JP2007114563A - Antiglare film, polarizing plate and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film which can effectively prevent reflection of external light and fall of contrast without reducing clearness of a high definition image due to miniaturization of pixel size or the like and on which desired fine ruggedness structure is effectively and stably formed with sufficient productivity and to provide a polarizing plate and a display device using the antiglare film. <P>SOLUTION: The antiglare film has 10 to 10,000/1mm<SP>2</SP>of fine protrusion structure parts, in which a major axis of a dot is 1 to 30μm and height of the dot is 0.5 to 10μm, on a base material film. Further a transparent resin layer is formed so as to cover the protrusion structure part and the protrusion structure part and the transparent resin layer have different refractive indexes. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antiglare film, a polarizing plate, and a display device, and more particularly to an antiglare film, a polarizing plate, and a display device that are excellent in antiglare property and that have a desired fine uneven structure formed effectively and stably with good productivity.

  In recent years, development of thin and light notebook computers has been progressing. Along with this, the demand for thinner and higher performance protective films for polarizing plates used in display devices such as liquid crystal display devices is also increasing. Also, a computer provided with an anti-glare layer for improving visibility, and also provided with an anti-glare layer that prevents reflections and scatters the reflected light with a rough surface to obtain display performance with less glare. A liquid crystal image display device (also referred to as a liquid crystal display) such as a word processor or the like has been widely used.

  Various types and performance improvements have been made to the antireflection layer and antiglare layer depending on the application, and various front plates with these functions are attached to the polarizer of a liquid crystal display, etc., to improve visibility on the display. Therefore, a method of providing an antireflection function or an antiglare function is used.

  The antiglare layer reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflection of the reflected image is noticeable when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is to prevent it from becoming.

  By providing an appropriate fine concavo-convex structure on the outermost surface of the front plate of the image display device, the above properties can be provided. For example, there are various methods such as a method using fine particles (for example, refer to Patent Document 1) and a method for embossing the surface (for example, refer to Patent Document 2).

  However, in the method using fine particles, since the fine concavo-convex structure is formed only by containing the fine particles in the binder layer, it is necessary to disperse the fine particles appropriately. It was difficult to form stably, and it had a great obstacle to obtaining a sufficient anti-glare effect as an antiglare film. In particular, in the method using fine particles, the density of fine particles cannot be controlled, and the height of the convex portion is higher than the surroundings in a portion where a plurality of fine particles overlap, so that it is impossible to stably form a uniform uneven structure. It was a drawback. Moreover, the method of forming a fine concavo-convex structure by embossing is inferior in productivity, and it is extremely difficult to form a fine concavo-convex structure stably.

In recent years, a display device having high anti-glare property and high contrast has been demanded as image quality has been improved. For example, the outermost surface of the liquid crystal display device has insufficient contrast with a conventional antiglare film such as a fine particle method, and reflection of external light becomes a problem with a clear hard coat antireflection film. In order to cope with this drawback, many techniques relating to an antiglare antireflection film obtained by coating an antiglare film with an antireflection layer (low refractive index layer) due to light interference have been proposed (for example, Patent Documents 3 to 8). reference.). However, these methods have not yet achieved sufficient anti-glare properties and contrast in obtaining a display device with higher visibility.
JP 59-58036 A JP-A-6-234175 JP 2001-281410 A Japanese Patent Laid-Open No. 2004-4404 JP 2004-125985 A JP 2004-24967 A JP 2004-4777 A JP 2003-121620 A

  Therefore, the present invention has been made in view of the above problems, and its purpose is to effectively capture external light and reduce contrast without deteriorating the sharpness of a high-definition image due to a reduction in pixel size or the like. An object of the present invention is to provide an antiglare film in which a desired fine uneven structure can be effectively and stably formed with good productivity, and to provide a polarizing plate and a display device using the film.

  The above object of the present invention is achieved by the following configurations.

(1) On the substrate film, 10 to 10,000 fine convex structures having a major axis of dots of 1 to 30 μm and a dot height of 0.5 to 10 μm per 1 mm ² , and the convex structures The anti-glare film is characterized in that a transparent resin layer is formed so as to cover the surface, and the refractive index of the convex structure portion and that of the transparent resin layer are different.

  (2) The antiglare film as described in 1 above, wherein an antireflection layer or an antifouling layer is further formed on the transparent resin layer.

  (3) The surface roughness (Ra) of the surface of the antiglare layer constituted by the convex structure portion and the transparent resin layer is 50 to 1000 nm, and the average center-to-center distance (Sm) of the convex portion or the concave portion is 10 to 200 μm. 3. The antiglare film as described in 1 or 2 above.

  (4) The antiglare film as described in any one of 1 to 3 above, wherein the thickness of the transparent resin layer is 1 to 5 μm thick with respect to the height of the convex structure portion.

  (5) The antiglare film as described in any one of (1) to (4) above, wherein the convex structure part or the transparent resin layer is an actinic ray curable resin.

  (6) The antiglare film according to any one of (1) to (4), wherein the convex structure portion or the transparent resin layer is a thermosetting resin.

  (7) The antiglare film as described in any one of (1) to (6) above, wherein the convex structure part contains fine particles having a particle size of 5 to 300 nm.

  (8) A polarizing plate using the antiglare film described in any one of 1 to 7 above.

  (9) A display device using the antiglare film described in any one of 1 to 7 and the polarizing plate described in 8 above.

  According to the present invention, it is possible to effectively prevent reflection of external light and a decrease in contrast without reducing the sharpness of a high-definition image due to a reduction in pixel size or the like, and a desired fine concavo-convex structure can be effectively produced with high productivity. -The anti-glare film formed stably can be provided, and also the polarizing plate and display apparatus using the same can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The antiglare film of the present invention produces a convex structure (also called a dot) by a pattern production method such as a gravure method, a screen printing method, a flexographic printing method, and an ink jet method, and the convex structure portion is actinic rays or heated. Then, a transparent resin layer is uniformly coated thereon by a thin film uniform coating method such as a micro gravure method, an extrusion coating method, a wire bar method, a flexographic printing method, and an ink jet method. At this time, the convex structure portion has a constant random arrangement by means of FM screening or the like within the plane, and the height is uniformly produced within a certain range, so that the surface roughness (Ra) is stable over the entire surface. In addition, since the unevenness is not formed at uniform intervals, moire is not generated between the pixels of the display. By appropriately setting the height of the convex structure and the film thickness of the transparent resin layer, irregularities with moderate and stable surface roughness are formed on the surface of the transparent resin layer, while maintaining the antiglare effect and light. Since an increase in haze due to scattering is suppressed and white turbidity due to scattered light is suppressed, an image with high contrast can be seen. Further, by making the refractive index of the convex structure portion different from the refractive index of the transparent resin layer, an internal scattering effect is generated, and it can be suppressed that transmitted light from the display side is glaring.

  According to the above method, an anti-glare film can be produced even at a printing speed of 10 m / min or more and 500 m / min, and reflection of external light can be achieved without deteriorating the sharpness of high-definition images. And an anti-glare film that can effectively and stably form a desired fine uneven structure with good productivity, an anti-glare anti-reflection film, a polarizing plate and a display device using the same Has been found to be obtained.

<Production of convex structure>
In the following, an example of a method for producing the convex structure portion is shown, but the present invention is not limited to this.

<Example of forming convex structure by flexographic printing>
In general, flexographic printing is a printing method using a relief printing plate made of a flexible rubber or resin and a solvent-based evaporation-drying ink mainly composed of water or alcohol.

  A convex structure is formed in a pattern on the surface of the base film using flexographic printing, and a transparent resin layer is further formed thereon on a thin film such as a micro gravure method, extrusion coating method, wire bar method, flexographic printing method, and ink jet method. By applying uniformly by the uniform application method, a fine concavo-convex structure can be formed while maintaining high productivity.

  First, flexographic printing preferably used in the present invention will be described with reference to the drawings.

  1 and 2 are schematic views showing an example of flexographic printing according to the present invention.

  The substrate film 10 that runs continuously is sandwiched between a plate cylinder 3 constituted by an impression cylinder 5, a resin plate roll 2, and a seamless resin plate 1 that forms a fine uneven structure on the substrate film after transfer printing. The ink 8 is supplied to the plate cylinder 3 by the anilox roll 4 in which the transfer ink amount is adjusted, and transfer printing is performed on the base film.

  In flexographic printing, ink supply to the plate cylinder 3 is performed by the anilox roll 4, and the amount of ink on the anilox roll surface is generally controlled by the doctor blade method shown in FIG. 1 or the two-roll method shown in FIG. Known to. In the two-roll system shown in FIG. 2, the ink 8 is transferred from the ink pan to the anilox roll 4 by the fountain roll 7 and further supplied to the plate cylinder 3 to transfer transfer the ink to the transparent substrate film 10. In addition to adjusting the number of engraved lines of the anilox roll 4, the depth of the cell, and the shape of the ink 8 according to the method of FIG. 2, the nip pressure between the fountain roll 7 and the anilox roll 4 (which tends to fluctuate) The method shown in FIG. 1 is preferred in the present invention because the ink supply amount is controlled and there is a problem that the ink transfer amount is not stable.

  As another method, FIG. 3 shows a schematic diagram of flexographic printing in which ink is supplied by an extrusion coater.

  The ink 8 is directly extruded onto the seamless resin plate 1 mounted on the resin plate roll 2 by an extrusion coater 9, and is transferred and printed onto a base film 10 that is sandwiched between the plate cylinder 3 and the impression cylinder 5 and continuously running. In this apparatus, since there is no anilox roll, the amount of ink supplied depends on the accuracy of the extrusion coater.

  In the doctor blade system shown in FIG. 1, the amount of ink transferred to the plate cylinder 3 is determined by the number of engraved lines of the anilox roll 4 and the shape of the cell, and can be stabilized as the amount of ink transferred. The ink that fills the cells of the anilox roll scrapes excess ink on the surface of the anilox roll with a doctor blade. Therefore, the transferred ink is determined by the number of engraving lines, the shape of the cell, and the volume. Then, the anilox roll cell is subjected to, for example, copper plating on the surface of the iron cylinder as necessary, the cell is formed on the surface by engraving, and the surface processing with hardness is performed by nickel or chromium plating. The material of anilox roll includes a type in which the surface of the iron cylinder is plated with copper or the like, or a type with ceramic coating. In the present invention, however, the type is ceramic coated in terms of wear resistance and easy thinning of the number of engraving lines. Is preferred.

  FIG. 4 is a perspective view of the anilox roll.

  FIG. 5 is a perspective view for explaining an anilox cell.

  As shown in FIG. 4, the anilox roll 4 can be formed by chemical corrosion in the same manner as a gravure plate provided on a copper surface. It is desirable to provide the cell b by engraving. The surface of the anilox roll is usually made by chrome plating after pressing with a mill, but from the point of wear resistance, corrosion resistance and ink transfer properties, inorganic oxides such as chromium oxide and tungsten carbide are formed by spraying. Those are preferred.

  The sculpture shape of the anilox roll 4 is not particularly limited in addition to the lattice type cell, although there are shapes such as a helical type, a pyramid type, a diagonal type, a hexagonal honeycomb pattern, etc. A honeycomb pattern is preferable from the viewpoint of reproducibility of ink transfer during high-speed printing. The number of engraving lines and the depth d of the cell b shown in FIGS. 4 and 5 greatly affect the amount of ink transferred, and form a fine uneven structure on the antiglare film surface according to the present invention. It is preferable that 600 lines / 2.54 cm or more and the cell depth d is 5 to 30 μm. The selection of the engraving shape and the number of lines is considered in accordance with the type of substrate to be printed and the number of lines on the printing screen. However, a plastic film with a small number of lines is preferably used for a plastic film with low absorbability. And it is preferable that the bank a (non-recessed portion) of the cell should be small enough not to affect the wear resistance from the viewpoint that the ink charge amount can be increased. Specifically, the bank width w is set to 0.1 as the cell width. It is preferable to provide it at ˜0.5 times. The anilox roll controls the amount of ink supplied to the plate surface by flexing in flexographic printing. And abrasion and damage occur in the process of doctoring, which causes the cell to become shallow and the ink transfer amount to decrease. Therefore, compared with the conventional metal (iron or copper engraving, chrome plating finish), the ceramic anilox roll has a small amount of wear due to doctoring and can greatly contribute to the repetitive stability of the concavo-convex pattern.

  The present invention preferably uses a plate cylinder 3 on which a seamless resin plate 1 having a diameter of 50 to 1000 mm is mounted on a resin plate roll 2 and preferably an anilox roll 4 coated with ceramics by a flexographic printing apparatus as shown in FIG. Then, ink is transferred onto the base film 10 and irradiated with actinic rays or heated to form a convex structure on the base film.

  The material of the resin plate roll 2 is not particularly limited as long as it can maintain strength, and is preferably a metal such as iron, stainless steel, or aluminum, or a synthetic or natural rubber. A composite member may be used. In the present invention, the diameter of the resin plate roll 2 may be selected so that the diameter (roll diameter) when the seamless resin plate 1 is mounted on the resin plate roll 2 is in the range of 50 to 1000 mm. If the diameter of the seamless resin plate 1 is less than 50 mm, the rotational speed is too high to maintain the strength, and the repetition period of the pattern of the convex structure portion is short, so that the antiglare effect is lowered. If the diameter exceeds 1000 mm, the apparatus becomes too large, which is expensive to operate and disadvantageous in terms of cost. In addition, uneven rotation tends to occur, and the accuracy of pattern formation decreases.

  In the present invention, the resin plate used for the seamless resin plate 1 is preferably a photosensitive resin plate to which photopolymerization of a polymer and a monomer as a photoreactive substance is applied. This photosensitive resin plate is composed of a photopolymer, a monomer photopolymerized by exposure to ultraviolet light, a sensitizer that initiates photopolymerization between the polymer and the monomer, and a plasticizer that adjusts the physical properties of the plate material. The above pattern is engraved on the photosensitive resin plate by a conventional mask plate making, or directly applied by irradiating the photosensitive resin layer provided on the entire surface of the cylinder (axial core) by laser light. The pattern can also be engraved.

  As the photosensitive resin composition used in the present invention, those known for flexographic printing plates can be used. In general, a composition mainly composed of a binder polymer, at least one ethylenically unsaturated monomer and a photoinitiator is used. Furthermore, additives such as a sensitizer, a thermal polymerization inhibitor, a plasticizer, and a colorant can be included depending on the properties required for the photosensitive resin layer.

  As the binder polymer, for example, a thermoplastic elastomer obtained by polymerizing a monovinyl-substituted aromatic hydrocarbon monomer and a conjugated diene monomer is used. Examples of the monovinyl-substituted aromatic hydrocarbon monomer include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like, and examples of the conjugated diene monomer include butadiene and isoprene. Specific examples include a styrene-butadiene-styrene block copolymer and a styrene-isoprene-styrene block copolymer.

  The at least one ethylenically unsaturated monomer is compatible with a binder polymer, for example, an ester of an alcohol such as t-butyl alcohol or lauryl alcohol with acrylic acid or methacrylic acid, or lauryl maleimide, cyclohexyl maleimide, benzyl Maleimide derivatives such as maleimide, or alcohol and fumaric acid esters such as dioctyl fumarate, and polyhydric alcohols such as hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate And esters of acrylic acid and methacrylic acid.

  Photoinitiators include aromatic ketones such as benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, 2,2-diethoxyphenylacetophenone, etc. These are selected from known photopolymerization initiators such as benzoin ethers and used in combination.

  The photosensitive resin layer can be prepared by various methods. For example, the raw materials to be blended can be dissolved and mixed in a suitable solvent such as chloroform, tetrachloroethylene, methyl ethyl ketone, toluene, etc., and coated on a suitable support with a coater. It can be cast into the plate as it is to evaporate the solvent. Moreover, it can knead | mix with a kneader or a roll mill, without using a solvent, and can shape | mold into the board of desired thickness with an extruder, an injection molding machine, a press.

  When the photosensitive resin sheet is wound around the resin plate roll, it is necessary to accurately cut and use the sheet so that there is no gap between the ends of the photosensitive resin in order to form a seamless resin plate. Usually, after the photosensitive resin plate is wound around the resin plate roll, the photosensitive resin is heated to a temperature higher than the softening point of the photosensitive resin, and the ends of the photosensitive resin are melt-bonded. The heating time is usually 20 minutes to 1 hour, and is determined based on the fact that the ends are fused according to the temperature and the softening point of the resin. Next, it is preferable for seamlessness that the surface of the photosensitive resin is polished by a grinder to completely eliminate the joint, and at the same time the accuracy is increased, and then the heating treatment is performed again above the softening point of the photosensitive resin. Although the time depends on the temperature, it is about 10 to 40 minutes, and is performed until the entire surface of the photosensitive resin becomes glossy. If the heating is continued for a long time, the accuracy of the printing plate is impaired, so it is desirable to process within one hour. In addition, a photosensitive resin layer can be applied seamlessly so that there is no direct seam on the base material such as rubber, polyester film, aluminum plate, steel plate, or aluminum resin plate roll that can be mounted on a cylinder.

  In the present invention, the rubber hardness of the seamless resin plate is preferably in the range of 30 to 80 degrees, and it is preferable that the rubber hardness of the resin plate be in this range in order to perform transfer printing of a fine uneven structure with accuracy and stability. Since the rubber hardness of the roll-shaped seamless resin plate 1 is also affected by the thickness of the resin plate, it is preferably in the range of 30 to 80 degrees in the resin plate having a thickness in the range of 0.5 to 10 mm. More preferably, it is in the range of 40 to 80 degrees.

  If the rubber hardness of the resin plate is less than 30 degrees, the plate is too soft and it is difficult to form a desired fine concavo-convex structure, and the plate itself is easily worn, which is not preferable. When the rubber hardness of the resin plate exceeds 80 degrees, the plate cylinder rotates at a high speed and lacks flexibility when printing and the reproducibility of the ink transfer amount becomes poor. The rubber hardness is indicated by a value measured with a durometer or the like according to the method described in JIS K 6253.

  Mask engraving is used as a method of imprinting a pattern with a fine relief structure on a seamless resin plate. In mask plate making, a resin plate provided with a layer of a photosensitive resin material is covered with a negative film as an original mask and exposed. The photosensitive resin layer is cured or insolubilized by light, particularly ultraviolet energy having a wavelength of 350 to 450 nm. The uncured resin in the unexposed portion is maintained in a soluble state in water, an aqueous alkali solution, or an organic solvent such as alcohol. Therefore, by washing out the unexposed portion with a solvent corresponding to the unexposed portion (developing step), only the exposed portion remains and forms a relief plate (flexographic plate).

  Further, as a recent printing plate method, a complete endless plate can be produced by directly engraving a cured resin plate with a laser beam or an engraving machine based on a corrected image signal. Alternatively, an unexposed photosensitive resin plate is scanned with a laser beam modulated with a corrected image signal in the form of a cylinder and patterned, and then developed by a normal method, from the viewpoint of forming an endless plate.

By the flexographic printing, 10 to 10,000 fine convex structures with a long diameter of dots of 1 to 30 μm and a height of dots of 0.5 to 10 μm are produced per 1 mm ² on the base film. The convex structure portion is formed.

  The dot height defined in the present invention is defined as the height from the base film surface that is the base to the top of the dot (convex structure), and the major axis is the dot in contact with the substrate (convex). It is defined as the maximum length of the structure bottom).

The fine convex structure on the surface can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, an optical interference type surface roughness measuring instrument is used to measure two-dimensionally about a range of about 4000 μm ² (55 μm × 75 μm), and the convex portion is color-coded and displayed from the bottom side as a contour line. The height of the convex portion and the convex portion diameter, which is the major axis of the convex structure portion, are measured. Further, the number of convex structure parts can be obtained by converting the number of convex parts obtained per 1 mm ² . These measurements are obtained as an average value by measuring arbitrary 10 points of the corresponding part of the base film.

<Example of forming convex structure by inkjet method>
Next, an example of forming the convex structure portion by the ink jet method used in the present invention will be described.

  FIG. 6 is a cross-sectional view showing an example of an ink jet head that can be used in the ink jet method used in the present invention.

  6A is a cross-sectional view of the ink jet head, and FIG. 6B is an enlarged view taken along line AA in FIG. 6A. In the figure, 11 is a substrate, 12 is a piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall, 14 is a common liquid chamber constituent member, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 Is a nozzle plate, 16a is a nozzle, 17 is a drive circuit printed board (PCB), 18 is a lead portion, 19 is a drive electrode, 20 is a groove, 21 is a protective plate, 22 is a fluid resistance, 23 and 24 are electrodes, 25 Is an upper partition, 26 is a heater, 27 is a heater power source, 28 is a heat transfer member, and 30 is an ink-jet head.

  In the integrated inkjet head 30, the laminated piezoelectric element 12 having the electrodes 23 and 24 is grooved in the direction of the flow path 13a corresponding to the flow path 13a, so that the groove 20 and the driving piezoelectric element 12b. And non-driving piezoelectric element 12a. The groove 20 is filled with a filler. The flow path plate 13 is joined to the piezoelectric element 12 subjected to the groove processing through the upper partition wall 25. That is, the upper partition 25 is supported by the non-driving piezoelectric element 12a and the wall 13b that separates the adjacent flow path. The width of the driving piezoelectric element 12b is slightly narrower than the width of the flow path 13a. When the driving piezoelectric element 12b selected by the driving circuit on the driving circuit printed board (PCB) is applied with a pulsed signal voltage, the driving piezoelectric element 12b. The element 12b changes in the thickness direction, and the volume of the flow path 13a changes via the upper partition wall 25. As a result, ink droplets are ejected from the nozzles 16a of the nozzle plate 16.

  Heaters 26 are bonded to the flow path plate 13 via heat transfer members 28, respectively. The heat transfer member 28 is provided around the nozzle surface. The heat transfer member 28 is intended to efficiently transfer the heat from the heater 26 to the flow path plate 13, carry the heat from the heater 26 to the vicinity of the nozzle surface, and warm the air in the vicinity of the nozzle surface. A material with good conductivity is used. For example, metals such as aluminum, iron, nickel, copper, and stainless steel, or ceramics such as SiC, BeO, and AlN are preferable materials.

  When the piezoelectric element is driven, the piezoelectric element is displaced in a direction perpendicular to the longitudinal direction of the flow path, and the volume of the flow path is changed. By the change in volume, ink droplets are ejected from the nozzle. The piezoelectric element is given a signal that keeps the flow path volume constantly reduced, and after the displacement of the selected flow path in the direction of increasing the flow volume, the displacement that reduces the flow volume again is applied. By applying a pulse signal to be applied, ink is ejected as ink droplets from a nozzle corresponding to the flow path.

  FIG. 7 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

  7, (a) of FIG. 7 is a sectional view of the head portion, and (b) of FIG. 7 is a plan view of the nozzle plate. In the figure, 10 is a transparent substrate film, 31 is an ink droplet, 32 is a nozzle, and 29 is an actinic ray irradiation part. The ink droplet 31 ejected from the nozzle 32 flies in the direction of the transparent substrate film 10 and adheres. The ink droplets that have landed on the transparent substrate film 10 are immediately irradiated with actinic rays from the actinic ray irradiating unit disposed upstream thereof and cured. Reference numeral 35 denotes a back roll for holding the transparent substrate film 10.

  In the present invention, as shown in FIG. 7B, the nozzles of the ink jet head section are preferably arranged in a staggered manner, and are provided in multiple stages in parallel in the transport direction of the transparent substrate film 10. Is preferred. Further, it is preferable that fine vibrations are applied to the ink jet head portion during ink ejection so that ink droplets land randomly on the transparent substrate. Thereby, generation | occurrence | production of an interference fringe can be suppressed. The fine vibration can be given by a high frequency voltage, a sound wave, an ultrasonic wave or the like, but is not particularly limited thereto.

  As the method for forming the convex structure portion used in the present invention, it is preferable to use an ink jet method in which small droplets of ink are formed from multiple nozzles. FIG. 8 shows an example of an ink jet system that can be preferably used in the present invention.

  8, (a) of FIG. 8 is a method (line) in which the inkjet head 30 is arranged in the width direction of the transparent substrate film 10 and a convex structure portion is formed on the surface of the transparent substrate film 10 while being conveyed. FIG. 8B shows a method (flat head method) in which the inkjet head 30 moves in the sub-scanning direction and forms a convex structure portion on the surface thereof. FIG. 8C shows an inkjet method. The head 30 is a method (capstan method) in which a convex structure is formed on the surface of the transparent substrate film 10 while scanning in the width direction, and any method can be used. From the viewpoint of productivity, the line head method is preferable. In addition, 29 described in (a) to (c) of FIG. 8 is an actinic ray irradiation unit used when an actinic ray curable resin described later is used as the ink.

  Moreover, in this invention, you may provide another actinic ray irradiation part in the downstream of the conveyance direction of the transparent base film of (a) of FIG. 8, (b), (c).

  In the present invention, in order to form a fine convex structure, the ink droplet is preferably 0.1 to 100 pl, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl. By ejecting ink droplets under the above conditions, it is possible to obtain a fine convex structure in which the major axis of the dots is 1 to 30 μm and the height of the dots is 0.5 to 10 μm.

  The viscosity of the ink droplets is preferably 0.1 to 100 mPa · s at 25 ° C., more preferably 0.1 to 50 mPa · s.

  The convex structure forming method is not limited to the above-described flexographic method and inkjet method, and any method that can form a desired pattern such as a gravure printing method, a screen printing method, and a lithographic printing method may be used. Because the production method is fast and minute convex structures can be formed, the ink jet method can flexibly change the presence pattern of the convex structures, and the cross-sectional shape of the convex structure can be formed into a bowl shape, and a transparent resin layer is provided. It is excellent in that it is easy to make the surface shape smooth and uneven.

  The convex structure has a constant size and height of a dot having a major axis of 1 to 30 μm, more preferably 3 to 10 μm, and a dot height of 0.5 to 10 μm, more preferably 2 to 5 μm. It is preferable that the dots are arranged at random by a method such as FM screening. Here, the major axis of the dot represents the diameter when the dot is circular, and the diameter converted into the same area when the dot is triangular, quadrangular, polygonal, or indefinite. The dot height refers to the difference in height between the substrate film surface and the highest dot portion.

  The FM screening method is a method for expressing light and shade by modulating the interval between dots, that is, the frequency, and the frequency of hitting the basic dots (dot density). The FM screening method is sometimes called a random screening method or a stochastic screening method. The FM screening method refers to a method of modulating the interval between dots, that is, periodicity. Specifically, the crystal raster screening method (Agfa Gebalt), the diamond screen method (Rhinotype Hell), the class screening method and the full-tone screening method (Cytex), the velvet screening method ( Ugura Cohan), Accutone Screening (Dannery), Megadot Screening (American Color), Clear Screening (Seacolor), Monet Screening (Barco) Yes. Although all of these methods have different dot generation algorithms, it is a method of expressing shading by changing the dot density, and can be said to be various aspects of the FM screening method.

  In FM screening, the size of dots on which ink is placed is constant, and the frequency of dot appearance changes according to the density of the image. Since the size of each dot in FM screening is smaller than a so-called halftone dot, a required pattern can be reproduced with high resolution. Unlike so-called halftone dots, dots in FM screening are not periodically arranged. The FM screening has a feature that moire does not occur because the dot arrangement is not periodic.

<Transparent resin layer>
The transparent resin layer of the present invention is produced by coating by a general thin film uniform coating method such as a micro gravure method, an extrusion coating method, a wire bar method, a flexographic printing method, or an ink jet method. The transparent resin layer is coated on the above-described convex structure portion, covers the convex structure portion, and smoothes the irregularities formed only by the convex structure portion, thereby obtaining a preferable surface shape, thereby providing an antiglare property. Can be expressed.

  The thickness of the transparent resin layer is preferably 1 to 5 μm thick with respect to the height of the convex structure portion. Further, in order to cover the entire surface of the convex structure portion, the coating liquid film thickness is preferably 2 to 5 times the height of the convex structure portion. The convex structure portion can be completely covered by the thick coating solution film, but if it is too thick, it is affected by drying unevenness during drying and the film thickness uniformity is impaired. Of the resins contained in the transparent resin layer, 50% or more is preferably the same as the resin used for the convex structure portion, and this ensures sufficient adhesion between the convex structure portion and the transparent resin layer. Can do.

  The convex structure and transparent resin layer ink of the present invention are silicone oil, modified silicone oil, silicone surfactant, fluorine surfactant, fluorine resin, fluorine oligomer, fluorine modified silicone oil, fluorine silane cup. It is preferable to contain 0.1 parts by mass or more and 5 parts by mass or less of an activator such as a ring agent. If the addition amount is too large, the transparent resin layer cannot be applied onto the convex structure portion due to the water / oil repellent effect, which is not preferred, and if the addition amount is small, the shape of the convex structure may not be constant. Since the amount of the surfactant depends on the ink composition, the solvent composition, and the surface energy of the base substrate, it is not essential to add the surfactant.

(Silicone oil or silicone surfactant)
Silicone oils used in the present invention can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic groups bonded to silicon atoms. Straight silicone oil refers to those bonded with a methyl group, a phenyl group, or a hydrogen atom as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

Silicone oil Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc. 1-2. Reactive silicone oil: methyl hydrogen substitution, etc. Modified silicone oil Modified silicone oil was born by introducing various organic groups into dimethyl silicone oil 2-1. Non-reactive silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc.
Alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with a long-chain alkyl group or a phenylalkyl group,
Polyether-modified silicone oil is a silicone-based polymer surfactant in which hydrophilic polyoxyalkylene is introduced into hydrophobic dimethyl silicone,
Higher fatty acid-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with higher fatty acid ester,
Amino-modified silicone oil is a silicone oil having a structure in which a part of methyl group of silicone oil is substituted with aminoalkyl group,
The epoxy-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is replaced with an epoxy group-containing alkyl group,
The carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group 2-2. Reactive silicone oil: amino, epoxy, carboxyl, alcohol substitution, etc. Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2000 to 50,000. If the number average molecular weight is less than 1,000, the drying property of the coating film decreases, and conversely, the number average molecular weight. When it exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  As specific products, Nippon Unicar Co., Ltd. L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ-3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, and the like.

  As the silicone surfactant used in the present invention, one obtained by substituting a part of methyl group of silicone oil with a hydrophilic group can be used. The position of substitution includes a side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

  A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydrophilic group includes a hydroxyl group of a polyhydric alcohol, a polyoxyalkylene chain (poly Oxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant used in the present invention preferably has dimethylpolysiloxane as a hydrophobic group.

  When a nonionic surfactant composed of a dimethylpolysiloxane having a hydrophobic group and a polyoxyalkylene having a hydrophilic group is used, unevenness of the low refractive index layer, which will be described later, and antifouling properties of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191 and the like.

  Moreover, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle at a plurality of locations so as to cover the surface of the silica fine particle by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

  Among these silicone oils or silicone surfactants, those having a polyether group are preferred.

  The refractive index of the ink can be selected in the range of 1.35 to 1.9. The ink transmittance is 80% or more, preferably 90% or more.

  The viscosity of the ink is preferably 0.1 to 10 Pa · s, more preferably 0.5 to 8 Pa · s at a measurement temperature of 40 ° C. If the viscosity is less than 0.1 Pa · s, the viscosity is too low to obtain a pattern having a desired shape, and if it exceeds 10 Pa · s, the fluidity of the ink is poor and the transferability of the ink is also unfavorable. The viscosity of the ink is not particularly limited as long as it is tested with a viscometer calibration standard solution specified in JIS Z 8809, and a rotary, vibration or capillary type viscometer can be used. . As a viscometer, it can be measured with a Saybolt viscometer, a Redwood viscometer, etc., for example, Tokimec Co., Ltd., conical plate type E type viscometer, Toki Sangyo E Type Viscometer, manufactured by Tokyo Keiki Co., Ltd. B-type viscometer BL, Yamaichi Denki Co., Ltd. FVM-80A, Nametor Kogyo Viscoliner, Yamaichi Denki Co., Ltd. VISCO MATE MODEL VM-1A, and the like.

  The actinic ray curable resin preferably used for the convex structure portion ink and transparent resin layer of the present invention will be described.

  The actinic ray curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic ray curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with actinic rays other than ultraviolet rays and electron beams may be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .

  An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, JP-A No. 59-151112).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, preferred examples of the epoxy actinic ray reactive compound are shown.

(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
(B) A compound having a glycidyl ether group by reacting epichlorohydrin, ethylene oxide and / or propylene oxide with a compound having two phenolic OHs such as bisphenol A. (c) Glycidyl ether of 4,4'-methylenebisphenol (D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin (e) Compound having alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) ) Adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxy Rhohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1 '-Methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- 5 ', 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane (f) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthalate, diglycidyl Phthalate (g) Diglycidyl ether of glycol, such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) di Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (h) Glycidyl ester of polymer acid, for example, polyglycidyl ester of polyacrylic acid, polyester diglycidyl ester (i) Polyhydric alcohol Glycidyl ethers such as glycerin triglycidyl ether, trimethylolpropane triglyceride Dil ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether (j) As diglycidyl ether of 2-fluoroalkyl-1,2-diol, the low refractive index substance (K) Examples of the fluorine-containing alkane-terminated diol glycidyl ether include fluorine-containing epoxy compounds of the fluorine-containing resin of the low refractive index material, and the like. I can do it.

  The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  When the above epoxy compound is cured with actinic rays, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy actinic light-reactive compound is a compound capable of releasing a cationic polymerization initiating substance upon irradiation with actinic light, and particularly preferably, cationic polymerization is initiated by irradiation. A group of double salts of onium salts that release potent Lewis acids.

  The actinic ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is a preferable actinic ray reactive resin because it is not affected by oxygen in the reaction system.

  The actinic ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with actinic rays. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  A typical example is a compound represented by the following general formula (a).

Formula (a)
[(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{w +} [MeX _v ] ^w-
In the formula, the cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), and R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _v ] ^w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetra Examples thereof include fluoroarsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among such onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic halonium salts described in JP-A-50-151996, 50-158680, etc. VIA group aromatic onium salts described in Kaisho 50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402, Preference is given to oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-B-49-17040, thiopyrilum salts described in US Pat. No. 4,139,655, and the like. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the case of an actinic ray reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for the actinic ray reactive compound are sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet reactive compound, Preferably they are 1 mass part-10 mass parts. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the actinic ray curable resin composition useful in the present invention, the photopolymerization initiator is generally 0.1 to 15 parts by mass with respect to 100 parts by mass of the actinic ray curable epoxy resin (prepolymer). Is more preferable, and addition of 1 mass part-10 mass parts is more preferable.

  An epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an actinic ray radical polymerization initiator and an actinic ray cationic polymerization initiator in combination.

  In the present invention, an oxetane compound can also be used. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, 3,3-dimethyloxetane and the like. In the present invention, any of a monomer, an oligomer and a polymer may be used.

  Specific examples of the ultraviolet curable resin that can be used in the present invention include, for example, Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B. (Asahi Denka Kogyo Co., Ltd.), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T -102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX -9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, CR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB), RC-5015, RC-5016, RC-5020, RC -5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, Dainippon Ink & Chemicals, Inc.), Aurex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) , SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.), RCC-15C (produced by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) (Made by Co., Ltd.), or other commercially available products.

  Further, when an ultraviolet curable resin is used as the actinic ray curable resin, an ultraviolet absorber may be included in the ultraviolet curable resin composition to the extent that does not hinder the photocuring of the ultraviolet curable resin. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like. However, it is not limited to these.

The ink according to the present invention preferably contains an antistatic agent such as conductive fine particles such as SnO ₂ , ITO, ZnO, and crosslinked cationic polymer particles. In the present invention, it is preferable to add an antistatic agent to the transparent resin layer.

  In the present invention, it is also preferable to contain fine particles in the ink for adjusting the refractive index. For example, inorganic fine particles or organic fine particles can be added.

  Examples of the inorganic fine particles include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Calcium phosphate and the like are preferable, and an inorganic compound containing silicon and zirconium oxide are more preferable, and silicon dioxide is particularly preferably used. These include particles having a shape such as a spherical shape, a flat plate shape, and an amorphous shape.

  As the fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.) can be used.

  As the fine particles of zirconium oxide, commercially available products such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  The organic fine particles include polymethacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicon resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  In this invention, it is preferable that a convex structure part contains the said microparticles | fine-particles, and the average particle diameter has preferable 5-300 nm, More preferably, it is 20-100 nm. You may contain 2 or more types of microparticles | fine-particles from which a particle size and refractive index differ. Moreover, it is preferable that content is 5-50 mass% with respect to a convex structure part.

  In the present invention, when the convex structure portion or the transparent resin layer contains an actinic ray curable resin, the actinic ray irradiation method includes transferring the ink onto the transparent substrate, evaporating the solvent, and the like, Irradiation is preferred. The timing of irradiation can be determined in consideration of the pattern shape to be formed. For example, when the ink is solvent-free, irradiation is performed immediately after transfer printing to 2 minutes later, and when the ink includes a solvent, the solvent in the ink Irradiation can be performed immediately after evaporating to 2 min.

  The term “immediately after transfer printing of the ink in the present invention onto the transparent substrate, or immediately after the solvent in the ink has been volatilized” specifically refers to a period of 5 seconds after the ink is transferred. Irradiation with actinic rays may be performed to such an extent that the fluidity of the ink is lowered and a desired pattern shape can be formed, and a half-cured state may be used. In this case, it can be cured completely by irradiating an active light source separately installed on the downstream side. In the present invention, it is preferable to use an actinic radiation curable resin for forming the convex structure and forming the transparent resin layer.

The actinic ray that can be used in the present invention can be used without limitation as long as it is a light source that activates the actinic ray curable resin formed in a pattern with ultraviolet rays, electron beams, γ rays, etc. Electron beams are preferable, and ultraviolet rays are particularly preferable in that they are easy to handle and high energy can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 1 mJ / cm ² or more, more preferably 20 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

  In the present invention, the oxygen concentration in the atmosphere at the time of active ray irradiation is preferably 10% or less, particularly preferably 1% or less. In order to obtain this atmosphere, it is effective to introduce nitrogen gas or the like.

  Moreover, in this invention, in order to advance the hardening reaction of actinic light efficiently, a base film etc. can also be heated. The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method such as spraying hot air on the surface of transfer-printed ink. Moreover, you may heat continuously by using the back roll used on the opposite side across the base film of a flexographic printing part as a heat roll.

  The heating temperature cannot be generally specified depending on the type of actinic ray curable resin to be used, but is preferably in a temperature range that does not affect the base film such as thermal deformation, and is preferably 30 to 200 ° C. Furthermore, 50-120 degreeC is preferable, Most preferably, it is 70-100 degreeC.

  Next, a thermosetting resin that can be used for the convex structure portion or the ink for the transparent resin layer of the present invention will be described.

  Examples of the thermosetting resin that can be used in the present invention include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, thermosetting polyamide imides, and the like.

As the unsaturated polyester resin, for example, orthophthalic acid resin, isophthalic acid resin, terephthalic acid resin, bisphenol resin, propylene glycol-maleic acid resin, dicyclopentadiene or derivatives thereof are introduced into the unsaturated polyester composition. Low styrene volatile resin with low molecular weight or added film-forming wax compound, low shrinkage with thermoplastic resin (polyvinyl acetate resin, styrene / butadiene copolymer, polystyrene, saturated polyester, etc.) Resin, unsaturated polyester brominated directly with Br ₂ , or reactive type such as copolymerization of het acid or dibromoneopentyl glycol, halides such as chlorinated paraffin, tetrabromobisphenol and antimony trioxide, phosphorus Compound combinations Additive-type flame retardant resin that uses sesame or aluminum hydroxide as an additive, toughness resin that is hybridized with polyurethane or silicone, or toughened with IPN (high strength, high elastic modulus, high elongation), etc. is there.

  Examples of the epoxy resin include glycidyl ether type epoxy resins including bisphenol A type, novolak phenol type, bisphenol F type, brominated bisphenol A type, glycidyl amine type, glycidyl ester type, cyclic aliphatic type, and heterocyclic epoxy type. Special epoxy resins containing

  As the vinyl ester resin, for example, an oligomer obtained by ring-opening addition reaction of an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid is dissolved in a monomer such as styrene. There are also special types such as vinyl monomers having vinyl groups at the molecular ends and side chains. Examples of vinyl ester resins of glycidyl ether type epoxy resins include bisphenol type, novolak type, brominated bisphenol type, etc., and special vinyl ester resins include vinyl ester urethane type, isocyanuric acid vinyl type, side chain vinyl ester type, etc. There is.

  The phenol resin is obtained by polycondensation using phenols and formaldehyde as raw materials, and there are a resol type and a novolac type.

  Examples of thermosetting polyimide resins include maleic acid-based polyimides such as polymaleimide amine, polyamino bismaleimide, bismaleimide / O, O'-diallyl bisphenol-A resin, bismaleimide / triazine resin, and nadic acid-modified polyimide. And acetylene-terminated polyimide.

  A part of the actinic ray curable resin described above can also be used as a thermosetting resin.

  In addition, you may use suitably the antioxidant and ultraviolet absorber which were described in the ink containing actinic-light curable resin for the ink which consists of a thermosetting resin used for this invention.

  In the present invention, when the pattern formed by flexographic printing contains a thermosetting resin, the heating method is preferably performed immediately after the ink is transferred onto the base film.

  The term “immediately after the transfer transfer of the ink in the present invention on the base film” is specifically preferably the heating of the ink at the same time as the transfer printing or within 5 seconds. Can be raised. For example, the base film can be wound on a heat roll, and ink can be transferred onto the heat roll, and more preferably at the same time as the transfer printing or between 2 seconds. In addition, if the distance between the nozzle part and the heating part is too close and heat is transferred to the head part, the nozzle part is clogged due to curing at the nozzle part, so care must be taken. Further, if the heating interval exceeds 5 seconds as necessary, a smooth fine concavo-convex structure can be obtained by causing the flow-printed ink to flow and deform.

  The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method such as spraying hot air on the surface of transfer-printed ink. In addition, the back roll provided on the opposite side with the base film of the flexographic printing unit interposed therebetween may be continuously heated as a heat roll. The heating temperature cannot be generally defined by the type of thermosetting resin to be used, but is preferably in a temperature range that does not affect the heat deformation of the transparent substrate, preferably 30 to 200 ° C, Furthermore, 50-120 degreeC is preferable, Especially preferably, it is 70-100 degreeC.

  In the ink according to the present invention, any of the above-mentioned actinic ray curable resins and thermosetting resins can be used for producing the convex structure or the transparent resin layer, but preferably an actinic ray curable resin is used. It is.

  The ink according to the present invention may contain 0 to 99.9% by mass of a solvent as necessary. For example, the actinic ray curable resin monomer component or the thermosetting resin monomer component may be dissolved or dispersed in an aqueous solvent, or an organic solvent may be used. An organic solvent having a low boiling point or a high boiling point can be appropriately selected and used, and the addition amount, type and composition of these solvents are preferably adjusted appropriately in order to adjust the viscosity of the ink.

  Examples of the solvent that can be used in the ink according to the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ketones such as diacetone alcohol Alcohols; aromatic hydrocarbons such as benzene, toluene, xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellsolve, butylcellsolve, ethylcarbitol, butylcarbitol, diethylcellsolve, Glycol ethers such as diethyl carbitol and propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, amino acetate Esters and the like; dimethyl ether, and diethyl ether, water and the like, they can be used alone or in combination. Further, those having an ether bond in the molecule are particularly preferred, and glycol ethers are also preferably used.

  Specific examples of glycol ethers include, but are not limited to, the following solvents. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ac, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether Ac, ethylene glycol Examples thereof include diethyl ether, and Ac represents acetate. In the ink according to the present invention, among the above solvents, a solvent having a boiling point of less than 100 ° C. is preferably used. These solvents are desirably volatilized and dried as quickly as desired pattern shape is maintained after transfer printing. Alternatively, the pattern shape can be controlled by mixing different volatile solvents and changing the ratio.

  The transparent resin layer is an actinic ray curable resin, photopolymerization initiator, thermoplastic resin, photoreaction initiator, photosensitizer, ultraviolet absorber, fine particles, thermosetting, which has been described in detail in the above-mentioned convex structure section. A hard coat coating composition can be prepared by appropriately using a resin and a solvent, and coating is performed on the convex structure portion by any coating method.

  The coating method of the transparent resin layer is not particularly limited, but the hard coat coating composition is a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, an ink jet method, or a flexographic printing method. It is preferable to coat.

  FIG. 9 shows that a convex structure is formed on a base film in a pattern, and a transparent resin layer is further applied so that the transparent resin layer covers both the convex structure and the portion without the convex structure. It is the schematic diagram which showed a mode that various unevenness | corrugations were formed.

  The surface roughness (Ra) of the concavo-convex structure on the surface of the transparent resin layer of the present invention is 50 to 1000 nm, more preferably 100 to 500 nm. Moreover, it is preferable that the average center distance (Sm) of the uneven structure of the transparent resin layer surface is 10-200 micrometers, More preferably, it is 10-50 micrometers. Beyond these ranges, it becomes difficult to achieve both an antiglare effect and contrast. The Ra and Sm can be controlled by adjusting the height of the convex structure, the arrangement of the convex structure pattern, the thickness of the transparent resin layer, the physical properties such as the viscosity of the ink composition used for the transparent resin layer, and the like.

  A feature of the present invention is that the convex structures and the transparent resin layer have different refractive indexes. The refractive indexes of the two are preferably different from 0.02 to 0.2, and more preferably from 0.03 to 0.1. The refractive index of the convex structure portion is preferably higher than the refractive index of the transparent resin layer, which causes internal scattering in the antiglare layer of the present invention, and the transmitted light emitted from the display is partially collected. It is possible to prevent the light from being seen and glancing from a visual angle. As means for increasing the refractive index of the convex structure portion from the transparent resin layer, there are a method of containing a high refractive index resin and a method of adding high refractive index fine particles to the resin.

  FIG. 10 is a schematic view of the concavo-convex structure formed by a transparent resin layer preferable for the present invention formed on a base film.

  FIG. 10A is a perspective view of the fine concavo-convex structure, and FIG. 10B is a cross-sectional view. The height of the convex portion when the surface roughness (Ra) is determined is indicated by e in the figure and refers to the height difference between the convex portion and the concave portion. The uneven structure on the surface of the transparent resin layer can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, the unevenness is measured two-dimensionally within a certain range by an optical interference type surface roughness measuring device, and the unevenness is color-coded as contour lines from the bottom side and displayed. Here, the height of each fine concavo-convex structure on the basis of the adjacent concave bottom is obtained and used as an average value.

  The average center-to-center distance (Sm) between adjacent convex portions or concave portions is the same as that defined as the average length of the contour element curve in JIS B0601, and is represented by g (in this case, the convex portion). However, the vertex of a convex part or a recessed part is made into the center of this convex part or a recessed part, and the distance between adjacent convex parts or recessed part centers is averaged. The average distance between protrusions or recesses can be measured by a stylus type surface roughness measuring machine, for example, a fine uneven structure surface through a measuring needle having a diameter of 1 mm with a tip portion made of diamond having a conical shape with an apex angle of 55 degrees. By scanning the top in a certain direction and measuring the movement change in the vertical direction of the measuring needle in that case, it is possible to obtain knowledge as a surface roughness curve recorded, and from the result, the distance between the convex part or the concave part is obtained. The average value can be obtained by measurement. Alternatively, it can be measured by an optical interference type surface roughness measuring machine as described above.

  The surface roughness (Ra) defined in the present invention is defined by JIS B0601, and refers to a value obtained by the following formula expressed in micrometers (μm).

  As a method for measuring the surface roughness (Ra), it can be obtained by adjusting the humidity for 24 hours in a 25 ° C., 65% RH environment under conditions where the measurement samples do not overlap each other, and then measuring in the above environment. The non-overlapping conditions mentioned here are, for example, a method of winding with the edge portion of the sample raised, a method of stacking paper between the sample and the sample, a frame made of cardboard, etc., and fixing its four corners One of the methods. Examples of the measuring apparatus that can be used include a RSTPLUS non-contact three-dimensional micro surface shape measuring system (a typical example of an optical interference type surface roughness measuring machine) manufactured by WYKO.

  Next, FIG. 11 shows an example of formation of a convex structure portion by flexographic printing preferably used in the present invention, and formation of a transparent resin layer by a coating method using a coater that is subsequently performed.

  In FIG. 11, the base film 502 fed out from the roll 501 is transported, and a pattern-like convex structure portion is applied by flexographic printing in the flexographic printing portion A. Here, the ink liquid is supplied from the ink supply tank 508 to the anilox roll 510, and the ink is transferred to the resin plate 509 having a pattern structure which is a flexographic printing unit. When the actinic ray curable resin is used for the transfer printed ink, the actinic ray irradiation unit 506A disposed after the resin plate 509 which is a flexographic printing unit is irradiated with actinic rays such as ultraviolet rays. Harden. When the ink uses a thermosetting resin, the ink is heated and cured by a drying zone 505A, for example, a heat plate. A method of heating the back roll 504A as a heat roll is also preferable.

  In the flexographic printing part A, the actinic ray irradiation part 506A and the resin plate 509 are arranged at an appropriate interval so that the irradiation light of the actinic ray irradiation part 506A does not directly affect the ink of the resin plate 509. It is preferable to install a light shielding wall or the like between the light irradiation unit 506A and the resin plate 509. Further, the resin plate 509 is covered with a heat insulating cover so that the heat of the drying zone 505A does not directly affect the ink of the resin plate 509, or the drying air in the drying zone 505A is blocked as shown in the figure. It is preferable to install such a partition.

  The base film 502 that has been cured to such an extent that the pattern formed by the transfer-printed ink can be maintained is cured by evaporating unnecessary organic solvent or the like in the drying zone 505A.

  Next, in the transparent resin layer application part B, the composition for hard coat layer supplied from the coater 503 is applied to the entire surface including the convex structure part, and an uneven structure is formed between the convex structure part non-formation part. When the transparent resin layer contains an actinic ray curable resin, actinic rays are irradiated by the actinic ray irradiation units 506B and 506C. Further, it is dried and solidified by the drying zone 505B.

  In the actinic ray irradiation sections 506A, B, and C, it is preferable to irradiate the base film 502 on the back rolls 504A, B, and C whose temperature is controlled to 20 to 120 ° C. with actinic rays.

  In the present invention, the method of forming a pattern-like convex structure portion by flexographic printing is preferably formed while the base film is transferred at 1 to 500 m / min, preferably 10 to 300 m / min.

  The base film used for transfer printing of the ink is preferably free from unevenness in charging, and is preferably charged immediately before, or may be uniformly charged.

  Also, the anti-glare property such as haze and transmission sharpness is measured for the pattern formed by transfer printing of ink, and it is confirmed that it is a predetermined value, and when the deviation or fluctuation is confirmed, the result is fed back. It is preferable to adjust the ink and replace the resin plate.

<Base film>
The base film used in the present invention is easy to manufacture, has good adhesion to the actinic radiation curable resin layer, is optically isotropic, is optically transparent, etc. Is mentioned as a preferable requirement.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, cellulose ester-type films, such as a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polyester-type film, a polycarbonate Film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol Film, syndiotactic polystyrene film, polycarbonate film, nor Runen resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, may be mentioned acrylic film or a glass plate or the like. Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable.

  The norbornene-based resin film preferably used in the present invention is an amorphous polyolefin film having a norbornene structure, such as APO manufactured by Mitsui Petrochemical Co., Ltd., ZEONEX manufactured by Nippon Zeon Co., Ltd., manufactured by JSR Co., Ltd. ARTON etc.

  In the present invention, it is particularly preferable to use a cellulose ester film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used. As a commercially available cellulose ester film, for example, Konica Minoltac, product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UY, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5 (manufactured by Konica Minolta Opto, Inc.) From the viewpoint of production, cost, transparency, adhesiveness and the like are preferably used. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

《Anti-glare anti-reflection film》
In the present invention, the antiglare antireflection film is preferably provided with the following low refractive index layer on the surface having the fine uneven structure of the antiglare film having the convex structure and the transparent resin layer.

  In particular, in the present invention, the low refractive index layer is preferably coated with a low refractive index layer coating solution containing hollow silica-based fine particles having an outer shell layer and porous or hollow inside.

<Low refractive index layer>
The refractive index of the low refractive index layer according to the present invention is preferably lower than the refractive index of the substrate film as the support, and is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm.

  The film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm.

  The composition for forming a low refractive index layer used in the present invention comprises (a) an organosilicon compound represented by the following general formula (1) or a hydrolyzate thereof or a polycondensate thereof, and (b) an outer shell layer. It is preferable that hollow silica-based fine particles having a porous or hollow interior constitute the composition.

General formula (1) Si (OR) ₄
(In the formula, R is an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms.)
In addition, a silane coupling agent, a curing agent, and the like may be added as necessary.

[Hollow silica fine particles]
First, hollow silica-based fine particles having the outer shell layer represented by (b) and having a porous or hollow interior will be described.

  The hollow silica-based fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the contents are solvent, gas or porous It is a hollow particle filled with a porous material. The low refractive index layer may contain either (I) composite particles or (II) hollow particles, or may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such hollow fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow fine particles to be used are appropriately selected according to the thickness of the transparent coating to be formed, and may be in the range of 2/3 to 1/10 of the thickness of the transparent coating such as the low refractive index layer to be formed. desirable. These hollow fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use silicate monomers and oligomers with a low polymerization degree, which are coating liquid components described later. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, when the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. In addition, components other than silica may be contained. Specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, particles having a small pore volume and a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a low refractive index. is there.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed.

(Organic silicon compound)
In the organosilicon compound represented by the general formula (1), R represents an alkyl group having 1 to 4 carbon atoms.

  Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

  As a method of adding to the low refractive index layer, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these tetraalkoxysilane, pure water, and alcohol is added to the dispersion of the hollow silica fine particles. The silicic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles. At this time, tetraalkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  In the present invention, the low refractive index layer may contain a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (2).

  The fluorine-substituted alkyl group-containing silane compound represented by the general formula (2) will be described.

In the formula, R ^{1 to} R ⁶ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, 6 to 12 carbon atoms, preferably 6 carbon atoms. 10 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkylaryl groups, arylalkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkenyl groups, or 1 to 6 carbon atoms, preferably 1 to 3 alkoxy groups, a hydrogen atom or a halogen atom.

Rf represents-(C _a H _b F _c )-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, as such a fluorine-containing silicone compound, (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (MeO) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H Examples include methoxydisilane compounds represented by ₄ Si (OC ₂ H ₅ ) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , and the like.

  If the fluorine-containing alkyl group-containing silane compound is included as a binder, the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer which is the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.

  In addition, when a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only the hydrophobic property but also the slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch strength can be obtained. I can do it. Furthermore, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage of the binder is equal to or close to that of the conductive layer. Since it is a thing, the transparent film excellent in adhesiveness with the conductive layer can be formed. Furthermore, when the transparent film is heat-treated, the conductive layer is not peeled off due to the difference in shrinkage rate, and a portion having no electrical contact is not generated in the transparent conductive layer. For this reason, sufficient electroconductivity can be maintained as a whole film.

  A transparent film containing a fluorine-substituted alkyl group-containing silane compound and hollow silica-based fine particles having the outer shell layer and being porous or hollow inside has high scratch strength and is evaluated by eraser strength or nail strength. The film strength is high, the pencil hardness is high, and a transparent film excellent in strength can be formed.

  The low refractive index layer according to the present invention may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  Examples of the polymer used as the other binder of the low refractive index layer include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin.

  The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder has a function of adhering the hollow silica fine particles and maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap.

(solvent)
The low refractive index layer according to the present invention preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The content of the organic solvent is preferably 1 to 4% by mass of the solid content concentration in the low refractive index layer coating composition. The organic solvent is preferably 1% by mass or more in order to prevent coating unevenness and achieve a uniform film thickness, and if it exceeds 4% by mass, the drying load increases, which is not preferable because the size of the drying apparatus is increased and the time is increased.

<High refractive index layer>
In the present invention, in order to improve the antireflection property, a plurality of the following high refractive index layers can be provided below the low refractive index layer.

  The high refractive index layer preferable for the present invention preferably contains (c) metal oxide fine particles having an average particle diameter of 10 to 200 nm, (d) a metal compound, and (e) an ionizing radiation curable resin.

(Metal oxide fine particles)
The high refractive index layer of the present invention preferably contains metal oxide fine particles. The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the above can be used, and these metal oxide fine particles are doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is preferably used as a main component, and particularly preferably indium tin oxide (ITO).

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles may be measured from an electron micrograph by a scanning electron microscope (SEM) or the like, or measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. May be. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the base film as a support, and is preferably in the range of 1.50 to 1.90 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more kinds of surface treatments may be combined.

  The thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The ratio of the metal oxide fine particles to be used and a binder such as ionizing radiation curable resin, which will be described later, varies depending on the type of metal oxide fine particles, the particle size, etc. The latter one is preferable.

  The amount of the metal oxide fine particles used in the present invention is preferably 5% by mass to 85% by mass in the high refractive index layer, more preferably 10% by mass to 80% by mass, and most preferably 20% to 75% by mass. preferable. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength deteriorates.

  The metal oxide fine particles are supplied to a coating solution for forming a high refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  In the present invention, metal oxide fine particles having a core / shell structure may be further contained. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, tin-doped indium oxide, antimony-doped tin oxide, etc. can be used. Titanium may be the main component.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles decreases, and when the coating amount is too small, the light resistance is deteriorated. Two or more kinds of metal oxide fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, U.S. Pat. No. 3,410,708, JP-B-58-47061, U.S. Pat. No. 2,885,366, and U.S. Pat. No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. I can do it.

(Metal compound)
As the metal compound used in the present invention, a compound represented by the following general formula (3) or a chelate compound thereof can be used.

Formula (3) _An MB _xn
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the above formula (3) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of accelerating the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against moisture mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.

(Ionizing radiation curable resin)
The ionizing radiation curable resin is added as a binder for the metal oxide fine particles to improve the film formability and physical properties of the coating film. As the ionizing radiation curable resin, a monomer or oligomer having two or more functional groups that cause polymerization reaction directly by irradiation of ionizing radiation such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator is used. Can be used. Examples of the functional group include a group having an unsaturated double bond such as a (meth) acryloyloxy group, an epoxy group, and a silanol group. Among these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. Examples of such ionizing radiation curable resins include polyfunctional acrylate compounds and the like, and the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. It is preferable that it is a compound chosen from these. Here, the polyfunctional acrylate compound is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate preferred. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  The addition amount of the ionizing radiation curable resin is preferably less than 50% by mass in the solid content in the high refractive index composition.

  In order to accelerate the curing of the ionizing radiation curable resin according to the present invention, the photopolymerization initiator and the acrylic compound having two or more polymerizable unsaturated bonds in the molecule are in a mass ratio of 3: 7 to 1: 9. It is preferable to contain.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof.

(solvent)
Examples of the organic solvent used for coating the high refractive index layer of the present invention include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol). , Cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexane Triol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether) , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine) , Ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide) Etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.) ), Sulfones (for example, sulfolane, etc.), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

(Anti-fouling layer)
The antiglare film or antiglare antireflection film of the present invention preferably has an antifouling layer on the outermost layer.

  The antifouling layer preferable for the present invention preferably contains a fluorine-containing silane compound in the antifouling layer forming composition, and is prepared by coating a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. In particular, the fluorine-containing silane compound is preferably silazane or alkoxysilane.

  In addition, among the silane compounds having the fluoroalkyl group or the fluoroalkyl ether group, the fluoroalkyl group in the silane compound is bonded to Si atoms at a ratio of 1 or less to one Si atom, and the remaining Is preferably a silane compound which is a hydrolyzable group or a siloxane bond group.

  The hydrolyzable group here is a group such as an alkoxy group, for example, and becomes a hydroxyl group by hydrolysis, whereby the silane compound forms a polycondensate.

  For example, the silane compound is usually reacted with water (in the presence of an acid catalyst if necessary) in the range of room temperature to 100 ° C. while distilling off by-produced alcohol. As a result, the alkoxysilane is (partially) hydrolyzed to cause a partial condensation reaction, and can be obtained as a hydrolyzate having a hydroxyl group. The degree of hydrolysis and condensation can be adjusted as appropriate depending on the amount of water to be reacted, but in the present invention, water is not actively added to the silane compound solution used for antifouling treatment, and after preparation, It is preferable to dilute and use the solid content concentration of the solution in order to cause a hydrolysis reaction mainly by moisture in the air during drying.

  Preferably, in the composition for forming an antifouling layer, the silane compound having a fluoroalkyl group is represented by the following general formula (4), and the concentration of the silane compound is diluted to 0.01 to 5% by mass. Use antifouling treatment.

Formula _{(4) CF 3 (CF 2} ) m (CH 2) n -Si- (ORa) 3
Here, m is an integer of 1-10. n is an integer of 0-10. Ra represents the same or different alkyl group.

  In the compound represented by the general formula (4), Ra has 3 or less carbon atoms and is preferably an alkyl group composed of only carbon and hydrogen, for example, a group such as methyl, ethyl, isopropyl and the like.

Examples of the silane compound having a fluoroalkyl group or fluoroalkyl ether group preferably used in the present invention include CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ). ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC _{3 H 7) 3, CF 3} (CF 2) 7 (CH 2) 2 Si (OCH 3) (OC 3 H 7) 2, CF 3 (CF 2) 7 _{CH 2) 2 Si (OCH 3} ) 2 OC 3 H 7, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 ( OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₅ ( _{CH 2) 2 Si (CH 3} ) (OCH 3) 2, CF 3 (CF 2) 5 (CH 2) 2 Si (CH 3) (OC 3 H 7) 2, CF 3 (CF 2) 2 O (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ), C ₇ F ₁₅ CH ₂ O (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ O (CH ₂ ) ₃ Si Examples include (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , but not limited thereto.

  Examples of the fluorine-based silane compound include KP801M and X-24-9146 manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba Silicones Co., Ltd. XC98-A5382, XC98-B2472, Daikin Industries, Ltd. OPTOOL DSX, and FG5010 manufactured by Fluoro Technology Co., Ltd. As the compound for surface treatment, perfluoroalkylsilazane, perfluoroalkylsilane, or perfluoropolyether group-containing silane compound, particularly perfluoroalkyltrialkoxysilane, perfluoropolyethertrialkoxysilane, Examples include perfluoropolyether ditrialkoxysilane.

  When these silane compounds are used, they are diluted to 0.01 to 10% by mass, preferably 0.03 to 5% by mass, more preferably 0.05 to 2% by mass in an organic solvent not containing fluorine. It is preferable to use in.

  In the present invention, an organic solvent containing no fluorine is preferably used to prepare the silane compound solution, and the following may be mentioned.

  As a solvent of the coating composition for the antifouling layer used in the present invention, propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, propylene glycol mono (C1-C4). Specific examples of the alkyl ether include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether and the like. The propylene glycol mono (C1 to C4) alkyl ether ester includes propylene glycol monoalkyl ether acetate, specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, etc., alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, t-butanol, cyclohexanol , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate and ethyl butyrate, hydrocarbons such as benzene, toluene and xylene, dioxane, N, N-dimethylformamide and other solvents. Alternatively, these solvents are used by being appropriately mixed. The solvent to be mixed is not particularly limited to these.

  Particularly preferred solvents are one or more organic solvents selected from ethanol, isopropyl alcohol, propylene glycol, and propylene glycol monomethyl ether.

  Among these solvents, those having a boiling point of less than 100 ° C. (low boiling solvent) such as methanol, ethanol and isopropyl alcohol, and boiling points of 100 ° C. or more such as propylene glycol monomethyl ether and n-butyl alcohol. (Boiling point solvent) is preferably used in combination, and in particular, those having a boiling point of 60 to 98 ° C. and those having a boiling point of 100 to 160 ° C. are preferably used in combination. The ratio of the low boiling point solvent and the high boiling point solvent when used in combination is preferably 98.0% by mass or more and the high boiling point solvent is 0.5 to 2% by mass in the composition.

  In the antifouling layer forming composition used in the present invention, it is preferable to add an acid to adjust the pH to 5.0 or less. Since the acid promotes hydrolysis of the silane compound and acts as a catalyst for the polycondensation reaction, the polycondensation film of the silane compound can be easily formed on the surface of the substrate, and the antifouling property can be improved. The pH is preferably in the range of 1.5 to 5.0. If the pH is 1.5 or less, the acidity of the solution is too strong, and the container or the piping may be damaged. Preferably it is the range of pH2.0-4.0.

  In the present invention, it is preferable not to positively add water to the silane compound solution used for the antifouling treatment, but to cause a hydrolysis reaction by moisture in the air after the preparation, mainly at the time of drying. Therefore, it is used when the solid content concentration of the solution is diluted. If too much water is added to the treatment liquid, the pot life is shortened accordingly.

  In the present invention, sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, boric acid, hydrofluoric acid, preferably an inorganic acid such as hydrochloric acid and nitric acid, an organic acid having a sulfo group (also referred to as a sulfonic acid group) or a carboxyl group, For example, acetic acid, polyacrylic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfonic acid and the like are used. The organic acid is more preferably a compound having a hydroxyl group and a carboxyl group in one molecule. For example, a hydroxydicarboxylic acid such as citric acid or tartaric acid is used. The organic acid is more preferably a water-soluble acid. For example, in addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvin. Acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. Also, benzoic acid, hydroxybenzoic acid, atorvaic acid and the like can be used as appropriate.

  The addition amount is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the partial hydrolyzate of the silane compound. Further, the amount of water added is not limited as long as the partial hydrolyzate can theoretically be hydrolyzed by 100%, and an amount equivalent to 100% to 300%, preferably an amount equivalent to 100% to 200% is added. Good.

  By using a fluorine-containing silane compound, it is not only preferable in terms of lowering the refractive index of the antifouling layer and imparting water and oil repellency, but also has an effect of being highly scratch resistant and particularly excellent in blocking between films. .

(Formation of antireflection layer)
In the present invention, the method for providing the antireflection layer is not particularly limited, but it is preferably formed by coating.

  In the present invention, an antireflection layer is formed by a step of forming a concavo-convex structure with a convex structure portion and a transparent resin layer on a base film and sequentially coating with the above high refractive index layer composition and low refractive index layer composition. It is preferable to manufacture. It is also preferable to coat the antifouling layer.

  Although the structure of a preferable anti-glare antireflection film is shown below, it is not limited to these.

  Here, the antiglare layer of the present invention means a layer comprising the convex structure portion and the transparent resin layer according to the present invention.

Base film / Anti-glare layer of the present invention / Low refractive index layer Base film / Anti-glare layer of the present invention / High refractive index layer / Low refractive index layer Base film / Antistatic layer / Anti-glare layer of the present invention / Low refractive index layer Base film / Antistatic layer / Anti-glare layer of the present invention / High refractive index layer / Low refractive index layer Base film / Anti-glare layer of the present invention / Low refractive index layer / Anti-fouling layer Base film / Anti-glare layer of the present invention / High refractive index layer / Low refractive index layer / Anti-fouling layer Substrate film / Antistatic layer / Anti-glare layer / Low refractive index layer / Anti-fouling layer Substrate film / Antistatic Layer / antiglare layer of the present invention / high refractive index layer / low refractive index layer / antifouling layer In the present invention, after the antiglare layer of the present invention is formed, the surface of the antiglare layer of the present invention is subjected to surface treatment, The low refractive index layer according to the present invention is preferably formed on the surface of the antiglare layer of the present invention that has been subjected to the surface treatment. It is also preferable to subject the low refractive index layer to a surface treatment before providing the antifouling layer.

Examples of the surface treatment include cleaning methods, alkali treatment methods, flame plasma treatment methods, high frequency discharge plasma methods, electron beam methods, ion beam methods, sputtering methods, acid treatments, corona treatment methods, atmospheric pressure glow discharge plasma methods, and the like. An alkali treatment method and a corona treatment method are preferable, and an alkali treatment method can be used particularly preferably. The corona treatment is a treatment performed by applying a high voltage of 1 kV or more between the electrodes under atmospheric pressure and discharging it. An apparatus commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Can be used. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof, and a roll lined with ceramics, silicon, EPT rubber, hyperon rubber, or the like. It is done. The frequency used for the corona treatment used in the present invention is a frequency of 20 kHz to 100 kHz, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Will occur. The output of the corona treatment is 1 to 5 w · min. / M ² but ² to 4 w · min. An output of / m ² is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. If the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

  The alkali treatment method is not particularly limited as long as it is a method in which a film coated with a hard coat layer is immersed in an alkaline aqueous solution.

  As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and an aqueous sodium hydroxide solution is particularly preferable.

  The alkali concentration of the aqueous alkali solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by mass, and more preferably 0.5 to 15% by mass.

  The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.

  The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water.

  Each layer of the antireflection layer uses a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a micro gravure coating method and an extrusion coating method on a base film. And can be formed by coating. At the time of application, the base film is preferably wound up in a roll shape after being unwound from a state wound in a roll shape with a width of 1.4 to 4 m, performing the above-described application, drying and curing treatment. .

  Furthermore, the anti-glare antireflection film of the present invention is obtained by laminating the antireflection layer on the base film and then heat-treating it in the range of 50 to 150 ° C. and 1 to 30 days in the state of being wound in a roll. It can manufacture by the manufacturing method to perform. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C, it is preferably a period of 3 days or more and less than 30 days, and if it is 150 ° C, a range of 1 to 3 days is preferable. Usually, it is preferable to set it at a relatively low temperature so that the heat treatment effect on the outside of the winding, the center of the winding, and the core is not biased, and it is preferable to carry out at around 50 to 80 ° C. for about 3 to 7 days.

  In order to stably perform the heat treatment, it is necessary to perform in a place where the temperature and humidity can be adjusted, and it is preferable to perform in a heat treatment chamber such as a clean room without dust.

  When winding an antiglare film coated with a functional thin film such as the antireflection layer or antifouling layer into a roll, the wound core may be of any material, whether it is a cylindrical core. However, it is preferably a hollow plastic core, and the plastic material may be any heat-resistant plastic that can withstand the heat treatment temperature. For example, phenol resin, xylene resin, melamine resin, polyester Resins such as resins and epoxy resins are listed. A thermosetting resin reinforced with a filler such as glass fiber is preferable.

  The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.

  In this way, when the heat treatment is performed in a state where the functional thin film is coated on the long base film and the roll wound around the plastic core is wound, it is preferable to rotate the roll, The rotation is preferably performed at a speed of 1 rotation or less per minute, and may be continuous or intermittent. Moreover, it is preferable to perform rewinding of the roll once or more during the heating period.

  In order to rotate the long antiglare film roll wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber.

  In the case of intermittent rotation, the stop time is preferably within 10 hours, the stop position is preferably made uniform in the circumferential direction, and the stop time is within 10 minutes. More preferred. Most preferred is continuous rotation.

  As for the rotation speed in continuous rotation, the time required for one rotation is preferably 10 hours or less, and if it is early, it becomes a burden on the apparatus, so the range of 15 minutes to 2 hours is substantially preferable.

  In the case of a dedicated carriage having a rotation function, it is preferable that the optical film roll can be rotated during movement and storage. In this case, rotation is effective as a countermeasure against black bands that occur when the storage period is long. Function.

(Polarizer)
The polarizing plate can be produced by a general method. Using a fully saponified polyvinyl alcohol aqueous solution on at least one surface of a polarizing film prepared by subjecting the back side of the antiglare film and the antiglare antireflection film of the present invention to alkali saponification treatment and immersion drawing in an iodine solution It is preferable to stick them together. The film may be used on the other surface, or another polarizing plate protective film may be used. Commercially available cellulose ester films (for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, preferably Konica Minolta) Used. In contrast to the antiglare film and the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, 30 to 300 nm, and Rt of 70 to 400 nm. It is preferable to have a phase difference. These can be produced, for example, by the method described in JP-A-2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the antiglare film and the antiglare antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the optical film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

(Display device)
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The antiglare film and antiglare antireflection film of the present invention are reflective, transmissive, transflective LCD or TN, STN, OCB, HAN, VA (PVA, MVA), IPS. It is preferably used in LCDs of various drive systems such as. Further, the antiglare film and the antiglare antireflection film of the present invention are excellent in flatness and are preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. In particular, in a large-screen display device having a screen size of 30 or more, especially 30 to 54, there is no white spot in the periphery of the screen, and the effect is maintained for a long time, and a remarkable effect is obtained in the MVA liquid crystal display device. Is recognized. In particular, there was little color unevenness, glare and wavy unevenness, which is the object of the present invention.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
[Production of Cellulose Ester Film 1]
A cellulose ester solution (dope) was prepared using the following cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent, and a cellulose ester film 1 was prepared by a solution casting film forming method.

Cellulose ester (cellulose triacetate, acetyl group substitution degree 2.9, Mn = 16000, Mw / Mn = 1.8) 100 kg
Plasticizer (trimethylolpropane tribenzoate) 5kg
Plasticizer (ethyl phthalyl ethyl glycolate) 5kg
UV absorber (Tinubin 109, manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0 kg
UV absorber (Tinuvin 171 manufactured by Ciba Specialty Chemicals Co., Ltd.)
1.0 kg
Fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) 0.3kg
Solvent (methyl acetate) 440kg
Solvent (ethanol) 110kg
A cellulose ester solution (dope) was prepared using the above cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent.

  Next, the cellulose ester solution whose temperature was adjusted to 33 ° C. was fed to a die and uniformly cast from a die slit onto a stainless steel belt. The cast part of the stainless steel belt was heated from the back with hot water of 37 ° C. After casting, the dope film on the metal support (which is called a web after casting on the stainless steel belt) is dried by applying hot air of 44 ° C., and the residual solvent in the peeling is peeled off at 120 mass%. The web end is gripped with a tenter while the residual solvent amount is from 35% by mass to 10% by mass, and is stretched in the width direction. It extended | stretched so that it might become 1.1 times the draw ratio. After stretching, the width is maintained for several seconds, then the tension in the width direction is relaxed, then the width is released, and further transported for 20 minutes in the third drying zone set at 125 ° C. for drying. The cellulose ester film 1 having a width of 1.5 m, a film thickness of 80 μm, and a length of 3000 m was produced.

[Preparation of antiglare film 1 by adding fine particles]
On the surface of the cellulose ester film 1 (B surface side; surface in contact with a support mirror surface such as a stainless steel band used in the casting film forming method; support side), the following coating solution 1 for hard coat layer has a pore diameter of 20 μm. A hard coat layer coating solution is prepared by filtration through a polypropylene filter, and this is applied using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp with an illuminance of 0.1 W / cm ^2. Thus, the coating layer was cured with an irradiation dose of 0.1 J / cm ² to form an anti-glare hard coat layer having a thickness of 5 μm, thereby producing an anti-glare film 1. It was 0.55 micrometer as a result of measuring the average surface roughness (Ra) about the formed unevenness | corrugation using the optical interference type surface roughness measuring machine by WYKO.

  Further, the average center distance of the convex portions was 77 μm.

  A coating solution excluding synthetic silica fine particles was separately prepared from the coating solution 1 for hard coat layer, and a film prepared under the same coating and curing conditions as described above was measured with an Abbe refractometer. The refractive index was 1.517. Met.

(Hard coat layer coating solution 1)
The following materials were stirred and mixed to obtain hard coat layer coating solution 1.

Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 200 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
25 parts by weight Propylene glycol monomethyl ether 110 parts by weight Ethyl acetate 110 parts by weight Synthetic silica fine particles Average particle size 1.8 μm 40 parts by weight Surfactant (silicone surfactant; FZ2207 (manufactured by Nippon Unicar)) 10% by weight propylene glycol monomethyl ether Solution) 0.6 parts by mass in solid content [Preparation of antiglare film 2 by embossing]
In the production of the cellulose ester film 1, a roll provided with a mold after the stretching treatment by a tenter (after forming the unevenness, the height of the convex part is 1 μm, the convex part size (long side) is 10 μm, and the distance between the convex parts is 50 μm. A B-side of the film (the side in contact with the stainless steel band support is the B-side, with the film containing the solvent sandwiched between the concavo-convex forming part consisting of a fine roll and the back roll, and the opposite side is the A side. In the same manner, except that a hot roll provided with a mold on the side is pressed, a back roll is placed on the A side, and irregularities are formed on the B side by passing between both rolls. An embossed cellulose ester film 2 was produced. In addition, the static elimination wire was installed in the uneven | corrugated formation vicinity vicinity, and charging of the film was suppressed.

On the surface of the embossed cellulose ester film 2 (B side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method; support side), the following coating liquid 2 for hard coat layer Is filtered through a polypropylene filter having a pore size of 20 μm to prepare a hard coat layer coating solution, which is applied using a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp with an illuminance of 0.1 W. / in cm ^2, thereby curing the coated layer to irradiation dose as 0.1 J / cm ^2, to prepare an antiglare film 2 to form an antiglare hard coat layer having a thickness of 5 [mu] m.

  It was 0.82 micrometer as a result of measuring the average surface roughness (Ra) about the formed unevenness | corrugation using the optical interference type surface roughness measuring machine made from WYKO. The average center distance of the convex portions was 65 μm.

  A film prepared by separately applying the hard coat layer coating solution 2 under the same coating and curing conditions as described above was measured with an Abbe refractometer, and the refractive index was 1.521.

(Hard coat layer coating solution 2)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 60 parts by mass Trimethylolpropane triacrylate 40 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Ethyl acetate 50 parts by mass Propylene glycol monomethyl ether 50 parts by mass Silicon compound (BYK-307 (manufactured by Big Chemie Japan)) 0.5 parts by mass [Anti-glare film 3 having a convex structure by flexographic printing) 16 production]
Using the apparatus of FIG. 11, the following convexity was formed on the surface of the cellulose ester film 1 produced above (A surface side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method; support side). The coating liquids 1 to 3 for the structure part were prepared by filtering with a polypropylene filter having a pore diameter of 20 μm, and a convex structure part was formed by flexographic printing using the manufacturing apparatus of FIG. As a flexographic printing pattern, a crystal raster screening method manufactured by Agfa Gehwald was used, and a pattern having a density of 2400 to 4000 dpi and 1 to 10% density was used.

After forming the convex structure portion, after drying at 90 ° C. in the drying zone 505A, using an ultraviolet lamp 506A, curing was performed at an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² . . Moreover, the coating liquid supply amount from the anilox roll was controlled to control the average height of the convex structure portion.

(Seamless resin plate specifications)
Photosensitive resin plate: Core-shell type microgel obtained by reacting 98 parts of 2-hydroxyethyl acrylate and 1 part of butanediol diacrylate, 20 parts of methacrylic acid and 80 parts of N-butyl acrylate A photosensitive resin composition obtained by mixing 71 g of (core / shell = 2/1), 25 g of trimethylolpropane ethoxytriacrylate and 4 g of 2,2-dimethoxy-2-phenylacetophenone on a polyester film having a thickness of 2 mm After coating, the substrate was exposed at 1000 mJ / cm with ultraviolet light having a wavelength of 360 nm to obtain a printing original plate for laser engraving. Next, the fine concavo-convex structure was engraved under the following laser engraving conditions, and mounted on the resin plate roll while evacuating as shown in FIG. 1. When the whole was heated at 120 ° C. for 20 minutes, the joints disappeared and a seamless resin plate was obtained. .

  The resin plate diameter was 500 mm, and the rubber hardness of the resin plate was 50. Rubber hardness was measured with a durometer according to the method described in JIS K 6253.

  On the convex structure part thus prepared, the following coating solutions 1 to 3 for the transparent resin layer were applied by changing the film thickness by a reduced pressure extrusion method, and antiglare films 3 to 16 shown in Table 1 were produced. .

[Preparation of Antiglare Films 17 to 30 having Convex Structures by Inkjet Method]
On the surface of the cellulose ester film 1 (B surface side; surface in contact with a support mirror surface such as a stainless steel band used in the casting film forming method; support side), the following convex structure part coating liquids 4 to 6 are applied by an inkjet method. Ink droplets were emitted at 2 to 16 pl, 0.2 seconds after drying, and cured by irradiating with ultraviolet rays at an irradiation intensity of 100 mJ / cm ² from the actinic ray irradiating portion to form a convex structure portion.

  As the inkjet emitting device, a line head method (FIG. 8A) was used, and 10 inkjet heads having 256 nozzles having a nozzle diameter of 3.5 μm were prepared. An ink jet head having the structure shown in FIG. 7 was used. The ink supply system is composed of an ink supply tank, a filter, a piezo-type ink jet head, and piping. The ink supply tank to the ink jet head section is insulated and heated (40 ° C.), and the emission temperature is 40 ° C. The driving frequency was 20 kHz. In addition, about the anti-glare films 17, 18, and 29, the convex structure part was produced by making an ink droplet into 1 pl or less using the electrostatic system inkjet.

  On the convex structure part thus prepared, the following coating solutions 1 to 3 for the transparent resin layer were applied by changing the film thickness by a reduced pressure extrusion method, and antiglare films 17 to 30 described in Table 1 were produced. .

(Convex structure coating solution 1)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Ethyl acetate 50 parts by mass Propylene glycol monomethyl ether 50 parts by mass Silicon compound (BYK-307 (manufactured by Big Chemie Japan)) 0.2 parts by mass The above composition is mixed and stirred to prepare convex structure part coating liquid 1 did.

The convex structure coating solution 1 was measured by Abbe's refractometer after coating and drying, and curing the film with an ultraviolet illuminance of 0.1 W / cm ² and an irradiation dose of 0.1 J / cm ² . The refractive index was 1.522.

(Convex structure coating solution 2)
Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 100 parts by weight Trimethylolpropane triacrylate 30 parts by weight ITO dispersed particles (average particle size 65 nm) 70 parts by weight Photopolymerization initiator (Irgacure 184 (Ciba Specialty) Chemicals Co., Ltd.))
10 parts by mass Silicon compound (BYK-307 (manufactured by Big Chemie Japan)) 0.2 parts by mass Propylene glycol monomethyl ether 100 parts by mass Ethyl acetate 100 parts by mass The above composition is mixed and stirred to prepare a convex structure part coating liquid 2 did.

The convex structure coating solution 2 was measured by Abbe's refractometer after coating and drying and curing the film with an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² . The refractive index was 1.556.

(Convex structure coating solution 3)
Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 100 parts by weight Trimethylolpropane triacrylate 50 parts by weight Titanium oxide fine particle dispersion (silicon oxide fine particle concentration 20% by weight, dispersion solvent isopropanol, particle size 35 nm) 50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
10 parts by mass Propylene glycol monomethyl ether 100 parts by mass Methyl ethyl ketone 100 parts by mass Oil-repellent surfactant (polydimethylsiloxane; KF96 (manufactured by Shin-Etsu Chemical))
0.2 part by mass The above composition was mixed and stirred to prepare a convex structure part coating solution 3.

The film prepared by coating the convex structure portion coating solution 3 after coating and drying and curing with an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² was measured with an Abbe refractometer, The refractive index was 1.573.

(Convex structure coating solution 4)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Ethyl acetate 150 parts by mass Propylene glycol monomethyl ether 150 parts by mass Silicon compound (BYK-307 (manufactured by Big Chemie Japan)) 0.2 parts by mass The above composition is mixed and stirred to prepare convex structure part coating liquid 4 did.

A film prepared by coating the convex structure part coating liquid 4 after coating and drying, and curing with an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² , was measured with an Abbe refractometer, The refractive index was 1.522.

(Convex structure coating solution 5)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 100 parts by mass Trimethylolpropane triacrylate 30 parts by mass ITO dispersed particles (average particle size 65 nm) 70 parts by mass Photopolymerization initiator (Irgacure 184 (Ciba Specialty) Chemicals Co., Ltd.))
10 parts by mass Silicon compound (BYK-307 (produced by Big Chemie Japan)) 0.2 parts by mass Propylene glycol monomethyl ether 300 parts by mass Isopropanol 300 parts by mass The above composition is mixed and stirred to prepare and adjust the convex structure part coating liquid 5 did.

The convex structure coating solution 5 was measured by Abbe's refractometer after coating and drying, and curing the ultraviolet light with an illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² . The refractive index was 1.556.

(Convex structure coating solution 6)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) 100 parts by mass Trimethylolpropane triacrylate 30 parts by mass Titanium oxide fine particle dispersion (silicon oxide fine particle concentration 20% by mass, dispersion solvent isopropanol, particle size 35 nm) 50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
10 parts by mass Propylene glycol monomethyl ether 100 parts by mass Methyl ethyl ketone 150 parts by mass Surfactant (polydimethylsiloxane; KF96 (manufactured by Shin-Etsu Chemical)) 0.2 parts by mass The above composition is mixed and stirred to prepare a convex structure part coating liquid 6 did.

The film prepared by coating the convex structure portion coating solution 6 after coating and drying and curing with an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² was measured with an Abbe refractometer, The refractive index was 1.573.

(Transparent resin layer coating solution 1)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 60 parts by mass Trimethylolpropane triacrylate 40 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Ethyl acetate 50 parts by mass Propylene glycol monomethyl ether 50 parts by mass Silicon compound (BYK-307 (manufactured by Big Chemie Japan)) 0.5 parts by mass The above composition is mixed and stirred to prepare a transparent resin layer coating solution 1 did.

The transparent resin layer coating liquid 1 was measured by Abbe's refractometer after coating and drying, and the film was prepared by curing with an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² . The refractive index was 1.522.

(Transparent resin layer coating solution 2)
Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku) 100 parts by mass Trimethylolpropane triacrylate 30 parts by mass ITO dispersed particles (average particle size 65 nm) 70 parts by mass Surfactant (silicone surfactant; FZ2207 (Nihon Unicar)
0.5 parts by mass of photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Propylene glycol monomethyl ether 50 parts by mass Methyl ethyl ketone 500 parts by mass The viscosity of the coating solution was 3 ° C as a result of measurement using a B-type viscometer BL manufactured by Tokyo Keiki Co., Ltd.

  The said composition was mixed and stirred and the transparent resin layer coating liquid 2 was prepared.

The transparent resin layer coating liquid 2 was measured by Abbe's refractometer after coating and drying, and curing the film with a UV illuminance of 0.1 W / cm ² and an irradiation dose of 0.1 J / cm ² . The refractive index was 1.556.

(Transparent resin layer coating solution 3)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 100 parts by mass Trimethylolpropane triacrylate 30 parts by mass Silicon oxide fine particle dispersion (silicon oxide fine particle concentration 20% by mass, dispersion solvent isopropanol, particle size 35 nm) 100 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
10 parts by mass surfactant (silicone surfactant; FZ2207 (Nihon Unicar))
0.5 part by mass The above composition was mixed and stirred to prepare a transparent resin layer coating solution 3.

The transparent resin layer coating solution 3 was measured by Abbe's refractometer after the coating and drying, and the film prepared by curing with an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² ; The refractive index was 1.471.

<Measurement, evaluation>
(Measurement of convex structure part diameter, convex structure part height, number of convex structure parts, Ra, Sm)
The convex structure part diameter, convex structure part height, and number of convex structure parts (per 1 mm ² ) were measured using an optical interference type surface roughness measuring machine manufactured by WYKO, using a film sample before applying the transparent resin layer. , Measured in a two-dimensional manner in the range of about 4000 μm ² (55 μm × 75 μm), and the convex portion is color-coded and displayed as a contour line from the bottom side, and the convex portion height and the long diameter of the convex structure portion are based on the film surface. The diameter of the convex portion was measured. The number of convex structure portions was determined by converting the number of convex structure portions obtained per 1 mm ² . These measurements were obtained as an average value by measuring arbitrary 10 points of the corresponding part of the base film.

  The surface roughness (Ra) and the average center-to-center distance (Sm) are determined by the measurement method of JIS B0601 using a film sample after applying the transparent resin layer and using an optical interference type surface roughness measuring machine manufactured by WYKO. It was measured.

(Anti-glare effect)
In an office with a window, each film was spread on a desk, and fluorescent lighting on the ceiling and reflection of external light on the film were evaluated as follows.

5: The outline of the fluorescent lamp and the external light are blurred and I don't care about the reflection at all 4: Between 5 and 3 3: The outline of the fluorescent lamp and the reflection of the external light are slightly recognized 2: 3: 1 Middle of 1: The outline of the fluorescent lamp and the external light are understood and the reflection is worrisome (glare)
About the produced film, the glare was determined visually.

5: I don't know the glare at all. 4: I can understand the glare very slightly. 3: I can see a slight glare. 2: Between 3 and 1. 1: I'm worried about the glare.
About the produced film, the cloudiness was determined visually.

5: I don't care about white turbidity at all 4: Intermediate between 5 and 3 3: Somewhat anxious about white turbidity 2: Intermediate between 3 and 1 1: Very anxious about white turbidity Table 1 shows the above measurement and evaluation results .

  From Table 1, the antiglare film 1 provided with a fine concavo-convex structure by addition of fine particles was inferior in glaring and clouded due to dispersion of fine particle dispersibility. The antiglare film 2 provided with a fine relief structure by embossing was slightly inferior in antiglare effect and glare, and white turbidity was also observed. Further, the height and size of the fine concavo-convex structure differed between the head and the tail of the antiglare film 2, and when the mold was observed, clogging was caused by the film dissolved in a part of the mold.

  On the other hand, the anti-glare films 3 to 28 of the present invention were excellent in anti-glare effect and glare, and were at a level that did not bother the white turbidity. In addition, the height and size of the fine concavo-convex structure at the head and tail of the antiglare film were uniform, and it was found that the film has high uniformity and production stability.

Example 2
Next, the following surface treatment was performed on the hard coat surfaces of the antiglare films 1 to 30 produced in Example 1.

<surface treatment>
Alkaline treatment: Each anti-glare film was immersed in a 1.5 mol / l-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then washed with a 0.5 mass% -H ₂ SO ₄ aqueous solution at room temperature. It was immersed for 30 seconds to neutralize, washed with water and dried.

[Preparation of antiglare antireflection film]
Next, the following low refractive index layer was coated on the transparent resin layer of the antiglare films 1 to 30.

(Preparation of antireflection layer: low refractive index layer)
The following low refractive index layer coating composition 1 is applied by an extrusion coater, dried at 100 ° C. for 1 minute, cured by irradiation with ultraviolet rays of 0.1 J / cm ² , and further thermally cured at 120 ° C. for 5 minutes. A low refractive index layer was provided so as to have a thickness of 95 nm, and antiglare and antireflection films 1 to 30 were produced. The refractive index of this low refractive index layer was 1.37.

  Moreover, about the produced anti-glare antireflection film, a spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm using a spectrophotometer (manufactured by JASCO Corporation). Since the antireflection performance is better as the reflectance is smaller in a wide wavelength region, the minimum reflectance at 450 to 650 nm was obtained from the measurement results. In the measurement, the back surface on the observation side was roughened, and then light absorption processing was performed using a black spray to prevent reflection of light on the back surface of the film, and the reflectance was measured. As a result of the measurement, all of the antiglare antireflection films had a reflectance of 0.7 to 1.2 and showed good results.

(Preparation of low refractive index layer coating composition 1)
<Preparation of tetraethoxysilane hydrolyzate A>
Hydrolyzate A was prepared by mixing 289 g of tetraethoxysilane and 553 g of ethanol, adding 157 g of 0.15% aqueous acetic acid solution thereto, and stirring in a water bath at 25 ° C. for 30 hours.

Tetraethoxysilane hydrolyzate A 110 parts by mass Hollow silica-based fine particle (P-2 below) dispersion 30 parts by mass KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass Linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Unicar Co., Ltd.) 10% propylene glycol monomethyl ether solution 3 parts by mass Propylene glycol monomethyl ether 400 parts by mass Isopropyl alcohol 400 parts by mass <Preparation of hollow silica-based fine particle P-2 dispersion>
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al 2 O 3 were simultaneously added to the mother liquor. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass. (Process (a))
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles was prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Subsequently, a hollow silica-based fine particle (P-2) dispersion having a solid content concentration of 20% by mass in which the solvent was replaced with ethanol using an ultrafiltration membrane was prepared.

The thickness of the first silica coating layer of the hollow silica-based fine particles was 3 nm, the average particle size was 47 nm, MOx / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter was measured by a dynamic light scattering method.

[Preparation of polarizing plate]
Subsequently, a polarizing plate was produced using each antiglare antireflection film 1-30.

  A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Next, in accordance with the following steps 1 to 5, a polarizing film, the antiglare antireflection film 1 to 30, and a cellulose ester film on the back side are bonded together with Konica Minoltak KC8UCR-5 (manufactured by Konica Minolta Opto Co., Ltd.) for polarization. A plate was made. The polarizing plate protective film on the back side was a cellulose ester film having a retardation, and retardation values were Ro = 43 nm and Rt = 132 nm.

  Step 1: Soaked in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizing film.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Lightly wipe off the excess adhesive adhering to the polarizing film in Step 2, place it on the cellulose ester film treated in Step 1, and then stack and arrange so that the antireflection layer is on the outside did.

Step 4: The antiglare antireflection film, the polarizing film, and the cellulose ester film sample laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Step 5: A sample obtained by bonding the polarizing film, the cellulose ester film, and the antiglare antireflection film 1 to 30 prepared in Step 4 in a dryer at 80 ° C. is dried for 2 minutes to produce polarizing plates 1 to 30. did.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plate on the surface of the commercially available 32-inch liquid crystal television (MVA type cell) that was previously bonded was peeled off, and the prepared polarizing plates 1 to 30 were each bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the cellulose ester film having a retardation is on the liquid crystal cell side, and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices 1 to 30 were respectively produced.

<Evaluation>
The obtained liquid crystal display devices 1 to 30 are observed in an environment as shown in FIG. 12, and the anti-glare effect, glare, and the blackness when the following visibility and moving images are displayed are respectively shown below. Visual evaluation was made according to the criteria. In addition, 10 40W fluorescent lamps (FLR40S-EX-D / M manufactured by Matsushita Electric) were installed on the ceiling. Moreover, it evaluated in the state which external light inserts from a window.

(Visibility and black spots when displaying video)
As described above, a moving image of a TV program was displayed on the same display in an environment where artificial lighting by a fluorescent lamp and external light from a window were inserted from the ceiling, and a comparative experiment was performed. A moving image was observed at a position 1 m away from the front of the display, and sensory evaluation was performed.

5: I don't mind the reflection of the fluorescent lamp at the top of the screen, and the center of the screen looks black even when there is external light. Middle 3: Slight reflection of fluorescent light at the top of the screen is observed, and the center of the screen is slightly tired after observation if there is external light 2: Intermediate between 1: 3 and 1: 1: Fluorescence at the top of the screen The reflection of the light is recognized, the center of the screen lacks black spots due to the influence of external light, and eyes are tired when looking at the structure of the antiglare antireflection film / liquid crystal display device and the evaluation results are shown in Table 2 below. Shown in

  From Table 2, the liquid crystal display device 1 provided with a fine concavo-convex structure by addition of fine particles was inferior in blackness due to the improvement in antiglare effect and glare probably due to dispersion of fine particle dispersibility. The liquid crystal display device 2 provided with a fine concavo-convex structure by embossing had difficulty in forming a uniform concavo-convex structure, and was inferior in glaring and blackening.

  On the other hand, it is clear that the liquid crystal display devices 3 to 28 using the antiglare antireflection film of the present invention are excellent in the antiglare effect, glare and blackness.

It is a schematic diagram which shows an example of the flexographic printing used for this invention. It is a schematic diagram of the flexographic printing by a two-roll system. It is a schematic diagram of the flexographic printing which supplies ink with an extrusion coater. It is a perspective view of an anilox roll. It is a perspective view for demonstrating the cell of an anilox. It is sectional drawing which shows an example of the inkjet head which can be used for the inkjet method which concerns on this invention. It is the schematic which shows an example of the inkjet head part and nozzle plate which can be used by this invention. It is a schematic diagram which shows an example of the inkjet system which can be preferably used by this invention. It is the schematic diagram which showed a mode that gentle unevenness | corrugation was formed by covering both the convex structure part and the part without a convex structure part with a transparent resin layer. It is a schematic diagram of the fine concavo-convex structure preferable for the present invention. It is an example of the method of forming fine uneven structure on a base film by flexographic printing. It is the figure which showed typically the environment at the time of observation when an anti-glare antireflection film is applied to a liquid crystal display device.

Explanation of symbols

501 Film roll 502 Base film 503 Coater 504A, B, C Back roll 505A, B Drying zone 506A, B, C UV irradiation unit 508 Ink supply tank 509 Flexo resin plate 510 Anilox roll

Claims (9)

On the base film, 10 to 10,000 fine convex structures having a major axis of dots of 1 to 30 μm and a dot height of 0.5 to 10 μm per 1 mm ² , and further covering the convex structures An antiglare film characterized in that a transparent resin layer is formed as described above, and the convex structure portion and the transparent resin layer have different refractive indexes. The antiglare film according to claim 1, further comprising an antireflection layer or an antifouling layer formed on the transparent resin layer. The surface roughness (Ra) of the surface of the antiglare layer constituted by the convex structure part and the transparent resin layer is 50 to 1000 nm, and the average center distance (Sm) of the convex part or the concave part is 10 to 200 μm. The antiglare film according to claim 1 or 2. The antiglare film according to any one of claims 1 to 3, wherein a thickness of the transparent resin layer is 1 to 5 µm thick with respect to a height of the convex structure portion. The antiglare film according to any one of claims 1 to 4, wherein the convex structure part or the transparent resin layer is an actinic ray curable resin. The anti-glare film according to any one of claims 1 to 4, wherein the convex structure part or the transparent resin layer is a thermosetting resin. The anti-glare film according to any one of claims 1 to 6, wherein the convex structure part contains fine particles having a particle diameter of 5 to 300 nm. A polarizing plate using the antiglare film according to any one of claims 1 to 7. A display device comprising the antiglare film according to any one of claims 1 to 7 and the polarizing plate according to claim 8.

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