JP5616191B2 - Mold for producing nanostructure and method for producing the same - Google Patents

Description

  The present invention relates to a mold for producing a nanostructure using a nanostructure, and more specifically, a nanostructure having improved strength, durability and the like for producing a nanostructure using a nanostructure. The present invention relates to a mold for manufacturing and a method for manufacturing the same.

  For flat panel displays (hereinafter abbreviated as “FPD”) such as liquid crystal display (LCD) and plasma display (PDP), it is indispensable to install an antireflection body such as an antireflection film in order to ensure the visibility It is. In addition, it may be necessary to suppress unnecessary reflection on a front plate such as a display shelf or a forehead; a cover plate such as a specimen box; a building material such as a window or a door; a surface of a structure such as an object;

  As such an antireflective body, (1) a method generally referred to as a dry method, that is, a dielectric multilayer film produced by a vapor phase process and realizing a low reflectance by an optical interference effect, (2) in general Known is a wet method, that is, a method in which a low refractive index material is coated on a substrate film. In addition, as a technique completely different from these, (3) a technique in which a low reflectivity is expressed by imparting a nanostructure to the surface is also known.

  Various studies have been made on nanostructures such as antireflective bodies provided with the nanostructure of (3) above as a method for improving the antireflection performance. For example, an anode formed by anodizing an aluminum material A method is known in which a combination of formation of an oxide film and etching of the anodic oxide film is used as a mold and the shape is transferred to a nanostructure such as an antireflection body (Patent Documents 1 to 6). .

Such a nanostructure is obtained by producing a template having tapered holes on the surface of an aluminum material by alternately repeating anodic oxidation and hole enlargement treatment, and transferring the template to the nanostructure-forming material. . That is, at least Patent Documents 2 and 4 to 6 describe a method for producing a mold made of anodized porous alumina having the following steps.
(1) A step of forming an alumina layer by anodizing an aluminum substrate.
(2) A step of removing the alumina layer.
(3) A step of forming the pores by anodizing again after the step (2).
(4) A step of subjecting the pores to a pore size expansion process.
(5) A step of anodizing again after the step (4).
(6) A step of alternately repeating the step (4) and the step (5).

  However, there has been little consideration for improving durability against repeated operations (transfer operations) in which a nanostructure forming material is embedded in a mold (template) and then the mold (template) is peeled off. However, no one has noticed a change in the performance of the nanostructure obtained after repeating the transfer operation, and has not studied the configuration and form of the mold, focusing on this.

  In the method using a template made of the above-mentioned anodized porous alumina, it is described that in step (6), the process ends with a pore diameter expansion process in order to generate an optimum tapered shape essential on the surface of the nanostructure as a template. ing.

  However, since the mold is made of aluminum, the mold is soft as the mold. If the mold is repeatedly transferred to the nanostructure forming material using the mold, the mold surface may be damaged or the mold surface may be worn. Thus, the durability of such a mold was extremely inferior. The anodized porous alumina layer on the surface of the mold is inherently high in hardness but thin, so it causes cracking, peeling, etc. due to stress, eventually affecting the softness of the underlying aluminum and inferior in durability. Conceivable.

  On the other hand, a technique for increasing the thickness of the anodized film of aluminum is known (for example, Patent Document 7). However, while maintaining various performances as a mold for producing a mold (template) having a nanostructure on the surface, that is, “a nanostructure such as an antireflection body using a nanostructure”, There is no known technique for increasing the thickness of the anodized film in order to improve durability as a mold. Furthermore, there has hardly been a problem per se for making the mold (template) for producing the nanostructure sufficiently durable to withstand repeated use.

  On the other hand, as a method for producing a mold (template) having a nanostructure on the surface, that is, a mold for producing a “nanostructure such as an antireflection body using a nanostructure”, etching is completed. It is considered preferable to obtain a good taper shape, and even if anodization is performed after the last etching, anodization is finally performed in a short time in order to reduce the bottom of the taper shape. However, durability was not required for the anodized film formed by anodization there (Patent Documents 4 and 6).

  In other words, there is no known technique for increasing the thickness of the anodized film as a mold, and in addition, in a mold that is normally considered to depend only on the hardness of the surface, increasing the thickness of the anodized film. Therefore, it is not known at all that the durability of the mold itself is improved, and the nanostructure obtained from the mold can be maintained in good form and physical properties after repeated use as a nanostructure mold.

  In order to improve durability, it is also known to improve durability, wear resistance, and peeling properties by using anodized porous alumina as a mold and obtaining a new mold having the same shape with a material such as metal. (Patent Documents 2 and 4 to 6), however, producing a new mold has problems such as a complicated process and cost.

JP 2003-043203 A JP 2005-156695 A JP 2007-086283 A JP 2009-299190 A JP 2009-258743 A WO2006 / 059686 Publication Japanese Patent Laid-Open No. 62-185898

  The present invention has been made in view of the above-described background art. The inventor first creates nanostructures in order to reduce the total number of steps, reduce the cost per nanostructure, and the like. I thought to make the mold for the purpose of durability. That is, the subject is providing the mold body for nanostructure preparation which has scratch resistance and durability to this mold body, and the manufacturing method of the mold body for nanostructure preparation.

  As a result of diligent studies to solve the above problems, the present inventor normally considered that only the hardness of the surface is effective, and “the mold for producing a nanostructure using a nanostructure” It has been found that the durability of the mold is improved by adjusting the form and film thickness of the anodic oxide film of the body. More specifically, in the anodic oxide film formed on the surface of the aluminum material, after forming the tapered layer having the tapered portion, the anodic oxide film is further formed to have a thickness greater than the thickness of the tapered layer. It was found that the durability of the mold was remarkably improved.

  For that purpose, the two steps of forming the anodized film and etching the anodized film are repeated on the surface of the aluminum material to create an anodized film having a tapered portion, and further anodizing is performed. Then, an anodic oxide film having a pore-shaped portion is formed below the anodic oxide film having a tapered shape portion, with a film thickness equal to or greater than that of the anodic oxide film having the tapered shape portion. The inventors have found that the durability of the mold is remarkably improved and have reached the present invention.

  That is, the present invention is a mold for producing a nanostructure using nanostructures, in which an anodized film is formed on the surface of an aluminum material. The pore has an average period of 50 nm to 400 nm with respect to the direction, and the pore is composed of a tapered portion and a pore-shaped portion below the tapered portion, and the tapered portion is wide open on the surface of the anodized film. And has a tapered shape that gradually becomes thinner as it enters the deep portion, and the pore-shaped portion has a pore shape with substantially the same diameter, and has a tapered shape having the tapered-shaped portion. The present invention provides a mold for producing a nanostructure characterized by having a pore-shaped layer having a pore-shaped portion continuously below the layer.

  The present invention also relates to a method of manufacturing a mold for producing a nanostructure using a nanostructure, wherein the aluminum material has pores with an average period of 50 nm or more and 400 nm or less in at least one direction. Two steps of forming an anodized film and etching the anodized film are repeated on the surface of the substrate to form a tapered layer having a tapered portion, and further, anodization is performed to form a lower portion of the tapered layer. And providing a method for producing a mold for producing a nanostructure, wherein a pore-shaped layer having a pore-shaped portion is formed so that the layer thickness is equal to or greater than the thickness of the tapered layer. is there.

  The present invention also provides a mold for producing a nanostructure, characterized in that the mold is produced using the method for producing a mold for producing a nanostructure.

  The present invention also provides a nanostructure-forming material or a material obtained by curing the nanostructure-forming material after the nanostructure-forming material is embedded in the nanostructure-producing mold. The present invention provides a nanostructure characterized by being peeled from a production mold.

  According to the present invention, it is possible to provide a mold for producing a nanostructure with improved strength, durability, and the like. Specifically, it is a mold for producing a nanostructure for producing a nanostructure that prevents reflection of light, and even if the nanostructure is produced continuously or intermittently, It is possible to provide a mold body for producing a nanostructure in which the mechanical strength, durability, etc. of the mold body are improved such that a large or fine scratch is hardly attached, the mold body is not easily worn away, and the nanostructure is not destroyed. .

  As a result, even if nanostructures produced using such molds are obtained from molds that have undergone repeated transfer processes, there is very little increase in reflectance and haze, and damage to molds The occurrence of defects in the nanostructure due to the above is extremely small. Accordingly, since many nanostructures can be obtained from one mold, it is possible to provide a mold for producing a nanostructure that always replicates a nanostructure having a stable and constant property.

  In addition, the nanostructure-forming mold of the present invention is applied by, for example, a nanostructure-forming material at the start or end of a printing machine that repeats embedding and peeling (transfer) of the nanostructure-forming material. It is possible to suppress the occurrence of “slipping” between the formed film and the mold body, and damage to the mold surface (particularly, the tapered shape portion).

  In addition, in the case where there is a risk that the surface of the mold body may be damaged due to the contamination of the nanostructure forming material with dust, foreign matter, etc., or the adhesion of foreign matter or foreign matter to the film substrate or mold body. The mold for producing a nanostructure can prevent scratches with a strong hardness. In particular, when using a continuous printing machine that repeatedly embeds and peels off (transfers) the nanostructure forming material, the nip pressure is increased so that the nanostructure forming material is completely embedded even if the printing speed is increased. Therefore, if small dust, foreign matter, etc. are mixed, the surface of the mold body is likely to be damaged. Particularly in that case, the mold for producing a nanostructure of the present invention has a high surface hardness. Since the strength is strong, it is possible to prevent such scratches.

It is a schematic diagram of the longitudinal cross-section which shows an example of the anodic oxide film in the mold for nanostructure production of this invention. It is a schematic diagram of the longitudinal cross-section which shows an example of the anodic oxide film in the conventional mold body for nanostructure production. (Example 4) which is a 10,000 times SEM photograph of the longitudinal cross-section of the whole anodized film in the nanostructure preparation mold of the present invention. 100,000 times the longitudinal section of the taper-shaped layer (the uppermost part of the pore-shaped layer is also shown below) which mainly shows the taper-shaped part of the anodized film in the mold for producing a nanostructure of the present invention (Example 4). It is a SEM photograph of 100,000 times the longitudinal section of the anodic oxide film in the mold for producing a nanostructure having no conventional pore-shaped layer (Comparative Example 1). (Example 4) which is a 100,000 times as many SEM photograph of the longitudinal cross section of the surface of the nanostructure produced using the mold for nanostructure production of the present invention. It is a SEM photograph of 100,000 times the longitudinal cross section of the surface of the nanostructure produced using the conventional mold for producing a nanostructure (Comparative Example 1). It is a schematic diagram which shows an example of the manufacturing method of the nanostructure using the mold for nanostructure preparation of this invention. It is a schematic diagram which shows an example of the manufacturing method which manufactures a nanostructure continuously using the mold for nanostructure preparation of this invention.

[Nanostructures using nanostructures]
The mold for producing a nanostructure of the present invention (hereinafter sometimes simply referred to as “mold”) is for producing a nanostructure such as an antireflection body utilizing the nanostructure. The nanostructure of the present invention includes an antireflection body having an antireflection function for light on the surface, a high transmittance body having improved light transmittance, and the like. “Nanostructures using nanostructures” have, for example, a structure called a moth-eye structure on the surface, and generally from the outermost surface in contact with a gas such as air to the inside of the nanostructure. As the film enters, the portion of the nanostructure gradually increases. Therefore, the reflection is prevented by gradually increasing the refractive index as it enters the nanostructure. In general, if there is a surface whose refractive index changes abruptly (discontinuously), the regular reflectance increases. In addition, examples of the form of the surface of the “nanostructure using nanostructures” in the present invention include those described in any of the above-mentioned patent documents.

  A preferred form of the “nanostructure using nanostructure” has a convex portion having an average height of 100 nm or more and 1000 nm or less or a concave portion having an average depth of 100 nm or more and 1000 nm or less on the surface, and the convex portion or the concave portion is at least It exists with an average period of 50 nm or more and 400 nm or less with respect to a certain direction. If the average height or the average depth is too small, good optical properties may not be exhibited, and if it is too large, production may be difficult. In the case where the convex part and the concave part are connected and have a wavy structure, the average length of the highest part (above the convex part) and the deepest part (below the concave part) may be 100 nm or more and 1000 nm or less. Particularly preferred for the same reason.

  In the “nanostructure using nanostructure”, it is preferable that the convex portion or the concave portion is arranged on the surface so that an average period in at least one direction is 50 nm or more and 400 nm or less. The convex part or the concave part may be arranged at random or may be arranged with regularity. In any case, it is preferable in terms of antireflection properties and transmission improvement properties that the convex portions or the concave portions are arranged substantially uniformly over the entire surface of the nanostructure. Further, it is only necessary that the average period be at least 50 nm to 400 nm in one direction, and the average period does not have to be 50 nm to 400 nm in all directions.

  Since the mold for producing a nanostructure is for producing the nanostructure as described above, the mold for producing a nanostructure of the present invention also has the above form on the surface. Is preferred.

[Nanostructure fabrication mold]
The mold for producing a nanostructure of the present invention has an anodized film formed on the surface of an aluminum material, and the anodized film has pores with an average period of 50 nm to 400 nm in at least one direction. The pore has a tapered portion and a pore-shaped portion.

<1. Aluminum material>
The aluminum material in the present invention may be a material whose main component is aluminum, and may be pure aluminum (1000 series) or an aluminum alloy. The pure aluminum in the present invention is aluminum having a purity of 99.00% or more, preferably a purity of 99.50% or more, and more preferably a purity of 99.85% or more. The aluminum alloy is not particularly limited, and examples thereof include an Al—Mn alloy (3000 series), an Al—Mg alloy (5000 series), and an Al—Mg—Si alloy (6000 series). Among these, pure aluminum (1000 series); aluminum alloy 5005; in terms of excellent workability and corrosion resistance due to the relatively small amount of Mg added, and a good mold for producing a nanostructure can be obtained. An improved alloy of aluminum alloy 5005 (for example, 58D5 made by Nippon Light Metal) or the like is preferable.

  In addition, as the aluminum material in the present invention, a material obtained by evaporating aluminum on the surface of a base material can be preferably used. As a base material, metals, such as stainless steel, copper, titanium, and aluminum; Glass; Ceramics; Plastic etc. can be used preferably. A conventional method can be used for vapor deposition of aluminum, and the vapor deposition film thickness is preferably 1 to 30 μm.

  The aluminum material in the present invention is not particularly limited, and an aluminum plate, an extruded tube, a drawn tube, or the like that has been industrially rolled may be used for cost reduction or processing simplification, rolling unevenness, or surface scratches. In order to remove corrosion, dirt, etc., the surface may be used after normal polishing, and in order to improve the light transmission performance such as haze of the nanostructure, higher level polishing is performed. Also good. Ra when performing high level polishing is preferably 0.1 μm or less, more preferably 0.03 μm or less, and particularly preferably 0.02 μm or less. Ry is preferably 1 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.35 μm or less. Here, Ra and Ry are values obtained according to JIS B0601 (1994), Ra is “arithmetic mean roughness”, and Ry is “maximum height”.

<2. Anodized film>
The anodic oxide film 2 in the present invention is an oxide having a pore 3 on the surface that is formed by reacting oxygen and aluminum generated by electrolysis of water by passing an electric current in an acid solution using the aluminum material 8 as an anode. It is an aluminum film. Although the total thickness of the anodic oxide film 2 is not particularly limited, the lower limit is preferably 600 nm or more, more preferably 1000 nm or more, particularly preferably 2000 nm or more, and particularly preferably 4000 nm from the viewpoint of durability of the mold for producing a nanostructure. The above is more preferable. On the other hand, the upper limit is preferably 50000 nm or less, more preferably 20000 nm or less, particularly preferably 10,000 nm or less, and still more preferably 8000 nm or less.

<3. Pore>
As shown in FIG. 1, the anodized film 2 in the present invention has pores 3 on the surface thereof. The pore 3 exists at an average period of 50 nm or more and 400 nm or less in at least one direction. As shown in FIG. 1, the pore 3 is a cocktail glass comprising a tapered shape portion 4 and a pore shape portion 5. It has a shape like On the other hand, as shown in FIG. 2, the conventional anodic oxide coating 2 of the mold for producing a nanostructure has the pore 3 composed only of the tapered portion 4.

  The average period of the pore 3 is at least 50 nm or more in a certain direction, but is preferably 100 nm or more. Moreover, although it is 400 nm or less, 250 nm or less is preferable. Further, it is only necessary that the average period be at least 50 nm to 400 nm in one direction, and the average period does not have to be 50 nm to 400 nm in all directions. If the average period is too short or too long, the nanostructure to be produced may not have a sufficient antireflection effect.

<3-1. Tapered shape>
As shown in FIG. 1, the tapered portion 4 in the present invention corresponds to the bowl portion at the upper portion of the cocktail glass shape, and the shape is wide open on the surface of the anodized film 2, and as it enters the deep portion. It has a tapered shape that gradually gets thinner. When the nanostructure is manufactured, the nanostructure forming material 11 is embedded in the tapered portion 4 to serve as a template for manufacturing the nanostructure. In the anodized film 2, the layer having the tapered portion 4 is referred to as a “tapered layer”.

  The layer thickness of the tapered layer 6 is not particularly limited, but is preferably 100 nm or more, more preferably 150 nm or more, and particularly preferably 250 nm or more. Moreover, it is preferable that it is 1000 nm or less, It is more preferable that it is 600 nm or less, It is especially preferable that it is 400 nm or less. If the thickness of the taper-shaped layer 6 is too thin, the effect of reducing the reflectivity of the nanostructure formed using the tape-shaped layer 6 as a template may not be obtained. In addition to being difficult, the process time of anodic oxidation and etching becomes too long and wasted, the durability as the mold 1 is inferior, and the mechanical properties of the nanostructure formed by using it as a mold are inferior Sometimes.

<3-2. Pore shape part>
As shown in FIG. 1, the pore shape portion 5 in the present invention corresponds to the stem (leg) portion at the lower portion of the cocktail glass shape, and the shape is a pore shape having substantially the same diameter. The diameter of the pores is not particularly limited. When producing the nanostructure, the nanostructure-forming material 11 is not substantially embedded in the pore-shaped part 5 and does not function as a template for producing the nanostructure. The pore-shaped portion 5 has the effect of increasing the Vickers hardness of the mold body 1 and improving the durability. On the other hand, the conventional mold for producing a nanostructure does not have the pore-shaped portion 5 as shown in FIG.

  When the anodic oxide film 2 is removed from the bath and dried, the whole pores become thin and the pores may be filled. Then, the pores corresponding to the stem (leg) portion of the cocktail glass may be partially or wholly lost (or clogged). However, even in such a case, in the present invention, it is referred to as a “pore shape portion”. Therefore, the pore-shaped portion 5 does not have to have literal pores extending from the top to the bottom. In the present invention, the pore shape portion 5 may be sealed. Although it does not specifically limit as a sealing hole, Natural sealing etc. are mentioned. Further, the pores may be branched or coalesced in the middle.

  In the anodized film 2, a layer that exists under the tapered layer 6 and has the pore-shaped portion 5 is referred to as a “pore-shaped layer”. The thickness of the pore-shaped layer 7 is not particularly limited, but it is desirable that the thickness be sufficient to increase the mechanical strength of the mold 1. Specifically, it is preferably 600 nm or more, more preferably 1000 nm or more, particularly preferably 2000 nm or more, and further preferably 4000 nm or more. On the other hand, the upper limit is preferably 50000 nm or less, more preferably 20000 nm or less, particularly preferably 10,000 nm or less, and still more preferably 8000 nm or less. If the layer thickness of the pore-shaped layer 7 is too thin, the durability of the mold body 1 may be inferior. On the other hand, if it is too thick, many crater-like defects occur or the surface becomes rough. In some cases, the haze of the nanostructure produced in (1) may increase. On the other hand, if it is too thick, the anodic oxidation time becomes long, and the cost of the mold may increase.

  The layer thickness of the pore-shaped layer 7 with respect to the layer thickness of the taper-shaped layer 6 is not particularly limited, but the antireflection effect of the resulting nanostructure, the durability of the mold 1, the ease of manufacturing the mold 1, etc. From this point, it is preferably 1 or more times (that is, a state in which the pore-shaped layer 7 is formed with a layer thickness of the taper-shaped layer 6 or more), more preferably 2 or more, and particularly preferably 4 or more. 10 times or more is more preferable. On the other hand, the upper limit is not particularly limited, but is preferably 100 times or less, more preferably 50 times or less, and particularly preferably 40 times or less. When combined with the layer thickness of the taper-shaped layer 6, the layer thickness of the taper-shaped layer 6 is preferably 1000 nm or less, and the layer thickness of the pore-shaped layer 7 is preferably equal to or greater than the layer thickness of the taper-shaped layer 6.

<3-3. Physical properties of molds for producing nanostructures>
The Vickers hardness of the mold for producing a nanostructure is preferably 40 or more, more preferably 60 or more, particularly preferably 200 or more, further preferably 300 or more, and most preferably 600 or more. If it has an above-described form and / or if the manufacturing method mentioned later is used, the value of this Vickers hardness can be achieved.

[Preparation of mold for nanostructure preparation]
The mold 1 for producing a nanostructure of the present invention is formed by repeating two steps of forming an anodic oxide film (anodic oxidation (a1)) and etching the anodic oxide film on the surface of the aluminum material 8 to be tapered. An anodic acid value film having a shape portion is formed and further anodized to form an anodized film having a pore shape portion under the anodized film having a tapered shape portion (anodization (a2)). )I do. It is preferable to form the anodic oxide film having the pore-shaped part with a film thickness equal to or greater than the film thickness of the anodic oxide film having the tapered part. “Anodized film layer having a tapered portion formed after repeating the formation of the anodized film and etching of the anodized film corresponds to the tapered layer 6 and has the pore-shaped portion. Corresponds to the pore-shaped layer 7 described above.

  Another aspect of the present invention is a method of manufacturing a mold for producing a nanostructure using nanostructures, and has pores with an average period of 50 nm or more and 400 nm or less in at least one direction. On the surface of the aluminum material, a taper-shaped layer having a taper-shaped portion is formed by repeating two steps of forming an anodized film (anodizing (a1)) and etching the anodized film. Anodization (a2)) is performed, and a pore-shaped layer having a pore-shaped portion is formed below the tapered layer so that the layer thickness is equal to or greater than the thickness of the tapered layer. This is a method for producing a mold for producing a nanostructure. The above-described mold for producing a nanostructure is preferably manufactured by the above-described manufacturing method.

  The method for producing a mold for producing a nanostructure of the present invention only needs to have at least the above-described steps. If the mold for producing a nanostructure as described above can be substantially produced in the form, it is in the middle or later. Etching or anodization may be performed, and such a manufacturing method is also included in the present invention. For example, even if etching or anodization is performed during or after the formation of the anodic oxide film having the pore-shaped part after the formation of the anodic oxide film having the taper-shaped part, the morphological effect is substantially affected. Otherwise, it is included in the production method of the present invention. In addition, if the form is an anodized film layer having a tapered portion as described above, it is defined as a “tapered layer” and has a pore shape substantially as described above. As long as the layer is a layer, the obtained layer is defined as a “pore-shaped layer” even if etching or anodic oxidation is performed during or after. In other words, as a result, if the pore diameter is substantially equal, even if etching or anodization is performed, the portion is defined as a “pore-shaped layer”.

  The surface of the aluminum material 8 may be polished before the anodic oxide film 2 is formed. As a method for polishing the surface of the aluminum material 8, any one of mechanical polishing, chemical polishing, and electrolytic polishing may be used, or any combination thereof may be used. For example, electrolytic polishing alone, mechanical polishing alone, a combination of electrolytic polishing and chemical polishing, a combination of mechanical polishing and chemical polishing, a combination of electrolytic polishing and mechanical polishing, a combination of electrolytic polishing, mechanical polishing, and chemical polishing are preferred. Electrolytic polishing alone or a combination including electrolytic polishing is more preferable. Among them, the method of carrying out electropolishing after mechanical polishing is particularly preferable in terms of easy processing. By polishing the surface of the aluminum material 8, the surface of the aluminum material 8 becomes uniform, and the mold body 1 obtained by processing the surface of the aluminum material 8 is a nanostructure having a small haze and significantly improved light transmission performance. Can be made.

<1. Formation of anodized film having tapered portion>
<1-1. Anodization (a1)>
The electrolytic solution of the anodic oxidation (a1) in the present invention is not particularly limited as long as it is an acid solution. For example, any of sulfuric acid-based, oxalic acid-based, phosphoric acid-based, chromic acid-based, etc. may be used. An oxalic acid-based electrolyte is preferable in that the size and shape of the shape portion 4 can be obtained.

  The conditions for anodizing (a1) are not particularly limited as long as the mold body 1 having the above-described shape can be formed. Conditions for using oxalic acid as the electrolytic solution are as follows. That is, the concentration is preferably 0.01 to 0.5M, more preferably 0.02 to 0.3M, and particularly preferably 0.03 to 0.1M. The applied voltage is preferably 20 to 120V, more preferably 40 to 110V, particularly preferably 60 to 105V, and still more preferably 80 to 100V. The liquid temperature is preferably 0 to 50 ° C, more preferably 1 to 30 ° C, and particularly preferably 2 to 10 ° C. The treatment time for one time is preferably 5 to 500 seconds, more preferably 10 to 250 seconds, particularly preferably 15 to 200 seconds, and further preferably 20 to 100 seconds. If the anodic oxidation is performed under such conditions, the tapered layer 6 in the anodic oxide film 2 of the nanostructure producing mold 1 can be manufactured in combination with the following etching conditions. Note that the same conditions as described above are preferable for other acids.

  When the voltage is too large, the average interval of the formed tapered portions 4 becomes too large, and the average period of the convex portions or concave portions formed on the surface of the nanostructure obtained by the mold 1 is May be too large. On the other hand, when the voltage is too small, the average interval between the formed tapered portions 4 becomes too small, and the average of the convex portions or concave portions formed on the surface of the nanostructure obtained by the mold 1 The period may become too small. In the nanostructure producing mold 1 of the present invention, it is essential that the pores 3 existing on the surface thereof exist at an average period of 50 nm or more and 400 nm or less with respect to at least one direction. Adjusted to enter.

  That is, the anodized film of the taper-shaped layer 6 having the taper-shaped portion 4 is prepared by using a bath liquid having an oxalic acid concentration of 0.01 M to 0.5 M, an applied voltage of 20 V to 120 V, and a liquid temperature of 0 ° C. to 50 ° C. The above-described method for producing a mold for producing a nanostructure, which includes at least a step of forming at a temperature of ° C or less, is particularly preferable.

<1-2. Etching>
Etching is mainly performed to increase the hole diameter of the tapered portion 4 of the pore 3 and to obtain a desired shape. Adjusting the hole diameter, height, depth, taper shape, etc. of the tapered portion 4 formed on the anodized film 2 on the surface of the aluminum material 8 by combining the anodization (a1) and etching. Can do.

  The etching method can be used without particular limitation as long as it is a generally known method. For example, as the etching solution, an acid solution such as phosphoric acid, nitric acid, acetic acid, sulfuric acid, chromic acid, or a mixture thereof can be used. Phosphoric acid or nitric acid is preferable, and phosphoric acid is particularly preferable in that a necessary dissolution rate can be obtained and a more uniform surface can be obtained.

  The concentration, immersion time, temperature, and the like of the etching solution may be appropriately adjusted so that a desired shape is obtained. The conditions for phosphoric acid are as follows. That is, the concentration of the etching solution is preferably 1 to 20% by mass, more preferably 1.2 to 10% by mass, and particularly preferably 1.5 to 2.5% by mass. The liquid temperature is preferably 30 to 90 ° C, more preferably 35 to 80 ° C, and particularly preferably 40 to 60 ° C. One treatment time (immersion time) is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 40 minutes, particularly preferably 45 seconds to 20 minutes, and further preferably 1 minute to 10 minutes. If the etching is performed under such conditions, the tapered layer 6 can be manufactured in combination with the above-described anodic oxidation (a1) conditions. Note that the same conditions as described above are preferable for other acids.

  The desired taper-shaped layer 6 can be obtained by combining the anodization (a1) and etching. “Combination” means that the process of anodizing (a1) first and then etching is repeated alternately. It is also preferable to wash with water between each treatment. The number of times of anodization (a1) and etching may be appropriately adjusted so as to obtain a desired shape, but the number of combinations is preferably 5 to 20 times, more preferably 7 to 18 times, and more preferably 10 to 14 times. Particularly preferred.

  In the case of obtaining the tapered layer 6 of the anodic oxide film 2 in the nanostructure producing mold 1 of the present invention, a particularly preferred combination is anodic oxidation (a1) with an aqueous oxalic acid solution and etching with an aqueous phosphoric acid solution. That is. The overall preferred conditions are a combination of each of the preferred conditions described above.

<2. Formation of anodized film having pore-shaped part (anodized (a2))>
The anodic oxide film having a pore shape in the present invention is preferably formed after forming an anodic oxide film having a taper-shaped portion by repeating two steps of formation of the anodic oxide film and etching of the anodic oxide film. This corresponds to the pore-shaped layer 7 described above. When the anodic oxidation is further performed after the taper-shaped layer is formed, the pores 3 formed by the anodic oxidation are formed following the bottom of the tapered pores 3 and extend downward. The anodizing (a2) electrolytic solution for forming the pore-shaped layer 7 and the formation conditions are the anodizing (a1) electrolytic solution (type, concentration, etc.) described in the section of the anodized film having a tapered portion. And formation conditions (liquid temperature, applied voltage, etc.) can be used, and the preferred ranges are also the same.

  That is, the anodic oxide film of the pore-shaped layer 7 having the pore-shaped portion 5 is formed using a bath liquid having an oxalic acid concentration of 0.01 M to 0.5 M, an applied voltage of 20 V to 120 V, and a liquid temperature of 0 ° C. The above-described method for producing a nanostructure producing mold including at least the step of forming at 50 ° C. or lower is particularly preferable.

  There are no particular limitations on the conditions for forming the anodic oxide film having the pore-shaped portion, and the anodic oxide film having the pore-shaped portion should be formed in the same manner as the conditions for forming the anodic oxide film having the tapered portion. Can do. The electrolytes may be the same or different, but are preferably the same. After the taper-shaped layer 6 is obtained by repeating the two steps of forming the anodic oxide film and etching the anodic oxide film, it may be put again in the electrolytic solution for forming the anodic oxide film having the pore-shaped portion. In addition, it is preferable to form the anodic oxide film having a pore shape with the electrolytic solution used for forming the anodic acid value film having the tapered portion, from the viewpoint that the electrolytic solution tank is small. The anodization (a1) and the anodization (a2) are preferably substantially the same except for the electrolysis time.

  The treatment time (electrolysis time) for forming the anodic oxide film having the pore-shaped portion may be appropriately adjusted so as to obtain a desired layer thickness. For example, when oxalic acid is used as the electrolytic solution, 5 minutes to 4 hours are preferable, 15 minutes to 3 hours are more preferable, 30 minutes to 2 hours are particularly preferable, and 45 minutes to 1 hour is more preferable. The processing time (electrolysis time) for forming the anodic oxide film having the pore-shaped portion is not less than the total anodic oxidation (a1) time excluding the etching time, etc. To preferred. Note that the same conditions as described above are preferable for other acids.

  The pore-shaped layer 7 is preferably formed with a film thickness equal to or greater than the taper-shaped layer 6 and is not particularly limited, but is preferably 2 to 50 times, more preferably 4 to 30 times, and even more preferably 10 to 20 times. . Below the lower limit, the pore-shaped layer 7 may be too thin and the durability of the mold body 1 may be inferior. On the other hand, if it is too thick, many crater-like defects are generated, and the surface is roughened and the mold body 1 is made. In some cases, the haze of the nanostructure increases. On the other hand, if it is too thick, the anodic oxidation time becomes long, and the cost of the mold may increase.

  As described above, as shown in FIGS. 1 and 3, a nanostructure is produced in which the anodized film 2 composed of the pore-shaped layer 7 and the tapered layer 6 is formed on the aluminum material 8. The mold 1 is produced.

  The mold body is excellent in surface hardness and durability. Further, the mold body is transferred once or twice using the mold body as a mold, and has the same or inverted shape manufactured by a material such as metal. New molds can be obtained. That is, the mold according to the present invention is not only directly transferred to a nanostructure-forming material, which will be described later, and directly manufactured into a nanostructure, but also transferred to a new material such as a metal, from the new material. It is also used to produce a mold body. Thereafter, nanostructures can be manufactured using the new mold.

  In addition, a layer made of a material having high hardness such as Ni or W can be laminated on the mold by a known method.

[Configuration and fabrication of nanostructures]
The nanostructure of the present invention is obtained by embedding the nanostructure-forming material 11 in the nanostructure-producing mold 1 and then curing the nanostructure-forming material 11 or the material in which the nanostructure-forming material 11 is cured. It is obtained by peeling from the nanostructure producing mold 1. After embedding the nanostructure forming material 11, if necessary, the nanostructure forming material 11 is cured from the mold body 1 after being cured by light irradiation, electron beam irradiation and / or heating.

  Therefore, the nanostructure has an extremely fine surface structure in which convex portions or concave portions exist with an average period of 50 nm or more and 400 nm or less in at least one direction. Furthermore, it is preferable to have a structure generally referred to as a “moth-eye structure” because it has good antireflection performance.

  There is no restriction | limiting in particular as the said nanostructure formation material 11, Either a thermoplastic composition and a curable composition can be used conveniently. In order to give mechanical strength suitable for the nanostructure, it is preferable to use a curable composition from the viewpoint of peelability from the anodized film 2 serving as a mold (peelability from the tapered portion 4).

<1. Thermoplastic composition>
The thermoplastic composition is not particularly limited as long as it becomes soft by heating to the glass transition temperature or the melting point. For example, an acrylonitrile-styrene polymer composition, an acrylonitrile-chlorinated polyethylene-styrene polymer, for example. Styrene polymer compositions such as compositions, styrene- (meth) acrylate polymer compositions, budadiene-styrene polymer compositions; vinyl chloride polymer compositions, ethylene-vinyl chloride polymer compositions, Ethylene-vinyl acetate polymer composition, propylene polymer composition, propylene-vinyl chloride polymer composition, propylene-vinyl acetate polymer composition, chlorinated polyethylene composition, chlorinated polypropylene composition Polyolefin-based compositions such as; ketone-based polymer compositions; polyacetal-based compositions; Ester-based composition; polycarbonate-based composition; polyvinyl acetate-based compositions, polyvinyl composition, polybutadiene composition, the poly (meth) acrylate-based composition, and the like.

<2. Curable composition>
A curable composition is a composition which hardens | cures by light irradiation, electron beam irradiation, and / or a heating. Especially, the curable composition hardened | cured by light irradiation or electron beam irradiation is preferable from an above-described point.

<2-1. Curable composition cured by light irradiation or electron beam irradiation>
There is no limitation in particular as "the curable composition hardened | cured by light irradiation or electron beam irradiation" (henceforth abbreviated as "photocurable composition"), Acrylic polymerizable composition or methacrylic polymerizable composition ( In the following, abbreviated as “(meth) acrylic polymerizable composition”), a composition that can be cross-linked with a photoacid catalyst, and the like can be used, but the (meth) acrylic polymerizable composition has the above-mentioned nanostructure. In order to give suitable mechanical strength, it is preferable from the viewpoints of peelability from the mold body 1 and preparation of nanostructures having various physical properties because of abundant compound groups.

<2-2. Thermosetting composition>
The thermosetting composition in the present invention is not particularly limited as long as it is a composition that undergoes polymerization to form a polymer network structure upon heating and does not return to its original state after curing. Composition, xylene-based polymerizable composition, epoxy-based polymerizable composition, melamine-based polymerizable composition, guanamine-based polymerizable composition, diallyl phthalate-based polymerizable composition, urea-based polymerizable composition (urea-based polymerizable) Composition), unsaturated polyester-based polymerizable composition, alkyd-based polymerizable composition, polyurethane-based polymerizable composition, polyimide-based polymerizable composition, furan-based polymerizable composition, polyoxybenzoyl-based polymerizable composition, Examples thereof include a maleic acid-based polymerizable composition, a melamine-based polymerizable composition, and a (meth) acrylic polymerizable composition. Examples of the phenolic polymerizable composition include a resol type phenol resin. Examples of the epoxy polymerizable composition include bisphenol A-epichlorohydrin resin, epoxy novolac resin, alicyclic epoxy resin, brominated epoxy resin, aliphatic epoxy resin, polyfunctional epoxy, and the like. Examples of the unsaturated polyester polymerizable composition include orthophthalic acid, isophthalic acid, adipic acid, het acid, diallyl phthalate, and the like. Among these, as the thermosetting composition, a (meth) acrylic polymerization composition is preferable.

  Further, the nanostructure-forming material 11 may further contain a binder polymer, fine particles, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a release agent, a lubricant, a leveling agent, and the like. it can. These can be appropriately selected from conventionally known ones.

<Method for producing nanostructure>
The method for producing the nanostructure using the mold 1 of the present invention is not limited, but for example, the following method is preferable. That is, the nanostructure-forming material 11 is collected on the base material 13 and applied to a uniform film thickness using a coating machine such as a bar coater or applicator or a spacer. Here, as the “substrate”, a film of polyethylene terephthalate (hereinafter abbreviated as “PET”), triacetyl cellulose, or the like is suitable. Then, the mold body 1 of the present invention is bonded. After bonding, in the case of a curable composition, the film surface is cured by ultraviolet irradiation or electron beam irradiation and / or heat. Alternatively, the nanostructure forming material 11 may be directly placed on the mold 1 and a coating film having a uniform film thickness may be produced using a coating machine or a spacer. Thereafter, the obtained nanostructure is peeled from the mold 1 to produce a nanostructure.

  This manufacturing method will be described in detail with reference to FIG. 8, but the present invention is not limited to the specific mode of FIG. That is, an appropriate amount of the nanostructure forming material 11 is supplied or applied to the nanostructure manufacturing mold 1 (FIG. 8A), and the base material 13 is bonded obliquely with the roller 14 side as a fulcrum (FIG. 8 ( b)). The nanostructure-producing mold 1, nanostructure-forming material 11 and base material 13 bonded together are moved to a roller 14 (FIG. 8 (c)), and are subjected to pressure bonding with the roller. The structure of the taper-shaped portion 4 of the structure manufacturing mold 1 is transferred to a nanostructure forming material 11 and molded (FIG. 8D). At this time, the nanostructure-forming material 11 is embedded in the nanostructure-producing mold 1. Then, after hardening this if necessary, it peels from this type body 1 for nanostructure production (Drawing 8 (e)), and nanostructure 15 is obtained.

  FIG. 9 is a schematic view of an example of a method / apparatus for continuously producing the nanostructure 15, but the present invention is not limited to the range shown in the schematic view. That is, the nanostructure-forming material 11 is attached to the nanostructure-producing mold 1, a force is applied by the roller 14, and the base material 13 is bonded to the nanostructure-producing mold 1 from an oblique direction. Then, the structure of the tapered portion 4 included in the nanostructure manufacturing mold 1 is transferred to the nanostructure forming material 11. If necessary, this is cured using a curing device 16 and then peeled from the nanostructure producing mold 1 to obtain a nanostructure 15. The support roller 17 is installed so as to pull the nanostructure 15 upward.

  At the time of bonding, by using the roller 14 and bonding at an angle, the nanostructure 15 without bubbles and without defects is obtained. In addition, when the roller 14 is used, a linear pressure (nip pressure) is applied, so that the pressure can be increased. Therefore, it is possible to manufacture a nanostructure having a large area, and the pressure can be easily adjusted. In addition, it becomes possible to manufacture the nanostructure 15 having a uniform film thickness integrated with the base material 13 and predetermined optical properties. Furthermore, since it can be continuously manufactured, the productivity is excellent.

  On the other hand, when a continuous printing machine that continuously embeds and peels (transfers) the nanostructure forming material 11 as shown in FIG. 9 is used, the nanostructure forming material 11 is embedded in the tapered portion 4. For this reason, the linear pressure (nip pressure) can be set high. However, if the linear pressure (nip pressure) is increased, the surface of the mold body 1 is more likely to be damaged when foreign matter or the like is mixed. However, even in such a case, if the nanostructure producing mold 1 of the present invention is used, since the surface hardness is high and the strength is high, it is possible to prevent such scratches from occurring. The production mold 1 can be used stably and repeatedly.

  The nanostructure may be formed of a thermoplastic resin, but it is also preferable that the curable resin is polymerized by light irradiation, electron beam irradiation and / or heating. In that case, there is no particular limitation on the wavelength of light in the case of light irradiation. The light containing visible light and / or ultraviolet light is preferable in that the carbon-carbon double bond of the (meth) acryloyl group can be favorably polymerized in the presence of the photopolymerization initiator if necessary. Particularly preferred is light containing ultraviolet rays. The light source is not particularly limited, and a known light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a halogen lamp, or various lasers can be used. In the case of irradiation with an electron beam, the intensity and wavelength of the electron beam are not particularly limited, and a known method can be used.

  In the case of polymerization by heat, the temperature is not particularly limited, but is preferably 80 ° C. or higher, particularly preferably 100 ° C. or higher. Moreover, 200 degrees C or less is preferable and 180 degrees C or less is especially preferable. If the polymerization temperature is too low, the polymerization may not proceed sufficiently. If it is too high, the polymerization may become non-uniform or the substrate may be deteriorated. The heating time is not particularly limited, but is preferably 5 seconds or longer, and particularly preferably 10 seconds or longer. Moreover, 10 minutes or less are preferable, 2 minutes or less are especially preferable, and 30 seconds or less are still more preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these, unless the summary is exceeded.

Example 1
As an aluminum material, a 99.85% rolled aluminum plate (thickness 2 mm) is polished for 10 minutes by using a single-sided flat buff polishing machine (manufactured by Speedfam) and an alumina-based abrasive (manufactured by Fujimi Abrasives). A mirror surface was obtained. The polished surface was scrubbed and then subjected to non-erodible degreasing treatment.

  Furthermore, the taper-shaped layer which has a taper-shaped part was produced by the combination of the following anodic oxidation (a1) conditions and the etching treatment conditions of the formed anodic oxide film shown below.

<Conditions for anodization (a1)>
Working solution: 0.05M oxalic acid voltage: DC voltage temperature of 80V: 5 ° C
Time: 30 seconds

<Etching conditions>
Working solution: 2% by mass Phosphoric acid temperature: 50 ° C
Time: 2 minutes

  By repeating the anodic oxidation (a1) and the etching 10 times alternately, a tapered layer having a tapered part with an average period of 200 nm, a diameter of the opening 160 nm, and a depth of 300 nm was obtained.

<Conditions for anodization (a2)>
Working solution: 0.05M oxalic acid voltage: DC voltage temperature of 80V: 5 ° C
Time: 2 minutes

  After forming the taper-shaped layer, anodic oxidation (a2) was performed to obtain a nanostructure manufacturing mold having a pore-shaped layer 7 having a layer thickness of 300 nm (0.3 μm) below the taper-shaped layer. .

<Preparation of nanostructure>
The photocurable composition shown below, which is a nanostructure-forming material, was collected on a colorless and transparent PET film having a thickness of 75 μm, and applied with a bar coater NO28 so as to have a uniform film thickness. Thereafter, the molds obtained above were bonded together, and it was confirmed that the photocurable composition was filled in the taper-shaped portion, and then polymerized and cured by irradiation with ultraviolet rays. After curing, the film was peeled from the mold to obtain a nanostructure having convex portions with an average height of 300 nm on the surface with an average period of 200 nm. The thickness of the nanostructure was 85 μm including the thickness of the PET film.

<Preparation of photocurable composition>
11.8 parts by mass of the compound (1) represented by the following formula (1), 23.0 parts by mass of the following compound (2), 45.2 parts by mass of tetraethylene glycol diacrylate, 20.0 parts by mass of pentaerythritol hexaacrylate, And 2.0 mass parts of 1-hydroxy cyclohexyl phenyl ketone was mix | blended as a photoinitiator, and the photocurable composition was obtained.

The compound (1) is a compound represented by the following formula (1).
[In the formula (1), X represents a dipentaerythritol (having 6 hydroxyl groups) residue. ]

The compound (2) is
2HEA--IPDI-(polyester of terminal hydroxyl group having a weight average molecular weight of 3500 of adipic acid and 1,6-hexanediol)-IPDI--2HEA
It is a compound shown by these. Here, “2HEA” represents 2-hydroxyethyl acrylate, “IPDI” represents isophorone diisocyanate, and “-” represents a bond of an isocyanate group and a hydroxyl group by the following normal reaction.
-NCO + HO- → -NHCOO-

Example 2
In Example 1, except that the time of anodic oxidation (a2) in the formation of the anodic oxide film having the pore shape was 6 minutes and the depth of the pore shape layer was 700 nm (0.7 μm), Example 1 In the same manner, a mold for producing a nanostructure and a nanostructure were obtained.

Example 3
In Example 1, except that the time of anodization (a2) in the formation of the anodic oxide film having a pore shape was 20 minutes and the depth of the pore shape layer was 1700 nm (1.7 μm), Example 1 In the same manner, a mold for producing a nanostructure and a nanostructure were obtained.

Example 4
In Example 1, except that the time of anodization (a2) in the formation of the anodic oxide film having the pore shape was 60 minutes and the depth of the pore shape layer was 4700 nm (4.7 μm), Example 1 In the same manner, a mold for producing a nanostructure and a nanostructure were obtained. FIG. 3 is a cross-sectional photograph of the obtained nanostructure-producing mold, FIG. 4 is a cross-sectional photograph of the tapered layer portion of the obtained nanostructure-producing mold, and a cross-section of the obtained nanostructure. A photograph is shown in FIG.

Example 5
In Example 1, except that the time of anodization (a2) in the formation of the anodic oxide film having a pore shape was 120 minutes and the depth of the pore shape layer was 9700 nm (9.7 μm), Example 1 In the same manner, a mold for producing a nanostructure and a nanostructure were obtained.

Comparative Example 1
In Example 1, a nanostructure-producing mold and a nanostructure were obtained in the same manner as in Example 1 except that an anodic oxide film having a pore shape was not formed. FIG. 5 shows a cross-sectional photograph of the obtained mold for producing a nanostructure, and FIG. 7 shows a cross-sectional photograph of the nanostructure.

<Evaluation>
Evaluation Example 1
The surface hardness and durability of the mold for producing a nanostructure obtained in Examples 1 to 5 and Comparative Example 1, and the nanostructure obtained using the mold for producing the nanostructure The reflectance and haze were measured as follows. The results are shown in Table 1.

Evaluation example 2
The spectrum of the reflectance of 380 nm to 780 nm of the mold for producing a nanostructure obtained in Example 4 and Comparative Example 1 was measured as follows. The respective results are shown in FIGS.

[surface hardness]
A test piece was cut out from the mold for producing a nanostructure and measured by a conventional method using a micro Vickers hardness meter (manufactured by Mitutoyo Corporation, HM-211).

[durability]
The surface of the mold for nanostructure fabrication is placed on a 2 cm ² area with Bencot Clean EA-8 (Asahi Kasei Fibers Co., Ltd., clean room wiper) loaded with a load of 100 gf. Ten reciprocations were rubbed. Then, it determined visually by the following references | standards.
A: No change in the friction part (very good durability)
○: One or two scratches are generated in the friction part (good durability)
Δ: 3-4 scratches are generated in the friction part (slightly low durability but acceptable level)
X: 5 or more scratches are generated in the friction part (durability is poor)

[Reflectance]
Black tape was affixed to the back surface (PET side) of the nanostructure, and a 5 ° incident absolute reflectance was measured using a self-recording spectrophotometer “UV-3150” manufactured by Shimadzu Corporation. A sample having a 5 ° incident absolute reflectance of 0.1% or less was considered good.

[Haze]
Visible light haze was measured using a haze meter HM-150 manufactured by Murakami Color Research Laboratory. A haze of 5 or less was considered good.

[Thickness of anodized film (tapered layer) and anodized film (pore shaped layer)]
Stress was applied to the surface of the mold, the anodized film was peeled off, SEM photographs of 10,000 times and 100,000 times the cross section were taken, and the thickness of each layer was measured by measuring with a ruler.

[Total thickness of anodized film]
Stress was applied to the surface of the mold to peel off the anodized film, and SEM photographs of 10,000 times and 100,000 times the cross section were taken and measured with a ruler.

  From Table 1, all of Examples 1 to 5 which are nanostructure-producing molds of the present invention are excellent in surface hardness (Vickers hardness) and durability. Examples 3 to 3 No. 5 was particularly excellent in surface hardness and durability. On the other hand, the nanostructure-producing mold having no pore-shaped portion, that is, having no pore-shaped layer, obtained in Comparative Example 1 has a slightly higher surface hardness than the aluminum substrate (Reference Example 1). In addition, the durability was poor.

  Furthermore, the nanostructures produced with these nanostructure production molds were excellent in “reflectance” and “haze”. That is, as shown in FIGS. 8 and 9, even if a pore-shaped layer is formed on the mold body, that is, even if anodization (a2) is added after repeating anodization and etching, it can be obtained. The nanostructures produced with the molds were not inferior in “reflectance” or “haze”.

Evaluation Example 3
Using the nanostructure-producing mold obtained in Example 4 and the nanostructure-producing mold obtained in Comparative Example 1, the nanostructure-forming material is continuously embedded and peeled off (transferred). When a nanostructure was produced using a continuous printing machine designed to repeat the above, when the nanostructure production mold of Example 3 was used, the nanostructure could be produced without any problem up to 10,000 m. In the case of using the mold for producing the nanostructure of Comparative Example 1, at the time of producing 1000 m, a defect that seems to be caused by the adhesion of foreign matter occurred, and the depression of the mold can be confirmed with the naked eye. It was. That is, since the durability of the mold was inferior, a problem occurred in the production of the nanostructure, and at that time, the mold had to be replaced with a new one.

  The mold for producing a nanostructure of the present invention has a thread between a device such as a film and a mold at the start of the printing press, that is, at the start of production of the nanostructure and / or at the end of the stall. Can be prevented, and the mold can be prevented from being damaged. At the stage of continuous printing, small trash and foreign matter are mixed into the resin that is the nanostructure forming material, or small trash and foreign matter adhere to the substrate and mold, resulting in a high nip. Even when there is a risk of damaging the mold body due to pressure, the scratches are prevented with strong hardness.

  As described above, the mold for producing a nanostructure of the present invention is excellent in surface strength, durability, etc., and therefore, for example, an antireflection body is required to ensure good visibility. LCDs, PDPs and other FPDs; front panels such as display shelves and foreheads; cover plates such as specimen boxes; building materials such as windows and doors; surfaces of structures such as objects; etc. -It is widely used suitably for production of nanostructures in the field.

DESCRIPTION OF SYMBOLS 1 Nanostructure preparation type | mold 2 Anodic oxide film 3 Pore 4 Tapered shape part 5 Pore shape part 6 Taper shape layer 7 Pore shape layer 8 Aluminum material 9 Aluminum 11 Nanostructure formation material 13 Base material 14 Roller 15 Nano Structure 16 Curing device 17 Support roller

Claims (13)

A mold for producing a nanostructure using nanostructures, in which an anodized film is formed on the surface of an aluminum material that is an aluminum plate, an extruded tube or a drawn tube ,
The anodized film has pores with an average period of 50 nm or more and 400 nm or less with respect to at least one direction,
The pore is composed of a taper-shaped portion and a pore-shaped portion below the taper-shaped portion, and the taper-shaped portion is wide open on the surface of the anodized film and gradually decreases as it enters the deep portion. And the pore shape portion is a pore shape having substantially the same diameter,
A mold for producing a nanostructure, comprising a pore-shaped layer having a layer thickness of 1000 nm or more having a pore-shaped portion continuously below the tapered layer having the tapered-shaped portion. Nanostructure fabrication mold of claim 1, wherein the layer thickness of the tapered layer is 100nm or more 1000nm or less. The nanostructure-producing mold according to claim 1 or 2, wherein the pore-shaped layer has a layer thickness of 2000 nm or more. The mold for producing a nanostructure according to claim 1 or 2, wherein the total film thickness of the anodic oxide film is 2000 nm or more.   The mold for producing a nanostructure according to any one of claims 1 to 4, wherein at least a part of the pore-shaped portion of the pore is sealed.   The mold for producing a nanostructure according to any one of claims 1 to 5, wherein the Vickers hardness is 40 or more. The method for producing a mold for producing a nanostructure according to any one of claims 1 to 6, wherein the aluminum has a pore with an average period of 50 nm or more and 400 nm or less with respect to at least one direction. A taper-shaped layer having a taper-shaped portion is formed on the surface of an aluminum material which is a plate, an extruded tube or a drawn tube by repeating two steps of forming an anodized film and etching the anodized film. Oxidizing to form a pore-shaped layer having a pore-shaped portion at a layer thickness of 1000 nm or more so that the layer thickness is equal to or greater than the layer thickness of the tapered layer under the tapered layer. A method for producing a mold for producing a nanostructure.   Using a bath solution having an oxalic acid concentration of 0.01 M or more and 0.5 M or less, the anodized film of the tapered layer having the tapered part and / or the anodized film of the pore shaped layer having the pore shaped part, The method for producing a mold for producing a nanostructure according to claim 7, comprising at least a step of forming at an applied voltage of 20 V or more and 120 V or less and a liquid temperature of 0 ° C. or more and 50 ° C. or less.   8. The etching according to claim 7, wherein the etching is performed using an etching solution having a phosphoric acid concentration of 1% by mass to 20% by mass with a liquid temperature of 30 ° C. or more and 90 ° C. or less and a processing time of 10 seconds or more and 60 minutes or less. 8. A method for producing a mold for producing a nanostructure according to 8.   A nanostructure producing mold, which is produced using the method for producing a nanostructure producing mold according to any one of claims 7 to 9.   The nanostructure-forming material or the nanostructure-forming material after the nanostructure-forming material is embedded in the nanostructure-producing mold according to any one of claims 1 to 6 A nanostructure formed by peeling a cured material from the mold for producing a nanostructure.   The nanostructure according to claim 11, wherein the nanostructure-forming material is a thermoplastic composition, or "a curable composition that is cured by light irradiation, electron beam irradiation and / or heating".   The nanostructure according to claim 11 or 12, wherein the nanostructure is an antireflection body.