JP2006053511A - Antidazzle polarizing film layered body and liquid crystal display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antidazzle polarizing film layered body having high antidazzle property imparted and improved in viewing angle characteristics without increasing haze, and to provide a liquid crystal display excellent in antidazzle property and display characteristics by using the layered body. <P>SOLUTION: The antidazzle polarizing film layered body 10 comprises an antidazzle layer 15, a linear polarizer 30 and an optical anisotropic layer 40 layered in this order. The antidazzle layer 15 has an antidazzle plane having a large number of fine spheres formed on the surface. When the antidazzle plane is observed from above for spheric domains, spheric domains having 0.1 to 10 μm height and 25 to 2,500 μm<SP>2</SP>area possess ≥90% of the entire surface and a flat portion possesses ≤10% of the entire surface. The optical anisotropic layer 40 shows optically negative or positive uniaxial property with its optical axis inclined by 5 to 50° from the normal direction of the film. The layered body 10 is disposed in the display surface side of a TN liquid crystal cell 50 to obtain a liquid crystal display. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polarizing film laminate suitably used for a liquid crystal display device and the like and a liquid crystal display device using the same.

  Liquid crystal display devices are increasingly used for portable TVs, notebook personal computers, etc. due to their characteristics such as light weight, thinness, and low power consumption. Today, they are also being applied to video viewing equipment such as large TVs. Yes. In a liquid crystal display device used for the purpose of displaying an image such as a television receiver, the visibility, particularly the contrast ratio when observed from the front and the contrast ratio when observed from an oblique direction, that is, viewing angle characteristics, is regarded as important. The

  In a conventional twisted nematic (hereinafter abbreviated as TN) type liquid crystal display device, viewing angle characteristics are not sufficient due to anisotropy of a phase difference caused by a pretilt of a liquid crystal substance in a cell. Japanese Patent Application Laid-Open No. 6-214116 (Patent Document 1) discloses an optically anisotropic layer that exhibits negative uniaxiality and has an optical axis that is inclined with respect to the film surface. Disposing between a liquid crystal cell and a polarizing plate in a liquid crystal display device. Japanese Patent Application Laid-Open No. 10-186356 (Patent Document 2) discloses an optical compensation film obtained by fixing a nematic hybrid alignment formed by a liquid crystalline polymer exhibiting positive uniaxiality in a liquid crystal state, It is also disclosed that this optical compensation film is applied to a TN liquid crystal display device to increase the viewing angle. By using such an optically anisotropic layer having an optical axis oblique to the film surface as an optical compensation film, the viewing angle in the TN liquid crystal display device is improved.

  On the other hand, image display devices such as liquid crystal display devices, when external light is reflected on the image display surface, remarkably impairs the visibility. Therefore, in applications such as televisions and personal computers where importance is placed on image quality and visibility. Usually, a process for preventing these reflections is performed on the surface of the display device. As anti-reflection processing, so-called anti-glare processing that blurs the reflected image by scattering incident light by forming fine irregularities on the surface can be realized at a relatively low cost. It is suitably used for such applications. As a film that imparts such antiglare properties, for example, JP 2002-365410 A (Patent Document 3) is an optical film having fine irregularities formed on the surface, and on the surface of the film, An antiglare optical film is disclosed in which a light beam is incident from a direction of −10 ° with respect to a normal line and a reflected light profile when a reflected light from the surface alone is observed satisfies a specific relationship.

  Further, although not directly related to the antiglare optical film, a technique for etching the surface of glass with hydrofluoric acid is also known. For example, in JP-A-2002-90732 (Patent Document 4), concave portions having an average diameter of about 6 μm are formed on a glass surface by two-stage etching using hydrofluoric acid, and thus concave and convex portions are formed. It is described that the glass is used as a reflector for a liquid crystal display panel.

JP-A-6-214116 JP-A-10-186356 JP 2002-365410 A JP 2002-90732 A (Claims, paragraphs 0049 to 0055, Examples 1 and 2)

  Now, in general, it is said that it is necessary to use an antiglare film having a high haze value of 20% or more in order to prevent reflection of external light and ensure sufficient visibility. High-value anti-glare films have been widely used in notebook personal computers and televisions. However, the antiglare film showing a high haze value of 20% or more has a problem that the contrast measured in a bright room is lowered due to its wide reflection and scattering characteristics. Another problem is that the contrast measured in a dark room, which is inherent in a liquid crystal display device, is reduced.

  As a result of intensive studies to solve such problems, the present inventor has arranged an antiglare layer having a specific surface shape on one side of a linear polarizer, and a film on the surface opposite to the antiglare layer. It has been found that the above-mentioned problems in the liquid crystal display device can be solved by arranging an optically anisotropic layer having an optical axis inclined from the normal direction, and various studies have been made to complete the present invention. It was.

  Accordingly, an object of the present invention is to provide an antiglare polarizing film laminate that is provided with high antiglare properties and improved viewing angle characteristics without increasing the haze value. Another object of the present invention is to provide a liquid crystal display device having sufficient antiglare properties and good display characteristics by using this antiglare polarizing film laminate.

That is, the antiglare polarizing film laminate according to the present invention comprises an antiglare layer, a linear polarizer and an optically anisotropic layer laminated in this order, and the antiglare layer has a number of fine spherical surfaces on the surface. Of the spherical domains that are divided and observed when the antiglare surface is observed from above, the height is in the range of 0.1 to 10 μm, and the area is The domain in the range of 25 to 2500 μm ² occupies 90% or more of the entire surface, and the area occupied by the flat portion is 10% or less of the entire surface, and the optically anisotropic layer is optically It is negative or positive uniaxial, and its optical axis is inclined 5 to 50 ° from the normal direction of the film.

  In this anti-glare polarizing film laminate, the anti-glare layer is made of glass with fine irregularities formed on the surface by etching with an aqueous solution containing hydrogen fluoride, and the shape is formed on a transparent resin film. It is advantageous that a fine spherical surface is formed on a transparent resin film by copying. Here, the transparent resin film may be an ultraviolet curable resin or a thermoplastic resin. The antiglare layer can have a haze value of 10% or less. In addition, the optically anisotropic layer is particularly advantageously optically negative uniaxial.

  Furthermore, according to the present invention, there is provided a liquid crystal display device in which polarizing plates are arranged on both surfaces of a liquid crystal cell in which a TN type liquid crystal is sandwiched between two electrode substrates, and the polarizing plate located on the display surface side is: There is also provided a liquid crystal display device which is any one of the above antiglare polarizing film laminates, and is disposed so that the optically anisotropic layer side faces the liquid crystal cell.

  Although the antiglare polarizing film laminate of the present invention has antiglare properties due to the formation of fine irregularities on the surface, the haze value can be lowered, and this can be applied to a liquid crystal display device, particularly a TN liquid crystal. When applied to a liquid crystal display device that performs display by controlling the alignment state, high contrast can be obtained. Further, the liquid crystal display device of the present invention has high antiglare performance and high contrast, so it is bright and has excellent visibility.

  Hereinafter, the present invention will be described in detail with appropriate reference to the accompanying drawings. FIG. 1 is a schematic cross-sectional view showing an example of a polarizing film laminate according to the present invention, FIG. 2 is an example of a Voronoi diagram for explaining Voronoi division, and FIG. 3 is for obtaining an antiglare layer. FIG. 4 is a cross-sectional view schematically showing the progress of etching, and FIG. 5 is a cross-sectional schematic view showing an example of the liquid crystal display device according to the present invention. FIG. 6 is a schematic sectional view showing another example of the liquid crystal display device according to the present invention.

With reference to FIG. 1, the anti-glare polarizing film laminated body 10 of this invention is the thing which the anti-glare layer 15, the linear polarizer 30, and the optically anisotropic layer 40 were laminated | stacked in this order. The anti-glare layer 15 has an anti-glare surface having a number of fine spherical surfaces formed on the surface, and among the spherical domains that are divided and observed when the anti-glare surface is observed from above, Is in the range of 0.1 to 10 μm, the domain having an area in the range of 25 to 2500 μm ² occupies 90% or more of the entire surface, and the area occupied by the flat portion is 10% or less of the entire surface. Consists of things. The optically anisotropic layer 40 is optically negative or positive uniaxial, and has an optical axis inclined by 5 to 50 ° from the normal direction of the film.

  Here, when the antiglare surface of the antiglare layer 15 is viewed from above, it is observed in the same manner as so-called Voronoi division. Voronoi division will be described with reference to FIG. 2 showing an example of a Voronoi diagram. As shown in this figure, when several points (called mother points) are arranged on a plane, the plane can be divided according to which mother point is closest to any point in the plane. Is called Voronoi diagram, and the division is called Voronoi division. Each section including one generating point obtained by division is called a Voronoi region (or domain). In FIG. 2, only one Voronoi region is hatched. In the example shown in this figure, the number of generating points is 10, and the Voronoi region is divided into 10. In general, in the Voronoi diagram, the number of generating points coincides with the number of Voronoi regions. The boundary line of the Voronoi region is called a Voronoi boundary, and the intersection of the Voronoi boundaries is called a Voronoi point.

  When the antiglare surface according to the present invention is viewed from above with a microscope or the like, it is observed in a state of being divided into polygonal domains in the same manner as the Voronoi division as shown in FIG. However, the Voronoi is not divided by setting the generating point. Each domain forms a spherical surface, and the portion that is a straight line in FIG. 4 corresponding to the Voronoi boundary is observed as a straight line when viewed from above, but when viewed in a longitudinal section along the straight line, A convex or concave curve.

This anti-glare surface is a shape in which almost the entire surface is covered with fine spherical convexes or concaves. That is, among the domains composed of the fine spherical surfaces constituting the antiglare surface, the domain having a height in the range of 0.1 to 10 μm and an area in the range of 25 to 2500 μm ² is 90% of the entire surface. %, And the area occupied by the flat portion is 10% or less of the entire surface. As can be seen from the above description, the area of the domain here is not the surface area of the spherical surface but the projected area on the film surface or the area of a polygon that is observed in a plan view from above. . The domain area of 25 to 2500 μm ² corresponds to the diameter of 5 to 50 μm, assuming that the square root is the domain diameter.

  The antiglare surface having the surface shape as described above can be produced by several methods. For example, glass having fine irregularities formed on the surface by etching with an aqueous solution containing hydrogen fluoride is embossed. A method of using as a mold and copying the irregular shape on a transparent resin film is advantageously employed.

As the original plate of the embossing mold, general glass mainly composed of SiO ₂ can be used. The glass can be soda-lime glass called blue glass, borosilicate glass called white glass, quartz glass, or the like. Any glass that can be etched with an aqueous solution containing hydrogen fluoride and is isotropically dissolved with this aqueous solution can be used without any particular limitation. In the process of transferring to the film, it is exposed to processes such as heat pressing or irradiation with ionizing radiation in a state where the transparent substrate coated with ionizing radiation curable resin is in close contact with the uneven surface. It is desirable that the material be durable. Therefore, it is desired that the glass material has high resistance to heat and ionizing radiation and high mechanical strength. For this purpose, borosilicate glass or quartz glass is preferably used.

  Further, if the embossing mold is cylindrical, embossing can be continuously performed on a continuous long film. Therefore, the glass preferably has a cylindrical shape. From the viewpoint of ease, the glass material is preferably borosilicate glass or quartz glass. Borosilicate glass is sold under the product names such as “Pyrex” and “Tempax” by Corning (Asahi Techno Glass Co., Ltd. in Japan) and Schott, for example. These can be used.

  The glass is etched by contact with an aqueous solution containing hydrogen fluoride. By this etching, a fine concavo-convex shape is formed in which concave shapes substantially consisting of spherical surfaces are arranged on the surface substantially without gaps. For this purpose, it is preferable to generate fine scratches on the surface of the glass in advance.

As described in the background section, etching using hydrofluoric acid is generally known as a technique for generating an uneven shape on a glass surface. In Patent Document 4 described above, unevenness is formed by such a method. It is disclosed that the glass is used as a reflector for a liquid crystal display panel. Specifically, primary etching is performed with a first etching solution containing hydrogen fluoride and ammonium fluoride, and the surface of the glass is inhomogeneous due to insoluble salts generated by reaction with SiO ₂ which is the main component of the glass. After forming a protective film, thereby causing etching with hydrofluoric acid to proceed inhomogeneously and forming fine recesses on the surface, a second etching solution consisting essentially of hydrofluoric acid containing no ammonium compound The secondary etching is performed to form a hemispherical concave curved surface starting from the above-mentioned concave portion. The most common glass is soda lime glass. Unevenness can be formed on the glass surface by such two-step etching, and this can be used as a mold for the antiglare layer.

  However, in the case of borosilicate glass or quartz glass that can easily realize a roll shape, the etching rate of the glass itself is slow, so that the balance between the insoluble salt precipitation conditions and the resulting surface irregularity formation conditions cannot be balanced, and ammonium fluoride is used. Therefore, it cannot be said that the formation stability of the irregularities is very high. In order to avoid such a problem, it is effective to generate fine scratches (cracks) on the surface of the glass before etching, and to etch with an aqueous solution containing hydrogen fluoride in this state. As a method for generating fine scratches on the surface of the glass, for example, blasting can be mentioned.

  Therefore, in a preferred embodiment, after forming fine scratches on the surface, glass having fine irregularities formed on the surface by contacting with an aqueous solution containing hydrogen fluoride is used as a mold, and the irregularities on the surface are formed. Transfer to the surface of the transparent resin film. This method will be described with reference to FIG. 3 showing each step in a schematic sectional view.

  FIG. 3A shows an example in which blasting is employed as a means for generating scratches (cracks) 21 on the surface of the glass 20. When the blasting agent 28 collides with the surface of the glass 20 with an appropriate pressure, fine scratches 21 and 21 are formed.

  Next, in the etching step shown in FIG. 5B, the glass 20 is brought into contact with an aqueous solution (etching solution) containing hydrogen fluoride to perform etching. At this time, the etching solution contacts the surface of the glass 20, penetrates into the inside of the scratches 21 and 21, reaches the tip thereof, and sequentially melts the contacting surface. As a result, the concavities sequentially expand concentrically around the tips of the scratches 21 and 21. In FIG. 1B, a broken line indicates that the glass is melted sequentially from the original glass surface 22 to the glass surfaces 23 and 24 during the etching. At the end of etching, a fine concavo-convex shape is formed in which a large number of concave shapes 25 made of substantially spherical surfaces are arranged substantially without gaps, and the glass mold 26 is formed.

  Using the glass mold 26 thus obtained, the uneven surface 25 is transferred to the film 16 as shown in FIG. The film 16 can be composed of a single thermoplastic transparent resin. In this case, the thermoplastic resin film 16 may be pressed against the concave / convex surface 25 of the mold 26 in a heated state and shaped by hot pressing. . Moreover, the film 16 can also be comprised by what formed the ionizing radiation-curing-type resin layer 18 on the surface of the transparent base film 17 as illustrated to (C) of FIG. 3, In this case, By bringing the ionizing radiation curable resin layer 18 into contact with the uneven surface 25 of the mold 26 and irradiating the ionizing radiation to cure the resin layer 18, the uneven shape of the mold 26 is transferred to the ionizing radiation curable resin layer 18. The These films will be described in detail later.

  After transferring the concavo-convex shape of the mold 26, the film 16 is peeled from the mold 26 as shown in FIG. 4D to obtain an antiglare film (antiglare layer) 15.

  The progress of the etching shown in FIG. 3B will be described in more detail with reference to FIG. 4 which is an enlarged view of that portion, focusing on only one scratch 21. In this figure as well, the original glass surface is represented by reference numeral 22, and the glass is sequentially dissolved into the glass surfaces 23 and 24 as the etching progresses, and an uneven surface 25 is formed at the end of the etching. ing.

It is assumed that the scratch 21 is formed as shown in FIG. When the glass 20 is brought into contact with the etching solution in this state, the etching solution comes into contact with the glass surface and penetrates into the scratch 21 and reaches the tip 21a. Then, the etching solution sequentially dissolves the glass in contact with the etching solution. That is, melting (etching) gradually proceeds in a planar manner from the original glass surface 22, the glass is melted laterally from the scratch 21, and the hemispherical glass is melted from the tip 21 a. It will dissolve. Assuming that etching has progressed from the original glass surface 22 to a depth h ₁ (glass surface 23) substantially equal to the depth of the scratch 21, the etched surface starting from the tip 21a of the scratch 21 has a radius of approximately h ₁ and is almost hemispherical. It becomes a concave surface.

As the etching proceeds further, this concave surface expands concentrically with the previous hemisphere, but the glass surface is also scraped from the position of reference numeral 23 to the position of reference numeral 24 at the same time. It remains as a partial spherical surface with a small inclination with respect to. In FIG. 4, the state where the etching has progressed to a depth h ₂ that is about twice the depth of the scratch 21 is also indicated by a broken line as the glass surface 24. Eventually, the concave surface 25 which is a small part of the spherical surface remains. The height h ₃ from the original glass surface 22 to the glass surface remaining at the end of etching is defined as the etching depth.

  In FIG. 4, for the sake of drawing, it is shown that the etching has been completed when the etching has progressed to a depth of about three times the depth of the scratch 21, but in practice the etching is advanced to a deeper depth. Is preferred. In other words, the depth of the scratch 21 is preferably very small compared to the etching depth. In addition, the display is such that the flat portion remains at the end of the etching, but this is because the drawing was made by paying attention to only one scratch 21. In fact, it is different from the scratch at the adjacent position. Since the concave surface expands, a flat portion is practically not left at the end of etching.

  In this way, the glass surface is dissolved to some extent by etching, and in a preferred form, fine scratches are formed on the glass surface prior to etching, so the glass used must have a certain thickness, The thickness is preferably 1 mm or more, particularly 2 mm or more.

  Returning to FIG. 3, the surface of the glass 20 on which fine scratches 21 are generated by blasting or the like is treated with an etching solution that isotropically dissolves, so that the concave surface 25 that is substantially spherical is the surface of the glass 20. Many are formed. Since the size of the recess formed by etching depends on the depth of the scratches 21 generated by the blasting process and the etching depth, it is desirable to perform the blasting process as homogeneously as possible. Each domain of the polyspherical surface formed by etching is observed in the same manner as the Voronoi-divided Voronoi region described above with reference to FIG. The size of each domain is represented by the area of each domain.

  The depth of the fine scratches 21 generated by the blast treatment is preferably 10 μm or less, and more preferably 2 μm or less. The haze expressed by the antiglare layer tends to be higher as the etching depth is shallower and the average depth of the fine scratches 21 formed before the etching is deeper. If it exceeds 10 μm, the haze of the antiglare layer becomes too high. The area of each domain tends to increase as the etching depth increases and as the average depth of the fine scratches 21 formed before etching increases.

The antiglare layer obtained by transferring the uneven surface of the glass formed by etching onto a transparent resin film has a domain area in the range of 25 to 2500 μm ² and exhibits a haze value of 10% or less. For this purpose, the average depth of the fine scratches 21 generated on the glass surface by blasting before etching is preferably 5 μm or less, and more preferably 2 μm or less. The etching depth is preferably 10 times or more of the average depth of the fine scratches 21 generated by the blasting process, more preferably 20 times or more, particularly 50 times or more. Preferably, it is 300 μm or less, more preferably 100 to 200 μm. When the etching depth exceeds 300 μm, the area of the domain becomes too large, and in the antiglare layer obtained by transferring the unevenness to the transparent resin film, the area occupied by the domain in the area range of 25 to 2500 μm ² May be less than 90% of the entire surface.

  The required etching time varies depending on the type of glass, the concentration of the etchant, the etching conditions, etc., but the same result can be obtained if the etching depth is constant no matter which glass is used. be able to.

The polyspherical shape formed by etching is such that a domain having an area in the range of 25 to 2500 μm ² occupies 90% or more of the entire surface. For this reason, it is desirable to perform the blasting process as homogeneously as possible. In order to increase the homogeneity of the domain area, the particle size distribution of the blasting agent used for the blasting treatment is preferably as close to monodispersion as possible. When the particle size distribution of the blasting agent is wide, the depth distribution of the fine scratches 21 is widened, and the distribution is generated in each spherical domain formed by etching, and the area having an area of 25 to 2500 μm ² occupies. Since the ratio may be less than 90% of the entire surface, it is not preferable.

  The particle shape of the blasting agent 28 is preferably as close to a spherical shape as possible. If the blasting agent is spherical, the collision with the glass at the time of blasting is single, which is effective for enhancing the homogeneity of the depth of fine scratches.

  The average particle size of the blasting agent 28 can be appropriately selected depending on the blasting conditions, but is preferably 180 μm or less, more preferably 100 μm or less. When the particle size of the blast particles exceeds 180 μm, the blast pressure becomes extremely low and the blasting operation itself becomes difficult when the depth of the fine scratches 21 is set to 2 μm or less. As a result, there is a possibility that the flat portion existing on the uneven surface obtained by etching the glass after blasting may exceed 10% of the entire surface, and the anti-glare obtained by transferring the shape using this as a mold The surface is not preferable because the antiglare property is weak and it is difficult to sufficiently reduce the reflection.

  Commercially available blasting agents that can be used for this purpose include, for example, zirconia beads “TZ-B53” (average particle size 53 μm) sold by Tosoh Corporation, “TZ-B90” (average particle size 90 μm), etc. Further, micro zircon beads “MB-20” (average particle size 20 μm) sold by Material Science Co., Ltd., “MB-40” (average particle size 34 μm) and the like are also included.

  In order to reduce the depth of the fine scratches 21 formed by the blasting process to 2 μm or less, the blasting pressure is changed from 0.01 to 0.05 MPa (gauge pressure, the same shall apply hereinafter) to the particle size of the blasting agent. It is preferable to select it accordingly. That is, a condition is adopted in which scratches are formed so that a substantially spherical concave shape is formed on the glass surface with substantially no gap by subsequent etching. When the blast pressure increases, the size of the fine recesses obtained as a result of etching becomes too large, and the pattern becomes rough. On the other hand, if the blast pressure is too low, the blast particles cause an elastic collision on the glass surface, and the density of effective fine cracks is drastically reduced. As a result, there is a possibility that the flat portion existing on the uneven surface obtained by etching the glass after blasting may exceed 10% of the entire surface, and the anti-glare obtained by transferring the shape using this as a mold The surface is not preferable because the antiglare property is weak and it is difficult to sufficiently reduce the reflection. The tendency to reduce the density of effective fine cracks when the blast pressure is small is prominent when the blast particles are small enough to be less than 50 μm. Further, if the blast pressure is less than 0.01 MPa, the stability of the blasting operation itself is lowered, which is not preferable. Although it depends on the particle size of the blasting agent, if the blasting pressure is within the range of 0.01 to 0.05 MPa and it is appropriately combined with the particle size of the blasting agent, fine scratches with a depth of 2 μm or less are increased on the glass surface. The density can be generated efficiently.

In order to impart sufficient antiglare properties to the obtained antiglare layer, the blasting agent should be used in an amount of 10 g or more per 4 cm ² of glass area, and preferably 100 g or more. When the amount of blasting agent used per 4 cm ^{2 of} glass area is less than 10 g, the effective fine crack density is insufficient, so that the recesses generated after etching become too sparse. As a result, the flat portion present on the uneven surface obtained after etching may exceed 10% of the entire surface, and the antiglare surface obtained by transferring the shape using this as a mold has antiglare properties. This is not preferable because it is weak and may not be able to reduce the reflection sufficiently.

The etching solution may contain hydrogen fluoride and have an ability to dissolve SiO ₂ which is a main component of glass. From such a viewpoint, the concentration of hydrogen fluoride (HF) is appropriately selected from the range of about 1 to 50% by weight. If the concentration of hydrogen fluoride is too low, the ability to dissolve SiO ₂ or the etching rate is extremely reduced. On the other hand, if the concentration is too high, hydrogen fluoride itself tends to volatilize. The concentration of hydrogen fluoride in the etching solution is preferably 5% by weight or more, more preferably 10% by weight or more, and preferably 40% by weight or less, more preferably 35% by weight or less. In order to increase the etching stability and the etching rate, an ammonium salt such as ammonium fluoride and a protonic acid such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid can be added to the etching solution.

The etching temperature should be appropriately set in order to obtain a necessary etching rate, but is preferably in the range of 10 to 60 ° C., more preferably 20 ° C. or more and 50 ° C. or less. In addition to the fact that a practical etching rate cannot be obtained at 10 ° C. or lower, the reaction product of SiO ₂ and hydrogen fluoride crystallizes and precipitates on the glass surface, and the resulting fine uneven surface becomes rough, Surfaces other than the polyspherical shape are formed, and as a result, the antiglare surface tends to be whitish. On the other hand, when the etching temperature exceeds 60 ° C., the liquid composition changes during etching due to evaporation of hydrogen fluoride, which is not preferable.

  After etching is complete, the glass is immediately washed thoroughly with water, preferably pure water, and then dried to form an embossing mold.

  The glass having a concavo-convex shape formed on the surface thus obtained is used as a mold 26 for transferring the shape to the surface of the film 16 as described above with reference to FIG. At this time, the shape of the mold can be transferred to the film surface by an arbitrary method. For example, a glass mold 26 having a concavo-convex shape is hot-pressed on the surface of a thermoplastic resin film, and the concavo-convex shape of the glass mold 26 is transferred to the surface of the thermoplastic resin film, or an ionizing radiation curable resin is used as a transparent resin film. The surface of the glass mold 26 is coated with the ionizing radiation curable resin coating layer in an uncured state, and is made to adhere to the uneven surface of the glass mold 26, and cured by irradiation with ionizing radiation through the film or the glass mold. A method of transferring the shape can be employed. After the transfer, the antiglare layer 15 is obtained by peeling the film 16 from the mold as shown in FIG. From the viewpoint of mechanical strength such as prevention of surface scratches, a method using an ionizing radiation curable resin is preferably employed.

  The transparent resin used at this time may be a film having substantially optical transparency. Specific examples include cellulose resins such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate, cycloolefin polymers, polycarbonate, polymethyl methacrylate, polysulfone, polyether sulfone, and polyvinyl chloride. Cycloolefin-based polymers are resins that use cyclic olefins such as norbornene and dimethanooctahydronaphthalene as monomers, and commercially available products such as “ARTON” sold by JSR Corporation and Zeon Corporation. There are “Zeonoa” and “Zeonex” (both are trade names).

  Among these, a transparent resin film having thermoplasticity composed of polymethyl methacrylate, polycarbonate, polysulfone, polyether sulfone, cycloolefin polymer, etc., was pressed or pressure-bonded at an appropriate temperature on a glass mold having an uneven shape. Then, by peeling, the uneven shape on the glass mold surface can be used to transfer to the film surface. Moreover, the uneven | corrugated shape of glass can also be transcribe | transferred directly on the polarizing plate surface using a polarizing plate as a transparent film.

  On the other hand, as the ionizing radiation curable resin when transferring the shape using the ionizing radiation curable resin, a compound having one or more acryloyloxy groups in the molecule is preferably used. In order to improve the strength, a trifunctional or higher functional acrylate, that is, a compound having three or more acryloyloxy groups in the molecule is more preferably used. Specific examples include trimethylolpropane triacrylate, trimethylolethane triacrylate, glycerin triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like. Also, an acrylate compound having a urethane bond in the molecule is preferably used in order to impart flexibility to the antiglare surface and make it difficult to break. Specifically, there are two molecules of a compound having at least one hydroxyl group with an acryloyloxy group in the molecule, such as trimethylolpropane diacrylate and pentaerythritol triacrylate, and a diisocyanate compound such as hexamethylene diisocyanate and tolylene diisocyanate. Examples include urethane acrylates such as adducts. In addition, other acrylic resins such as ether acrylates and ester acrylates that initiate radical polymerization by ionizing radiation and cure can also be used.

  Also, cationically polymerizable ionizing radiation curable resins, such as epoxy-based and oxetane-based resins, can be used as the resin in which irregularities are shaped after curing. In this case, for example, a cationically polymerizable polyfunctional oxetane compound such as 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene or bis (3-ethyl-3-oxetanylmethyl) ether, and (4 A mixture with a photocationic initiator such as -methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate is used.

  When curing an acrylic ionizing radiation curable resin by irradiation with ultraviolet rays, a radical is generated when irradiated with ultraviolet rays, and an ultraviolet radical initiator is added to start the polymerization / curing reaction. It is done. The ultraviolet irradiation is performed from the glass mold surface side or the transparent resin film surface side, but when the ultraviolet irradiation is performed from the transparent resin film surface side, the radical reaction is performed in the ultraviolet wavelength region where the film can be transmitted. In order to initiate the reaction, an initiator that initiates a radical reaction from the visible region to the ultraviolet region is used.

  Examples of the ultraviolet radical initiator that initiates a radical reaction by ultraviolet irradiation include 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- In addition to hydroxy-2-methyl-1-phenylpropan-1-one and the like, in particular, when the ultraviolet curable resin is cured by irradiating ultraviolet rays through a transparent resin film containing an ultraviolet absorber, bis (2, 4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. A phosphorus-based photoradical initiator having absorption in the water is preferably used.

  When the glass mold with fine irregularities formed on the surface by etching is flat, the mold surface and a transparent resin film coated with an uncured ionizing radiation curable resin are used. After the ionizing radiation curable resin is cured by irradiating the ionizing radiation from the transparent resin film surface side or the glass mold surface side in a state of being in close contact so as to be in contact, the substrate film is peeled off from the glass mold, and the mold Is transferred to the surface of the transparent film.

  When the glass mold is roll-shaped and the uneven shape of the mold is transferred using an ionizing radiation curable resin, the transparent resin film adheres to the glass roll the surface on which the uncured ionizing radiation curable resin is applied. In this state, ionizing radiation is irradiated, and after curing, the substrate film is peeled off from the roll mold, so that the shape can be continuously transferred to the transparent film surface.

  The ionizing radiation can be ultraviolet rays or electron beams, but ultraviolet rays are preferably used from the viewpoint of ease of handling and safety. As the ultraviolet light source, a high-pressure mercury lamp, a metal halide lamp, or the like is preferably used, but a metal halide lamp that contains a large amount of visible light components is preferably used particularly when irradiated through a transparent substrate containing an ultraviolet absorber. . In addition, “V-valve” and “D-valve” (both trade names) manufactured by Fusion are also preferably used. The irradiation dose may be a dose sufficient to solidify the UV curable resin until it can be released from the mold. However, in order to further improve the surface hardness, irradiation is performed again from the coated surface side after release. Also good.

  According to the method as described above, the antiglare layer (antiglare film) obtained can generally have a haze value of 20% or less, but as described above, the haze value is 10% or less. Is particularly preferred. The haze value is a value represented by (diffuse transmittance / total light transmittance) × 100 (%).

  Thus, when a glass having a large number of concave shapes formed on the surface is used as a mold and the shape is transferred onto the transparent resin film, the resulting antiglare surface of the transparent resin film has a large number of substantially spherical surfaces. It has a convex shape. On the other hand, when it is desired that the antiglare surface has a large number of concave shapes consisting of substantially spherical surfaces, for example, the surface shape of a glass having a large number of concave shapes consisting of almost spherical surfaces on the surface is temporarily applied to the resin surface. After copying, the surface shape of the resin mold may be formed on the surface of another transparent resin film in accordance with the above description using the resin as a mold.

In the present invention, among the spherical domains that are divided and observed when the antiglare surface thus formed is observed from above, the height is in the range of 0.1 to 10 μm, and the area is 25 to 2, The domain in the range of 500 μm ² occupies 90% or more of the entire surface, and the area occupied by the flat portion is made 10% or less of the entire surface. If so, it is represented by the difference in elevation between the highest point and the lowest point of the portion corresponding to the Voronoi boundary that defines the domain. On the other hand, if the domain has a concave shape, the height at this time is represented by an altitude difference between the lowest point and the highest point corresponding to the Voronoi boundary that defines the domain.

  For observation and measurement of the surface shape of the antiglare surface, a non-contact three-dimensional surface shape / roughness measuring machine is advantageously used. The horizontal resolution required for the measuring instrument 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 the non-contact three-dimensional surface shape / roughness measuring apparatus suitable for the observation / measurement include the “New View 5000” series, which is a product of Zygo Corporation in the United States and is available from Zygo Corporation in Japan. The measurement area is preferably wider, and is at least 100 μm × 100 μm or more, preferably 500 μm × 500 μm or more.

  In the present invention, as described above with reference to FIG. 1, the antiglare layer 15 obtained as described above is disposed on one surface of the linear polarizer 30, and the other surface of the linear polarizer 30 is disposed on the other surface. The optically anisotropic layer 40 is disposed to form the antiglare polarizing film laminate 10. The linear polarizer 30 may be a type generally known as a polarizing film or a polarizing plate that transmits linearly polarized light that vibrates in one direction orthogonal to each other in the film plane and absorbs linearly polarized light that vibrates in the other direction. . Specifically, a polyvinyl alcohol film that has been uniaxially stretched and dyed with a high dichroic dye and further subjected to boric acid crosslinking can be used. There are iodine-based polarizers using iodine as the high-dichroic dye and dye-based polarizers using dichroic organic dyes as the high-dichroic dye, both of which can be used. Further, such a polyvinyl alcohol linear polarizer itself may be used, or a polarizing plate in which a protective film made of a transparent polymer such as triacetyl cellulose is laminated on one side or both sides of the polyvinyl alcohol linear polarizer. It may be.

  The optically anisotropic layer 40 disposed on one surface of the linear polarizer 30 is optically negative or positive uniaxial, and its optical axis is inclined by 5 to 50 ° from the normal direction of the film. .

  First, an optically anisotropic layer which is optically negative uniaxial and whose optical axis is inclined 5 to 50 ° from the normal direction of the film will be described. Optically negative uniaxiality expresses negative refractive index anisotropy in which the refractive index in the optical axis direction is smaller than the average refractive index in a plane perpendicular to the optical axis direction. An optically anisotropic layer 40 that exhibits such negative refractive index anisotropy and whose azimuth angle of the optical axis is inclined by 5 to 50 ° from the normal direction of the substrate can be used. As such an optically anisotropic layer, for example, as described in Patent Document 1, an organic compound, particularly a compound having a liquid crystallinity and having a discotic molecular structure, or a liquid crystal property is not shown. After the compound that expresses negative refractive index anisotropy by an electric field or a magnetic field is coated on a transparent resin film made of triacetylcellulose or the like, the optical axis is inclined between 5 and 50 ° from the film normal direction. A film oriented so as to be preferably used. The orientation may be not only one direction but also, for example, a so-called hybrid orientation in which the inclination gradually increases from one side of the film to the other side.

  Examples of organic compounds having a discotic molecular structure exhibiting liquid crystallinity include low-molecular or high-molecular discotic liquid crystals, such as alkyl groups, alkoxy groups, alkyls, etc., on a mother nucleus having a planar structure such as triphenylene, torquesen, and benzene. Examples include those in which linear substituents such as substituted benzoyloxy groups and alkoxy-substituted benzoyloxy groups are bonded in a radial manner. Among them, those that do not absorb in the visible light region are preferable.

  These organic compounds having a disk-like molecular structure are not only used alone, but may be used in combination with several kinds as necessary in order to obtain the orientation necessary for the present invention, or high It can be used by mixing with other organic compounds such as a molecular matrix. The organic compound used as a mixture is compatible with an organic compound having a disk-like molecular structure, or can disperse an organic compound having a disk-like molecular structure in a particle size that does not scatter light If it is, it will not specifically limit. A film having a liquid crystal compound layer provided on a transparent substrate film made of a cellulose resin and having an optical axis inclined with respect to the film normal is, for example, “WV film” from Fuji Photo Film Co., Ltd. Can be used because it is sold under the brand name

  Next, an optically anisotropic layer that is optically positive uniaxial and whose optical axis is inclined by 5 to 50 ° from the normal direction of the film will be described. Optically positive uniaxiality expresses positive refractive index anisotropy in which the refractive index in the optical axis direction is larger than the average refractive index in a plane perpendicular to the optical axis direction. An optically anisotropic layer 40 that exhibits such positive refractive index anisotropy and whose azimuth angle of the optical axis is inclined by 5 to 50 ° from the normal direction of the substrate can also be used. As such an optically anisotropic layer, for example, as described in Patent Document 2, an organic compound having an elongated rod-like structure, particularly a molecular structure that exhibits nematic liquid crystallinity and imparts positive optical anisotropy Or a compound that does not exhibit liquid crystallinity but exhibits positive refractive index anisotropy by an electric field or a magnetic field is formed on a transparent substrate film, and the optical axis is 5 to 50 from the film normal direction. Examples thereof include films obtained by orienting so as to incline between °. The orientation may be not only one direction but also, for example, a so-called hybrid orientation in which the inclination gradually increases from one side of the film to the other side. A film made of a nematic liquid crystal compound is provided on a transparent substrate film, and the optical axis is inclined with respect to the film normal, for example, sold under the trade name “NH film” by Nippon Oil Corporation. So you can use this.

In addition, a thin film can be formed by vacuum deposition, and a dielectric that exhibits positive refractive index anisotropy when deposited is deposited on a transparent substrate film from a direction inclined with respect to the normal line. By doing so, it is also possible to obtain an optically anisotropic layer that is optically positive uniaxial and whose optical axis is inclined 5 to 50 ° from the normal direction of the film. The dielectric used for this purpose 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 terms of stability against heat acting during vacuum deposition. It is done. Examples of the inorganic dielectric include tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ ), silicon dioxide (SiO ₂ ), silicon monoxide (SiO), bismuth oxide (Bi ₂ O ₅ ), neodymium oxide (Nd ₂ ). A metal oxide such as O ₃ ) is preferably used in terms of excellent transparency. Among metal oxides, those having a refractive index anisotropy and a hard film quality such as tantalum oxide, tungsten oxide, and bismuth oxide are more preferably used.

  The antiglare layer 15 subjected to the shaping process is bonded to one side of the linear polarizer 30 as described above, and an optically negative or positive uniaxial property is formed on the opposite surface of the linear polarizer 30. Thus, the optically anisotropic layer 40 whose optical axis is inclined by 5 ° to 50 ° from the normal direction of the film is laminated to obtain an antiglare polarizing film laminate 10 (FIG. 1). At this time, the antiglare layer 15 is laminated so that the surface subjected to the shaping process (uneven surface) is the outside, that is, the side not facing the linear polarizer 30. Moreover, when the optically anisotropic layer 40 is a transparent base film provided with a layer of a substance that exhibits refractive index anisotropy, the transparent base film side is the linear polarizer 30 side. Are laminated. For the lamination, an adhesive having excellent transparency such as an acrylic pressure-sensitive adhesive is advantageously used.

  An optically anisotropic uniaxial optically anisotropic layer whose optical axis is inclined between 5 and 50 ° from the normal direction of the film, a polarizing plate bonded to one side of a linear polarizer, That is, a laminate having the configuration of the linear polarizer 30 / optically anisotropic layer 40 in FIG. 1 is also commercially available. For example, “Sumikaran SR-F862” sold by Sumitomo Chemical Co., Ltd. is of this type. Such an optically anisotropic layer having an optically negative uniaxial property and an optically anisotropic layer whose optical axis is inclined by 5 to 50 ° from the normal direction of the film is bonded to a linear polarizer. The antiglare layer 15 described above can be bonded to the side opposite to the isotropic layer to obtain the antiglare polarizing film laminate 10.

  The antiglare polarizing film laminate 10 as shown in FIG. 1 can be combined with a liquid crystal cell in which a TN liquid crystal is sandwiched between two substrates to form a liquid crystal display device. An example of this case is shown in FIGS. In these examples, the liquid crystal cell 50 is obtained by sandwiching a TN type liquid crystal 57 between two cell substrates 51 and 52 having electrodes 54 and 55 formed on one side facing each other.

  Such a TN type liquid crystal cell 50 is usually provided with polarizing plates on both sides thereof. In the present invention, one polarizing plate, particularly the polarizing plate located on the display surface, that is, the viewing side is shown in FIG. Such an antiglare polarizing film laminate 10 composed of the antiglare layer 15 / the linear polarizer 30 / the optically anisotropic layer 40 is used. At this time, the optically anisotropic layer 40 side is disposed so as to face the liquid crystal cell 50. The optically anisotropic layer 40 and the liquid crystal cell 50 of the antiglare polarizing film laminate 10 are bonded via an adhesive 60. A backlight 70 is disposed on the back side of the liquid crystal cell 50 and serves as a light source for the liquid crystal cell 50.

  The configurations of the antiglare polarizing film laminate 10, the liquid crystal cell 50, and the backlight 70 are the same in FIGS. 5 and 6, but the structure between the liquid crystal cell 50 and the backlight 70 is different. That is, in the example shown in FIG. 5, the polarizing plate 35 is disposed on the back side of the liquid crystal cell 50 via the adhesive 60. On the other hand, in the example shown in FIG. 6, the optically anisotropic layer 45 and the polarizing plate 35 are arranged in this order on the back side of the liquid crystal cell 50 via the adhesive 60.

  The polarizing plate 35 on the back side may be a general polarizing plate that transmits linearly polarized light that vibrates in one direction orthogonal to each other in the film plane and absorbs linearly polarized light that vibrates in the other direction. Specifically, it is possible to use a polyvinyl alcohol film that has been uniaxially stretched and dyed with a high dichroic dye, and further subjected to boric acid crosslinking, and usually has a protective film made of a transparent polymer on one or both sides. Used in a laminated state. The optically anisotropic layer 45 on the back side in the example shown in FIG. 6 is optically negative or positive uniaxial as in the optically anisotropic layer 40 used in the antiglare polarizing film laminate 10, and the light The axis may be inclined 5 to 50 ° from the normal direction of the film.

  In order to make the viewing angle characteristic and the display characteristic good, it is preferable to dispose an optically anisotropic layer 45 on the back side as shown in FIG. In this case, as described above, the optically anisotropic uniaxial optically anisotropic layer whose optical axis is inclined by 5 to 50 ° from the normal direction of the film is a linear polarizer. The polarizing plate bonded on one side can be used as a laminated product of the optically anisotropic layer 45 / polarizing plate 35 in FIG.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, “%” and “part” representing the content or amount used are based on weight unless otherwise specified.

Example 1
Borosilicate glass plate (trade name “Pyrex”, 5cm □, 4mm thickness) manufactured by Asahi Techno Glass Co., Ltd., and zirconia beads (trade name “TZ-B53”, average particle size 53μm) manufactured by Tosoh Corp. Used and blasted. The amount of blasting agent (zirconia beads) used was 100 ml, the blast pressure was 0.03 MPa, the distance from the blast nozzle to the glass plate was 40 cm, and the blast gun was fixed. The blasting process was completed in about 5 minutes. The glass plate after blasting remained almost transparent, but when observed with a reflective microscope manufactured by Keyence, many fine cracks were generated on the surface at a depth of about 1 to 1.5 μm. It was confirmed.

  The glass after blasting is etched by immersing it in an etching solution of hydrogen fluoride / ammonium fluoride / sulfuric acid / water in a weight ratio of 5/1/1/10 at a temperature of 40 ° C. for 1 hour. To prepare a glass mold. The etching depth was 100 μm.

  Separately, in a 50% ethyl acetate solution of dipentaerythritol hexaacrylate, a photopolymerization initiator “Lucylin TPO” (chemical name: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BASF) was used as a resin component. An ultraviolet curable resin solution was prepared by adding 5 parts per 100 parts of dipentaerythritol hexaacrylate. This ultraviolet curable resin solution was applied to a triacetyl cellulose film manufactured by Fuji Photo Film Co., Ltd. using a # 20 bar coater and dried at 80 ° C. for 5 minutes. This coated film is brought into close contact with a glass mold whose surface has been roughened by the previous etching using a hand roller so that the coated surface of the UV curable resin is on the etched surface side of the glass mold, and a high pressure mercury lamp is used. For 1 minute. Then, the thing in the state which curable resin hardened | cured on the triacetyl cellulose film was peeled from the glass plate, and the anti-glare film was obtained.

The surface shape of this anti-glare film was observed and processed with a non-contact three-dimensional surface shape / roughness measuring instrument “New View 5010” manufactured by Zygo Corporation, and the entire surface was covered with fine spherical convex portions. It was confirmed that there was no flat part. Further, when the area distribution of each domain is obtained from the result of this image processing, the area of the domain is in the range of 25 to 2500 μm ² , and the spherical domain having a height of 0.1 to 10 μm is 100 in the entire region. % Was confirmed. The haze value of this antiglare film was measured using a haze computer “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd. and found to be 3.4%.

  Separately, optically negative uniaxial discotic liquid crystal molecules are applied and fixed on the substrate, and the optical axis is in a hybrid orientation in which the optical axis is sequentially inclined between 5 and 50 ° from the normal direction of the film. The optically anisotropic layer (trade name “WV film”, manufactured by Fuji Photo Film Co., Ltd.) whose apparent optical axis is in the direction of about 18 ° from the normal is one side of a polyvinyl alcohol-iodine linear polarizer. A linear polarizer / optically anisotropic layer laminate (trade name “Sumikaran SR-F862A”, Sumitomo Chemical Co., Ltd.) with a triacetylcellulose film attached to the other side of the polarizer. Prepared).

  Next, the polarizing plate on the display surface side and the back surface side of the monitor for personal computers on which a commercially available TN type TFT liquid crystal display element is mounted is peeled off, and instead of the original polarizing plate, the above linear polarizer / optical difference is removed. Adhesive on both sides of the liquid crystal cell so that the absorption layer of the anisotropic layer laminate “Sumikaran SR-F862A” coincides with the absorption axis of the original polarizing plate and the optically anisotropic layer is on the liquid crystal cell side. It was pasted through. Furthermore, the antiglare film obtained above was bonded to the polarizing plate on the display surface side through an adhesive, and the liquid crystal display device with an antiglare layer was produced.

  The personal computer was activated in the dark room, and the brightness of the liquid crystal display device in the black display state and the white display state was measured using a luminance meter “BM7” manufactured by Topcon Corporation, and the contrast was calculated. Here, the contrast is represented by the ratio of the luminance in the white display state to the luminance in the black display state. As a result, the contrast measured in the darkroom of the liquid crystal display device was 300. On the other hand, the evaluation system was moved into a bright room and the reflected state was visually observed as a black display state. As a result, almost no reflection was observed, and it was confirmed that this liquid crystal display device had antiglare properties.

Example 2
The glass mold was prepared in the same manner as in Example 1 except that the blasting particles were changed to TZ-SX17 (average particle size 35 μm) manufactured by Tosoh Corporation and the blasting pressure was set to 0.04 MPa. Then, an antiglare film was prepared. The haze value of this antiglare film was 1.0%. When this antiglare film was bonded to a liquid crystal display element together with a linear polarizer / optically anisotropic layer laminate “Sumikaran SR-F862A” in the same manner as in Example 1, the contrast in the dark room was It was confirmed that it has a high display characteristic of 330 and has a sufficient antiglare property and good display characteristics.

Example 3
A glass mold was prepared in the same manner as in Example 1 except that the blast particles were changed to TZ-SX17 (average particle size 35 μm) manufactured by Tosoh Corporation and the blast pressure was set to 0.05 MPa. Then, an antiglare film was prepared. The haze value of this antiglare film was 5.5%. When this antiglare film was bonded to a liquid crystal display element together with a linear polarizer / optically anisotropic layer laminate “Sumikaran SR-F862A” in the same manner as in Example 1, the contrast in the dark room was It was confirmed to have a high display property with a high 297 and sufficient antiglare property.

Example 4
A glass mold was prepared in the same manner as in Example 1 except that the blast particles were changed to TZ-B90 (average particle size 90 μm) manufactured by Tosoh Corporation and the blast pressure was set to 0.05 MPa. Then, an antiglare film was prepared. The haze value of this antiglare film was 7.0%. This antiglare film was bonded to a liquid crystal display element together with a linear polarizer / optically anisotropic layer laminated product “Sumikaran SR-F862A” in the same manner as in Example 1, and evaluated. Contrast measured in a dark room Was 282, and it was confirmed that it had good antiglare properties and good display characteristics.

  In the above Examples 1 to 4, if the glass is changed to a tubular one and the surface is subjected to blasting and etching under substantially the same conditions as a mold, an antiglare film can be obtained in a continuous roll shape. Can do. Tubular borosilicate glass is also available from Asahi Techno Glass Co., Ltd. under the trade name “Pyrex”.

Comparative Example 1
A glass mold was produced in the same manner as in Example 1 except that the blast pressure was set to 0.1 MPa, and an antiglare film was further produced. When the glass plate after the blasting treatment in this example was observed with a reflection microscope, cracks generated on the surface varied in depth between about 10 to 30 μm. Further, the surface shape of the obtained antiglare film was observed with the same non-contact type three-dimensional surface shape / roughness measuring instrument “New View 5010” as in Example 1, and image processing was performed. However, most of the domains had an area exceeding 2,500 μm ² . The haze value of this antiglare film was 55%. When this anti-glare film was bonded to a liquid crystal display element together with a linear polarizer / optically anisotropic layer laminate “Sumikaran SR-F862A” in the same manner as in Example 1, the anti-glare property was sufficient. However, the contrast in the dark room was as low as 151, and it was confirmed that the display characteristics were not sufficient.

Comparative Example 2
The glass mold was prepared in the same manner as in Example 1 except that the blast particles were changed to TZ-SX17 (average particle size 35 μm) manufactured by Tosoh Corporation and the blast pressure was changed to 0.01 MPa. Then, an antiglare film was prepared. When the surface shape of the obtained antiglare film was observed with a reflection microscope and subjected to image processing, the area occupied by the flat portion was 18% of the entire surface. The haze value of this antiglare film was 5.4%. When this antiglare film was bonded to a liquid crystal display element together with a linear polarizer / optically anisotropic layer laminate “Sumikaran SR-F862A” in the same manner as in Example 1, the contrast in the dark room was Although it was as high as 280, the antiglare performance was extremely insufficient, and it was confirmed that the visibility was poor.

Comparative Example 3
The polarizing plate on the display surface side and the back surface side of the monitor for the personal computer equipped with the same TN type TFT liquid crystal display element used in Example 1 was peeled off, and the display surface side was used in Example 1. The same linear polarizer / optically anisotropic layer laminate, with a glare-proof layer on the polarizing plate side. Sumitomo Chemical Co., Ltd. polarizing plate laminate with anti-glare layer "Sumikaran SR-F862A-AG6" (Haze value 24%) was bonded via an adhesive on the optically anisotropic layer side so that the absorption axis of the polarizing plate coincided with the absorption axis of the original polarizing plate. Note that the antiglare surface of the polarizing plate laminate “Sumikaran SRF862A-AG6” used here is an uneven surface, but it is not a polyspherical surface. In addition, on the back of the liquid crystal display element, a polyvinyl alcohol-iodine polarizing plate “Sumikaran SR-1862A” manufactured by Sumitomo Chemical Co., Ltd. is used so that its absorption axis coincides with the absorption axis of the original polarizing plate. It was pasted through. When this liquid crystal display device was evaluated by the same method as in Example 1, it was confirmed that although the antiglare property was sufficient, the contrast value in the dark room was as low as 218, and the display characteristics were not sufficient.

  The results of the above examples and comparative examples are summarized in Table 1.

[Table 1]
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example comparison example
1 2 3 4 1 2 3
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Anti-glare surface shape Polyspherical polyspherical polyspherical polyspherical polyspherical polyspherical nonspherical
Shape Shape Shape Shape Shape Shape Surface shape─────────────────────────────────────────
Area 25 ~ 2,500μm ² ,
Proportional area ratio of height 0.1 to 10 μm 100% 100% 95% 100% 10% 50% −
Flat area ratio 0% 0% 0% 0% 0% 18% −
Haze 3.4% 1.0% 5.5% 7.0% 55% 5.4% 24%
────────────────────────────────────────
Contrast 300 330 297 282 151 280 218
Anti-glare ^* ○ ○ ○ ○ ○ × ○
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
^* Anti-glare property ○: Sufficient anti-glare property. X: Reflection is large.

It is a cross-sectional schematic diagram which shows the example of the polarizing film laminated body which concerns on this invention. It is an example of a Voronoi diagram for demonstrating Voronoi division. It is a cross-sectional schematic diagram which shows the preferable form for obtaining a glare-proof layer for every process. It is sectional drawing which shows the progress of an etching typically. It is a cross-sectional schematic diagram which shows an example of the liquid crystal display device which concerns on this invention. It is a cross-sectional schematic diagram which shows another example of the liquid crystal display device which concerns on this invention.

Explanation of symbols

10: Anti-glare polarizing film laminate,
15 ... Anti-glare layer,
16 …… Transfer film,
17: Transparent substrate film,
18 …… Ionizing radiation curable resin or its cured product,
20 …… Glass,
21 …… Scratches formed on the glass surface by blasting,
21a …… The tip of the wound
22 …… The original glass surface,
23, 24 ... Glass surface during etching,
25 ...... Concave shape (uneven surface) formed in glass,
26 …… Glass mold,
28 …… Blasting agent,
30: Linear polarizer,
35 …… Back side polarizing plate,
40: Optically anisotropic layer,
45... Rear side optical anisotropic layer,
50 ... Liquid crystal cell,
51, 52 …… Cell substrate,
54, 55 ... electrodes,
57 …… TN type liquid crystal,
60 …… Adhesive,
70 …… Backlight.

Claims (6)

Antiglare layer, linear polarizer and optically anisotropic layer are laminated in this order,
The anti-glare layer has an anti-glare surface having a number of fine spherical surfaces formed on the surface, and the height of each spherical domain that is divided and observed when the anti-glare surface is observed from above. Is in the range of 0.1 to 10 μm, the domain in the range of 25 to 2500 μm ² occupies 90% or more of the entire surface, and the area occupied by the flat portion is 10% or less of the entire surface,
The optically anisotropic layer is optically negative or positive uniaxial, and its optical axis is inclined by 5 to 50 ° from the normal direction of the film. body.   The antiglare layer has a fine spherical surface obtained by copying the shape onto a transparent resin film, using as a mold glass with fine irregularities formed on the surface by etching with an aqueous solution containing hydrogen fluoride. 2. An antiglare polarizing film laminate according to 1.   The antiglare polarizing film laminate according to claim 2, wherein the transparent resin film is an ultraviolet curable resin or a thermoplastic resin.   The antiglare layer is an antiglare polarizing film laminate according to any one of claims 1 to 3, wherein the antiglare layer has a haze value of 10% or less.   The anti-glare polarizing film laminate according to claim 1, wherein the optically anisotropic layer is optically negative uniaxial.   A liquid crystal display device in which polarizing plates are arranged on both sides of a liquid crystal cell in which a twisted nematic liquid crystal is sandwiched between two electrode substrates, and the polarizing plate located on the display surface side is as defined in claim 1. An antiglare polarizing film laminate according to any one of the above, wherein the optically anisotropic layer side is disposed so as to face the liquid crystal cell.

Images