is expressed by a two-dimensional function g(x, y). The obtained two-dimensional function g(x, y) is subjected to Fourier transform in the following equation (18) to calculate a two-dimensional function G(f _x , f _y ), as shown in the following formula (19), The square of the absolute value of the two-dimensional function G(f _x , f _y ) is obtained, and the two-dimensional power spectrum Γ(f _x , f _y ) is obtained. Here, x and y represent the 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 reciprocal dimension of length.

In the formula (18), the π is a pi, and i is an imaginary unit.

Γ( f _x , f _y )=| G ( f _x , f _y )| ² (19)

The two-dimensional power spectrum f(f _x , f _y ) represents the spatial frequency distribution of the pattern. In general, since the antiglare film is required to be isotropic, the pattern for producing an 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 pattern can be expressed only by one dimensional function Γ(f) from the distance f of the origin (0, 0). Next, a method of obtaining a 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 two-dimensional power spectrum of the gradient of the pattern is expressed as a polar coordinate in the manner of the equation (20).

Γ( f _x , f _y )=Γ( f cosθ, f sinθ)...(20)

Here, the angle in the θ-system Fourier space. The one-dimensional function Γ(f) can be obtained by calculating the rotation average of the two-dimensional function Γ (fcos θ, fsin θ) represented by the polar coordinates in the manner of the equation (21). The one-dimensional function Γ(f) is obtained from the rotational average of the two-dimensional function Γ(f _x , f _y ) of the two-dimensional power spectrum of the gradient of the pattern, hereinafter also referred to as the one-dimensional power spectrum Γ(f).

In order to obtain a good precision the antiglare film of the present invention, the spatial dimension of one preferred power spectral line frequency 0.002μm intensity pattern Γ (0.002) ^-1 0.01μm in the spatial frequency intensity Γ (0.01) ^-1 of the in ratio Γ (0.01) / Γ (0.002 ) of 1.5 or more and 6 or less, the spatial frequency intensity Γ (0.002) ^-1 0.002μm in the intensity of the spatial frequency 0.02μm ^-1 Γ (0.02) of the ratio Γ (0.02) / Γ (0.002) 0.3 to 5, the spatial frequency intensity 0.002μm Γ (0.002) ^-1 and the intensity of the spatial frequency 0.04μm Γ (0.04) in a ratio of ^-1 Γ (0.04) / Γ (0.002 ) 3 Above 13 or below.

When the two-dimensional power spectrum of the pattern is obtained, the two-dimensional function g(x, y) of the gradient is usually obtained as a discrete function. At this time, the two-dimensional power spectrum can be calculated by the discrete Fourier transform. One dimensional power spectrum of the pattern is obtained in the same way from the two-dimensional power spectrum of the pattern.

In order to obtain the surface irregular shape as a uniform continuous curved surface, the average value of the two-dimensional function g(x, y) is preferably set to the maximum value of the two-dimensional function g(x, y) and the two-dimensional function g(x). , y) is 30 to 70% of the difference between the minimum values. When the concave-convex surface of the mold is produced by a lithography method, the two-dimensional function g(x, y) is the aperture ratio of the pattern. When the mold uneven surface is produced by the lithography method, the aperture ratio of the pattern described herein is defined. The aperture ratio of the photoresist used in the lithography method is a positive photoresist, which means that when the image data of the coating film of the positive photoresist is drawn, the exposed area of the exposed area is relative to the total surface of the coating film. The proportion of the region. On the other hand, the aperture ratio when the photoresist used in the lithography method is a negative photoresist means that the unexposed area is opposed to the coating film when the image film of the negative photoresist is drawn. The ratio of the total surface area. The lithography method is an aperture ratio at the time of one exposure, and means a ratio of a light-transmitting portion having a light-transmitting portion and a mask of the light-shielding portion.

The anti-glare film of the present invention can be obtained by comparing the intensity ratio of one-dimensional power spectrum of the pattern to Γ(0.01)/Γ(0.002), Γ(0.02)/Γ(0.002), Γ(0.04)/Γ(0.002). In the above range, a desired mold is produced and produced by the first method using the mold.

In order to produce a pattern having such a power ratio of one-dimensional power spectrum, a pattern made by a random dot (dot) is pre-made, or a random luminance distribution having a random number or a pseudo-number generated by a computer is used to determine the shading. A pattern (preparation pattern) from which components of a specific spatial frequency range are removed. The removal of the components of the specific spatial frequency range may be performed by passing the preliminary pattern through a band pass filter.

In order to manufacture an anti-glare film having an anti-glare layer formed with a surface uneven shape according to a predetermined pattern, a mold having a surface unevenness formed by transferring the surface uneven shape formed according to a predetermined pattern onto a concave-convex surface of a transparent support is manufactured. The first method using the mold described above is characterized in that an anti-glare layer is formed on the transparent support.

The imprint method is exemplified by a photoimprint method using a photocurable resin, a thermal imprint method using a thermoplastic resin, or the like. Among them, from the viewpoint of productivity, photolithography is preferred.

Photoimprinting on a transparent support (transparent support) A method of forming a photocurable resin layer, pressing the photocurable resin layer against the uneven surface of the mold, and curing the shape of the mold concave and convex surface of the mold onto the photocurable resin layer. Specifically, the photocurable resin layer formed by applying a photocurable resin to a transparent support is irradiated with light from the transparent support side in a state in which it is in close contact with the uneven surface of the mold (this light is used to make a photocurable resin) In the case of curing, the photocurable resin (photocurable resin contained in the photocurable resin layer) is cured, and then the transparent support having the photocurable resin layer formed thereon is peeled off from the mold. The anti-glare film obtained by such a manufacturing method has an optical anti-glare layer after curing. In addition, it is preferable that the photocurable resin is an ultraviolet curable resin, and when the ultraviolet curable resin is used, the light to be irradiated is ultraviolet light (using ultraviolet curing as a photocurable resin). The imprint method of a 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 in the imprint method described here, a transparent support may be replaced with a polarizing film.

The type of the ultraviolet curable resin used in the UV imprint method is not particularly limited, and it can be suitably used from commercially available resins depending on the type of transparent support used and the type of ultraviolet rays used. The ultraviolet curable resin contains a concept of a monomer (polyfunctional monomer), an oligomer, a polymer, and a mixture thereof which are photopolymerized by ultraviolet irradiation. Further, by using a photoinitiator appropriately selected in accordance with the kind of the ultraviolet curable resin, a resin which can be cured even if the wavelength is longer than ultraviolet light can be used. A suitable example of the ultraviolet curable resin and the like will be described later.

For the transparent support used in the UV imprint method, for example, a glass or a plastic film or the like can be used. The plastic film can be used as long as it has appropriate transparency and mechanical strength. Specifically, for example, an acetyl cellulose resin such as TAC (triethylene fluorene cellulose); an acrylic resin; a polycarbonate resin; a polyester resin such as polyethylene terephthalate; and polyethylene; A transparent resin film such as a polyolefin resin such as polypropylene. The transparent resin film may be a solvent cast film or a squeeze film.

The thickness of the transparent support is, for example, 10 to 500 μm, preferably 10 to 100 μm, more preferably 10 to 60 μm. When the thickness of the transparent support 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 difficult to generate glare.

On the other hand, the hot stamping method is a method in which a transparent resin film formed of a thermoplastic resin is heated and pressed against the uneven surface of the mold in a softened state to transfer the surface uneven shape of the uneven surface of the mold to the transparent resin film. The transparent resin film used in the hot stamping method may be any one which is substantially optically transparent, and specifically, a transparent resin film which is exemplified by the UV imprint method.

Next, a method of manufacturing a mold used in the imprint method will be described.

In the method of manufacturing a mold, the molding surface of the mold is capable of transferring the surface uneven shape formed by the predetermined pattern onto the transparent support (an anti-glare layer capable of forming a surface uneven shape formed according to a predetermined pattern) The range of the concave and convex surface of the mold is not particularly limited, in order to have a good fine The anti-glare layer of the surface uneven shape is preferably produced with good reproducibility, and is preferably a lithography method. Further, the lithography method preferably includes [1] a first plating step, [2] a first polishing step, [3] a photosensitive resin film forming step, a [4] exposure step, and a [5] developing step. [6] First etching step, [7] photosensitive resin film peeling step, [8] second plating step, [9] second plating step, and [10] second polishing step.

Fig. 8 is a view schematically showing an example of the first half of the method for manufacturing a mold. Figure 8 is a schematic representation of the mold profile in each step. Hereinafter, each step of the method for producing an anti-glare film producing mold of the present invention will be described in detail with reference to FIG.

[1] 1st 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 applying copper plating to the surface of the substrate for a mold, the adhesion and gloss of chrome plating in the second plating step described later can be improved. Since the copper plating system has high coating property and strong smoothing action, it can fill a small unevenness, a void, or the like of the base material for a mold to form a flat and shiny surface. Therefore, by applying copper plating to the surface of the substrate for a mold, even if chrome plating is applied in the second plating step described later, it is considered that the roughness of the chrome-plated surface existing in the fine unevenness of the substrate and the void can be solve. Therefore, even if the surface unevenness shape (fine uneven surface shape) according to the predetermined pattern is formed on the base molding surface for the mold, the influence of the surface of the susceptor (substrate for the mold) such as minute irregularities or voids can be sufficiently prevented. Displacement.

For the 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 contains the concept of copper and copper alloy. The copper plating may be electroplating or electroless plating, and the copper plating in the first plating step is preferably an electroplating. Further, the preferred plating layer in the first plating step may be formed not only by a copper plating layer but also by a copper plating layer and a plating layer made of a metal other than copper.

When the plating layer formed by copper plating on the surface of the substrate for a mold is too thin, the influence of the surface of the susceptor (fine irregularities, voids, cracks, and the like) cannot be completely excluded, and therefore the thickness thereof is preferably 50 μm or more. The upper limit of the thickness of the plating layer is not limited, but it is preferably about 500 μm or less when considering the cost or the like.

The substrate for the mold is preferably a substrate made of a metal material. Further, from the viewpoint of cost, aluminum, iron, and the like are preferable in terms of the material of the metal material. Further, from the viewpoint of ease of handling of the substrate for a mold, it is particularly preferable to use a substrate made of lightweight aluminum as a substrate for a mold. Further, the aluminum or iron described herein does not need to be each a pure metal, and may be an alloy mainly composed of aluminum or iron.

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

[2] First grinding step

In the subsequent grinding step, plating is applied in the first plating step The copper mold is ground on the surface (plating layer) of the substrate. 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 through the first polishing step. 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 in order to form a desired precision, whereby the surface of the base material for the mold remains. Subtle processing marks. Therefore, even if a plating (preferably copper plating) layer is formed by the first plating step, the processing marks may remain. Moreover, even if the plating in the first plating step is applied, the surface of the substrate for a mold does not necessarily become completely smooth. In other words, for the substrate for a mold having a surface having such a deep processing mark or the like, even if the steps [3] to [10] described later are carried out, the surface unevenness of the surface of the obtained mold and the surface unevenness according to the predetermined pattern are obtained. In the case where the shapes are different, or sometimes the irregularities derived from the processing marks or the like are contained. When an anti-glare film is produced using a mold in which the influence of the processing marks or the like is left, the optical characteristics such as the anti-glare property of the object cannot be sufficiently exhibited, and there is a concern that an unexpected influence may be caused.

The polishing method to be applied in the first polishing step is not particularly limited, and a polishing method in accordance with the shape and characteristics of the substrate for a mold to be polished is selected. Specific examples of the polishing method applicable to the first 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 superfinishing method, lapping, fluid polishing method, and buffing polishing method can be used. Further, mirror surface cutting can be performed by using a cutting tool in the polishing step so that the surface of the substrate for the mold becomes a mirror surface. In this case, the material/shape of the cutting tool can be determined by the type of the material (metal material) of the substrate for the mold, and the sintered carbonization tool and CBN knife are used. With a tool, a ceramic turning tool, a diamond cutter, etc., it is preferable to use a diamond cutter from the viewpoint of processing precision. The surface roughness after polishing is expressed by the center line average roughness Ra according to JIS B 0601, 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 surface roughness of the mold of the finally obtained mold may remain. Further, the lower limit of the center line average roughness Ra is not particularly limited. Therefore, from the viewpoint of the processing time (polishing time) and the processing cost in the first polishing step, the lower limit may be defined.

[3] Photosensitive resin film forming step

Next, a photosensitive resin film forming step will be described with reference to Fig. 8 .

In the photosensitive resin film forming step, a solution (photosensitive resin solution) obtained by dissolving a photosensitive resin in a solvent is applied to the surface of the substrate 40 for mirror polishing obtained by the first polishing step. 41, heating/drying is further performed to form a photosensitive resin film (photoresist film). In the eighth embodiment, the photosensitive resin film 50 is formed on the surface 41 of the mold substrate 40 (Fig. 8(b)).

As the photosensitive resin, a conventionally known photosensitive resin can be used, and it can be used as it is, or can be used as a photoresist, or can be purified by filtration or the like as needed. For example, in the case of a negative photosensitive resin having a photosensitive partially hardened property, a monomer or prepolymer, a double stack 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 of a nitride and a diene rubber, a polyvinyl cinnamate compound, or the like. Further, in the case of a positive photosensitive resin having a property of dissolving a photosensitive portion by development and leaving only an unsensed portion, a phenol resin can be used. , a novolac resin system, and the like. Such a positive or negative photosensitive resin can be easily obtained as a positive photoresist or a negative photoresist from the market. 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, and may be mixed with a commercially available photoresist as a photoresist. Use a photosensitive resin solution.

In order to apply the photosensitive resin solution to the surface 41 of the substrate 40 for a mold, it is preferred to use a solvent for forming a smoother photosensitive resin film to select an optimum solvent, and to dissolve/dilute the photosensitive resin. A photosensitive resin solution obtained by the solvent. Such a solvent is selected depending on the kind of the photosensitive resin and its solubility. Specifically, for example, it is selected from a ceramide solvent, a propylene glycol solvent, an ester solvent, an alcohol solvent, a ketone solvent, a highly polar solvent, and the like. When a commercially available photoresist is used, an optimum photoresist can be selected as the photosensitive resin solution depending on the type of the solvent contained in the photoresist or an appropriate preliminary test.

The method of applying the photosensitive resin solution to the mirror-polished surface of the substrate for a mold can be applied from liquid concave coating, spray coating, dip coating, spin coating, roll coating, wire coating, and gas. Among known methods such as knife coating, blade coating, curtain coating, and ring coating, the shape of the substrate for a mold or the like is selected. The thickness of the photosensitive resin film after coating is preferably in the range of 1 to 10 μm after drying, more preferably in the range of 6 to 9 μm.

[4] Exposure step

Next, the exposure step is performed by exposing the target pattern to the photosensitive resin film 50 formed by the photosensitive resin film forming step. The step of 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, and for example, a g line (wavelength: 436 nm) of a high pressure mercury lamp, and an h line (wavelength: 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 mode may be a single exposure mode using a mask corresponding to the pattern of the purpose, or may be a drawing mode. Furthermore, the pattern of the purpose is as described above, so that the intensity ratio of the spatial frequency of the one-dimensional power spectrum is Γ(0.01)/Γ(0.002), Γ(0.02)/Γ(0.002), and Γ(0.04)/Γ(0.002) ) set to a respective predetermined preferred range.

In the method for producing a mold, in order to form the uneven shape of the surface of the mold with higher precision, it is preferable to expose the intended pattern on the photosensitive resin film in a state of being precisely controlled. In order to expose in such a state, it is preferable to make a target pattern as image data on a computer, and draw a laser according to the pattern of the image data by laser light emitted from a computer-controlled laser head (laser) Draw on the photosensitive resin film. When performing laser drawing, for example, a general-purpose laser drawing device such as a printing plate can be used. A commercially available product of such a laser drawing device is, for example, a Laser Stream FX (Think Laboratory).

Fig. 8(c) is a view schematically showing a state in which the photosensitive resin film 50 is exposed to the pattern. When the photosensitive resin film 50 contains a negative photosensitive resin (for example, when a negative photoresist is used as a photosensitive resin solution), it is exposed. The region 51 receives the exposure energy and performs a crosslinking reaction of the photosensitive resin, and the solubility in the developing solution to be described later is lowered. Therefore, the unexposed area 52 in the developing step is dissolved by the developing 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), the exposed region 51 receives exposure energy and the bonding of the photosensitive resin is cut off, and the like. Therefore, it is easily dissolved in the developing liquid described later. Therefore, in the developing step, the exposed region 51 is dissolved by the developing liquid, and only the unexposed region 52 remains on the surface of the substrate to become the mask 60.

[5] imaging steps

In the development step, when the photosensitive resin film 50 contains a negative photosensitive resin, the unexposed region 52 is dissolved by the developing solution, and the exposed region 51 remains on the substrate for a 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 developing solution, and the unexposed region 52 remains on the substrate for a 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 masking action in a first etching step to be described later, in the substrate for a mold which is formed by using a predetermined pattern as a photosensitive resin film.

The developing liquid used in the developing step can be selected from conventionally known ones depending on the type of photosensitive resin to be used. For example, examples of the developing liquid include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia; and primary amines such as ethylamine and n-propylamine. a secondary amine such as diethylamine or di-n-butylamine; a tertiary amine such as triethylamine or methyldiethylamine; such as dimethyl An alcohol amine such as an alcohol amine or a triethanolamine; a quaternary ammonium compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or trimethylhydroxyethylammonium hydroxide; dissolved in, for example, pyrrole, piperidine, etc. An alkaline aqueous solution such as a cyclic amine; an organic solvent such as xylene or toluene.

The developing method in the developing step is not particularly limited, and immersion development, spray development, brush development, ultrasonic imaging, or the like can be used.

Fig. 8(d) is a view schematically showing a state in which a negative type is used as a photosensitive resin after the development step. In Fig. 8(d), the unexposed region 52 is dissolved by the developing solution, 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. Fig. 8(e) is a view schematically showing a state in which a positive type is used as a photosensitive resin after the development step. In Fig. 8(e), the exposed region 51 is dissolved by the developing solution, and only the unexposed region 52 remains on the surface of the substrate, and the photosensitive resin film in this region 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 development step is used as a mask, and the surface of the substrate for the mold is mainly etched in the plating layer in the unmasked region.

Fig. 9 is a view schematically showing a preferred example of the latter half of the method of manufacturing the mold. Fig. 9(a) is a view schematically showing a state in which the plating layer of the maskless region is mainly etched by the etching step. In the plating layer below the mask 60, the photosensitive resin film acts as a mask 60 and is not etched, but is etched from the maskless region 45 as the etching progresses. Therefore, near the boundary between the area having the mask 60 and the unmasked area 45, the mask The plating layer under the 60 is also etched. Thus, in the vicinity of the boundary between the region having the mask 60 and the unmasked region 45, the plating layer under the mask 60 is also etched, which is called side etching.

The etching treatment in the first etching step is usually performed by etching with an iron (III) chloride (FeCl ₃ ) solution, a copper (II) chloride (CuCl ₂ ) solution, or an alkali etching solution (Cu(NH ₃ ) ₄ Cl ₂ ). In the liquid, the plating layer (metal surface) of the region of the mask 60 is mainly etched in the surface of the substrate for the mold. In the etching treatment, a strong acid such as hydrochloric acid or sulfuric acid may be used as the etching liquid. When the plating layer is formed by plating, etching treatment may be performed by reverse electrolytic etching by applying a potential opposite to that during plating. The surface unevenness shape formed by the substrate for a mold during the etching treatment is based on 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 etching in the etching step. The type of the treatment is different, and it cannot be generalized. 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 slightly isotropically etched. The amount of etching referred to herein is the thickness of the plating layer which is removed by etching.

The etching amount in the first etching step is preferably from 1 to 20 μm, more preferably from 1 to 8 μm, still more preferably from 3 to 5 μm. When the amount of etching is less than 1 μm, the mold has almost no surface unevenness and a mold having a nearly flat surface. Therefore, even if an anti-glare film is produced by using the mold, the anti-glare film has almost no surface unevenness. An image display device equipped with such an anti-glare film cannot display sufficient anti-glare properties. Further, when the amount of etching is too large, the uneven surface of the finally obtained mold has a large difference in unevenness. Even if an anti-glare film is produced using the mold, a map of the anti-glare film is disposed Like a display device, it is sometimes impossible to sufficiently suppress the occurrence of whitening. The etching treatment in the etching step can be performed by one etching treatment, or the etching treatment can be carried out by dividing the etching treatment twice or more. In the case where the etching treatment is carried out in two or more steps, the total amount of etching in the etching treatment of two or more times is preferably 1 to 20 μm.

[7] Photosensitive resin film peeling step

Next, the photosensitive resin film peeling step is a step of performing the function of the mask 60 in the first etching step and removing the photosensitive resin film remaining on the substrate for the mold, preferably by completely removing the mold by this step. A photosensitive resin film remaining on the substrate is used. In the photosensitive resin film peeling step, it is preferred to use a peeling liquid to dissolve the photosensitive resin film. The peeling liquid system can be prepared by changing the concentration, pH, and the like of the developer as a developing solution. Alternatively, the photosensitive resin film may be peeled off by changing the temperature of the development step, the immersion time, or the like, in the same manner as the development liquid used in the development step. 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.

(b) of FIG. 9 is a view schematically showing a state in which the photosensitive resin film used as the mask 60 in the first etching step is completely dissolved and removed by the photosensitive resin film peeling step. The first surface uneven shape 46 is formed on the surface of the substrate for a mold by the mask 60 by the photosensitive resin film and the etching treatment.

[8] Second etching step

The second etching step is the first table formed by the first etching step The surface uneven shape 46 is further passivated 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 second etching process, the shape of 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 having a gentle slope is formed. The state of the uneven 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 electrolytic etching may be used. 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 amount of etching in the second etching process. 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 be whitened. On the other hand, when the etching amount of the second etching treatment is too large, the unevenness of the surface unevenness shape formed by the first etching step is almost eliminated. Lost, it becomes a case of a mold having an almost flat surface. An anti-glare film produced by using such a mold having an almost flat surface may have insufficient anti-glare properties. 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 9 to 12 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

In the second plating step, the substrate for a mold which has been subjected to the steps [6] and [7] above, preferably the surface of the substrate for a mold which has been subjected to the steps [6] to [8] above. It is plated (preferably chrome plating described later). By performing the second plating step, the surface uneven shape 47 of the substrate for a mold can be made gentle, and the surface of the mold can be protected by the plating. (d) of FIG. 9 shows a state in which the chrome plating layer 71 is formed on the second surface uneven shape 47 formed by the second etching treatment, and the surface uneven shape is passivated (the mold uneven surface 70).

The plating layer formed by the second plating step is preferably chrome-plated from the viewpoint of high gloss, high hardness, small friction coefficient, and good release property. Among the chrome plating, the special type is called chrome plating which exhibits good gloss such as gloss chrome plating and decorative chrome plating. The chrome plating is usually carried out by electrolysis, and in the case of the plating bath, an aqueous solution containing chromic anhydride (CrO ₃ ) and a small amount of sulfuric acid can be used as the plating solution. The thickness of the chrome plating layer can be controlled by adjusting the current density and the electrolysis time.

By the surface of the substrate for the mold after the second etching treatment The surface irregular shape is chrome-plated, and in addition to passivating the shape, a mold having an improved surface hardness can be obtained. To the extent that the shape passivation at this time is controlled, the largest factor is the thickness of the chrome layer. If the thickness is thin, the degree of shape passivation becomes insufficient, and the anti-glare film obtained by using such a mold has a ratio of the reflectance R (30) to the reflectance R (40) R (40) / R (30). Above 0.0025. On the other hand, if the thickness of the chrome plating layer is too thick, the ratio R(40)/R(30) will be less than 0.00001. The present inventors have found that an anti-glare film for an image display device which is excellent in preventing the occurrence of whitening and which has excellent anti-glare properties is effective in producing a mold so that the thickness of the chromium plating layer becomes a predetermined range. That is, the thickness of the chrome plating layer is preferably in the range of 2 to 10 μm, more preferably in the range of 3 to 6 μm.

The chrome plating layer formed in the second plating step is preferably formed so that the Vickers hardness is 800 or more. More preferably, it is formed in a manner of becoming 1000 or more. When the Vickers hardness of the chrome plating layer is less than 800, when the antiglare film is produced using a mold, the durability of the mold tends to be lowered.

[10] 2nd grinding step

In the final stage of the mold manufacturing, the second polishing step of applying the surface (chromium plating layer) of the chrome-plated mold substrate in the second plating step is performed. The chrome plating has a luster, a high hardness, a small friction coefficient, and a good release property. However, since the internal stress is high when the chrome plating layer is formed, micro cracks are generated on the surface. The method for producing a mold used in the method for producing an anti-glare film of the present invention preferably satisfies the roughness of a slight surface shape caused by micro-cracking of chrome plating through the second polishing step. Use the surface shape caused by chrome micro cracking When an anti-glare film is produced by a mold having a rough residual shape, scattering of the surface becomes strong and whitening occurs. Further, when the occurrence density of the microcracks is distributed, the antiglare film produced by using the mold may have a strong scattering point and a weak point, and may cause unevenness.

The polishing method to be applied in the second polishing step is preferably a method of selectively grinding the surface shape of the mold by the micro-cracking without slightly affecting the mold uneven surface 70 formed by the second plating step. Specific examples of such a polishing method include polishing, fluid polishing, and jet polishing. The amount of polishing in which the amount of the chromium plating layer is removed in the second polishing step is preferably 0.03 μm or more and 0.2 μm or less. When the amount of polishing is less than 0.03 μm, the effect of solving the surface roughness caused by microcracking becomes insufficient. On the other hand, when the amount of polishing is higher than 0.2 μm, the uneven surface 70 of the mold generates a flat region. When an anti-glare film is produced using a mold that produces a flat region, there is a problem that the anti-glare property is insufficient.

The above-described preferred photoimprint method as a method for producing the antiglare film of the present invention will be described below. As described above, as a photoimprinting method, a UV imprint method is particularly preferred. Here, an imprint method using an active energy ray-curable resin will be specifically described.

In order to continuously produce 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 have the following steps: [P1] coating a coating liquid containing an active energy ray-curable resin a coating step of forming a coating layer on a transparent support that is continuously transported; and [P2] is transparent to the surface of the coating layer by pressing against the surface of the mold The main hardening step of irradiating the active energy ray on the side of the support.

Further, when the antiglare film of the present invention is produced by photoimprinting, it is more preferable to further include the following steps: [P3] after the coating step [P1], before the hardening step [P2], in the coating layer The end region of both of the width directions is irradiated with a preliminary hardening step of the active energy ray.

Hereinafter, each step will be described in detail with reference to the drawings. Fig. 10 is a view schematically showing a preferred example of a manufacturing apparatus used in the method for producing an anti-glare film of the present invention. The arrows in Fig. 10 indicate the transport direction of the film or the direction of rotation of the rolls.

[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. In the coating step, for example, as shown in FIG. 10, the coating liquid containing the active energy ray-curable resin composition is applied to the transparent support 81 discharged from the delivery roller 80 in the application region 83.

The application of the coating liquid to the transparent support 81 can be performed by, for example, a gravure coating method, a micro gravure coating method, a rod coating method, a knife coating method, a pneumatic blade coating method, or an anastomosis coating method (kiss Coating), mold coating method, etc. are carried out.

(transparent support)

As long as the transparent support 81 is translucent, for example, glass, a plastic film, or the like can be used. As far as the plastic film is concerned, it is sufficient as long as it has moderate transparency and mechanical strength. Specifically, it has been exemplified as a UV imprint method. Any of the transparent supports can be used, and in order to further continuously manufacture the anti-glare film of the present invention by photoimprinting, a person having moderate flexibility is selected.

For the purpose of improving the coatability of the coating liquid and the adhesion between the transparent support and the coating layer, various surface treatments can be applied to the surface (coating layer side surface) of the transparent support 81. Examples of the surface treatment include corona discharge treatment, glow discharge treatment, acid surface treatment, alkali surface treatment, ultraviolet irradiation treatment, and the like. Further, another layer such as a primer layer may be formed on the transparent support 81, and a coating liquid may be applied to the other layer.

Further, as the antiglare film of the present invention, in order to improve the adhesion between the transparent support and the polarizing film when manufacturing the polarizing film, it is preferred to first surface the transparent support by various surface treatments. The surface on the opposite side of the cloth layer is hydrophilized. This surface treatment can be carried out after the manufacture of the anti-glare film.

(coating liquid)

The coating liquid contains an active energy ray-curable resin, and usually contains a photopolymerization initiator (radical polymerization initiator). Various additives such as a solvent such as a light-transmitting fine particle or an organic solvent, a leveling agent, a dispersing agent, an antistatic agent, an antifouling agent, and a surfactant may be contained as needed.

(1) Active energy ray-curable resin

As the active energy ray-curable resin, for example, a compound containing a polyfunctional (meth) acrylate compound can be applied. The polyfunctional (meth) acrylate compound refers to a compound having at least two (meth) acryloxy groups in the molecule. Specific examples of the polyfunctional (meth) acrylate compound include, for example, a polyhydric alcohol and a (meth)acrylic acid ester compound, and a urethane (meth) acrylate. A polyfunctional polymerizable compound containing two or more (meth) acrylonitrile groups, such as a polyester, a (meth) acrylate compound, or a (meth) acrylate epoxy ester compound.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, and propanediol. Butane diol, pentane diol, hexane diol, neopentyl glycol, 2-ethyl-1,3-hexane diol, 2,2'-thiodiethanol, 1,4-ring a diol such as hexane dimethanol; an alcohol having 3 or more elements such as trimethylolpropane, glycerin, neopentyl alcohol, diglycerin, dipentaerythritol or di-trimethylolpropane.

Specific examples of the ester of a polyhydric alcohol and (meth)acrylic acid include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and 1,6-hexane two. Alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetrahydroxyl Methyl methane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tetramethylol methane tetra(meth)acrylate, pentatriol tri(meth)acrylic acid Ester, 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.

Examples of the urethane (meth) acrylate compound include an organic isocyanate having a plurality of isocyanate groups in one molecule, and a urethane reaction with a (meth)acrylic acid derivative having a hydroxyl group. Things. Examples of the organic isocyanate having a plurality of isocyanate groups in one molecule include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, and benzodimethyl group. An organic isocyanate having two isocyanate groups in one molecule such as isocyanate or dicyclohexylmethane diisocyanate; one molecule which is modified by isomeric cyanurate, modified by an adduct, or modified by diurea An organic isocyanate having three isocyanate groups or the like. Examples of the (meth)acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, neopentyl alcohol triacrylate.

In the case of the polyester (meth) acrylate compound, a polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid is preferred. Suitable hydroxyl group-containing polyesters are hydroxyl group-containing polyesters obtained by esterification of a polyol with a carboxylic acid or a compound having a plurality of carboxyl groups and/or an anhydride thereof. The polyol is the same as the aforementioned compound. Further, examples of the phenols other than the polyhydric alcohol include bisphenol A and the like. Examples of the carboxylic acid include formic acid, acetic acid, butyric acid, benzoic acid, and the like. Examples of the compound having a plurality of carboxyl groups and/or an acid anhydride thereof include maleic acid, citric acid, fumaric acid, itaconic acid, adipic acid, p-citric acid, maleic anhydride, phthalic anhydride, and benzoic acid. Formic acid, cyclohexane dicarboxylic anhydride, and the like.

Among the above polyfunctional (meth) acrylate compounds, hexane diol di(meth) acrylate and neopentyl glycol are preferred from the viewpoint of improvement in strength of the cured product and ease of availability. Di(meth)acrylic acid Ester, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, two An ester compound such as pentaerythritol hexa(meth)acrylate; an adduct of hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate; isophorone diisocyanate and (meth)acrylic acid 2- An adduct of hydroxyethyl ester; an adduct of toluene diisocyanate and 2-hydroxyethyl (meth)acrylate; an addition of an isophorone diisocyanate and a 2-hydroxyethyl (meth)acrylate The product; and the biuret are modified with an adduct of isophorone diisocyanate and 2-hydroxyethyl (meth)acrylate. Further, these polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more.

The active energy ray-curable resin may contain a monofunctional (meth) acrylate compound in addition to the above polyfunctional (meth) acrylate compound. The monofunctional (meth) acrylate compound may, for example, be methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate or isobutyl (meth) acrylate, ( Tert-butyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydroanthracene (meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, ethionyl (meth)acrylate, benzyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phenoxy (meth) acrylate, epoxy Ethyl modified phenoxy (meth) acrylate, propylene oxide (meth) acrylate, sulfhydryl Phenol (meth) acrylate, ethylene oxide modified (meth) acrylate, propylene oxide modified nonyl phenol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, 2-(Methyl) propylene oxime ethyl 2-hydroxypropyl phthalate, dimethylaminoethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, etc. Base) acrylates. 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 may be, for example, the aforementioned polyfunctional (meth) acrylate compound, that is, an ester compound of a polyol and a (meth) acrylate, a urethane (meth) acrylate compound, a polyester (A) An oligomer such as a dimer or a trimer of an acrylate compound or a phenoxy (meth)acrylate.

The other polymerizable oligomers may be exemplified by a reaction of a polyisocyanate having at least two isocyanate groups in the molecule and a polyol having at least one (meth) acryloxy group. Ester (meth) acrylate oligomer. The polyisocyanate may, for example, be a polymer of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or benzodimethyl diisocyanate, and has at least one (A) The propylene oxy group-containing polyol may, for example, be a hydroxyl group-containing (meth) acrylate obtained by esterification of a polyhydric alcohol with (meth)acrylic acid, and the polyhydric alcohol may, for example, be 1, 3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trihydroxyl Methylpropane, glycerol, neopentyl alcohol, dipentaerythritol, and the like. The having at least one (meth) propylene oxime One of the alcoholic hydroxyl groups of the polyol-based polyol is esterified with (meth)acrylic acid while the alcoholic hydroxyl group remains in the molecule.

Further, examples of other polymerizable oligomers include a reaction of a compound having a plurality of carboxyl groups and/or an acid anhydride thereof, and a polyol having at least one (meth)acryloxyloxy group. Polyester (meth) acrylate oligomer. The compound having a plurality of carboxyl groups and/or an acid anhydride thereof may be the same as those described for the polyester (meth) acrylate of the above polyfunctional (meth) acrylate compound. Further, the polyol having at least one (meth) acryloxy group may be the same as those described for the urethane (meth) acrylate oligomer.

In addition to the above polymeric oligomers, further examples of the urethane (meth) acrylate oligomers include hydroxyl group-containing polyesters, hydroxyl group-containing polyethers or hydroxyl groups ( A compound obtained by reacting a hydroxyl group of a methyl acrylate to an isocyanate. Suitable hydroxyl group-containing polyesters are hydroxyl group-containing polyesters obtained by esterification of a polyol with a carboxylic acid or a compound having a plurality of carboxyl groups and/or an anhydride thereof. The polyhydric alcohol or a compound having a plurality of carboxyl groups and/or an acid anhydride thereof may be the same as those described for the polyester (meth) acrylate compound of the polyfunctional (meth) acrylate compound. Suitable hydroxyl group-containing polyethers are hydroxyl group-containing polyethers obtained by adding one or two or more kinds of alkylene oxides and/or ε-caprolactone to a polyol. The polyol may be the same as those used in the aforementioned hydroxyl group-containing polyester. The hydroxyl group-containing (meth) acrylate to be used may be the same as those described for the urethane (meth) acrylate oligomer of the polymerizable oligomer. In the case of isocyanates, it is preferred to have one or more differences in the molecule. The cyanate group-based compound is particularly preferably a divalent isocyanate compound such as toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.

These polymerizable oligomer compounds may be used alone or in combination of two or more.

(2) Photopolymerization initiator

The photopolymerization initiator can be appropriately selected in accordance with the kind of active energy ray which is suitable for 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-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a thioxanthone system can be used. A photopolymerization initiator, a triazine-based photopolymerization initiator, an oxadiazole-based photopolymerization initiator, and the like. Further, as the photopolymerization initiator, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4 can also be used. , 4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, diphenylethylenedione, 9,10- Phenanthrene, camphorquinone, methyl phenylglyoxylate, titanium titanate compound, and the like. The photopolymerization initiator is usually used in an amount of from 0.5 to 20 parts by weight, preferably from 1 to 5 parts by weight, per 100 parts by weight of the active energy ray-curable resin.

In order to improve the applicability to a transparent support, the coating liquid may contain a solvent, such as an organic solvent. In terms of the organic solvent, the viscosity can be selected from the following: aliphatic hydrocarbons such as hexane, cyclohexane, and octane; aromatic hydrocarbons such as toluene and xylene; ethanol, 1-propanol, and the like. Alcohols such as propanol, 1-butanol and cyclohexanol; methyl ethyl ketone, methyl isobutyl ketone, ring Ketones such as ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl Glycol ethers such as phenyl ether and propylene glycol monoethyl ether; esterified glycol ethers such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; 2-methoxyethanol, 2- Ethoxyethanol, 2-butoxyethanol, etc. Cyrus; 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2- A carbitol such as butoxyethoxy)ethanol or the like. These solvents may be used singly or in combination of several kinds as needed. The above organic solvent must be evaporated after coating. Therefore, the boiling point is preferably in the range of 60 ° C to 160 ° C. Further, the saturated vapor pressure at 20 ° C is preferably in the range of 0.1 kPa to 20 kPa.

When the coating liquid contains a solvent, it is preferred to provide a drying step of evaporating the solvent and drying it after the coating step and before the first curing step. The drying system is carried out, for example, as shown in Fig. 10, by passing the transparent support 81 having the coating layer through the drying zone 84. The drying temperature is appropriately selected depending on the type of solvent or transparent support to be used. Generally, it is in the range of 20 ° C to 120 ° C, but is not limited thereto. Moreover, when there are a plurality of drying furnaces, the temperature of the drying furnace can be changed one by one. The thickness of the coated layer after drying is preferably from 1 to 30 μm.

In this way, a laminate in which a transparent support and a coating layer are laminated can be formed.

[P2] hardening step

In this step, the active energy ray is irradiated from the transparent support side to the surface of the coating layer by pressing the concave-convex surface (forming surface) of the mold having the desired surface unevenness shape, and the coating layer is hardened to be transparent. Support shape The step of forming a hardened resin layer. Thereby, the coating layer is hardened, and the surface uneven shape of the uneven surface of the mold is transferred to the surface of the coating layer. The mold used herein is a roll, and is manufactured by using a base material for a roll mold in the mold manufacturing method described above.

This step is, for example, as shown in Fig. 10, by pre-hardening which is further irradiated with the active energy ray irradiation device 86 by having passed through the application zone 83 (the dry zone 84 when drying is performed, and the preliminary hardening step described later is performed). The layered body of the coating layer of the region is irradiated with the active energy ray by using the active energy ray irradiation device 86 such as an ultraviolet ray irradiation device disposed on the side of the transparent support 81.

First, the roll-shaped mold 87 is pressed against the surface of the coating layer of the laminated body subjected to the hardening step by using a crimping device such as the nip roller 88, and the active energy ray irradiation device 86 is used in this state to illuminate from the transparent support 81 side. The coating layer 82 is hardened by the active energy ray. Here, "curing the coating layer" means that the active energy ray-curable resin contained in the coating layer receives the energy of the active energy ray to cause a curing reaction. The use of the nip rolls is effective for preventing air bubbles from entering between the coating layer of the laminate and the mold. One or a plurality of active energy ray irradiation devices can be used.

After the active energy ray irradiation, the laminated system is peeled off from the mold 87 with the nip roller 89 on the outlet side as a fulcrum. The obtained transparent support and the hardened coating layer are used as an antiglare layer to obtain an antiglare film of the present invention. The resulting anti-glare film is usually wound by a film winding device 90. In this case, for the purpose of protecting the anti-glare layer, the protective film containing polyethylene terephthalate or polyethylene may be provided with re-peelability. The adhesive layer is attached to the surface of the anti-glare layer and wound up. In addition, although the case where the mold used here is a roll shape has been described, a mold other than a roll shape can also be used. Further, after being peeled off from the mold, additional active energy ray irradiation may be performed.

The active energy ray used in this step can be appropriately selected from the group consisting of ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays, etc., depending on the type of active energy ray-curable resin contained in the coating liquid. Among these, ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferable from the viewpoint of easy operation and high energy (as in the above, in the case of photoimprinting, UV imprinting is preferred).

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

Further, as for the electron beam, a Cockcroft-Walton type, a van de Graaff type, a resonance transformer type, an insulating core transformer type, and a straight type can be cited. An electron beam having an energy of 50 to 1000 keV (preferably 100 to 300 keV) released by various electron beam accelerators such as Dynamitron type and high frequency type.

When the active energy ray is ultraviolet ray, the cumulative amount of light in the ultraviolet ray of UVA 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, since the transparent support absorbs the ultraviolet rays on the short-wavelength side, the amount of the ultraviolet light UVV (395 to 445 nm) in the wavelength region including the visible light is preferably adjusted so as to suppress the absorption. . The cumulative amount of light in the UVV 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 cumulative amount of light is less than 100 mJ/cm ² , the hardening of the coating layer is insufficient, and the hardness of the obtained antiglare layer is lowered, or the unhardened resin is attached to the guide roller or the like, which tends to cause contamination of the step. Further, when the cumulative amount of light exceeds 3,000 mJ/cm ² , the transparent support may be shrunk from the heat radiated from the ultraviolet irradiation device to cause wrinkles.

[P3] preliminary hardening step

This step is a step of irradiating the both ends of the transparent support of the coating layer in the width direction to the active energy rays before the hardening step, and preliminarily hardening the both end regions. Figure 11 is a schematic cross-sectional view of the preliminary hardening step. In Fig. 11, the end portion 82b of the coating layer in the width direction (the direction orthogonal to the conveying direction) is a region including the end portion of the coating layer and having a predetermined width from the end portion.

In the preliminary hardening step, by hardening the end region in advance, the adhesion between the end portion and the transparent support 81 is further improved, and in the step after the hardening step, a part of the hardened resin is prevented from being peeled off and dropped. The steps are polluted. The end region 82b can be an area of, for example, 5 mm or more and 50 mm or less from the end portion of the coating layer 82.

The irradiation of the active energy ray of the end region of the coating layer is referred to in Figures 10 and 11, for example, by having been coated The transparent support 81 of the coating layer 82 of the region 83 (the drying zone 84 when dried) is irradiated with an active energy ray irradiation device 85 such as an ultraviolet ray irradiation device provided in the vicinity of both end portions of the coating layer 82 side. The energy line is carried out. The active energy ray irradiation device 85 may be provided on the side of the transparent support 81 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 line and the source of the light source are the same as the main hardening step. When the active energy ray is ultraviolet ray, the cumulative amount of light in the ultraviolet ray of UVA 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 irradiating at 50 mJ/cm ² or more, deformation in the main hardening step can be more effectively prevented. In addition, when it exceeds 400 mJ/cm ² and the hardening reaction progresses excessively, the boundary between the hardened portion and the uncured portion may be peeled off due to a difference in film thickness or strain of internal stress.

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

The anti-glare film of the present invention obtained in the above manner can be used for an image display device or the like, and is usually used as a polarizing film for the identification side protective film of the identification-side polarizing plate (that is, disposed in the image display device). surface). Further, as described above, when a polarizing film is used as the transparent support, an anti-glare film having a polarizing film-integrated type can be obtained. Therefore, the polarizing film-integrated anti-glare film can be used in an image display device. The image display device including the anti-glare film of the present invention has sufficient anti-glare property in 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 "part" indicating the content or usage amount are based on weight unless otherwise noted. The evaluation method of the mold or the anti-glare film in the following examples is as follows.

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

(power spectrum of the composite amplitude calculated from the elevation of the surface relief shape)

The elevation of the surface uneven shape of the antiglare layer of the antiglare film as the measurement sample was measured using a three-dimensional microscope PLμ 2300 (manufactured by Sensofar Co., Ltd.). In order to prevent the warpage of the sample, an optically transparent adhesive is used, and the surface of the measurement sample opposite to the antiglare layer is bonded to the glass substrate, and then provided for measurement. At the time of measurement, the magnification of the objective lens was set to 10 times and the measurement was performed. The horizontal resolutions Δx and Δy were both 1.66 μm, and the measurement area was 1270 μm × 950 μm. From the central portion of the obtained measurement data, 512 × 512 (measurement area: 850 μm × 850 μm) data were sampled, and the elevation of the surface uneven shape (surface unevenness of the antiglare layer) of the antiglare film was determined as a two-dimensional The function h(x, y). Next, calculate the two-dimensional function of the composite amplitude from the two-dimensional function h(x, y) (x, y). The wavelength λ when calculating the composite amplitude was set to 550 nm. The two-dimensional function (x, y) The discrete Fourier transform is performed to obtain a two-dimensional function Ψ(f _x , f _y ). Calculate the two-dimensional function H(f _x ,f _y ) of the two-dimensional power spectrum by squaring the absolute value of the two-dimensional function Ψ(f _x ,f _y ), and calculate the power spectrum of one of the functions of the distance f from the origin. One-dimensional function H(f). The elevation of the surface concavo-convex shape at each of the five samples was measured, and the average value of the one-dimensional function H(f) of the one-dimensional power spectrum calculated from the data was used as a one-dimensional function of the one-dimensional power spectrum of each sample. H(f).

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

(haze)

The total haze of the anti-glare film is bonded to the glass substrate by the surface opposite to the anti-glare layer of the measurement sample by using an optically transparent adhesive, and the anti-glare is applied to the glass substrate. The film was irradiated with light from the side of the glass substrate, and the anti-glare film was measured by a haze meter "HM-150" manufactured by Murakami Color Research Laboratory Co., Ltd. according to the method of JIS K 7136. The surface haze is obtained by subtracting the internal haze from the total haze by the following formula: surface haze = total haze - internal haze internal haze is determined by the internal haze of the anti-glare film The anti-glare layer of the measurement sample after the total haze was measured was measured by glycerin-attached to a triacetone cellulose film having a haze of almost 0, and then measured in the same manner as the total haze.

(penetration clarity)

The penetration 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 K 7105. At this time, in order to prevent the warpage of the sample, an optically transparent adhesive was used, and the surface of the measurement sample opposite to the antiglare layer was bonded to the glass substrate, and then provided for measurement. In this state, light was incident from the glass substrate side, and measurement was performed. Here, the measured values are the total values of the respective values of the respective types of optical combs in which the widths 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.

(reflection resolution measured at a light incident angle of 45°)

By using the Suga test machine (share) system according to the method of JIS K 7105 The image sharpness measuring device "ICM-1DP" measures the reflection sharpness of the anti-glare film. At this time, in order to prevent the warpage of the sample, an optically transparent adhesive was used, and the surface of the measurement sample opposite to the antiglare layer was bonded to the black acrylic substrate, and then it was measured. In this state, light was incident at 45° from the side of the anti-glare layer, and measurement was performed. Here, the measured value is a total value of four kinds of 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, respectively.

(reflection resolution measured at a light incident angle 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 K 7105. At this time, in order to prevent the warpage of the sample, an optically transparent adhesive was used, and the surface of the measurement sample opposite to the antiglare layer was bonded to the black acrylic substrate, and then it was measured. In this state, light was incident at 60° from the side of the anti-glare layer, and measurement was performed. Here, the measured value is a total value of four kinds of 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, respectively.

(reflectance ratio)

In the anti-glare layer of the anti-glare film, the parallel light of the He-Ne laser from the wavelength of 543.5 nm is irradiated from the direction inclined by 30° to the normal line of the anti-glare film, and is in the plane containing the film normal and the irradiation direction. The measurement of the change in the angle of reflectance is performed. For the measurement of reflectance, "3292 03 Optical power sensor" and "3292 Optical power meter" manufactured by Yokogawa Electric Co., Ltd. were used. At this time, in order to prevent the sample from being warped, an optically transparent adhesive is used, and the surface opposite to the antiglare layer of the measurement sample is bonded to the black acrylic substrate. Provide the assay.

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

(Reflex glare, visual assessment of whitening)

In order to prevent reflection from the back surface of the anti-glare film, the anti-glare film is bonded to the surface of the measurement sample which is opposite to the anti-glare layer and bonded to the black acrylic resin plate, and the fluorescent lamp is brightened. In the room, the degree of reflection glare of the fluorescent lamp and the degree of whitening were visually observed by visual observation from the side of the anti-glare layer. Regarding the reflected glare, the degree of the reflected glare when the antiglare film was viewed from the front and the degree of the reflected glare when observed at an inclination of 30° were evaluated, respectively. The reflected glare and the whitening system were evaluated in the following stages on the basis of the following three stages of 1 to 3, respectively.

Reflective glare:

1: No reflected glare was observed.

2: Reflected glare was slightly observed.

3: Reflected glare is clearly observed.

Albino:

1: No whitening was observed.

2: A little whitening was observed.

3: Clearly observed whitening.

(assessment of glare)

Glare is evaluated in the following order. That is, first, a photomask having a pattern of a unit cell represented by a plan view in Fig. 12 is prepared. In the figure, the unit cell 100 is attached to a transparent substrate to form a hook shape with a line width of 10 μm. A (hook-shaped) chrome-shielding pattern 101, the portion where the chrome-shielding pattern 101 is not formed is the opening portion 102. Here, the size of the unit cell is 211 μm × 70 μm (height × width), and the size of the opening is 201 μm × 60 μm (height × width). The unit lattice shown in the figure is vertically and horizontally arranged side by side to form a photomask.

Then, as shown in the schematic cross-sectional view of Fig. 13, the chrome-shielding pattern 111 of the mask 113 is placed on the light box 115, and the anti-glare film 110 is adhered with the anti-glare layer as a surface using an adhesive. A sample formed on the glass plate 117 is placed on the mask 113. A light source 116 is disposed in the light box 115. In this state, the degree of glare was evaluated in seven stages by visual observation at a position 119 of about 30 cm from the sample. In Stage 1, the state of glare was not confirmed at all, the state of strong glare was observed in Stage 7, and the state of glare was slightly observed in Stage 4.

(comparison assessment)

The polarizing plate on both sides of the front and back sides was peeled off from a commercially available liquid crystal television ["KY-32EX550" manufactured by SONY Co., Ltd.]. In place of the original polarizing plates, a polarizing plate "SUMIKALAN SRDB831E" manufactured by Sumitomo Chemical Co., Ltd. is attached to the back side and displayed by an adhesive so that the absorption axes thereof coincide with the absorption axes of the original polarizing plates. On the surface side, the antiglare film shown in each of the following examples was bonded to the display surface side polarizing plate with an uneven surface as a surface via an adhesive. The liquid crystal television thus obtained was started in a dark room, and the bright portion of the black display state and the white display state was measured using a bright portion meter "BM5A" type manufactured by TOPCON Co., Ltd., and the contrast was calculated. Here, the contrast is expressed by the ratio of the bright portion of the white display state to the bright portion of the black display state. The result will be fitted with anti-glare The contrast measured in the state of the film is expressed by the ratio of the contrast measured in the state in which the antiglare film is not attached.

[4] Evaluation of patterns used in the manufacture of anti-glare films

The created pattern data is used as a 2-gradient binary image data, and the gradient is represented by a two-dimensional discrete function g(x, y). The horizontal resolutions Δx and Δy of the discrete function g(x, y) are both set to 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 ). The square of the absolute value of the two-dimensional function G(f _x ,f _y ) is calculated, and the two-dimensional function Γ(f _x ,f _y ) of the two-dimensional power spectrum is calculated, and one of the functions of the distance f from the origin is calculated. One-dimensional function Γ(f).

<Example 1>

(Production of mold for manufacturing anti-glare film)

A ballard copper plater was prepared on the surface of an aluminum roll (JIS A6063) having a diameter of 300 mm. The Ballard copper plating system includes a copper plating layer/silver plating thin layer/surface copper plating layer, and the entire thickness of the plating layer is set to be about 200 μm. The copper-plated surface is mirror-polished, and a photosensitive resin is applied onto the polished copper-plated surface, and dried to form a photosensitive resin film. Next, the pattern in which the pattern A shown in FIG. 14 is repeatedly arranged is exposed on the photosensitive resin film by laser light, and development is performed. This was carried out by using Laser Stream FX (manufactured by Think Laboratory) by exposure and development of laser light. As the photosensitive resin film, those containing a positive photosensitive resin are used. Here, the pattern A is produced by a plurality of Gaussian function type band pass filters having a pattern having a random luminance distribution, the aperture ratio is 45%, and the spatial frequency of the one-dimensional power spectrum is 0.002 μm ^-1 in the intensity Γ ( 0.002) with the spatial frequency intensity of the Γ 0.01μ m ^-1 (0.01) ratio Γ (0.01) / Γ (0.002 ) 2.7 system, the spatial frequency intensity Gamma] (0.002) in the spatial frequency of 0.002μm ^-1 0.02μm ^- strength Γ (0.02) in a ratio of ¹ Γ (0.02) / Γ (0.002 ) 0.5 system, the spatial frequency intensity 0.002μm Γ (0.002) ^-1 0.04μm in the spatial frequency intensity Γ (0.04) ^-1 of the in The ratio (0.04) / Γ (0.002) is 3.7.

Then, the first etching treatment is performed with a copper (II) chloride solution. The amount of etching at this time was set to be 4 μm. The photosensitive resin film was removed from the roll after the first etching treatment, and the second etching treatment was performed with a copper (II) chloride solution. The amount of etching at this time was set to be 12 μm. Then, chrome processing is performed. At this time, the chrome plating thickness was set to be 4 μm. The chrome-plated roller was subjected to a rubbing treatment under the following conditions to prepare a mold A.

Abrasive material: Micro-polishing (alumina abrasive material with a particle size of 0.05 μm) (made by Musashino Electronics Co., Ltd.)

Grinding cloth: red cloth (made by Musashino Electronics Co., Ltd.)

Roll rotation speed: 60rpm

Pressing pressure: 1.1kPa

(production of anti-glare film)

The following components were prepared by dissolving in ethyl acetate at a solid concentration of 60%, and after curing, an ultraviolet curable resin composition A having a film exhibiting a refractive index of 1.53 was formed.

60 parts of pentaerythritol triacrylate

The ultraviolet curable resin composition A was applied onto a triacetonitrile cellulose (TAC) film having a thickness of 60 μm so that the thickness of the dried coating layer was 5 μm, and it was set in a dryer set at 60 ° C. Dry for 3 minutes. The dried film was pressed against the molding surface (surface having the surface uneven shape) of the previously obtained mold A by a rubber roller so that the dried coating layer became the mold side, and was adhered to each other. In this state, light from a high-pressure mercury lamp having a strength of 20 mW/cm ² was irradiated to an amount of 200 mJ/cm ² from the TAC film side, and the coating layer was cured to produce an anti-glare film. Then, the obtained antiglare film was peeled off from the mold to prepare a transparent antiglare film A having an antiglare layer on the TAC film.

<Example 2>

The mold B was produced in the same manner as in the production of the mold A of Example 1 except that the chrome plating thickness in the chrome plating was set to 3 μm, and the anti-glare was produced in the same manner as in Example 1 except that the mold A was replaced with the mold B. membrane. This anti-glare film is used as the anti-glare film B.

<Example 3>

The mold C was produced in the same manner as in the production of the mold A of Example 1, except that the thickness of the chrome plating in the chrome plating was set to 5 μm, and the anti-glare was produced in the same manner as in Example 1 except that the mold A was replaced with the mold C. membrane. This anti-glare film is used as the anti-glare film C.

<Example 4>

A mold D was produced in the same manner as in the production of the mold A of Example 1, except that the pattern in which the pattern B shown in Fig. 15 was repeatedly arranged was exposed to laser light on the photosensitive resin film, except that the mold was used. An anti-glare film was produced in the same manner as in Example 1 except that A was replaced with the mold D. This anti-glare film is used as the anti-glare film D. Here, the pattern B is formed by a plurality of Gaussian function type band pass filters having a pattern having a random luminance distribution, an aperture ratio of 45%, and a spatial frequency of a one-dimensional power spectrum of 0.002 μm ^-1 . (0.002) The ratio of the strength Γ(0.01) in the spatial frequency of 0.01 μm ^-1 Γ(0.01)/Γ(0.002) is 3.5, the spatial frequency is 0.002 μm ^-1 in the strength Γ(0.002) and the spatial frequency is 0.02 μm ^- strength Γ (0.02) in a ratio of ¹ Γ (0.02) / Γ (0.002 ) 0.42 based spatial frequency intensity 0.002μm Γ (0.002) ^-1 0.04μm in the spatial frequency intensity Γ (0.04) ^-1 of the in The ratio (0.04) / Γ (0.002) is 5.5.

<Example 5>

A mold E was produced in the same manner as in the production of the mold A of Example 1, except that the pattern in which the pattern C shown in Fig. 16 was repeatedly arranged was exposed to laser light on the photosensitive resin film, except that the mold was used. An anti-glare film was produced in the same manner as in Example 1 except that A was replaced with the mold E. This anti-glare film is used as the anti-glare film E. Here, the pattern C is formed by a plurality of Gaussian function type band pass filters having a pattern having a random luminance distribution, the aperture ratio is 45%, and the spatial frequency of the one-dimensional power spectrum is 0.002 μm ^-1 . (0.002) The ratio of the strength Γ(0.01) in the spatial frequency of 0.01 μm ^-1 (0.01) / Γ (0.002) is 3.8, the spatial frequency is 0.002 μm ^-1 in the strength Γ (0.002) and the spatial frequency is 0.02 μm ^- strength Γ (0.02) in a ratio of ¹ Γ (0.02) / Γ (0.002 ) 0.50 based spatial frequency intensity 0.002μm Γ (0.002) ^-1 0.04μm in the spatial frequency intensity Γ (0.04) ^-1 of the in The ratio (0.04) / Γ (0.002) is 7.5.

<Comparative Example 1>

The mold F was produced in the same manner as in the production of the mold A of Example 1, except that the thickness of the chrome plating in the chrome plating was set to 2 μm, and the same manner as in Example 1 was carried out except that the mold A was replaced with the mold F. Glare film. This anti-glare film is used as the anti-glare film F.

<Comparative Example 2>

An aluminum roll having a diameter of 200 mm (A6063 of JIS) was placed on the photosensitive resin film by laser light exposure except that the pattern D shown in FIG. 17 was repeatedly arranged, and the mold A of Example 1 was used. The mold G was produced in the same manner as in the production, and an anti-glare film was produced in the same manner as in Example 1 except that the mold A was replaced with the mold G. This anti-glare film is used as the anti-glare film G. Here, the pattern D is formed by a plurality of Gaussian function type band pass filters having a pattern having a random luminance distribution, the aperture ratio is 45%, and the spatial frequency of the one-dimensional power spectrum is 0.002 μm ^-1 . (0.002) The ratio of the strength Γ(0.01) in the spatial frequency 0.01μm ^-1 Γ(0.01)/Γ(0.002) is 4.2, the spatial frequency is 0.002μm ^-1 in the strength Γ(0.002) and the spatial frequency is 0.02μm ^- strength Γ (0.02) in a ratio of ¹ Γ (0.02) / Γ (0.002 ) train 14, the spatial frequency intensity 0.002μm Γ (0.002) ^-1 0.04μm in the spatial frequency of the intensity of Γ ^-1 (0.04) of The ratio (0.04) / Γ (0.002) is 208.

<Comparative Example 3>

The surface of a 300 mm diameter aluminum roll (JIS A5056) was mirror-polished, and the zirconia beads TZ-SX-17 were placed on the ground aluminum surface using a blast apparatus (manufactured by Fujia Co., Ltd.). (TOSOH (manufactured by TOSOH), average particle diameter: 20 μm) was sprayed at a pressure of 0.1 MPa (gauge pressure, hereinafter synonymous), and the amount of beads used was 8 g/cm ² (the amount of use per 1 cm ^{2 of the} surface area of the roll, synonymous below) , causing irregularities on the surface of the aluminum roll. The obtained aluminum roll with irregularities was subjected to electroless nickel plating to prepare a mold H. At this time, the thickness of the electroless nickel plating was set to be 15 μm. An anti-glare film was produced in the same manner as in Example 1 except that the mold A was replaced with the mold H. This anti-glare film is used as the anti-glare film H.

<Comparative Example 4>

Ballard copper plating was applied to the surface of an aluminum roll (JIS A5056) having a diameter of 200 mm. The Ballard copper plating system includes a copper plating layer/silver plating thin 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 beads "TZ-SX-17" (TOSOH) was used for the polishing surface by using a blowing device (manufactured by Fujira Co., Ltd.). : 20 μm), blowing at a pressure of 0.05 MPa (gauge pressure, hereinafter synonymous), and a bead usage amount of 6 g/cm ^{2 to} cause irregularities on the surface of the aluminum roll. The obtained copper-plated aluminum roll with irregularities was subjected to chrome plating to prepare a mold 1. At this time, the chrome plating thickness was set to be 6 μm. An anti-glare film was produced in the same manner as in Example 1 except that the mold A was replaced with the mold 1. This anti-glare film was used as the anti-glare film I.

[Evaluation Results]

The anti-glare film obtained in the above examples and comparative examples will be evaluated. Presented in Table 1.

The anti-glare films A to E (Examples 1 to 5) satisfying the requirements of the present invention have excellent anti-glare properties regardless of front or tilt, even if they are low in haze, and the effects of whitening and glare are also sufficient. . On the other hand, the anti-glare film F (Comparative Example 1) was whitened. The anti-glare film G (Comparative Example 2) had insufficient anti-glare property when observed obliquely. The anti-glare film H (Comparative Example 3) is susceptible to glare. The antiglare film I (Comparative Example 4) had insufficient antiglare property when observed obliquely.

(industrial availability)

The anti-glare film of the invention can be used for images such as liquid crystal displays Display device.

Since the drawings of the present specification are merely illustrative, they are not representative of the technical features of the present invention. Therefore, there is no designated representative map in this case.

Claims (2)

An anti-glare film comprising: a transparent support; and an anti-glare layer having a fine surface irregular shape formed on the transparent support, the anti-glare film having the following characteristics: a total haze of 0.1% or more and 3% or less, The surface haze is 0.1% or more and 2% or less, and the ratio of the reflectance R (30) of the reflection angle of 30° to the reflectance of the reflection angle of 40° (R) is R with respect to the light incident at an incident angle of 30°. 40) / R (30) is 0.00001 or more and 0.0025 or less, and the power spectrum of the composite amplitude obtained by the power spectrum algorithm described below satisfies any of the following conditions (1) to (3): (1) Power spectrum the spatial frequency of the intensity H 0.002μm ^-1 (0.002), and spatial frequency power spectrum of the intensity of H 0.01μm ^-1 (0.01) ratio H (0.01) / H (0.002 ) 0.02 to 0.6; (2) power the spatial frequency spectrum of the intensity of H 0.002μm ^-1 (0.002), and spatial frequency power spectrum of the intensity of 0.02μm ^-1 H (0.02) the ratio H (0.02) / H (0.002 ) 0.005 to 0.05; and ( 3) spatial power spectrum of the frequency intensity H 0.002μm ^-1 (0.002), and spatial frequency power spectrum of the intensity of 0.04μm ^-1 H (0.04) the ratio H (0.04) / H (0.002 ) 0.0005 to less than 0.01 ;<Power Spectrum Algorithm> (A) Previous The average of the elevation of the surface concavo-convex shape determines the average plane of the virtual plane; (B) determines the lowest elevation point including the lowest point of the surface concavo-convex shape, and is parallel to the virtual plane of the average plane, and the elevation of the surface concavo-convex shape including the surface a highest point, parallel to the highest elevation surface of the virtual plane of the average plane; (C) for a plane wave having a wavelength of 550 nm emitted from the highest elevation plane from a direction perpendicular to the main normal direction of the lowest elevation plane A power spectrum of the composite amplitude when the composite amplitude of the highest elevation surface is calculated from the elevation of the surface relief shape and the refractive index of the anti-glare layer. The anti-glare film according to claim 1, wherein the penetration clarity measured by using five optical combs having a width of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm in the dark portion and the bright portion is used. The sum of Tc is 375% or more, and the sum of the reflection resolutions measured by the light incident angle of 45° is used for the four types of optical combs having the widths of the dark portion and the bright portion of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. ) is 180% or less, and the sum of the reflection resolutions Rc(60) measured by using four kinds of optical combs having a width of 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm in the dark portion and the bright portion at a light incident angle of 60° is 240% or less.