JP2009066962A - Method for manufacturing antiglare film, and antiglare film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an antiglare film, and the antiglare film easily coping with demanded antiglare property, high in production efficiency without increasing cost, and having no influence on the performance of a product in use. <P>SOLUTION: The method for manufacturing the antiglare film having an uneven surface manufactured by a solution casting method of casting a dope with resin dissolved in a solvent, on a continuously turning endless support body to form a web, then separating the web from the endless support body and drying it, is characterized in that the surface of the endless support body is covered with a resin layer of uneven shape and that the web formed by casting the dope on the resin layer is separated in a state of a residual solvent being 30-80% and dried to transfer the uneven shape, thus forming the uneven surface. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an antiglare film and an antiglare film.

  In recent years, high-performance optical films provided with an antireflection function, an antistatic function and the like have been demanded with full-color display of notebook personal computers, mobile phones and the like or with high definition of displays. For example, a computer provided with an anti-glare layer for improving visibility, providing an anti-glare layer for preventing reflections, and providing an anti-glare layer with an uneven surface to obtain reflected display performance with less glare. And liquid crystal image display devices (also called liquid crystal displays) such as word processors are demanded.

  The antireflection layer and antiglare layer are improved in various types and performances depending on the application, and various films having these functions are placed on the front of the liquid crystal display to reflect on the display for improved visibility. A method of imparting a prevention function or an antiglare function is used. These optical films used as the front plate are provided with an antireflection layer or an antiglare layer formed by coating or sputtering.

  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. Further, the surface of the display is often touched by hand, and it is also required that the display is not damaged.

  In recent years, there has been a demand for thinner and thinner films for display devices, or a wider antiglare film for larger screens. In particular, an anti-glare film having excellent flatness is required for a large screen, but a conventional anti-glare film has a particularly wide width, and a thin film cannot have excellent flatness, and has a wide scratch resistance. A sufficient area was not obtained.

  Conventionally, in order to obtain an antiglare film, a method of adding relatively large inorganic or organic particles and fine particles to an antiglare layer and providing irregularities on the surface is known. There was a problem of foreign matter failure during manufacturing. As a response to these problems, studies have been made so far. For example, when producing a triacetyl cellulose film having an antiglare property by a solution casting method, the support surface on which the dope is cast is roughened by a chemical etching method, a frist method, a sand blast method, etc. A manufacturing method for providing irregularities on a film surface is known (for example, see Patent Document 1). However, in this method, since the shape of the uneven surface is fixed to the support surface, in order to improve the antiglare property, the shape of the uneven surface of the support surface must be changed. This has the problem of preparing the body and making this cost expensive. In addition, it takes time to provide the support with an irregular surface shape, which makes it difficult to respond immediately to market demands.

  In addition, a method of providing an antiglare antireflection film by embossing after providing an antireflection layer on a support is known. (For example, refer to Patent Document 2.) However, in this method, the deterioration of the polarizing plate after the antiglare antireflection film is bonded to the polarizer, and the hard coat layer and the antireflection layer have minute cracks and humidity. In particular, when an optical compensation film is provided on the back surface of the polarizing plate, the retardation value tends to fluctuate and the viewing angle characteristics fluctuate.

  A method is known in which a dope is cast on a support by a solution casting method, peeled off from the support, and then a concavo-convex shape is formed on the film surface by a mold roll for forming a concavo-convex surface (see, for example, Patent Document 3). However, with this method, when forming a concavo-convex shape on the film surface with a mold roll for forming a concavo-convex surface, there is a risk that the formation of the concavo-convex shape on the film surface becomes unstable if the film transport speed is high due to the shape of the concavo-convex surface. In order to form a stable concavo-convex shape, the transfer rate becomes a rate-limiting step, which is a cause of difficulty in increasing production efficiency.

Under such circumstances, it is easy to respond to the required anti-glare property, and without increasing the cost, the production efficiency is high, and the production method of the anti-glare film and the anti-glare property that does not affect the performance of the used product. Development of film is desired.
Japanese Patent Laid-Open No. 10-119067 JP 2003-207602 A JP 2005-156615 A

  The present invention has been made in view of the above situation, and its purpose is to easily cope with the required anti-glare property, without increasing the cost, with high production efficiency, and without affecting the performance of the product used. It is providing the manufacturing method of an anti-glare film, and an anti-glare film.

  The above object of the present invention has been achieved by the following constitution.

  1. A dope in which a resin is dissolved in a solvent is cast on an endless support that is continuously rotated to form a web, and then the web is peeled off from the endless support and dried. A method for producing an antiglare film having an uneven surface, wherein the surface of the endless support is coated with a resin layer having an uneven shape, and the dope is cast on the resin layer to form a web. Thereafter, the web is peeled off in a state where the residual solvent is 30% to 80% and dried to transfer the uneven shape and form the uneven surface. Manufacturing method.

  2. 2. The antiglare film having a concavo-convex surface as described in 1 above, wherein the resin layer is formed on the endless support, and then a mold is pressed against the resin layer to form a concavo-convex shape. Manufacturing method.

  3. The resin layer is formed with an uneven shape by forming a resin layer on an endless support and then pressing a mold having at least two different centerline average roughness Ra on the resin layer. A method for producing an antiglare film having an uneven surface according to 1.

  4). The resin layer has an uneven surface according to 1 above, wherein a resin layer forming solution to which a particulate material is added is applied onto an endless support, and an uneven shape is formed on the surface of the resin layer. A method for producing an antiglare film.

  5). The resin layer is characterized in that a resin layer forming solution to which a particulate material having at least two different average particle diameters is applied is applied onto an endless support, and an uneven shape is formed on the surface of the resin layer. 2. A method for producing an antiglare film having an uneven surface as described in 1 above.

  6). 6. The method for producing an antiglare film according to any one of 1 to 5, wherein the uneven shape formed on the surface of the resin layer has a center line average roughness Ra of 3 μm to 10 μm.

  7. An antiglare film produced by the method for producing an antiglare film described in any one of 1 to 6 above.

  To provide a method for producing an anti-glare film and an anti-glare film that can easily cope with the required anti-glare property, do not increase costs, have high production efficiency, and do not affect the performance of the product used. It was possible to respond quickly to the demands of the market without increasing costs.

  The embodiment of the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited to this.

  FIG. 1 is a schematic view of an apparatus for producing an antiglare film by a solution casting method. FIG. 1A is a schematic view of an apparatus for producing an antiglare film by a solution casting method using an endless belt support as an endless support. FIG. 1A is a schematic view of an apparatus for producing an antiglare film by a solution casting method using an endless drum support as an endless support. The present invention relates to a method for producing an antiglare film in which a concavo-convex shape is formed on the surface of a film formed by casting a dope on an endless support and forming the film.

  The manufacturing apparatus shown in FIG.

  In the figure, reference numeral 1a denotes a production apparatus for a solution casting method for an antiglare film. The manufacturing apparatus 1 a includes a casting process 101, a first drying process 102, a stretching process 103, a second drying process 104, and a winding process 105.

  The casting step 101 includes an endless belt support 101a having a resin layer having a concavo-convex shape formed on the surface, a casting die 101b for casting a dope 2 in which a resin is dissolved in a solvent, and a heating to the endless belt support 101a. Device 101c. The endless belt support 101a is held by a roll 101a1 and a roll 101a2, and can be rotated (in the direction of the arrow in the figure).

  Reference numeral 3 denotes a web in which the dope 2 is cast on an endless belt support 101a. 4 shows the peeling roll which peels the web of the solidified state. The thickness of the web 3 can be set as necessary so that the thickness of the antiglare film collected in the winding process 105 becomes a set film thickness.

  The dope 2 is produced using a resin material for an antiglare film using a mixed solvent composed of a good solvent and a poor solvent.

  The heating device 101c is disposed to remove the solvent so that the dope 2 cast on the endless belt support 101a can be peeled from the endless belt support 101a.

  The heating device 101c includes a drying box 101c1, a first heating air supply device 101d disposed in the drying box 101c1, a second heating air supply device 101e, and an exhaust pipe 101f. The first heated air supply device 101d has a heated air supply pipe 101d1 and a header 101d2. The second heated air supply device 101e has a heated air supply pipe 101e1 and a header 101e2.

  The temperature of the web on the endless belt support 101a on the first heated air supply device 101d side and the temperature of the web on the endless belt support 101a on the second heated air supply device 101e side are the amount of residual solvent at the time of peeling. The temperature is set according to the type of solvent used in consideration of the maintenance of the uneven shape formed on the web at the time, the conveying speed accompanying the evaporation time of the solvent, foaming accompanying the solvent evaporation, productivity, and the like.

  The wind pressure of the heating air supplied from the first heating air supply device 101d and the second heating air supply device 101e is preferably 50 Pa to 5000 Pa in consideration of the uniformity of solvent evaporation. The temperature of the heated air supplied to the web 3 on the endless belt support 101a by the first heated air supply device 101d may be dried at a constant temperature, or several steps in the moving direction of the endless belt support 101a. It may be supplied separately. The supply of the heating air supplied to the web 3 on the endless belt support 101a by the second heating air supply device 101e is the same.

  Although the heating device 101c shown in this figure shows a case where heated air is used, the heating means is not particularly limited. Besides this, for example, a method of heating the web on the endless belt support 101a with an infrared heater, For example, a method of blowing warm air to the back surface of the endless belt support 101a and heating from the back surface side can be used, and can be appropriately selected as necessary.

  As the endless belt support 101a to be used, a metal belt support having a mirror-finished surface is used as a base, and a resin layer having a concavo-convex shape formed on the surface is provided. The endless belt support 101a to be used will be described later.

  The residual solvent amount of the web 3 when the web 3 is peeled from the endless belt support 101a is 30% by mass to 80% by mass. If it is less than 30% by mass, the adhesive force between the endless belt support 101a and the cast film becomes strong, and a micro-scratch is generated in the concavo-convex shape of the web 3 at the time of peeling. When it exceeds 80 mass%, since it becomes difficult to maintain the uneven shape formed on the web 3, it is not preferable.

  The concentration of the resin for forming the antiglare film of the dope 2 is preferably higher because the drying load after casting on the metal support can be reduced, but the concentration of the resin for forming the antiglare film is higher. If too much, an increase in load at the time of filtration, a decrease in filtration accuracy, etc. occur. The concentration for achieving both of these is preferably 10% by mass to 35% by mass, and more preferably 15% by mass to 25% by mass.

  When the web 4 is peeled from the endless belt support 101a, the web 3 is stretched in the MD (Machine Direction) direction by the peeling tension and the subsequent conveying tension. Therefore, in the present invention, the web is peeled from the endless belt support 101a. It is preferable that the peeling and conveyance tension at the time be 200 N / m to 400 N / m.

  The first drying step 102 includes a drying box 102a having a drying air intake port 102b and a discharge port 102c, an upper conveyance roll 102d that conveys the web 3, and a lower conveyance roll 102e. It is possible to adjust the amount of solvent contained in the web 3 before entering the stretching step 103 in the first drying step 102.

  The drying temperature varies depending on the amount of residual solvent of the web when entering the stretching process, but it takes into account condensation on the surface of the web accompanying evaporation of the solvent, adjustment of the residual solvent amount, stretching ratio, foaming of the solvent, etc. What is necessary is just to select and determine suitably with the amount of residual solvents in the range of -80 degreeC, and it may dry at fixed temperature and may be divided and divided into several steps of temperature.

  The stretching step 103 includes an outer box 103a having a dry air intake port 103b and a discharge port 103c, and a tenter stretching device 103d placed in the outer box 103a. The tenter used in the tenter stretching apparatus 103d is not particularly limited, and examples thereof include a clip tenter and a pin tenter, which can be selected and used as necessary. In the tenter stretching apparatus 103d, it is possible to stretch the web 4 in the transport direction (MD direction) or in the direction perpendicular to the transport direction (TD direction) as necessary.

  The dry air intake port 103b and the discharge port 103c may be reversed. Although the case where heated air is used as the solvent removing means in the stretching step 103 is shown, the solvent removing means is not particularly limited, and other examples include infrared rays.

  The second drying step 104 includes a drying box 104a having a drying air intake port 104b and a discharge port 104c, an upper conveyance roll 104d that conveys the web 3, and a lower conveyance roll 104e.

  In the 2nd drying process 104, you may use heating air, infrared rays alone, or heating air and infrared drying together. It is preferable to use heated air in terms of simplicity. This figure shows the case where heated air is used. The drying temperature varies depending on the amount of residual solvent of the web when entering the drying process, but the range of 30 ° C. to 180 ° C. is considered in consideration of the stability of the uneven shape of the surface, drying time, shrinkage unevenness, stability of the amount of expansion and contraction And may be selected as appropriate depending on the amount of residual solvent, and may be dried at a constant temperature, or may be divided into three to four stages of temperature, and may be divided into several stages of temperature.

  The residual solvent amount of the antiglare film after the drying treatment in the second drying step 104 is 0.01% by mass to 1.5% by mass in consideration of the load of the drying step, the dimensional stability stretch rate during storage, and the like. Is preferred. In the present invention, the web formed in the casting step is gradually removed in the second drying step 104, and the web in which the total residual solvent amount is 1.5% by mass or less is referred to as an antiglare film.

  The winding and collecting step 105 has a winding device (not shown), and winds the antiglare film 5 having the residual solvent amount set in the second drying step 104 to a necessary length to be wound around the winding core. 105a shows the roll-shaped anti-glare film wound up by the winding core. The temperature at the time of winding is preferably cooled to room temperature in order to prevent scratches and loosening due to shrinkage after winding. The winder to be used may be a commonly used winder, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress.

  The manufacturing apparatus shown in FIG.

  In the figure, reference numeral 1a 'denotes an apparatus for producing a resin film solution casting method. The manufacturing apparatus 1 a ′ includes a casting process 101 ′, a first drying process 102, a stretching process 103, a second drying process 104, and a winding process 105. The difference from the manufacturing apparatus 1a shown in FIG. 1 (a) is that the casting process 101 in FIG. 1 (a) uses an endless belt support, whereas in FIG. Using a drum support. The first drying step 102, the stretching step 103, the second drying step 104, and the winding step 105 are all the same as in FIG.

  The casting step 101 ′ is a die for casting an endless drum support 101′a having a resin layer having a concavo-convex shape on the surface and a dope 2 ′ in which a resin is dissolved in a solvent to the endless drum support 101′a. 101'b and a heating device 101'c. The endless drum support 101′a is pivotally supported and can be rotated (in the direction of the arrow in the figure).

  Reference numeral 3 'denotes a web in which a dope 2' is cast on an endless drum support 101'a. 4 'shows the peeling roll which peels the web of the solidified state. The thickness of the web 3 ′ can be set as necessary so that the thickness of the antiglare film collected in the winding process 105 becomes the set film thickness.

  The heating device 101'c is arranged to remove the solvent so that the dope 2 'cast on the endless drum support 101'a can be peeled from the endless drum support 101'a. The heating device 101'c has a drying box 101'c1, a heated air supply device disposed in the drying box 101'c1, and an exhaust pipe 101'e. The heated air supply device 101'd has a heated air supply pipe 101'd1 and a header 101'd2.

  The temperature of the web on the endless drum support 101'a depends on the amount of residual solvent at the time of peeling, maintenance of the uneven shape formed on the web at the time of peeling, the conveyance speed with the evaporation time of the solvent, productivity, and solvent evaporation. Considering foaming, etc., set the temperature according to the type of solvent used.

  The wind pressure of the heating air supplied from the heating air supply device is preferably 50 Pa to 5000 Pa in consideration of the uniformity of solvent evaporation.

  The temperature of the heated air supplied to the web 3 on the endless drum support 101'a by the heated air supply device 101'd may be dried at a constant temperature, or the rotation direction of the endless drum support 101'a In this case, the temperature may be divided into several stages.

  Although the heating device 101'c shown in this figure shows the case where heated air is used, the heating means is not particularly limited. In addition, for example, the web on the endless drum support 101'a is made of an infrared heater. A method of heating, a method of heating from the inside of the endless drum support 101′a, and the like can be mentioned, and can be appropriately selected as necessary.

  As the endless drum support 101′a to be used, a metal drum having a mirror-finished surface is used as a base, and a resin layer having a concavo-convex shape formed on the surface is provided. The endless belt support of FIG. It has the same configuration as the body 101a.

  The amount of residual solvent when the web 3 is peeled from the endless drum support 101′a is the same as that of the endless belt support 101a shown in FIG.

  When the web 3 is peeled from the endless drum support 101 ′ a, the web 3 is stretched in the MD (Machine Direction) direction due to the peeling tension and the subsequent transport tension. Therefore, in the present invention, from the endless drum support 101 ′ a The peeling and conveying tension when peeling the web is preferably 200 N / m to 400 N / m. Other symbols are the same as those in FIG.

  In the case of the manufacturing apparatus 1 ′ a shown in this figure, the amount of residual solvent is peeled off from the endless drum support, and in each of the first drying step 102, the stretching step 103, the second drying step 104, and the winding step 105. The stretch ratio, the stretch ratio, etc. are the same as in FIG.

  The value of the residual solvent amount (% by mass) according to the present invention is defined as B when the web (antiglare film) having a certain size is dried at 115 ° C. for 1 hour. When the mass of the web (antiglare film) before drying is A, it is a value obtained by ((AB) / B) × 100 = residual solvent amount (mass%).

  FIG. 2 is an enlarged schematic view of the endless belt support shown in FIG. FIG. 2A is an enlarged schematic cross-sectional view of a portion indicated by P in FIG. FIG. 2B is an enlarged schematic view of a portion indicated by P in FIG. FIG. 2C is an enlarged schematic plan view of the endless belt support shown in FIG.

  In the figure, 101a3 indicates a metal belt support of the endless belt support base 101a, and 101a4 indicates a resin layer provided on the metal belt support 101a3. The surface 101a5 of the resin layer 101a4 is provided with an uneven shape having a center line average roughness Ra of 3 μm to 10 μm. When the center line average roughness Ra is less than 3 μm, the unevenness level is insufficient and the required anti-glare function may not be obtained. When the center line average roughness Ra exceeds 10 μm, the antiglare function may be deteriorated. The center line average roughness Ra is a value measured using a small surface roughness measuring machine SJ-402 manufactured by Mitutoyo Corporation.

  E indicates the thickness of the resin layer 101a4. The thickness E indicates the thickness from the top of the convex portion having the maximum height to the surface of the metal belt support among the concave and convex shapes provided on the surface. The thickness E is preferably 0.8 mm to 1.5 mm in consideration of film strength, service life, heat conduction efficiency, drying time, and the like. The thickness E indicates a value measured using a CCD laser displacement sensor LK-080 manufactured by Keyence Corporation.

  F indicates the width of the resin layer 101a4. The width F is 10 mm to 20 mm wider than the width of the dope for forming an antiglare film to be cast in consideration of the transport position variation of the endless belt support or the endless drum, casting position stability, the amount of resin material used, and the like. It is preferable.

  The resin used for the resin layer 101a4 is not particularly limited as long as it has resistance to the solvent of the dope to be used and resistance to the temperature for removing the solvent in the dope. Thermoplastic resin, ultraviolet ray and electron beam Examples thereof include actinic ray irradiation treatment such as irradiation, moisture curing treatment, two-component mixing or heat treatment curable resin. Examples of the thermoplastic resin include gelatin and polyvinyl alcohol. As the actinic radiation curable resin, it is preferable to use 1) a compound containing two or more epoxy groups in one molecule, and 2) a resin containing at least a compound that generates a cation upon irradiation with light at a temperature of 10 to 150 ° C. . Examples of the type (mainly epoxy type) epoxy-type UV-curable prepolymer and monomer that are polymerized by cationic polymerization include a prepolymer containing two or more epoxy groups in one molecule. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyls of aromatic polyols. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. One of these prepolymers can be used alone, or two or more thereof can be mixed and used. Moreover, the compound which has an oxetane group is also mentioned as active ray curable resin.

  As the moisture curable type, there is one in which an isocyanate group-containing urethane polymer is a main component at a molecular end, and this isocyanate group reacts with moisture to form a crosslinked structure. Examples of moisture curable resins include TE030 and TE100 manufactured by Sumitomo 3M, Hibon 4820 manufactured by Hitachi Chemical Co., Ltd., Bondmaster 170 series manufactured by Kanebouenu SSC, Macroplast QR 3460 manufactured by Henkel, and Esdyne series manufactured by Sekisui Chemical Co., Ltd. Is mentioned.

  As the thermosetting resin, curing proceeds with heating, and the cured molecule generally becomes a three-dimensional network. For example, ethylene / vinyl acetate copolymer (EVA), polyester, polyamide, thermoplastic Examples include elastomers and polyolefins.

  The following two methods can be cited as a method for forming the uneven shape on the surface of the resin layer shown in the figure. 1) A method in which a resin layer is formed on an endless support, and a mold for forming an uneven shape is pressed against the surface of the formed resin layer. 2) When forming a resin layer on an endless support, a method may be mentioned in which a coating solution in which particles are mixed in a resin is applied on the endless support and dried. Below, it attaches and demonstrates to the method of forming uneven | corrugated shape on the surface of a resin layer.

  FIG. 3 is a schematic flow diagram of a method for forming a concavo-convex shape on the surface of a resin layer using a mold.

  Hereinafter, a method for forming a concavo-convex shape on the surface of a resin layer using a mold according to a flowchart will be described.

  In Step 1, a resin supply device 6 that coats resin on the endless metal belt support 101 a 3 of the base of the endless support that is held by the roll 101 a 1 and the roll 101 a 2 and can be rotated (in the direction of the arrow in the drawing). Is disposed. The position where the resin supply device 6 is disposed is not particularly limited, but a place where the casting die is installed is preferable because it is not necessary to add new equipment. As the resin supply device, a brass V-shaped box called a hopper, a Giesser, a casting box or the like is preferable. In addition, a casting die or an extrusion coater that is normally used as the coating apparatus may be used, but it is necessary to newly provide a coating liquid feeding pipe and a feeding pump.

  In Step 2, the resin supply device 6 is filled with a resin solution 7 for forming a resin layer. The amount to be filled is filled in advance by the calculation necessary for coating one endless metal belt support from the coating width, the thickness after drying and the length of the endless metal belt support 101a3. The height of the supply port 601 of the resin supply device 6 is adjusted so that the endless metal belt has a required thickness, and the resin solution 7 is allowed to flow down naturally and is coated on the surface of the endless metal belt support 101a3.

  In Step 3, the resin solution 7 is applied to one end of the endless metal belt support 101a3. Thereafter, the thickness of the coating film applied by pressing a straight tubular heater (not shown) called a sheathed heater is corrected.

  In Step 4, an uneven surface forming mold roll 8 having a shape with a center line average roughness Ra of 0.05 μm to 10 μm, which is a mold for imparting an uneven shape to the surface of the coating film, is disposed at a position corresponding to the roll 101a2. Then, the metal belt support is moved once while being pressed against the surface of the coating film, and the uneven shape is transferred to the surface of the coating film. By transferring, an uneven shape having a center line average roughness Ra of 0.05 μm to 10 μm is formed on the surface of the coating film.

  The pressing force when pressing the uneven surface forming mold roll against the surface of the resin coating is 5 to 500 N / cm in linear pressure, more preferably 30 to 500 N / cm, the type of resin used, the uneven shape to be formed, Appropriately determined in consideration of temperature and the like. In addition, it is also possible to form a concavo-convex shape having a center line average roughness Ra of 3 μm to 10 μm on the surface of the coating film by pressing at least two molds having different center line average roughness Ra on the mold roll for forming the concavo-convex surface. is there.

  Thereafter, the resin is cured in accordance with the type of resin used, and the uneven shape is fixed, whereby the resin layer 101a4 having an uneven shape with a center line average roughness Ra of 3 μm to 10 μm is formed on the surface. Examples of the method for curing the resin include heating in the case of a thermosetting resin, irradiation with ultraviolet rays in the case of an ultraviolet curable resin, and drying in the case of a thermoplastic resin.

  Also in the case where the endless support is the endless drum support shown in FIG. 1B, a resin layer having an uneven shape with a center line average roughness Ra of 3 μm to 10 μm is formed according to the flow of Step 1 to Step 4 shown in this figure. It is possible.

  FIG. 4 is a schematic flow diagram of a method for forming irregularities on the surface of the resin layer using particles.

  Hereinafter, a method for forming a concavo-convex shape on the surface of a resin layer using particles according to a flowchart will be described.

  In Step 1, a resin supply device 6 that coats resin on the endless metal belt support 101 a 3 of the base of the endless support that is held by the roll 101 a 1 and the roll 101 a 2 and can be rotated (in the direction of the arrow in the drawing). Is disposed. The position where the resin supply device 6 is disposed is not particularly limited, but a place where the casting die is installed is preferable because it is not necessary to add new equipment. As the resin supply device, a brass V-shaped box called a hopper, a Giesser, a casting box or the like is preferable. In addition, a casting die or an extrusion coater that is normally used as the coating apparatus may be used, but it is necessary to newly provide a coating liquid feeding pipe and a feeding pump.

  In Step 2, the resin supply device 6 is filled with a resin solution 8 for resin layer formation in which particles are dispersed. The amount to be filled is filled in advance by the calculation necessary for coating one endless metal belt support from the coating width, the thickness after drying and the length of the endless metal belt support 101a3. In accordance with the filling, the height of the supply port 601 of the resin supply device 6 is adjusted so that the endless metal belt support has a required thickness, and the resin solution 8 is allowed to flow down naturally on the surface of the endless metal belt support 101a3. Paint. The average particle size of the particles used is preferably 3 μm to 10 μm. An average particle diameter shows the value measured with the Nikkiso Co., Ltd. product Microtrac particle size distribution measuring apparatus MT3300EXII. In addition, it is also possible to add at least two types of particle materials having different average particle diameters to be used. The particle solid content of the resin solution 8 varies depending on the particle diameter and resin film thickness to be used, but is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the resin.

  The particles were dispersed by the following method. As the disperser for dispersing the fine particles, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersing silicon dioxide fine particles, a medialess disperser is preferred because of its low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. A high-pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube.

  When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 10 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 20 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable. The high-pressure dispersing apparatus as described above includes an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as a homogenizer manufactured by Izumi Food Machinery Co., Ltd. Examples include UHN-01 manufactured by Wakki Co., Ltd.

  In Step 3, the resin solution 8 is applied to one end of the endless metal belt support 101a3. Thereafter, the thickness of the coating film applied by applying a straight tubular heater (not shown) called a sheathed heater is corrected. Thereafter, a resin layer 101a4 having an uneven shape with a center line average roughness Ra of 3 μm to 10 μm is formed on the surface by curing the resin in accordance with the type of resin used. Examples of the method for curing the resin include heating in the case of a thermosetting resin or a thermoplastic resin, and irradiation with ultraviolet rays in the case of an ultraviolet curable resin.

  Also in the case where the endless support is the endless drum support shown in FIG. 1B, a resin layer having an uneven shape with a center line average roughness Ra of 3 μm to 10 μm is formed according to the flow of Step 1 to Step 4 shown in this figure. It is possible.

  The particles dispersed in the resin solution are not particularly limited and include inorganic fine particles or organic fine particles. Examples of inorganic fine particles include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Calcium phosphate and the like are preferable, and an inorganic compound containing silicon and zirconium oxide are more preferable, and silicon dioxide is particularly preferably used. These include particles having a shape such as a spherical shape, a flat plate shape, and an amorphous shape.

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

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

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

As shown in FIGS. 1 to 4, the following effects can be obtained by producing a resin film using an endless support having a resin film having an uneven surface formed on the endless support.
1) Since it is possible to produce an antiglare film in accordance with the casting speed, it is possible to prevent a decrease in production efficiency.
2) Since the uneven shape is not directly formed on the endless support, the cost of the antiglare film can be suppressed.
3) Since it is easy to form a resin film in accordance with the required uneven shape, it is possible to easily change the performance of the antiglare film and to quickly respond to the demand.

  Next, the material used for manufacturing the antiglare film of the present invention will be described.

(Resin material)
There is no particular limitation as long as it is a resin that forms a resin film. For example, cellulose ester resins such as cellulose diacetate resin, cellulose triacetate resin, cellulose acetate butyrate resin, and cellulose acetate propionate resin, polyester resins, and polycarbonate resins Resin, polyarylate resin, polysulfone (including polyethersulfone) resin, polyethylene terephthalate resin, polyester resin such as polyethylene naphthalate resin, polyethylene resin, polypropylene resin, cellophane, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene vinyl Alcohol resin, syndiotactic polystyrene resin, polycarbonate resin, cycloolefin resin, polymethylpentene resin, polyether Ketone resins, polyether ketone imide resin, polyamide resin, fluorine resin, nylon resin, polymethylmethacrylate resin, and acrylic resin. Among these, cellulose ester resins, cycloolefin resins, polycarbonate resins, and polysulfone (including polyethersulfone) resins are preferable. In the present invention, cellulose ester resins, cycloolefin resins, and polycarbonate resins are particularly preferable in production. From the viewpoints of cost, transparency, adhesion and the like, it is preferably used.

  The cellulose ester resin according to the present invention will be described. The cellulose ester-based resin is preferably cellulose acetate resin, cellulose propionate resin, cellulose butyrate resin, cellulose acetate butyrate resin, or cellulose acetate propionate resin. Among them, cellulose acetate butyrate resin, cellulose acetate phthalate resin, cellulose acetate Propionate resin is preferably used.

  In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or butyryl group is Y, a cellulose ester resin having a mixed fatty acid ester of cellulose in which X and Y are in the following ranges is preferably used.

Formula (I) 2.0 ≦ X + Y ≦ 2.6
Formula (II) 0.1 ≦ Y ≦ 1.2
Furthermore, a cellulose acetate propionate (total acyl group substitution degree = X + Y) resin of 2.4 ≦ X + Y ≦ 2.6 and 1.4 ≦ X ≦ 2.3 is preferable. Among them, 2.4 ≦ X + Y ≦ 2.6, 1.7 ≦ X ≦ 2.3, 0.1 ≦ Y ≦ 0.9, cellulose acetate propionate resin, cellulose acetate butyrate (total acyl group substitution degree = X + Y ) Resins are preferred. The portion not substituted with an acyl group usually exists as a hydroxyl group. These cellulose ester resins can be synthesized by a known method. The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  When a cellulose ester resin is used as the antiglare film of the present invention, the cellulose used as the raw material for the cellulose ester resin is not particularly limited, but includes cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like. I can list them. Moreover, the cellulose ester-type resin obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose ester resins use an organic acid such as acetic acid or an organic solvent such as methylene chloride, It can obtain by making it react with a cellulose raw material using such a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. The cellulose ester resin used in the present invention is obtained by mixing and reacting the above acylating agent amounts in accordance with the degree of substitution. In the cellulose ester resin, these acylating agents react with hydroxyl groups of cellulose molecules. To do. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  As described above, the cellulose ester-based resin used in the present invention may be propionate group or butyrate in addition to acetyl group such as cellulose acetate propionate resin, cellulose acetate butyrate resin, or cellulose acetate propionate butyrate resin. A mixed fatty acid ester of cellulose to which a group is bonded is particularly preferably used. In addition, the cellulose acetate propionate resin containing a propionate group as a substituent is excellent in water resistance and is useful as a film for a liquid crystal image display device.

  The number average molecular weight of the cellulose ester-based resin is preferably 40000 to 200000, and has a high mechanical strength when molded, and an appropriate dope viscosity in the case of a solution casting method, and more preferably 50000 to 150,000. . The weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably in the range of 1.4 to 4.5.

  The cycloolefin resin according to the present invention will be described. The cycloolefin resin used in the present invention is composed of a polymer resin containing an alicyclic structure. A preferred cycloolefin resin is a resin obtained by polymerizing or copolymerizing a cyclic olefin. Examples of the cyclic olefin include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2,4. Unsaturated hydrocarbons of polycyclic structures such as 6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclo Examples thereof include monocyclic unsaturated hydrocarbons such as octene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene, and derivatives thereof. These cyclic olefins may have a polar group as a substituent. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Or a carboxylic anhydride group is preferred.

  Preferred cycloolefin resins may be those obtained by addition copolymerization of monomers other than cyclic olefins. Addition copolymerizable monomers include ethylene, propylene, 1-butene, 1-pentene, and other ethylene or α-olefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Examples include dienes such as 1,4-hexadiene and 1,7-octadiene.

The cyclic olefin is obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction. The polymerization is carried out in the presence of a catalyst. Examples of the addition polymerization catalyst include a polymerization catalyst composed of a vanadium compound and an organoaluminum compound. As a catalyst for ring-opening polymerization, a polymerization catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound, and a reducing agent; or titanium, vanadium, zirconium, tungsten, molybdenum And a polymerization catalyst composed of a metal halide such as acetylacetone compound and an organoaluminum compound. The polymerization temperature, pressure and the like are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of -50 ° C to 100 ° C and a polymerization pressure of 0 to 490 N / cm ² .

  The cycloolefin resin according to the present invention is preferably a resin obtained by polymerizing or copolymerizing a cyclic olefin, followed by a hydrogenation reaction to change the unsaturated bond in the molecule to a saturated bond. The hydrogenation reaction is performed by blowing hydrogen in the presence of a known hydrogenation catalyst. Examples of hydrogenation catalysts include cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, transition metal compounds such as titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium / alkyl. Homogeneous catalyst consisting of a combination of metal compounds; heterogeneous metal catalyst such as nickel, palladium, platinum; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth And a heterogeneous solid-supported catalyst in which a metal catalyst such as palladium / alumina is supported on a carrier.

  Or the following norbornene-type resin is also mentioned as a cycloolefin resin. The norbornene-based resin preferably has a norbornene skeleton as a repeating unit. Specific examples thereof include, for example, JP-A-62-252406, JP-A-62-2252407, and JP-A-2-133413. JP, JP 63-145324, JP 63-264626, JP 1-224017, JP 57-8815, JP 5-2108, JP 5-39403. JP-A-5-43663, JP-A-5-43834, JP-A-5-70655, JP-A-5-279554, JP-A-6-206985, JP-A-7-62028, JP-A-8-176411, JP-A-9-241484, JP-A-2001-277430, JP-A-2003-139 No. 50, JP-A No. 2003-14901, JP-A No. 2003-161832, JP-A No. 2003-195268, JP-A No. 2003-111588, JP-A No. 2003-211589, JP-A No. 2003-268187 Gazette, JP-A-2004-133209, JP-A-2004-309799, JP-A-2005-121183, JP-A-2005-164632, JP-A-2006-72309, JP-A-2006-178191, Although what was described in Unexamined-Japanese-Patent No. 2006-215333, Unexamined-Japanese-Patent No. 2006-268065, Unexamined-Japanese-Patent No. 2006-299199 etc. is mentioned, It is not limited to these. Moreover, these may be used individually by 1 type and may use 2 or more types together. Specifically, ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, APPEL manufactured by Mitsui Chemicals, Inc. (APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) and the like are preferably used.

  The molecular weight of the cycloolefin polymer according to the present invention is appropriately selected depending on the purpose of use, but polyisoprene measured by gel permeation chromatography method of cyclohexane solution (toluene solution when the polymer resin does not dissolve). Alternatively, when the weight average molecular weight in terms of polystyrene is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, the mechanical strength and molding processability of the molded body are highly balanced. It is preferable.

  Moreover, when a low-volatile antioxidant is blended at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the cycloolefin polymer, it can effectively prevent the polymer from being decomposed or colored during the molding process. I can do it.

  The polycarbonate resin according to the present invention will be described. There are various types of polycarbonate resins, and aromatic polycarbonates are preferable from the viewpoint of chemical properties and physical properties, and bisphenol A polycarbonates are particularly preferable. Among them, more preferred is a bisphenol A derivative in which a benzene ring, a cyclohexane ring, or an aliphatic hydrocarbon group is introduced into bisphenol A, and these groups are introduced asymmetrically with respect to the central carbon. A polycarbonate having a structure in which the anisotropy in the unit molecule is reduced, obtained by using the obtained derivative is preferable. For example, one in which two methyl groups on the central carbon of bisphenol A are replaced with a benzene ring, and one hydrogen on each benzene ring in bisphenol A is replaced asymmetrically with respect to the central carbon by a methyl group or a phenyl group The polycarbonate resin obtained is preferable. Specifically, 4,4′-dihydroxydiphenylalkane or a halogen-substituted product thereof can be obtained by a phosgene method or a transesterification method. For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane 4,4'-dihydroxydiphenylbutane and the like. In addition, for example, polycarbonate resins described in JP-A-2006-215465, JP-A-2006-91836, JP-A-2005-121813, JP-A-2003-167121 and the like can be mentioned. It is done.

  The antiglare film made of the polycarbonate resin used in the present invention may be used by mixing with a transparent resin such as a polystyrene resin, a methyl methacrylate resin, or a cellulose acetate resin, or at least of the cellulose acetate film. A polycarbonate resin may be laminated on one surface.

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

(Dope)
The solvent used for preparing the dope may be any solvent that can dissolve the resin, and even a solvent that cannot be dissolved alone can be dissolved by mixing with another solvent. Can be used. In general, a mixed solvent composed of a good solvent and a poor solvent is used. In addition, what melt | dissolves resin to be used independently is defined as a good solvent, and what swells or does not melt | dissolve independently is defined as a poor solvent. For example, in the case of a cellulose ester resin, the good solvent and the poor solvent change depending on the acyl group substitution degree of the cellulose ester. 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. In the case of a cellulose ester resin, 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.

  Since the good solvent and the poor solvent differ depending on the resin to be used, it will be described in the case of a cellulose ester resin. Examples of the good solvent include methylene chloride, 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-2-methyl-2-propanol, 1,1 , 1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane and the like, but organic halogen compounds such as methylene chloride, Dioxolane derivatives, methyl acetate, ethyl acetate, acetone and the like are mentioned as preferred organic solvents (that is, good solvents). That.

  Examples of the poor solvent include alcohols having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, methyl ethyl ketone, methyl isobutyl ketone, propyl acetate, and monochloro. Examples thereof include benzene, benzene, cyclohexane, tetrahydrofuran, methyl cellosolve, ethylene glycol monomethyl ether, and the like. These poor solvents can be used alone or in combination of two or more.

  Next, a method for preparing a dope using a cellulose ester resin will be described. As a method for dissolving the cellulose ester resin when preparing the dope, a general method can be used. 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 formation of massive undissolved materials called gels and mamacos. In addition, a method in which a cellulose ester resin is mixed with a poor solvent and wetted or swollen, and then a good solvent is 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.

  The heating temperature with the addition of a solvent is preferably higher 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 resin can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester resin 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. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / 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 a normal 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.

(Plasticizer)
Although it does not specifically limit as a plasticizer, Phosphate ester plasticizer, phthalate ester plasticizer, trimellitic acid ester plasticizer, pyromellitic acid plasticizer, glycolate plasticizer, citrate plasticizer Polyester plasticizers can be preferably used. Examples of the phosphate ester include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like. Examples of the phthalic acid ester include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, and butyl benzyl phthalate. Examples of trimellitic acid plasticizers include tributyl trimellitate, triphenyl trimellitate, triethyl trimellitate, and the like. Examples of the pyromellitic acid ester plasticizer include tetrabutyl pyromellitate, tetraphenyl pyromellitate, and tetraethyl pyromellitate. Examples of glycolic acid esters include triacetin, tributyrin, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate. Examples of the citrate plasticizer include triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, and acetyl tri-n- (2-ethylhexyl) citrate. 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 molecular weight of the polyester is preferably in the range of 500 to 2000 in terms of weight average molecular weight from the viewpoint of compatibility with the cellulose ester.

  In the present invention, it is particularly preferable to use a plasticizer having a vapor pressure of less than 1333 Pa at 200 ° C., more preferably a compound having a vapor pressure of 666 Pa or less, and more preferably 1 to 133 Pa. The non-volatile plasticizer is not particularly limited, and examples thereof include arylene bis (diaryl phosphate) ester, tricresyl phosphate, trimellitic acid tri (2-ethylhexyl), and the above polyester plasticizer. These plasticizers can be used alone or in combination of two or more.

  In consideration of dimensional stability and processability, the plasticizer can be added in an amount of 1 to 40% by mass, preferably 3 to 20% by mass, based on the cellulose ester resin. More preferably, it is 4 to 15% by mass. If the amount is less than 3% by mass, a smooth cut surface cannot be obtained when slitting or punching, resulting in increased generation of chips.

  It is preferable to add an antioxidant or an ultraviolet absorber to the antiglare film of the present invention. As the antioxidant, a hindered phenol compound is preferably used, and 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl). -4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( , 5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate Etc. In particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di-t A phosphorus-based processing stabilizer such as -butylphenyl) phosphite may be used in combination. The amount of these compounds added is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose ester.

  In addition, heat stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, and alkaline earth metal salts such as calcium and magnesium may be added. Good.

  The antiglare film produced by the production method of the present invention can be used for a polarizing plate or a liquid crystal display member. In this case, an ultraviolet absorber is used to prevent deterioration of the polarizing plate or the liquid crystal. Preferably used.

  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. Specifically, the transmittance at 380 nm is preferably less than 10%, more preferably less than 5%.

  Specific examples of preferably used ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. For example, the ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 are preferably used. Moreover, the polymeric ultraviolet absorbers described in JP-A-6-148430 and JP-A-12-273437 are also preferably used. Or you may add the ultraviolet absorber described in Unexamined-Japanese-Patent No. 10-152568.

  Among these ultraviolet absorbers, benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers are preferable ultraviolet absorbers. Although the specific example of a benzotriazole type ultraviolet absorber is given to the following, this invention is not limited to these.

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3) '-Tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy -3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethyl) Butyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl)- -Chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Specialty Chemicals), octyl-3- [ 3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Specialty Chemicals)
Specific examples of the benzophenone-based ultraviolet absorber are shown below, but the present invention is not limited thereto. 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane) It is done.

  The ultraviolet absorber may be added by dissolving the ultraviolet absorber in an organic solvent such as alcohol, methylene chloride, dioxolane and the like, or adding it directly to the dope composition. For an inorganic powder that does not dissolve in an organic solvent, it is preferable to use a dissolver or a sand mill in the organic solvent and the cellulose ester resin to disperse and then add to the dope. The amount of the ultraviolet absorber used is preferably 0.1% by mass to 2.5% by mass in consideration of the effect as an ultraviolet absorber, transparency, and the like. Furthermore, Preferably, it is 0.8 mass%-2.0 mass%.

  In addition, fine particles as a matting agent may be added to the cellulose ester-based resin film in order to prevent the films from sticking to each other or to impart slipperiness to facilitate handling. The fine particles include inorganic compound fine particles and organic compound fine particles. Inorganic compounds include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, etc. More preferred is an inorganic compound containing silicon or zirconium oxide, but silicon dioxide is particularly preferably used since the turbidity of the cellulose ester laminated film can be reduced.

  As fine particles of silicon dioxide, for example, AEROSIL-200, 200V, 300, R972, R972V, R974, R976, R976S, R202, R812, R805, OX50, TT600, RY50, RX50, NY50, NAX50, NA50H manufactured by Aerosil Co., Ltd. NA50Y, NX90, RY200S, RY200, RX200, R8200, RA200H, RA200HS, NA200Y, R816, R104, RY300, RX300, R106, and the like. Among these, AEROSIL-200V and R972V are preferable in terms of controlling dispersibility and particle size.

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

  As an organic compound, polymers, such as a silicone resin, a fluororesin, and an acrylic resin, are preferable, for example, Among these, a silicone resin is preferably used.

  Among the above-described silicone resins, those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (above Toshiba Silicone Co., Ltd.) ) Etc. can be used.

  The primary average particle size of the fine particles according to the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm, from the viewpoint of keeping the haze low.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter. Larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

  Silicon dioxide fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. Further, for example, Aerosil 200V and Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.) are commercially available, and these can be used.

  The apparent specific gravity was calculated by the following equation by measuring a weight of silicon dioxide fine particles in a graduated cylinder and measuring the weight at that time.

Apparent specific gravity (g / liter) = Mass of silicon dioxide (g) ÷ Volume of silicon dioxide (liter)
Examples of the method for preparing a dispersion of fine particles according to the present invention include the following three types.

<< Preparation Method A >>
After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the solvent and the fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose ester is added to the solvent and dissolved by stirring. As the cellulose ester added here, it is particularly preferable to add the solid material of the present invention. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose ester to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

  Preparation method A is excellent in dispersibility of silicon dioxide fine particles, and preparation method C is excellent in that silicon dioxide fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a preferable preparation method that is excellent in both dispersibility of the silicon dioxide fine particles and that the silicon dioxide fine particles are less likely to reaggregate.

《Distribution method》
The concentration of silicon dioxide when the silicon dioxide fine particles are mixed with a solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass. A higher dispersion concentration is preferable because liquid turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

  The amount of silicon dioxide fine particles added to cellulose ester is preferably 0.01 to 0.3 parts by mass, more preferably 0.05 to 0.2 parts by mass, and more preferably 0.0 to 0.2 parts by mass with respect to 100 parts by mass of cellulose ester. Most preferred is 08 to 0.12 parts by mass. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the lower the haze and the fewer agglomerates.

  As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersing silicon dioxide fine particles, a medialess disperser is preferred because of its low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. A high-pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.613 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  The high-pressure dispersing apparatus as described above includes an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer. Examples include UHN-01 manufactured by Wako Co., Ltd.

  These fine particles may be uniformly distributed in the thickness direction of the film, but it is more preferable that they are mainly distributed so as to exist mainly in the vicinity of the surface. It is preferable to add fine particles mainly to the dope arranged on the surface layer side using a dope of a seed or more because a film having high slip properties and low haze can be obtained. It is preferable to add fine particles mainly to two dopes on the surface layer side using three kinds of dopes.

  Moreover, the anti-glare film which has a preferable impedance can also be obtained by adding the electroconductive substance to the film of this invention. Although it does not specifically limit as an electroconductive substance, The antistatic agent etc. which have compatibility with an ionic electroconductive substance, electroconductive fine particles, or a cellulose ester can be used.

  Here, the ion conductive substance is a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples thereof include ionic polymer compounds.

  Examples of the ionic polymer compound include anionic polymer compounds such as those described in JP-B-49-23828, JP-A-49-23827, and JP-A-47-28937, such as JP-B-55-734, JP-A-50- An ionene type polymer having a dissociating group in the main chain, as shown in Japanese Patent No. 54672, Japanese Patent Publication Nos. 59-14735, 57-18175, 57-18176, 57-56059, etc. No. 13223, No. 57-15376, No. Sho 53-45231, No. 55-145578, No. 55-65950, No. 55-67746, No. 57-11342, No. 57-19735, No. Sho-58- No. 56858, JP-A 61-27853, and 62-9346, a cationic pender having a cationic dissociation group in the side chain It can be mentioned door type polymers, and the like.

Examples of the conductive fine particles include conductive metal oxides. As an example of the metal oxide, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , or a composite oxide thereof is preferable. In particular, ZnO, TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Nb, Ta, etc. to TiO ₂ , and addition of Sb, Nb, halogen elements, etc. to SnO ₂ . Addition is effective. The amount of these different atoms added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.

Further, the volume resistivity of these conductive metal oxide powders is 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less, the primary particle diameter is 10 nm or more and 0.2 μm or less, and the major structure has a long diameter. It is preferable that a powder having a specific structure of 30 nm or more and 6 μm or less contains 0.01% or more and 20% or less in volume fraction in at least a part of the region of the film.

  It is particularly preferable to contain an ionene conductive polymer described in JP-A-9-203810 or a quaternary ammonium cation conductive polymer having intermolecular crosslinking.

  The characteristic of the cross-linked cationic conductive polymer is the dispersible granular polymer obtained, and it can have a high concentration and high density of the cationic component in the particles, so it has not only excellent conductivity. No deterioration of conductivity was observed even under low relative humidity, and although the particles were well dispersed in the dispersed state, the adhesion of the particles was good in the film-forming process after coating, so the film strength was also low. It is strong and has excellent adhesion to other substances such as substrates, and has excellent chemical resistance.

  The dispersible granular polymer, which is a crosslinked cationic conductive polymer, generally has a particle size range of about 0.01 μm to 0.3 μm, preferably a particle size of 0.05 μm to 0.15 μm. As used herein, the term “dispersible particulate polymer” is a polymer that appears to be a clear or slightly turbid solution by visual observation but appears as a particulate dispersion under an electron microscope.

  The addition of the antistatic agent or matting agent is preferably included in the surface layer portion (portion of 10 μm from the surface) of the optical film, and the antistatic agent and / or matting agent is added to the surface of the film by a method such as co-casting. It is preferable to contain. Specifically, a dope A containing a conductive material and / or a matting agent and a dope B substantially not containing these are used, and the dope B is cast so that the dope A is present on at least one side of the dope B. It is preferable.

  If necessary, an antistatic agent, a flame retardant, a lubricant, an oil agent, a matting agent, and other additives may be added.

  The anti-glare film produced by the production method of the present invention can be used as an anti-glare anti-reflection film by providing at least one anti-reflection layer on the anti-glare film. It can be used for polarizing plates and liquid crystal display devices.

  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
(Preparation of an endless belt support whose surface is coated with an uneven resin layer)
An endless belt support shown in FIG. 1A having a resin layer having a surface centerline average roughness Ra of 3 μm was produced according to the flow shown in FIG.

(Preparation of substrate)
An endless belt-like substrate was prepared, which was held by two holding rolls as shown in FIG.

(Preparation of mold roll for forming uneven surface)
A stainless steel concave / convex surface forming mold roll having a diameter of 100 mm and a width of 1800 mm having a concave / convex shape with a center line average roughness Ra of 3 μm on the surface was prepared.

(Application of coating solution for resin layer formation)
A hopper was used as the resin layer forming coating solution shown below as a resin supply device, and the hopper was placed at a height of 3.3 mm from the endless belt surface at the position where the die was placed. Thereafter, one round was applied on the prepared substrate with a thickness of 1.0 mm and a width of 1800 mm, and the coating film was corrected with a sheathed heater to keep the thickness of the coating film constant.

Preparation of coating solution for resin layer formation
Resin: 30 parts by mass of gelatin
Solvent: 70 parts by weight of water
Hardener: 0.3 parts by weight of chrome alum Application conditions Substrate rotation speed 4 m / min
Coating liquid temperature 40 ℃
(Formation of irregularities on the surface of the resin layer)
After applying the resin layer forming coating solution on the substrate and making the thickness uniform, the prepared uneven surface forming mold roll is rotatably installed on the roll holding the substrate, and the pressing force is 50 N. / Cm, the endless belt support was moved at 4 m / min, and the uneven shape was transferred for one round. Thereafter, the resin coating film was cured by heat treatment at a temperature of 90 ° C. to fix the uneven shape, and an uneven shape with a center line average roughness Ra of 3 μm was formed on the surface. The center line average roughness Ra indicates a value measured using a CCD laser displacement sensor LK-080 manufactured by Keyence Corporation.

(Preparation of antiglare film)
(Preparation of dope)
<Fine particle dispersion>
Fine particles (Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.)) 11 parts by mass (average diameter of primary particles 16 nm, apparent specific gravity 90 g / liter)
89 parts by mass of ethanol or more was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle additive solution>
The following cellulose ester resin was added to a dissolution tank containing methylene chloride and heated to completely dissolve, and this was then added to Azumi Filter Paper No. Azumi Filter Paper No. Filtered using 244. While finely stirring the filtered cellulose ester solution, the fine particle dispersion was slowly added thereto. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.

Methylene chloride 99 parts by mass Cellulose acetate propionate (acetyl group substitution degree 1.5, propionyl group substitution degree 1.0, total acyl group substitution degree 2.5) 4 parts by mass Fine particle dispersion 11 parts by mass <Preparation of main dope >
A main dope having the following composition was prepared. First, methylene chloride as a good solvent and ethanol as a poor solvent were added to the pressure dissolution tank. Cellulose acetate propionate resin was added to a pressure dissolution tank containing a solvent while stirring. This was heated and stirred to completely dissolve, and a plasticizer and an ultraviolet absorber were further added and dissolved. This was designated as Azumi Filter Paper No. The main dope was prepared by filtration using 244.

  The main dope was added so as to be 100 parts by mass and 5 parts by mass of the fine particle additive solution, and sufficiently mixed with an in-line mixer (Toray static in-tube mixer Hi-Mixer, SWJ) to obtain a dope.

<Composition of main dope>
Methylene chloride 390 parts by mass Ethanol 80 parts by mass Cellulose acetate propionate (acetyl group substitution degree 1.5, propionyl group substitution degree 1.0, total acyl group substitution degree 2.5) 100 parts by mass Plasticizer: Aromatic terminal ester Sample No. 4 5 parts by mass Plasticizer: Trimethylolpropane tribenzoate 5.5 parts by mass UV absorber: Tinuvin 109 (manufactured by Ciba Specialty Chemicals)
1 part by mass UV absorber: Tinuvin 171 (manufactured by Ciba Specialty Chemicals)
1 part by mass (production of antiglare film)
The prepared endless belt support having a concavo-convex shape with a center line average roughness Ra of 3 μm formed on the surface is used, and the manufacturing apparatus shown in FIG. 1 (a) is used on the endless belt support in the casting process. The prepared dope was cast with a casting width of 1780 mm. The amount of residual solvent when the web is peeled off by changing the casting speed is changed as shown in Table 1, and after passing through the first drying process, stretching process, second drying process, and winding process, the width is 1500 mm and the thickness is 80 μm. An antiglare film was prepared under the conditions shown below and sample No. 101-105.

  The value of the residual solvent amount (% by mass) is determined by assuming that the mass of the web (antiglare film) when the web (antiglare film) having a certain size is dried at 115 ° C. for 1 hour is B, and the web before drying. When the mass of (antiglare film) is A, ((A−B) / B) × 100 = value obtained by the amount of residual solvent (mass%).

  The drying conditions after the casting process are shown below.

Drying conditions for the first drying step The peel tension from the endless belt support was set at 150 N / m, and the drying temperature for the first drying step was 50 ° C.

Drying conditions for the second drying step The drying temperature for the second drying step was 110 ° C.

Winding process The winder was wound at a tension of 200 N / m using a constant tension method.

Evaluation Each sample No. Table 1 shows the results obtained by measuring the antiglare property according to the following methods and evaluating according to the following evaluation ranks.

Measurement method of anti-glare property Place each sample on a flat and flat table, and arrange a 40W fluorescent lamp (Matsushita Electric FLR40S-EX-D / M) with a height of 1.5m so that the sample table can be illuminated obliquely. The height is fixed and the reflection is judged visually.

Evaluation rank of anti-glare ○: The outline of the fluorescent lamp and the external light are blurred and the reflection is not at all △: The outline of the fluorescent lamp and the reflection of the external light are slightly recognized ×: The outline of the fluorescent lamp , And understand the external light

  The effectiveness of the present invention was confirmed.

Example 2
(Preparation of an endless belt support whose surface is coated with an uneven resin layer)
An endless belt support shown in FIG. 1A having a resin layer having a surface centerline average roughness Ra of 3 μm was produced according to the flow shown in FIG.

(Preparation of substrate)
An endless belt-like substrate was prepared, which was held by two holding rolls as shown in FIG.

(Application of coating solution for resin layer formation)
A coating solution for forming a resin layer containing particles having an average particle size of 3 μm shown below was used as a resin supply device using a hopper so as to be 3.3 mm in height from the endless belt surface at the position of the die. Thereafter, one round was applied on the prepared substrate with a thickness of 1 mm and a width of 1800 mm, and the coating film was corrected with a sheathed heater to keep the thickness of the coating film constant.

Preparation of coating solution for resin layer formation
Resin: 30 parts by mass of gelatin
Solvent: 70 parts by weight of water
Hardener: Chrome alum 0.3 parts by mass
Particles: 9 parts by mass of silica The dispersion of the particles is T.K. K. The dispersion was prepared by stirring with a homomixer MARKII.

Application condition Substrate rotation speed 4m / min
Temperature 40 ℃
(Formation of irregularities on the surface of the resin layer)
After applying a coating solution for forming a resin layer on the substrate and making the thickness uniform, heat treatment is performed at a temperature of 90 ° C. to cure the resin coating, and an uneven surface with a center line average roughness Ra of 3 μm A resin layer having was formed. The center line average roughness Ra was measured by the same method as in Example 1.

(Preparation of antiglare film)
(Preparation of dope)
<Fine particle dispersion>
The same fine particle dispersion as in Example 1 was prepared in the same manner as in Example 1.

<Fine particle additive solution>
The same fine particle additive solution as in Example 1 was prepared in the same manner as in Example 1.

<Preparation of main dope>
The same main dope as in Example 1 was prepared in the same manner as in Example 1.

(Preparation of antiglare film)
The prepared endless belt support having a concavo-convex shape with a center line average roughness Ra of 3 μm formed on the surface is used, and the manufacturing apparatus shown in FIG. 1 (a) is used on the endless belt support in the casting process. The prepared dope was cast with a casting width of 1780 mm. The amount of residual solvent when peeling the web by changing the casting speed is changed as shown in Table 2, and after passing through the first drying step, stretching step, second drying step, and winding step, the width is 1500 mm and the thickness is 80 μm. An antiglare film of No. 1 was prepared under the same conditions as in Example 1. 201-205.

Evaluation Each sample No. Table 2 shows the results obtained by measuring the antiglare property by the same method as in Example 1 and evaluating according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 3
(Preparation of an endless belt support whose surface is coated with an uneven resin layer)
The endless belt support shown in FIG. 1A having a resin layer having a surface centerline average roughness Ra as shown in Table 4 was produced according to the flow shown in FIG.

(Preparation of substrate)
An endless belt-like substrate was prepared, which was held by two holding rolls as shown in FIG.

(Preparation of mold roll for forming uneven surface)
As shown in Table 3, two concave / convex surface forming mold rolls having a diameter of 100 mm and different in centerline average roughness Ra were prepared. 3-a to 3-e.

(Application of coating solution for resin layer formation)
A hopper was used as the resin layer forming coating solution shown below as a resin supply device, and was installed at a die installation position so that the height was 3.3 mm from the endless belt surface. Thereafter, one round was applied on the prepared substrate with a thickness of 1.0 mm and a width of 1800 mm, and the coating film was corrected with a sheathed heater to keep the thickness of the coating film constant.

Preparation of coating solution for resin layer formation
Resin: 30 parts by mass of gelatin
Solvent: 70 parts by weight of water
Hardener: 0.3 parts by weight of chrome alum Application conditions Substrate rotation speed 4 m / min
Temperature 40 ℃
(Formation of irregularities on the surface of the resin layer)
After applying a coating solution for forming a resin layer on the substrate and making the thickness uniform, two sets of prepared mold roll No. 3-a to 3-h are rotatably installed on the roll holding the substrate at a right angle to the conveying direction of the endless belt support, and the pressing force is 50 N / cm, and the endless belt support is 4 m / min. The concavo-convex shape was transferred to the resin coating for one round. Thereafter, the endless belt support coated with a resin layer having a surface center line average roughness Ra as shown in Table 4 is fixed by heating and curing the resin coating film at a temperature of 90 ° C. Prepare No. 3-1 to 3-5. The center line average roughness Ra was measured by the same method as in Example 1.

(Preparation of antiglare film)
(Preparation of dope)
<Fine particle dispersion>
The same fine particle dispersion as in Example 1 was prepared in the same manner as in Example 1.

<Fine particle additive solution>
The same fine particle additive solution as in Example 1 was prepared in the same manner as in Example 1.

<Preparation of main dope>
The same main dope as in Example 1 was prepared in the same manner as in Example 1.

(Preparation of antiglare film)
The prepared endless belt support No. 3-1 to 3-6 were used, and the dope prepared on the endless belt support in the casting process was cast with a casting width of 1780 mm using the manufacturing apparatus shown in FIG. The amount of residual solvent when the web is peeled off by changing the casting speed is changed as shown in Table 5, and after passing through the first drying step, stretching step, second drying step, and winding step, the width is 1500 mm and the thickness is 80 μm. An antiglare film of No. 1 was prepared under the same conditions as in Example 1. 301 to 323.

Evaluation Each sample No. Table 5 shows the results of measuring 301 to 323 and measuring the antiglare property by the same method as in Example 1 and evaluating according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 4
(Preparation of an endless belt support whose surface is coated with an uneven resin layer)
An endless belt support shown in FIG. 1A having a resin layer having a surface centerline average roughness Ra as shown in Table 8 was prepared according to the flow shown in FIG.

(Preparation of substrate)
An endless belt-like substrate was prepared, which was held by two holding rolls as shown in FIG.

(Preparation of particles)
Two types of particles A and B having different average particle diameters as shown in Table 6 were prepared, and mixed particles mixed at a ratio as shown in Table 6 were prepared. 4-a to 4-e. The mixing ratio of the particles indicates the mixing ratio (%) when the resin layer forming coating solution is prepared. Silica was used for the particles.

(Preparation of coating solution for resin layer formation)
The prepared mixed particle No. 4-a to 4-e were used to prepare a resin layer forming coating solution having the composition shown below. 4-A to 4-E.

Preparation of coating solution for resin layer formation
Resin: 30 parts by mass of gelatin
Solvent: 70 parts by weight of water
Hardener: Chrome alum 0.3 parts by mass
Particle: Mixed particle No. 4-a to 4-e 9 parts by mass See Table 6 for the mixing ratio of the mixed particles. The particles were dispersed by the same method as in Example 2.

(Application of coating solution for resin layer formation)
Each of the prepared coating solutions for resin layer formation No. 4-A to 4-E were used as resin supply devices using a hopper, and were installed at a die installation position so that the height from the surface of the endless belt was 3.3 mm. Thereafter, one round was applied on the prepared substrate with a thickness of 1.0 mm and a width of 1800 mm, and the coating film was corrected with a sheathed heater to keep the thickness of the coating film constant.

Application condition Substrate rotation speed 4m / min
Temperature 40 ℃
(Formation of irregularities on the surface of the resin layer)
Each coating solution for forming a resin layer No. After 4-A to 4-E are applied and the thickness is made uniform, the resin coating film is cured by heat treatment at a temperature of 90 ° C., and has a surface centerline average roughness Ra as shown in Table 7. An endless belt support coated with a resin layer was prepared. 4-1 to 4-5. The center line average roughness Ra was measured by the same method as in Example 1. A resin layer was formed. The center line average roughness Ra was measured by the same method as in Example 1.

(Preparation of antiglare film)
(Preparation of dope)
<Fine particle dispersion>
The same fine particle dispersion as in Example 1 was prepared in the same manner as in Example 1.

<Fine particle additive solution>
The same fine particle additive solution as in Example 1 was prepared in the same manner as in Example 1.

<Preparation of main dope>
The same main dope as in Example 1 was prepared in the same manner as in Example 1.

(Preparation of antiglare film)
The prepared endless belt support No. 4-1 to 4-5 were used, and the dope prepared on the endless belt support in the casting process was cast at a casting width of 1780 mm using the manufacturing apparatus shown in FIG. The amount of residual solvent when the web is peeled off by changing the casting speed is changed as shown in Table 8, and after passing through the first drying step, stretching step, second drying step, and winding step, the width is 1500 mm and the thickness is 80 μm. An antiglare film of No. 1 was prepared under the same conditions as in Example 1. 401 to 423.

Evaluation Each sample No. Table 8 shows the results obtained by measuring the antiglare property by the same method as in Example 1 and evaluating according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

Example 5
(Preparation of an endless belt support whose surface is coated with an uneven resin layer)
An endless belt support shown in FIG. 1 (a) having a resin layer with the surface centerline average roughness Ra varied was produced according to the flow shown in FIG.

(Preparation of substrate)
An endless belt-like substrate was prepared, which was held by two holding rolls as shown in FIG.

(Preparation of mold roll for forming uneven surface)
A mold roll for forming a concave / convex surface made of stainless steel having a diameter of 100 mm and a width of 1800 mm having a concave / convex shape whose center line average roughness Ra was changed as shown in Table 9 was prepared. 5-a to 5-h.

(Application of coating solution for resin layer formation)
A hopper was used as the resin layer forming coating solution shown below as a resin supply device, and was installed at a die installation position so that the height was 3.3 mm from the endless belt surface. Thereafter, one round was applied on the prepared substrate with a thickness of 1.0 mm and a width of 1800 mm, and the coating film was corrected with a sheathed heater to keep the thickness of the coating film constant.

Preparation of coating solution for resin layer formation
Resin: 30 parts by mass of gelatin
Solvent: 70 parts by weight of water
Hardener: 0.3 parts by weight of chrome alum Application conditions Substrate rotation speed 4 m / min
Temperature 40 ℃
(Formation of irregularities on the surface of the resin layer)
After applying the resin layer forming coating solution on the substrate and making the thickness uniform, each prepared uneven surface forming mold roll No. 5-a to 5-h are sequentially installed on a roll holding the base body so as to be rotatable at right angles to the conveying direction of the endless belt support, with a pressing force of 50 N / cm and an endless belt support of 4 m / min. The concavo-convex shape was transferred to one round. Thereafter, the resin coating film is cured by heat treatment at a temperature of 90 ° C. to fix the uneven shape, and an endless belt support having an uneven shape having a center line average roughness Ra as shown in Table 10 is formed on the surface. No. 5-1 to 5-8.

  The center line average roughness Ra was measured by the same method as in Example 1.

(Preparation of antiglare film)
(Preparation of dope)
<Fine particle dispersion>
The same fine particle dispersion as in Example 1 was prepared in the same manner as in Example 1.

<Fine particle additive solution>
The same fine particle additive solution as in Example 1 was prepared in the same manner as in Example 1.

<Preparation of main dope>
The same main dope as in Example 1 was prepared in the same manner as in Example 1.

(Preparation of antiglare film)
The prepared endless belt support No. 5-1 to 5-8 are used in the production apparatus shown in FIG. 1A, and the dope prepared on the endless belt support in the casting process is cast with a casting width of 1780 mm. The amount of residual solvent when the web is peeled off by changing the casting speed is changed as shown in Table 11, and after passing through the first drying step, stretching step, second drying step, and winding step, the width is 1500 mm and the thickness is 80 μm. An antiglare film of No. 1 was prepared under the same conditions as in Example 1. 501-549.

Evaluation Each sample No. Table 11 shows the results obtained by measuring the antiglare property by the same method as in Example 1 and evaluating according to the same evaluation rank as in Example 1.

  The effectiveness of the present invention was confirmed.

It is a schematic diagram of the manufacturing apparatus of the anti-glare film by a solution casting method. FIG. 2 is an enlarged schematic view of the endless belt support shown in FIG. It is a schematic flowchart of the method of forming an uneven | corrugated shape on the surface of a resin layer using a casting_mold | template. It is a schematic flowchart of the method of forming uneven | corrugated shape on the surface of a resin layer using particle | grains.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a, 1a 'Manufacturing apparatus 101, 101' Casting process 101a Endless belt support 101a3 Metal belt support 101a4 Resin layer 101a5 Surface 101'a Endless drum support 101b, 101'b Casting die 101c, 101'c Heating device 101c1, 101'c1 Drying box 101d First heated air supply device 101e Second heated air supply device 101'd Heated air supply device 102 First drying step 103 Stretching step 104 Second drying step 105 Winding step 2, 2 'Dope 3, 3 'web 4, 4' peeling roll

Claims (7)

A dope in which a resin is dissolved in a solvent is cast on an endless support that is continuously rotated to form a web, and then the web is peeled off from the endless support and dried. A method for producing an antiglare film having an uneven surface,
The surface of the endless support is coated with a resin layer having an uneven shape,
After casting the dope on the resin layer to form a web,
By peeling the web in a state where the residual solvent is 30% to 80% and drying,
A method for producing an antiglare film having an uneven surface, wherein the uneven shape is transferred to form the uneven surface. 2. The antiglare property having an uneven surface according to claim 1, wherein the resin layer is formed with an uneven surface by forming a resin layer on an endless support and then pressing a mold against the resin layer. A method for producing a film. The resin layer is characterized in that, after forming a resin layer on an endless support, a mold having at least two different center line average roughness Ra is pressed against the resin layer to form an uneven shape. Item 2. A method for producing an antiglare film having an uneven surface according to Item 1. 2. The uneven surface according to claim 1, wherein the resin layer is formed by applying a resin layer forming solution to which a particulate material is added on an endless support to form an uneven shape on the surface of the resin layer. A method for producing an antiglare film. The resin layer is characterized in that a resin layer forming solution to which a particulate material having at least two different average particle diameters is applied is applied onto an endless support, and an uneven shape is formed on the surface of the resin layer. The manufacturing method of the anti-glare film which has an uneven surface of Claim 1. 6. The method for producing an antiglare film according to claim 1, wherein the uneven shape formed on the surface of the resin layer has a center line average roughness Ra of 3 μm to 10 μm. An anti-glare film produced by the method for producing an anti-glare film according to claim 1.

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