JP2011102881A - Anti-glare film, method of manufacturing the same, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glare film capable of suppressing gloss reflection, and also, achieving high contrast. <P>SOLUTION: The anti-glare film includes: a base material having an uneven surface; and a hard coat layer formed on the uneven surface of the base material. The hard coat layer has an uneven pattern imitating the uneven surface of the base material, on the surface thereof. In the range of the tilt angle of 1.5 to 3.5°, the tilt angle distribution of the uneven surface of the hard coat layer becomes one-tenth of the tilt angle distribution in the tilt angle of 0°. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antiglare film, a method for producing the same, and a display device. Specifically, the present invention relates to an antiglare film having a hard coat layer on a substrate.

  Conventionally, surface treatment such as AG (Anti-Glare) has been performed on the front surface of the display device in order to reduce the reflection of the image display device. In the AG treatment, irregularities are formed on the surface of a display device or the like, and reflection of external light is reduced by light scattering. The unevenness of the AG treatment is formed by coating a resin composition containing fine particles on a substrate and projecting the fine particles from the surface of the coating film. However, since fine particles protrude from the coating film and the surface is formed by protrusions having a steep angle, scattering reflection is strong, and the contrast of the display device is lowered in an external light environment.

  Therefore, in recent AG processing, so-called high-contrast AG processing, which can suppress a decrease in contrast of the display device even under an external light environment, has been studied. As such high-contrast AG processing, a method is considered in which a natural surface phenomenon such as convection is used to form a gradual surface roughness by waviness and reduce projections having steep angles (for example, patents). Reference 1).

Japanese Patent No. 4155336

  However, when the steep angle component is reduced, the reflected light tends to be gathered in the vicinity of regular reflection, so that gloss reflection tends to be strong (see FIG. 1). When gloss reflection becomes strong in this way, reflection may be felt strongly under external light. For example, in a room surrounded by a white wall or a window where external light is incident, the effect of gloss reflection is stronger than the reduction of diffuse reflection, so the surface of a display device with high contrast AG is subjected to conventional AG. On the contrary, you can feel the reflection more strongly than the thing.

  Accordingly, an object of the present invention is to provide an antiglare film that can suppress glossy reflection and obtain high contrast, a method for producing the same, and a display device.

In order to solve the above-mentioned problem, the first invention
A substrate having an uneven surface;
A hard coat layer formed on the uneven surface of the substrate,
The hard coat layer has an uneven shape on the surface following the uneven surface of the substrate,
The inclination angle distribution of the concavo-convex surface of the hard coat layer is an antiglare film that is 1/10 of the inclination angle distribution of the inclination angle of 0 ° within the range of the inclination angle of 1.5 ° to 3.5 °. .

The second invention is
Applying an ionizing radiation curable resin containing an inorganic oxide filler and a viscosity modifier on the uneven surface of the substrate;
Drying the applied ionizing radiation curable resin;
Curing the dried ionizing radiation curable resin and forming a hard coat layer on the substrate,
In the drying process, the surface of the inorganic oxide filler and the viscosity modifier form a bond, thereby increasing the viscosity of the ionizing radiation curable resin, and the increased ionizing radiation curable resin is the uneven surface of the substrate. Follow
Production of an antiglare film in which the inclination angle distribution of the concavo-convex surface of the hard coat layer is 1/10 of the inclination angle distribution of the inclination angle of 0 ° within the inclination angle range of 1.5 ° to 3.5 °. Is the method.

  In the present invention, the inclination angle distribution of the concavo-convex surface of the hard coat layer is set to 1/10 of the inclination angle distribution of the inclination angle of 0 ° within the inclination angle range of 1.5 ° to 3.5 °. Thereby, regular reflection intensity can be reduced and gloss reflection can be suppressed. Further, it is possible to suppress the cloudiness due to scattering reflection and obtain a high contrast.

  As described above, according to the present invention, gloss reflection can be suppressed and high contrast can be obtained.

FIG. 1 is a graph showing the diffuse reflection characteristics of a conventional antiglare film. FIG. 2 is a cross-sectional view showing a configuration example of the antiglare film according to the first embodiment of the present invention. FIG. 3 is a plan view showing an example of the shape of the uneven surface of the substrate. FIG. 4 is a graph showing a preferable range of the minimum distance R _m and the maximum distance R _M of the structure. FIG. 5 is a flowchart for explaining an example of a method for producing an antiglare film according to the first embodiment of the present invention. 6A to 6C are process diagrams for explaining an example of a method for producing an antiglare film according to the first embodiment of the present invention. 7A to 7D are process diagrams for explaining an example of a method for producing an antiglare film according to the first embodiment of the present invention. 8A to 8C are process diagrams for explaining an example of a method for producing an antiglare film according to the first embodiment of the present invention. FIG. 9 is a cross-sectional view showing one configuration of the liquid crystal display device according to the second embodiment of the present invention. FIG. 10 is a graph showing the measurement results of the surface shapes of the TAC film and hard coat layer of Example 1. 11A and 11B are graphs showing the diffuse reflection characteristics of the antiglare films of Examples 1 and 3 and Comparative Examples 1 to 3. FIG. FIG. 12 is a graph showing strength ratios of the antiglare films of Examples 1 to 3 and Comparative Examples 1 to 3. 13A to 13C are diagrams illustrating calculation results of autocorrelation functions of the antiglare films of Example 1, Comparative Example 2, and Comparative Example 4. FIG. FIG. 14A and FIG. 14B are diagrams showing the observation results of the film surfaces that are the base shapes of Example 1 and Comparative Example 3. FIG. FIG. 15 is a graph showing the cumulative frequency distribution of the inclination angle of the substrate uneven surface of Example 1 and Comparative Example 3. FIG. 16 is a graph showing the standardization frequency of the inclination angle of the uneven surface of the base material of Example 1 and Comparative Example 3. FIG. 17 is a graph showing the normalized frequency of the inclination angle of the hard coat layer uneven surface of Examples 1 to 3. FIG. 18 is a graph showing the normalized frequency of the inclination angle of the hard coat layer uneven surface of Comparative Examples 1-3.

Embodiments of the present invention will be described in the following order with reference to the drawings.
1. First embodiment (example of anti-glare film)
2. Second Embodiment (Example in which an antiglare film is applied to the surface of a display device)

<1. First Embodiment>
[1.1. Structure of antireflection film]
FIG. 2 is a cross-sectional view showing a configuration example of the antiglare film according to the first embodiment of the present invention. This antiglare film is an optical film having a concavo-convex shape on the surface and scattering reflected light by the concavo-convex shape. As shown in FIG. 2, the antiglare film 1 includes a base material 11 having an uneven surface and a hard coat layer 12 formed on the uneven surface of the base material 11. The concavo-convex surface of the base material 11 is configured by repeatedly forming a structure 11 a which is a concave portion or a convex portion on the surface of the base material 11. In FIG. 2, an example in which the structure 11a is a convex portion is shown.

  The total light transmittance is preferably 92% or more. This is because if it is 92% or more, the amount of light from the backlight can be maintained without deteriorating the transparency of the substrate 11. The haze is preferably 1.5% or less. This is because if it is 1.5% or less, it is possible to suppress the scattering of the backlight light and the scattering of the surface reflected light, and black can be visually recognized as black. The internal haze is preferably 0.5% or less. This is because if it is 0.5% or less, scattering of backlight light can be suppressed, and the color can be visually recognized as a more natural color. The haze is a sum of surface haze and internal haze.

(Base material)
FIG. 3 is a plan view showing an example of the shape of the uneven surface of the substrate 11. As shown in FIG. 3, structures 11 a that are concave portions or convex portions are irregularly (randomly) formed on the surface of the base material 11. This structure 11 is preferably formed irregularly in two dimensions or three dimensions. This is because the surface of the hard coat layer 12 can be irregularly irregularly formed two-dimensionally or three-dimensionally by forming the surface of the hardcoat layer that follows the uneven surface of the substrate 11. . Moreover, it is preferable that the size of the bottom surface of the structure 11a changes irregularly. This is because the period of the concavo-convex shape (swell) on the surface of the hard coat layer can be irregularly changed by forming such a hard coat layer surface that follows the concavo-convex surface of the substrate 11. Here, the two-dimensional irregularity means that the structures 11a or irregularities are irregularly formed in the in-plane direction of the antiglare film 1 or the substrate 11. The three-dimensional irregularity means that the structures 11a or irregularities are irregularly formed in the in-plane direction of the antiglare film 1 or the substrate 11, and the antiglare film 1 or the substrate 11 is irregular. In the thickness direction, the structure 11a or irregularities are irregularly formed.

  The structure 11a preferably has a side surface that extends from the top to the bottom of the structure 11a. When it has such a shape, it is preferable that the bottom surfaces of the adjacent structures 11a are in contact with each other or substantially in contact with each other. Examples of the shape of the structure 11a that is the concave portion or the convex portion include a dome shape, a cone shape, and a column shape. However, the shape is not limited to these shapes, and may be arbitrarily set according to desired optical characteristics. You can choose. Examples of the dome shape include a hemispherical shape and a semi-elliptical spherical shape. Examples of the cone shape include a cone shape with a sharp tip, a cone shape with a curvature at the tip, and a cone shape with the tip cut off. Specific examples include a cone shape, a truncated cone shape, an elliptical cone shape, an elliptical truncated cone shape, a polygonal pyramid shape, and a polygonal truncated cone shape. Examples of the shape of the polygonal pyramid include a quadrangular pyramid, a hexagonal pyramid, and an octagonal pyramid. Examples of the columnar shape include a columnar shape and a polygonal columnar shape. Examples of the shape of the polygonal column include a quadrangular column, a hexagonal column, and an octagonal column. In addition, shape anisotropy may be imparted to the structure 11a. From the viewpoint of adjusting the optical characteristics in the horizontal direction and the vertical direction of the display device, for example, in two orthogonal directions among the in-plane directions of the substrate 11 It is preferable to impart shape anisotropy. Specifically, examples of the shape of the structure 11a having shape anisotropy include an elliptical columnar shape, a semi-elliptical spherical shape, an elliptical truncated cone shape, and a polygonal columnar shape or a polygonal pyramid shape extended in one direction.

  Examples of the shape of the bottom surface of the structure 11a include a circular shape, an elliptical shape, and a polygonal shape. Examples of the polygonal shape of the bottom surface include a quadrangular shape, a hexagonal shape, and an octagonal shape. When the bottom surface of the structure 11a is an elliptical shape or a polygonal shape, the structure 11a is arranged on the substrate surface so that the bottom surface shape of the structure 11a is aligned in the same direction, for example. Specifically, when the bottom surface of the structure 11a is elliptical, the long axis direction or the short axis direction is aligned in the same direction. When the bottom surface of the structure 11a is polygonal, the corners having the same angle are arranged so as to be aligned in the same direction. The shape of the bottom surface of the structure 11a is preferably selected according to desired characteristics. For example, when the shape of the bottom surface of the structure 11a is an elliptical shape, the major axis direction is smoother as compared with the minor axis direction, so that it is less susceptible to external light from the major axis direction. Therefore, the display screen can be prevented from becoming whitish. In addition, since the concave and convex shape is rough in the short axis direction as compared with the long axis direction, it is possible to ensure good antiglare properties. That is, when the bottom surface of the structure 11a is elliptical, the antiglare film 1 having high antiglare property and high contrast as a whole can be obtained.

It is preferable that the structure 11a satisfies the following relationships (1) to (3). It is because generation | occurrence | production of a moire can be suppressed and the anti-glare film 1 excellent in anti-glare property and contrast can be obtained.
(1) The size of bottoms of the structures 11a is, the minimum distance R _m or more, randomly varying within a maximum distance R _M or less.
(However, the minimum distance R _{m is} the minimum value of the shortest distance from the center of gravity of the bottom surface of the structure 11a to the periphery of the bottom surface, and the maximum distance R _{M is} the maximum distance from the center of gravity of the bottom surface of the structure 11a to the periphery of the bottom surface. Maximum value)
(2) The bottom surfaces of the structures 11a are in contact with or substantially in contact with each other.
(3) The minimum distance R _m and the maximum distance R _M of the bottom surface of the structure 11a satisfy the relationship of R _m / R _M ≦ 0.9.
If the relationship (1) is not satisfied and the size of the bottom surface of the structure 11a does not change at random, moire occurs. When the relationship (2) is not satisfied and the bottom surfaces of the structures 11a are not in contact with each other or are not substantially in contact with each other, the filling rate is reduced and the antiglare property is reduced. If the relationship of (3) is not satisfied and the ratio exceeds 0.9, the arrangement becomes regular and moire tends to occur. Here, that the bottom surfaces of the structures 11a are substantially in contact with each other means that the bottom surfaces of the structures 11a are adjacent to each other within a range of 0 μm to 80 μm.

FIG. 4 shows a preferred range for the minimum distance R _m and the maximum distance R _M of the structure. As shown in FIG. 4, it is preferable to satisfy the relationship of R _m / R _M ≦ 0.9. The minimum distance R _m and the maximum distance R _M of the structure 11a are preferably in the range of R _m <R _M ≦ 75 μm, more preferably 10 μm ≦ R _m <R _M ≦ 75 μm. When the minimum distance R _m is less than 10 μm, the anti-glare property increases when trying to obtain anti-glare property, and the anti-glare property decreases when trying to suppress the anti-cloudiness property. That is, it becomes difficult to achieve both antiglare properties and suppression of cloudiness. When the maximum distance R _M exceeds 75 μm, the surface is rough, or when the screen is viewed, it is glaring.

Minimum distance if the R _m and the maximum distance R _M satisfy the relationship _{R m / R M ≦ 0.9,10μm ≦} R m <R M ≦ 75μm, the average irregularity height PV of the surface of the hard coat layer 12 is, 0 It is preferable that it is in the range of 15 μm ≦ PV ≦ 1.6 μm. When PV is less than 0.15 μm, antiglare properties tend not to be obtained. When PV exceeds 1.6 μm, the cloudiness increases and the cloudiness tends to exceed 0.64%. The turbidity is preferably 0.64% or less. This is because if it is 0.64% or less, the scattering of backlight light and the scattering of surface reflected light can be suppressed, and black can be visually recognized as black. PV indicates the height between the highest point of the convex portion (structure 11a) and the lowest point of the valley (formed between adjacent convex portions).

When the bottom surface of the structure 11a is circular, the minimum distance R _m is the minimum radius R _m and the maximum distance R _M is the maximum radius R _M in each of the above relationships. Further, the bottom surface of the structures 11a, if it is elliptical, the minimum distance R _m is the minimum value R _m of the short axis (short diameter), the maximum distance R _M is the long axis length (major axis) it is the maximum value R _M of.

It is preferable to further arrange the structure 11a in a gap formed between the bottom surfaces of the structure 11a. This is because by further disposing such structures 11a, the filling rate of the structures 11a can be increased, the flat portions can be reduced, and the antiglare property can be increased. The shortest distance from the center of gravity of the bottom of the structure 11a is disposed in the gap to the peripheral edge of the bottom, for example, it is set below the minimum distance R _m of the structure 11a described above. It is preferable that the height of the structure 11a changes continuously in conjunction with the size of the bottom surface.

  The substrate 11 is, for example, a plastic substrate having transparency. As the shape of the substrate 11, for example, a film having transparency can be used. Here, the film is defined to include a sheet. As a material of the base material 11, for example, a known polymer material can be used. Specific examples of known polymer materials include triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), poly Examples include acrylate, polyether sulfone, polysulfone, polypropylene (PP), diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin, urea resin, urethane resin, and melamine resin. The thickness of the substrate 11 is preferably 38 to 100 μm from the viewpoint of productivity, but is not particularly limited to this range.

(Hard coat layer)
The hard coat layer 12 is for imparting both the scratch resistance and the antiglare property to the surface of the substrate 11, that is, the surface of a polarizer or a display device. It is a resin layer. The hard coat layer 12 is obtained by applying, drying and curing the resin composition on the uneven surface of the substrate 11. The hard coat layer 12 has a concavo-convex shape following the concavo-convex surface of the substrate 11 on the surface. This uneven shape is preferably a continuous wavefront that follows the uneven surface of the substrate 11. The concavo-convex shape is preferably a two-dimensional or three-dimensional irregular concavo-convex shape. It is because generation | occurrence | production of a moire can be suppressed. The positions of the concave and convex portions of the hard coat layer 12 preferably correspond to the positions of the concave and convex portions of the base material 11, respectively. The amount of unevenness on the surface of the hard coat layer is, for example, smaller than the amount of unevenness on the surface of the substrate, and the amount of unevenness tends to decrease as the coating thickness of the hard coat layer increases. The cross section of the hard coat layer when cut in an arbitrary direction is preferably a continuous wave shape. Thereby, a smooth wave | undulation can be formed in the hard-coat layer surface, and light can be diffused by this wave | undulation. Here, the continuous wavefront means that the hard coat layer surface is smoothly connected without discontinuities and steps, and specifically, can be differentiated at any point on the hard coat layer surface.

  The concavo-convex surface of the hard coat layer 12 includes a plurality of protrusions having side surfaces extending from the top portion toward the bottom portion. By providing a plurality of projections having such side surfaces, the uneven surface of the antiglare film 1 can be formed by gentle undulation. That is, the scattering range of external light can be narrowed without impairing the antiglare property. Among the plurality of protrusions, the bottom surfaces of adjacent protrusions are in contact with each other or substantially in contact with each other. With such a relationship, the filling rate of protrusions on the uneven surface of the antiglare film 1 can be increased, the flat portion can be reduced, and the antiglare property can be increased. Here, the fact that the bottom surfaces of the protrusions are almost in contact means that the distance between the bottom surfaces of the protrusions is adjacent within a range of 0 μm to 80 μm. It is preferable that the height of the protruding portion formed on the surface of the hard coat layer 12 continuously changes in conjunction with the size of the bottom surface. This is because the spectroscopic phenomenon can be further suppressed by continuously changing the height of the protruding portion. When there is a spectroscopic phenomenon, when a distant fluorescent lamp is reflected, a rainbow pattern is generated around the fluorescent lamp.

  The shape of the bottom surface of the protrusion is preferably at least one of a circular shape, an elliptical shape, and a polygonal shape, and more preferably a polygonal shape. When the shape of the bottom surface of the protrusion is at least one of a circular shape, an elliptical shape, and a polygonal shape, the high-angle surface inclination tends to be reduced. When the shape of the bottom surface of the protrusion is a polygonal shape, the filling ratio of the protrusion on the uneven surface of the hard coat layer 12 can be increased, the flat portion can be reduced, and the antiglare property can be increased.

  The inclination angle distribution of the concavo-convex surface of the hard coat layer 12 is 1/10 of the inclination angle distribution of the inclination angle of 0 ° within the range of the inclination angle of 1.5 ° to 3.5 °. When it is less than 1.5 °, when applied as an antiglare film, the specular reflection intensity is strong, and there is a tendency that reflection is a concern. If it exceeds 3.5 °, when applied as an antiglare film, the influence of diffuse reflection of external light becomes prominent, so that the whole tends to appear cloudy.

The light diffusely reflected on the uneven surface of the hard coat layer 12 preferably has substantially the same intensity within a range of −4 ° to 4 °, more preferably −8 ° to 8 °. . By applying almost the same intensity of reflected light within this range, when applied as an anti-glare film, reflection can be strongly prevented, and since only regular reflection does not protrude, gloss reflection can be suppressed. is there. Further, the ratio (G ₁₀ / G ₀ ) of the reflection gain G ₁₀ of 10 ° or more to the reflection gain G ₀ of 0 ° is preferably 1/100 or less. By satisfying this relationship, when applied as an antiglare film, the cloudiness can be suppressed.

[1.2. Method for producing antireflection film]
Next, an example of a method for producing an antiglare film according to the first embodiment of the present invention will be described with reference to the flowchart shown in FIG. 5 and the process diagrams shown in FIGS.

(Resist layer formation process)
First, in step S1, a resist layer 22 is formed on the surface of the substrate 21 that is a workpiece (see FIG. 6A). Examples of the shape of the base material 21 that is a workpiece include a plate shape, a sheet shape, a film shape, a block shape, a columnar shape, and a cylindrical shape. As a material of the resist layer 22, for example, either an inorganic resist or an organic resist can be used. In addition, when the base material 21 has column shape or cylindrical shape, it is preferable to form the resist layer 22 in those outer peripheral surfaces. If necessary, in the pre-process of step S1, the surface of the base material 21, which is the workpiece, may be plated to form a plating layer such as copper plating.

(Exposure process)
Next, in step S2, for example, an exposure pattern 22a is formed on the resist layer 22 by irradiating the resist layer 22 with laser light L1 (see FIG. 6B). Examples of the shape of the exposure pattern 22a include a circular shape, an elliptical shape, and a polygonal shape. For example, the minimum distance R _m or more, with randomly changing the size of the exposure patterns 22a in the maximum distance R _M or less in the range, while in contact with the exposure patterns 22a to each other or in contact with almost the resist layer with a laser beam L 22 Irradiate. Further, the minimum distance R _m and the maximum distance R _{M of} the exposure pattern 22a are set to satisfy the relationship of R _m / R _M ≦ 0.9. Note that when the bottom surface of the exposure pattern 22a is circular in each relationship above, the minimum distance R _m is the minimum radius R _m, the maximum distance R _M is the maximum radius R _M. Further, when the bottom surface of the exposure pattern 22a is elliptical, the minimum distance R _m is the minimum value R _m of the short axis (short diameter), the maximum distance R _M is the long axis length of (long diameter) it is the maximum value R _M.

(Development process)
Next, in step S3, the resist layer 22 on which the exposure pattern 22a is formed is developed. Thereby, the opening part 22b according to the exposure pattern 22a is formed in the resist layer 22 (refer FIG. 6C). 6C shows an example in which a positive resist is used as the resist and the opening 22b is formed in the exposed portion, but the resist is not limited to this example. That is, a negative resist may be used as the resist and the exposed portion may be left.

  The minimum distance d between adjacent openings 22b is preferably 1 μm or more and (D2 × 4) μm or less. Here, D2 is an etching depth (amount) by re-etching (second etching process). When the minimum distance is less than 1 μm, the walls between the recesses having a columnar shape or the like are broken and connected at the time of re-etching, so that flat portions increase and the antiglare property tends to decrease. When the minimum distance exceeds (D2 × 4) μm, even if the entire surface of the base material 21 is re-etched, the flat portion increases and the antiglare property tends to decrease.

(Etching process)
Next, in step S4, the surface of the base material 21 is etched using the resist layer 22 in which the opening 22b is formed as a mask. Thereby, the recessed part 21a is formed (refer FIG. 7A). As the etching, for example, either dry etching or wet etching can be used, but it is preferable to use wet etching in view of simple facilities. As the etching, for example, either isotropic etching or anisotropic etching can be used, and it is preferable to select appropriately according to the desired shape of the structure 11a.

  The depth D1 of the etching process is preferably 0.5 μm or more and 10 μm or less. If it is less than 0.5 μm, it is necessary to reduce the film thickness of the hard coat layer 12 in order to maintain the antiglare property, and the pencil hardness tends to decrease. Or, by the re-etching process, the depth of the concave portion becomes shallow, or the flat portion increases, and the antiglare property tends to decrease. On the other hand, if the thickness exceeds 10 μm, it is necessary to increase the thickness of the hard coat layer 12 in order to produce a rough feeling after applying the hard coat paint or to suppress white turbidity, and the curl tends to increase. In addition, the transfer speed tends to decrease and productivity tends to decrease. As an etchant, for example, a cupric chloride etchant (cupric chloride, hydrochloric acid, water) can be used, but is not limited thereto.

(Resist stripping process)
Next, in step S5, the resist layer 22 formed on the substrate surface is removed by ashing or the like (see FIG. 7B). Thereby, the recessed part 21a which has the same depth (for example, 5 micrometers) is formed in the base-material surface, for example. That is, an uneven surface is formed on the substrate surface.

(Re-etching process)
Next, in step S6, the entire uneven surface of the substrate 21 is re-etched. Thereby, the plurality of recesses 21a formed on the surface of the base material 21 can be changed from, for example, a columnar shape to a dome shape, and a master 23 having a smooth uneven surface is obtained (see FIG. 7C). The uneven surface of the master 23 is obtained by inverting the uneven surface of the substrate 11.

(Plating process)
Next, in step S7, the uneven surface of the master 23 is plated as necessary to form a plating layer (not shown) such as nickel plating or chrome plating. By forming the plating layer in this way, it is possible to improve wear durability for long-term use.

(Shape transfer process)
Next, in step S8, the master 23 is pressed against the smooth surface of the base 11 and the base 11 is heated to transfer the uneven shape of the master 23 to the base 11 (see FIG. 7D). . Thereby, the base material 11 which has an uneven surface is obtained.

(Coating process)
Next, in step S9, a resin composition (hereinafter also referred to as a paint as appropriate) 13 is applied onto the uneven surface of the substrate 11 (see FIG. 8A). The coating method is not particularly limited, and a known coating method can be used. Known coating methods include, for example, micro gravure coating method, wire bar coating method, direct gravure coating method, die coating method, dip method, spray coating method, reverse roll coating method, curtain coating method, comma coating method, knife coating. Method, spin coating method and the like.

(Resin composition)
As a resin composition, what has the characteristic that a viscosity rises and fluidity | liquidity is lost in the drying process (step S10) which is a post process is preferable. This is because the resin composition can follow the uneven surface of the substrate 11 in the drying step, which is a subsequent step. From the viewpoint of ease of production, the resin composition is preferably an ionizing radiation curable resin that is cured by light or an electron beam, or a thermosetting resin that is cured by heat. As the ionizing radiation curable resin, a photosensitive resin composition curable by light is preferable, and an ultraviolet curable resin composition curable by ultraviolet light is most preferable. The ionizing radiation curable resin or thermosetting resin preferably contains an inorganic oxide filler, a viscosity modifier, and a solvent. It is because a resin composition can be made to follow the uneven surface of the base material 11 in the drying process which is a post process by including these materials.

(UV curable resin composition)
The ultraviolet curable resin composition contains, for example, an acrylate, a photopolymerization initiator, an inorganic oxide filler, a viscosity modifier, and a solvent. Moreover, it is preferable that the ultraviolet curable resin composition further contains an antifouling agent from the viewpoint of imparting antifouling properties. Moreover, it is preferable that an ultraviolet curable resin composition further contains a leveling agent from a viewpoint of the wettability improvement to the base material 11. FIG. In addition, the ultraviolet curable resin composition preferably further contains an antistatic agent from the viewpoint of imparting an antistatic function to the antiglare film 1. Moreover, you may make it an ultraviolet curable resin composition further contain the organic or inorganic filler which provides an internal haze to a hard-coat as needed. Thus, when a filler is contained, it is preferable that the refractive index difference of a filler and a matrix is 0.01 or more. The average particle size of the filler is preferably 0.1 to 1 μm. Moreover, you may make it an ultraviolet curable resin composition further contain a light stabilizer, a flame retardant, antioxidant, etc. as needed.

  Hereinafter, the acrylate, the photopolymerization initiator, the inorganic oxide filler, the viscosity modifier, the solvent, the antistatic agent, the antifouling agent, and the leveling agent will be sequentially described.

(Acrylate)
As the acrylate, it is preferable to use a monomer and / or an oligomer having two or more (meth) acryloyl groups. As this monomer and / or oligomer, for example, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyol (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate and the like are used. be able to. Here, the (meth) acryloyl group means either an acryloyl group or a methacryloyl group. Here, the oligomer refers to a molecule having a molecular weight of 500 or more and 60000 or less.

(Photopolymerization initiator)
As the photopolymerization initiator, those appropriately selected from known materials can be used. As a known material, for example, a benzophenone derivative, an acetophenone derivative, an anthraquinone derivative, or the like can be used alone or in combination. The blending amount of the polymerization initiator is preferably 0.1% by mass or more and 10% by mass or less in the solid content. If it is less than 0.1% by mass, the photocurability is lowered, which is substantially unsuitable for industrial production. On the other hand, when it exceeds 10 mass%, when the amount of irradiation light is small, odor tends to remain in the coating film. Here, solid content means all the components which comprise the hard-coat layer 12 after hardening, for example, all components other than a solvent and a viscosity modifier. Specifically, for example, acrylate, photopolymerization initiator, inorganic oxide filler, antistatic agent, leveling agent, antifouling agent, and the like are referred to as solid content.

(Inorganic oxide filler)
Examples of the inorganic oxide filler include silica, alumina, zirconia, antimony pentoxide, zinc oxide, tin oxide, indium tin oxide (ITO), indium oxide, and antimony-doped tin oxide: ATO), aluminum zinc oxide (AZO), and the like can be used. The surface of the inorganic oxide filler is preferably surface-treated with an organic dispersant having a functional group such as a (meth) acryl group, a vinyl group, or an epoxy group at the terminal. As the organic dispersant, for example, a silane coupling agent having the above functional group at the terminal is suitable. Examples of the silane coupling agent having an acryl group at the terminal include KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the silane coupling agent having a methacryl group at the terminal include KBM-502, KBM-503, KBE-502, and KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the silane coupling agent having a vinyl group at the terminal include KA-1003, KBM-1003, and KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the silane coupling agent having an epoxy group at the terminal include KBM-303, KBM-403, KBE-402, and KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd. In addition to the silane coupling agent, an organic carboxylic acid may be used. By using the inorganic oxide filler surface-treated in this way, in the curing step of the coating film described later, the inorganic oxide filler is integrated with an acrylate such as a (meth) acrylic monomer and / or oligomer around it, The coating film hardness and flexibility are improved.

  The inorganic oxide filler preferably has an OH group or the like on its surface. Thereby, in the process of drying the coating film to be described later, in the process of evaporating the solvent, the OH group on the surface of the inorganic oxide filler and the functional group of the viscosity modifier are hydrogen-bonded or coordinate-bonded, The viscosity increases and preferably the paint gels. As the viscosity increases in this way, the coating material follows the uneven shape of the base material 11, and an uneven shape that follows the uneven shape of the base material 21 is formed on the surface of the paint.

  The average particle diameter of the inorganic oxide filler is, for example, 1 nm or more and 100 nm or less. The inorganic oxide filler content is preferably 10% by mass or more and 70% by mass or less in the solid content. The total solid content is 100% by mass. If it is less than 10% by mass, the system will not increase in viscosity during the solvent evaporation process, or the amount of the viscosity modifier necessary for increasing the viscosity will increase too much, causing the paint to become turbid or the coating film hardness to deteriorate. There is. On the other hand, when it exceeds 70 mass%, there exists a tendency for the flexibility of a cured film to fall.

(Viscosity modifier)
Examples of the viscosity modifier include a hydroxy group (OH group), a carboxyl group (COOH group), a urea group (—NH—CO—NH—), an amide group (—NH—CO—), and an amino group (NH ₂ ). A molecule having a group can be used, and it is preferable to use a molecule having two or more functional groups selected from these functional groups. Moreover, as a viscosity modifier, it is preferable to use the molecule | numerator which has a carboxyl group from a viewpoint of suppressing aggregation of an inorganic oxide filler. It is also possible to apply known anti-sagging agents and anti-settling agents. Examples of the viscosity modifier include BYK-405, BYK-410, BYK-411, BYK-430, BYK-431 manufactured by Big Chemie Japan Co., Ltd. Floren G-700, Floren G-900 and the like are preferable. It is preferable that the compounding quantity of a viscosity modifier is 0.001-5 mass parts with respect to 100 mass parts of all the coating materials. It is preferable that the optimum blending amount is appropriately selected according to the material type and blending amount of the inorganic oxide filler, the material type of the viscosity modifier, and the desired hard coat film thickness.

(solvent)
The solvent is preferably a solvent that dissolves a resin raw material such as acrylate to be used, has good wettability with the base material 11, and does not whiten the base material 11. Examples of such solvents include acetone, diethyl ketone, dipropyl ketone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, methyl acetate, and ethyl acetate. , Ketones such as propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, sec-amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate or Carboxylic acid esters, methanol, ethanol, isopropanol, n-butanol, sec-butanol, tert-butanol and other alcohols, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane It can be mentioned ethers. These solvents may be used singly or as a mixture of two or more components. Furthermore, solvents other than those exemplified above can be added as long as the performance of the resin raw material is not impaired.

(Antistatic agent)
As described above, the resin composition preferably further contains an antistatic agent. The antistatic agent preferably contains at least one of a quaternary ammonium salt, a conductive polymer, an ionic liquid, and conductive fine particles.

  As the quaternary ammonium salt, a compound having a quaternary ammonium base in the molecule is preferably used. As the compound having a quaternary ammonium base in the molecule, a monomer and / or oligomer having one or more quaternary ammonium bases and one or more (meth) acryloyl groups may be used. preferable. An antistatic function can be imparted to the hard coat layer 12 by the quaternary ammonium base in the molecule. In addition, since the monomer and / or oligomer has a (meth) acryloyl group, it is integrated with a matrix resin or the like by ultraviolet irradiation. Thereby, bleed-out of the quaternary ammonium salt is suppressed.

  Examples of the compound having a quaternary ammonium base in the molecule include methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloylaminopropyltrimethylammonium chloride, methacryloylaminopropyltrimethylammonium chloride, acryloyloxyethyldimethylbenzylammonium chloride. , Methacryloyloxyethyldimethylbenzylammonium chloride, methacryloylaminopropyldimethylbenzylammonium chloride, methacryloyloxyethyltrimethylammonium methylsulfate, methacryloylaminopropyltrimethylammonium methylsulfate, methacryloyloxyethyldimethyl Le ethylammonium ethyl sulfate, methacryloyl aminopropyl dimethyl ethyl ammonium ethylsulfate, methacryloyloxyethyl trimethyl ammonium p- toluenesulfonate, and the like methacryloylamino trimethylammonium p- toluenesulfonate.

  Examples of the conductive polymer include substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and one or two (co) polymers selected from these. In particular, polypyrrole, polythiophene, poly N-methylpyrrole, poly-3-methylthiophene, poly-3-methoxythiophene, poly (3,4-ethylenedioxythiophene), and one or two selected from these (co-) Polymers are preferred.

  As the conductive polymer, it is preferable to select a polymer having good compatibility with the ultraviolet curable resin composition. When the compatibility is poor, the amount of the conductive polymer necessary for obtaining the desired antistatic performance increases, leading to deterioration of mechanical properties, coloring (transparency deterioration), and the like.

  It is preferable that a conductive polymer contains a dopant from a viewpoint of an electroconductive improvement. Examples of the dopant include halogen compounds, Lewis acids, and protonic acids. Specific examples include organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, fullerenes, hydrogenated fullerenes, carboxylic fullerenes, and sulfonated fullerenes. A polyethylene dioxythiophene solution doped with polystyrene sulfonic acid is preferable in that it has a relatively high thermal stability and a low degree of polymerization, and thus is advantageous in transparency after coating film formation.

(Anti-fouling agent)
As described above, the resin composition preferably further contains an antifouling agent. As the antifouling agent, it is preferable to use a silicone oligomer and / or a fluorine-containing oligomer having one or more (meth) acryl groups, vinyl groups, or epoxy groups. When it is necessary to impart alkali resistance to the antiglare film 1, it is preferable to use a fluorine-containing oligomer. It is preferable that the compounding quantity of the said silicone oligomer and / or a fluorine oligomer is 0.01 to 5 mass% of solid content. If it is less than 0.01% by mass, the antifouling function tends to be insufficient. On the other hand, when it exceeds 5 mass%, there exists a tendency for coating-film hardness to fall. Examples of the antifouling agent include RS-602 and RS-751-K manufactured by DIC Corporation, CN4000 manufactured by Sartomer, Optool DAC-HP manufactured by Daikin Industries, Ltd., and X-22 manufactured by Shin-Etsu Chemical Co., Ltd. It is preferable to use -164E, FM-7725 manufactured by Chisso Corporation, EBECRYL350 manufactured by Daicel-Cytec Corporation, TEGORad2700 manufactured by Degussa Corporation, and the like.

(Leveling agent)
As described above, the ultraviolet curable resin composition preferably further contains a known leveling agent from the viewpoint of improving wettability to the substrate 11. The blending amount of the leveling agent is preferably 0.01% by mass or more and 5% by mass or less of the solid content. If it is less than 0.01% by mass, the wettability tends to be insufficiently improved. When it exceeds 5 mass%, there exists a tendency for coating-film hardness to fall.

(Drying process)
Next, in step S10, the solvent is volatilized by drying the resin composition 13 coated on the uneven surface of the substrate 11. The drying conditions are not particularly limited, and may be natural drying or artificial drying that adjusts the drying temperature, drying time, and the like. However, when wind is applied to the surface of the paint at the time of drying, it is preferable not to generate a wind pattern on the surface of the coating film. Further, the drying temperature and drying time can be appropriately determined depending on the boiling point of the solvent contained in the paint. In that case, it is preferable to select the drying temperature and the drying time in a range in which the base material 11 is not deformed by heat shrinkage in consideration of the heat resistance of the base material 11.

  As the solvent evaporates, the solids concentration of the paint increases, and the inorganic oxide filler and the viscosity modifier form a network through bonds such as hydrogen bonds or coordination bonds in the system, increasing the viscosity. Increase viscosity. By increasing the viscosity in this manner, the uneven shape of the base material 11 remains on the surface 13s of the dried resin composition (see FIG. 8B). That is, moderate smoothness is formed on the surface 13s of the dried resin composition, and antiglare properties are exhibited. As described above, when the fat composition has a high viscosity in the process of solvent evaporation, the resin composition after drying follows the uneven shape of the substrate 11 and exhibits anti-glare properties. On the other hand, when the UV curable resin composition does not increase in viscosity, the uneven shape of the substrate 11 is crushed by the dried resin composition, and the antiglare property cannot be obtained.

(Curing process)
Next, in step S11, the resin composition 13 dried on the uneven surface of the substrate 111 is cured by, for example, ionizing radiation irradiation L2 or heating. Thereby, the hard coat layer 12 having a smooth uneven shape is formed (see FIG. 8C). As the ionizing radiation, for example, an electron beam, an ultraviolet ray, a visible ray, a gamma ray, an electron beam or the like can be used, and an ultraviolet ray is preferable from the viewpoint of production equipment. The integrated irradiation dose is preferably selected as appropriate in consideration of the curing characteristics of the resin, suppression of yellowing of the resin and the substrate 11, and the like. Moreover, it is preferable to select suitably as atmosphere of irradiation according to the kind of resin composition, For example, the atmosphere of inert gas, such as air, nitrogen, and argon, is mentioned.
Thus, the intended antiglare film 1 is obtained.

  In addition, the formation method of the base pattern (uneven pattern of the base material 11) may be any method as long as it has projection diameter distribution selectivity, random arrangement, height controllability, projection shape (tilt) controllability, and the like. It is not limited to the forming method. For example, after applying a resist on a metal mold, a computer-generated random pattern is ablated and removed by laser light, and a protrusion is formed on the metal mold roll with an etchant that dissolves the metal. Further, it is also possible to use a method in which this laser etching technique is repeated in multiple stages using a pattern obtained by incrementing / decrementing the diameter of the base pattern. After pattern formation by these methods, the inclination can be made gentle by peeling the resist and etching the whole.

  When a random pattern is generated by a computer, if the diameter distribution of the circular pattern is narrowed or the arrangement between patterns is restricted in order to increase the pattern density, the randomness will be reduced, and the moire will be reduced when applied to a display device. Although not generated, the reflected light tends to be dispersed. For this reason, it is preferable that the circular pattern has a wide diameter distribution and that there is no restriction on arrangement. For example, the diameter distribution of the circular pattern is preferably 10 μm to 200 μm, more preferably 20 μm to 170 μm, and still more preferably 20 μm to 140 μm. By selecting the diameter distribution range of such a circular pattern, the maximum value of the autocorrelation function can be suppressed to 0.1 or less, and the spectral phenomenon can be reduced. The diameter distribution on the bottom surface of the structure of the base material 11 is substantially the same as that of the circular pattern generated by the computer described above.

  In order to achieve desired diffuse reflection angle characteristics, it is preferable to adjust the etching depth of the mold and the total etching time after the resist is removed. In addition, it is preferable to apply a resin whose leveling property is adjusted by adding an inorganic filler, a viscosity modifier, or the like on the uneven surface of the substrate 11 while adjusting the film thickness.

  As described above, according to the first embodiment, the antiglare film 1 includes the base material 11 having an uneven surface and the hard coat layer 12 formed on the uneven surface of the base material 11. The hard coat layer 12 has an uneven shape following the uneven surface of the substrate 11 on the surface. The inclination angle distribution of the concavo-convex surface of the hard coat layer 12 is 1/10 of the inclination angle distribution of the inclination angle of 0 ° within the range of the inclination angle of 1.5 ° to 3.5 °. Thereby, gloss reflection can be suppressed and high contrast can be obtained. Moreover, the anti-glare film 1 having high contrast can be realized even under external light by reducing the specular reflection intensity and suppressing the cloudiness due to scattering reflection.

  By applying a resin composition prepared so as to have a shape following property on a base formed by controlling the surface roughness, it is possible to control the diffuse reflection angle characteristics at a low angle of 10 ° or less. As the reflection characteristics, it is possible to obtain substantially the same intensity in a specific angle range selected from the range of ± 4 ° to ± 8 °, and to reduce the reflection gain to a high angle of 10 ° or more to 1/100 or less. preferable. Thereby, while reducing the specular reflection intensity, it is possible to suppress the white turbidity due to scattering reflection and to obtain high contrast even under external light. Moreover, high contrast can be obtained even under external light illumination, and a reflected image can be significantly suppressed. In addition, sufficient mechanical strength to be applied to the display device surface can be imparted.

<2. Second Embodiment>
[Configuration of liquid crystal display device]
FIG. 9 is a cross-sectional view showing one configuration of the liquid crystal display device according to the second embodiment of the present invention. As shown in FIG. 9, the liquid crystal display device includes a backlight 3 that emits light, and a liquid crystal panel 2 that displays an image by temporally and spatially modulating the light emitted from the backlight 3. Polarizers 2a and 2b are provided on both surfaces of the liquid crystal panel 2, respectively. The polarizer 2b on the display surface side of the liquid crystal panel 2 is provided with an antiglare film 1 that is an optical film.
Hereinafter, the backlight 3, the liquid crystal panel 2, and the antiglare film 1 constituting the liquid crystal display device will be sequentially described.

(Backlight)
As the backlight 3, for example, a direct type backlight, an edge type backlight, and a planar light source type backlight can be used. The backlight 3 includes, for example, a light source, a reflecting plate, an optical film, and the like. Examples of the light source include a cold cathode fluorescent lamp (CCFL), a hot cathode fluorescent lamp (HCFL), organic electroluminescence (OEL), and inorganic electroluminescence (IEL). ) And a light emitting diode (LED).

(LCD panel)
Examples of the liquid crystal panel 2 include a twisted nematic (TN) mode, a super twisted nematic (STN) mode, a vertically aligned (VA) mode, and a horizontal alignment (In-Plane Switching: IPS). Mode, Optically Compensated Birefringence (OCB) mode, Ferroelectric Liquid Crystal (FLC) mode, Polymer Dispersed Liquid Crystal (PDLC) mode, Phase Transition Guest Host (Phase) A display mode such as Change Guest Host (PCGH) mode can be used.

  For example, polarizers 2a and 2b are provided on both surfaces of the liquid crystal panel 2 so that their transmission axes are orthogonal to each other. The polarizers 2a and 2b allow only one of the orthogonal polarization components of incident light to pass through and block the other by absorption. As the polarizers 2a and 2b, for example, a polyvinyl alcohol (PVA) film with an iodine complex or a dichroic dye arranged in a uniaxial direction can be used. It is preferable to provide protective layers, such as a triacetyl cellulose (TAC) film, on both surfaces of the polarizers 2a and 2b. Thus, when providing a protective layer, it is preferable to set it as the structure which this protective layer serves as the base material of the anti-glare film 1 as well. This is because the polarizers 2a and 2b can be thinned by using such a configuration.

(Anti-glare film)
Since the anti-glare film 1 is the same as that of the first embodiment described above, description thereof is omitted.

  According to the second embodiment, since the antiglare film 1 is provided on the display surface of the liquid crystal display device, it is possible to improve the antiglare property and scratch resistance on the display surface of the liquid crystal panel 2.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.

In this example, the film thickness (average film thickness) of the hard coat layer was as follows using a stylus type surface roughness measuring instrument (trade name: Surfcorder ET4000, manufactured by Kosaka Laboratory Ltd.). It is what I have sought.
First, a 6 mmφ cylindrical contact terminal is used, and the hard coating layer is brought into contact with the hard coating layer with a low load that does not crush the hard coating layer, and the thickness of the antiglare film is measured at five arbitrary points. did. Then, simply adding the average thickness of the measured antiglare film, an average value was obtained D _A total thickness antiglare film. Next, the thickness of the uncoated part of the same anti-glare film was measured at arbitrary 5 points. Then, simply adding the average thickness of the measured substrate (TAC film), to obtain an average thickness D _B of the base material. Next, it subtracted the mean thickness D _B of the base material from the average value D _A total thickness antiglare film was the value and the film thickness of the hard coat layer.

Example 1
First, as a transfer roll master, a roll-shaped base material in which the surface of an iron core (φ100 mm, surface length 300 mm) was subjected to copper plating was prepared. Next, a photoresist was applied to the surface of the roll plated with copper to form a photoresist layer. Next, a circular random pattern having a minimum diameter D _{m of} 20 μm to a maximum diameter D _{M of} 140 μm was generated by a computer. Next, based on this generated pattern, the resist layer formed on the outer peripheral surface of the substrate was exposed with laser light, and then the exposed resist layer was developed. Thereby, the opening part according to the said production | generation pattern was formed in the resist layer. Next, the outer peripheral surface of the base material was wet-etched using the resist layer in which the opening was formed as a mask. Next, the resist layer was removed from the outer peripheral surface of the base material, and the entire outer peripheral surface of the base material 11 was wet etched again. Thereby, the roll original disc in which the smooth unevenness | corrugation was formed in the outer peripheral surface was obtained.

  Next, the unevenness of the roll master was transferred onto the surface of a TAC film (Fuji Photo Film Co., Ltd., film thickness: 80 μm). Thereby, the TAC film which has smooth unevenness | corrugation on the surface was obtained. Next, the surface shape of the TAC film was evaluated with a stylus type surface roughness measuring instrument (trade name: Surfcorder ET4000, manufactured by Kosaka Laboratory Ltd.). The result is shown in FIG. 10A. Ra (arithmetic average roughness) = 0.903 μm, Rz (ten-point average roughness) = 2.907 μm, RSm (average length of roughness curve elements) = 65 μm.

Next, an ultraviolet curable resin composition having the following composition was coated on the concavo-convex surface of the TAC film with a # 14 wire bar, and then the coated ultraviolet curable resin composition was 1. Dry for 5 minutes. Next, the dried UV curable resin composition was irradiated with 350 mJ / cm ² of UV in a nitrogen atmosphere to form a 5 μm thick hard coat layer on the TAC film. Thus, the intended antiglare film was obtained.

<Formulation of UV curable resin composition>
Hexafunctional urethane acrylic oligomer 35.3 parts by mass (manufactured by Kyoeisha Chemical Co., Ltd., trade name: UA-510H)
17.65 parts by mass of pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMMT)
40 parts by mass of silica filler having an average particle size of 25 nm (however, the filler surface was treated with a silane coupling agent having an acrylic group at the end (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.))
5 parts by mass of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184)
2 parts by mass of fluorine-containing bifunctional acrylic oligomer (manufactured by DIC Corporation, trade name: RS-602)
Leveling agent 0.05 parts by mass (Kyoei Chemical Co., Ltd., trade name: KL-600)
Viscosity modifier 0.025 parts by mass (Kyoei Chemical Co., Ltd., trade name: G700)
Solvent: IPA 15 parts by mass Cyclohexanone 71.9 parts by mass

  Next, the surface shape of the hard coat layer was evaluated with a stylus type surface roughness measuring instrument. The result is shown in FIG. 10B. Ra (arithmetic average roughness) = 0.182 μm, Rz (ten-point average roughness) = 0.886 μm, and RSm (average length of roughness curve elements) = 85 μm. In addition, a moderately smooth uneven shape was formed on the surface of the hard coat layer, following the uneven shape of the film. This is because in the drying process, the silica filler and the viscosity modifier formed a bond, and the ultraviolet curable resin composition increased in viscosity and followed the uneven shape of the TAC film.

(Example 2)
An antiglare film was obtained in the same manner as in Example 1 except that the ultraviolet curable resin composition was applied with a # 12 wire bar and the thickness of the hard coat layer was changed to 4 μm.

(Example 3)
First, an uneven surface was formed on the TAC film in the same manner as in Example 1. Next, after coating the UV curable resin composition of the following composition on the concavo-convex surface of the TAC film with a # 18 wire bar, the UV curable resin composition was dried in a drying oven at 65 ° C. for 1.5 minutes. It was. Next, the dried UV curable resin composition was irradiated with 350 mJ / cm ² of UV in a nitrogen atmosphere to form a 5 μm thick hard coat layer on the TAC film. Thus, the intended antiglare film was obtained.

<Formulation of UV curable resin composition>
Hexafunctional urethane acrylic oligomer 35.3 parts by mass Pentaerythritol tetraacrylate 17.65 parts by mass Silica filler with an average particle size of 25 nm 40 parts by mass (however, the filler surface was treated with a silane coupling agent having an acrylic group at the end)
Photopolymerization initiator 5 parts by mass Fluorine-containing bifunctional acrylic oligomer 2 parts by mass Leveling agent 0.05 parts by mass Viscosity modifier 0.033 parts by mass Solvent: IPA 56.700 parts by mass Cyclohexanone 116.5 parts by mass Since the company name and the product name of the supplier are the same as in Example 1, the description is omitted.

(Comparative Example 1)
First, an ultraviolet curable resin composition having the following composition was coated on a flat surface of a TAC film (Fuji Photo Film Co., Ltd., film thickness: 80 μm) that had not been transferred with a # 5 wire bar. . Next, the applied ultraviolet curable resin composition was dried in an oven at 80 ° C. for 2 minutes. Next, the dried ultraviolet curable resin composition was irradiated with ultraviolet rays at 100 mJ / cm ² to form a hard coat layer having a thickness of 8 μm on the TAC film. Thus, the intended antiglare film was obtained.

<Formulation of UV curable resin composition>
Hexafunctional urethane acrylic oligomer 100 parts by mass Acrylic polyol-based polymer 5 parts by mass Crosslinkable styrene beads 3 parts by mass (manufactured by Sekisui Plastics Co., Ltd., trade name: SBX6, average particle size 6 μm)
Photopolymerization initiator 3 parts by mass Solvent: t-butanol 153 parts by mass The name of the company from which the material other than the crosslinkable styrene beads is obtained and the product name are the same as those in Example 1 and therefore will not be described.

  Next, the surface of the antiglare film was observed with a laser microscope and an optical microscope, and the state of the fine particles was evaluated. As a result, it was found that the fine particles were dispersed and surface irregularities were formed by the protrusion of the fine particles.

(Comparative Example 2)
First, an ultraviolet curable resin composition having the following composition was coated with a # 16 wire bar on a flat surface of a TAC film (Fuji Photo Film Co., Ltd., film thickness: 80 μm) that was not shape-transferred. . Next, the applied ultraviolet curable resin composition was dried in an oven at 80 ° C. for 2 minutes. Next, the dried UV curable resin composition was irradiated with 500 mJ / cm ² of UV in a nitrogen atmosphere to form a hard coat layer having a thickness of 15 μm on the TAC film. Thus, the intended antiglare film was obtained.

<Formulation of UV curable resin composition>
Hexafunctional urethane acrylic oligomer 95 parts by mass Acrylic polyol-based polymer 5 parts by mass Crosslinkable MS beads 27.5 parts by mass (manufactured by Sekisui Plastics Co., Ltd., trade name: Techpolymer, refractive index 1.515, average particle size 5. 0μm, coefficient of variation 7)
Photopolymerization initiator Irgacure 184 5 parts by mass Solvent: Toluene 89 parts by mass Dimethyl carbonate 73 parts by mass The company name and the trade name of the materials other than the crosslinkable MS beads are the same as in Example 1 Omitted.

  Next, the surface of the antiglare film was observed with a laser microscope and an optical microscope, and the state of the fine particles was evaluated. As a result, it was found that the fine particles formed an aggregate in the hard coat layer surface, and this flocculation was taken as one peak, and a gentle undulation was formed on the hard coat layer surface.

(Comparative Example 3)
An anti-glare film was obtained in the same manner as in Example 1 except that re-etching after peeling of the resist layer was not performed during the production of the roll master, and the film thickness of the hard coat layer was changed to 7 μm.

(Comparative Example 4)
The diameter distribution of the circular pattern used at the time of producing the roll master is set to the minimum diameter D _m : 60 μm to the maximum diameter D _M : 75 μm, and the thickness of the hard coat layer is set to 7 μm without re-etching after the resist layer is peeled off. Except for this, an antiglare film was obtained in the same manner as in Example 1.

  The following evaluation was performed with respect to the antiglare films of Examples 1 to 3 and Comparative Examples 1 to 4 obtained as described above.

(20 ° gloss)
The 20 ° glossiness of the antiglare film was measured as follows. In order to suppress the influence of the back surface reflection and evaluate the glossiness of the antiglare film, the produced antiglare film was black acrylic plate (Mitsubishi Rayon Co., Ltd., 3 mm thick) with an optical adhesive having a haze of 0.5% or less. Product name: Acrylite L 502). Next, the glossiness of 20 ° was measured with a microtrigloss manufactured by Gardner, based on the perpendicular line on the surface of the acrylic plate. The results are shown in Table 1.

(Diffuse reflection angle characteristics)
In order to suppress the influence of back surface reflection and measure the diffuse reflection characteristics of the antiglare film itself, the back surface of the antiglare film is coated with a black acrylic plate (Mitsubishi Rayon Co., Ltd.) with an optical adhesive having a haze of 0.5% or less. Bonded to a product made by company, product name: Acrylite L 502). Next, using a goniophotometer (trade name: GP-1-3D, manufactured by Optec Co., Ltd.), the incident light collimated from the −5 ° direction with respect to the sample surface (perpendicular to the acrylic plate surface) is irradiated and specular reflection is performed. The reflected light intensity was obtained under darkroom conditions by scanning from −5 ° to 10 ° with the direction set to 0 °. At this time, the luminance meter of the goniophotometer had a 1 ° field of view. The half-value angle, 1/10 angle, and 10 ° gain obtained from the reflection intensity were obtained. The results are shown in Table 2. Note that “1/10 angle” indicates an angle at which the gain is 1/10 of the 0 ° gain. 11A and 11B show the diffuse reflection characteristics of Examples 1 and 3 and Comparative Examples 1 to 3. FIG.

(Characteristic evaluation under light environment)
In order to confirm the darkness of the sun and the reflection of people and background in a light environment, the evaluation was performed as follows. First, the polarizing plate with anti-glare was peeled off from the panel surface of Sony LCD TV BRAVIA KDL-40F1, and a polarizing plate having a TAC surface without anti-glare treatment was bonded. Next, the antiglare films of Examples and Comparative Examples were bonded to the upper layer with an optical adhesive having a haze of 0.5% or less. The display screen of this liquid crystal television was visually confirmed under ambient illumination with an illuminance of 800 Lux, and edge blurring, reflection, and cloudiness were evaluated according to the following criteria. The evaluation results are shown in Table 2 by “◯” mark, “Δ” mark, and “X” mark.

(Edge blur)
○: The edge of the object is blurred so that it cannot be determined what is reflected △: The edge of the object is blurred, but it can be determined what is reflected ×: The edge of the object is clearly visible

(A feeling of reflection)
○: Reflected image intensity is weak, and the reflection is not noticed at all △: Reflected, but not noticeable if it is concentrated on the image ×: Reflected image intensity is strong, when viewing the image Worried

(Cloudiness)
○: Black is tightened and the contrast is high even in bright places. △: Black is floating, but it is not a problem when viewing images. ing

(Anti-fouling properties)
The antifouling properties were evaluated by the pure water contact angle (CA-XE type manufactured by Kyowa Interface Science Co., Ltd.), fingerprint wiping properties, and the repelling / wiping properties of oily magic (Zebra Co., Ltd. Mackey Black).

In Table 1, the structure of the anti-glare film of Examples 1-3 and Comparative Examples 1-4 is shown.

In Table 2, the evaluation result of the anti-glare film of Examples 1-3 and Comparative Examples 1-4 is shown.

From the above evaluation results, the following was found.
In the anti-glare films of Examples 1 to 3, the edge of the object is blurred so that it cannot be determined what is reflected, and the specular reflection intensity is also low, so the reflection is not bothered at all and the wall is not Even in a relatively bright room, the cloudiness is low and looks black. In contrast, in the anti-glare film of Comparative Example 1, the edge of the object is so blurred that it is impossible to determine what is reflected, and although the reflection is not worrisome, the cloudiness is strong and the room is bright. Then black appears to float. In the films of Comparative Examples 2 to 4, although the edge of the object is blurred, since the gloss is strong, the blurred image is strongly observed and the reflection is anxious.

  In addition, when the uneven surface is formed of particles as in Comparative Examples 1 and 2, when trying to increase the antiglare property, the cloudiness increases, and when the high angle gain is decreased, the gloss reflection increases, so that it is bright. It is difficult to obtain a highly antiglare and high contrast film in a room. On the other hand, as in Examples 1 to 3, the surface shape can be freely designed by applying and curing a resin having shape followability on the shape-transferred base, in a bright room. However, an antiglare film having high antiglare and high contrast can be obtained. However, as in Comparative Example 3, when a roll for shape transfer is not re-etched, a sharp cylindrical base is formed, and a thick resin composition is applied to fill a steep slope. There is a problem that the glossy reflection is increased due to the gentle undulation shape. For this reason, it is preferable to control the shape of the base, the shape following property of the resin, and the film thickness.

(Strength ratio)
In the diffuse reflection characteristic, the ratio of the maximum gain intensity to the minimum gain intensity in a certain angle range was taken. For example, within the reflection angle of ± 2 degrees, the maximum gain of Example 1 is 13.4 and the minimum gain is 8.2, so this ratio is 1.6. Similarly, the reflection angle range is plotted on the horizontal axis, and the gain ratio plotted on the vertical axis is shown in FIG.

(Surface shape autocorrelation function)
The measurement of the autocorrelation function of the surface shape was calculated by RBX3300H Lite manufactured by Ryoka System Co., Ltd. using a VertScan 2.0 system. In order to force the distortion of the antiglare film, the antiglare film was fixed to a slide glass, and the objective lens was 10 times, the intermediate lens was 0.5 times, and observation was performed with a phase mode having a wavelength of 520 nm. At this time, the horizontal resolution was 1.7 μm, and the vertical resolution was 0.01 nm. The calculation results of the autocorrelation function are shown in FIGS. 13A to 13C. Moreover, the observation result of the film surface used as the foundation | substrate shape of Example 1 and Comparative Example 3 is shown to FIG. 14A and FIG. 14B.

  Further, the autocorrelation function measured by VertScan shows broad characteristics in Examples 1 to 3 in which the uneven surface was formed by shape transfer and Comparative Example 2 in which the uneven surface was formed by fine particles, and the maximum value was also shown. It was as low as about 0.1. On the other hand, in Comparative Example 4 where the pattern arrangement is relatively regular, several peaks are observed in the autocorrelation function, and the value is as large as 0.4, and this film reflects a fluorescent lamp. Color separation that seems to be due to diffraction was observed. In addition, since the film of the comparative example 1 had high uneven | corrugated roughness, the jump of data occurred in the case of a measurement, and it was not able to calculate.

(Cumulative frequency of tilt angle)
A tilt angle was calculated from roughness measurement data of a stylus type surface roughness measuring instrument (trade name: Surfcorder ET4000, manufactured by Kosaka Laboratory Ltd.), and a histogram of angle distribution was created. The result is shown in FIG.

(Normalization frequency of tilt angle)
The tilt angle is calculated from the roughness measurement data of the stylus type surface roughness tester (trade name: Surfcorder ET4000, manufactured by Kosaka Laboratory Ltd.), a histogram of the angle distribution is created, and standardized at a frequency of 0 ° And plotted. The results are shown in FIGS.

  From FIGS. 17 and 18, in Examples 1 to 3, the inclination angle distribution of the concavo-convex surface of the hard coat layer is an inclination having an inclination angle of 0 ° within a range of an inclination angle of 1.5 ° to 3.5 °. It can be seen that the angular distribution is 1/10. On the other hand, in Comparative Examples 1 to 3, the inclination angle distribution of the concavo-convex surface of the hard coat layer is an inclination angle distribution having an inclination angle of 0 ° within the inclination angle range of 1.5 ° to 3.5 °. It turns out that it is not 1/10 of.

  As mentioned above, although embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, Various deformation | transformation based on the technical idea of this invention is possible.

  For example, the configurations, methods, shapes, materials, numerical values, and the like given in the above-described embodiments are merely examples, and different configurations, methods, shapes, materials, numerical values, and the like may be used as necessary.

  The configurations of the above-described embodiments can be combined with each other without departing from the gist of the present invention.

  Moreover, you may make it use the anti-glare film which concerns on the above-mentioned embodiment for a display apparatus as an anti-Newton-Ring (Anti Newton-Ring: ANR) film. By using it as an ANR film in this way, it is possible to suppress the generation of Newton rings or to reduce the generation of Newton rings to the extent that it does not matter.

  Moreover, although the above-mentioned embodiment demonstrated as an example the case where the anti-glare film which concerns on this invention is applied to a liquid crystal display device, the anti-glare film which concerns on this invention is with respect to various display apparatuses other than a liquid crystal display device. Is applicable. For example, CRT (Cathode Ray Tube) display, Plasma Display Panel (PDP), Electro Luminescence (EL) display, Surface-conduction Electron-emitter Display (SED), etc. The antiglare film according to the present invention can be applied to various display devices.

DESCRIPTION OF SYMBOLS 1 Anti-glare film 2 Liquid crystal panel 2a, 2b Deflector 3 Back light 11 Base material 11a Structure 12 Hard coat layer 21 Base material 21a Recess 22 Resist layer 22a Exposure pattern 22b Opening 23 Master 13 Resin composition 13s Surface

Claims (11)

A substrate having an uneven surface;
A hard coat layer formed on the uneven surface of the substrate,
The hard coat layer has an uneven shape on the surface following the uneven surface of the substrate,
The anti-glare film in which the unevenness distribution of the concavo-convex surface of the hard coat layer is 1/10 of the inclination distribution of the inclination angle of 0 ° within the range of the inclination angle of 1.5 ° to 3.5 °. The light diffusely reflected by the uneven surface of the hard coat layer has substantially the same intensity within the range of −4 ° to 4 ° and has a reflection gain of 10 ° or more with respect to the reflection gain G ₀ of 0 °. anti-glare film according to claim 1, wherein the ratio of _{G 10 (G 10 / G 0} ) is 1/100 or less. The light diffusely reflected by the uneven surface of the hard coat layer has substantially the same intensity within a range of −8 ° to 8 ° and has a reflection gain of 10 ° or more with respect to a reflection gain G ₀ of 0 °. anti-glare film according to claim 1, wherein the ratio of _{G 10 (G 10 / G 0} ) is 1/100 or less. The hard coat layer is obtained by applying, drying and curing an ionizing radiation curable resin on the uneven surface of the substrate,
The anti-glare film according to claim 1, wherein the ionizing radiation curable resin contains an inorganic oxide filler and a viscosity modifier.   The anti-glare film according to claim 4, wherein the inorganic oxide filler and the viscosity modifier form a bond. The substrate has a structure that is a recess or a protrusion,
The uneven surface of the substrate is formed by the structure,
2. The antiglare film according to claim 1, wherein the bottom surface of the structure is circular or elliptical. The structure has a side surface extending from the top to the bottom of the structure,
The antiglare film according to claim 6, wherein the bottom surfaces of the adjacent structures are in contact with each other or substantially in contact with each other. The bottom surface of the structure is circular,
The antiglare film according to claim 6, wherein the distribution of the diameter of the bottom surface is 10 μm or more and 200 μm or less.   A display apparatus provided with the anti-glare film of any one of Claims 1-8. Applying an ionizing radiation curable resin containing an inorganic oxide filler and a viscosity modifier on the uneven surface of the substrate;
Drying the applied ionizing radiation curable resin;
Curing the dried ionizing radiation curable resin, and forming a hard coat layer on the substrate,
In the drying step, the surface of the inorganic oxide filler and the viscosity modifier form a bond, thereby increasing the viscosity of the ionizing radiation curable resin and increasing the viscosity of the ionizing radiation curable resin. Follow the uneven surface of the substrate,
The inclination angle distribution of the uneven surface of the hard coat layer is 1/10 of the inclination angle distribution of the inclination angle of 0 ° within the inclination angle range of 1.5 ° to 3.5 °. Production method. Before the coating process,
Producing a master having an uneven surface;
A step of transferring the uneven surface of the master to a base material and producing a base material having the uneven surface,
The production process of the master is
Forming a resist layer on the surface of the substrate;
Forming a predetermined pattern of openings in the resist layer on the substrate;
Etching the base material using the resist layer having the openings of the predetermined pattern as a mask, and forming an uneven surface on the surface of the base material; and
The method for producing an antiglare film according to claim 10, further comprising: removing the resist layer from the surface of the base material and etching the entire uneven surface of the base material again.