JP2007187971A - Antiglare antireflection film, its manufacturing method, polarizing plate and display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare antireflection film which can effectively prevent the reflecting-in of external light or the lowering of contrast without degrading the sharpness of a high-definition image due to the downsizing of a pixel size or the like and in which a desired fine rugged structure is effectively and stably formed in high productivity, and to provide a polarizing plate and a display apparatus using the film. <P>SOLUTION: The antiglare antireflection film has a hard coat layer and a low refractive index layer as projections formed on a substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antiglare antireflection film and a method for producing the same, and more particularly to an antiglare antireflection film in which display of external light is small and suppresses a decrease in contrast in a display device, and a method for producing the same.

  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, the method using fine particles cannot control the existence density of fine particles, and the height of the convex portions is higher than the surroundings in a portion where a plurality of fine particles overlap, so that a stable and uniform fine concave-convex structure cannot be formed. 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.

Further, in recent years, as image quality has been improved, a display device having high anti-glare property and high contrast has been demanded. 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 antireflection film which can be prevented and which has a desired fine concavo-convex structure formed effectively and stably with good productivity, and further provides a polarizing plate and a display device using the same.

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

  1. An antiglare antireflection film comprising a hard coat layer and a low refractive index layer formed in a convex shape on a support.

  2. 2. The antiglare antireflection film as described in 1 above, wherein the low refractive index layer formed in the convex shape covers an area of 85% or more of the surface of the hard coat layer.

  3. The refractive index of the low refractive index layer formed in the convex shape is 1.5 or less, and the center line average roughness (Ra) of the surface of the antiglare antireflection film is 0.5 μm or less, The average anti-glare antireflection film as described in 1 or 2 above, wherein the mean valley interval (Sm) is 5 to 200 μm or less.

  4). 4. The antiglare reflection according to any one of 1 to 3, wherein the low refractive index layer formed in the convex shape contains at least an active energy ray-curable material and low refractive index fine particles. Prevention film.

  5. 4. The antiglare antireflection film as described in any one of 1 to 3 above, wherein the low refractive index layer formed in the convex shape contains at least a sol-gel material and low refractive index fine particles.

  6). 6. The prevention according to any one of 1 to 5, wherein the support is at least one film selected from a cellulose ester film, a polyester film, a norbornene resin film, and a polycarbonate film. Dazzling antireflection film.

  7). A polarizing plate, wherein the antiglare antireflection film according to any one of 1 to 6 is bonded to at least one surface.

  8). A display device using the antiglare antireflection film described in any one of 1 to 6 or the polarizing plate described in 7 above.

  9. An antiglare reflection characterized by having a hard coat layer and a low refractive index layer formed in a convex shape on a support, and the low refractive index layer is formed by a printing method, an inkjet method or a spray process The manufacturing method of a prevention film.

  10. 10. The method for producing an antiglare antireflection film as described in 9 above, wherein the low refractive index layer formed in the convex shape is formed by a plurality of times of printing, ink jetting or spraying.

  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 antireflection film formed stably and its manufacturing method can be provided, and also a polarizing plate and a display device 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 antireflection film of the present invention is characterized by having a hard coat layer and a low refractive index layer formed in a convex shape on a support.

  The present invention has a hard coat layer and a low refractive index layer formed in a convex shape on a support, and the convex low refractive index layer covers an area of 85% or more of the surface of the hard coat layer, With the antiglare antireflection film having an antiglare antireflection film having a center line average roughness (Ra) of 0.5 μm or less and an average peak-valley spacing (Sm) of 5 to 200 μm or less, high definition An antiglare antireflection film capable of preventing a decrease in contrast is stably provided.

  In the conventional method of forming an antiglare antireflection film by covering the entire hard coat layer containing fine particles and imparting antiglare properties with a low refractive index layer or embossing, fine unevenness Since it was difficult to maintain the uniformity of the structure, the antiglare effect, glare, white turbidity, and blackness at the time of image display were at insufficient levels.

  In the present invention, in order to form the low refractive index layer in a convex shape, a convex portion (dot dot) is formed by a pattern production method such as a gravure method, a screen printing method, a flexographic printing method, an ink jet method, or a spray process that is a printing method. It can also be obtained by curing and fixing the convex portions by actinic rays or heating. At this time, the convex portions are arranged in a random manner by means such as FM screening 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 and spacing of the protrusions, irregularities with moderate and stable surface roughness are formed on the surface of the antiglare antireflection film, maintaining the antiglare effect and haze due to light scattering. Is suppressed, and white turbidity due to scattered light is suppressed, so that a high-contrast image can be seen.

  According to the above method, it is possible to produce an antiglare antireflection film even at a printing speed of 10 m / min or more and 500 m / min, and without reducing the sharpness of high-definition images. And anti-glare antireflection film in which a desired fine concavo-convex structure can be effectively and stably formed with good productivity, and a polarizing plate and a display device using the same can be obtained. This is what we found.

  Hereinafter, the present invention will be described in detail.

<Formation of convex low refractive index layer>
The convex low refractive index layer of the present invention is preferably obtained by a pattern production method such as a gravure method, a screen printing method, a flexographic printing method, an ink jet method, or a spray process, which is a printing method.

  Although an example of the formation method of a convex-shaped low refractive index layer is shown below, this invention is not limited to this.

<Example of forming convex portions 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. In the present invention, the ink is a low refractive index layer forming material.

  The 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 continuously running support 10 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 support after transfer printing, and is transferred by a doctor blade 6 to transfer ink. The ink 8 is supplied to the plate cylinder 3 by the anilox roll 4 whose amount is adjusted, and transfer printing is performed on the support.

  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 supplied from the ink pan to the anilox roll 4 by the fountain roll 7 and further supplied to the plate cylinder 3 to transfer the ink to the support 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 support 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 have a great influence on the amount of ink transferred, and the fine concavo-convex structure on the surface of the antiglare antireflection film according to the present invention can be obtained. In order to form, 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. 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 to the support 10 and irradiated with actinic rays or heated to form convex portions on the support.

  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 fast to maintain the strength, and the repetition cycle of the convex pattern is short, and the anti-glare effect is lowered, which is not preferable. 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 with a fine uneven shape with high 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, it is not preferable because the plate is too soft and it is difficult to form a desired fine uneven shape, and the plate itself is easily worn. 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 plate making is used as a method for imprinting a pattern with fine irregularities 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.

  The viscosity of the low refractive index layer forming ink used for flexographic printing 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 fine uneven structure 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.

  In any case, a composition within the above viscosity range can be obtained by adjusting the constitution of the following low refractive index layer forming composition.

<Example of forming convex parts by screen printing>
In the present invention, it is also preferable to form the convex portion by screen printing. The height of the convex portions and the arrangement of the convex portions can be arbitrarily processed by screen printing, and a desired antiglare layer can be obtained both in the plane and in the thickness direction.

  In the screen printing method, a screen on which a predetermined pattern is formed is placed on a support, and a printing material (a composition for forming a convex portion, in the case of the present invention, a low refractive index layer forming material) is placed on the screen. . Then, the squeegee is moved at a predetermined pressure, angle, and speed. Thereby, the printing material is transferred onto the support through the pattern of the screen. Next, the transferred material is heated, cured, and dried. When forming a convex part by a screen printing method, resin material is not restricted to photocurable resin, For example, thermosetting resins and thermoplastic resins, such as an epoxy resin and an acrylic resin, can also be used. As thermoplastic resins, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polymethacrylate resin, polyacrylate resin, polystyrene resin, polyamide resin, polyethylene resin, polypropylene resin, fluororesin, polyurethane resin , Polyacrylonitrile resin, polyvinyl ether resin, polyvinyl ketone resin, polyether resin, polyvinyl pyrrolidone resin, saturated polyester resin, polycarbonate resin, chlorinated polyether resin and the like. The resin material is preferably used in the form of a paste by dissolving the resin in an appropriate solvent.

<Example of forming protrusions by inkjet method>
The height of the convex portions and the arrangement of the convex portions can be arbitrarily processed by ink jet printing, and a desired antiglare layer can be obtained both in the plane and in the thickness direction. Even ink-jet printing can cause moire problems. This problem can be solved by applying vibration to the inkjet head during ejection and eliminating the regularity of the landing positions.

  An example of the formation of convex portions by the ink jet system preferably 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 support, 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 support 10 and adheres. The ink droplets that have landed on the support 10 are immediately irradiated with actinic rays from an actinic ray irradiating unit disposed upstream thereof, and are cured. Reference numeral 35 denotes a back roll that holds the support 10.

  In the present invention, as shown in FIG. 7B, the nozzles of the inkjet head unit are preferably arranged in a staggered manner, and are preferably provided in multiple stages in parallel in the transport direction of the support 10. . In addition, 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 support. 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.

  It is preferable to use an ink jet method for forming the convex portions according to the present invention by ejecting small ink droplets 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 head method) in which the inkjet head 30 is arranged in the width direction of the support 10 and a convex portion is formed on the surface of the support 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 portion on the surface thereof, and FIG. 8C shows the inkjet head 30 with the support. 10 is a method (capstan method) for forming a convex portion on the surface while scanning in the width direction on the surface 10 and any method can be used. In the present invention, the line head method is used from the viewpoint of productivity. Is preferred. Note that reference numeral 29 in FIGS. 8A to 8C denotes an actinic ray irradiation unit used when a low refractive index layer forming material 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 support body of (a), (b), (c) of FIG.

  In this invention, in order to form a fine convex part, 0.1-100 pl is preferable as an ink droplet for low refractive index layer formation, 0.1-50 pl is more preferable, and 0.1-10 pl is especially preferable.

  Further, 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.

<Example of convex formation by spraying>
Although the spraying process preferably used for forming the convex part of the present invention is not particularly limited, it is preferable to use a slot nozzle spraying device. The slot nozzle spray device has a plurality of coating liquid nozzle holes for discharging the coating liquid in the coating width direction. The coating solution nozzle holes may be arranged in a line in the coating width direction or in a staggered manner. And a gas nozzle hole for ejecting gas in the vicinity of the coating liquid nozzle hole, and a mechanism for colliding the gas ejected from the nozzle with the coating liquid ejected from the coating liquid nozzle hole to form a droplet. Have.

  As a slot nozzle spray device that can be preferably used in the present invention, for example, a device described in JP-A-6-170308 can be applied.

  Also, a slot nozzle spray coating device disclosed in JP-A-5-309310 can be preferably used in the present invention. Further, in the present invention, the slot nozzle spray coating apparatus described in JP-A-2004-906 can be preferably used particularly from the viewpoint of coating uniformity, coating ease, and the like.

  As a method of improving the uniformity of the spray state over the coating width using such a slot nozzle spray device, it is possible to relatively reduce the viscosity of the coating liquid and to increase the gas pressure ejected from the gas nozzle. . Further, the uniformity of spraying can be improved by reducing the area of the opening end of the coating liquid nozzle of the slot nozzle spray device and by reducing the pitch of the opening end.

  The viscosity of the coating solution is preferably 0.1 to 250 mPa · s, more preferably 0.1 to 50 mPa · s, and still more preferably 0.1 to 20 mPa · s. By applying to a slot nozzle spray device, it is possible to spray droplets uniformly over the coating width.

  In order to spray droplets uniformly over the coating width, the static surface tension of the coating solution is adjusted to 20 to 70 mN / m, preferably 20 to 50 mN / m, more preferably 20 to 40 mN / m. It is to do.

  Further, when a gas internal pressure is 10 kPa or more, preferably 20 kPa or more, more preferably 50 kPa or more when a gas is collided with a coating liquid to form a droplet using a slot nozzle spray device or the like, uniform spraying is performed. easy. The gas flow rate is 3.5 CMM / m or more, preferably 7 CMM / m or more, and more preferably 10 CMM / m or more.

  By using the above-mentioned means, the coating liquid can be evenly supplied onto the support even when the coating liquid is small, by scattering in the form of discontinuous droplets instead of continuous fibers over the coating width. As a result, the convex portion formation can be made uniform. Further, since the discontinuous droplets are supplied onto the support and the amount of the coating liquid is reduced, no drying load is applied.

  Next, a specific form of the slot nozzle spray coating device used for forming the convex portion will be described.

  FIG. 9 is a schematic cross-sectional view showing an example of a slot nozzle spray device including a slot nozzle spray unit.

  The slot nozzle spray unit 41 has a pair of internal die blocks 43a and 43b, and external die blocks 42a and 42b on the outer sides of the pair of internal die blocks 43a and 43b, and between the pair of internal die blocks 43a and 43b. The coating solution nozzle C is formed on the inner die block 43a and the outer die block 42a, and the gas nozzle D is formed between the inner die block 43b and the outer die block 42b.

  In FIG. 9, the slot nozzle spray portion 41 has a pair of gas nozzles D having a gas pocket A and a coating liquid nozzle C having a coating liquid pocket B. The coating solution has a viscosity (preferably 0.1 to 250 mPa · s) that can form droplets without forming a fiber shape. For example, a coating solution such as a function-imparting compound-containing solution is placed in the preparation kettle 44, and a pump 45, a flow meter 46 is supplied to the coating liquid pocket B and guided to the coating liquid nozzle 43. On the other hand, pressurized air is supplied to the gas pocket A from the pressurized air source 47 through the valve 48 to the gas nozzle 42. At the time of coating, the coating liquid is supplied from the preparation tank 44 so that the coating amount becomes a prescribed coating amount from the coating liquid nozzle C, and at the same time, pressurized air is sprayed from the pair of gas nozzles D to form the coating liquid in droplets, 10 is sprayed and deposited. In the production method of the present invention, it is a great feature that the coating liquid can be sprayed as fine droplets instead of fibers. By supplying the coating liquid as fine droplets to the surface of the support 10, it is possible to form a highly uniform convex portion at high speed without a drying load.

  Next, with reference to FIG. 10, the slot nozzle spray section and the formation and flight state of the droplets formed there will be described.

  In FIG. 10, the coating liquid E discharged from the coating liquid nozzle C is subdivided into droplets by the compressed air G supplied from the gas nozzle D provided in the vicinity of both sides of the coating liquid nozzle C and is spherical. The droplet particles 50 are close to each other, fly and land uniformly on the surface of the support 10 across the gap L5. The area range of the droplet particles 50 of the coating liquid landing on the support 10 is preferably always uniform, but in particular, the length in the transport direction (denoted by the drop length L5 in the figure) extends over the coating width. It is preferable that it is uniform. Further, it is preferable that the spread angle θ of the droplet group sprayed on the object to be coated with the opening end of the coating liquid nozzle C as a base point is uniform over the coating width.

<FM screening method>
In the present invention, it is preferable that the protrusions are randomly arranged by a method such as FM screening.

  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.

  The convex portion forming method is not limited to the above-described flexo method, screen printing, ink jet method, and spray processing, and any method can be used as long as it can form a desired pattern, such as a gravure printing method or a lithographic printing method. The flexographic printing method has a high production speed and can form minute convex parts, and the inkjet method can flexibly change the presence pattern of convex parts, and the cross-sectional shape of the convex parts can be formed into a bowl-like shape. It is excellent in that it is easy to make the surface shape after providing a gentle unevenness.

  The convex-shaped low refractive index layer of the present invention is preferably formed by convex portions that are discrete and do not cover the entire support surface. The convex portions have 50% or more, preferably 70% or more, more preferably 80% or more, of independent convex portions that are not bonded to each other, and the convex portions have an area of the entire hard coat layer provided on the support surface. It is preferable to cover 50% or more, more preferably 85% or more, and particularly preferably 90% or more. Moreover, it is preferable that the low refractive index layer formed in a convex shape is formed by a plurality of times of printing, ink jetting or spraying.

  FIG. 11 is a schematic view of a convex-shaped low refractive index layer preferable for the present invention formed on a hard coat layer. A mode that the convex-shaped low refractive index layer 12 is coated on the hard-coat layer 11 provided in the base film 10 surface is shown.

  Fig.11 (a) is a perspective view of a convex part, FIG.11 (b) is sectional drawing of a convex part. The height of the convex portion is indicated by e in the figure, and refers to the height difference between the convex portion apex and the adjacent concave portion bottom, and the height is preferably 0.5 to 5 μm. If it is less than 0.5 μm, it is difficult to obtain an antiglare effect, and if it exceeds 5 μm, the feeling of roughness increases in visibility, which is not preferable. The height of the convex portion 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 with respect to the concave bottom adjacent to each convex portion is determined and used as an average value.

  The size of the convex portion is indicated by f in the figure, and when the concave and convex portions are color-coded like contour lines from the bottom side using the above-mentioned commercially available optical interference type surface roughness measuring machine or the like, the convex portion is based on the concave bottom. The length of the convex portion when the height of the convex portion is 5% higher is defined as the size of the convex portion, and is indicated by the average value. At this time, the size of the convex portion of the present invention is preferably 1 to 30 μm, and if it is less than 1 μm, it is difficult to obtain an antiglare effect, and if it exceeds 30 μm, the feeling of roughness increases in visibility, which is not preferable.

  Furthermore, the center line average roughness (Ra) of the antiglare antireflection film surface having the convex-shaped low refractive index layer formed is 0.5 μm or less, and the average mountain-valley interval (Sm) is 5 to 200 μm or less. It is preferable to control the formation of the convex portion.

  It is preferable that the average peak-valley interval (Sm) of a convex part is 5-200 micrometers, More preferably, it is 30-150 micrometers. Even if it is less than 5 μm or more than 200 μm, the antiglare effect is reduced, which is not preferable. The average distance between the convex portions can be measured by a stylus type surface roughness measuring machine or the like. It is possible to obtain knowledge as a surface roughness curve by measuring the change in the vertical direction of the measuring needle in that case and measuring the change in the vertical direction of the measuring needle. 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.

  What is necessary is just to obtain | require the average of what measured the convex part height, the magnitude | size, and the average peak-valley space | interval (Sm) of 100 convex parts.

  The antiglare antireflection film surface having a convex-shaped low refractive index layer according to the present invention preferably has a centerline average roughness Ra defined by JIS B 0601 of 0.01 to 0.5 μm. Ra is preferably 0.07 to 0.5 μm, and most preferably Ra is 0.1 to 0.5 μm. For example, Ra increases the anti-glare part, and vice versa. For example, Ra can be varied by 0.05 μm or more.

  The centerline average 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).

  The measurement method of the center line average roughness (Ra) can be determined by measuring in the above environment after conditioning for 24 hours in a 25 ° C., 65% RH environment under conditions where the measurement samples do not overlap each other. . 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 manufactured by WYKO.

  FIG. 12 is a schematic view of a cross-sectional view and a plan view showing an example of the formation of a convex portion according to the present invention. First, a hard coat layer is provided on a support, and a first low refractive index layer is formed in a convex shape on the surface thereof. After semi-curing or curing and fixing, a second low refractive index layer is further formed in a desired pattern. The flow which forms in a convex-shaped shape and is fixed by hardening is shown. The effect of the present invention can be obtained by forming the first low refractive index layer in a convex shape in a pattern, but the second low refractive index layer is further formed in a convex shape on the first low refractive index layer. The formation is preferable because it can suppress the occurrence of glare and moire.

  FIG. 13 shows an example of a manufacturing method in which convex portions are formed on a base film by flexographic printing (a) once and (b) multiple times of flexographic printing. Specifically, an example of a manufacturing process for forming a convex-shaped low refractive index layer by flexographic printing after coating a hard coat layer on a base film by a coating method is shown.

  In FIG. 13A, the base film 502 fed out from the roll 501 is conveyed, and a hard coat layer is applied by the first coater 503 of the extrusion system at the first coater station A. At this time, the hard coat layer may be a single layer structure or a plurality of layers. Further, the film thickness may be changed in the width direction. Substrate film 502 coated with a hard coat layer is then dried in drying zone 505A. Drying is performed from both surfaces of the base film 502 by warm air with controlled temperature and humidity. When an active energy ray curable resin is used as a binder for the hard coat layer, after drying, the active energy ray irradiation unit 506A cures by irradiating active energy rays, for example, ultraviolet rays, etc. It is also possible to control the conditions to be in a half cure state. In the active energy ray irradiation unit 506A, the base film 502 can be irradiated in a state of being wound on a back roll whose temperature is controlled at 20 to 120 ° C.

  Subsequently, although it is conveyed to the flexographic printing part B which provides the low-refractive-index layer using flexographic printing, it is preferable that a hard-coat layer is a half-cure state. The ink liquid for forming the low refractive index layer 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 fine concavo-convex structure which is a flexographic printing portion.

  Further, it is also preferable to perform transfer printing gently so that the shape of the convex portion is not greatly deformed or crushed by impact due to transfer printing. For example, it is also preferable to adjust the ink viscosity, the rubber hardness of the resin plate, the printing speed, and the like.

  When the active energy ray curable resin is used, the transfer-printed ink is irradiated with actinic rays, for example, ultraviolet rays or the like at the actinic ray irradiation unit 506B arranged after the resin plate 509 that is a flexographic printing unit. To cure. When the ink uses a thermosetting resin, the ink is heated and cured by a drying zone 505B, for example, a heat plate. A method of heating the back roll 504B as a heat roll is also preferable.

  In the flexographic printing part B, the active energy ray irradiation part 506B and the resin plate 509 are arranged at an appropriate interval so that the irradiation light of the active energy ray irradiation part 506B does not directly affect the ink of the resin plate 509. Alternatively, it is preferable to install a light shielding wall or the like between the active energy ray irradiation unit 506B 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 505B does not directly affect the ink of the resin plate 509, or the drying air in the drying zone 505B 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 fine uneven structure formed by the transfer-printed ink can be maintained is evaporated in the drying zone 505B, and then an unnecessary organic solvent is evaporated in the active energy ray irradiation unit 506C. Irradiation with active energy rays completes the curing.

  In the portion of the active energy ray irradiation unit 506C, it is preferable to irradiate the base film 502 on the back roll 504C whose temperature is controlled to 20 to 120 ° C. with the active energy ray.

  FIG. 13B is an example of a method for forming a convex portion by a plurality of flexographic printings. A flexographic printing portion C in which the diameter of the resin plate is changed is installed after the flexographic printing portion B in FIG. The manufacturing flow for performing printing twice is shown.

  It is preferable to form the convex part formation method by flexographic printing of this invention, conveying a base film at 1-500 m / min, Preferably it is 10-300 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, measure the anti-glare properties such as haze and transmission sharpness of the fine concavo-convex structure formed by transfer printing of ink, confirm that it is a predetermined value, and if the deviation or fluctuation is confirmed, the result is It is preferable to adjust the ink and replace the resin plate by feedback. The measurement is preferably performed after all the irregularities are formed and the resin is cured, and may be performed during the formation of the irregularities. For example, more appropriate feedback control can be performed by performing measurement after forming a relatively large unevenness and then forming a finer unevenness.

(Low refractive index layer)
The present invention is characterized in that it has a hard coat layer and a low refractive index layer formed in a convex shape on a support, and the convex portion is formed by the printing method, the ink jet method or the spray processing. Is. Hereinafter, the low refractive index layer forming ink which is the low refractive index layer forming composition will be described.

  The low refractive index layer of the present invention has convex portions formed in a pattern, and particularly in the present invention, the refractive index of the low refractive index layer is 1.5 or less, and the low refractive index formed in a convex shape. In a preferred embodiment, the layer contains at least an active energy ray-curable material and low refractive index fine particles, or contains at least a sol-gel material and low refractive index fine particles.

  Among them, the low refractive index fine particles used in the present invention are preferably hollow silica fine particles having an outer shell layer and porous or hollow inside.

  Examples of the low refractive index layer of the present invention include a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by active energy rays (hereinafter also referred to as “fluorinated resin before crosslinking”), a low refractive index layer by a sol-gel method, In addition, it is preferable to use a low refractive index layer or the like having a low refractive index fine particle and a binder polymer and having voids between or inside the particles. If the refractive index of the low refractive index layer is low, it is preferable because the antireflection performance is improved, but it is difficult from the viewpoint of imparting strength to the low refractive index layer. From this balance, the refractive index of the low refractive index layer is preferably 1.3 to 1.5, and more preferably 1.35 to 1.49.

  A preferred example of the fluorine-containing resin before crosslinking is a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3- Dioxole, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. Can be mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). In the latter, it is possible to introduce a crosslinked structure by adding a compound having a group that reacts with a functional group in the polymer and one or more reactive groups after copolymerization, as disclosed in JP-A-10-25388 and 10-147739. In the issue. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is cross-linked by heating due to a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with active energy rays (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator or an epoxy group and a photo acid generator, active energy ray curing It is a type. In the present invention, it is preferable to use an active energy ray curable resin.

  Further, in addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), OPSTAR (JSR), etc. Can be mentioned.

  It is also preferable to use various sol-gel materials as the low refractive index layer forming ink. As such a sol-gel material, metal alcoholates (alcolates such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  As the low refractive index layer, it is also preferable to use a layer formed by using inorganic or organic fine particles and forming microvoids between or within the fine particles. The average particle diameter of the fine particles is preferably from 0.5 to 200 nm, more preferably from 1 to 100 nm, further preferably from 3 to 70 nm, and most preferably from 5 to 40 nm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible.

  The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or metal halide, and most preferably a metal oxide or metal fluoride. . As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferable, and Mg, Ca, B and Si are more preferable. An inorganic compound containing two kinds of metals may be used. A particularly preferred inorganic compound is silicon dioxide, ie silica.

  The microvoids in the inorganic fine particles can be formed, for example, by cross-linking silica molecules forming the particles. Crosslinking silica molecules reduces the volume and makes the particles porous. (Porous) inorganic fine particles having microvoids are prepared by a sol-gel method (described in JP-A-53-112732 and JP-B-57-9051) or a precipitation method (described in APPLIED OPTICS, 27, 3356 (1988)). Can be directly synthesized as a dispersion. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, silicon dioxide sol) may be used. The inorganic fine particles having microvoids 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) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone) are preferable.

  The organic fine particles are also preferably amorphous. The organic fine particles are preferably polymer fine particles synthesized by polymerization reaction of monomers (for example, emulsion polymerization method). The organic fine particle polymer preferably contains a fluorine atom. The proportion of fluorine atoms in the polymer is preferably 35 to 80% by mass, and more preferably 45 to 75% by mass. It is also preferable to form microvoids in the organic fine particles by, for example, cross-linking the polymer forming the particles and reducing the volume. In order to crosslink the polymer forming the particles, it is preferable to use 20 mol% or more of the monomer for synthesizing the polymer as a polyfunctional monomer. The ratio of the polyfunctional monomer is more preferably 30 to 80 mol%, and most preferably 35 to 50 mol%. Examples of the monomer used for the synthesis of the organic fine particles include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene) as examples of monomers containing fluorine atoms used to synthesize fluorine-containing polymers. , Perfluoro-2,2-dimethyl-1,3-dioxole), fluorinated alkyl esters of acrylic acid or methacrylic acid, and fluorinated vinyl ethers. A copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom may be used. Examples of monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate). , Methacrylates (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrenes (for example, styrene, vinyl toluene, α-methyl styrene), vinyl ethers (for example, methyl vinyl ether), vinyl esters ( Examples thereof include vinyl acetate and vinyl propionate), acrylamides (for example, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides and acrylonitriles. Examples of polyfunctional monomers include dienes (eg, butadiene, pentadiene), esters of polyhydric alcohols and acrylic acid (eg, ethylene glycol diacrylate, 1,4-cyclohexane diacrylate, dipentaerythritol hexaacrylate), Esters of polyhydric alcohol and methacrylic acid (for example, ethylene glycol dimethacrylate, 1,2,4-cyclohexanetetramethacrylate, pentaerythritol tetramethacrylate), divinyl compounds (for example, divinylcyclohexane, 1,4-divinylbenzene), divinyl Examples include sulfones, bisacrylamides (eg, methylenebisacrylamide) and bismethacrylamides.

  Microvoids between particles can be formed by stacking at least two fine particles. When spherical fine particles having the same particle diameter (completely monodispersed) are closely packed, microvoids between fine particles having a porosity of 26% by volume are formed. When spherical fine particles having the same particle diameter are simply filled with cubic particles, microvoids between fine particles having a porosity of 48% by volume are formed. In an actual low-refractive index layer, the particle size distribution of fine particles and intra-particle microvoids exist, so the porosity varies considerably from the above theoretical value.

  The porosity of the low refractive index layer of the present invention is preferably 3 to 50%, and a porosity in this range can be obtained by selecting the shape and particle size of the particles.

  The porosity can be measured by a BET adsorption method or a mercury porosimeter, for example, a mercury porosimeter manufactured by Shimadzu Corporation.

  When the porosity is increased, the refractive index of the low refractive index layer is lowered. By stacking microparticles to form microvoids and adjusting the particle size of microparticles, the size of interparticle microvoids can be easily adjusted to an appropriate value (does not scatter light and cause problems in the strength of the low refractive index layer). Can be adjusted. Furthermore, by making the particle diameters of the fine particles uniform, it is possible to obtain an optically uniform low refractive index layer in which the size of microvoids between particles is uniform. As a result, the low refractive index layer is microscopically a microvoided porous film, but can be made optically or macroscopically uniform. The interparticle microvoids are preferably closed in the low refractive index layer by fine particles and a polymer. The closed air gap also has an advantage that light scattering on the surface of the low refractive index layer is less than that of an opening opened on the surface of the low refractive index layer.

  By forming the microvoids, the macroscopic refractive index of the low refractive index layer becomes lower than the sum of the refractive indexes of the components constituting the low refractive index layer. The refractive index of the layer is the sum of the refractive indices per volume of the layer components. The refractive index of the constituent component of the low refractive index layer such as fine particles or polymer is larger than 1, whereas the refractive index of air is 1.00. Therefore, a low refractive index layer having a very low refractive index can be obtained by forming microvoids.

  The low refractive index layer forming ink preferably contains a polymer in an amount of 5 to 50% by mass. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer forming ink. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the low refractive index layer forming ink. The polymer of (3) is preferably formed by adding a monomer to the low refractive index layer forming ink and by polymerization reaction at the same time as or after coating the low refractive index layer. It is preferable to carry out a combination of two or all of the above (1) to (3), and to carry out a combination of (1) and (3) or a combination of (1) to (3). Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles are made of silicon dioxide, surface treatment with a silane coupling agent can be carried out particularly effectively. Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, 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, Examples include N-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-mercaptopropylmethyldimethyl Kishishiran, .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, γ-methacryloyloxypropylmethyldiethoxy as those having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxy Propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane are particularly preferred.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane couplings 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. The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Mention may be made of esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the low refractive index layer-forming ink and performing a polymerization reaction (if necessary, further a crosslinking reaction) simultaneously with or after the application of the low refractive index layer. A small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) may be added to the low refractive index layer forming ink. .

  Furthermore, the low refractive index layer-forming ink of the present invention preferably contains the following hollow silica fine particles as fine particles in order to reduce the refractive index.

  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 forming ink 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, if the coating layer thickness 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 degree of polymerization, which are ink 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 low refractive index cannot be obtained sufficiently. 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.

  In addition to the components (inorganic fine particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator) described above, the polymerization inhibitor, leveling agent, thickener, anti-coloring agent, ultraviolet absorber are included in the low refractive index layer forming ink. A silane coupling agent, an antistatic agent or an adhesion-imparting agent may be added.

  The low refractive index layer forming ink 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 forming ink. The organic solvent is preferably 1% by mass or more in order to prevent coating unevenness due to printing or ink jetting, and is preferably 1% by mass or more. Absent.

  The viscosity of the low refractive index layer-forming ink according to the present invention is preferably adjusted to an optimum viscosity appropriately for each method using the above materials by coating methods such as the printing methods, ink jet methods, and spray processing. In particular, it is effective to adjust by the content of the organic solvent.

The active energy ray used in the present invention can be used without limitation as long as it is an energy source that activates a compound such as ultraviolet ray, electron beam, γ ray, etc., but ultraviolet ray and electron beam are preferable, particularly easy handling and high energy. Ultraviolet rays are preferred because they 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 individual lamps, irradiation dose is preferably ^{20mJ / cm 2 ~10000mJ / cm 2} , more preferably from ^{100mJ / cm 2 ~2000mJ / cm 2} , particularly preferably 400 mJ / cm ² ~ 2000 mJ / cm ² .

《Hard coat layer》
The antiglare antireflection film of the present invention is provided with a hard coat layer on a support. As a method for coating the hard coat layer, those described later such as a gravure coater and a die coater can be used. The film thickness of the hard coat layer is preferably in the range of 3 to 20 μm, more preferably 5 to 15 μm, as a dry film thickness. If it is less than 3 μm, the scratch resistance is insufficient, and if it exceeds 20 μm, the flatness deteriorates.

  The hard coat layer according to the present invention is preferably an active energy ray curable resin layer.

  The active energy ray-curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.

  The UV curable acrylic urethane resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in US Pat. No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of photopolymerization initiators for these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photopolymerization initiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate-based photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photopolymerization initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the composition.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( 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 Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB Corporation); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan KK), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), etc. Can be selected as appropriate.

  Examples of specific compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. .

  The cured resin layer thus obtained may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index.

  The hard coat layer is preferably a hard coat layer having a center line average roughness (Ra) defined by JIS B 0601 of 0.001 to 0.1 μm.

  These hard coat layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method. After application, it is heat-dried and UV-cured.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without limitation. 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. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² , and particularly preferably 20 to 100 mJ / cm ² .

  The hard coat layer is preferably irradiated with ultraviolet rays after coating and drying, and the irradiation time for obtaining the necessary amount of active ray irradiation is preferably about 0.1 second to 1 minute, and the curing efficiency of the ultraviolet curable resin Or from the viewpoint of work efficiency, 0.1 to 10 seconds is more preferable.

Moreover, it is preferable that the illuminance of these active ray irradiation parts is 50-150 mW / m < ² >.

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. As a result, a film having further excellent flatness can be obtained.

  The hard coat layer coating solution may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the coating liquid include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), These may be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or may be used by mixing them. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  Furthermore, it is also preferable that the hard coat layer contains a fluorine-based or silicone-based surfactant described later. These improve the applicability to the lower layer. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

  As the silicon-based surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for system 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 ( Polyoxyethylene) 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 according to the present invention is characterized by having 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, the unevenness of the ultraviolet curable resin layer and the low refractive index layer and the antifouling property 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 so as to cover the surface of the silica fine particle at a plurality of locations 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.

  As the fluorine-based surfactant, a surfactant having a hydrophobic group having a perfluorocarbon chain can be used. As types, fluoroalkylcarboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, sodium 3- (fluoroalkyloxy) -1-alkylsulfonate, 3- (ω-fluoroalkanoyl-N-ethylamino) -1- Sodium propanesulfonate, N- (3-perfluorooctanesulfonamido) propyl-N, N-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonic acid Salt, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethyl Ruhonirugurishin salts, phosphoric acid bis (N- perfluorooctylsulfonyl -N- ethylamino ethyl) and the like. In the present invention, nonionic surfactants are preferred.

  These fluorosurfactants are commercially available under the trade names such as Megafac, F-Top, Surflon, Footagen, Unidyne, Florard, Zonyl and the like.

  A preferable addition amount is 0.01 to 3.0%, more preferably 0.02 to 1.0%, based on the solid content contained in the coating solution of the ultraviolet curable resin layer.

  However, other surfactants may be used in combination, and as appropriate, for example, anionic surfactants such as sulfonates, sulfates, and phosphates, and polyoxyethylene chain hydrophilic groups A nonionic surfactant such as an ether type or an ether ester type may be used in combination.

  The hard coat layer has a multilayer structure of two or more layers, and one of the layers may be a so-called antistatic layer containing, for example, conductive fine particles or an ionic polymer. As a color correction filter for the element, a color tone adjusting agent having a color tone adjusting function may be contained, and it is preferable to contain an electromagnetic wave blocking agent or an infrared absorber so as to have each function.

<Support>
The support used in the present invention is preferably a transparent film, more easily manufactured, good adhesion to the active energy ray-curable resin layer, optically isotropic, optical It is mentioned as preferable requirements that it is transparent in particular.

  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.

  Various polycarbonates can be used as the polycarbonate constituting the polycarbonate film preferably used in the present invention, but aromatic polycarbonate is preferable from the viewpoint of chemical properties and physical properties, and bisphenol A is particularly preferable. More preferably, bisphenol A derivatives obtained by introducing a benzene ring, cyclohexane ring, aliphatic hydrocarbon group, etc. into bisphenol A have anisotropy in the unit molecule obtained using a derivative introduced asymmetrically with respect to the central carbon. Polycarbonate with reduced structure is preferred. For example, two methyl groups in the central carbon of bisphenol A are substituted with benzene rings, and one hydrogen in each benzene ring of bisphenol A is asymmetrically substituted with respect to the central carbon with methyl groups, phenyl groups, etc. The polycarbonate obtained by using is mentioned.

  Specifically, 4,4′-dihydroxydiphenylalkane or a halogen-substituted product thereof is obtained by a phosgene method or a transesterification method. For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane, Examples include 4,4'-dihydroxydiphenylbutane.

  The production method of the polycarbonate film used in the present invention is not particularly limited. That is, any of an extrusion method, a solvent casting method, a calendar method, and the like may be used. In the present invention, a uniaxially stretched film or a biaxially stretched film may be used, but in terms of excellent surface accuracy, a film produced by a solvent cast method has a small optical isotropy and anisotropy. Then, the film produced by the extrusion method is more preferable.

  The polycarbonate used in the present invention has a glass transition point (Tg) of 110 ° C. or higher and a water absorption (measured under conditions of 23 ° C. water and 24 hours) of 0.3% or less. Is good. More preferably, Tg is 120 ° C. or higher and water absorption is 0.2% or less.

  Although it does not specifically limit as polyester which comprises the polyester-type film which can be preferably used for this invention, It is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components.

  The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples include cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, and phenylindanedicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.

  Among the polyesters having these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid as a dicarboxylic acid component and ethylene glycol as a diol component from the viewpoint of transparency, mechanical strength, dimensional stability, etc. And / or a polyester mainly composed of 1,4-cyclohexanedimethanol is preferred. Among them, a polyester mainly composed of polyethylene terephthalate or polyethylene-2,6-naphthalate, a copolymer polyester composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and two or more kinds of these polyesters A polyester having a mixture as a main constituent is preferred.

  As long as the polyester constituting the polyester film used in the present invention is within a range that does not impair the effects of the present invention, other copolymer components may be copolymerized or other polyesters may be mixed. Also good. Examples of these include the dicarboxylic acid components and diol components mentioned above, or polyesters composed thereof.

  For the purpose of improving the heat resistance of the film, a bisphenol compound, a compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio is preferably 1 to 20 mol% based on the bifunctional dicarboxylic acid constituting the polyester.

  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.

  Hereinafter, the cellulose ester film particularly preferably used in the present invention will be described in more detail.

(Cellulose ester film)
The cellulose ester used in the present invention is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 08-231761 Further, mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  If the molecular weight of the cellulose ester is too small, the tear strength decreases. However, if the molecular weight is too large, the viscosity of the cellulose ester solution becomes too high, and the productivity decreases. The molecular weight of the cellulose ester is preferably 70000-200000 in terms of number average molecular weight (Mn), more preferably 100,000-200000.

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Of these, cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group is usually present as a hydroxyl group. These can be synthesized by known methods.

  As the cellulose ester, cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from cotton linter (hereinafter sometimes simply referred to as a linter) alone or in combination.

  When a cellulose ester film is used in the present invention, the following plasticizer is preferably contained. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy For trimellitic acid plasticizers such as ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethylglycolate, butylphthalylbutylglycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl- Examples include 1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable. There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof. Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. Aromatic monocarboxylic acids possessed by them, or their derivatives. Particularly preferred is benzoic acid. The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Further, all of the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are.

  These plasticizers are preferably used alone or in combination.

  The amount of these plasticizers used is preferably from 1 to 20% by weight, particularly preferably from 3 to 13% by weight, based on the cellulose ester, in terms of film performance, processability and the like.

  It is preferable to add an ultraviolet absorber to the cellulose ester film used in the present invention. 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. For example, but not limited to.

  Although the specific example of the ultraviolet absorber used for this invention is given to the following, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Specialty Chemicals)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Specialty Chemicals)
UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber, which are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal, are preferable, and unnecessary coloring occurs. Less benzotriazole-based UV absorbers are particularly preferably used.

  Moreover, the ultraviolet absorber with the distribution coefficient described in Japanese Patent Application No. 11-295209 having a distribution coefficient of 9.2 or more is excellent in the surface quality of the film and in the coating property when used for the base film. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorber (or ultraviolet ray) described in the general formula (1) or general formula (2) of JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039. Absorbable polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  The cellulose ester film used in the present invention preferably contains fine particles. Examples of the fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydration. It is preferable to contain inorganic fine particles such as calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film. The average particle size of the secondary particles of the fine particles is in the range of 0.01 to 1.0 μm, and the content is preferably 0.005 to 0.3% by mass with respect to the cellulose ester. In many cases, fine particles such as silicon dioxide are surface-treated with an organic material, but such a material is preferable because it can reduce the haze of the film. Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, siloxane and the like. The larger the average particle size of the fine particles, the greater the mat effect, and on the contrary, the smaller the average particle size, the better the transparency. Therefore, the average particle size of the preferred primary particles is 5 to 50 nm, more preferably 7 to 16 nm. It is. These fine particles are usually present as aggregates in the cellulose ester film, and it is preferable to form irregularities of 0.01 to 1.0 μm on the surface of the cellulose ester film. Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc. manufactured by Aerosil, preferably AEROSIL (Aerosil) 200V, R972, R972V, R974, R202, and R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, AEROSIL (Aerosil) 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9 to 0.1. In the present invention, the fine particles may be dispersed together with cellulose ester, other additives, and an organic solvent at the time of preparing the dope, but in a sufficiently dispersed state like a fine particle dispersion separately from the cellulose ester solution. It is preferable to prepare the dope. In order to disperse the fine particles, it is preferably preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force. After that, it is preferable to disperse in a larger amount of organic solvent, merge with the cellulose ester solution, and mix with an in-line mixer to obtain a dope. In this case, an ultraviolet absorbent may be added to the fine particle dispersion to form an ultraviolet absorbent liquid.

  The deterioration inhibitor, the ultraviolet absorber and / or the fine particles may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.

  The organic solvent useful for forming the dope of the cellulose ester film used in the present invention can be used without limitation as long as it dissolves cellulose ester and other additives simultaneously. For example, as a chlorinated organic solvent, methylene chloride, as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and nitroethane. Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used. Particularly preferred is methyl acetate.

  Next, the manufacturing method of the cellulose ester film used for this invention is demonstrated.

  Cellulose ester film is produced by dissolving cellulose ester and additives in a solvent to prepare a dope, casting a dope onto an endless metal support that moves indefinitely, drying the cast dope as a web It is performed by the process of carrying out, the process of peeling from a metal support body, the process of extending | stretching or maintaining width, the process of drying further, and the process of winding up the finished film.

  The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope may be used alone or in combination, but it is preferable in terms of production efficiency to use a good solvent and a poor solvent of cellulose ester, and the more good solvent is, the more soluble the cellulose ester is. Is preferable. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the average acetylation degree (acetyl group substitution degree) of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4), cellulose Acetate propionate is a good solvent, and cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  A general method can be used as a method of dissolving the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. A method in which a cellulose ester is mixed with a poor solvent and wetted or swollen, and then a good solvent is further added and dissolved is also preferably used.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  A higher heating temperature with the addition of a solvent is preferable from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

Bright spot foreign matter is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate The number of bright spots with a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably 100 / cm ² or less, more preferably 50 or / m ² or less, more preferably 0 to 10 / cm ² or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by an ordinary method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting process is −50 ° C. to a temperature lower than the boiling point of the solvent, and a higher temperature is preferable because the web drying speed can be increased. May deteriorate. A preferable support body temperature is 0-40 degreeC, and 5-30 degreeC is still more preferable. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Further, in the drying step of the cellulose ester film, the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Especially preferably, it is 0-0.01 mass% or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a tenter method is used while drying the web.

  In order to produce a cellulose ester film, the web is stretched in the transport direction where the amount of residual solvent of the web immediately after peeling from the metal support is large, and further stretched in the width direction by a tenter method that grips both ends of the web with clips or the like. It is particularly preferred to do this. The preferred draw ratio in both the machine direction and the transverse direction is 1.05 to 1.3 times, and more preferably 1.05 to 1.15 times. It is preferable that the area is 1.12 times to 1.44 times, and preferably 1.15 times to 1.32 times due to longitudinal and lateral stretching. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction. When either the machine direction or the transverse direction draw ratio is less than 1.05 times, the flatness is greatly deteriorated by ultraviolet irradiation when forming the hard coat layer, and even when the draw ratio exceeds 1.3 times Deteriorates and haze increases.

  In order to stretch in the longitudinal direction immediately after peeling, peeling is preferably performed at a peeling tension of 210 N / m or more, particularly preferably 220 to 300 N / m.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 40 to 150 ° C, more preferably from 50 to 140 ° C in order to improve dimensional stability.

  Although the film thickness of a cellulose-ester film is not specifically limited, 10-200 micrometers is used preferably. More preferably, it is 10-70 micrometers, More preferably, it is 20-60 micrometers. Most preferably, it is 35-60 micrometers.

  A cellulose ester film having a width of 1 to 4 m is preferably used. In particular, those having a width of 1.4 to 4 m are preferably used, and particularly preferably 1.4 to 2 m. If it exceeds 4 m, conveyance becomes difficult.

  The cellulose ester film used in the present invention is preferably a transparent film having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film according to the present invention preferably has a thickness of 10 to 100 μm, and the moisture permeability is preferably 200 g / m ² · 24 hours or less at 25 ° C. and 90 ± 2% RH, Preferably, it is 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less. In particular, it is preferable that the film thickness is 10 to 60 μm and the moisture permeability is within the above range. Here, the moisture permeability of the film is measured according to the method described in JIS Z 0208.

  The antiglare antireflection film of the present invention is subjected to heat treatment in the range of 50 to 150 ° C. for 1 to 30 days in a state of being wound in a roll after providing the low refractive index layer on a support. It is preferable. 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 the antiglare antireflection film into a roll, the wound core may be any material as long as it is a cylindrical core, preferably a hollow plastic core, The plastic material may be any heat-resistant plastic that can withstand the heat treatment temperature, and examples thereof include resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin. 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.

(Polarizer)
The polarizing plate can be produced by a general method. The back side of the antiglare antireflection film of the present invention is alkali saponified and bonded to at least one surface of a polarizing film produced by immersion and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. preferable. 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 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, a phase difference of 30 to 300 nm, and Rt of 70 to 400 nm. Preferably it is. 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 it in combination with 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 anti-glare anti-reflection film of the present invention is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. It is preferably used in LCDs. Further, the antiglare antireflection film of the present invention is excellent in flatness and is 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, and the eyes were not tired even during long viewing.

  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 referred to as a web after casting on a 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 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 a 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. As a result of measuring the unevenness formed by using the optical interference surface roughness measuring machine manufactured by WYKO by the following convexity diameter, convexity height, Ra, Sm measurement method, the size of the convexity is 25 μm, the convexity The height was 0.8 μm, and the average surface roughness (Ra) was 0.55 μm. Moreover, the average peak-valley interval (Sm) of the convex portions was 77 μm.

(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.

  As a result of measuring the unevenness formed using an optical interference type surface roughness measuring machine manufactured by WYKO, the size of the convex portion was 20 μm, the height of the convex portion was 0.9 μm, and the average surface roughness (Ra) was 0.00. It was 75 μm. Moreover, the average peak-valley interval (Sm) of the convex part was 65 μm.

(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 0.5 parts by mass (BYK-307 (manufactured by Big Chemie Japan))
[Preparation of antiglare antireflection film]
Subsequently, the following low refractive index layer was coated on the hard coat layers of the antiglare films 1 and 2.

(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 and 2 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.

<Low refractive index layer coating composition 1>
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. did. 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 antiglare antireflection film 3 having convex low refractive index layer by flexographic printing method]
Using the apparatus of FIG. 13 (a), on the surface of the cellulose ester film 1 produced as described above (A 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 hard coat layer coating solution 2 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 and an irradiation dose of 0.1 J / cm ^2. As a result, the coating layer was cured to form a hard coat layer having a thickness of 5 μm. Subsequently, the following convex-shaped low refractive index layer-forming ink 1 was prepared by filtration through a polypropylene filter having a pore diameter of 20 μm, and the following seamless resin plate 1 was attached to form a convex-shaped low refractive index layer by flexographic printing. The flexographic printing pattern used was a crystal raster screening method manufactured by Agfa Gehwald, and a pattern having a density of 2400 to 4000 dpi and 1 to 10% density was used.

After forming the protrusion, after drying at 90 ° C. in the drying zone 505B, the UV lamp 506C is used to cure the ultraviolet light with an illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ^2. An antiglare antireflection film 3 having a partial low refractive index layer was produced.

  The resulting convex low refractive index layer covered an area of 85% of the hard coat layer surface. The size of the convex portion is 30 μm, the height of the convex portion is 1.0 μm, and the average surface roughness (Ra) of the convex-shaped low refractive index layer is measured. As a result, the convex portion is 0.45 μm. The average interval between the peaks and valleys (Sm) was 75 μm.

(Specifications of seamless resin plate 1)
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. Subsequently, the fine concavo-convex structure was engraved under the following laser engraving conditions, mounted on the resin plate roll while evacuating, and the whole was heated at 120 ° C. for 20 minutes.

  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.

(Laser engraving conditions)
Carbon dioxide laser output: 300 W, 50% output Engraving image: After printing, the FM screen pattern is adjusted so that the convex part height is 1.0 μm, the convex part size (long side) is 30 μm, and the distance between convex parts is 80 μm. The fine concavo-convex structure was engraved on the resin plate.

Anilox roll: 800 lines / 2.54 cm, cell volume 4 ml / m ² (manufactured by Neurong Co., Ltd., honeycomb pattern)
Ink supply: Steel doctor blade method (see Fig. 1)
(Convex-shaped low refractive index layer forming ink 1)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 100 parts by mass Trimethylolpropane triacrylate 30 parts by mass Hollow silica-based fine particle (P-2) dispersion 70 parts by mass 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 [Anti-glare having a convex low refractive index layer by flexographic printing method Production of antireflection film 4]
An antiglare antireflection film 4 was produced in the same manner as the antiglare antireflection film 3 except that the following convex low refractive index layer forming ink 2 was used.

The resulting convex low refractive index layer covered an area of 86% of the hard coat layer surface. Further, the size of the convex portion was 29 μm, the height of the convex portion was 1.0 μm, and the average surface roughness (Ra) of the convex-shaped low refractive index layer was measured, and as a result, it was 0.40 μm. The average peak-valley interval (Sm) of the convex portions was 78 μm.

(Convex-shaped low refractive index layer forming ink 2)
Tetraethoxysilane hydrolyzate A 100 parts by mass KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass Hollow silica-based fine particle (P-2) dispersion 70 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 [Preparation of antiglare antireflection film 5 having convex low refractive index layer by flexographic printing method]
Except for using the seamless resin plate 2 produced after printing the engraved image of the seamless resin plate so that the height of the convex portion is 0.8 μm, the size of the convex portion (long side) is 25 μm, and the distance between the convex portions is 70 μm. In the same manner as the antiglare antireflection film 4, an antiglare antireflection film 5 was produced.

The resulting convex low refractive index layer covered an area of 92% of the hard coat layer surface. Further, the size of the convex portion was 23 μm, the height of the convex portion was 0.8 μm, and the average surface roughness (Ra) of the convex-shaped low refractive index layer was measured, and as a result, it was 0.35 μm. The average peak-valley interval (Sm) of the convex portions was 71 μm.

[Preparation of antiglare antireflection film 6 having a convex low refractive index layer by flexographic printing]
Using the apparatus of FIG. 13B, after printing the seamless resin plate 1 and the engraved image of the seamless resin plate, the height of the convex portion is 0.3 μm, the size of the convex portion (long side) is 15 μm, and the distance between the convex portions. An antiglare antireflection film 6 was produced in the same manner as the antiglare antireflection film 4 except that the seamless resin plate 3 produced so as to have a thickness of 100 μm was used.

The resulting convex low refractive index layer covered an area of 95% of the hard coat layer surface. Further, the size of the convex portion was 28 μm, the height of the convex portion was 1.1 μm, and the average surface roughness (Ra) of the convex-shaped low refractive index layer was measured, and as a result, it was 0.35 μm. The average peak-valley interval (Sm) of the convex portions was 77 μm.

[Preparation of antiglare antireflection film 7 having convex low refractive index layer by inkjet method]
On the surface of the cellulose ester film 1 produced as described 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 hard coat layer coating solution 2 is applied to the microgravure coater. After drying at 90 ° C., the coating layer is cured using an ultraviolet lamp with an irradiation part with an illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² , and a thickness of 5 μm. A hard coat layer was formed. Next, 2 to 16 pl of ink droplets are ejected as an ink droplet by an ink jet method using the convex-shaped low refractive index layer forming ink 1, and the illuminance of ultraviolet rays is 0.1 W / cm from the active ray irradiated portion 0.2 seconds after drying. ² was cured at an irradiation amount of 0.1 J / cm ² to produce an antiglare antireflection film 7 having a convex low refractive index layer.

  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.

The resulting convex low refractive index layer covered an area of 95% of the hard coat layer surface. Further, the size of the convex portion was 35 μm, the height of the convex portion was 0.9 μm, and the average surface roughness (Ra) of the convex-shaped low refractive index layer was measured, and as a result, it was 0.30 μm. The average peak-valley interval (Sm) of the convex portions was 85 μm.

[Preparation of antiglare antireflection film 8 having convex low refractive index layer by screen printing]
On the surface of the cellulose ester film 1 produced as described 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 hard coat layer coating solution 2 is applied to the microgravure coater. After drying at 90 ° C., the coating layer is cured using an ultraviolet lamp with an irradiation part with an illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² , and a thickness of 5 μm. A hard coat layer was formed. Next, using the convex-shaped low refractive index layer forming ink 1, after forming convex portions by screen printing with the following screen plate, drying at 90 ° C. in a drying zone, and then using an ultraviolet lamp to illuminate ultraviolet rays. Was cured at 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² to prepare an antiglare antireflection film 8 having a convex low refractive index layer.

(Preparation of screen plate)
A stainless mesh fabric was pulled by a screen tension machine with an air stretcher and adhered to the screen frame, and then the photosensitive emulsion was uniformly applied to the screen mesh evenly. Next, a photomask (pattern original plate) was brought into intimate contact with the photosensitive emulsion surface, and the pattern was printed with a parallel exposure machine. This was developed by an automatic developing device to obtain a screen plate.

  Ink is put into the frame of the printing plate obtained in this way, moved while pressing the upper surface of the screen with a spatula called a squeegee, the ink is passed through the screen where there is no film, and extruded onto the upper surface of the printed material to obtain a printed material. It was.

  The resulting convex low refractive index layer covered an area of 88% of the hard coat layer surface. Further, the size of the convex portion was 31 μm, the height of the convex portion was 1.1 μm, and the average surface roughness (Ra) of the convex-shaped low refractive index layer was measured, and as a result, it was 0.50 μm. The average peak-valley interval (Sm) of the convex portions was 100 μm.

[Preparation of antiglare antireflection film 9 having convex low refractive index layer by spraying]
On the surface of the cellulose ester film 1 produced as described 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 hard coat layer coating solution 2 is applied to the microgravure coater. After drying at 90 ° C., the coating layer is cured using an ultraviolet lamp with an irradiation part with an illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² , and a thickness of 5 μm. A hard coat layer was formed. Next, using the convex-shaped low refractive index layer forming ink 1, a convex portion is formed by the slot nozzle spray device of FIG. 9, and then dried at 90 ° C. in a drying unit provided downstream of the printing unit, and then ultraviolet rays are formed. An antiglare antireflection film 9 was produced by using a lamp and curing at an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 0.1 J / cm ² .

The resulting convex low refractive index layer covered an area of 94% of the hard coat layer surface. Further, the size of the convex portion is 30 μm, the height of the convex portion is 1.0 μm, and the average surface roughness (Ra) of the convex-shaped low refractive index layer is measured, and as a result, is 0.45 μm. The average peak-valley interval (Sm) of the convex portions was 90 μm.

<Measurement, evaluation>
(Measurement of convex part diameter, convex part height, Ra, Sm)
The convex part diameter and convex part height were measured two-dimensionally in a range of about 4000 μm ² (55 μm × 75 μm) using the above-prepared film sample and using an optical interference surface roughness measuring machine manufactured by WYKO. The convex portions were color-coded as contour lines from the bottom side, and the convex portion height and the convex portion diameter as the size of the convex portions were measured with reference to the film surface.

  The surface roughness (Ra) and the average center-to-center distance (Sm) were measured by a measuring method of JIS B0601 using an optical interference type surface roughness measuring machine manufactured by WYKO.

(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 anti-glare antireflection film 1 provided with a fine uneven structure by addition of fine particles was inferior in glare or white turbidity due to dispersion of fine particle dispersibility. The antiglare antireflection film 2 provided with a fine concavo-convex structure by embossing was slightly inferior in the 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 tail of the antiglare antireflection 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 antireflection films 3 to 9 of the present invention were excellent in anti-glare effect and glare, and at a level where the cloudiness was not a concern. In addition, the height and size of the fine concavo-convex structure at the head and tail of the antiglare antireflection film are uniform, and it has been found that the antiglare antireflection film has high uniformity and production stability.

Example 2
[Preparation of polarizing plate]
Subsequently, the polarizing plate was produced by the following process using each anti-glare antireflection film 1-9 produced in Example 1.

  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.

  Then, according to the following processes 1-5, the polarizing film, the said anti-glare antireflection film 1-9, the cellulose ester film KC8UCR-5 (made by Konica Minolta Opto Co., Ltd.) on the back side were bonded together, and the polarizing plate was produced. 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: The polarizing film prepared in Step 4 in a dryer at 80 ° C., the cellulose ester film, and the antiglare antireflection films 1 to 9 are dried for 2 minutes to prepare polarizing plates 1 to 9. 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 cell) previously bonded was peeled off, and the above-prepared polarizing plates 1 to 9 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. It carried out so that it might face, and produced the liquid crystal display devices 1-9, respectively.

<Evaluation>
The obtained liquid crystal display devices 1 to 9 are observed in an environment as shown in FIG. 14, and the anti-glare effect, glare, and the blackness when the following visibility and moving images are displayed are 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 because of the dispersion of fine particle dispersibility and the improvement of antiglare effect and glare. 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 9 using the antiglare antireflection film of the present invention are excellent in the antiglare effect, glare and blackness.

Example 3
<Production of polycarbonate film>
The following dope composition was prepared.

<Dope composition>
Polycarbonate resin (viscosity average molecular weight 40,000, bisphenol A type) 100 parts 2- (2'hydroxy-3 ', 5'-di-t-butylphenyl) -benzotriazole 1.0 part Methylene chloride 430 parts Methanol 90 parts Above The composition was put into a sealed container, kept at 80 ° C. under pressure, and completely dissolved with stirring to obtain a dope composition A.

  Next, this dope composition A was filtered, cooled and kept at 33 ° C., cast uniformly on a stainless steel band, and dried at 33 ° C. for 5 minutes. Next, the drying time was adjusted to 65 nm at a retardation of 5 nm, and after peeling from the stainless steel band, drying was terminated while being conveyed by a number of rolls to obtain a polycarbonate film having a thickness of 80 μm.

<Preparation of norbornene resin film>
A reaction container having a capacity of 1000 ml substituted with nitrogen was charged with a solution of 1.5 g of Pd (CH ₃ CN) ₄ (BF ₄ ) ₂ dissolved in 100 ml of nitromethane. A solution prepared by dissolving 150 g of tetracyclo [4.4.0.12.5.17.10] -3-dodecene in 150 ml of nitromethane was added and reacted for 1 hour, 500 ml of methanol was added, and the precipitated resin was filtered. And recovered. The obtained resin was washed with a mixed solution of 300 ml of methanol and 40 ml of concentrated hydrochloric acid. Further, after washing with methanol, vacuum drying was performed at 60 ° C. to obtain a norbornene resin.

  The following dope composition was prepared.

<Dope composition>
Norbornene-based resin 100 parts 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole 1.0 part Methylene chloride 430 parts Methanol 90 parts The solution was kept at 80 ° C. under pressure and dissolved completely with stirring.

  The dope composition is then filtered, cooled and kept at 33 ° C., cast evenly on a stainless steel band, dried at 33 ° C. for 5 minutes, and then dried at 65 ° C. to a retardation of 5 nm. After adjusting and peeling from the stainless steel band, drying was completed while being conveyed by a number of rolls to obtain a norbornene-based resin film having a thickness of 80 μm.

<Production of polyester film>
0.0111 parts of titanium tetrabutoxide (TBT) was added to a mixture of 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, and the ester exchange reaction was carried out while gradually raising the temperature from 150 ° C to 240 ° C. It was. When the transesterification rate reached 98%, the reaction product was transferred to a polymerization reactor and subjected to a polymerization reaction under high temperature vacuum (final internal temperature 290 ° C.) to obtain polyethylene-2,6-naphthalate. .

  0.0104 part of phenylphosphonic acid was added to 100 parts of this polyethylene-2,6-naphthalate, mixed with a V-type blender, and then dried at 170 ° C. for 5 hours. Thereafter, it is melt-extruded from a die according to a conventional method, and rapidly cooled to produce an unstretched film having a thickness of 800 μm. Sequential biaxial stretching was performed, and heat setting was further performed at 220 ° C. for 10 seconds to prepare a biaxially oriented film having a thickness of 80 μm.

  The above-prepared polycarbonate film, norbornene resin film, and polyester film are used in place of the cellulose ester film 1 of Example 1, respectively, and the antiglare antireflection film 1 and the flexographic printing method by adding fine particles of Example 1 are used. The antiglare antireflection film 6 having a convex-shaped low refractive index layer by the anti-glare antireflection film 6 having a convex low-refractive index layer by the ink jet method and the anti-glare antireflection film 7 having a convex low-refractive index layer by the inkjet method are described in Table 3. Antiglare antireflection films 11 to 19 were prepared, and then polarizing plates 11 to 19 and liquid crystal display devices 11 to 19 were prepared using the obtained antiglare antireflection films 11 to 19 in the same manner as in Example 1. The same evaluation as in Example 1 was performed, and the results are shown in Table 3 below.

  From the above table, even if the support is changed, the result of Example 1 is reproduced, and compared with the antiglare antireflection film by adding fine particles, the antiglare antireflection film of the present invention has an antiglare effect, glare. It was confirmed that the contrast was excellent.

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 a schematic sectional drawing which shows an example of the slot nozzle spray apparatus containing a slot nozzle spray part. It is a schematic diagram which shows the formation and flight state of a slot nozzle spray part and the droplet formed there. It is a schematic diagram of the convex-shaped low refractive index layer preferable for this invention formed on a hard-coat layer. It is a schematic diagram of a cross-sectional view and a plan view showing an example of forming a convex portion according to the present invention. It is an example of the manufacturing flow which performs convex part formation 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

DESCRIPTION OF SYMBOLS 1 Seamless resin plate 2 Resin plate roll 3 Plate cylinder 4 Anilox roll 5 Impression cylinder 6 Doctor blade 7 Fan ten roll 8 Ink 9 Extrusion coater 11 Hard coat layer 10, 502 Base film 501 Film roll 503 Coater 504A, B, C Back roll 505A, B Drying zone 506A, B, C UV irradiation unit 508 Ink supply tank 509 Flexographic resin plate 510 Anilox roll

Claims (10)

An antiglare antireflection film comprising a hard coat layer and a low refractive index layer formed in a convex shape on a support. The anti-glare antireflection film according to claim 1, wherein the low refractive index layer formed in the convex shape covers an area of 85% or more of the surface of the hard coat layer. The refractive index of the low refractive index layer formed in the convex shape is 1.5 or less, and the center line average roughness (Ra) of the surface of the antiglare antireflection film is 0.5 μm or less, The anti-glare antireflection film according to claim 1, wherein an average mountain valley interval (Sm) is 5 to 200 μm or less. The anti-glare property according to any one of claims 1 to 3, wherein the low refractive index layer formed in the convex shape contains at least an active energy ray-curable material and low refractive index fine particles. Antireflection film. The anti-glare antireflection film according to any one of claims 1 to 3, wherein the low refractive index layer formed into a convex shape contains at least a sol-gel material and low refractive index fine particles. The said support body is at least 1 sort (s) of film chosen from a cellulose-ester type film, a polyester-type film, a norbornene-type resin film, and a polycarbonate-type film, The any one of Claims 1-5 characterized by the above-mentioned. Antiglare antireflection film. A polarizing plate, wherein the antiglare antireflection film according to any one of claims 1 to 6 is bonded to at least one surface. A display device using the antiglare antireflection film according to any one of claims 1 to 6 or the polarizing plate according to claim 7. An antiglare reflection characterized by having a hard coat layer and a low refractive index layer formed in a convex shape on a support, and the low refractive index layer is formed by a printing method, an inkjet method or a spray process The manufacturing method of a prevention film. The method for producing an antiglare antireflection film according to claim 9, wherein the low refractive index layer formed in the convex shape is formed by a plurality of times of printing, ink jetting, or spraying.

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