KR20110102837A - Anti-glare polarizing plate and image display apparatus using the same - Google Patents

Abstract

In this invention, the 1st which consists of a hardened | cured material of an epoxy resin containing curable composition on the surface on the opposite side to an antiglare layer in a transparent support body, and an antiglare film provided with a transparent support body and the uneven surface laminated | stacked on this provided with a polarizing film to be laminated via an adhesive layer, and the space ratio of the energy spectrum (H _{² 2)} of the energy spectrum (H ₁ ²⁾ and the spatial frequency of 0.04 ㎛ ^-1 elevation of the uneven surface at a frequency of 0.01 ㎛ ^-1 1 to 20, the ratio of the energy spectrum (H ₃ ² ) to the energy spectrum (H ₂ ² ) at a spatial frequency of 0.1 μm ⁻¹ is 0.1 or less, and the uneven surface of the antiglare layer has a surface having an inclination angle of 5 ° or less. An anti-glare polarizing plate containing% or more and an image display device using the same are provided.

Description

Anti-glare polarizing plate and image display device using the same {ANTI-GLARE POLARIZING PLATE AND IMAGE DISPLAY APPARATUS USING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-glare polarizing plate that can prevent whitening and glare while exhibiting excellent anti-glare performance, exhibits high contrast, and provides good visibility, and an image display device using the same.

In an image display device such as a liquid crystal display, a plasma display panel, a cathode ray tube (CRT) display, an organic electroluminescent (EL) display, and the like, when external light shines on the display surface, visibility is remarkably impaired. Conventionally, in order to prevent such external light from shining in, an image display device is used in televisions and personal computers which focus on image quality, video cameras and digital cameras used outdoors with strong external light, and mobile phones which display using reflected light. The anti-glare film for preventing the background reflection of external light is arrange | positioned at the surface of the. For example, in a liquid crystal display, the anti-glare polarizing plate which comprises the polarizing film which consists of polyvinyl alcohol resin normally, and the anti-glare film bonded together to this polarizing film using the polyvinyl alcohol-type adhesive agent is the visual recognition side of a liquid crystal panel. Is placed on.

For example, Japanese Laid-Open Patent Publication No. 2006-053371 discloses a mold having fine irregularities on its surface by sandblasting the polished mold substrate and then electroless nickel plating, thereby producing a triacetyl cellulose (TAC) film. The anti-glare film which transferred the uneven surface of the said mold to the surface of the photocurable resin layer by hardening | curing the photocurable resin layer formed on the uneven surface of the said mold is described.

The antiglare film is required for anti-glare and exhibits good contrast when disposed on the viewing side of the polarizing plate of the image display device, and the entire display surface is scattered by scattered light when disposed on the viewing side of the polarizing plate of the image display device. To suppress the occurrence of the so-called "whitening", which becomes whitish and the display becomes pale, and the surface irregularities of the pixels of the image display device and the anti-glare film when placed on the viewing side of the polarizing plate of the image display device It is desired to suppress the occurrence of so-called "glare", which interferes and, as a result, the luminance distribution becomes difficult to see. However, since the anti-glare film described in JP 2006-053371 A is produced using a mold having a concave-convex shape formed by sand blasting, the accuracy of the concave-convex shape imparted to the anti-glare film is not sufficient. In particular, there is a problem that "glare" is likely to occur because of the fact that there may be a relatively large uneven shape having a period of 50 µm or more.

Moreover, there existed a problem that when the polyvinyl alcohol-type adhesive agent used conventionally is used as an adhesive agent for bonding the polarizing film which consists of an anti-glare film and polyvinyl alcohol resin, the anti-glare polarizing plate which has high water resistance cannot be obtained.

Accordingly, an object of the present invention is to provide an anti-glare polarizing plate which exhibits excellent anti-glare properties and exhibits good contrast while preventing the visibility decrease due to the occurrence of "whitening" and "glare" and having excellent water resistance. have.

This invention is an anti-glare film provided with a transparent support body and an anti-glare layer which has an uneven surface laminated | stacked on this transparent support, and the polyvinyl laminated | stacked through the 1st adhesive bond layer on the surface on the opposite side to an anti-glare layer in a transparent support body. The anti-glare polarizing plate provided with the polarizing film which consists of alcohol-type resin films, Comprising: The 1st adhesive bond layer consists of hardened | cured material of the curable composition containing an epoxy resin, The uneven surface of the anti-glare layer at the space frequency of 0.01 micrometer <^-1> the energy spectrum of the altitude (H ₁ ^2), a space ratio (H ² _1/2 H ²⁾ in the range of 1 to 20 on the energy spectrum of the altitude of the concave-convex surface (H _{² 2)} at a frequency of 0.04 ㎛ ^-1 Ratio of the energy spectrum (H ₃ ² ) of the elevation of the uneven surface at a spatial frequency of 0.1 μm ⁻¹ and the energy spectrum (H ₂ ² ) of the elevation of the uneven surface of the surface at a spatial frequency of 0.04 μm ⁻¹ ( H _{3 ²} / H ^{2 2)} 0.1 a , And also the concave-convex surface, the slope angle provides a polarizing plate that includes the room overt 5 ° or less if 95% or more.

It is preferable that the anti-glare polarizing plate of this invention further includes optical compensation layers, such as a protective film or an optical compensation film laminated | stacked through the 2nd adhesive bond layer, on the surface on the opposite side to an anti-glare film in a polarizing film. An optical compensation layer may be laminated | stacked on the protective film laminated | stacked through the 2nd adhesive bond layer on the surface on the opposite side to an anti-glare film in a polarizing film.

The second adhesive layer is preferably made of a cured product of a curable composition containing an epoxy resin.

As a polarizing film, the polyvinyl alcohol-type resin film uniaxially stretched and the dichroic dye adsorption-oriented can be used preferably.

Moreover, this invention provides the image display apparatus provided with the said anti-glare polarizing plate and an image display element. In the image display apparatus of this invention, an anti-glare polarizing plate is arrange | positioned at the visual recognition side of an image display element with the anti-glare layer side outside.

The anti-glare polarizing plate of the present invention exhibits excellent anti-glare properties and can effectively prevent a decrease in visibility due to the occurrence of "whitening" and "glare" while exhibiting good contrast, and is excellent in water resistance.

1: is sectional drawing which shows typically a preferable example of the anti-glare polarizing plate of this invention.
It is a perspective view which shows typically the surface of the anti-glare film with which the anti-glare polarizing plate of this invention is equipped.
3 is a schematic diagram showing a state where a function h (x, y) representing an elevation is obtained discretely.
It is an example of the figure which showed the elevation of the fine uneven surface of the anti-glare layer with which the anti-glare polarizing plate of this invention is equipped by two-dimensional discrete function h (x, y).
FIG. 5 shows the energy spectrum H ² (f _x , f _y ) of the elevation obtained by the Discrete Fourier Transform of the two-dimensional function h (x, y) shown in FIG. 4 in white and black gradations.
FIG. 6 is a diagram showing a cross section at f _x = 0 of the energy spectrum H ² (f _x , f _y ) shown in FIG. 5.
It is a schematic diagram for demonstrating the measuring method of the inclination angle of a fine uneven surface.
It is a graph which shows an example of the histogram of the inclination-angle distribution of the fine uneven surface of the anti-glare layer with which an anti-glare film is equipped.
It is a figure which shows a part of image data which is a pattern which can be used in order to produce the anti-glare film with which the anti-glare polarizing plate of this invention is equipped.
FIG. 10 is a diagram showing energy spectra G ² (f _x , f _y ) obtained by discrete Fourier transforming the two-dimensional discrete functions g (x, y) of the gray scale shown in FIG.
FIG. 11 is a diagram showing a cross section at f _x = 0 of the energy spectrum G ² (f _x , f _y ) shown in FIG. 10.
It is a figure which shows typically a preferable example of the first half part of the manufacturing method of a metal mold | die.
It is a figure which shows typically a preferable example of the latter part of the manufacturing method of a metal mold | die.
It is a figure which shows typically the state which the uneven surface formed by the 1st etching process dulls by the 2nd etching process.
It is a figure which shows the pattern used when producing the metal mold | die of Example 1. FIG.
It is a figure which shows the pattern used when producing the metal mold | die of Example 2. FIG.
FIG. 17 is a diagram showing a cross section at f _x = 0 of the energy spectrum G ² (f _x , f _y ) of the patterns shown in FIGS. 15 and 16.

<Anti-glare Polarizing Plate>

1: is sectional drawing which shows typically a preferable example of the anti-glare polarizing plate of this invention. The anti-glare polarizing plate of the present invention, as shown in FIG. 1, has an anti-glare film 1 having an anti-glare layer 101 having a transparent support 102 and a fine uneven surface laminated on the transparent support 102. And the polarizing film 104 which consists of a polyvinyl alcohol-type resin film laminated | stacked through the 1st adhesive bond layer 103a on the surface on the opposite side to the anti-glare layer 101 in the transparent support body 102. As shown in FIG. The 1st adhesive bond layer 103a consists of hardened | cured material of the curable composition containing an epoxy resin. The anti-glare polarizing plate of the present invention, as in the example shown in FIG. 1, is a protective film laminated on the surface on the side opposite to the anti-glare film 1 in the polarizing film 104 via the second adhesive layer 103b or The optical compensation layer 105 may be further provided. An optical compensation layer can also be laminated | stacked on the protective film laminated | stacked through the 2nd adhesive bond layer 103b on the surface on the opposite side to the anti-glare film 1 in the polarizing film 104. FIG. EMBODIMENT OF THE INVENTION Hereinafter, the anti-glare polarizing plate of this invention is demonstrated in detail.

[1] antiglare film

(Antiglare layer)

The anti-glare film used for the anti-glare polarizing plate of this invention is equipped with the anti-glare layer which has a fine uneven surface (fine uneven surface) laminated | stacked on the transparent support body. This anti-glare layer has an energy spectrum (H ₁ ² ) of the elevation of the surface of the fine unevenness at a spatial frequency of 0.01 μm ⁻¹ , and an energy spectrum (H ₂ ² ) of the elevation of the surface of the fine unevenness at the spatial frequency of 0.04 μm ⁻¹ . The ratio (H ₁ ² / H ₂ ² ) is in the range of 1 to 20, and the energy spectrum (H ₃ ² ) of the elevation of the fine uneven surface at the spatial frequency of 0.1 μm ^{−1 and} at the spatial frequency of 0.04 μm ⁻¹ The ratio (H ₃ ² / H ₂ ² ) of the energy spectrum (H ₂ ² ) of the elevation of the fine uneven surface is 0.1 or less.

Conventionally, about the period of the fine uneven | corrugated surface of an anti-glare film, the average length (RSm) of the roughness curve element described in JIS B 0601, the average length (PSm) of the cross-sectional curve element, the average length (WSm) of a wrinkle curve element, etc. Was being evaluated. However, with such a conventional evaluation method, it was not possible to accurately evaluate a plurality of cycles included in the fine uneven surface. Therefore, the correlation between glare and fine concavo-convex surface and the correlation between anti-glare and fine concave-convex surface cannot be accurately evaluated, and the control of values such as RSm, PSm, WSm, etc. can be used to control anti-glare and combine antiglare with sufficient anti-glare performance. It was difficult to produce.

MEANS TO SOLVE THE PROBLEM In the anti-glare film in which the anti-glare layer in which the anti-glare layer which has a fine uneven surface is formed on a transparent support body, the fine uneven surface shows the specific spatial frequency distribution prescribed | regulated using "the energy spectrum of the elevation of the fine uneven surface." That is, the anti-glare film whose energy spectral ratio (H ₁ ² / H ₂ ² ) of the elevation is in the range of 1 to 20 and H ₃ ² / H ₂ ² is 0.1 or less shows excellent anti-glare performance and visibility by whitening It was found that deterioration of the film can be prevented, and even when applied to a high-definition image display device, high contrast is expressed without generating glare.

First, the energy spectrum of the elevation of the fine uneven surface of the antiglare layer will be described. It is a perspective view which shows typically the surface of the anti-glare film with which the anti-glare polarizing plate of this invention is equipped. As shown in FIG. 2, the anti-glare film 1 which concerns on this invention is equipped with the anti-glare layer which has the fine uneven surface comprised by the fine unevenness 2. As shown in FIG. Here, the "elevation of the fine concavo-convex surface" referred to in the present invention is an imaginary plane (the elevation of the height at the lowest point of the fine concavo-convex surface at an arbitrary point P on the antiglare film 1 surface). It means the straight line distance in the main normal direction 5 (normal line direction in the said imaginary plane) of an anti-glare film from 0 micrometer as a reference | standard. As shown in FIG. 2, when the rectangular coordinates in the anti-glare film surface are represented by (x, y), the elevation of the fine uneven surface can be expressed by the two-dimensional function h (x, y) of the coordinates (x, y). . In FIG. 2, the surface of the whole anti-glare film is shown by the projection surface 3. As shown in FIG.

The elevation of the fine uneven surface can be obtained from three-dimensional information of the surface shape measured by a device such as a confocal microscope, an interference microscope, an atomic force microscope (AFM), or the like. The horizontal resolution required for the measuring device is at least 5 µm or less, preferably 2 µm or less, and the vertical resolution is at least 0.1 µm or less, preferably 0.01 µm or less. Examples of non-contact three-dimensional surface shape and roughness measuring instruments suitable for this measurement include the New View 5000 series (manufactured by Zygo Corporation, available from Zaigo Co., Ltd. in Japan), and three-dimensional microscope PLμ2300 (manufactured by Sensofar Corporation). Can be. Since the resolution of the energy spectrum of the elevation is required to be 0.01 μm ⁻¹ or less, the measurement area is preferably at least 200 μm × 200 μm or more, and more preferably 500 μm × 500 μm or more.

Next, a method of obtaining the energy spectrum of the elevation from the two-dimensional function h (x, y) will be described. First, from the two-dimensional function h (x, y), the two-dimensional function H (f _x , f _y ) is obtained by the two-dimensional Fourier transform defined by the following formula (1).

Here, f _x and f _y are spatial frequencies in the x direction and the y direction, respectively, and have an inverse dimension of length. In the formula (1), pi is the circumference and i is an imaginary unit. By squaring the obtained two-dimensional functions H (f _x , f _y ), the energy spectrum H ² (f _x , f _y ) of the elevation can be obtained. This energy spectrum H ² (f _x , f _y ) represents the spatial frequency distribution of the fine uneven surface of the antiglare layer.

Hereinafter, the method of obtaining the energy spectrum of the elevation of the surface of the fine unevenness of the antiglare layer will be described in more detail. Three-dimensional information of the surface shape actually measured by the above confocal microscope, interference microscope, atomic force microscope, etc. is generally obtained as a discrete value, that is, an elevation corresponding to a plurality of measurement points. 3 is a schematic diagram showing a state where a function h (x, y) representing an elevation is obtained discretely. As shown in FIG. 3, the orthogonal coordinate in the antiglare film surface is represented by (x, y), and is divided on the projection surface 3 of the antiglare film by dividing every x in the x-axis direction in each x-axis direction and every y in the y-axis direction. When one line is represented by a broken line, in actual measurement, the elevation of the fine uneven surface is obtained as a discrete elevation value for each intersection of the broken lines on the projection surface 3 of the antiglare film.

The number of elevations obtained is determined by the measurement range and Δx and Δy. When the measurement range in the x-axis direction is X = MΔx and the measurement range in the y-axis direction is Y = NΔy, as shown in FIG. The number of elevations is (M + 1) × (N + 1).

As shown in FIG. 3, when the coordinate of the point of interest A on the projection surface 3 of the antiglare film is (jΔx, kΔy) (where j is 0 or more and M or less, k is 0 or more and N or less). , The elevation of the point P on the antiglare film surface corresponding to the spot A can be represented by h (jΔx, kΔy).

Here, the measurement intervals Δx and Δy depend on the horizontal resolution of the measuring device, and in order to accurately evaluate the fine uneven surface, as described above, both Δx and Δy are preferably 5 μm or less, and more preferably 2 μm or less. desirable. In addition, as mentioned above, as for the measurement range X and Y, all are 200 micrometers or more, and it is more preferable that all are 500 micrometers or more.

In this way, in the actual measurement, a function representing the elevation of the fine uneven surface is obtained as a discrete function h (x, y) having (M + 1) × (N + 1) values. Accordingly, the discrete function H (f _x , f _y ) is obtained by the discrete Fourier transform obtained by the measurement and the discrete Fourier transform defined by the following formula (2), and the discrete function H (f _x , f By squaring _y ), the discrete function H ² (f _x , f _y ) of the energy spectrum is obtained. L in Formula (2) is an integer of-(M + 1) / 2 or more (M + 1) / 2 or less, m is an integer of-(N + 1) / 2 or more (N + 1) / 2 or less . Further, Δf _x and Δf _y are spatial frequency intervals in the x direction and the y direction, respectively, and are defined by equations (3) and (4), respectively. Δf _x and Δf _y correspond to the horizontal resolution of the energy spectrum of the elevation.

It is an example of the figure which showed the elevation of the fine uneven surface of the anti-glare layer with which the anti-glare polarizing plate of this invention is equipped by two-dimensional discrete function h (x, y). In Fig. 4, the elevation is represented by a gradation of white and black. The discrete functions h (x, y) shown in FIG. 4 have 512 × 512 values, and the horizontal resolutions Δx and Δy are 1.66 μm.

5 shows the energy spectrum H ² (f _x , f _y ) of the elevation obtained by the discrete Fourier transform of the two-dimensional function h (x, y) shown in FIG. 4 in white and black gradations. The energy spectrum H ² (f _x , f _y ) of the elevation shown in FIG. 5 is also a discrete function having 512 × 512 values, and the horizontal resolution (Δf _x and Δf _y ) of the elevation of the energy spectrum is 0.0012 μm ⁻¹ . .

As shown in FIG. 4, since the fine uneven surface of the anti-glare layer included in the anti-glare polarizing plate of the present invention is formed of randomly formed unevenness, the energy spectrum H ² of the elevation is shown in FIG. 5. Likewise, it is symmetric about the origin. Therefore, the energy spectrum (H ₁ ² ) of the elevation at the spatial frequency of 0.01 μm ⁻¹ , the energy spectrum of the elevation at the spatial frequency of 0.04 μm ⁻¹ (H ₂ ² ) and the energy spectrum of the elevation at the spatial frequency of 0.1 μm ⁻¹ (H ₃ ² ) can be obtained from a cross section passing through the origin of the energy spectrum H ² (f _x , f _y ) which is a two-dimensional function. FIG. 6 shows a cross section at f _x = 0 of the energy spectrum H ² (f _x , f _y ) shown in FIG. 5. From FIG. 6, the energy spectrum (H ₁ ² ) of the elevation at the spatial frequency of 0.01 μm ⁻¹ is 4.4, and the energy spectrum (H ₂ ² ) of the elevation at the spatial frequency of 0.04 μm ⁻¹ is 0.35 and the spatial frequency of 0.1 μm ⁻¹ It can be seen that the energy spectrum (H ₃ ² ) of the elevation at is 0.00076, the ratio (H ₁ ² / H ₂ ² ) is 14, and the ratio (H ₃ ² / H ₂ ² ) is 0.0022.

As described above, in the antiglare layer according to the present invention, the energy spectrum (H ₁ ² ) of the elevation of the fine uneven surface at the spatial frequency of 0.01 μm ⁻¹ and the energy spectrum of the elevation at the spatial frequency of 0.04 μm ⁻¹ ( ratio ^{_{(H 1 2 / H 2 2}} ) of H _{² 2)} is in the range of 1 to 20 is I. When the ratio (H ₁ ² / H ₂ ² ) of the energy spectrum of the elevation is less than 1, the uneven shape of the long period of 100 μm or more included in the fine uneven surface of the antiglare layer is less, and the uneven shape of the short period of less than 25 μm This shows a lot. In such a case, background reflection of external light cannot be prevented effectively, and sufficient anti-glare performance cannot be obtained. On the other hand, the ratio (H ₁ ² / H ₂ ² ) of the energy spectrum of the elevation above 20 indicates that the uneven shape of the long period of 100 μm or more included in the surface of the fine unevenness is many, and the short period of less than 25 μm It shows that there are few uneven | corrugated shapes. In such a case, when the anti-glare polarizing plate is applied to a high-definition image display device, glare tends to occur. In order to suppress glare more effectively while showing better anti-glare performance, the ratio (H ₁ ² / H ₂ ² ) of the energy spectrum of the elevation is preferably in the range of 5-18, more preferably in the range of 8-15. Do.

Further, in the antiglare layer according to the present invention, the energy spectrum (H ₃ ² ) of the elevation of the fine uneven surface at the spatial frequency of 0.1 μm ⁻¹ and the energy spectrum of the elevation at the spatial frequency of 0.04 μm ⁻¹ (H ₂ ²⁾ ) Ratio (H ₃ ² / H ₂ ² ) is 0.1 or less, preferably 0.01 or less. When the ratio (H ₃ ² / H ₂ ² ) is 0.1 or less indicates that the short-period component of less than 10 μm included in the surface of the fine unevenness is sufficiently reduced, whereby the occurrence of whitening can be effectively suppressed. The short period component of less than 10 μm included in the fine concavo-convex surface does not contribute effectively to the anti-glare property, while scattering light incident on the fine concavo-convex surface causes whitening.

In the conventionally known anti-glare film disclosed in Japanese Patent Application Laid-Open No. 2006-053371, etc., the energy spectrum (H ₁ ² ) of the elevation of the surface of the fine uneven surface at the spatial frequency of 0.01 μm ⁻¹ and the spatial frequency of 0.04 μm ^{− Since} the ratio (H ₁ ² / H ₂ ² ) of the energy spectrum (H ₂ ² ) of the elevation at ₁ is larger than that of the present application, there is a problem that glare is likely to occur. Thus, to within the ratio ^{_{(H 1 2 / H 2 2}} ) the range of 1 to 20, there is a need to reduce the energy spectrum of the altitude of the fine concavo-convex surface in the spatial frequency ^{_{0.01 ㎛ -1 (H 1 2)}} . Thus, an anti-glare film having a minute uneven surface fine concavo-convex surface by reducing the energy spectrum (H ₁ ²⁾ of the elevation in the spatial frequency is 0.01 ㎛ ^-1, of greater than 0 ㎛ ^-1 0.04 ㎛ ^-1 or less, as described below It can manufacture suitably by using the pattern which shows the energy spectrum which does not have a maximum in a range. Here, "pattern" is image data which consists of two gradations (for example, image data binarized in white and black) or three gradations or more created by a calculator, which are typically used to form the fine uneven surface of the antiglare film. However, it may also include data (such as matrix data) that can be uniformly converted into the image data. Examples of data that can be uniformly converted into image data include data in which only coordinates and gradations of respective pixels are stored.

Thus, by forming a fine uneven surface of the anti-glare film by using a pattern showing an energy spectrum having no maximum value within the range of more than 0 μm ^{−1 and} 0.04 μm ⁻¹ or less, effectively forming the fine uneven surface at the spatial frequency of 0.01 μm ⁻¹ . It is possible to reduce the energy spectrum H ₁ ² of the elevation, and the ratio H ₁ ² / H ₂ ² can be set in the range of 1 to 20.

Furthermore, the ratio (H ₃ ² / H) of the energy spectrum (H ₃ ² ) of the elevation of the fine uneven surface at the spatial frequency of 0.1 μm ⁻¹ and the energy spectrum (H ₂ ² ) of the elevation at the spatial frequency of 0.04 μm ^{−1 ₂₂₎} in order to obtain the anti-glare film having a minute uneven surface more than 0.1, the energy spectrum of the pattern preferably has a maximum value within the 0.04 ㎛ ^-1 than the spatial frequency range of less than 0.1 ㎛ ^-1. By forming the fine uneven surface of the antiglare film using the pattern having such an energy spectrum, it is possible to effectively enlarge the energy spectrum (H ₂ ² ) of the elevation of the fine uneven surface at the spatial frequency of 0.04 μm ⁻¹ . (H ₃ ² / H ₂ ² ) can be 0.1 or less.

As a method of forming the fine concavo-convex surface of the antiglare film using such a pattern, a metal mold having a concave-convex surface is produced using the pattern, and the concave-convex surface of the metal mold is transferred to the surface of the resin layer formed on the base film. The method (embossing method) is preferable.

The inventors also found that it is more effective to effectively prevent whitening while exhibiting excellent anti-glare performance, so that the fine uneven surface of the anti-glare layer exhibits a specific inclination angle distribution. That is, in the anti-glare polarizing plate of the present invention, the fine uneven surface of the anti-glare layer includes 95% or more of the surface having an inclination angle of 5 ° or less. When the ratio of the surface whose inclination-angle is 5 degrees or less is less than 95%, the inclination-angle of the uneven surface becomes sharp, it collects the light from the surroundings, and it becomes easy to produce the whitening which becomes white the display surface as a whole. In order to suppress such a light condensing effect and prevent whitening, the higher the ratio of the surface whose inclination-angle of the fine uneven | corrugated surface is 5 degrees or less is high, it is preferable that it is 97% or more, and it is more preferable that it is 99% or more.

Here, with reference to FIG. 2, the "inclined angle of the fine uneven | corrugated surface" referred to in this invention is the local normal 6 which added the uneven | corrugated thing in this point at arbitrary points P of the anti-glare film 1 surface. Means the angle (surface inclination angle) (ψ) made with respect to the main normal direction 5 of an anti-glare film. Similarly to the elevation, the inclination angle of the fine uneven surface can be obtained from three-dimensional information of the surface shape measured by a device such as a confocal microscope, an interference microscope, an atomic force microscope (AFM).

It is a schematic diagram for demonstrating the measuring method of the inclination angle of a fine uneven surface. A concrete method of determining the inclination angle will be described. As shown in Fig. 7, the point of interest A on the virtual plane FGHI indicated by the dotted line is determined, and the point A on the x-axis passing therethrough is in the vicinity. For example, the points B and D are held substantially symmetrically with respect to the point A, and near the point of interest A on the y-axis passing through the point A, the point C is almost symmetrical with respect to the point A. And E), and determine the points Q, R, S, T on the antiglare film surface corresponding to these points B, C, D, and E. FIG. In FIG. 7, the rectangular coordinates in the antiglare film plane are represented by (x, y), and the coordinates in the antiglare film thickness direction are indicated by z. The plane FGHI is a straight line parallel to the x-axis passing through the point C on the y-axis, and similarly a straight line parallel to the x-axis passing through the point E on the y-axis and a point B on the x-axis. It is a surface formed by each intersection (F, G, H, I) with the straight line parallel to a y-axis, and similarly the straight line parallel to the y-axis which passes the point D on the x-axis. In addition, although FIG. 7 is drawn so that the position of the real anti-glare film surface may face upward with respect to the plane FGHI, although it is a matter of course according to the position which catches the point A of attention, the position of the real anti-glare film surface is flat (FGHI). Sometimes it comes above and sometimes it goes below.

The inclination angle is the actual anti-glare corresponding to the point P on the actual anti-glare film surface corresponding to the point A and the four points B, C, D, E caught in the vicinity of the point A. Each normal vector 6a, 6b, 6c, 6d of a polygonal 4 plane, i.e. four triangles (PQR, PRS, PST, PTQ), unfolded by a total of five points on the film plane (Q, R, S, T) The average normal vector (average normal vector is the same as the local normal 6 with the unevenness shown in FIG. 2) obtained by averaging the polar angle with respect to the main normal direction of the antiglare film. It can obtain by obtaining from three-dimensional information. After obtaining the inclination angle for each measurement point, the histogram is calculated.

It is a graph which shows an example of the histogram of the inclination-angle distribution of the fine uneven surface of the anti-glare layer with which an anti-glare film is equipped. In the graph shown in FIG. 8, the horizontal axis is an inclination angle, and is divided into 0.5 ° pitches. For example, the leftmost vertical bar indicates the distribution of the set in which the inclination angle is in the range of 0 to 0.5 °, and the angle increases by 0.5 ° as it goes to the right. In FIG. 8, the lower limit of a value is displayed for every 2 divisions of a horizontal axis, For example, the part which becomes "1" in a horizontal axis shows the distribution of a set in which the inclination-angle is in the range of 1-1.5 degrees. In addition, a vertical axis | shaft shows the distribution of an inclination-angle, and when it adds up, it is a value which becomes 1 (100%). In this example, the proportion of the face at the inclination angle of 5 degrees or less is approximately 100%.

In order to produce the anti-glare film in which the fine uneven surface of the anti-glare layer includes 95% or more of the surface having an inclination angle of 5 ° or less, a mold having an uneven surface is also produced using a pattern, and the uneven surface of the mold is described. It is preferable to employ | adopt the method (embossing method) which transfers to the surface of the resin layer formed on the film. In such an embossing method, the inclination angle of the fine concavo-convex surface of the antiglare layer is determined according to the manufacturing conditions of the mold having the concave-convex surface. Specifically, it can control by changing the etching amount of an etching process in the manufacturing method of the metal mold | die mentioned later. That is, by reducing the etching amount in the first etching step, it is possible to reduce the height difference of the first surface irregularities to be formed, and to increase the proportion of the surface having the inclination angle of 5 ° or less. In order to obtain the anti-glare film which has the fine uneven | corrugated surface containing 95% or more of surfaces in which the inclination angle is 5 degrees or less, it is preferable that the etching amount in a 1st etching process is 2-8 micrometers. When the etching amount is less than 2 µm, almost no irregularities are formed on the surface of the metal and almost flat molds are formed, so that the anti-glare film produced using such a mold does not exhibit sufficient anti-glare property. Moreover, when the etching amount exceeds 8 micrometers, there exists a possibility that the height difference of the uneven | corrugated shape formed in a metal surface becomes large, and the surface whose inclination-angle is 5 degrees or less may become less than 95%. The anti-glare film produced using such a metal mold may cause whitening.

Moreover, also the inclination angle of the fine uneven surface of an anti-glare layer can be controlled also by the etching amount in a 2nd etching process. By increasing the etching amount in the second etching step, it is possible to effectively slow down the portion where the surface slope of the first surface unevenness is steep, so that the proportion of the surface having the inclination angle of 5 ° or less can be increased. In order to obtain the anti-glare film which has the fine uneven | corrugated surface containing 95% or more of surfaces inclination angle 5 degrees or less, it is preferable to make the etching amount in a 2nd etching process into the range of 4-20 micrometers. If the etching amount is small, the effect of blunting the surface shape of the unevenness obtained by the first etching step is insufficient, and the optical properties of the antiglare film obtained by transferring the uneven shape are not very good. On the other hand, when the etching amount is too large, the uneven shape is almost eliminated and becomes an almost flat mold, so that the anti-glare property is not exhibited.

In this invention, an anti-glare layer can be comprised by hardened | cured material of curable resin, such as photocurable resin, or a thermoplastic resin, It is preferable to be comprised by hardened | cured material of photocurable resin especially. In the anti-glare layer, fine particles having a refractive index different from that of the cured resin or the thermoplastic resin may be dispersed. By dispersing the fine particles, glare can be more effectively suppressed.

When disperse | distributing the said microparticles | fine-particles to an anti-glare layer, it is preferable that the average particle diameter of microparticles | fine-particles is 5 micrometers or more, and it is more preferable that it is 6 micrometers or more. Moreover, the average particle diameter of microparticles | fine-particles can be about 10 micrometers or less, Preferably it is 8 micrometers or less. When the average particle diameter is less than 5 µm, the scattered light intensity on the wide-angle side due to the fine particles increases, and there is a tendency to decrease the contrast when the anti-glare polarizing plate is applied to the image display device.

In addition, the refractive index of the fine particle (n _b) and the light refractive index of the cargo or the thermoplastic resin of the curable resin ratio of _{(n r) (n b /} n r) is 0.93 or more 0.98 or less or 1.01 or more 1.04 or less is preferred, and 0.97 or more 0.98 It is more preferable that it is below or 1.01 or more and 1.03 or less. When the refractive index ratio (n _b / n _r ) is less than 0.93 or more than 1.04, the reflectance at the interface between the cured product of the curable resin or the thermoplastic resin and the fine particles increases, and as a result, the backscattering rises. This tends to lower the total light transmittance. The fall of the total light transmittance increases the haze of an anti-glare film, and causes the fall of contrast when it is applied to an image display apparatus. In addition, when the refractive index ratio (n _b / n _r ) is more than 0.98 and less than 1.01, since the internal scattering effect by the fine particles becomes small, in order to give a predetermined scattering characteristic to the antiglare layer and to obtain an anti-glare effect by the fine particles, It may be necessary to increase the amount of added.

Content of microparticles | fine-particles is 50 weight part or less normally with respect to 100 weight part of curable resin or a thermoplastic resin, Preferably it is 40 weight part or less. Moreover, it is preferable that it is 10 weight part or more, and, as for content of microparticles | fine-particles, it is more preferable that it is 15 weight part or more. When content of microparticles | fine-particles is less than 10 weight part, the glare suppression effect by microparticles | fine-particles may be inadequate.

It is preferable that the material which comprises microparticles | fine-particles satisfy | fills the said preferable refractive index ratio. As will be described later, in the present invention, the UV embossing method is preferably used for forming the antiglare layer, and the ultraviolet curable resin is preferably used in the UV embossing method. In this case, since the hardened | cured material of an ultraviolet curable resin often shows the refractive index around 1.50, as microparticles | fine-particles, it can select suitably according to the design of an anti-glare film among those whose refractive index is about 1.40-1.60. As microparticles | fine-particles, a resin bead and also what is almost spherical is used preferably. Examples of such suitable resin beads are given below.

Melamine beads (refractive index 1.57),

Polymethyl methacrylate beads (refractive index 1.49),

Methyl methacrylate / styrene copolymer resin beads (refractive index 1.50-1.59),

Polycarbonate beads (refractive index 1.55),

Polyethylene beads (refractive index 1.53),

Polystyrene beads (refractive index 1.6),

Polyvinyl chloride beads (refractive index 1.46),

Silicone resin beads (refractive index 1.46) and the like.

(Transparent support)

As a transparent support body used for an anti-glare film, a substantially optically transparent resin film is suitably used, for example, a triacetyl cellulose film, a polyethylene terephthalate film, a polymethyl methacrylate film, a polycarbonate film, a norbornene-based compound Thermoplastic resin films, such as a film which consists of amorphous cyclic polyolefin which are used, are mentioned. These thermoplastic resin films may be a solvent cast film, an extruded film, or the like. These resin films may be subjected to stretching treatment such as uniaxial stretching or biaxial stretching.

It is preferable that the thickness of a transparent support body is 20 micrometers or more from a handling viewpoint, and it is preferable that it is 100 micrometers or less from a viewpoint of thickness reduction of an image display apparatus, cost, etc. The thickness of the transparent support is more preferably 30 µm or more and 80 µm or less.

(Method for Producing Anti-glare Film)

The anti-glare film used for the anti-glare polarizing plate of this invention can be manufactured suitably by the method containing the following process (A) and (B).

(A) a process of producing a mold having an uneven surface based on a pattern showing an energy spectrum having no maximum value within a spatial frequency range of more than 0 µm ^{-1 and} 0.04 µm ^-1 or less;

(B) The process of transferring the uneven surface of a metal mold | die to the surface of the resin layer containing curable resin, such as photocurable resin, or thermoplastic resin formed on the transparent support body.

^Greater than 0 μm ^-1 By using the pattern which shows the energy spectrum which does not have a maximum in the spatial frequency range of 0.04 micrometer <^-1> or less, it becomes possible to form the fine uneven | corrugated surface which has said specific spatial frequency distribution with high precision. Moreover, the anti-glare layer which has a fine uneven | corrugated surface is produced by the method (embossing method) which manufactures the metal mold | die which has an uneven surface based on the said pattern, and transfers the uneven surface of the metal mold | die to the surface of the resin layer formed on the transparent support body. Can be obtained with high accuracy and reproducibility. Here, an "pattern" is typically an image composed of two gradations (for example, image data binarized in white and black) or three gradations created by a calculator, which is used to form a fine uneven surface of an antiglare film. Although it means data, data (matrix data, etc.) which can be converted uniformly to the said image data can also be included. Examples of data that can be uniformly converted into image data include data in which only coordinates and gradations of respective pixels are stored.

If the energy spectrum of the pattern used in the step (A) is, for example, image data, after converting the image data into binary gray image data of two gradations, the gradation of the image data is represented by a two-dimensional function g (x, y), The two-dimensional function g (x, y) obtained is Fourier transformed to calculate the two-dimensional function G (f _x , f _y ), and is obtained by squaring the obtained two-dimensional function G (f _x , f _y ). Here, x and y represent rectangular coordinates in the image data plane, and f _x and f _y represent the spatial frequency in the x direction and the spatial frequency in the y direction, respectively.

As in the case of obtaining the energy spectrum of the elevation of the fine uneven surface, also in the case of obtaining the energy spectrum of the pattern, the two-dimensional function g (x, y) of the gray scale is generally obtained as a discrete function. In this case, the energy spectrum is calculated by the Discrete Fourier Transform as in the case of obtaining the energy spectrum of the elevation of the fine uneven surface. Specifically, the energy spectrum G ² (f is calculated by calculating the discrete function G (f _x , f _y ) by the Discrete Fourier Transform defined by Equation (5), and by squaring the obtained discrete function G (f _x , f _y ). _x , f _y ) are obtained. Is the circumference and i is the imaginary unit. Further, M is the number of pixels in the x direction, N is the number of pixels in the y direction, l is an integer of -M / 2 or more and M / 2 or less, and m is an integer of -N / 2 or more and N / 2 or less. Furthermore, Δf _x and Δf _y are spatial frequency intervals in the x and y directions, respectively, and are defined by equations (6) and (7), respectively. (DELTA) x and (DELTA) y in Formula (6) and Formula (7) are horizontal resolution in an x-axis direction and a y-axis direction, respectively. On the other hand, when the pattern is image data, Δx and Δy are equal to the length in the x-axis direction and the length in the y-axis direction of one pixel, respectively. That is, when a pattern is created as image data of 6400 dpi, Δx = Δy = 4 μm, and when a pattern is created as image data of 12800 dpi, Δx = Δy = 2 μm.

FIG. 9 is a diagram showing a part of image data which is a pattern that can be used for producing the antiglare film of the present invention, and is represented by a gray scale two-dimensional discrete function g (x, y). The image data of the pattern shown in FIG. 9 was 2 mm x 2 mm in size, and was created at 12800 dpi.

FIG. 10 is a diagram showing energy spectra G ² (f _x , f _y ) obtained by discrete Fourier transforming the two-dimensional discrete functions g (x, y) of the gray scale shown in FIG. Figure 9 is the pattern shown in, because the randomly placed dots, the energy spectrum _{^{G 2 (f x, f y}} ) , as shown in Figure 10, is a symmetry around the origin. Therefore, the spatial frequency showing the maximum value of the energy spectrum G ² (f _x , f _y ) of the pattern can be obtained from the cross section passing through the origin of the energy spectrum. FIG. 11 is a diagram showing a cross section at f _x = 0 of the energy spectrum G ² (f _x , f _y ) shown in FIG. 10. From this, it can be seen that the pattern shown in FIG. 9 has a maximum value at a spatial frequency of 0.045 μm ⁻¹ but does not have a maximum value within a range of more than 0 μm ^{−1 and} 0.04 μm ⁻¹ or less.

The energy spectrum G ² (f _x , f _y ) of the pattern for producing the antiglare film is greater than 0 μm ⁻¹ In the case of having a maximum value in the spatial frequency range of 0.04 µm ^-1 or less, since the fine uneven surface of the obtained antiglare film does not exhibit the specific spatial frequency distribution described above, glare can not be combined with sufficient antiglare properties.

A pattern in which the energy spectrum G ² (f _x , f _y ) does not have a maximum within the spatial frequency range of more than 0 μm ^{−1 and} less than 0.04 μm ⁻¹ is randomly arranged in a plurality of dots, for example, as shown in FIG. 9. And it can create by arrange | positioning uniformly. One type of dot diameter arrange | positioned at random may be sufficient, and two or more types may be sufficient as it. In a pattern created by arranging a large number of dots randomly, the energy spectrum shows a first maximum value (maximum value at the minimum spatial frequency of the spatial frequency exceeding 0 μm ⁻¹⁾ at a spatial frequency that is an inverse of the average distance between the dots. . Therefore, in order to produce the pattern which does not have a maximum in the range whose energy spectrum is more than 0 micrometer ^{-1 and} 0.04 micrometer ^-1 or less, what is necessary is just to create a pattern so that the average distance between dots may be less than 25 micrometers. In addition, the ratio (H ₃ ) of the energy spectrum (H ₃ ² ) of the elevation of the fine uneven surface at the spatial frequency of 0.1 μm ⁻¹ of the antiglare film and the energy spectrum (H ₂ ² ) of the elevation at the spatial frequency of 0.04 μm ⁻¹ to a _² / H ^{2 2)} to 0.1 or less, the energy spectrum of the pattern, it is preferable to have a maximum value in excess of 0.04 ㎛ ^-1 spatial frequency range below 0.1 ㎛ ^-1. Such a pattern is obtained by making so that the average distance between dots exists in the range of more than 10 micrometers and less than 25 micrometers.

Moreover, the pattern obtained by passing the high pass filter which removes the low spatial frequency component below a specific spatial frequency from the pattern which arrange | positioned such a large number of dots at random can also be used. Further, a pattern obtained by passing a low-pass frequency component below a specific spatial frequency and a high-pass frequency component above a specific spatial frequency from a pattern created by arranging a plurality of dots randomly may be used.

As shown in FIG. 11, the energy spectrum of the pattern created by arranging many dots at random shows the maximum value which depends on the dot diameter of the arrange | positioning dot and the average distance between dots. Unnecessary components can be removed by passing this pattern through the high pass filter or the band pass filter. The energy spectrum of the pattern which passed the high pass filter or the bandpass filter in this way does not have a maximum in the spatial frequency range of more than 0 micrometer ^{-1 and} 0.04 micrometer ^-1 or less, since the component is removed by the filter. Further, it is possible to create a pattern having a more efficiently maximum value within the 0.04 ㎛ ^-1 than the spatial frequency range of less than 0.1 ㎛ ^-1. Here, when using the said high pass filter, in order to remove the local maximum in the spatial frequency range of more than 0 micrometer ^{-1 and} 0.04 micrometer ^-1 or less, it is preferable that the upper limit spatial frequency of the low spatial frequency component to remove is 0.04 micrometer ^-1 or less. Do. In addition, in the case of using the bandpass filter, in order to remove the maximum value within the spatial frequency range of more than 0 μm ^{−1 and} less than 0.04 μm ⁻¹ , and to have the maximum value within the spatial frequency range of more than 0.04 μm ⁻¹ and less than 0.1 μm ⁻¹ . The upper limit spatial frequency of the low spatial frequency component to be removed is preferably 0.04 µm ^-1 or less, and the lower limit spatial frequency of the high spatial frequency component to be removed is preferably 0.08 µm ^-1 or more.

In the case of creating a pattern using a method of passing a high pass filter, a band pass filter, or the like, a random brightness determined by a random number or pseudo random number generated by a calculator as a pattern before passing the filter. Patterns with distributions may also be used.

The detail of the method of manufacturing a metal mold | die based on the pattern obtained as mentioned above is mentioned later.

The said process (B) is a process of forming the anti-glare layer which has a fine uneven surface by the embossing method on a transparent support body. As an embossing method, the UV embossing method using a photocurable resin and the hot embossing method using a thermoplastic resin are illustrated, and UV embossing method is preferable especially from a viewpoint of productivity. In the UV embossing method, a photocurable resin layer is formed on the surface of the transparent support, and the photocurable resin layer is transferred to the photocurable resin layer surface by curing while pushing the photocurable resin layer onto the uneven surface of the mold. More specifically, a coating liquid containing a photocurable resin is coated on a transparent support, and the photocurable resin is irradiated with light such as ultraviolet rays from the transparent support side in a state in which the coated photocurable resin is brought into close contact with the uneven surface of the mold. The anti-glare film in which the uneven | corrugated shape of the metal mold | die was transferred to the photocurable resin layer (anti-glare layer) after hardening can be obtained by hardening resin, and peeling the transparent support body in which the photocurable resin layer after hardening was formed from the metal mold | die after that.

As the photocurable resin in the case of using the UV embossing method, an ultraviolet curable resin that is cured by ultraviolet rays is preferably used, but curing is performed even with visible light having a longer wavelength than ultraviolet rays by combining an appropriately selected photoinitiator with the ultraviolet curable resin. Possible resins can also be used. The kind of ultraviolet curable resin is not specifically limited, A commercially available suitable thing can be used. Suitable examples of the ultraviolet curing resin include one or two or more kinds of polyfunctional acrylates such as trimethylolpropane triacrylate and pentaerythritol tetraacrylate, Irgacure 907 (manufactured by Chiba Specialty Chemicals Co., Ltd.), Irgacure 184 (Chiba Specialty) It is a resin composition containing photoinitiators, such as Chemicals Corporation make) and Lucirin TPO (BASF Corporation make). The coating solution is prepared by adding fine particles, a solvent and the like to these ultraviolet curable resins as necessary.

(Manufacturing method of mold for anti-glare film production)

Next, the method of manufacturing the metal mold | die used for manufacture of an anti-glare film is demonstrated. The manufacturing method of the metal mold | die used for manufacture of the anti-glare film used for the anti-glare polarizing plate of this invention is not restrict | limited especially if it is a method which can obtain the predetermined surface shape based on the pattern mentioned above, The fine uneven surface of an anti-glare film In order to manufacture the resin with high accuracy and reproducibility, (i) the first plating step, (ii) the polishing step, (i) the photosensitive resin film forming step, (i) the exposure step, and (iv) the developing step It is preferable to include (i) a 1st etching process, (i) photosensitive resin film peeling process, and (i) 2nd plating process fundamentally. It is a figure which shows typically a preferable example of the first half part of the manufacturing method of a metal mold | die, and FIG. 13 is a figure which shows a preferable example of the latter half part of the manufacturing method of a metal mold | die. In FIG. 12 and FIG. 13, the cross section of the metal mold | die in each process is shown typically. Hereinafter, each process is explained in full detail, referring FIG. 12 and FIG.

(Iii) first plating process

In this process, copper plating or nickel plating is given to the surface of the base material used for a metal mold | die. Thus, by performing copper plating or nickel plating on the surface of the base material for metal mold | die, the adhesiveness and glossiness of chrome plating in a later 2nd plating process can be improved. This is because copper plating or nickel plating has a high coating property and a strong smoothing action, so as to fill a minute unevenness or cavity of the base material for a mold and to form a flat and glossy surface. By the characteristics of these copper plating or nickel plating, even if chromium plating is performed in the 2nd plating process mentioned later, the roughness of the chromium plating surface considered to originate in the minute unevenness | corrugation and a hole which existed in the base material is eliminated, and copper is further removed. Since the coating property of plating or nickel plating is high, generation | occurrence | production of a minute crack is reduced.

As the copper or nickel used in the first plating step, the respective pure metals may be used. In addition, an alloy mainly composed of copper or an alloy mainly composed of nickel may be used. Therefore, "copper" as used herein refers to copper and It is a meaning containing a copper alloy, and "nickel" is a meaning containing nickel and a nickel alloy. Copper plating and nickel plating may be performed by electrolytic plating or electroless plating, respectively, but electrolytic plating is usually employed.

When carrying out copper plating or nickel plating, if the plating layer is too thin, the influence of the underlying surface cannot be excluded, and the thickness thereof is preferably 50 µm or more. Although the upper limit of the plating layer thickness is not critical, it is preferable to set it to about 500 micrometers in consideration of cost.

As a metal material which comprises the base material for metal mold | die, aluminum, iron, etc. are mentioned from a cost viewpoint. In view of the convenience of handling, it is preferable to use lightweight aluminum. It may be aluminum or a railroad here, and a pure metal, respectively, In addition, the alloy which mainly uses aluminum or iron may be sufficient.

In addition, the shape of the base material for metal mold | die should just be a suitable shape conventionally employ | adopted in the field | area, For example, a cylindrical or cylindrical roll other than a flat plate shape may be sufficient. When a metal mold | die is produced using a roll base material, there exists an advantage that an anti-glare film can be manufactured in a continuous roll shape.

(Ii) polishing process

In the subsequent polishing process, the surface of the base material subjected to copper plating or nickel plating in the above-described first plating process is polished. Through this step, the surface of the substrate is preferably polished in a state close to the mirror surface. This is because the metal plate and the metal roll serving as the base material are often machined such as cutting or grinding in order to make the desired precision, and thus the processing marks remain on the surface of the base material, and the copper plating or nickel plating is performed. This is because these processing marks may remain, and the surface may not be completely smooth in the plated state. In other words, even if the process described below is performed on the surface where such deep processing marks and the like remain, the unevenness such as the processing marks may be deeper than the irregularities formed after each process, and the influence of the processing marks and the like may remain. When an anti-glare film is manufactured using such a metal mold | die, it may have an unexpected influence on an optical characteristic. In FIG. 12 (a), the base material for flat metal mold 7 is subjected to copper plating or nickel plating on its surface in the first plating process (about the copper plating or nickel plating layer formed in this process). (Not shown), and also the state which had the surface 8 polished by the mirror process is shown typically.

The method for polishing the surface of the substrate subjected to copper plating or nickel plating is not particularly limited, and any of mechanical polishing, electrolytic polishing and chemical polishing can be used. Examples of the mechanical polishing method include ultrafinishing, lapping, fluid polishing, buff polishing, and the like. In addition, you may make the base material surface 7 for metal mold | die mirror-mirror by mirror-cutting using a cutting tool. The material, shape, etc. of the cutting tool at this time are not particularly limited. Carbide bites, CBN bites, ceramic bites, diamond bites and the like can be used, but diamond bites are preferably used from the viewpoint of processing precision.

As for the surface roughness after grinding | polishing, it is preferable that center line average roughness Ra based on the specification of JISB0601 is 0.1 micrometer or less, and it is more preferable that it is 0.05 micrometer or less. If the centerline average roughness Ra after polishing is larger than 0.1 µm, there is a possibility that the influence of surface roughness after polishing remains on the uneven shape of the final mold surface. The lower limit of the center line average roughness Ra is not particularly limited and is appropriately determined in consideration of machining time, machining cost, and the like.

(Iii) Photosensitive resin film forming process

In the following photosensitive resin film formation process, the photosensitive resin is apply | coated as the solution which melt | dissolved photosensitive resin in the solvent, and heated and dried to the polished surface 8 of the base material 7 for mirrors which performed mirror polishing by the above-mentioned grinding | polishing process, To form a film. FIG. 12B schematically shows a state in which the photosensitive resin film 9 is formed on the polished surface 8 of the base material for metal mold 7.

Conventionally well-known photosensitive resin can be used as photosensitive resin. As a negative photosensitive resin which has a property which hardens a photosensitive part, the monomer and prepolymer of an acrylic ester which has an acryl group or a methacryl group in a molecule | numerator, a mixture of bis azide and diene rubber, a polyvinyl cinnamate type compound, etc. are used, for example. Can be. Moreover, a phenol resin type, a novolak resin type, etc. can be used as positive type photosensitive resin which has the property which a photosensitive part elutes by development and only an unphotosensitive part remains. Moreover, you may mix | blend various additives, such as a sensitizer, a development promoter, an adhesive modifier, and a coating property improving agent, with photosensitive resin as needed.

When applying these photosensitive resins to the polished surface 8 of the base material 7 for metal mold | die, it is preferable to dilute and apply in a suitable solvent, in order to form a favorable coating film. As the solvent, a cellosolve solvent, a propylene glycol solvent, an ester solvent, an alcohol solvent, a ketone solvent, a high polar solvent, or the like can be used.

As a method of applying the photosensitive resin solution, a known method such as meniscus coating, fountain coating, dip coating, rotary coating, roll coating, wire bar coating, air knife coating, blade coating and curtain coating can be used. It is preferable to make the thickness of a coating film into the range of 1-6 micrometers after drying.

(Iii) exposure process

In the following exposure process, the pattern whose energy spectrum does not have a maximum in the spatial frequency range of more than 0 micrometer ^{-1 and} 0.04 micrometer ^-1 or less is exposed on the photosensitive resin film 9 formed in the photosensitive resin film formation process mentioned above. . What is necessary is just to select suitably the light source used for an exposure process according to the photosensitive wavelength, sensitivity, etc. of the apply | coated photosensitive resin, For example, g line (wavelength: 436 nm) of high pressure mercury lamp, h line (wavelength: 405 nm) of high pressure mercury lamp, high pressure I-ray of mercury lamp (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 Excimer laser (wavelength: 193 nm), F2 excimer laser (wavelength: 157 nm), and the like.

In order to form the surface uneven shape of a metal mold | die and also the surface uneven | corrugated shape of an anti-glare layer with high precision, it is preferable to expose the said pattern on the photosensitive resin film in the exposure process in the exposure process, Specifically, It is preferable to create a pattern as image data on a computer, and draw a pattern on the photosensitive resin film by the laser beam emitted from a computer-controlled laser head based on the image data. In performing laser drawing, the laser drawing apparatus for printing plate preparation can be used. Examples of such a laser drawing apparatus include Laser Stream FX (manufactured by Sink Laboratories Co., Ltd.).

In FIG. 12C, the state in which the pattern is exposed on the photosensitive resin film 9 is schematically illustrated. In the case where the photosensitive resin film is formed of negative photosensitive resin, crosslinking reaction of the resin proceeds in the exposed region 10 by exposure, and the solubility in the developer described later is lowered. Therefore, the area | region 11 which is not exposed in the image development process is melt | dissolved by the developing solution, and only the exposed area | region 10 remains on a surface of a base material, and becomes a mask. On the other hand, in the case where the photosensitive resin film is formed of a positive photosensitive resin, the bond of the resin is cut in the exposed region 10 by exposure, and the solubility in the developer described later increases. Therefore, the exposed area 10 in the developing step is dissolved by the developing solution, and only the area 11 that is not exposed remains on the substrate surface to become a mask.

(Iii) developing process

In the subsequent developing step, when a negative photosensitive resin is used for the photosensitive resin film 9, the unexposed regions 11 are dissolved by a developer, and only the exposed regions 10 remain on the mold substrate. It acts as a mask in the subsequent first etching step. On the other hand, when positive type photosensitive resin is used for the photosensitive resin film 9, only the exposed area | region 10 is melt | dissolved by the developing solution, and the area | region 11 which is not exposed remains on the base material for metal mold | die, and is following agent It acts as a mask in one etching process.

A conventionally well-known thing can be used about the developing solution used for a developing process. For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, 1st amines, such as ethylamine and n-propylamine, diethylamine, di-n-butylamine, etc. Tertiary amines such as amines, triethylamine, methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide Alkaline aqueous solutions such as cyclic amines such as quaternary ammonium salts, pyrrole, and piperidine; And organic solvents such as xylene and toluene.

The developing method in the developing step is not particularly limited, and methods such as immersion development, spray development, brush development, and ultrasonic development can be used.

In FIG. 12 (d), a state in which the developing treatment is typically performed using a negative photosensitive resin in the photosensitive resin film 9 is shown. In FIG. 12C, the region 11 that is not exposed is dissolved by the developer, and only the exposed region 10 remains on the substrate surface to form the mask 12. FIG. 12E schematically illustrates a state where the development treatment is performed using a positive photosensitive resin on the photosensitive resin film 9. The region 10 exposed in FIG. 12C is dissolved by the developer, and only the region 11 that is not exposed remains on the substrate surface to become the mask 12.

(Iii) first etching step

In the following 1st etching process, after using the photosensitive resin film | membrane which remained on the surface of the metal mold | die base material after the above-mentioned image development process, the metal mold | die base material of a part without a mask is mainly etched, and an unevenness | corrugation is formed in the polished plating surface. FIG. 13A schematically shows a state in which the mold base 7 in the portion 13 without a mask is etched mainly by the first etching step. The mold base 7 under the mask 12 is not etched from the surface of the mold base, but etching proceeds from the portion 13 without the mask as the etching proceeds. Therefore, near the boundary between the mask 12 and the portion 13 without the mask, the base material 7 for the mold under the mask 12 is also etched. In the vicinity of the boundary between the mask 12 and the portion 13 without the mask, the etching of the substrate 7 for the mold under the mask 12 is also called side etching.

The etching treatment in the first etching step is usually performed using a ferric chloride (FeCl ₃ ) solution, cupric chloride (CuCl ₂ ) solution, alkaline etching solution (Cu (NH ₃ ) ₄ Cl ₂ ), or the like. Although it forms by corrosive, strong acid, such as hydrochloric acid and a sulfuric acid, can also be used, and reverse electrolytic etching which reverses the electric potential from when electroplating can also be used. Since the concave shape formed in the base material for a metal mold | die at the time of an etching process differs according to the kind of base metal, the kind of photosensitive resin film, the etching method, etc., it cannot say uniformly, but when an etching amount is 10 micrometers or less, it touches an etching liquid, It is etched approximately isotropically from the metal surface. Etching amount here is the thickness of the base material shaved by etching.

The etching amount in the first etching step is preferably 1 to 50 µm, more preferably 2 to 10 µm. In the case where the etching amount is less than 1 µm, since irregularities are hardly formed on the metal surface and become almost flat molds, anti-glare properties are not exhibited. Moreover, when etching amount exceeds 50 micrometers, the height difference of the uneven | corrugated shape formed in a metal surface becomes large, and there exists a possibility that whitening may arise in the image display apparatus which applied the anti-glare film produced using the obtained metal mold | die. In order to obtain the anti-glare film which has the fine uneven | corrugated surface containing 95% or more of surfaces in which the inclination angle is 5 degrees or less, it is more preferable that the etching amount in a 1st etching process is 2-8 micrometers. The etching process in a 1st etching process may be performed by one etching process, and you may divide an etching process into two or more times. When dividing an etching process two times or more, it is preferable that the sum total of the etching amount in two or more etching processes is in the said range.

(Iii) Photosensitive resin film peeling process

In the following photosensitive resin film peeling process, the remaining photosensitive resin film used as a mask in a 1st etching process is melt | dissolved and removed completely. In the photosensitive resin film peeling process, a photosensitive resin film is melt | dissolved using a peeling liquid. As the peeling solution, the same developer as described above can be used. By changing the pH, temperature, concentration, and immersion time of the stripping solution, the negative photosensitive resin film is completely dissolved by removing the photosensitive resin film of the exposed part when the negative photosensitive resin film is used, and the photosensitive resin film of the non-exposed part when the positive photosensitive resin film is used. do. There is no restriction | limiting in particular also about the peeling method in the photosensitive resin film peeling process, and methods, such as an immersion phenomenon, a spray image development, a brush image development, an ultrasonic image development, can be used.

FIG. 13B schematically shows a state in which the photosensitive resin film used as the mask 12 in the first etching step is completely dissolved and removed by the photosensitive resin film peeling step. The 1st surface uneven | corrugated shape 15 is formed in the surface of the metal mold | die base material by the etching using the mask 12 which consists of a photosensitive resin film.

(Iii) second plating process

Subsequently, chromium plating is performed on the formed uneven surface (first surface uneven shape 15) to reduce the uneven surface shape. In (c) of FIG. 13, the surface by which the unevenness | corrugation became slower than the 1st surface uneven | corrugated shape 15 by forming the chromium plating layer 16 in the 1st surface uneven | corrugated shape 15 formed by the etching process of a 1st etching process. The state in which [the surface 17 of chromium plating] is formed is shown.

As chromium plating, it is preferable to employ | adopt chromium plating which has gloss, the hardness is high, the friction coefficient is small, and can give favorable mold release property on the surfaces, such as a flat plate and a roll. Although it does not restrict | limit especially as such chromium plating, It is preferable to use chromium plating which expresses favorable gloss called so-called gloss chrome plating, decorative chromium plating, etc. Chromium plating is usually performed by electrolysis, and an aqueous solution containing chromic anhydride (CrO ₃ ) and a small amount of sulfuric acid is used as the plating bath. By adjusting the current density and the electrolysis time, the thickness of the chromium plating can be controlled.

On the other hand, it is not preferable to perform plating other than chromium plating in a 2nd plating process. Because in plating other than chromium, hardness and abrasion resistance are lowered, so that durability as a mold decreases, irregularities are worn out during use, and the mold is damaged. In the anti-glare film obtained from such a metal mold | die, it is highly likely that it will become difficult to acquire sufficient anti-glare function, and also the possibility that a defect will generate | occur | produce on an anti-glare film will become high.

In addition, surface polishing after plating is also undesirable. That is, it is preferable to use as the uneven surface of the metal mold | die transferred to the resin layer surface on a transparent support as it is, without giving the process of grind | polishing the surface after a 2nd plating process. The reason for this is that polishing may result in deterioration of optical characteristics because flat portions are formed on the outermost surface, and shape control with good reproducibility becomes difficult due to an increase in the shape control factor.

Thus, by performing chromium plating on the surface in which the fine surface uneven | corrugated shape was formed, the uneven | corrugated shape can be slowed down and the metal mold | die with the high surface hardness can be obtained. Although the slowing state of the unevenness at this time varies depending on the type of the base metal, the size and depth of the unevenness obtained from the first etching process, the type and thickness of the plating, and the like, but in general, in controlling the slowed state The biggest factor is also the plating thickness. When the thickness of chromium plating is thin, the effect which can slow the surface shape of the unevenness | corrugation obtained before chrome plating process is inadequate, and the optical characteristic of the anti-glare film obtained by transferring the uneven | corrugated shape is not very good. On the other hand, when the plating thickness is too thick, the productivity is deteriorated, and a projection-type plating defect called nodule is generated, which is not preferable. Therefore, it is preferable to exist in the range of 1-10 micrometers, and, as for the thickness of chromium plating, it is more preferable to exist in the range which is 3-6 micrometers.

It is preferable that the chromium plating layer formed in the said 2nd plating process is formed so that Vickers hardness may be 800 or more, and it is more preferable to form so that it may become 1000 or more. When the Vickers hardness of the chromium plating layer is less than 800, the durability at the time of use of the mold decreases, and the decrease in the hardness due to the chromium plating is likely to cause an abnormality in the plating bath composition, electrolytic conditions, etc. This is because there is a high possibility of adversely affecting the occurrence situation.

Furthermore, between the above-mentioned photosensitive resin film peeling process and (iv) 2nd plating process, the 2nd etching process which can slow the uneven surface formed by the 1st etching process by an etching process is included. It is preferable. In a 2nd etching process, the 1st surface uneven | corrugated shape 15 formed by the 1st etching process which used the photosensitive resin film as a mask can be made slow by an etching process. By this 2nd etching process, in the 1st surface uneven | corrugated shape 15 formed by the 1st etching process, the part whose surface inclination is a steep inclination disappears and the optical characteristic of the anti-glare film manufactured using the obtained metal mold | die was made in the preferable direction. Is changed. In FIG. 14, the second surface unevenness of the mold base 7 is blunted by the second etching treatment, and the portion of the surface inclined sharply slanted is blunted to have a gentle surface slope. The state in which 18 was formed is shown.

Similarly to the first etching step, the etching treatment of the second etching step also includes a ferric chloride (FeCl ₃ ) solution, cupric chloride (CuCl ₂ ) solution, and alkaline etching solution (Cu (NH ₃ ) ₄ Cl ₂ ) It is made by corroding the surface using, for example, a strong acid such as hydrochloric acid, sulfuric acid, or the like, or a reverse electrolytic etching which takes a potential opposite to that of electroplating. Since the slowing state of the unevenness after the etching treatment is different depending on the type of the base metal, the etching method and the size and depth of the unevenness obtained by the first etching step, and the like, it is not generally understood. The biggest factor is the etching amount. Etching amount here is also the thickness of the base material shaved by etching similarly to a 1st etching process. If the etching amount is small, the effect of blunting the surface shape of the unevenness obtained by the first etching step is insufficient, and the optical properties of the antiglare film obtained by transferring the uneven shape are not very good. On the other hand, when the etching amount is too large, the uneven shape is almost eliminated and becomes an almost flat mold, so that the anti-glare property is not exhibited. Therefore, it is preferable to carry out etching amount in the range of 1-50 micrometers, and to obtain the anti-glare film which has a fine uneven | corrugated surface containing 95% or more of the surface whose inclination-angle is 5 degrees or less, it must be in the range of 4-20 micrometers. It is more preferable. The etching treatment in the second etching step may also be performed by one etching treatment similarly to the first etching step, or may be performed by dividing the etching treatment two or more times. When dividing an etching process two times or more, it is preferable that the sum total of the etching amount in two or more etching processes becomes in the said range.

[2] polarizing film

Next, the polarizing film used for the anti-glare polarizing plate of this invention is demonstrated. In this invention, the polarizing film in which the dichroic dye adsorption-oriented was carried out to the uniaxially stretched polyvinyl alcohol-type resin film is used preferably. Polyvinyl alcohol-type resin which comprises a polarizing film is obtained by saponifying polyvinyl acetate type resin. As polyvinyl acetate type resin, the copolymer etc. of vinyl acetate and the other monomer copolymerizable with this besides the polyvinyl acetate which is a homopolymer of vinyl acetate are illustrated. As another monomer copolymerizable with vinyl acetate, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, etc. are mentioned, for example. The degree of saponification of the polyvinyl alcohol-based resin is usually in the range of 85 to 100 mol%, preferably 98 to 100 mol%. The polyvinyl alcohol-based resin may also be modified. For example, polyvinyl formal, polyvinyl acetal, and the like modified with aldehydes can also be used. The polymerization degree of polyvinyl alcohol-type resin is 1000-10000 normally, Preferably it is the range of 1500-10000.

The polarizing film used for this invention is the process of uniaxially stretching such a polyvinyl alcohol-type resin film, the process of dyeing a polyvinyl alcohol-type resin film with a dichroic dye, and adsorbing the dichroic dye, and a dichroic dye adsorb | sucking. It can manufacture through the process of processing the processed polyvinyl alcohol-type resin film with aqueous solution of boric acid, and the process of washing with water after the process by aqueous solution of boric acid.

Uniaxial stretching may be performed before dyeing with a dichroic dye, may be performed simultaneously with dyeing with a dichroic dye, or may be performed after dyeing with a dichroic dye. When uniaxial stretching is performed after dyeing with a dichroic dye, this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment. Of course, it is also possible to uniaxially stretch in these several steps. In order to uniaxially stretch, you may extend uniaxially between the rolls from which a circumferential speed differs, and you may uniaxially stretch using a hot roll. Dry stretching may be performed in the air, or wet stretching may be performed in a swelled state with a solvent. The draw ratio is usually about 4 to 8 times.

In order to dye a polyvinyl alcohol-type resin film with a dichroic dye, what is necessary is just to immerse a polyvinyl alcohol-type resin film in the aqueous solution containing a dichroic dye. As a dichroic dye, an iodine or a dichroic dye is specifically used.

When using iodine as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing iodine and potassium iodide is employ | adopted normally. The content of iodine in this aqueous solution is usually about 0.01 to 0.5 parts by weight per 100 parts by weight of water, and the content of potassium iodide is usually about 0.5 to 10 parts by weight per 100 parts by weight of water. The temperature of this aqueous solution is about 20-40 degreeC normally, and the immersion time in this aqueous solution is about 30 to 300 second normally.

On the other hand, when using a dichroic dye as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing water-soluble dichroic dye is employ | adopted normally. Content of the dichroic dye in this aqueous solution is about 0.001-0.01 weight part normally per 100 weight part of water. This aqueous solution may contain inorganic salts, such as sodium sulfate. The temperature of this aqueous solution is about 20-80 degreeC normally, and the immersion time in this aqueous solution is about 30-300 second normally.

Boric acid treatment after dyeing with a dichroic dye is performed by immersing the dyed polyvinyl alcohol-type resin film in boric-acid aqueous solution. Content of boric acid in boric-acid aqueous solution is about 100 weight part 2-15 weight part of water normally, Preferably it is about 5-12 weight part. When using iodine as a dichroic dye, it is preferable that this boric acid aqueous solution contains potassium iodide. Content of potassium iodide in boric-acid aqueous solution is about 2-20 weight part normally per 100 weight part of water, Preferably it is 5-15 weight part. Immersion time in boric acid aqueous solution is about 100 to 1200 second normally, Preferably it is about 150 to 600 second, More preferably, it is about 200 to 400 second. The temperature of boric-acid aqueous solution is 50 degreeC or more normally, Preferably it is 50-85 degreeC.

The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. A water washing process is performed by immersing the polyvinyl alcohol-type resin film which processed boric acid in water, for example. After water washing, a drying process is performed and a polarizing film can be obtained. The temperature of the water in a water washing process is about 5-40 degreeC normally, and immersion time is about 2 to 120 second normally. The drying treatment after that can be performed using a hot air dryer or a far infrared heater. Drying temperature is 40-100 degreeC normally. The processing time in a drying process is about 120 to 600 second normally.

In this way, the polarizing film which uniaxially stretches and consists of the polyvinyl alcohol-type resin film by which the iodine or dichroic dye was adsorption-oriented can be obtained. The thickness of a polarizing film can be about 1-50 micrometers, for example. This polarizing film is bonded to the transparent support of said anti-glare film using the adhesive agent (adhesive which forms a 1st adhesive bond layer) which consists of curable compositions containing the epoxy resin mentioned later.

[3] protective film

In the anti-glare polarizing plate of the present invention, from the viewpoint of mechanical strength, the protective film is preferably bonded to the surface on the side opposite to the side to which the anti-glare film of the polarizing film is bonded through the second adhesive layer described later. As a protective film, a transparent resin film is used preferably. Specific examples of the transparent resin film include, for example, cellulose resin films such as triacetyl cellulose films; Linear polyolefin resins such as polypropylene; Amorphous polyolefin resin film; Polyester-based resin film; (Meth) acrylic resin films; Polycarbonate-based resin film; Polysulfone resin film; And alicyclic polyimide resin film. Especially, a triacetyl cellulose film or an amorphous polyolefin resin film is used especially preferably.

The amorphous polyolefin resin usually has a polymerized unit of a cyclic olefin such as a norbornene or a polycyclic norbornene monomer, and may be a copolymer of a cyclic olefin and a chain olefin. Especially, thermoplastic saturated norbornene-type resin is typical. A polar group may be introduce | transduced into amorphous polyolefin resin. Examples of commercially available amorphous polyolefin-based resins include "Aton" [manufactured by JSR Corporation], "Zeonoa" [manufactured by Nihon Xeon Co., Ltd.], "Zonex" [manufactured by Nihon Xeon Co., Ltd.], and "APO". Mitsui Chemicals, Mitsui Chemicals, Mitsui Chemicals, etc. are mentioned. In the case of using such an amorphous polyolefin resin of a commercially available product, the amorphous polyolefin resin can be formed into a film by a known method such as a solvent casting method or a melt extrusion method.

The thickness of a protective film is the range of about 5-200 micrometers normally, Preferably it is 10-120 micrometers, More preferably, it is 10-85 micrometers.

[4] optical compensation layer

In the anti-glare polarizing plate of this invention, it is also preferable to provide the optical compensation layer laminated | stacked through the 2nd adhesive bond layer mentioned later on the surface on the opposite side to the side where the anti-glare film of a polarizing film is bonded instead of the said protective film. Do. Or this optical compensation layer may be laminated | stacked on the said protective film bonded by the surface on the opposite side to the side where the anti-glare film of a polarizing film is bonded. The optical compensation layer is a layer (including a film) for the purpose of retardation compensation or the like, and the optical compensation layer for the purpose of retardation compensation is also called "retardation plate (or retardation film)".

As an optical compensation layer, For example, birefringent film which consists of a stretched film of transparent resin, etc .; A film having an orientation fixed by a discotic liquid crystal or a nematic liquid crystal; Optical compensation films, such as a liquid crystal layer which consists of a discotic liquid crystal and a nematic liquid crystal, were formed on the base film. Especially, from a viewpoint of cost, durability, etc., the birefringent film which consists of a stretched film of transparent resin, etc. is used preferably. Since this birefringent film has high durability, it has a function as a protective film, and when using the said birefringent film, another protective film can be abbreviate | omitted.

Only one layer may be sufficient as the optical compensation layer laminated | stacked on a polarizing film, and multiple layers may be sufficient as it. When providing a some optical compensation layer, you may laminate | stack the same kind of optical compensation layer, or may laminate | stack a heterogeneous optical compensation layer. For example, a birefringent film made of another stretched film of a transparent resin may be laminated on the birefringent film made of a stretched film of transparent resin via an adhesive layer, or a discotic liquid crystal or nema on a birefringent film made of a stretched film of transparent resin. The tick liquid crystal may be aligned and fixed.

As transparent resin which comprises the said birefringent film, For example, Polycarbonate resin; Polyvinyl alcohol-based resins; Polystyrene resin; (Meth) acrylic resins such as polymethyl methacrylate; Linear polyolefin resins such as polypropylene; Polyarylate resins; Polyamide-based resins; Amorphous polyolefin resin etc. are mentioned. The stretched film may be processed by a suitable method such as uniaxial or biaxial. Moreover, the birefringent film which controlled the refractive index of the thickness direction of a film can also be used as an optical compensation film by adding shrinkage force and / or extending | stretching force in the state which bonded the heat shrinkable film to the film which consists of said transparent resin.

When laminating an optical compensation layer on a protective film, in view of simplicity of bonding operation, prevention of optical distortion, etc., bonding of the optical compensation layer and the protective film is performed using an adhesive (also called a pressure-sensitive adhesive). desirable. As an adhesive, the adhesive composition which uses an acryl-type polymer, a silicone type polymer, polyester, a polyurethane, a polyether, etc. as a base polymer can be used. Among them, it is excellent in optical transparency, maintains proper wettability and cohesion, and is excellent in adhesiveness to the substrate, and furthermore has weather resistance and heat resistance, and does not cause peeling problems such as floating or peeling under heating or humidifying conditions. It is preferable to use an acryl-type adhesive (an adhesive which uses an acrylic polymer as a base polymer). Examples of the base polymer of the acrylic pressure-sensitive adhesive include alkyl esters of (meth) acrylic acid having an alkyl group having 20 or less carbon atoms such as methyl group, ethyl group and butyl group, and functional group-containing acrylic monomers such as (meth) acrylic acid and hydroxyethyl (meth) acrylate; As the acrylic copolymer of, an acrylic copolymer having a glass transition temperature of 25 ° C. or less (preferably 0 ° C. or less) and a weight average molecular weight of 100,000 or more is preferably used.

Bonding of the optical compensation layer and a protective film using an adhesive forms an adhesive layer on a protective film or an optical compensation layer, and laminates the other to-be-joined material (optical compensation layer or protective film) through this adhesive layer, By bonding. The pressure-sensitive adhesive layer is formed by dissolving or dispersing the pressure-sensitive adhesive composition in an organic solvent such as toluene or ethyl acetate, for example, to prepare a 10 to 40% by weight solution, and coating it directly on a protective film or an optical compensation layer to form an pressure-sensitive adhesive layer. It can be performed by the method of forming a pressure-sensitive adhesive layer by forming a pressure-sensitive adhesive layer on a protective film in advance, and sticking it on a protective film or an optical compensation layer. Although the thickness of an adhesive layer is determined according to the adhesive force etc., the range of about 1-50 micrometers is suitable.

As needed, fillers, such as glass fiber, glass beads, resin beads, metal powder, and other inorganic powders, pigments, colorants, antioxidants, ultraviolet absorbers, etc. may be mix | blended with an adhesive layer. Examples of the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, nickel complex salt compounds and the like.

When the optical compensation layer is laminated directly on the polarizing film without passing through the protective film, the bonding of the optical compensation layer and the polarizing film is made using an adhesive. This adhesive agent forms a 2nd adhesive bond layer.

Next, the relationship between the optical compensation layer or the protective film as a retardation plate which the anti-glare polarizing plate of the present invention can include, and the driving mode of the liquid crystal cell included in the liquid crystal display device to which the anti-glare polarizing plate is applied will be described in detail. . The preferable aspect of the retardation plate or protective film which an anti-glare polarizing plate of this invention can comprise depends on the drive mode of the liquid crystal cell with which the liquid crystal display device to apply is equipped. Examples of the driving mode of the liquid crystal cell include a vertical alignment (VA) mode, an in-plane switching (IPS) mode, a twisted nematic (TN) mode, and the like.

(Vertical orientation mode)

In the vertical alignment mode, since the liquid crystal molecules are vertically aligned with respect to the cell substrate in the non-driven state, light passes through the liquid crystal layer without accompanied by a change in polarization. For this reason, by arranging linear polarizing plates so that the polarization axes are perpendicular to each other above and below the liquid crystal cell, a nearly perfect black display can be obtained when viewed from the front, and a high contrast ratio can be obtained. However, in the liquid crystal display device of the vertical alignment mode in which only the linear polarizing plate is arranged in such a liquid crystal cell, when viewed at an angle, the axial angle of the arranged linear polarizing plate is shifted at 90 °, and the rod-shaped liquid crystal molecules in the liquid crystal cell Due to the expression of birefringence, light leakage occurs, resulting in a markedly lower contrast ratio.

In the liquid crystal display device of the vertical alignment mode, in order to eliminate such light leakage, it is necessary to arrange the phase difference plate between the liquid crystal cell and the linear polarizing plate. In the vertical alignment mode, as described above, since the liquid crystal molecules are vertically aligned with respect to the cell substrate in the black display state, the liquid crystal layer has a refractive index in the in-plane slow axis direction of the liquid crystal layer n _x , the liquid crystal. When the refractive index in the in-plane fastening axis direction of the layer is n _y and the refractive index in the thickness direction of the liquid crystal layer is n _z , it can be regarded as a positive C-plate showing a relationship of n _x = n _y <n _z . Therefore, when the polarizing film and a refractive index of between the liquid crystal cell, in-plane refractive index in the slow axis direction of the film, n _x, in the in-plane fast axis refractive index n _y, the film in the direction of film thickness direction as n _z, n _x It is known that arranging both positive A-plates having a relationship of> n _y = n _z and negative C-plates having a relationship of n _x = n _y > n _z can properly eliminate light leakage. Further, Japanese Patent Laid-Open No. 2007-256766 discloses that a first retardation plate having a relationship of n _x > n _y ≥ n _z has a substantially parallel or almost orthogonal relationship with a transmission axis of a polarizing film whose slow axis is adjacent to each other. Arrange | positioned so that it may arrange | position a 2nd retardation plate which has a relationship of n _x ≒ n _y > n _z between the said 1st retardation plate and a cell board | substrate or between the other cell board | substrate and the polarizing film facing it. It is described.

When using the anti-glare polarizing plate of this invention for the liquid crystal display device of a vertical alignment mode, it is preferable to arrange | position a phase difference plate suitably so that it may become the structure mentioned above on the side opposite to the side to which the anti-glare film of the polarizing film was bonded. When applying the anti-glare polarizing plate of this invention to the liquid crystal display device of a vertical alignment mode, an example of the preferable embodiment of the anti-glare polarizing plate of this invention which considered cost, productivity, durability of an anti-glare polarizing plate, etc. is an anti-glare of a polarizing film. On the surface on the opposite side to the side to which the film is bonded, the 1st retardation plate which has a relationship of n _x > n _y ≥ n _z is laminated | stacked through the 2nd adhesive bond layer mentioned later, and an adhesive layer on this 1st retardation plate through such a structure of laminating the second phase difference plate having a relationship of _{n x ≒ n y> n z} . The first retardation plate having a relationship of n _x > n _y ≥ n _z can be obtained by uniaxially or biaxially stretching a film made of a transparent resin having positive refractive anisotropy under appropriate conditions. As transparent resin which has positive refractive index anisotropy, the cellulose resin, cyclic olefin resin, polycarbonate resin etc. which are represented by acylated cellulose, such as triacetyl cellulose, can be used. Here, cyclic olefin resin is resin which uses cyclic olefins, such as norbornene and dimethanooctahydro naphthalene, as a monomer, and is a commercial item, "Aton" [JSR Corporation make], "Zenooa" [Nihon] Xeon Corporation], "Xeonex" (Nihon Xeon Corporation), etc. are mentioned. Among these transparent resins, since the photoelastic coefficient is small and there is little occurrence of in-plane characteristic unevenness due to thermal distortion under use conditions, triacetyl cellulose or cyclic olefin resin is suitably used.

As the second retardation plate having a relationship of n _x ≒ n _y > n _z , for example, a discotic liquid crystal is coated on a base film, a cholesteric liquid crystal is applied on a base film with a short pitch, mica, and the like. The thing which formed the layer of the inorganic layer type compound on the base film, the thing which biaxially stretched the transparent resin film sequentially or simultaneously, an unstretched solvent cast film, etc. are mentioned. Commercially available retardation plates having a relationship of n _x ≒ n _y > n _z include, for example, "VAC film" (manufactured by Sumitomogagaku Co., Ltd.), "Fuji Tak Film" (manufactured by Fujishashin Film Co., Ltd.), and the like. have. Since this second retardation plate is n _x ≒ n _y , and therefore, the in-plane retardation value R ₀ is almost zero, even if it has some R ₀ values, it is necessary to specifically define the axial angle of the slow axis. none.

On the other hand, the in-plane retardation value (R ₀ ) and the retardation value (R _th ) in the thickness direction are n _x , the refractive index in the in-plane slow axis direction of the film (retardation plate), n _y , when the refractive index in the thickness direction of the film thickness of the n _z, film to d, are defined by the following formula (a) and formula (b), respectively.

R ₀ = (n _x -n _y ) × d (a)

R _th = [(n _x + n _y ) / 2-n _z ] × d (b)

In-plane retardation value (R ₀ ) of the film (retardation plate) and the retardation value (R _th ) in the thickness direction are commercially available retardation measuring apparatus [KOBRA- in a state where the film to be measured is bonded to a glass plate through, for example, an adhesive. The measurement can be performed directly using 21ADH (manufactured by Oshige Isokugiki Co., Ltd.). In such a phase difference measuring device, the in-plane retardation (R ₀ ) of the film is measured, for example, by the rotational analyzer method using monochromatic light having a wavelength of 559 nm, and on the other hand, the in-plane slow axis of the film is 40 degrees as the tilt axis. The retardation value (R ₄₀ ) at the time of inclination was measured, and n _x , n _y, and n _z were measured using the measured retardation value (R ₄₀ ), the thickness (d) of the film, and the average refractive index (n ₀ ) of the film. It calculates | requires and calculates the phase difference value (R _th ) of the thickness direction based on said Formula (b) from these values.

(IPS mode)

In the IPS mode, the orientation state of liquid crystal molecules is changed by a transverse electric field applying a voltage in parallel to the cell substrate surface. In the voltage-free state, the liquid crystal molecules are aligned parallel to the cell substrate surface. In the liquid crystal display device of such an IPS mode, in a configuration in which only a polarizing plate is disposed with a liquid crystal cell interposed therebetween, when viewed obliquely, the axial angle of the arranged linear polarizing plates is shifted from 90 °, and a rod shape in the liquid crystal cell. Due to the birefringence of the liquid crystal molecules of, light leakage occurs and the contrast ratio is considerably lowered.

In the IPS mode liquid crystal display device, in order to eliminate such light leakage, it is necessary to arrange a phase difference plate between a liquid crystal cell and a polarizing film. In the liquid crystal display device of the IPS mode, in order to compensate for the birefringence change of the liquid crystal layer due to the visual change, optically negative uniaxiality is used, and a phase difference plate in which the optical axis is parallel to the film plane or in the thickness direction is used. It is known that it is effective.

For example, Japanese Patent Application Laid-Open No. 10-54982 discloses a liquid crystal display device in IPS mode, wherein the optical axis is optically negative uniaxially between a liquid crystal cell and at least one polarizing plate, and its optical axis is relative to the film surface. Positioning parallel optical compensation films is described.

Japanese Unexamined Patent Application Publication No. 11-133408 discloses that a pair of polarizing plates in a liquid crystal display device in an IPS mode, more specifically, is perpendicular to a cell substrate surface with positive uniaxiality between a liquid crystal cell and a polarizing plate. It is described to arrange an optical compensation layer having an optical axis in the direction.

Japanese Laid-Open Patent Publication No. 2005-309110 discloses disposing an optical compensation film (retardation plate) having a different in-plane retardation value between a liquid crystal cell and a pair of polarizing plates up and down in a liquid crystal display device in IPS mode. It is.

Japanese Unexamined Patent Publication No. 2006-235576 discloses a birefringence including a phase difference plate present between a back side polarizing film and a liquid crystal cell, from a liquid crystal cell side surface of a back side polarizing film to a back side substrate surface of a liquid crystal cell. The sum of phase difference values R _{th in} the thickness direction of the layer is in the range of -40 nm to +40 nm, and the sum of their in-plane retardation values (R ₀ ) is in the range of 100 nm to 200 nm. A polarizing plate comprising at least one plate and having a polarizing film and a viewing side transparent protective layer provided on a side opposite to at least the side facing the liquid crystal cell as a front side polarizing plate, wherein the liquid crystal cell is disposed on the liquid crystal cell side surface of the polarizing film. It is described to use a polarizing plate in which the phase difference value R _{th in} the thickness direction between the front side substrate surface is in the range of -10 nm to +40 nm.

As a method of orienting the resin film in the thickness direction, for example, JP-A-H07-230007 discloses a film having heat shrinkability on at least one surface of a uniaxially stretched thermoplastic resin film, and heat shrinking the heat shrinkable film. A method of peeling and removing a heat-shrinkable film is disclosed after joining so that the direction is orthogonal to the stretch-axis direction of the uniaxially stretched thermoplastic resin film and performing heat shrink.

When using the anti-glare polarizing plate of this invention for the liquid crystal display device of IPS mode, it is preferable to arrange | position a protective film or retardation plate suitably so that it may become the structure mentioned above on the side opposite to the side to which the anti-glare film of the polarizing film was bonded. . When applying the anti-glare polarizing plate of this invention to the liquid crystal display device of IPS mode, an example of preferable embodiment of the anti-glare polarizing plate of this invention is on the surface on the opposite side to the side to which the anti-glare film of a polarizing film is bonded, It is a structure which laminated | stacks the protective film whose phase difference value (R _th ) of the thickness direction is a range of -10 nm to +40 nm through the 2nd adhesive bond layer mentioned later. With such a protective film having a thickness retardation value R _th in a range of −10 nm to +40 nm, a substantially non-oriented and thickness difference retardation value R _th available in the market is 10 nm. Hereinafter, cellulose acetate type resin films, such as a cyclic olefin resin film and triacetyl cellulose which are 5 nm or less, etc. are mentioned. Moreover, the thin cast solvent of cellulose acetate type resin films, such as a triacetyl cellulose, can also be used because the phase difference value (R _th ) of thickness direction becomes 40 nm or less.

When the anti-glare polarizing plate of the present invention has a protective film having a phase difference value R _{th in the} thickness direction in a range of -10 nm to +40 nm, as described above, the liquid crystal cell side of the polarizing film of the back side polarizing plate The sum of the phase difference values R _{th in} the thickness direction of the birefringent layer existing between the surface and the back side substrate surface of the liquid crystal cell is in the range of -40 nm to +40 nm, and these in-plane retardation values ( It is preferable that the sum of R ₀ ) is in the range of 100 nm to 200 nm. Examples of such birefringent layers include thermoplastic resin films uniaxially stretched and also oriented in the thickness direction; So-called negative A-plate (may be biaxial) obtained by uniaxially or biaxially stretching a thermoplastic resin film (polystyrene film or the like) having negative refractive index anisotropy; A lamination of so-called negative A-plates with positive uniaxiality, a negative C-plate with an optical axis in the film normal direction, and a negative uniaxiality with an optical axis parallel to the film plane, etc. For example.

(TN mode)

TN mode changes the orientation state of liquid crystal molecules with a vertical electric field which applies a voltage perpendicular | vertical to a cell substrate surface. In the TN mode, when the liquid crystal molecules are traced from one cell substrate to another cell substrate, the liquid crystal orientation in a voltage-free state is between the upper and lower substrates while facing in-plane parallel to the cell substrate in each portion. Is oriented parallel to the cell substrate surface to be at a 90 degree twisted (twisted) state.

In the conventional TN type liquid crystal display device, the viewing angle characteristic was not enough by the anisotropy of the refractive index resulting from the pretilt of the liquid crystal substance in a liquid crystal cell. Therefore, Japanese Patent Application Laid-Open No. 06-214116 discloses an optically anisotropic layer in which a negative uniaxiality is exhibited and the optical axis is disposed so that the optical axis is in an inclined direction with respect to the film surface is a liquid crystal cell and a polarizing plate in a TN type liquid crystal display device. It arrange | positions in between. Japanese Unexamined Patent Application Publication No. 10-186356 discloses an optical compensation film formed by immobilizing a nematic hybrid orientation formed when a liquid crystalline polymer exhibiting positive uniaxiality is in a liquid crystal state. It is also disclosed to apply to a TN type liquid crystal display device and to enlarge a viewing angle. Improvement of the viewing angle in a TN type liquid crystal display device is made by using such an optical anisotropic layer whose optical axis is in the inclination direction with respect to a film surface as an optical compensation film (retardation plate).

When using the anti-glare polarizing plate of this invention for the liquid crystal display device of TN mode, it is preferable to arrange | position the optical compensation film (retardation plate) as mentioned above on the opposite side to the side where the anti-glare film of the polarizing film was bonded. Do. When applying the anti-glare polarizing plate of this invention to the liquid crystal display device of TN mode, an example of preferable embodiment of the anti-glare polarizing plate of this invention is on the surface on the opposite side to the side to which the anti-glare film of a polarizing film is bonded, It is a structure which laminates a protective film through the 2nd adhesive bond layer mentioned later, and laminates the said optically anisotropic layer as a phase difference plate on this protective film. It is preferable that bonding of a protective film and retardation plate is made using adhesives, such as an acrylic adhesive. However, the optically anisotropic layer can also be laminated directly on the polarizing film. As an optically anisotropic layer, it is optically negative uniaxiality, the optical axis is an optically anisotropic layer inclined 5-50 degrees from the film normal direction, and optically positive uniaxiality, and the optical axis is from the normal direction of a film The optically anisotropic layer inclined at 5 to 50 degrees is suitable.

As an optically anisotropic layer that is optically negative uniaxial and whose optical axis is inclined 5 to 50 degrees from the normal direction of the film, for example, an organic compound, such as that described in JP-A-06-214116, among others A compound having liquid crystallinity, a compound having a disk-like molecular structure, and no liquid crystallinity, but having a negative refractive index anisotropy by an electric field or a magnetic field are coated on a transparent resin film made of triacetyl cellulose or the like, and optical The film etc. which were oriented so that an axis may incline 5-50 degrees from a film normal direction are used preferably. The orientation may be not only one direction but also a so-called hybrid orientation in which the slope is gradually increased from one side of the film to the other side, for example.

Examples of the organic compound having a disk-like molecular structure showing liquid crystallinity include an alkyl group, an alkoxy group, and an alkyl-substituted benzoyloxy group in a mother cell having a planar structure such as a low molecular or polymer discotic liquid crystal such as triphenylene, truncene, benzene, etc. The thing which linear substituents, such as an alkoxy substituted benzoyloxy group, couple | bonded radially is illustrated. Especially, it is preferable not to show absorption in visible region.

The organic compound which has a disk-shaped molecular structure can be used not only individually by 1 type, but also in combination of multiple types as needed, or it can mix and use with other organic compounds, such as a polymer matrix. As an organic compound used by mixing, it will not specifically limit, if it has compatibility with the organic compound which has a disk-shaped molecular structure, or can disperse | distribute the organic compound which has a disk-shaped molecular structure to the particle size which does not scatter light. Do not. A layer made of such a liquid crystalline compound is formed on a transparent base film made of cellulose resin, and an optical axis is inclined with respect to the film normal, for example, "WV film" (manufactured by Fujishashin Film Co., Ltd.) suitably. It is available.

Moreover, as an optically anisotropic layer which is optically positive uniaxial and whose optical axis is inclined 5 to 50 degrees from the normal direction of the film, an elongated rod, such as that described in JP-A-10-186356, for example. Organic compounds having a shape structure, among them compounds having a molecular structure that exhibits nematic liquid crystallinity and impart positive optical anisotropy, and compounds which do not exhibit liquid crystallinity but express positive refractive index anisotropy by electric or magnetic fields The film formed on the transparent base film which consists of cellulose resin etc., and orientated so that an optical axis may incline 5-50 degrees from a film normal line direction is mentioned. The orientation may be not only one direction but also a so-called hybrid orientation in which the slope is gradually increased from one side of the film to the other side, for example. A layer made of a nematic liquid crystal compound is formed on the transparent base film, and as the film whose optical axis is inclined with respect to the film normal, for example, "NH film" (manufactured by Nippon Seki Oil Co., Ltd.) can be suitably used.

In addition, a thin film can be formed by vacuum evaporation, and an optically positive uniaxiality is formed by depositing a dielectric material having positive refractive index anisotropy when deposited, on a transparent base film in a direction inclined with respect to its normal line. It is also possible to obtain an optically anisotropic layer in which the optical axis is inclined 5 to 50 degrees from the normal direction of the film. For this reason, the dielectric material used may be either a dielectric made of an inorganic compound or a dielectric made of an organic compound, but an inorganic dielectric is preferably used in view of stability to heat applied during vacuum deposition. Examples of the inorganic dielectric materials include tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), silicon dioxide (SiO ₂ ), silicon monoxide (SiO), bismuth oxide (Bi ₂ O ₅ ), and neodymium oxide (Nd ₂ O _3). Metal oxides, such as), are used preferably at the point of being excellent in transparency. Among the metal oxides, those in which refractive index anisotropy is easy to be expressed, such as tantalum oxide, tungsten oxide, bismuth oxide, and the like, are hardly used.

When using the optically anisotropic layer which laminated | stacked the layer of the dielectric material which expresses refractive index anisotropy on such a transparent base film, this optically anisotropic layer is a polarizing film so that the transparent base film side opposes a polarizing film or the protective film bonded to this. Or laminated on a protective film.

On the other hand, in TN mode, in order to further improve viewing angle characteristics and display characteristics, it is preferable to arrange | position an optically anisotropic layer also in the back side polarizing plate which pairs with a liquid crystal cell in between. As an optically anisotropic layer formed in a back side polarizing plate, the optically anisotropic layer in which the optical axis is inclined 5-50 degrees from the normal direction of a film by optically negative uniaxiality as mentioned above can be used preferably.

[5] adhesive layer

In this invention, as shown in FIG. 1, the anti-glare film 1 is laminated | stacked on one surface of the polarizing film 104 via the 1st adhesive bond layer 103a. In addition, when laminating | stacking the protective film or the optical compensation layer 105, they are laminated | stacked on the other surface of the polarizing film 104 via the 2nd adhesive bond layer 103b.

In this invention, as an adhesive agent which forms a 1st adhesive bond layer, the curable composition containing an epoxy resin (preferably it contains as a main component) is used. By using such a curable composition, the water resistance of the anti-glare polarizing plate obtained can be improved, and since high adhesive strength between an anti-glare film and a polarizing film can be obtained, durability of an anti-glare polarizing plate can be improved. Although the adhesive agent which forms a 2nd adhesive bond layer may be the same kind as the adhesive agent which forms a 1st adhesive bond layer, and may be a heterogeneous thing, like an 1st adhesive bond layer from an viewpoint of adhesiveness and durability, an epoxy resin is used. It is preferable to use the curable composition containing (preferably containing this as a main component). Here, an epoxy resin means the compound which has an average of 2 or more epoxy groups in a molecule | numerator, and is hardened by reaction, and contains an oligomer and a monomer other than a polymer.

The adhesion of the antiglare film and the polarizing film using the adhesive made of the above curable composition, the adhesion of the polarizing film and the protective film or the optical compensation layer, may cause active energy rays to be applied to the coating layer of the adhesive interposed between the films to be bonded. It can carry out by irradiating or heating, and hardening curable epoxy-type resin contained in an adhesive agent. The curing of the epoxy resin by irradiation or heating of this active energy ray is preferably performed by cationic polymerization. On the other hand, an active energy ray is a concept containing visible rays, an ultraviolet-ray, an X-ray, an electron beam, etc.

From the viewpoint of weather resistance, refractive index, cationic polymerizability, and the like, as the epoxy resin contained in the curable composition which is the adhesive, a hydrogenated epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin and the like can be exemplified.

The hydrogenated epoxy compound can be obtained by subjecting the aromatic polyhydroxy compound, which is a raw material of the aromatic epoxy resin, to a selective hydrogenation reaction in the presence of a catalyst and under pressure, followed by glycidyl ether. As an aromatic epoxy resin, For example, Bisphenol-type epoxy resins, such as the diglycidyl ether of bisphenol A, the diglycidyl ether of bisphenol F, and the diglycidyl ether of bisphenol S; Novolak-type epoxy resins, such as a phenol novolak epoxy resin, a cresol novolak epoxy resin, and a hydroxy benzaldehyde phenol novolak epoxy resin; Polyfunctional epoxy resins, such as glycidyl ether of tetrahydroxy phenylmethane, glycidyl ether of tetrahydroxy benzophenone, and epoxidized polyvinyl phenol, etc. are mentioned. Hydrogenated epoxy resin can be obtained by carrying out the above-mentioned hydrogenation reaction to aromatic polyhydroxy compounds, such as bisphenols, which are raw materials of these aromatic epoxy resins, and then reacting epichlorohydrin. Especially, the glycidyl ether of hydrogenated bisphenol A is suitable as a hydrogenation epoxy resin.

An alicyclic epoxy resin means the epoxy resin which has one or more epoxy groups couple | bonded with an alicyclic ring in a molecule | numerator. "The epoxy group couple | bonded with the alicyclic ring" means a bridge | crosslinking oxygen atom -O- in the structure shown by following formula, and m is an integer of 2-5 in a following formula.

In the above formula, a compound in which a group in the form in which one or a plurality of hydrogen atoms in (CH ₂ ) _m has been removed is bonded to another chemical structure may be an alicyclic epoxy resin. (CH ₂₎ 1 one or a plurality of hydrogen atoms in the _m is, may even be suitably substituted with a straight chain alkyl group such as methyl or ethyl groups. Among the alicyclic epoxy resins, those having an oxabicyclohexane ring (m = 3 in the above formula) and an oxabicycloheptan ring (m = 4 in the above formula) are preferable because they exhibit excellent adhesion. Is used. Although the alicyclic epoxy resin used preferably below is concretely illustrated, it is not limited to these compounds.

(a) Epoxycyclohexylmethylepoxycyclohexanecarboxylates represented by the following formula (I):

(Wherein R ¹ and R ² independently of one another represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(b) Epoxycyclohexanecarboxylates of alkanediols represented by the following formula (II):

(In formula, R <^3> and R <^4> represents a hydrogen atom or a C1-C5 linear alkyl group independently of each other, and n represents the integer of 2-20.).

(c) epoxycyclohexyl methyl esters of dicarboxylic acids represented by the following formula (III):

(Wherein R ⁵ and R ⁶ independently of each other represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and p represents an integer of 2 to 20).

(d) Epoxycyclohexyl methyl ethers of polyethylene glycol represented by the following formula (IV):

(Wherein R ⁷ and R ⁸ independently of one another represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and q represents an integer of 2 to 10).

(e) Epoxycyclohexylmethyl ethers of alkanediols represented by the following formula (V):

(Wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and r represents an integer of 2 to 20).

(f) a diepoxy citrisspiro compound represented by the following formula (VI):

(Wherein R ¹¹ and R ¹² independently of each other represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(g) Diepoxy monospiro compounds represented by the following formula (i):

(Wherein R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(h) Vinylcyclohexene diepoxides represented by the following formula (i):

(In formula, R <^15> represents a hydrogen atom or a C1-C5 linear alkyl group.).

(i) Epoxycyclopentyl ethers represented by the following formula (i):

(Wherein, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(j) diepoxytricyclodecanes represented by the following formula (i):

(Wherein R ¹⁸ represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

Among the alicyclic epoxy resins exemplified above, the following alicyclic epoxy resins are more preferably used for reasons such as relatively easy to obtain.

(A) esterified product of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid with (7-oxa-bicyclo [4.1.0] hepto-3-yl) methanol [in formula (I) , A compound of R ¹ = R ² = H],

(B) ester of 4-methyl-7-oxabicyclo [4.1.0] heptan-3-carboxylic acid with (4-methyl-7-oxa-bicyclo [4.1.0] hepto-3-yl) methanol Cargo [compound of Formula (I), R ¹ = 4-CH ₃ , R ² = 4-CH ₃ ],

(C) esterified product of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid with 1,2-ethanediol [Formula (II), wherein R ³ = R ⁴ = H, n = 2 compound〕,

(D) an esterified product of (7-oxabicyclo [4.1.0] hepto-3-yl) methanol with adipic acid [compound of R ⁵ = R ⁶ = H, p = 4 in formula (III)] ,

(E) esterified product of (4-methyl-7-oxabicyclo [4.1.0] hepto-3-yl) methanol with adipic acid [In formula (III), R ⁵ = 4-CH ₃ , R ⁶ = 4-CH ₃ , p = 4 compound],

(F) etherified product of (7-oxabicyclo [4.1.0] hepto-3-yl) methanol with 1,2-ethanediol [In formula (V), R ⁹ = R ¹⁰ = H, r = 2 compound].

Moreover, as an aliphatic epoxy resin, the polyglycidyl ether of an aliphatic polyhydric alcohol or its alkylene oxide adduct is mentioned. More specifically, diglycidyl ether of 1,4-butanediol; Diglycidyl ether of 1,6-hexanediol; Triglycidyl ether of glycerin; Triglycidyl ether of trimethylolpropane; Diglycidyl ether of polyethylene glycol; Diglycidyl ether of propylene glycol; And polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides (ethylene oxide, propylene oxide, etc.) to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin.

Epoxy-based resin illustrated above may be used individually by 1 type, and may use 2 or more types together.

The epoxy equivalent of epoxy resin is 30-3000 g / equivalent normally, Preferably it exists in the range of 50-1500 g / equivalent. When epoxy equivalent is less than 30 g / equivalent, the flexibility of the anti-glare polarizing plate after hardening may fall, or adhesive strength may fall. On the other hand, when it exceeds 3000 g / equivalent, compatibility with the other component contained in an adhesive may fall.

From the viewpoint of reactivity, cationic polymerization is preferably used as the curing reaction of the epoxy resin. Therefore, it is preferable that the curable composition which is an adhesive agent contains a cationic polymerization initiator. The cationic polymerization initiator generates cationic species or Lewis acids by irradiation or heating of active energy rays such as visible rays, ultraviolet rays, X-rays and electron beams to start the polymerization reaction of epoxy groups. It is preferable from the viewpoint of workability that any type of cationic polymerization initiator is latent. Hereinafter, cationic species or Lewis acids, which generate cationic species or Lewis acids by irradiation of active energy rays and start the polymerization reaction of epoxy groups, are referred to as "photocationic polymerization initiators", and cationic species or Lewis acids are generated by heat. The cationic polymerization initiator for starting the polymerization reaction of the epoxy group is referred to as "thermal cationic polymerization initiator".

In the method of curing the adhesive by irradiation of active energy rays using the photocationic polymerization initiator, curing at room temperature becomes possible, and the need to consider distortion due to heat resistance or expansion of the polarizing film is reduced, and the antiglare film (and A protective film or an optical compensation layer) and a polarizing film are favorable at the point which can adhere | attach well. Moreover, since a photocationic polymerization initiator acts catalytically by light, even if it mixes with an epoxy resin, it is excellent in storage stability and workability. As a photocationic polymerization initiator, For example, Aromatic diazonium salt; Onium salts such as aromatic iodonium salts and aromatic sulfonium salts; Iron-arene complex and the like.

Examples of the aromatic diazonium salts include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, and the like.

As an aromatic iodonium salt, For example, diphenyl iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluoro phosphate, diphenyl iodonium hexafluoro antimonate, di (4-nonylphenyl) iodonium hexa Fluorophosphate and the like.

Examples of the aromatic sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, and 4,4'-bis (diphenylsulfonate). Phono) diphenylsulfide bishexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluoroantimonate, 4,4 ' -Bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexa Fluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropyl thioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsul Ponyo-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide hexa Fluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenylsulfide tetrakis (pentafluorophenyl) borate, and the like. have.

In addition, examples of the iron-arene complex include xylene-cyclopentadienyl iron (II) hexafluoro antimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, and xylene-cyclopentadienyl iron (II) -tris. (Trifluoromethylsulfonyl) methane etc. are mentioned.

These photocationic polymerization initiators may be used independently, respectively, and may mix and use 2 or more types. Among these, aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorbing properties even in a wavelength range of 300 nm or more, and are excellent in curability and can give a cured product having good mechanical strength and adhesive strength.

These photo cationic polymerization initiators can readily obtain a commercial product, for example, "Kayalad PCI-220" and "Kayalad PCI-620" (above, Nihon Kayaku Co., Ltd.), "UVI-6990", respectively, as a brand name. (Manufactured by Union Carbide Co., Ltd.), "adeka footer SP-150" and "adeka footer SP-170" (above, ADEKA Corporation make), "CI-5102", "CIT-1370", "CIT-1682" "," CIP-1866S "," CIP-2048S "and" CIP-2064S "(above, Nippon Soda Co., Ltd.)," DPI-101 "," DPI-102 "," DPI-103 "," DPI-105 " , "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102" and "DTS-103" (above, Midori Chemical Co., Ltd. make) and "PI-2074" (Made by Rhodia) etc. are mentioned.

The compounding quantity of a photocationic polymerization initiator is 0.5-20 weight part normally with respect to 100 weight part of epoxy resins, Preferably it is 1 weight part or more, Preferably it is 15 weight part or less. When the compounding quantity of a photocationic polymerization initiator is less than 0.5 weight part with respect to 100 weight part of epoxy resins, hardening will become inadequate and there exists a tendency for the mechanical strength and adhesive strength of hardened | cured material to fall. Moreover, when the compounding quantity of a photocationic polymerization initiator exceeds 20 weight part with respect to 100 weight part of epoxy resins, since the ionic substance in hardened | cured material increases, the hygroscopicity of hardened | cured material may become high and durability performance may fall.

When using a photo cationic polymerization initiator, curable composition can contain a photosensitizer further as needed. By using a photosensitizer, the reactivity of cationic polymerization can be improved and the mechanical strength and adhesive strength of hardened | cured material can be improved. As a photosensitizer, a carbonyl compound, an organic sulfur compound, a persulfide, a redox type compound, an azo and a diazo compound, a halogen compound, a photoreducing dye etc. are mentioned, for example.

As a specific example of a photosensitizer, Benzoin derivatives, such as benzoin methyl ether, benzoin isopropyl ether, and (alpha), (alpha)-dimethoxy- (alpha)-phenylacetophenone; Benzophenone derivatives such as benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; Thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropyl thioxanthone; Anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; Acridon derivatives such as N-methylacridone and N-butylacridone; In addition, (alpha), (alpha)-diethoxy acetophenone, benzyl, a fluorenone, a xanthone, a uranyl compound, a halogen compound, etc. are mentioned. These photosensitizers may be used independently, respectively, and may mix and use 2 or more types. It is preferable to contain a photosensitizer in the range of 0.1-20 weight part in 100 weight part of curable compositions.

On the other hand, as a thermal cationic polymerization initiator, a benzyl sulfonium salt, a thiophenium salt, a thiornium salt, benzyl ammonium, a pyridinium salt, a hydradinium salt, carboxylic acid ester, a sulfonic acid ester, an amine imide, etc. are mentioned. These thermal cationic polymerization initiators can obtain a commercial item easily, For example, "Adekao-futon CP77" and "Adekao-futone CP66" (above, ADEKA Corporation make), "CI-2639", and "CI" are all brand names, for example. -2624 "(above, Nippon Soda Co., Ltd.)," San-Ade SI-60L "," San-Ade SI-80L ", and" San-Ade SI-100L "(above, San-Shin-Kagaku Kogyo Co., Ltd.) etc. are mentioned.

The epoxy resin contained in the adhesive may be cured by either photo cationic polymerization or thermal cationic polymerization, or may be cured by both photo cationic polymerization and thermal cationic polymerization. In the latter case, it is preferable to use a photocationic polymerization initiator and a thermal cationic polymerization initiator together.

Moreover, the curable composition which is an adhesive may further contain compounds which accelerate cationic polymerization, such as oxetane and polyols.

Oxetane is a compound which has a 4-membered ring ether in a molecule | numerator, for example, 3-ethyl-3-hydroxymethyl oxetane, 1, 4-bis [(3-ethyl-3- oxetanyl) methoxymethyl] Benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexoxymethyl) oxetane And phenol novolac oxetane. These oxetanes can obtain a commercial item easily, For example, all are brand names "Aron oxetane OXT-101", "Aron oxetane OXT-121", "Aron oxetane OXT-211", "Aron jade" Cetane OXT-221 "and" Aron oxetane OXT-212 "(all are manufactured by Toagosei Co., Ltd.) etc. are mentioned. These oxetanes are contained in curable composition normally in the ratio of 5-95 weight%, Preferably it is 30-70 weight%.

It is preferable that acidic groups other than a phenolic hydroxyl group do not exist, for example, polyol compounds, polyester polyol compounds, polycaprolactone polyol compounds, polyol compounds which have a phenolic hydroxyl group, and polycarbonate which do not have functional groups other than a hydroxyl group Polyol compounds and the like. The molecular weight of these polyols is 48 or more normally, Preferably it is 62 or more, More preferably, it is 100 or more, More preferably, it is 1000 or less. These polyols are contained in a curable composition in 50 weight% or less normally, Preferably it is 30 weight% or less.

In addition, as long as the adhesiveness of the curable composition is not impaired, other additives such as an ion trap, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, an antifoaming agent, and the like are blended. can do. Examples of the ion trapping agent include inorganic compounds such as powdered bismuth type, antimony type, magnesium type, aluminum type, calcium type, titanium type, and a mixed type thereof. As antioxidant, a hindered phenol type antioxidant etc. are mentioned, for example.

After coating the adhesive agent which consists of curable compositions containing an epoxy resin as mentioned above to at least one bonding surface of a to-be-joined material (polarizing film, anti-glare film, protective film, an optical compensation layer), the coated adhesive is interposed. By bonding the objects to be joined to each other and irradiating or heating an active energy ray, the uncured adhesive layer can be cured to obtain the anti-glare polarizing plate of the present invention. The thickness of an uncured adhesive bond layer is 50 micrometers or less normally, Preferably it is 20 micrometers or less, More preferably, it is 10 micrometers or less. As a coating method of an adhesive agent, various coating methods, such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater, can be used, for example. At this time, since each coating system has an optimum viscosity range, respectively, you may make a curable composition contain a solvent for viscosity adjustment. It is preferable to use what melt | dissolves a curable composition satisfactorily as a solvent, without reducing the optical performance of a polarizing film, For example, organic solvents, such as hydrocarbons represented by toluene and esters represented by ethyl acetate, are mentioned.

When bonding a protective film or an optical compensation layer on the opposite side to the side to which the anti-glare film of a polarizing film is bonded, you may bond a glare-proof film and a protective film or an optical compensation layer step by step, and bonding both in one step. You may.

In joining a to-be-joined thing with an adhesive agent, the adhesion process, such as a saponification process, a corona discharge process, a primer process, an anchor coating process, may be previously given to at least one joining surface of a to-be-joined object.

When curing the adhesive by irradiation of active energy rays, the light source to be used is not particularly limited, but has a luminescence distribution at a wavelength of 400 nm or less, such as low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, chemical lamp, black light lamp, A microwave excited mercury lamp, a metal halide lamp, etc. can be used. Although the intensity | strength of light irradiation to an adhesive agent may differ for every composition, it is preferable that the irradiation intensity of the wavelength range effective for activation of a polymerization initiator exists in the range of 0.1-100 mW / cm <2>. When the intensity of light irradiation to the adhesive is less than 0.1 mW / cm 2, the reaction time is too long, and when it exceeds 100 mW / cm 2, the yellowing of the adhesive or the heat generated during polymerization of the curable composition may cause It may cause deterioration. Although light irradiation time to an adhesive agent is controlled for every composition, it does not restrict | limit in particular, It is preferable to set so that accumulated light quantity expressed as a product of irradiation intensity and irradiation time may be in the range of 10-5000 mJ / cm <2>. . If the accumulated amount of light to the adhesive is less than 10 mJ / cm 2, the generation of active species derived from the polymerization initiator may not be sufficient, and curing of the adhesive may be insufficient. Moreover, when accumulated light amount exceeds 5000 mJ / cm <2>, irradiation time becomes very long and it may become disadvantageous for productivity improvement.

In the case of curing the adhesive by heat, heating can be carried out by a generally known method, and the conditions thereof are not particularly limited, but heating is generally performed at a temperature higher than the temperature at which the cationic species or Lewis acid are generated by the thermal cationic polymerization initiator. The specific heating temperature is, for example, about 50 to 200 ° C.

Even in the case of curing under conditions of irradiation or heating of active energy rays, various functions of the anti-glare polarizing plate, such as polarization degree, transmittance and color of the polarizing film, transparency of the anti-glare film or protective film, and phase difference characteristics of the optical compensation layer, are lowered. It is preferable to harden | cure in the range which is not.

<Image display device>

This invention also provides the image display apparatus provided with the anti-glare polarizing plate of this invention mentioned above, and an image display element. In the image display apparatus of this invention, an anti-glare polarizing plate is arrange | positioned at the visual recognition side of an image display element with the anti-glare layer side outside. That is, the anti-glare polarizing plate of this invention is used suitably as a front side polarizing plate, and is arrange | positioned at the visual recognition side of an image display element so that the uneven surface of the anti-glare film, ie, an anti-glare layer side, may be an outer side (visual recognition side). As an image display element, the liquid crystal cell is sealed between upper and lower board | substrates, and the liquid crystal cell which changes the orientation state of a liquid crystal by voltage application, and displays an image is typical. As described above, the driving mode of the liquid crystal cell may be various modes such as a vertical alignment (VA) mode, an in-plane switching (IPS) mode, and a twisted nematic (TN) mode. have.

The anti-glare polarizing plate may be directly bonded to the surface of the image display element, or may be bonded to the surface of the image display element via, for example, a protective film or an optical compensation layer as described above.

The image display apparatus provided with the anti-glare polarizing plate of this invention can scatter incident light by the unevenness | corrugation of the surface which an anti-glare film has, and can apply a background reflection image, and provides outstanding visibility. In addition, even when the anti-glare polarizing plate of the present invention is applied to a high-definition image display device, glare does not occur as seen in a conventional anti-glare film, and sufficient background reflection prevention, whitening prevention, glare suppression, and suppression of contrast reduction It shows excellent performance.

Yes

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited to these Examples. The evaluation method of the anti-glare film used for the anti-glare polarizing plate and the pattern for anti-glare film manufacture in the following examples is as follows.

[1] Measurement of surface shape of antiglare film used for antiglare polarizing plate

The surface shape of the anti-glare film was measured using the three-dimensional microscope "PLμ2300" (manufactured by Sensofar). In order to prevent curvature of a sample, it bonded to the glass substrate so that the uneven surface might become the surface using the optically transparent adhesive, and used for the measurement. When measuring, the magnification of the objective lens was made 10 times. The horizontal resolutions (Δx and Δy) were both 1.66 μm and the measurement area was 850 μm × 850 μm.

(Ratio of energy spectra of elevation (H ₁ ² / H ₂ ² ) and ratio (H ₃ ² / H ₂ ² ))

From the measurement data obtained above, the elevation of the fine concavo-convex surface of the antiglare film is obtained as the two-dimensional function h (x, y), the obtained two-dimensional function h (x, y) is discrete Fourier transformed, and the two-dimensional function H (f _x , f _y ) is obtained. Saved. Two-dimensional function H (f _x, f _y) square by calculating a two-dimensional function of the energy spectrum ^{_{H 2 (f x, f y}} ), f x = 0 cross-sectional curve in H ₂ (0, f _y) from, the space obtain an energy spectrum (H ₁ ²⁾ and spatial energy spectrum (H _{² 2)} at a frequency of 0.04 ㎛ ^-1 at a frequency of 0.01 ㎛ ^-1, it was calculated the ratio ^{_{(H 1 2 / H 2 2}} ) of the energy spectrum. In addition, an energy spectrum (H ₃ ² ) at a spatial frequency of 0.1 μm ⁻¹ was obtained, and the ratio (H ₃ ² / H ₂ ² ) of the energy spectrum was also calculated.

(Inclined angle of the fine uneven surface)

Based on the measurement data obtained above, it calculated based on the algorithm mentioned above, the histogram of the inclination-angle of the uneven surface was created, the distribution for every inclination-angle was calculated | required from it, and the ratio of the surface whose inclination-angle is 5 degrees or less was calculated.

[2] Measurement of optical properties of antiglare film used for antiglare polarizing plate

(Haze)

The haze of the antiglare film was measured by the method specified in JIS K 7136. Specifically, haze was measured using a haze meter "HM-150 type" (manufactured by Murakamishikisai Kijutsugenkusho) in accordance with this standard. In order to prevent curvature of an anti-glare film, it bonded to the glass substrate so that an uneven surface might become a surface using the optically transparent adhesive, and used for the measurement. In general, when the haze increases, the image becomes dark when applied to the image display device, and as a result, the front contrast tends to decrease. Therefore, the lower one of haze is preferable.

[3] Evaluation of anti-glare performance and contrast of anti-glare polarizing plate

In the dark room, the backlight of the produced liquid crystal display device is turned on, and the luminance of the liquid crystal display device in the black display state and the white display state using the luminance meter "BM5A type" (manufactured by Topcon Co., Ltd.). Was measured to calculate the contrast. The contrast is expressed by the ratio of the luminance of the white display state to the luminance of the black display state. Subsequently, this evaluation system was moved into a clear room, it was made into the black display state, and the background reflection state and whitening were visually observed. Subsequently, it was made into the white display state in the bright room, and the glare was also observed visually. The criteria for evaluating background reflection, whitening and glare are as follows.

Background Reflection 1: No background reflection is observed.

2: A little background reflection is observed.

3: Background reflection is clearly observed.

Whitening 1: Whitening is not observed.

2: A little whitening is observed.

3: Whitening is observed clearly.

Glare 1: no glare is observed.

2: Very little glare is observed.

3: severe glare is observed.

[4] Water resistance evaluation of anti-glare polarizing plate

About the produced anti-glare polarizing plate, water resistance was evaluated by the method shown next. First, the antiglare polarizing plate was cut to a size of 5 cm × 2 cm with a long side parallel to the absorption axis (the stretching direction of the polarizing film) of the antiglare polarizing plate to prepare a sample, and the dimensions of the long side direction were measured accurately. did. Here, the polarizing film has a unique color uniformly throughout the entire surface due to the adsorbed iodine. Subsequently, about 80% of the length direction of the sample was immersed in the 60 degreeC water tank, and hold | maintained for 4 hours in the state which hold | maintained one short side of the said sample. Then, the sample was taken out from the water tank, the moisture was wiped off, and the polarizing plate was observed. By this warm water immersion, the polarizing film of a sample shrinks. Moreover, by this warm water immersion, iodine elutes from the periphery of the polarizing film which contact | connects warm water, and the part in which the color fell out exists in the periphery of a sample. The shrinkage of the polarizing film and the degree of color loss are measured by measuring the distance from the end of the sample (the end of the antiglare film) to the region where the color peculiar to the polarizing film remains in the shrinked polarizing film at the center of the sample short side. It evaluated and made erosion length. The smaller the erosion length, the smaller the shrinkage and color loss of the polarizing film, that is, the higher the water resistance as the antiglare polarizing plate.

[5] Evaluation of pattern for antiglare film production

The gray level of the created pattern data was represented by the two-dimensional discrete function g (x, y). The horizontal resolutions (Δx and Δy) of the discrete functions g (x, y) were both 2 m. The obtained two-dimensional discrete function g (x, y) was discrete Fourier transformed to obtain a two-dimensional function G (f _x , f _y ). Two-dimensional function G (f _x, f _y) by the squared spectral two-dimensional function G ² of energy by (f _x, f _y) for calculation, and f _x = 0, the cross-sectional curve in G ² (0, f _y) from, 0 ㎛ ^-1 excess was evaluated whether or not the maximum value in the spatial frequency range of 0.04 ㎛ ^-1 or less.

&Lt; Example 1 >

(A) Preparation of Polarizing Film

After dipping a polyvinyl alcohol film having an average degree of polymerization of about 2400 and a saponification degree of 99.9 mol% or more and a thickness of 75 μm in pure water at 30 ° C., the aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.02 / 2/100 at 30 ° C. Immersed. Then, it immersed at 56.5 degreeC in the aqueous solution whose weight ratio of potassium iodide / boric acid / water is 12/5/100. Subsequently, after wash | cleaning with the pure water of 8 degreeC, it dried at 65 degreeC and obtained the polarizing film in which iodine adsorption-orientated to polyvinyl alcohol. Stretching was mainly carried out in the iodine dyeing and boric acid treatment steps, and the total draw ratio was 5.3 times.

(B) Production of a mold for producing an antiglare film

The thing which copper ballad plating was given to the surface of the aluminum roll (A5056 by JIS) of diameter 200mm was prepared. Copper ballad plating consists of a copper plating layer / thin silver plating layer / surface copper plating layer, and the thickness of the whole plating layer was set so that it might be set to about 200 micrometers. The copper plating surface was mirror-polished, the photosensitive resin was apply | coated to the polished copper plating surface, and it dried and formed the photosensitive resin film. Subsequently, the pattern which consisted of the pattern which consists of image data shown in FIG. 15 repeatedly and repeatedly arranged in succession was exposed and developed by the laser beam on the photosensitive resin film. Exposure and development by a laser beam were performed using "Laser Stream FX" (manufactured by Sink Laboratories Co., Ltd.). Positive photosensitive resin was used for the photosensitive resin film. The pattern shown in FIG. 15 removes low-space frequency components having a spatial frequency of 0.04 μm ⁻¹ or less and high-space frequency components of 0.1 μm ⁻¹ or more with respect to a pattern in which a large number of dots having a dot diameter of 12 μm are randomly arranged. This is written by applying a bandpass filter.

Then, the 1st etching process was performed with the cupric chloride liquid (etching amount: 3 micrometers). The photosensitive resin film was removed from the roll after the first etching treatment, and the second etching treatment was again performed with cupric chloride liquid (etching amount: 10 µm). Then, the chrome plating process was performed so that chrome plating thickness might be set to 4 micrometers, and the metal mold | die A was produced.

(C) Production of antiglare film

Photocurable resin composition "GRANDIC 806T" (manufactured by Dainippon Inkyagagaku Kogyo Co., Ltd.) was dissolved in ethyl acetate to obtain a solution having a concentration of 50% by weight, and "Lucirine TPO" as a photopolymerization initiator (manufactured by BASF Corporation, Chemical Name: 2,4,6-trimethylbenzoyldiphenylphosphine oxide) was added 5 parts by weight per 100 parts by weight of the curable resin component to prepare a coating solution. Next, this coating liquid was apply | coated so that the coating thickness after drying might be set to 6 micrometers on the triacetyl cellulose (TAC) film of 80 micrometers in thickness, and it dried for 3 minutes in the dryer set to 60 degreeC. The TAC film after drying was pressed by the rubber roll so that the photocurable resin composition layer might become a metal mold | die to the uneven surface of the metal mold A obtained previously. In this state, the light from the high-pressure mercury lamp of 20 mW / cm <2> intensity | strength was irradiated so that it might become 200 mJ / cm <2> by h-ray-converted light quantity, and the photocurable resin composition layer was hardened. Thereafter, the TAC film was peeled from the mold for each cured resin, and a transparent antiglare film A made of a laminate of a cured resin (antiglare layer) having a concave-convex surface and a TAC film was produced.

(D) Preparation of adhesive agent which consists of curable composition which has epoxy resin as a main component

100 parts by weight of bis (3,4-epoxycyclohexylmethyl) adipate, 25 parts by weight of diglycidyl ether of hydrogenated bisphenol A and a photo cationic polymerization initiator [4,4'-bis (diphenylsulfonio) di Phenyl sulfide bishexafluorophosphate] 2.2 parts by weight of the mixture was then degassed to obtain an adhesive made of a curable composition. In addition, the photocationic polymerization initiator was mix | blended as a 50 mass% propylene carbonate solution.

(E) Preparation of Anti-glare Polarizer

The said adhesive agent was coated by the 3-micrometer bar coater on the surface (TAC film surface) on the opposite side to the side in which the anti-glare layer of the anti-glare film A was formed, and the said polarizing film was laminated | stacked on it. Moreover, the corona discharge of the stretched norbornene-type resin film ("ZEONOR", Nippon Zeon Co., Ltd. product) (hereinafter also referred to as a norbornene film) as a protective film with a thickness of 70 µm with a corona discharge treatment on the surface. After the said adhesive agent was coated by the 3 micrometer bar coater on the process surface, this norbornene film was laminated | stacked on the surface on the opposite side to the side which the anti-glare film of the polarizing film is bonded on the adhesive coating surface side. Thereafter, ultraviolet irradiation was performed with an ultraviolet irradiation device (lamp: Fusion D lamp, accumulated light amount: 1000 mJ / cm 2) having a belt conveyor, and left at room temperature for 1 hour to obtain an anti-glare polarizing plate A.

(F) Preparation of liquid crystal display device

A liquid crystal panel is taken out from a commercially available liquid crystal television ("LC-32GH3", manufactured by Sharp Co., Ltd.) on which the liquid crystal display element (liquid crystal panel) of the vertical alignment mode is mounted, and a polarizing plate is peeled from the liquid crystal cell, and the back of the liquid crystal cell is carried out. On the (backlit side) side, the polarizing plate "Sumikaran SRW842E" [manufactured by Sumitomogagaku Co., Ltd.] is used on the front surface (viewing side) of the liquid crystal cell. It bonded together through the adhesive layer so that it might correspond to the absorption axis direction of the polarizing plate, and the liquid crystal panel was produced. Subsequently, this liquid crystal panel was assembled with the structure of a backlight / light-diffusion plate / liquid crystal panel, and the liquid crystal display device A was produced.

<Example 2>

In the exposure process in metal mold | die manufacture, the pattern which consisted of the pattern which consists of image data shown in FIG. 16 continuously and repeating is lined up on the photosensitive resin film by laser beam, and the etching in a 1st etching process is carried out. The metal mold | die B was produced like Example 1 except having set the amount to be 5 micrometers, and setting the etching amount in a 2nd etching process to be 12 micrometers. An anti-glare film B was produced in the same manner as in Example 1 except that the obtained mold B was used. In addition, the anti-glare polarizing plate B and the liquid crystal display device B were produced like Example 1 except having used the anti-glare film B. The pattern shown in FIG. 16 removes low-space frequency components with a spatial frequency of 0.035 μm ⁻¹ or less and high-space frequency components of 0.135 μm ⁻¹ or more for a pattern in which a large number of dots having a dot diameter of 12 μm are randomly arranged. This is written by applying a bandpass filter.

Comparative Example 1

The surface of the aluminum roll (A5056 by JIS) with a diameter of 300 mm was mirror-polished, and a zirconia bead TZ-SX-17 (Tosho) was used on a polished aluminum surface using a blasting device (manufactured by Fuji Seisakusho Co., Ltd.). (Manufacture), average particle diameter: 20 micrometers] was blasted by 0.1 MPa (gauge pressure) of blast pressure, 8 g / cm <2> (use amount per cm <2> of surface area of a roll), and the unevenness | corrugation was given to the surface. The electroless nickel plating process was performed about the aluminum roll which the obtained unevenness | corrugation produced, and the metal mold | die C was produced. At this time, it set so that electroless nickel plating thickness might be set to 15 micrometers. An anti-glare film C was produced in the same manner as in Example 1 except that the obtained mold C was used. In addition, the anti-glare polarizing plate C and the liquid crystal display device C were produced like Example 1 except having used the anti-glare film C.

Comparative Example 2

To 100 parts by weight of water, 1.8 parts by weight of a carboxyl group-modified polyvinyl alcohol "Kurarefobal KL318" (modification degree 2 mol%) sold by Kuraray Co., Ltd. is dissolved, and Sumika is a water-soluble polyamide epoxy resin. 1.5 weight part of "Sumirez resin 650" (solid solution of 30 weight% of solid content) sold from Chemtex Co., Ltd. was added, and it melt | dissolved and prepared the polyvinyl alcohol-type adhesive agent.

Subsequently, after saponification-processing the surface on the opposite side to the side where the anti-glare layer of the anti-glare film A was formed, the said polyvinyl alcohol-type adhesive agent was coated by the 10 micrometers bar coater on the saponification process surface, and the said polarizing film was laminated | stacked on it. Furthermore, after coating the said polyvinyl alcohol-type adhesive agent with a 10 micrometer bar coater to the corona discharge treatment surface of the norbornene film (the same thing as Example 1) as a protective film which corona-discharge-treated the surface, this norbornene film is And it laminated | stacked on the surface on the opposite side to the side to which the anti-glare film of the polarizing film is bonded on the adhesive-coating surface side. Thereafter, the mixture was dried at 80 ° C. for 5 minutes, and further cured at room temperature for one day to obtain an anti-glare polarizing plate D.

The measurement and evaluation result of said [1]-[4] was put together in Table 1 and Table 2. In addition, and shows a cross section in the Figure 17, Example 1 and Example 2 A mold of the energy spectrum resulting from a pattern used in the making of the mold _{^{B G 2 (f x, f}} y) in f _x = 0 in. It can be seen from FIG. 17 that the energy spectra of the patterns used in Examples 1 and 2 do not show maximum values in the spatial frequency range of more than 0 μm ^{−1 and} 0.04 μm ⁻¹ or less.

Example 1 Example 2 Comparative Example 1 Anti-glare Polarizer A B C mold A B C Surface shape energy
Ratio of spectrum
H ₁ ² / H ₂ ² 19 4 41 H ₃ ² / H ₂ ² 0.002 0.001 0.003 % Of face with tilt angle less than or equal to 5 ° 100 100 100 Optical properties Haze (%) 0.4 0.6 0.4 Anti-glare property Background One One One all sorts of flowers One One One Glare One One 3 Contrast 1950 1950 1950

Example 1 Comparative Example 2 Water resistance Erosion Length (mm) 0.5 2.1

From the results shown in Table 1, the anti-glare polarizing plate A and the anti-glare polarizing plate B which satisfies all the requirements of the present invention showed no glare at all, exhibited sufficient anti-glare property, and no whitening. Moreover, high contrast was also exhibited when arrange | positioning to an image display apparatus. Moreover, as shown in Table 2, since the anti-glare polarizing plate A of this invention uses the curable composition which has an epoxy resin as a main component as an adhesive agent, water resistance was also high.

On the other hand, glare was generated in the anti-glare polarizing plate C of Comparative Example 1 in which the ratio (H ₁ ² / H ₂ ² ) of the energy spectrum did not satisfy the requirements of the present invention. In addition, the anti-glare polarizing plate D of Comparative Example 2 using the polyvinyl alcohol-based adhesive was inferior in water resistance.

Claims (10)

Anti-glare film comprising an anti-glare layer having a transparent support and an anti-glare layer laminated on the transparent support, and a polyvinyl alcohol system laminated on the surface on the side opposite to the anti-glare layer in the transparent support through a first adhesive layer. As an anti-glare polarizing plate provided with the polarizing film which consists of a resin film,
The said 1st adhesive bond layer consists of hardened | cured material of the curable composition containing an epoxy resin,
The ratio (H ₁ ² ) of the energy spectrum (H ₁ ² ) of the elevation of the uneven surface at the spatial frequency of 0.01 μm ⁻¹ and the energy spectrum (H ₂ ² ) of the elevation of the uneven surface at the spatial frequency of 0.04 μm ⁻¹ / H ₂ ² ) is in the range of 1-20,
The ratio of the spatial frequency 0.1 ㎛ ^-1 energy spectrum of the altitude of the concave-convex surface in the ₍₃ H ²⁾ and a spatial frequency energy spectrum of the altitude of the concave-convex surface in ^{_{0.04 ㎛ -1 (H 2 2)}} (H 3 2 / H ₂ ² ) is 0.1 or less,
The uneven surface is anti-glare polarizing plate comprising 95% or more of the inclination angle of 5 ° or less. The anti-glare polarizing plate according to claim 1, further comprising a protective film laminated on the surface on the side opposite to the anti-glare film in the polarizing film via a second adhesive layer. The anti-glare polarizing plate according to claim 2, further comprising an optical compensation layer laminated on the protective film. The anti-glare polarizing plate of claim 3, wherein the optical compensation layer is an optical compensation film. The anti-glare polarizing plate according to claim 2, wherein the second adhesive layer is made of a cured product of a curable composition containing an epoxy resin. The anti-glare polarizing plate according to claim 1, further comprising an optical compensation layer laminated on the surface on the side opposite to the anti-glare film in the polarizing film via a second adhesive layer. The anti-glare polarizing plate of claim 6, wherein the optical compensation layer is an optical compensation film. The anti-glare polarizing plate according to claim 6, wherein the second adhesive layer is made of a cured product of a curable composition containing an epoxy resin. The anti-glare polarizing plate according to claim 1, wherein the polarizing film is uniaxially stretched and is made of a polyvinyl alcohol-based resin film in which a dichroic dye is adsorbed and oriented. The anti-glare polarizing plate of Claim 1 and an image display element are provided,
The said anti-glare polarizing plate is arrange | positioned at the visual recognition side of the said image display element with the anti-glare layer side outside.

Images