JP5229206B2 - Method for producing antireflection film - Google Patents

Description

  The present invention relates to a molding stamper, a method for producing an antireflection film, and an antireflection film. More specifically, a molding stamper capable of forming a defect-free antireflection layer without causing foaming, a method for producing an antireflection film using the molding stamper, and a reflection produced using the molding stamper It relates to a prevention film.

  A film having an antireflection layer having a moth-eye structure is known as an antireflection film. The moth-eye structure is a concavo-convex structure having fine protrusions, which literally resemble the form of “moth eyes”. An antireflection layer having such a moth-eye structure is abruptly equivalent to one having a gradient in refractive index with respect to incident light, for example, when the protrusions are formed with a period smaller than the wavelength of the visible light region. It utilizes the characteristic that the difference in refractive index is eliminated, and hardly reflects incident light.

  The anti-reflection layer having a moth-eye structure uses a molding stamper having a shaping mold having a moth-eye structure. After the resin is applied onto the molding stamper, the resin is cured, and as a result, the moth-eye structure has a moth-eye structure on the surface of the cured resin layer. The structure is a transfer formed. As a method for producing a molding stamper, for example, a production method by a laser interference method, a production method by a photolithography process, a production method by an anodic oxidation method (see Patent Document 1), a production method by nanoparticle formation, and a production method by dry etching Etc. are being studied. The molding stamper manufactured by these production methods has an extremely fine uneven structure in any case, and therefore, in order to repeatedly produce an antireflection film using the molding stamper, a resin is applied. It is necessary to prevent as much as possible “foaming” from forming on the shaping die of the molding stamper and adhesion of foreign matters to the shaping die of the molding stamper as much as possible.

  By the way, Patent Documents 2 and 3 describe a method of manufacturing a lens sheet with a molding stamper (also referred to as a molding die) provided with a predetermined shaping die. Specifically, in Patent Document 2, a resin is applied on a mold with a multiple nozzle, a resin reservoir is formed on the resin after spreading over the entire surface, a base member is stacked on the resin reservoir and a base is formed. A method is described in which a resin reservoir is uniformly stretched from above a member with a pressure roll and then the resin is cured to manufacture a lens sheet. In this method, it is said that air bubbles mixed between the base member and the mold can be pushed out in a step of uniformly stretching the resin reservoir with a pressure roll.

  Further, in Patent Document 3, an ultraviolet curable resin is injected into one region or a plurality of regions of a mold and then smoothed with a roll to planarize, and at the same time, an ultraviolet curable resin is applied to the unsmoothed region of the mold. After injecting, smoothing with a roll and flattening, laminating a translucent base material on the flattened ultraviolet curable resin, and then squeezing from above to adhere the ultraviolet curable resin and the base material, Thereafter, a method for producing a lens sheet by irradiating ultraviolet rays from a substrate to cure the ultraviolet curable resin is described. In this method, it is said that entrainment of bubbles at the interface between the mold and the resin can be prevented by performing smoothing.

Special Table 2003-531962 WO98 / 23978 (international pamphlet) JP 2007-307782 A

  The present inventor prepared a molding stamper prepared by anodizing a shaping mold for shaping the moth-eye structure, and used the molding stamper to prevent reflection of the moth-eye structure by the method described in Patent Document 2. An antireflective film having a layer was produced. However, when the obtained antireflection film was observed by applying light, many streaky shadows were observed. The shadow coincided with the line applied with multiple nozzles. Further, an antireflection film having an antireflection layer having a moth-eye structure was also produced by the method described in Patent Document 3 using the same molding stamper. The shadow of was observed. The cause of the shadow is when the curable resin 102 is applied to the shaping mold 110 of the molding stamper 100 and the base film 103 is placed and the curable resin 102 is stretched by the roll 105 as shown in FIG. As shown in FIG. 12 (B), air 104 remains in the bell-shaped concave portion 101 of the shaping mold 110 coated with the curable resin 102, and as a result, as shown in FIG. It was inferred that this was because the height of the protrusion formed on the surface of the antireflection layer was different between the protrusion 106 ′ in the coated portion and the protrusion 106 in the non-coated portion.

  Further, as shown in FIG. 12C, the air 104 remaining in the recess 101 is mixed into the ultraviolet curable resin 102 as fine bubbles, and there is a problem that bubbles are present in the obtained antireflection layer. was there.

  Further, as shown in FIG. 12C, when the air 104 in the bell-shaped recess 101 and the ultraviolet curable resin 102 come into contact with each other, the curing of the ultraviolet curable resin 102 is hindered. The shaping mold 110 of the molding stamper 100 that remains in the concave portion 101 of the stamper 100 and is repeatedly used thereafter is contaminated and clogged, resulting in a problem that the moth-eye structure to be manufactured thereafter is defective.

  The present invention has been made to solve the above-mentioned problems, and its purpose is to produce an antireflection film in which the shaping mold is not clogged with a resin, no shadow is observed, and no bubbles are involved. Another object of the present invention is to provide a molding stamper for use in the manufacturing process. Another object of the present invention is to provide a method for producing an antireflection film using such a molding stamper. A further object of the present invention is to provide an antireflection film obtained by the production method.

  In order to solve the above-mentioned problems, a molding stamper according to the present invention has a protrusion having a period smaller than the wavelength in the visible light region and an antireflection layer having a height of 150 nm to 450 nm. A quadrilateral molding stamper having a shaping region in which a mold is formed and a non-shaped region in which the shaping mold is not formed, wherein the non-shaped region is on one side of the quadrilateral It is provided with a predetermined width along, and is used for placing a curable resin extending on the shaping region.

  According to this invention, since the non-shaped region where the shaping mold is not formed is used for placing the curable resin to be stretched on the shaped region, after the curable resin is placed on the non-shaped region, If the curable resin is extended from one side of the stamper toward the opposite side of the stamper, the curable resin is filled with the movement of the curable resin without leaving air in the concave portion of the shaped region. . As a result, the presence of air prevents the curable resin from being hardened in the recesses, so that the shaping mold is not clogged with the resin, and there is no entrainment of bubbles in the obtained antireflection layer. In the antireflection film having the antireflection layer shaped by such a molding stamper, the antireflection layer has no defect and no shadow is observed.

  In the molding stamper according to the present invention, the shaped region has a concavo-convex structure produced by an anodic oxidation method, and the non-shaped region has a flat metal surface.

  The non-shaped region having a flat metal surface is a region that can be used as a power feeding portion for producing the shaped region by an anodic oxidation method. According to the present invention, the non-shaped region can be used as a region on which the curable resin is placed.

  In the molding stamper according to the present invention, a release treatment is performed on the shaping region.

  According to this invention, in the shaping area | region where the mold release process was performed, mold release of the curable resin hardened | cured after being extended to the shaping area | region becomes easy.

  The method for producing an antireflection film according to the present invention for solving the above-mentioned problem is a method for producing an antireflection film having an antireflection layer having a fine concavo-convex structure, and is a shaping for forming the antireflection layer A quadrilateral molding stamper having a shaping area where a mold is formed and a non-shaped area where the shaping mold is not formed, wherein the non-shaped area is along one side of the quadrilateral A step (A) of preparing a dedicated pallet on which a molding stamper used for placing an ionizing radiation curable resin provided with a predetermined width and extending to the shaping region is prepared; and the ionization on the non-shaped region While pressing the pressing member from the step (B) of placing the radiation curable resin, the step (C) of placing the base film on the molding stamper, and the base film on the ionizing radiation curable resin. Move A step (D) of stretching the ionizing radiation curable resin over the entire surface of the molding stamper, a step (E) of curing the ionizing radiation curable resin by irradiating ionizing radiation from the base film side, and after curing A step (F) of peeling the integrated body of the ionizing radiation curable resin and the base film from the molding stamper in that order.

  According to this invention, in the molding stamper placed on the dedicated pallet in the step (A), the non-shaped area where the shaping mold is not formed is used for placing the curable resin that extends to the shaping area. Therefore, if the curable resin is put on the non-shaped region in the step (B), and then the curable resin is stretched on the shaped region from one side of the stamper to the opposite side in the step (D). As the curable resin moves, the curable resin is filled without air remaining in the concave portion of the shaping region. As a result, the presence of air prevents the curable resin from being hardened in the recesses, so that the shaping mold is not clogged with the resin, and there is no entrainment of bubbles in the obtained antireflection layer. The antireflection film obtained by such a production method has no defect in the antireflection layer and no shadow is observed.

  In the method for producing an antireflection film according to the present invention, the fine concavo-convex structure has a protrusion having a period smaller than the wavelength in the visible light region, and the height of the protrusion is 150 nm to 450 nm. For shaping.

  According to this invention, it is preferable that the fine uneven structure of the molding stamper is the above-described embodiment, and as a result, an antireflection layer having a moth-eye structure with good antireflection properties can be formed.

  In the method for producing an antireflection film according to the present invention, the ionizing radiation curable resin is formed into a rectangular region having a predetermined length H and a predetermined width W along one side of the quadrilateral in the non-shaped region. Put it on.

  According to this invention, since the ionizing radiation curable resin is placed on a rectangular region having a predetermined length H and a predetermined width W along one side of the quadrilateral molding stamper, the ionizing radiation curable resin is The forming region is extended from one side of the molding stamper toward the opposite side of the side. As a result, with the movement of the ionizing radiation curable resin, the ionizing radiation curable resin is filled without air remaining in the concave portion of the shaping region. According to such a manufacturing method, the curing of the curable resin in the recess is inhibited by the presence of air, and the shaping mold is not clogged with the resin, and bubbles are also involved in the obtained antireflection layer. Absent. Further, the obtained antireflection film has no defect in the antireflection layer and no shadow is observed.

  In the method for producing an antireflection film according to the present invention, when the predetermined length H of the rectangular region is equally divided into 12 regions, the ionizing radiation curability placed on each of at least a second region from both ends of the rectangular region. The amount of resin is set to be larger than the amount of ionizing radiation curable resin placed on at least each of the four central regions.

  According to the present invention, when the rectangular area is equally divided into 12 areas, the amount of ionizing radiation curable resin placed on each of at least the second areas from both ends of the rectangular area is set to at least the central four areas. Since the amount of the curable resin is larger than the amount of the curable resin, the ionizing radiation curable resin is not spilled from the molding stamper when the pressing member is stretched, and is stretched by the pressing member from one side of the molding stamper to the other side. Can do.

  An antireflection film according to the present invention for solving the above problems is an antireflection film produced by the method for producing an antireflection film according to the present invention, comprising: a base film; and the base film Provided with an antireflection layer made of ionizing radiation curable resin, the antireflection layer has protrusions having a period smaller than the wavelength in the visible light region, and the height of the protrusions is 150 nm to 450 nm. The shadow is not visible when exposed to visible light.

  According to this invention, since the antireflection layer of the above aspect is provided, the protrusions having a period smaller than the wavelength of the visible light region are formed at a certain height such that no shadow is visible when the visible light is applied. Yes. As a result, it can be provided as an antireflection film having an antireflection layer having a moth-eye structure with good antireflection properties.

  According to the molding stamper according to the present invention, after placing the curable resin on the non-shaped region, if the curable resin is extended on the shaping region from one side of the stamper to the opposite side of the side, As the curable resin moves, the curable resin is filled without leaving air in the concave portions of the shaping region. Therefore, the presence of air inhibits the curing of the curable resin in the concave portions, and the shaping mold is made of resin. There is no clogging and there is no entrainment of bubbles in the resulting antireflection layer. As a result, the antireflection film having the antireflection layer formed by such a molding stamper has no defect in the antireflection layer and no shadow is observed.

  According to the method for producing an antireflection film according to the present invention, the curing of the curable resin in the recess is inhibited by the presence of air, and the shaping mold is not clogged with the resin, and the obtained reflection is obtained. Since an antireflection film in which bubbles are not entrained in the prevention layer can be produced, an antireflection film having no defects in the antireflection layer and no shadow can be efficiently produced.

  According to the antireflection film of the present invention, the protrusions having a period smaller than the wavelength of the visible light region are formed at a certain height such that no shadow is visible when the visible light is applied. It can be provided as an antireflection film having an antireflection layer having a good moth-eye structure.

It is typical sectional drawing which shows an example of the stamper for shaping | molding which concerns on this invention. FIG. 2 is a schematic plan view of the molding stamper shown in FIG. 1. It is a flowchart which shows the process order of the manufacturing method of the antireflection film concerning this invention. It is a typical perspective view which shows the fixing method of the molding stamper which concerns on this invention. It is explanatory drawing of the manufacturing method of the antireflection film concerning this invention. It is a typical top view explaining a resin mounting process and an extending process. It is sectional drawing (the 1) for demonstrating the manufacturing method of the antireflection film which concerns on this invention. It is sectional drawing (the 2) for demonstrating the manufacturing method of the antireflection film which concerns on this invention. It is a top view which shows the form after mounting curable resin on the stamper for shaping | molding. It is typical sectional drawing which shows an example of the antireflection film concerning this invention. It is typical sectional drawing which shows another example of the antireflection film concerning this invention. It is typical sectional drawing which shows the conventional manufacturing method of an antireflection film.

  Hereinafter, a molding stamper, an antireflection film manufacturing method, and an antireflection film according to the present invention will be specifically described with reference to the drawings. The following description and drawings show embodiments of the present invention, and it goes without saying that modifications including the gist of the present invention are included in the scope of the present invention.

[Molding stamper]
As shown in FIGS. 1 and 2, the molding stamper 2 according to the present invention includes a shaping region R1 where the shaping die 23 is formed and a non-shaped region R2 where the shaping die 23 is not formed. It has a stamper. The shaping mold 23 is a plate for shaping the fine concavo-convex structure 13 (moth eye structure) having antireflection ability on the curable resin 14 which is stretched after being stretched on the shaping mold 23. is there.

  The shaping mold 23 of the molding stamper 2 is produced by various conventionally known methods. For example, a manufacturing method using a laser interference method, a manufacturing method using a photolithography process, a manufacturing method using an anodic oxidation method, a manufacturing method using nanoparticle formation, a manufacturing method using dry etching, and the like can be given. The molding stamper 2 formed by forming the shaping mold 23 by these methods can be preferably used as a shaping mold for the extremely fine uneven structure 13 in any case.

  Among them, the molding stamper 2 in which the shaping mold 23 is formed by an anodic oxidation method can be preferably used. The forming stamper 2 in which the shaping mold 23 is formed by an anodic oxidation method is formed by anodizing an aluminum plate or an alloy plate thereof (hereinafter referred to as “aluminum plate”), or an aluminum film or an alloy thereof on a glass plate. After the film is formed, the film is anodized. Specifically, as described in Patent Document 1, first, an aluminum plate (including an alloy plate) or an aluminum film (including an alloy film) is used. Anodized to form an anodic oxide film having pores, then etched to enlarge the pore diameter, and then subjected to a second anodic oxidation to form further pores in the pores, Next, the pore size is increased by etching, and the pore size enlargement process is repeated as necessary to form the shaping mold 23 having desired pores (bell-shaped recesses). . Such a method is advantageous in that a molding stamper 2 having a large area can be formed.

  The molding stamper 2 can be formed of various materials derived from the manufacturing method thereof, and is not particularly limited. For example, when the anodic oxidation method is used as described above, an aluminum plate (including an alloy plate), an insulator such as a glass plate, or a metal or metal oxide other than aluminum such as SUS is used as the base. An aluminum film (including an alloy film) formed thereon is used. The thickness of the molding stamper is not particularly limited, but is about 0.5 mm to 10 mm. The thickness of the aluminum film when the aluminum film is formed on the substrate is not particularly limited, but is generally 500 nm to 1.5 μm.

  The size of the molding stamper 2 is arbitrary according to the size of the antireflection region required for the antireflection film 10, and the shape thereof is a quadrangle (rectangle or square) in plan view. Here, the antireflection region is an effective formation region of the shaping mold 23 that forms the antireflection layer 12 (referred to as “shaped region R1”). In this invention, as shown in FIG.1 and FIG.2, it has the shaping area | region R1 in which the shaping mold 23 is formed, and the non-shaped shaping area | region R2 in which the shaping mold 23 is not formed. In addition, the code | symbol 16 in FIG.1 and FIG.2 etc. is a boundary of shaping | molding area | region R1 and non-shaped area | region R2.

  As shown in FIG. 2, the non-shaped region R2 is along one side (short side of length L1) of the molding stamper 2 having a quadrilateral shape (short side length L1 × long side length L2) in a plan view. , Provided in a band shape with a predetermined width L3. The non-shaped region R2 is not provided with the shaping mold 23 and is a flat surface. When the shaping mold 23 is formed by an anodic oxidation method, the non-shaped region R2 is a flat metal surface that is not anodized. This flat metal surface can be used as a power feeding portion for producing the shaping region R1 by an anodic oxidation method.

  In the non-shaped region R2, a curable resin 14 for extending the shaped mold 23 is placed. Therefore, it is necessary to have a size corresponding to the amount of the curable resin 14 corresponding to the area of the shaping region R1. Therefore, the size of the non-shaped region R2 is arbitrarily set according to the size of the shaped region R1, in other words, according to the amount of the curable resin 14 placed on the shaped region R1.

  As shown in FIG. 2, the shaping region R1 is a region other than the non-shaped region R2 from the entire region of the molding stamper 2, and has a short side length (L1) × long side length (L2). -L3). The shaping region R1 is provided with a shaping die 23 formed by, for example, an anodic oxidation method or other methods, but the shaping die 23 is not formed at the peripheral portion or is somewhat disturbed. There may be a portion which is the shaping mold 23. Such parts are often severed eventually. On the shaping region R1, the curable resin 14 placed on the non-shaped region R2 is stretched by a pressing member 5 such as a nip roll. When the antireflection film 10 is used as a front film of a display, for example, the shaping region R1 has a size including one or two (including many) sizes of the display.

  In the case where the shaping region R1 is formed by an anodic oxidation method, an infinite number of bell-shaped concave portions are formed in the shaping region R1. The bell-shaped recess is for shaping the protrusion 15 forming the moth-eye structure on the antireflection layer 12. As shown in FIG. 10, the moth-eye structure projection 15 has a period P (pitch) smaller than the wavelength in the visible light region, and has a height h in the range of 150 nm to 450 nm. Here, the wavelength in the visible light region is 380 nm to 780 nm. Therefore, the period P of the protrusion 15 shaped by the shaping mold 23 is smaller than the wavelength in the visible light region, that is, 380 nm or less. Note that the period P of the protrusion 15 is a period in a two-dimensional direction, and may be regular or irregular. However, if it is regular, coloring due to interference may occur, and therefore it is preferably irregular.

  It is preferable that a mold release process is performed on the shaping mold 23 (bell-shaped recess) in the shaping region R1. By performing the mold release treatment, the curable resin after being stretched and cured in the shaping region R1 can be easily peeled off. As the mold release treatment, a mold release agent such as a fluorine-based resin (for example, “OPTOOL HD-1100, 2100 series” manufactured by Daikin Kasei Co., Ltd., “EGC-1720” manufactured by Sumitomo 3M Limited), etc. It can be applied to the surface of the molding stamper by a method such as brush coating, dip coating, spin coating, spray coating, dispenser coating, etc., and release treatment can be performed. Moreover, in order to maintain the mold release effect, a rinsing process may be provided in which heat treatment is performed at a predetermined temperature or excess mold release agent is removed. In particular, alumite obtained by anodizing aluminum tends to be inferior in releasability with respect to the curable resin. Therefore, it is desirable to perform a release treatment. In addition, you may mix | blend the material which improves mold release property in curable resin. Examples of such materials include phosphate esters and phosphonate esters.

  The mass of the molding stamper 2 is not particularly limited, and it is desirable that the molding stamper 2 has a mass that does not lift even by the force F that peels off the integral 10 ′ from the molding stamper 2 in the peeling process shown in FIG. 3. When the molding stamper 2 is lifted in the peeling process, the peeling angle between the integrated object 10 'and the molding stamper 2 at the time of peeling changes and the process conditions fluctuate. May not be shaped, and the yield may decrease. The molding stamper 2 preferably has a peel strength F in the range of 0.020 to 2.0 N / 25 mm when the integral 10 ′ is peeled off from the molding stamper 2. The mass of 2 is desirably a value exceeding the peeling strength F. For example, if the peeling strength F of the molding stamper 2 having a width L1 is 0.020 N / 25 cm, the mass (kg) of the molding stamper 2 exceeds 0.020 N ÷ 9.8 × (L1 / 25). If the peel strength F of the molding stamper 2 having a width L1 is 2.0 N / 25 cm, the mass (kg) of the molding stamper 2 is 2.0 N ÷ 9.8 × (L1 / 25) It will exceed. The molding stamper 2 having such a mass does not lift even with the above-described peeling strength.

  As described above, the molding stamper 2 according to the present invention is used for placing the curable resin 14 that extends in the shaping region R1 in the non-shaped region R2 where the shaping mold 23 is not formed. When the curable resin 14 is placed on the shaping region R1 from the one side of the molding stamper 2 toward the opposite side of the molding stamper 2 after the curable resin 14 is placed on the region R2, the curable resin 14 moves. The curable resin 14 is filled without air remaining in the concave portion of the shaping region R1. As a result, the presence of air prevents the curing of the curable resin 14 in the recess, and the shaping mold 23 is not clogged with the curable resin 14, and the obtained antireflection layer 12 has no bubbles. There is no entrainment. In the antireflection film 10 having the antireflection layer 12 formed by such a molding stamper 2, the antireflection layer 12 has no defect and no shadow is observed.

[Method for producing antireflection film]
As shown in FIGS. 10 and 11, an antireflection film 10 obtained by the method for producing an antireflection film according to the present invention includes a base film 11 and an ionizing radiation curable resin 14 provided on the base film 11. And an antireflection layer 12 made of at least. The surface of the antireflection layer 12 is formed with a fine concavo-convex structure 13 (moth eye structure) that provides antireflection performance.

  As shown in FIGS. 3 and 5, the manufacturing method according to the present invention for manufacturing such an antireflection film 10 includes a shaping region R1 in which a shaping mold 23 is formed and a non-forming mold 23 in which the shaping mold 23 is not formed. A step (A) of preparing a dedicated pallet 1 on which a molding stamper 2 having a shaping region R2 is placed, a step (B) of placing an ionizing radiation curable resin 14 on the non-shaped region R2, and a molding The step (C) of placing the base film 11 on the stamper 2 and the pressing member 5 are moved from above the base film 11 on the ionizing radiation curable resin 14 while being pressed, thereby forming the ionizing radiation curable resin 14. A step (D) of stretching the entire surface of the stamper 2, a step (E) of curing the ionizing radiation curable resin 14 by irradiating the ionizing radiation 6 from the base film 11 side, and the ionizing radiation curable resin 14 after curing. (Anti-reflective With a layer 12) and the step of peeling the single piece 10 'of the base film 11 from the molding stamper 2 (F), at its order.

  Hereinafter, each component will be described in detail.

(Preparation process)
The preparation step (A) is a step of preparing the dedicated pallet 1 on which the molding stamper 2 is placed. The dedicated pallet 1 is a process member on which a molding stamper 2 is placed and returns through each process in turn. The dedicated pallet 1 is usually composed of a metal plate such as a stainless steel plate or an aluminum alloy plate. The size of the dedicated pallet 1 is not particularly limited as long as the guide member 3 can be provided around the molding stamper 2 as shown in FIG. As shown in FIG. 4, the dedicated pallet 1 is placed in contact with at least three sides of the molding stamper 2 to place the molding stamper 2 at a predetermined position (the center position of the dedicated pallet 1). A guide member 3 is preferably provided.

  Since the molding stamper 2 is as described above, the description thereof is omitted here.

  As shown in FIG. 4, the guide member 3 is a member that abuts at least three sides of the molding stamper 2 and places the molding stamper 2 at a predetermined position. Here, as shown in FIG. 6, at least three sides are a guide member 3 ′ provided in the moving direction of the pressing member 5 and guide members 3 ″, 3 ″ provided in a direction orthogonal to the moving direction. That's it. The reason why the guide member 3 opposite to the moving direction of the pressing member 5 is excluded from the essential guide member is that the guide member 3 is not loaded when the pressing member 5 is moved. As shown in FIG. 4, it is preferable that four guide members 3 are usually provided so as to abut on the four sides of the molding stamper 2.

  The material of the guide member 3 is not particularly limited. For example, a material such as an aluminum plate, a SUS plate, or a plastic plate that does not interfere with the process, such as generation of absorbed heat and shape change even when irradiated with ionizing radiation. I just need it. As shown in FIG. 6, the size of the guide member 3 is sufficient if it has a length that makes contact with the molding stamper 2 at a predetermined length in a substantially central region of each side of the molding stamper 2. The length is not particularly limited. In FIG. 6, an example is described in which the length is equal to or longer than half the short side length L1 of the molding stamper 2 and is equal to or longer than half the long side length L2. As shown in FIG. 6, the shape of the guide member 3 is usually a quadrilateral, and the shape is not particularly limited. The guide member 3 is desirably the same as or lower than the height of the molding stamper 2 so as not to hinder the movement of the pressing member 5 described later. Such a guide member 3 may be fixed on the dedicated pallet 1 with an adhesive or an adhesive, or may be mechanically fixed with a screw, a bolt, a nut, or the like, or magnetically fixed with a magnet or the like. May be. By using the dedicated pallet 1 provided with such a guide member 3, it is easy to place and remove the molding stamper 2, which is convenient for replacement and maintenance.

  The dedicated pallet 1 to the molding stamper 2 may be provided with a temperature control mechanism. If the dedicated pallet 1 to the molding stamper 2 having the temperature control mechanism are set in advance to a predetermined temperature and then resin molding is performed, adverse effects based on changes in the resin viscosity due to the ambient temperature can be suppressed. As a result, it is possible to ensure a stable shaping area at all times in the molding stamper 2.

  The molding stamper 2 is placed on the dedicated pallet 1 by the placing table 8 shown in FIG. The mounting table 8 is provided with a dedicated pallet 1 in which a guide member 3 is fixed in advance at a predetermined position (a position where the molding stamper 2 is fixed). The molding stamper 2 is positioned on the dedicated pallet 1 by the guide member 3. Placed in a fixed manner. The placed molding stamper 2 is transferred to the resin loading step, which is the next step, by the transport device.

(Resin loading process)
The resin placing step (B) is a step of placing a predetermined amount of ionizing radiation curable resin 14 on a predetermined portion on the non-shaped region R2, as shown in FIG. 2 and FIGS. Since the non-shaped region R2 is as described in the explanation column of the molding stamper 2, the description thereof is omitted, but as shown in FIG. 2, a quadrilateral (short side length L1 × long side length) is seen in a plan view. Is provided in a strip shape with a predetermined width L3 along one side (short side of length L1) of the molding stamper 2 having a length L2. By placing the ionizing radiation curable resin 14 on the non-shaped region R2, the forming region can be moved by one stretch (one pass) of the pressing member 5 from one side of the molding stamper 2 to the other side. The ionizing radiation curable resin 14 is filled without leaving air in the concave portion of R1. Such a filling means does not generate the remaining air as in the conventional case of placing the ionizing radiation curable resin 14 on the shaping region R1, and can solve the problem caused by the remaining air.

  In particular, the ionizing radiation curable resin 14 is preferably placed in a rectangular region (see FIG. 9) having a predetermined length H and a predetermined width W along one side of the quadrilateral in the non-shaped region R2. By placing the ionizing radiation curable resin 14 on the rectangular region, when the ionizing radiation curable resin 14 is stretched over the shaping region R1 by the pressing member 5, the same air residue as described above is not generated, and the ionizing radiation is not generated. There is an advantage that the curable resin 14 does not spill from the molding stamper 2. More specifically, as shown in FIG. 9, the rectangular region (H × W) of the non-shaped region R2 has a length H extending along the short side of the length L1 and a predetermined interval from the short side. A width W extending in the long-side direction across S3. The length H is 60% to 95% of the length L1, and is a region separated from the long sides of both sides by a predetermined interval S1, S2. The intervals S1 and S2 are set in consideration of the fact that the ionizing radiation curable resin 14 does not spill from the molding stamper 2 and is stretched by one pass. Specifically, the intervals S1 and S2 are 10 mm to It is preferable that it is about 100 mm. Further, the interval S3 from the short side is also set in consideration that the ionizing radiation curable resin 14 is not spilled from the molding stamper 2 and is stretched by one pass. Specifically, the interval S3 is 10 mm to It is preferable that it is about 100 mm. In the present application, the relationship between the short side and the long side of the molding stamper 2 may be switched.

  As shown in FIG. 9, when the rectangular region (H × W) of the non-shaped region R2 is divided into 12 regions (a1 to a12) by dividing the predetermined length H of the rectangular region into 12 regions, the rectangular region The amount of ionizing radiation curable resin placed on each of at least the second regions (a2, a11) from both ends of the resin is larger than the amount of ionizing radiation curable resin placed on each of the four central regions (a5, a6, a7, a8). To do. By setting the amount of the ionizing radiation curable resin to be placed on the rectangular region in this way, the ionizing radiation curable resin 14 does not spill from the shaping region R1 when the pressing member 5 is stretched, so that one side of the molding stamper 2 It can be extended by the pressing member 5 from the side toward the other side.

  By adjusting the amount of the ionizing radiation curable resin 14 in the above relationship, the ionizing radiation curable resin 14 may be spilled from the molding stamper 2 in the process of extending the ionizing radiation curable resin 14 over the entire shaping region R1. Absent. As a result, it is possible to prevent problems such as spilled ionizing radiation curable resin 14 scattering and contaminating the shaping mold of the molding stamper 2 at the time of peeling. In the present application, “at least the central four regions (a5, a6, a7, a8)” may include the a4 region and the a9 region in the four regions (a5, a6, a7, a8). Further, the a3 region and the a10 region may be included. In addition, the a1 region and the a12 region at both ends of the rectangular region usually have a smaller amount of resin than the second region (a2, a11) from both ends.

  A predetermined amount of the ionizing radiation curable resin 14 is placed on the molding stamper 2 by the resin flow nozzle 4 as shown in FIGS. More specifically, a fixed multiple dispenser nozzle or a movable dispenser nozzle is used as the resin flow nozzle 4.

  The fixed-type multiple dispenser nozzle has two or more nozzles arranged at equal intervals along one side of the molding stamper 2, and is fixed in various ways, for example, 6, 8, 10, 12, etc. A type multiple dispenser nozzle can be used. In the fixed multiple dispenser nozzle, the position of each nozzle with respect to the molding stamper 2 is fixed, and therefore, a predetermined amount of ionizing radiation curable resin 14 having the above-described relationship is caused to flow down to the non-shaped region R2. The control is performed by controlling the discharge amount from each nozzle. For example, when 12 nozzles are used, the discharge amount from the second and eleventh nozzles is larger than the discharge amount from the fifth to eighth nozzles, for example, at least second from both ends of the rectangular area. The amount of ionizing radiation curable resin placed on each of the regions (a2, a11) can be made larger than the amount of ionizing radiation curable resin placed on each of the four central regions (a5, a6, a7, a8).

  On the other hand, the movable dispenser nozzle is a nozzle that moves along one side of the molding stamper 2. This movable dispenser nozzle may be composed of one dispenser nozzle or may be composed of two or more dispenser nozzles. In the movable dispenser nozzle, the position relative to the molding stamper 2 is not fixed, and the ionizing radiation curable resin 14 moves while flowing down from one side of the molding stamper 2 toward the other side. Control for causing the predetermined amount of ionizing radiation curable resin 14 having the above relationship to flow down to the non-shaped region R2 is performed by controlling the discharge amount from the moving nozzle. For example, the amount of ionizing radiation curable resin placed on each of at least the second regions (a2, a11) from the both ends of the rectangular region at least at the middle point, less at the middle point, and more at the end again at the end. The amount of ionizing radiation curable resin placed on each of the four central regions (a5, a6, a7, a8) can be increased. Such control is performed by arbitrarily setting the movement speed and the discharge amount. For example, the control is performed by changing the discharge amount while moving at a constant movement speed, or by setting the discharge amount to be a constant while changing the transfer speed. Is called.

  Thus, since the resin flow nozzle 4 for placing the ionizing radiation curable resin 14 on the rectangular region (H × W) of the non-shaped region R2 is a fixed multiple dispenser nozzle or a movable dispenser nozzle, it will be described later. It is possible to place the ionizing radiation curable resin 14 on the rectangular region (H × W) by controlling the amount that the ionizing radiation curable resin 14 does not spill from the shaping region R1 when the pressing member 5 is stretched. As a result, the ionizing radiation curable resin 14 can be stretched by the pressing member 5 from one side of the molding stamper 2 toward the other side in a manner that does not spill from the shaping region R1.

  As the ionizing radiation curable resin 14, a monomer (monomer) that is polymerized and cured by a reaction such as crosslinking with ionizing radiation, or a prepolymer or an oligomer is used. As the monomer, for example, a radical polymerizable monomer, specifically, 2-ethylhexyl (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) Examples thereof include various (meth) acrylates such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Examples of the prepolymer (or oligomer) include radically polymerizable prepolymers, specifically, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, triazine (meth) acrylate, and the like. (Meth) acrylate prepolymers, polythiol prepolymers such as trimethylolpropane trithioglycolate, pentaerythritol tetrathioglycolate, and unsaturated polyester prepolymers. Other examples include cationically polymerizable prepolymers such as novolac epoxy resin prepolymers and aromatic vinyl ether resin prepolymers. Here, the notation (meth) acrylate means acrylate or methacrylate. These monomers or prepolymers may be used alone or in combination of two or more types of monomers, two or more types of prepolymers, or one type of monomer, depending on the required performance, coating suitability, etc. A mixture of the above and one or more prepolymers can be used.

  As the photopolymerization initiator, in the case of a radically polymerizable monomer or prepolymer, a benzophenone-based, acetophenone-based, thioxanthone-based, benzoin-based compound, etc., or in the case of a cationic polymerization-based monomer or prepolymer, , Metallocene-based, aromatic sulfonium-based and aromatic iodonium-based compounds are used. These photopolymerization initiators are added in an amount of about 0.1 to 5 parts by weight with respect to 100 parts by weight of the composition comprising the monomer and / or prepolymer.

  Typical examples of the ionizing radiation include ultraviolet rays and electron beams. In addition, electromagnetic waves such as visible light, X-rays, and γ rays, or charged particle beams such as α rays can also be used.

  Additives are appropriately added to the ionizing radiation curable resin 14 as necessary. Examples of additives include heat stabilizers, radical scavengers, plasticizers, surfactants, antistatic agents, antioxidants, ultraviolet absorbers, infrared absorbers, dyes (colored dyes, colored pigments), extender pigments, Examples thereof include a light diffusing agent.

  In the present invention, the ionizing radiation curable resin 14 is placed on the non-shaped region R2, and then the base film 11 is placed as will be described later, and the base film 11 and the ionizing radiation curable are further pressed by the pressing member (roll) 5. The resin 14 is moved while being pressed and stretched to fill the bell-shaped recess without leaving air. That is, the base film 11 and the ionizing radiation curable resin 14 are moved while being pressed by the pressing member 5. By such a process, the ionizing radiation curable resin 14 is filled so as to flow into the bell-shaped concave portion of the shaping region R1. The flow of the ionizing radiation curable resin 14 is affected by the viscosity of the ionizing radiation curable resin 14. A preferable viscosity at which filling is performed favorably is in the range of 5 to 2000 mPa · s, and a more preferable viscosity is in the range of 50 to 1200 mPa · s.

  After the ionizing radiation curable resin 14 is placed on the molding stamper 2 in this way, it is transferred to the substrate film placing step which is the next step by the transport device.

(Base film loading process)
As shown in FIGS. 5 (C) and 7 (B), the base film mounting step (C) is performed after the ionizing radiation curable resin 14 is placed on the non-shaped region R2 of the molding stamper 2 and then molded. This is a step of placing the base film 11 on the stamper 2 for use. For example, a method of supplying the molding stamper 2 on an automatic machine or manually from a stacker on which the base film 11 is laminated can be mentioned. Examples of the automatic machine include a device that holds the upper surface of the base film 11 (a non-molding surface on which the antireflection layer is not formed on the base film 11) and places it on a predetermined position on the molding stamper 2, for example. Can do. Although the magnitude | size of the base film 11 is not specifically limited, Usually, it is a sheet-like film of the same magnitude | size or the magnitude | size comparable as the stamper 2 for a shaping | molding.

  The base film 11 may be selected from various materials having various thicknesses in consideration of required transparency such as desired transparency, mechanical strength, and adhesiveness with the ionizing radiation curable resin 14. The thickness of the base film 11 may be a film, a sheet, or a plate. Usually, a resin transparent film is preferably used. Such a base film 11 is preferably a film based on an acrylic resin (used here as a concept including a methacrylic resin), a polyester resin, or the like, but is not limited thereto. Specific examples of the resin material include cellulose resins such as triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymer Polymers, polyester resins such as terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymer, polyester thermoplastic elastomer, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, cyclic polyolefin, polyvinyl chloride, polyvinylidene chloride Halogen-containing resins such as polyether sulfone resin, polyacrylic resin, polyurethane resin, polycarbonate resin, styrene resin such as polystyrene, polyamide Fat, polyimide resins, polysulfone resins, polyether resins, polyether ketone, (meth) acrylonitrile and the like can be used. Among them, the biaxially stretched PET film is preferable in that it has excellent transparency and durability, and has heat resistance that does not cause thermal deformation even when subjected to ionizing radiation irradiation treatment or heat treatment in the subsequent steps. Moreover, when using as a protective surface film of the polarizing plate for liquid crystal displays, a triacetyl cellulose film is suitable.

  The thickness of the base film 11 is usually preferably about 50 μm to 3000 μm, but is not limited thereto. The light transmittance of the base film 11 is ideally 100% for the front installation of the display device, but it is preferable to select a light transmittance of 80% or more. If necessary, the surface of the base film 11 is provided with an easy-adhesion layer in order to improve the adhesion with the ionizing radiation curable resin 14 described above, or a surface such as corona discharge treatment, plasma treatment, or flame treatment. Processing may be performed. As an easily bonding layer, it comprises from resin which has adhesiveness in both the base film 11 and the ionizing radiation-curable resin 14. FIG. The resin for the easy adhesion layer is appropriately selected from resins such as urethane resin, epoxy resin, polyester resin, acrylic resin, and chlorinated polypropylene.

  Further, a composite film may be used as the base film 11. As the composite film, for example, as shown in FIG. 11, a polarizer protective film 11a, a primer layer 11b provided on one surface thereof, and a protective film 11c provided on the other surface can be exemplified. In addition, the adhesive layer may be provided between the polarizer protective film 11a and the protective film 11c, and the polarizing film 11a is 1st polarizer protective film / polarizer A / 2nd polarizer protective film. It may be a three-layer structure.

  When the base film 11 is placed on the molding stamper 2, the ionizing radiation curable resin 14 spreads on the molding stamper 2 by the weight of the base film 11. After being placed, the base film 11 adheres to the resin spread on the molding stamper 2 and does not shift during transportation. The other end of the base film 11 that is not on the ionizing radiation curable resin 14 may be floated or may be placed on the molding stamper 2 as it is. The base film 2 is placed on the molding stamper 2 after the ionizing radiation curable resin 14 flows down on the molding stamper 2 and then the ionizing radiation curable resin 14 flows out of the molding stamper 2. It is desirable to carry out as quickly as possible so that foreign matter or the like does not fall on the molding stamper 2. For example, it is preferable to carry out within 60 seconds after the ionizing radiation curable resin 14 flows down on the molding stamper 2.

  After the base film 11 is placed on the molding stamper 2 in this way, it is transferred to a resin stretching process, which is the next process, by a transport device.

(Resin stretching process)
As shown in FIGS. 5 (D), 6 and 7 (C), the resin stretching step (D) is performed with the pressing member 5 on the base film 11 on the ionizing radiation curable resin 14. 11 and the ionizing radiation curable resin 14 are moved while being pressed, and the ionizing radiation curable resin 14 placed in the non-shaped region R <b> 2 is stretched over the entire surface of the molding stamper 2.

  The pressing member 5 is not particularly limited, but usually a nip roll having an arbitrary diameter is used. The diameter of the nip roll is one of the important factors for filling the ionizing radiation curable resin 14 without leaving air in the bell-shaped concave portion of the shaping region R1. The diameter correlates with the viscosity of the ionizing radiation curable resin 14 and the moving speed of the nip roll, but is preferably, for example, a diameter of 100 to 800 mm. The nip roll may have a temperature control function. The viscosity of the ionizing radiation curable resin 14 can be adjusted by pressing and moving the nip roll while controlling the temperature of the nip roll, so that the ionizing radiation curable resin 14 is moved into the bell-shaped recess of the shaping region R1. It is preferable to use it effectively when filling without leaving.

  As shown in FIG. 6, the pressing member 5 moves in one pass from the non-shaped region R2 on which the ionizing radiation curable resin 14 is placed toward the opposite side. At that time, the pressing member 5 moves while pressing the base film 11 from above to below. In this step, the ionizing radiation curable resin 14 pressed through the base film 11 by the pressing member 5 can be stretched over the entire surface of the molding stamper 2. The moving speed of the pressing member 5 such as a nip roll is also an important factor for filling the ionizing radiation curable resin 14 without leaving air in the bell-shaped concave portion of the shaping region R1. The moving speed is related to the viscosity of the ionizing radiation curable resin 14 and the diameter of the nip roll. For example, the moving speed is preferably 0.5 to 10 m / min, and preferably 1 to 3 m / min. More preferred. If the moving speed of the pressing member 5 (for example, the nip roll) is too low, the productivity is poor. On the other hand, if the moving speed of the pressing member 5 (for example, the nip roll) is too large, the curable resin is sufficiently contained in the concave portion of the molding stamper 2. It may not fill or cause bubbles.

  The pressing and movement of the pressing member 5 can be performed, for example, in the form shown in FIG. As shown in FIG. 6A, a nip roll (reference numeral 5 is used) is disposed on the guide member 3 that abuts the side adjacent to the non-shaped region R2, particularly the rectangular region (H × W), and thereafter. When the dedicated pallet 1 is transferred by the conveying device, the nip roll 5 rotates while pressing the base film 11 on the molding stamper 2 from above, and the ionizing radiation between the base film 11 and the molding stamper 2 is rotated. The curable resin 14 is stretched in the traveling direction of the nip roll 5. The movement of the nip roll at this time may be performed by the rotational movement of the nip roll itself, or may be performed by transferring the dedicated pallet 1 by the transport device.

  The pressing force of the pressing member 5 is arbitrarily set in consideration of the amount of ionizing radiation curable resin 14 and the like. If the pressing force is too strong, the ionizing radiation curable resin 14 quickly flows from the molding stamper 2 into the shaping region R1, and air is trapped in the bell-shaped recess, or the ionizing radiation curable resin 14 is molded into the molding stamper. It may spill from 2. On the other hand, if the pressing force is weak, the ionizing radiation curable resin 14 may not spread over the entire surface of the molding stamper 2.

  The relative movement of the pressing member 5 extends the ionizing radiation curable resin 14 over the entire surface of the molding stamper 2. Here, the entire surface means a shaping mold forming region provided in the molding stamper 2. When the shaping mold 23 is provided up to the periphery of the molding stamper 2, ionizing radiation curing is performed. The conductive resin 14 is stretched to the periphery without spilling from the molding stamper 2. Further, for example, when the shaping mold is provided from the periphery of the molding stamper 2 to about 10 mm inside, for example, the ionizing radiation curable resin 14 is stretched to that portion without spilling from the molding stamper 2. In addition, the periphery of the ionizing radiation curable resin 14 that has been stretched is often cut in order to finally limit it to a predetermined dimension (product dimension or the like).

  In order to stretch the ionizing radiation curable resin 14 from the molding stamper 2 "without spilling", as described above, the position, amount, shape, and pressing member 5 on which the ionizing radiation curable resin 14 is placed. This can be realized by setting the pressing force of.

  After the ionizing radiation curable resin 14 is stretched over the entire surface of the molding stamper 2 in this manner, the ionizing radiation curable resin 14 is transferred to the curing step, which is the next step, by the transport device.

(Curing process)
The curing step (E) is a step of curing the ionizing radiation curable resin 14 by irradiating the ionizing radiation 6 from the base film 11 side, as shown in FIGS. 5 (E) and 8 (D). Since the base film 11 transmits ionizing radiation, the ionizing radiation 6 is irradiated from the base film 11 side. As described above, the ionizing radiation 6 is typically an ultraviolet ray or an electron beam, but other than this, an electromagnetic wave such as a visible ray, an X-ray or a γ ray, or a charged particle beam such as an α ray may be used. it can. A commercially available device can be used as the ionizing radiation irradiating apparatus 7 for irradiating such ionizing radiation. However, by arranging the ionizing radiation irradiating device 7 in a direction orthogonal to the transfer direction of the dedicated pallet 1, it can be cured in one pass during the transfer. . Usually, since an ultraviolet curable resin is used, the ultraviolet curable resin is cured by irradiating ultraviolet rays having a wavelength of 365 nm with an ultraviolet irradiation device as ionizing radiation.

  After the ionizing radiation curable resin 14 is cured in this way, it is transferred to the peeling process, which is the next process, by the transport device.

(Peeling process)
In the peeling step (F), as shown in FIGS. 5 (F) and 8 (E), the integrated 10 'of the ionizing radiation curable resin 14 and the base film 11 after curing is removed from the molding stamper 2. This is a peeling process. As shown in FIG. 8E, it is convenient to pull off the single object 10 ′ by holding the side of the single object 10 ′ on the non-shaped region R2 side and pulling it upward.

  At this time, as described above, it is desirable that the mass of the molding stamper 2 is adjusted so that it does not float even by the force F that peels the integral 10 ′ from the molding stamper 2. When the molding stamper 2 is lifted in the peeling process, the peeling condition between the integrated object 10 ′ and the molding stamper 2 at the time of peeling changes to change the process conditions. It may occur and cannot be shaped accurately, and the yield may decrease. The peeling strength F when the integral 10 ′ is peeled off from the molding stamper 2 is preferably in the range of 0.020 to 2.0 N / 25 mm. With such a peeling strength F, the molding stamper 2 does not float. Thus, the mass of the molding stamper 2 is set as described above.

  The peel strength is a value based on JIS K 6854-1, and is represented by a value at a width of 25 mm when the integrated object 10 ′ is pulled up in a direction of 90 ° with respect to the surface. Actually, it can be evaluated by an actual measurement value when the width is 25 mm.

(Other processes)
The antireflection film 10 thus peeled off is cut from the cutting line 17 in the ionizing radiation curable resin layer in the non-shaped region R2 where the uneven structure 13 is not formed, as shown in FIG. Moreover, it will become the anti-reflective film 10 as a product through various processes after that as needed. For example, a step of cutting the periphery of the shaping region R1, a step of providing a protective film (masking film) for protecting the antireflection layer 12 on the concavo-convex structure 13, and the like may be provided.

  As described above, according to the method for producing an antireflection film of the present invention, the forming mold 23 placed on the dedicated pallet 1 in the step (A) is not formed with the forming mold 23. Since area | region R2 is used in order to mount the curable resin 14 extended in the shaping area | region R1, curable resin 14 is mounted in the non-shaped area | region R2 in a process (B), and curable resin 14 is used in a process (D) after that. Is stretched on the shaping region R1 from one side of the molding stamper 2 toward the opposite side of the molding stamper 2, the air is not left in the concave portion of the shaping region R1 along with the movement of the curable resin 14. Is filled. As a result, the presence of air prevents the curing of the curable resin 14 in the recesses, and the shaping mold 23 is not clogged with the resin, and the resulting antireflection layer 12 is free of bubbles. . In the antireflection film 10 obtained by such a manufacturing method, the antireflection layer 12 has no defect and no shadow is observed.

[Antireflection film]
The antireflection film 10 according to the present invention is manufactured by the above-described manufacturing method according to the present invention, and includes a base film 11 and an ionizing radiation curable resin 14 provided on the base film 11. And an antireflection layer 12. The antireflection layer 12 has a protrusion 15 having a period P smaller than the wavelength of the visible light region, and the protrusion 15 has a height h of 150 nm to 450 nm, and has a shadow when irradiated with visible light. It is characterized by being invisible.

  The base film 11 and the antireflection layer 12 constituting the antireflection film 10 are various base films 11 (including the above-described composite film, see FIG. 11) and the above-described manufacturing method. Since the antireflection layer 12 (ionizing radiation curable resin 14) can be applied, the description thereof is omitted here. A large number of protrusions 15 are provided on the surface of the antireflection layer 12, and the concavo-convex structure 13 having the protrusions 15 is formed by the shaping mold 23 included in the molding stamper 2 described above. The antireflection layer 12 includes a concavo-convex structure 13 having protrusions 15 and a base portion that is a base portion of the concavo-convex structure 13. The thickness of the base is desirably 2 to 30 μm.

  The protrusions 15 provided on the surface of the antireflection layer 12 are provided with a period P smaller than the wavelength in the visible light region. Here, since the “wavelength in the visible light region” is a wavelength of 380 nm to 780 nm, the “wavelength in the visible light region or less” means a wavelength of 380 nm or less. Accordingly, the protrusions 15 are provided with a period (pitch) P of 380 nm or less. The period P may be regular or irregular, but is usually provided with an irregular period P of 50 nm to 200 nm. Since the projections 15 are provided with such a period P, the refractive index is equivalent to that having a gradient with respect to the incident light, and the abrupt refractive index difference is eliminated, so that the incident light is hardly reflected. The adjustment of the period P reflects the period of the concave portion provided in the molding stamper 2, and the adjustment of the period P can be performed by controlling the period of the concave portion of the molding stamper 2.

  Moreover, although the height h of the protrusion 15 is 150 nm to 450 nm, a structure suitable for various displays as an antireflection film can be obtained by setting the height in this range. If the height h of the protrusion 15 is less than 150 nm, the antireflection function in the long wavelength region of the visible light region may be inferior. If it exceeds 450 nm, the individual protrusion structure is fragile and is resistant to external impacts such as scratches. May be easily damaged. The height h of the protrusion 15 reflects the depth of the concave portion provided in the molding stamper 2, and the height h can be adjusted by controlling the depth of the concave portion of the molding stamper 2. .

  The antireflection film 10 in which the protrusions 15 of the antireflection layer 12 are provided with the period P and the height h has a peel strength F from the molding stamper 2 in the range of 0.020 to 2.0 N / 25 mm. Is preferred. The concavo-convex structure 13 of the antireflection layer 12 having such a peeling strength F does not require an excessive force at the time of peeling, and as a result, it can prevent the resin from being crushed or dispersed causing defects in the fine concavo-convex structure 13. it can. Therefore, the fact that the period P and the height h of the protrusion 15 are within the above range means that the protrusion 15 is peeled off with the peeling strength F within this range. It can be said.

  Since the antireflection film 10 according to the present invention includes the antireflection layer 12 of the above aspect, the protrusion 15 having a period P smaller than the wavelength in the visible light region is constant so that no shadow is visible when the visible light is applied. The height h is formed. As a result, it can be provided as an antireflection film having the antireflection layer 12 having a moth-eye structure with good antireflection properties. Moreover, since the antireflection film 10 is formed by placing the ionizing radiation curable resin 14 on the non-shaped region R2 of the molding stamper 2 and extending it from that position with one pass, the conventional streak pattern is not seen. There are remarkable features.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
An aluminum steel plate having a thickness of 15 mm is used as the dedicated pallet 1, and a molding stamper 2 produced by an anodic oxidation method is used as the molding stamper 2. Four guide members 3 for fixing on the top were bonded to positions corresponding to the respective sides of the molding stamper 2. The molding stamper 2 is obtained by repeating anodization and etching of pure aluminum (purity 99.9%), and the shaping region R1 in which the shaping die 23 is formed and the shaping die 23 are formed. And a non-shaped region R2. The bell-shaped concave portion of the shaping mold 23 formed in the shaping region R1 has a bell-shaped concave portion having a period of about 110 nm to 130 nm and a depth of 350 nm to 400 nm. It has a mold 23. After forming the shaping mold 23, a mold release agent (trade name: OPTOOL HD-1100, manufactured by Daikin Kasei Sales Co., Ltd.) is applied to the surface of the shaping mold by a spin coating method, and a mold release treatment is performed. Left under for 24 hours. Then, in order to remove an excessive mold release agent, it rinsed with the special diluent and was made to dry at room temperature. The molding stamper 2 has a short side length L1 of 420 mm, a long side length L2 of 530 mm, and a thickness of 1.75 mm. The non-shaped region R2 is provided with a width of 60 mm along the short side. The molding stamper 2 has a weight of 1200 g. The guide member 3 is rectangular and has a long side length of 380 mm, a short side length of 50 mm, and a thickness of 1.70 mm.

  After placing the molding stamper 2 on the dedicated pallet 1, the UV curable resin 14 was placed on the non-shaped region R2 (length L1: 420 mm and width L3: 60 mm) of the molding stamper 2. Specifically, a width W8 mm × short side parallel to the long side at a distance S3 of 35 mm from the side on the length L1 side of the non-shaped region R2 and a distance S1, S2 of 30 mm from both sides on the length L2 side The ultraviolet curable resin 14 was allowed to flow down into a rectangular region having a length of H350 mm parallel to the horizontal axis. The ultraviolet curable resin 14 was an acrylic resin curable resin, and the flow rate was controlled to flow down while moving the movable dispenser nozzle along the short side while changing the scanning speed. Specifically, the discharge is performed in a large amount at the beginning, the amount is decreased in the vicinity of the intermediate point, and the amount is increased again at the end, and the predetermined length H of the rectangular region shown in FIG. 9 is equally divided into 12 regions (a1 to a12). Then, the amount of ionizing radiation curable resin placed on each of at least the second regions (a2, a11) from both ends is the amount of ionizing radiation curable resin placed on each of at least the four regions (a5, a6, a7, a8). The discharge rate was adjusted by changing the scanning speed so as to increase the flow rate. More specifically, if the relative discharge amount is within the parentheses, a1 (5), a2 (6), a3 (5), a4 (3) to a9 (3), a10 (5), a11 (6), It was set as a12 (5). The viscosity of the ultraviolet curable resin is about 500 mPa · sec.

  Within 60 seconds after the flow of the ultraviolet curable resin, a PET film having a thickness of 125 μm is placed as the base film 11 on the ultraviolet curable resin 14, and then placed on the molding stamper 2. While being pressed from above the film 11, the film was moved in one pass, and the ultraviolet curable resin 14 was stretched over the entire surface of the molding stamper 2. At this time, the ultraviolet curable resin 14 was not spilled from the molding stamper 2. After that, as shown in FIG. 5, the ultraviolet curable resin 14 was cured by irradiating the substrate film 11 with ultraviolet rays 6 having a wavelength of 365 nm by the ultraviolet irradiation device 7. The thickness of the ultraviolet curable resin 14 after curing was about 13 μm. Thereafter, the integral 10 ′ of the cured ultraviolet curable resin 14 and the base film 11 was peeled off from the molding stamper 2, and the antireflection film 10 was obtained. The actual measured value of the peel strength F at this time was about 1.5N. When this was converted into a width of 25 mm, it was about 0.09 N / 25 mm. The peel strength was measured according to JIS K 6854-1.

  The surface of the antireflection layer 12 of the obtained antireflection film 10 is provided with countless fine protrusions 15 having a period P of 110 nm to 130 nm and a height h of 280 nm to 320 nm. The antireflection layer 12 having such a concavo-convex structure 13 did not cause a conventional shadow when a 100 W halogen lamp was applied. Further, there was no defect at all, and reflection of visible light of about 380 nm to 780 nm could be effectively prevented.

[Comparative Example 1]
In Example 1, a fixed multiple dispenser nozzle is used in place of the movable dispenser nozzle, and the molding stamper 2 is transported in a state where the molding stamper 2 is placed on the dedicated pallet 1. The UV curable resin was allowed to flow down as it passed through the lower part. Specifically, from a position separated by a distance S3 of 35 mm from the side on the length L1 side of the non-shaped region R2, to 12 regions a1 to a12 obtained by dividing the predetermined length H of the rectangular region shown in FIG. In the entire region, an equal amount of ultraviolet curable resin was allowed to flow down in a length of 100 mm in parallel with a width of 3 mm × long side L2.

  Thereafter, an antireflection film was obtained by the same production method as in Example 1. As a result of observing the transmitted light by applying a 100 W halogen lamp to the obtained antireflection film, the portion where the ultraviolet curable resin was dropped showed a blackish shadow pattern. When such an antireflection film was affixed to the surface of the liquid crystal panel and turned on, a similar pattern was seen, confirming that it was inappropriate as an antireflection film.

1 Dedicated Pallet 2 Molding Stamper 3, 3 ', 3 "Guide Member 4 Resin Flowing Nozzle 5 Pressing Member (Pressing Roll)
6 Ionizing radiation (UV)
7 Ionizing radiation irradiation device (UV lamp)
8 Mounting table 9 Peeling table 10 Anti-reflection film 10 'Integral object 11 Base film 12 Anti-reflection layer 13 Concave and convex structure (moth eye structure)
14 Curable resin after flowing down 15 Protrusion 16 Boundary 17 Cutting line 21 Base material 22 Shaped layer 23 Shaped mold

R1 Shaped region R2 Non-shaped region L1 Short side length of molding stamper L2 Long side length of molding stamper L3 Width of non-shaped region H Length of predetermined part (rectangular region) where resin flows down W Resin Width of predetermined portion (rectangular region) flowing down a1 to a12 Each region divided into 12 regions by dividing predetermined length H of rectangular region into 12 regions S1, S2, S3 Distance from sides of molding stamper P Projection period h Projection height

Claims (4)

A method for producing an antireflection film having an antireflection layer having a fine concavo-convex structure,
A shaping region in which a shaping die having a concave portion is formed by anodizing an aluminum plate or an aluminum alloy plate for forming an antireflection layer or an aluminum film or aluminum alloy film formed on a substrate, and the shaping A quadrilateral molding stamper having a non-shaped region that is a flat surface on which no mold is formed, wherein the non-shaped region is provided with a predetermined width along one side of the quadrilateral and A step (A) of preparing a dedicated pallet on which a molding stamper used for placing an ionizing radiation curable resin extending to the shaping region is placed;
Placing an ionizing radiation curable resin on the non-shaped region (B);
A step (C) of placing a base film on the molding stamper;
From above the base film on the ionizing radiation curable resin, the pressing member is moved while pressing, and the concave portion of the shaping region is filled without leaving air, and the ionizing radiation curable resin is used for the molding. Extending the entire surface of the stamper (D);
Irradiating ionizing radiation from the base film side to cure the ionizing radiation curable resin (E);
A method for producing an antireflection film, comprising: a step (F) of peeling an integrated product of the ionizing radiation curable resin and the base film after curing from the molding stamper in that order.   The fine concavo-convex structure is a shaping mold for forming an antireflection layer having protrusions having a period smaller than the wavelength of the visible light region and having a protrusion height of 150 nm to 450 nm. The manufacturing method of antireflection film of description.   The antireflection according to claim 1 or 2, wherein the ionizing radiation curable resin is placed in a rectangular region having a predetermined length H and a predetermined width W along one side of the quadrilateral within the non-shaped region. A method for producing a film. When the predetermined length H of the rectangular region is equally divided into 12 regions, the amount of ionizing radiation curable resin placed on each of at least the second regions from both ends of the rectangular region is placed on each of at least the four central regions. The method for producing an antireflection film according to claim 3, wherein the amount is greater than the amount of ionizing radiation curable resin.

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