JP5614436B2 - Method for correcting a shaped plate for manufacturing an antireflective article and method for manufacturing a shaped plate for manufacturing an antireflective article - Google Patents

Description

  The present invention relates to a mold for manufacturing an antireflection article used for manufacturing an antireflection article for preventing reflection by closely arranging a number of microprotrusions at intervals of not more than the shortest wavelength of the wavelength band of electromagnetic waves for preventing reflection. It relates to a manufacturing method.

  In recent years, regarding an antireflection film, which is a film-shaped antireflection article, there has been proposed a method for preventing reflection by arranging a large number of microprotrusions closely on the surface of a transparent substrate (transparent film) (patent) Reference 1-6). This method utilizes the principle of a so-called moth-eye structure, and the refractive index for incident light is continuously changed in the thickness direction of the substrate, whereby a discontinuous interface of refractive index is obtained. Is eliminated to prevent reflection.

  Such a moth-eye structure uses a mold for manufacturing a mold or the like having a shape obtained by inverting a fine concavo-convex shape composed of a large number of microprojections, and transfers the concavo-convex shape to an arbitrary resin layer. In general, it is manufactured by molding. Accordingly, as a method for producing an antireflection film having a moth-eye structure, a resin layer is formed on a substrate with a curable resin such as an ultraviolet curable resin, and then the resin layer is formed using the above-described production plate. A method of forming a moth-eye structure on the surface of the material and further curing the resin layer can be used. According to such a production method, the antireflection film can be continuously produced by a simple method and with high production efficiency.

  Further, as the mold plate having the moth-eye structure, a mold having a recess formed by a laser interference method (for example, Patent Documents 1 to 3) or a mold having a recess formed by an anodic oxidation method (for example, a patent document) 4-6) are used. Among them, the anodic oxidation method has advantages in that the position where the recess is formed can be made random, and that a recess having a uniform shape over a large area can be formed. For example, those formed by anodic oxidation have been widely used.

  This anti-reflective article is desired to be efficiently produced by a roll-to-roll method using a so-called roll plate formed on the peripheral side surface of a concavo-convex shape for forming a moth-eye structure as a forming plate. Various ideas have been proposed for production using such a roll plate (Patent Document 7).

  By the way, it has been found that the roll plate used for forming this type of moth-eye structure is deteriorated by production, and as a result, the properties of the antireflection article are deteriorated. When this point was examined in detail, there was a case where the fine concavo-convex structure was attached to the resin layer subjected to shaping and partially peeled off from the roll plate during peeling after shaping. As a result, it was found that a point-like or area-like defect occurred in the roll plate.

  Thus, it was necessary to regenerate and replace the shaping plate having the same fine uneven structure as before the deterioration. For example, when the mold plate is a general mold, as a method for reducing a large amount of cost for this replacement, Patent Document 2 discloses a fine unevenness as a mold used for molding a moth-eye structure. There is disclosed a method of using a replica mold (master plate) manufactured through a replication process by mold taking and reversing once or twice from the original mold instead of the original mold (mother plate) whose shape is first formed. . Since the master plate of the mold can be readily reproduced from the mother plate, this method is excellent in industrial productivity, cost, etc., and can easily be replaced when the mold is deteriorated.

  However, the method of remanufacturing and replacing the anti-reflective article manufacturing plate every time it is finely deteriorated is not limited to the mold, for example, a resin-based molding plate. Nevertheless, it still remains a major factor in raising the running cost of the production line for anti-reflective articles, and a new method that can keep the running cost of the entire production line lower has been demanded.

JP-T-2001-517319 JP 2004-205990 A JP 2004-287238 A JP 2001-272505 A JP 2002-286906 A International Publication No. 2006/059686 Pamphlet JP 2005-156695 A

  The present invention has been made in view of such circumstances, and relates to a mold for producing an antireflection article used for producing an antireflection article having a so-called moth-eye structure. It is an object of the present invention to provide a method for correcting a shaped plate for manufacturing an antireflective article, which can correct deterioration of a fine concavo-convex structure for use in a simple method.

  The present inventor has conducted extensive research to solve the above-mentioned problems, and as a countermeasure against the deterioration of the mold, this is discarded and the new mold is not re-produced. This led to the idea that the deteriorated portion is filled with a curable resin, and this curable resin is molded with a film having a moth-eye structure, thereby correcting the deteriorated portion of the deteriorated mold. The invention has been completed.

    Specifically, the present invention provides the following.

  (1) A method for correcting a deteriorated portion of a shaping plate for manufacturing an antireflective article used for forming an uneven shape of an antireflective article, the step of filling the deteriorated portion with a curable repair agent, and the uneven shape being a surface A step of pressing the curable repair plate formed on the surface to the curable repair agent to form a concavo-convex shape on the curable repair agent, and curing the curable repair agent on which the concavo-convex shape is shaped The correction method of the shaping plate for anti-reflective article manufacture provided with a process and the process of peeling the said shaping plate for repair from the said curable repair agent.

  According to (1), when a part of the concavo-convex shape of the shaping plate for manufacturing an antireflective article is deteriorated, only the deteriorated portion is corrected by a simple method without requiring a complete replacement of the shaping plate. be able to.

  (2) The method for correcting a shaped plate for producing an antireflective article according to (1), wherein the curable repair agent is an ultraviolet curable resin.

  According to (2), since the ultraviolet curable resin is excellent in processing suitability at the time of correction, the deteriorated portion can be corrected accurately with higher accuracy.

  (3) The method for correcting a shaped plate for producing an antireflective article according to (1), wherein the curable repair agent is liquid glass.

  According to (3), since the liquid glass has a high hardness after curing, it is possible to further improve the durability of the modified anti-reflective article-manufacturing shaped plate.

  (4) The mold plate for repair is the same shape or substantially the same shape as the mold plate having the same or substantially the same shape as the mold plate for manufacturing the antireflective article, and has a concavo-convex relationship. The method for correcting a shaped plate for producing an antireflective article according to any one of (1) to (3), which is a film in which an inverted uneven shape is shaped.

  According to (4), for example, a film in which the concavo-convex shape is formed by the anti-reflective article manufacturing shaping plate can be used as a repairing shaping plate for correcting a deteriorated portion of the shaping plate. As a result, it is possible to obtain a repairing plate at a low cost, and to greatly reduce the cost for the correction of the antireflection article manufacturing plate.

  (5) A method for producing an antireflective article-making shaped plate used for forming an uneven shape of an antireflective article, wherein the anti-reflective article-producing shaped plate according to any one of (1) to (4) The manufacturing method of the shaping plate for anti-reflective article manufacture provided with the correction process of the uneven | corrugated shape by the correction method of this.

  According to (5), the maintenance cost of the shaping plate in the manufacturing process of the antireflection article can be reduced, and the total production cost can be compressed while maintaining the quality of the antireflection article.

  With respect to the antireflection article having the moth-eye structure, when a part of the shaping plate is deteriorated as production continues, the deteriorated part can be repaired easily and at low cost.

It is a figure which shows the anti-reflective article which can be manufactured with the shaping | molding plate for anti-reflective article manufacture which concerns on this invention. It is a figure where it uses for description of the manufacturing process which manufactures an antireflective article with the shaping plate for antireflective article manufacture which concerns on this invention. It is a figure where it uses for description of the correction method of the shaping plate for anti-reflective article manufacture of this invention.

<Anti-reflective article manufacturing mold plate and anti-reflective article manufactured thereby>
FIG. 1 is a view showing an antireflection article having a moth-eye structure, which is a typical example of an antireflection article that can be produced by a shaping plate for producing an antireflection article according to the present invention. This antireflection article 1 is manufactured by forming an antireflection surface 3 having a fine uneven shape on a base material 2 made of a transparent film. Here, as the substrate 2, various transparent films such as TAC (Triacetylcellulose), acrylic, PET (Polyethylene terephthalate), PC (Polycarbonate), and the like can be applied. On the surface of the base material 2, a fine uneven shape is formed on the curable resin 4 such as an ultraviolet curable resin by using a shaping plate for producing an antireflective article such as a mold for producing an antireflective article. By doing so, the antireflection surface 3 is formed. The antireflection article 1 is formed so that the refractive index gradually changes in the thickness direction due to the fine uneven shape of the antireflection surface 3, and the reflection of incident light can be prevented in a wide wavelength range by the principle of the moth-eye structure. it can.

  Further, the fine uneven shape formed on the antireflection surface 3 may be formed by a large number of single-peaked protrusions having a single apex, but is not limited thereto. . For example, it is more preferable that at least some of the convex portions are multimodal convex portions having a plurality of vertices. Such a multi-peak convex portion having a plurality of vertices has a relatively thicker hem portion relative to the size in the vicinity of the vertex than a single-peak convex portion. Thereby, it can be said that the multimodal convex part is excellent in mechanical strength compared with the monomodal convex part. Accordingly, when there are multi-peaked convex portions having a plurality of vertices, it is considered that the antireflection article has improved scratch resistance as compared with the case of only the single-peaked convex portions. Furthermore, when external force is applied to the anti-reflective article, the external force is distributed and received at more vertices than when only a single-peaked convex part is used. Thus, it is possible to make the protrusions difficult to damage, thereby reducing local deterioration of the antireflection function and further reducing the occurrence of appearance defects.

  FIG. 2 is a diagram illustrating a manufacturing process of the antireflection article 1. In this manufacturing process, first, the curable resin 4 is applied to the substrate 2 by a die (not shown) (A). In addition, about application | coating of the curable resin 4, not only the case by a die | dye but various methods are applicable. Subsequently, the pressing roller 6 presses and presses the anti-reflective article producing mold plate 5 and the substrate 2, thereby bringing the curable resin 4 into close contact with the substrate 2, and forming the anti-reflective article producing step. The fine recesses formed on the surface of the plate 5 are sufficiently filled with the curable resin 4 (B). In this state, for example, when the curable resin 4 is an ultraviolet curable resin, the curable resin 4 is cured by irradiation with ultraviolet rays, thereby forming a fine uneven shape (C). Then, the base material 2 is peeled from the shaping plate 5 for manufacturing an antireflective article through a peeling roller (not shown) (D).

  In FIG. 2, the case where the anti-reflective article manufacturing shaping plate 5 is in the form of a sheet has been described in order to simply explain the method of manufacturing the anti-reflective article. As a metal roll-shaped mold, the concavo-convex shape of the mold is continuously formed on a long base material 2 made of a roll material by a roll-to-roll process. An antireflection article having a structure can be mass-produced extremely efficiently.

  Here, the concavo-convex shape of the shaping plate 5 for producing an antireflection article can be formed by various conventionally known methods. As a typical example, when the shaping plate for manufacturing an antireflection article is a metal mold, the wavelength of visible light is obtained by utilizing anodization of aluminum on the peripheral side surface of a metallic base material. Fine irregularities can be formed with the following repetition cycle. For this reason, the metal mold is manufactured using a material in which the base material itself is made of aluminum, or is provided with an aluminum layer directly on the surface of the base material made of copper or the like or through various intermediate layers. be able to. The uneven shape when the shaping plate 5 for manufacturing an antireflective article is a metal mold is formed by densely forming fine holes in the aluminum layer of the metal base material by repeating anodizing treatment and etching treatment. The fine hole can be formed by digging and gradually increasing the diameter of the fine hole. As a result, fine holes with a gradually decreasing hole diameter are formed densely in the metal base material. By using such a mold as the shaping plate 5 for manufacturing the antireflective article, a fine uneven shape corresponding to the fine holes can be formed on the surface of the antireflective article 1. In addition, as said metal base material, copper, stainless steel, etc. can also be used, and Ni, Ti, Cr, etc. can also be laminated | stacked on the outermost surface layer.

  The anti-reflective article producing mold plate 5 does not necessarily have to be a mold as described above, and the mother of the anti-reflective article producing mold plate 5 is made of a resin, glass, film, or the like. It is also possible to use it as a material, and the correction method for the anti-reflective article-manufacturing plate of the present invention (hereinafter also simply referred to as “correction method”) is, of course, in the correction of these non-metal forming plates. Can also be preferably used. However, a more remarkable cost reduction effect can be obtained by applying to a large roll-shaped mold in which fine holes are formed by anodic oxidation as described above, such as those with high replacement costs.

<Method for correcting a shaped plate for production of antireflective articles>
Before describing the details of the correction method of the present invention, first, an example of a process of generating the deteriorated portion 52 of the shaping plate 5 for manufacturing an antireflective article, which is a processing target of the correction method of the present invention, will be described. . In the manufacturing process of the antireflection article 1 shown in FIG. 2, when the base material 2 after molding is peeled off (FIG. 2D), the concavo-convex shape of the shaping plate 5 for manufacturing the antireflection article is very small. A part may adhere to the curable resin 4 and be peeled off locally from the shaping plate 5 for producing an antireflective article. Thereby, the deterioration part 52 generate | occur | produces because deterioration of the uneven | corrugated shape of the shaping plate 5 for antireflective article manufacture (FIG. 3 (A)) progresses gradually (FIG. 3 (B)).

  Conventionally, as a countermeasure against such partial deterioration, the shaped plate 5 for manufacturing an antireflective article is continuously used as long as the deterioration mode and area of the deteriorated part 52 are practically acceptable, and the deteriorated part When the deterioration mode of 52 or the area of the deteriorated portion exceeded the allowable range, the shaping plate 5 for manufacturing the antireflective article was completely replaced.

  However, as shown in FIG. 3, according to the correction method of the present invention, as will be described in detail below, the deterioration portion 52 can be corrected by a simple method while sufficiently recovering the reflection performance of the antireflection article. By carrying out in a unique way, the life until the replacement of the shaping plate 5 for manufacturing the antireflective article can be greatly extended, thereby increasing the productivity of the antireflective article and improving the overall manufacturing process. Operating costs can be greatly reduced.

  FIG. 3 is a diagram schematically showing the process in each step of the method for correcting the shaping plate 5 for manufacturing an antireflective article when a deteriorated portion 52 occurs in a part of the shaping plate 5 for manufacturing an antireflective article. is there. Hereinafter, with reference to FIG. 3, specific details of the method for correcting a shaped plate for producing an antireflective article according to the present invention will be described.

  FIG. 3A is a schematic diagram of the shaping plate 5 for manufacturing an antireflective article in a state where no deterioration has occurred. On the other hand, FIG. 3 (B) is a schematic view of the shaped plate 5 for manufacturing an antireflective article in a state in which deterioration has progressed and the deteriorated portion 52 has expanded to an area that requires correction.

  When a deteriorated portion 52 as shown in FIG. 3 (B) is generated in the anti-reflective article manufacturing shaped plate 5, in the correction method of the present invention, first, as shown in FIG. 3 (C), deterioration occurs. The curable repair agent 7 is dropped by the dispenser 8 onto the deteriorated portion 52 of the anti-reflective article manufacturing shaping plate 5 which has been progressed, and an appropriate amount is filled.

  Curing repair agent 7 includes urethane acrylate, acrylate monomer, UV curable resin containing 2-hydroxypropyl acrylate, liquid glass, thermosetting resin, water glass, acrylate resin (instant adhesive) Etc.) can be used as appropriate. Among these, an ultraviolet curable resin or liquid glass can be particularly preferably used as the curable repair agent 7.

  As the ultraviolet curable resin, a conventionally known resin can be used without any particular limitation. Specifically, a product name “3021J” (manufactured by Three Bond Co., Ltd.) or the like that can be easily obtained from the market can be preferably used. The UV curable resin can be easily adjusted for the amount of dripping depending on the size of the deteriorated part (applicability for minute amount application by viscosity and surface tension), is easy to cure, and has little thermal dependence, so the dimensional change with temperature It is difficult to cause post-deformation. Furthermore, the effect of volume change due to the curing reaction can be reduced, the hardness of the material can be adjusted, and the workability at the time of correction is excellent. Therefore, it is preferable as the curable repair agent 7 in that it can be more accurately corrected so as to bring the deteriorated portion closer to the state before deterioration. In addition, since the material affinity with the resin-based molding plate is particularly good, it can be particularly preferably used when a resin-made molding plate for producing an antireflection article is modified.

A conventionally well-known liquid glass can be used without particular limitation. The liquid glass is a silica solution whose main component is silicon dioxide (SiO ₂ ) and exists as a liquid at room temperature in a sealed container or the like. When this is applied to the object surface and kept in contact with air, it can be cured to a solid glassy material. Specifically, a product name “room temperature stable glass (glass paint)” (manufactured by Moritec Kamemura Glass Paint Division Co., Ltd.) and the like which can be easily obtained from the market can be preferably used. Liquid glass has high hardness and is excellent in durability when used as a shaping plate. Therefore, it is preferable as the curable repair agent 7 in that the durability of the modified anti-reflective article production shaped plate can be further improved. The curing process is relatively easy, and in particular when a solvent system is selected, the surface tension can be adjusted, and the volume change during curing can be suppressed.

  Subsequently, in the correction method of the present invention, as shown in FIG. 3 (D), the curing mold plate for repair 9 having a concavo-convex shape formed on the surface thereof is in a state where curing is slightly advanced within a moldable range. A concavo-convex shape is formed on the curable repair agent 7 by pressing against the curable repair agent 7 in a semi-cured state (FIG. 3E).

  As the repairing plate 9 for repair, corresponding unevenness capable of forming a desired uneven shape on the surface of the semi-cured curable repair agent 7 filled in the deteriorated portion of the antireflection article manufacturing plate 5 A resin film, a resin sheet, or a metal plate having a shape formed on the surface thereof can be used. In particular, if the uneven shape of the non-deteriorated portion 51 of the shaping plate 5 for manufacturing an antireflective article and the corresponding uneven shape in which the unevenness is reversed, or a similar uneven shape, such a resin film is used. Can be used more preferably.

  Furthermore, for example, the antireflective article 1 in which the concavo-convex shape is shaped by the shaping plate 5 for producing the antireflective article, itself, can be used as the shaping plate 9 for repair as it is. Such an antireflection article 1 is formed with a corresponding concavo-convex shape in which the concavo-convex is reversed with the non-deteriorated portion 51 of the shaping plate 5 for manufacturing the antireflective article. By pressing on the liquid surface of the repair agent 7, the same or substantially the same uneven shape as the non-deteriorated portion 51 can be formed on the liquid surface of the curable repair agent 7. According to this, it is not necessary to separately produce a repairing mold plate or the like having a desired special concavo-convex shape formed on its surface, and the correction method of the present invention can be carried out at a lower cost. The shape before deterioration can be reproduced very faithfully.

  After uneven | corrugated shape shaping | molding to the surface of said curable repair agent 7, the curable repair agent 7 of a semi-hardened state is hardened until it becomes desired hardness. Curing may be performed under necessary conditions according to the type of curable repair agent 7 and the required hardness.

  After the above curing, the curable repair agent 7 is obtained from the anti-reflective article manufacturing shaped plate 5 in which the uneven shape is corrected by forming the desired uneven shape in the place where the deteriorated portion 52 was formed. The repairing mold plate 9 that is pressed over the surface is peeled off (FIG. 3F). Thereby, the correction part 51A can be formed in the shaping plate 5 for manufacturing an antireflective article in which the deteriorated part 52 is generated, and the corrected antireflection article manufacturing mold 5A can be obtained.

  In addition, in the shaping plate 5 for manufacturing the antireflection article, the minimum area of the deteriorated portion 52 that needs to be modified varies depending on the deterioration mode and the antireflection performance required for the antireflection article 1, so it is unambiguous. It is not stipulated. However, in general, when the deteriorated portion 52 is substantially circular, for example, when the diameter is about 50 μm to 150 μm, a substantial adverse effect occurs on the antireflection article 1. It is necessary to modify the mold 5 for use. According to the correction method of the present invention, the above-described diameter can be easily applied to a minute deteriorated portion having a diameter of about 30 μm to 50 μm. Moreover, it is possible to cope with a further large deterioration portion.

<Other embodiments>
The specific configuration suitable for the implementation of the present invention has been described in detail above. However, the present invention is not limited to the configuration of the above-described embodiment, and further the conventional configuration without departing from the spirit of the present invention. Can be combined.

  For example, in the above-described embodiment, a correction method in the case where deterioration due to use has occurred in an existing anti-reflective article manufacturing mold plate has been described. However, the present invention is not limited to this, for example, a new anti-reflective article manufacture It can also be used as a method for performing a necessary correction process in the manufacturing process when manufacturing a mold for printing. Thus, the manufacturing method of the shaping plate for antireflective article manufacture which contains the method substantially the same as the correction method of this invention as the 1 step, and the shaping plate for antireflective article manufacture manufactured in this way Is also within the scope of the present invention.

  In addition, according to the correction method of the present invention, in the actual operation, with the deterioration of the surface irregularity shape, the metal anti-reflective article manufacturing shaped plate that was replaced in about 0.25 to 1 month has been conventionally used. It has been confirmed by an operational test that the period until the replacement is extended to about 2 to 4 times. The method for correcting a shaping plate for producing an anti-reflective article according to the present invention is a method of extending the life of the shaping plate for producing an anti-reflective article and shortening the operation stop period when replacing the shaping plate for producing an anti-reflective article. This is a method that can contribute to greatly increasing the productivity of the preventive article.

DESCRIPTION OF SYMBOLS 1 Antireflection article 2 Base material 3 Antireflection surface 4 Curable resin 5, 5A Molding plate for antireflection article manufacture 51 Non-deterioration part 51A Correction part 52 Deterioration part 6 Press roller 7 Curable repair agent 8 Dispenser 9 Repairing supplement Type plate

Claims (5)

A method for correcting a deteriorated portion of a shaping plate for producing an antireflective article used for forming an uneven shape of an antireflective article,
The concavo-convex shape is an concavo-convex shape formed by closely arranging a large number of microprojections at an interval equal to or shorter than the shortest wavelength of the wavelength band of the electromagnetic wave for preventing reflection,
The deteriorated portion is a recess formed by partially peeling away the uneven shape formed on the surface,
The correction method is as follows:
Filling the curable repair agent into the concave portion of the deteriorated portion by dripping a curable repair material ;
A step of pressing the repairing mold plate having a concavo-convex shape formed on the surface thereof to the curable repair agent dripped onto the deteriorated portion and shaping the concavo-convex shape onto the curable repair agent dripped onto the deteriorated portion. When,
A step of curing the curable repair agent having an uneven shape formed thereon;
A method of correcting the shaping plate for producing an antireflective article, comprising the step of peeling the shaping plate for repair from the curable repair agent.   The method for correcting a shaped plate for producing an antireflective article according to claim 1, wherein the curable repair agent is an ultraviolet curable resin.   The method for correcting a shaping plate for producing an antireflective article according to claim 1, wherein the curable repair agent is liquid glass.   The repairing plate is the same shape or substantially the same shape, and the concavo-convex relationship is reversed by the molding plate having the same or substantially the same uneven shape as that of the anti-reflective article manufacturing shaped plate. The method for correcting a shaped plate for production of an antireflective article according to any one of claims 1 to 3, wherein the uneven shape is shaped. A method for producing a shaped plate for the production of an antireflective article used for forming an uneven shape of an antireflective article,
The manufacturing method of the shaping plate for anti-reflective article manufacture provided with the correction process of the uneven | corrugated shape by the correction method of the shaping plate for anti-reflective article manufacture in any one of Claim 1 to 4.

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