WO2016084745A1 - Moule, procédé de fabrication de moule, et pellicule antireflet - Google Patents

Moule, procédé de fabrication de moule, et pellicule antireflet Download PDF

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Publication number
WO2016084745A1
WO2016084745A1 PCT/JP2015/082735 JP2015082735W WO2016084745A1 WO 2016084745 A1 WO2016084745 A1 WO 2016084745A1 JP 2015082735 W JP2015082735 W JP 2015082735W WO 2016084745 A1 WO2016084745 A1 WO 2016084745A1
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Prior art keywords
mold
antireflection film
aluminum alloy
moth
less
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PCT/JP2015/082735
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English (en)
Japanese (ja)
Inventor
隆裕 中原
美穂 山田
箕浦　潔
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シャープ株式会社
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Priority to JP2016561562A priority Critical patent/JP6458051B2/ja
Publication of WO2016084745A1 publication Critical patent/WO2016084745A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements

Definitions

  • the present invention relates to a mold, a method for manufacturing the mold, and an antireflection film.
  • the “mold” here includes molds used in various processing methods (stamping and casting), and is sometimes referred to as a stamper. It can also be used for printing (including nanoprinting).
  • An optical element such as a display device or a camera lens used for a television or a mobile phone is usually provided with an antireflection technique in order to reduce surface reflection and increase light transmission.
  • an antireflection technique in order to reduce surface reflection and increase light transmission. For example, when light passes through the interface of a medium with a different refractive index, such as when light enters the interface between air and glass, the amount of transmitted light is reduced due to Fresnel reflection, etc., and visibility is reduced. is there.
  • This method utilizes the principle of a so-called moth-eye structure, and the refractive index for light incident on the substrate is determined from the refractive index of the incident medium along the depth direction of the irregularities. By continuously changing the refractive index, the reflection in the wavelength region to be prevented from being reflected is suppressed.
  • the moth-eye structure has an advantage that it can exhibit an antireflection effect with a small incident angle dependency over a wide wavelength range, can be applied to many materials, and can form an uneven pattern directly on a substrate. As a result, a low-cost and high-performance antireflection film (or antireflection surface) can be provided.
  • Patent Documents 2 to 4 As a method for producing a moth-eye structure, a method using an anodized porous alumina layer obtained by anodizing aluminum has attracted attention (Patent Documents 2 to 4).
  • anodized porous alumina layer obtained by anodizing aluminum will be briefly described.
  • a method for producing a porous structure using anodization has attracted attention as a simple method capable of forming regularly ordered nano-sized cylindrical pores (fine concave portions).
  • an acidic or alkaline electrolyte such as sulfuric acid, oxalic acid, or phosphoric acid
  • a voltage is applied using this as an anode
  • oxidation and dissolution proceed simultaneously on the surface of the substrate, and pores are formed on the surface.
  • An oxide film having the following can be formed. These cylindrical pores are oriented perpendicular to the oxide film and exhibit self-organized regularity under certain conditions (voltage, type of electrolyte, temperature, etc.). Is expected.
  • the porous alumina layer formed under specific conditions takes an array in which almost regular hexagonal cells are two-dimensionally filled with the highest density when viewed from the direction perpendicular to the film surface.
  • Each cell has a pore in the center, and the arrangement of the pores has periodicity.
  • the cell is formed as a result of local dissolution and growth of the film, and dissolution and growth of the film proceed simultaneously at the bottom of the pores called a barrier layer.
  • the cell size that is, the distance between adjacent pores (center-to-center distance) corresponds to approximately twice the thickness of the barrier layer and is approximately proportional to the voltage during anodization.
  • the diameter of the pores depends on the type, concentration, temperature, etc.
  • the pores of such porous alumina have an arrangement with high regularity (having periodicity) under a specific condition, an arrangement with irregularity to some extent or an irregularity (having no periodicity) depending on the conditions. ).
  • Patent Document 2 discloses a method of forming an antireflection film (antireflection surface) using a stamper having an anodized porous alumina film on the surface.
  • Patent Document 3 discloses a technique for forming a tapered concave portion in which the pore diameter continuously changes by repeating aluminum anodization and pore diameter enlargement processing.
  • Patent Document 4 discloses a technique for forming an antireflection film using an alumina layer in which fine concave portions have stepped side surfaces.
  • an antireflection film (antireflection surface) is provided by providing a concavo-convex structure (macro structure) larger than the moth eye structure in addition to the moth eye structure (micro structure). ) Can be given an anti-glare (anti-glare) function.
  • the two-dimensional size of the convex portion constituting the concave and convex that exhibits the antiglare function is 1 ⁇ m or more and less than 100 ⁇ m.
  • the “two-dimensional size” of the convex portion refers to the area equivalent circle diameter of the convex portion when viewed from the normal direction of the surface. For example, when the convex portion has a conical shape, The two-dimensional size corresponds to the diameter of the bottom surface of the cone. The same applies to the “two-dimensional size” of the recess.
  • a mold for forming a moth-eye structure on the surface (hereinafter referred to as “moth-eye mold”) can be easily manufactured.
  • the surface of an anodized aluminum film is used as it is as a mold, the effect of reducing the manufacturing cost is great.
  • the surface structure of the moth-eye mold that can form the moth-eye structure is referred to as an “inverted moth-eye structure”.
  • a method using a photocurable resin is known. First, a photocurable resin is applied on the substrate. Subsequently, the uneven surface of the moth-eye mold subjected to the release treatment is pressed against the photocurable resin in a vacuum. Thereafter, a photocurable resin is filled into the concavo-convex structure. Subsequently, the photocurable resin in the concavo-convex structure is irradiated with ultraviolet rays to cure the photocurable resin.
  • the anti-glare structure is previously formed separately from the step of forming the inverted moth-eye structure. It is necessary to perform a step of forming a concavo-convex structure for forming.
  • a concavo-convex structure for forming an antiglare structure is formed by mechanical means such as sand blasting or shot peening with a glass beat, in addition to the process of forming an inverted moth-eye structure. It is described to do.
  • Patent Document 5 a method for easily manufacturing a mold for manufacturing an antireflection film in which a moth-eye structure is superimposed on an antiglare structure. According to Patent Document 5, a mold suitable for producing an antireflection film having a haze value of 1% or more and 5% or less can be produced.
  • the present applicant together with other applicants, discloses a method for producing a mold substrate having an aluminum alloy layer having high specularity in Patent Documents 6 and 7.
  • the “mold substrate” refers to an object to be anodized and etched in the mold manufacturing process.
  • an antireflection film having no unnecessary haze can be formed.
  • the entire disclosure of Patent Documents 5 to 7 is incorporated herein by reference.
  • An object of the present invention is to provide an antireflection film having a novel structure, a mold suitably used for producing such an antireflection film, and a method for producing the mold.
  • An antireflection film includes a plurality of first protrusions having a two-dimensional size of 50 nm or more and less than 300 nm and a height of 50 nm or more and 300 nm or less when viewed from the normal direction of the surface.
  • Each of the plurality of first protrusions includes a plurality of annular protrusion groups in which the plurality of first protrusions are annularly arranged at a distance between adjacent ones of 50 nm or more and less than 300 nm.
  • the plurality of regions surrounded by each of the annular convex group includes a plurality of first regions having an average value of a major axis and a minor axis of more than 300 nm and not more than 800 nm.
  • the plurality of first regions do not have the plurality of first protrusions.
  • the plurality of first regions include a first region having two or more second protrusions that are smaller in height than the plurality of first protrusions.
  • a mold according to another embodiment of the present invention has a porous alumina layer on the surface, and the porous alumina layer has a two-dimensional size of 50 nm or more and less than 300 nm when viewed from the normal direction of the surface, A plurality of first recesses having a length of 50 nm or more and 300 nm or less, each of the plurality of first recesses having a plurality of first recesses arranged in an annular shape with an inter-adjacent distance of 50 nm or more and less than 300 nm.
  • a plurality of regions surrounded by each of the plurality of annular recess groups includes a plurality of first regions having an average value of a major axis and a minor axis of more than 300 nm and not more than 800 nm.
  • the mold further includes an aluminum alloy layer under the porous alumina layer, and the aluminum alloy layer includes aluminum and titanium.
  • the total thickness of the aluminum alloy layer and the porous alumina layer is 2 ⁇ m or more.
  • the mold further has an inorganic underlayer under the aluminum alloy layer.
  • the inorganic underlayer is a silicon oxide layer, a tantalum oxide layer, or a titanium oxide layer.
  • the thickness of the inorganic underlayer is preferably 50 nm or more and 300 nm or less.
  • the mold further includes a buffer layer between the inorganic base layer and the aluminum alloy layer, and the buffer layer includes aluminum, titanium, and oxygen or nitrogen.
  • a mold manufacturing method is a method for manufacturing the mold according to any one of the above, wherein (a) an aluminum alloy layer having a thickness of 2 ⁇ m or more is formed on a substrate. (B) forming a porous alumina layer having a plurality of fine recesses by partially anodizing the aluminum alloy layer; and (c) after the step (b), the porous alumina. A step of bringing the layer into contact with an etching solution to enlarge the plurality of fine concave portions of the porous alumina layer; and (d) further anodizing after the step (c), thereby Growing a concave portion.
  • the electrolyte used in the step of forming the porous alumina layer is, for example, an aqueous solution containing an acid selected from the group consisting of oxalic acid, tartaric acid, phosphoric acid, chromic acid, citric acid, and malic acid.
  • an aqueous solution of 10% by mass of phosphoric acid, an organic acid such as formic acid, acetic acid or citric acid, or a mixed solution of chromium phosphoric acid can be used.
  • an antireflection film having a novel structure a mold suitably used for producing such an antireflection film, and a method for manufacturing the mold are provided.
  • an antireflection film having a haze value of 1% or more and 12% or less a mold suitably used for producing such an antireflection film, and a method of manufacturing the mold are provided. .
  • FIG. 4B is a schematic cross-sectional view taken along line 1C-1C ′ in FIG. (A)
  • (b) is a schematic diagram for demonstrating the manufacturing method of the type
  • (A) is a surface SEM image of a mold substrate
  • (b) is a surface SEM image of a moth-eye mold
  • (c) is a surface SEM image of an antireflection film (Example 1).
  • (A) to (c) are surface SEM images of the antireflection films (Examples 2 to 4) according to the embodiment of the present invention. It is a surface SEM image of the antireflection film of a comparative example. It is a SEM image of the mold base material from which the thickness of an aluminum alloy layer differs, (a) and (b) are 6 micrometers in thickness (Example 1), (c) and (d) are 4 micrometers in thickness (Example) 2), (e), and (f) are an SEM image of a surface of a mold substrate having an aluminum alloy layer having a thickness of 3 ⁇ m (Example 4) and an SEM image of a cross section.
  • (A) is the surface SEM image of the antireflection film of Example 1
  • (b) is the surface SEM image of the antireflection film of Example 5.
  • (A) And (b) is a schematic diagram for demonstrating the manufacturing method of the type
  • (A) is a cross-sectional SEM image of a high-purity aluminum layer having a thickness of 4 ⁇ m
  • (b) is a surface SEM image of a high-purity aluminum layer having a thickness of 2 ⁇ m
  • (c) is a high-temperature having a thickness of 4 ⁇ m. It is the surface SEM image of the anti-reflective film formed using the type
  • an antireflection film according to an embodiment of the present invention a mold suitably used for producing such an antireflection film, and a method of manufacturing the mold will be described with reference to the drawings.
  • Embodiments of the present invention are not limited to the embodiments exemplified below.
  • a moth-eye mold described in Patent Document 5 a manufacturing method thereof, and a method of manufacturing an antireflection film using the moth-eye mold will be described.
  • the mold substrate used for the production of the moth-eye mold is different from the embodiment according to the present invention, but the method for producing the moth-eye mold by alternately performing the anodic oxidation and the etching or the moth-eye mold is used.
  • the method of forming the antireflection film is common to the embodiment according to the present invention.
  • a mold substrate having an aluminum film (a high purity aluminum film) is used.
  • an aluminum film 18p deposited on a substrate 12 is prepared.
  • the aluminum film 18p is formed of high purity aluminum, for example, with a purity of 99.99% by mass or more.
  • the thickness of the aluminum film 18p is 0.5 ⁇ m or more and 5 ⁇ m or less, and a plurality of crystal grains 18pa having an average crystal grain size of 200 nm or more and 5 ⁇ m or less exist on the surface 18ps of the aluminum film 18p.
  • FIG. 12A schematically shows a crystal grain boundary 18pb existing on the surface 18ps of the aluminum film 18p.
  • the aluminum film 18p can be formed using, for example, a vacuum film forming method such as a sputtering method or an electron beam evaporation method.
  • anodic oxidation (AO) and etching (Et) are alternately repeated a plurality of times on the aluminum film 18p, thereby obtaining the moth-eye mold 900A having the porous alumina layer 22 shown in FIG.
  • FIG. 12 (b) shows the structure of the finally obtained porous alumina layer 22, but here, for the sake of simplicity, a common structure is used regardless of changes in the shape and size of the fine recesses 22p. Indicated by reference numerals.
  • the porous alumina layer 22 is formed corresponding to the uneven shape of the surface 18 ps of the aluminum film 18 p. That is, the surface of the porous alumina layer 22 has a plurality of convex portions corresponding to the plurality of crystal grains 18pa of the aluminum film 18p. Further, the fine recess 22p of the porous alumina layer 22 is formed at a position corresponding to the surface of the crystal grain 18pa and the crystal grain boundary 18pb. That is, the fine recess 22p is formed between the plurality of protrusions and on the surface of the plurality of protrusions.
  • the porous alumina layer 22 is formed by anodizing the surface 18 ps of the aluminum film 18 p with an oxalic acid aqueous solution (concentration 0.06 mass%, liquid temperature 5 ° C.) at an applied voltage of 80 V for 30 seconds.
  • anodic oxidation conditions for example, the type of electrolytic solution, the applied voltage, and the anodic oxidation time
  • the interval between the minute recesses, the depth of the minute recesses, and the like can be adjusted.
  • the electrolytic solution used in the step of forming the porous alumina layer is, for example, an aqueous solution containing an acid selected from the group consisting of oxalic acid, tartaric acid, phosphoric acid, chromic acid, citric acid, and malic acid.
  • the porous alumina layer 22 obtained by anodic oxidation is brought into contact with an alumina etchant so as to be etched by a predetermined amount, thereby enlarging the hole diameter of the fine recess 22p.
  • an alumina etchant so as to be etched by a predetermined amount, thereby enlarging the hole diameter of the fine recess 22p.
  • the side surfaces (also referred to as pore walls) of the fine recesses 22p and the barrier layer can be etched almost isotropically.
  • the amount of etching (that is, the size and depth of the fine recess 22p) can be controlled by adjusting the type, concentration, and etching time of the etching solution.
  • the fine recesses 22p are enlarged by performing etching for 25 minutes using phosphoric acid (concentration 1 mol / L, liquid temperature 30 ° C.).
  • phosphoric acid concentration 1 mol / L, liquid temperature 30 ° C.
  • an aqueous solution of an organic acid such as formic acid, acetic acid, or citric acid or a mixed aqueous solution of chromium phosphoric acid can be used as the etching solution.
  • the aluminum film 18p is partially anodized again to grow a fine recess 22p in the depth direction and to thicken the porous alumina layer 22.
  • the side surface of the fine recess 22p is stepped.
  • the pore diameter of the fine concave portion 22p is further expanded by etching the porous alumina layer 22 by bringing it into contact with an alumina etchant.
  • the moth-eye mold 900A (FIG. 12B) is obtained.
  • the moth-eye mold 900A as a result of the porous alumina layer 22 being formed on the surface 18ps of the aluminum film 18p, a plurality of convex portions corresponding to the surface shapes of the plurality of crystal grains 18pa of the aluminum film 18p are formed on the surface.
  • the surface of the moth-eye mold 900A has a plurality of fine spaces between the plurality of convex portions (the portion corresponding to the crystal grain boundary 18pb) and between the plurality of convex portions (the portion corresponding to the surface of the crystal grain 18pa).
  • a concave portion 22p is formed.
  • the moth-eye mold 900A has a shape in which the moth-eye structure inverted with the concavo-convex structure having a two-dimensional size of 200 nm or more and 5 ⁇ m or less is superimposed, when an antireflection film is produced using the moth-eye mold 900A, A shape in which the concavo-convex structure having a two-dimensional size of 200 nm to 5 ⁇ m on the surface of the moth-eye mold 900A is inverted is formed. This shape can exhibit an antiglare function. That is, by using the moth-eye mold 900A, an antireflection film capable of exhibiting an antiglare function can be produced.
  • the fine recess 22p preferably has a two-dimensional size of 50 nm or more and less than 500 nm when viewed from the normal direction of the surface.
  • the two-dimensional size (opening diameter: D p ) of the fine concave portions 22p and the distance between the fine concave portions 22p (inter-adjacent distance D int ) are approximately the same.
  • the fine concave portions 22p are densely packed, and assuming that the shape of the fine concave portions 22p when viewed from the normal direction of the surface is a circle, the adjacent circles overlap each other, and the adjacent fine concave portions 22p A collar may be formed between them.
  • the depth (D depth ) of the fine recess 22p is about 10 nm or more and less than 1000 nm (1 ⁇ m).
  • the pore interval is 50 nm or more and less than 500 nm. What is necessary is just to apply the voltage in which a fine recessed part is formed.
  • Patent Document 5 by adjusting the film formation conditions when forming an aluminum film having a thickness of 0.5 ⁇ m or more, a plurality of crystal grains having an average crystal grain size of 200 nm to 5 ⁇ m are formed on the surface.
  • An existing aluminum film can be formed.
  • the upper limit of the aluminum film thickness is preferably 5 ⁇ m or less from the viewpoint of productivity.
  • an aluminum film having a total thickness of 1 ⁇ m and an average crystal grain size of 200 nm (Example 1) or a thickness by performing a process of forming an aluminum layer having a thickness of 200 nm by a sputtering method five times.
  • An aluminum film having a total thickness of 4.2 ⁇ m and an average crystal grain size of 700 nm is produced by performing the step of forming an aluminum layer having a thickness of 420 nm by sputtering 10 times.
  • an antireflection film can be produced as follows.
  • the ultraviolet curable resin 32C is irradiated with ultraviolet rays through the moth-eye mold 900A in a state where the ultraviolet curable resin 32C is applied between the surface of the workpiece 42 and the moth-eye mold 900A.
  • the ultraviolet curable resin 32C is cured by irradiating (UV).
  • the ultraviolet curable resin 32C may be applied to the surface of the workpiece 42 or may be applied to the mold surface (surface having a moth-eye structure) of the moth-eye mold 900A.
  • an acrylic resin can be used as the ultraviolet curable resin.
  • the concavo-convex structure of the moth-eye mold 900A (a structure in which the inverted moth-eye structure is superimposed on the concavo-convex structure constituted by a plurality of convex portions) is transferred.
  • a cured product layer of the cured UV curable resin 32 ⁇ / b> C is formed on the surface of the workpiece 42.
  • an antireflection film is obtained in which the moth-eye structure is superimposed on the concavo-convex structure in which the concavo-convex structure constituted by a plurality of convex portions having an average two-dimensional size of 200 nm to 5 ⁇ m is inverted. That is, an antireflection film in which the moth-eye structure is superimposed on the concavo-convex structure exhibiting an antiglare function having an average two-dimensional size of 200 nm to 5 ⁇ m is obtained.
  • the haze value of the obtained antireflection film can be controlled by controlling the crystal grain size and distribution of the aluminum layer, for example, the haze value is 2% or more. It is not easy to control to 6% or less. This is because the structure of the high-purity aluminum layer is easily changed depending on the deposition conditions.
  • a high-purity aluminum layer having a thickness of 4 ⁇ m or 2 ⁇ m has discontinuously large crystal grains (“abnormal particles”) compared to most crystal grains. Are easily formed, and gaps are formed around the abnormal particles.
  • abnormal particles discontinuously large crystal grains
  • fine concave portions are also formed on the side surfaces (surfaces facing the gaps) of the abnormal particles. Therefore, when an antireflection film is formed using a mold having such a porous alumina layer, large convex portions having small convex portions on the side surfaces are formed as shown in FIG. Large convex portions correspond to gaps formed around abnormal particles.
  • Such relatively large convex portions of the antireflection film are easily broken by friction, and reduce the scratch resistance of the antireflection film.
  • the haze of such an antireflection film is relatively large. For example, it is not easy to mass-produce an antireflection film having a haze value of 12% or less with good reproducibility.
  • Patent Documents 6 and 7 disclose a method of forming an aluminum alloy layer having a highly specular surface and a method of manufacturing a moth-eye mold using a mold substrate having such an aluminum alloy layer. ing. When the moth-eye molds described in Patent Documents 6 and 7 are used, an antireflection film having no unnecessary haze can be formed.
  • the present inventor has studied a method for producing a moth-eye mold capable of producing an antireflection film having an appropriate haze value using a mold substrate having an aluminum alloy layer described in Patent Document 6.
  • the appropriate haze value is, for example, 2% or more and 6% or less, and when pasted on a recent high-definition display panel, it does not deteriorate a high-definition image and has clearness and anti-glare property. Is expressed.
  • FIG. 1A is a surface SEM image of the antireflection film according to the embodiment (Example 1 described later), and FIG. 1B is a schematic plan view showing the surface structure of the antireflection film according to the embodiment.
  • FIG. 1C is a schematic cross-sectional view taken along line 1C-1C ′ of FIG.
  • the antireflection film 32A As understood from the comparison between the SEM photograph of FIG. 1A and the schematic diagram of FIG. 1B, the antireflection film 32A according to the embodiment of the present invention is as viewed from the normal direction of the surface. It has a plurality of first protrusions 32a having a two-dimensional size of 50 nm or more and less than 300 nm and a height of 50 nm or more and 300 nm or less, and each of the plurality of first protrusions 32a is adjacent to each other by 50 nm or more and less than 300 nm.
  • the plurality of first convex portions 32a arranged in a ring at an inter-distance includes a plurality of annular convex portion groups, and the plurality of regions surrounded by each of the plurality of annular convex portion groups is an average of a major axis and a minor axis
  • a plurality of first regions R1 having a value greater than 300 nm and less than or equal to 800 nm are included.
  • the major axis and minor axis of each first region R1 are substantially elliptical shapes passing through the apex of the first convex part 32a constituting the annular convex part group in the SEM image (see the broken lines in FIGS. 1A and 1B).
  • the annular convex portion group includes the first convex portions 32a arranged in a double annular shape, the major axis and the minor axis are obtained based on a substantially elliptical shape passing through the apex of the inner first convex portion 32a.
  • the first convex portion 32a does not exist in the first region R1.
  • the first convex portion 32a and the second convex portion 32b are basically formed on a flat support portion 32s.
  • the conventional antireflection film having an antiglare function such as Patent Document 5, has a structure in which a moth-eye structure is superimposed on a relatively large uneven structure that exhibits the antiglare function, whereas the antireflection film 32A according to the embodiment is used. Does not have a relatively large uneven structure that exhibits an antiglare function.
  • first regions R1 in which the average value of the major axis and the minor axis formed by the first convex portion 32a is greater than 300 nm and less than or equal to 800 nm are arranged to form the first region R1.
  • the first convex portion 32a is considered to exhibit an antiglare function.
  • FIGS. 2A and 2B are schematic views for explaining a mold manufacturing method according to an embodiment of the present invention.
  • the substrate 12 includes an inorganic base layer 14 formed on the substrate 12 as necessary, and an aluminum alloy layer 18 formed on the inorganic base layer 14.
  • a mold substrate is prepared.
  • the surface of the substrate 12 may be, for example, any one of a plane, a curved surface, and a roll surface.
  • the material of the substrate 12 may be an acid-resistant insulator such as glass, ceramic, or plastic.
  • the base material 12 may be an aluminum material, for example. Or what provided the insulator on the metal which is not aluminum, for example may be used. From the viewpoint of mass productivity, it is preferable to use a roll-shaped aluminum substrate.
  • the inorganic underlayer 14 is, for example, a silicon oxide layer, a tantalum oxide layer, or a titanium oxide layer.
  • the thickness of the inorganic underlayer 14 is preferably 50 nm or more and 300 nm or less.
  • the aluminum alloy layer 18 contains aluminum (Al) and titanium (Ti).
  • Al—Ti an alloy containing aluminum and titanium
  • the Ti content in the aluminum alloy layer 18 is preferably more than 0% by mass and less than 2.0% by mass, and more preferably more than 0% by mass and less than 1.0% by mass. When the Ti content is 1.0% by mass or more, it may be difficult to form the annular convex group, and the Ti content is most preferably about 0.5% by mass.
  • Nd neodymium
  • the thickness of the aluminum alloy layer 18 is 2 ⁇ m or more. In such a thick aluminum alloy layer 18, V-shaped depressions are formed between crystal grains as schematically shown in FIG. The size of the crystal grains is approximately over 300 nm.
  • the aluminum alloy layer 18 may further contain N (nitrogen). N can be introduced into the aluminum alloy layer, for example, by mixing it in an atmospheric gas when depositing the aluminum alloy layer by sputtering.
  • the aluminum alloy layer contains nitrogen (Examples 1 to 3), the nitrogen content preferably does not exceed 5.7% by mass, and is further 1.2% by mass to 2.0% by mass. preferable.
  • a porous alumina layer 22 obtained by alternately repeating anodic oxidation and etching on the surface of such an aluminum alloy layer 18 is a comparison formed on the surface forming V-shaped depressions between crystal grains.
  • the first recess 22a is large (deep) and the second recess 22b is relatively small (shallow) formed on the flat surface of the crystal grains.
  • the two-dimensional size is 50 nm or more and less than 300 nm, and the depth is 50 nm or more and 300 nm or less.
  • Each of the plurality of first recesses 22a includes a plurality of annular recess groups in which the plurality of first recesses 22a are annularly arranged at a distance between adjacent portions of 50 nm or more and less than 300 nm.
  • the first convex portion 32a of the antireflection film 32A corresponds to the structure in which the first concave portion 22a is transferred. 1 (a) and 1 (b), it can be seen that the first protrusions 32a are arranged in a double ring shape. It can also be seen that the first region R1 in the antireflection film 32A is formed corresponding to the crystal grains of the aluminum alloy layer 18. Therefore, the size of the first region R1 in the antireflection film 32A can be controlled by controlling the size of the crystal grains in the aluminum alloy layer 18.
  • the size of the crystal grains can be controlled by controlling the thickness of the aluminum alloy layer.
  • the size of the crystal grains is controlled by controlling the thickness of the aluminum alloy layer. Is considered the most suitable for mass production.
  • an aluminum alloy layer containing 0.5% by mass of Ti (Examples 1 to 3 further includes N of 1.2% by mass to 2.0% by mass).
  • a mold substrate having aluminum alloy layers having different thicknesses was used, and anodization (0.3 mass% oxalic acid aqueous solution, 10 ° C., 80 V) and etching (10 mass% phosphoric acid aqueous solution) were used. , 30 [deg.] C.) alternately, and anodizing 5 times and etching 4 times, a moth-eye mold 100A (see FIG. 2B) was produced.
  • As the substrate 12 a glass substrate or an aluminum pipe (rolled aluminum substrate) was used.
  • a tantalum oxide (Ta 2 O 5 ) layer having a thickness of 200 nm was formed.
  • the aluminum alloy layer 18 was formed by using a DC magnetron sputtering apparatus and introducing nitrogen gas (N 2 ) in addition to argon (Ar) gas as a sputtering gas as necessary.
  • N 2 nitrogen gas
  • Ar argon
  • the surface temperature of the inorganic underlayer 14 was controlled at 80 ° C.
  • Typical conditions are a sputtering gas (Ar gas) flow rate of 440 sccm, a vacuum degree during sputtering of 0.4 Pa, and a nitrogen gas flow rate when nitrogen gas is introduced is 10 sccm (for details, see Patent Reference 7).
  • anodizing time and etching time are also shown in Table 1 below. Since the sample form of the comparative example is different from those of Examples 1 to 4, conditions such as anodizing time and etching time cannot be directly compared, but the anodizing time is about 33 seconds and the etching time is about 25. Minutes.
  • Each antireflection film was produced by the method described with reference to FIG.
  • a TAC (triacetyl cellulose) film was used as the workpiece 42.
  • Table 1 shows the haze value of each antireflection film.
  • the haze value was measured using an integrating sphere turbidimeter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the projection was parallel light.
  • the sum of the straight transmitted light and the diffuse transmitted light was defined as the total light transmitted light, and the ratio of the diffuse transmitted light to the total light transmitted light was defined as the haze value.
  • FIG. 3A shows an SEM image of the surface of the mold substrate used in Example 1
  • FIG. 3B shows an SEM image of the surface of the moth-eye mold of Example 1
  • FIG. Shows an SEM image of the surface of the antireflection film.
  • the mold base material of Example 1 shown in FIG. 3A has an aluminum alloy layer with a thickness of 6 ⁇ m. Particles having a particularly large particle size that are visible in the center and lower right of the SEM image in FIG. 3A are abnormal particles.
  • the porous alumina layer on the surface of the moth-eye mold of Example 1 shown in FIG. 3B has a two-dimensional size of 50 nm or more and less than 300 nm and a depth of 50 nm or more when viewed from the normal direction of the surface. It has a plurality of first recesses of 300 nm or less. Each of the plurality of first recesses includes a plurality of annular recess groups in which the plurality of first recesses are annularly arranged at a distance between adjacent portions of 50 nm or more and less than 300 nm. The first recesses are randomly and uniformly formed on the surface of the abnormal particles.
  • the antireflection film of Example 1 shown in FIG. 3C has a two-dimensional size of 50 nm or more and 300 nm when viewed from the normal direction of the surface. And a plurality of first convex portions 32a having a height of 50 nm or more and 300 nm or less.
  • Each of the plurality of first convex portions 32a includes a plurality of annular convex portion groups in which the plurality of first convex portions 32a are annularly arranged at an adjacent distance of 50 nm or more and less than 300 nm.
  • the plurality of regions surrounded by each include a plurality of first regions R1 having an average value of a major axis and a minor axis of more than 300 nm and 800 nm or less.
  • the annular convex group composed of the first convex part 32a whose broken line passes substantially through the apex has an average size, and is surrounded by this annular convex group.
  • the major axis of the first region was 850 nm
  • the minor axis was 650 nm
  • the average value of the major axis and the minor axis was 750 nm.
  • the plurality of first regions in the antireflection film of Example 1 includes many first regions having an average value of the major axis and the minor axis of 750 nm.
  • region shown in Table 1 is also an average value of the major axis and minor axis of a 1st area
  • the value of the average diameter of the annular region in Table 1 will be described in detail later.
  • the average diameter of the annular region in Table 1 of Example 1 was 723.8 nm, and the haze value of the antireflection film was 11.48%.
  • FIGS. 4 (a) to 4 (c) show SEM images of the surfaces of the antireflection films according to Examples 2 to 4.
  • FIG. The thicknesses of the aluminum alloy layers of the mold base materials used for producing the moth-eye molds of Examples 2 to 4 are 4 ⁇ m, 4 ⁇ m, and 3 ⁇ m, respectively. In Examples 2 and 3, aluminum alloy layers having the same thickness were used, but the film forming conditions were different.
  • the major axis of the first region (the region within the dashed line) surrounded by the annular convex portion group indicated by the broken line passing through the apex is 800 nm
  • the minor axis is 500 nm.
  • the average value of the major axis and the minor axis was 650 nm.
  • the average diameter of the annular region in Table 1 of Example 2 was 572 nm, and the haze value of the antireflection film was 4.38%.
  • the major axis of the first region (the region within the broken line) surrounded by the annular convex group indicated by the broken line passing through the apex is 600 nm and the minor diameter.
  • the average value of the major axis and the minor axis was 525 nm.
  • the average diameter of the annular region in Table 1 of Example 3 was 514.8 nm, and the haze value of the antireflection film of Example 3 was 5.63%.
  • Example 2 and Example 3 differ in the film forming conditions of the aluminum alloy layer.
  • two targets two sources
  • Example 3 using one target (one source) in sputtering, the film was allowed to stand for a certain time each time a film having a thickness of 1000 nm was formed, thereby suppressing an increase in the temperature of the surface of the mold substrate during sputtering.
  • This difference in the film forming conditions is considered to be the difference in the size of the crystal grains of the aluminum alloy layer.
  • the major axis of the first region (the region within the dashed line) surrounded by the annular convex portion group indicated by the broken line passing through the apex is 350 nm
  • the minor axis is 250 nm.
  • the average value of the major axis and the minor axis was 300 nm.
  • the average diameter of the annular region in Table 1 of Example 4 was 543.4 nm, and the haze value of the antireflection film of Example 4 was 2.29%.
  • FIG. 5 is a surface SEM image of the antireflection film of the comparative example.
  • the anti-reflection film of the comparative example is a clear-type anti-reflection film that is currently on the market and does not have an anti-glare function, and the first protrusions are irregularly arranged and the first region is not formed. .
  • the size of the area indicated by the broken line in FIG. 5 is about 200 nm, which is substantially equal to the distance between the adjacent first convex portions.
  • the haze value of the antireflection film of the comparative example is as very small as 0.52%.
  • FIG. 6 shows SEM images of mold bases having different thicknesses of aluminum alloy layers.
  • FIGS. 6 (a) and 6 (b) show a thickness of 6 ⁇ m (Example 1), and FIGS. 6 (c) and 6 (d).
  • FIG. 6 shows SEM images of mold bases having different thicknesses of aluminum alloy layers.
  • FIGS. 6 (a) and 6 (b) show a thickness of 6 ⁇ m (Example 1)
  • FIGS. 6 (c) and 6 (d) Is a SEM image of a mold substrate having an aluminum alloy layer having a thickness of 4 ⁇ m (Example 2) and FIGS. 6E and 6F having a thickness of 3 ⁇ m (Example 4). It is
  • FIGS. 7 is a surface SEM image of an antireflection film formed using a moth-eye mold produced using mold bases having different thicknesses of aluminum alloy layers.
  • FIGS. 7 (a) and 7 (b) are thicknesses. 7 ⁇ m (Example 1)
  • FIGS. 7 (c) and (d) are aluminum with a thickness of 4 ⁇ m (Example 2)
  • FIGS. 7 (e) and (f) are aluminum with a thickness of 3 ⁇ m (Example 4).
  • the aluminum alloy layer having a thickness of 6 ⁇ m has large abnormal particles.
  • the aluminum alloy layer having a thickness of 4 ⁇ m has abnormal particles as can be seen from the SEM images of FIGS. 6C and 6D, but the size is 6 ⁇ m. Much smaller than the size of abnormal particles in the aluminum alloy layer.
  • the aluminum alloy layer having a thickness of 3 ⁇ m does not have abnormal particles. Thus, when the thickness of the aluminum alloy layer exceeds 3 ⁇ m, abnormal particles are included, and as the thickness of the aluminum alloy layer increases, the abnormal particles also increase.
  • FIGS. 7A, 7B, 7C, and 7D When the surface SEM images of the antireflection film shown in FIGS. 7A, 7B, 7C, and 7D are viewed, the moth-eye for the moth eye manufactured using the mold base material having the aluminum alloy layer containing abnormal particles is shown.
  • a recess having a size corresponding to abnormal particles is formed in the antireflection film formed using the mold.
  • FIGS. 7A and 7B abnormal particles contained in an aluminum alloy layer having a thickness of 6 ⁇ m are very large (area circle equivalent diameter is 3 ⁇ m or more).
  • An annular ridge is formed.
  • 7C and 7D a recess having a size corresponding to the abnormal particle is formed, but an annular ridge is not seen.
  • the antireflection film having an annular ridge has low scratch resistance. That is, if the surface of the antireflection film is rubbed with, for example, a cloth (for example, Savina MX manufactured by KB Seiren Co., Ltd., savina is a registered trademark), the annular ridge is destroyed, and the surface may appear cloudy. is there. Therefore, such an antireflection film is not preferable for applications requiring scratch resistance (for example, portable terminals such as smartphones).
  • the photocurable resin when the concave portion has a size corresponding to abnormal particles, the photocurable resin is used for the moth-eye mold in the transfer process when forming the antireflection film. It tends to remain in the recess, and as a result, it may be difficult to use the moth-eye mold continuously.
  • the antireflection film is formed by the roll-to-roll method, there is a problem that the length of the continuous formation of the antireflection film is shortened and the production efficiency is lowered.
  • the thickness of the aluminum alloy layer of the mold base is preferably less than 6 ⁇ m, and more preferably 4 ⁇ m or less. Moreover, in order to suppress the formation of a recess having a size corresponding to abnormal particles, the thickness of the aluminum alloy layer is preferably 3 ⁇ m or less.
  • FIG. 8 is a surface SEM image of the antireflection film formed using a moth-eye mold produced using mold bases having different thicknesses of the aluminum alloy layer
  • FIG. 8A shows a thickness of 6 ⁇ m ( Example 1)
  • FIG. 8B is a surface SEM image of an antireflection film formed using a moth-eye mold produced using a mold substrate having an aluminum alloy layer having a thickness of 4 ⁇ m (Example 2). It is.
  • FIG. 8 is a surface SEM image of the antireflection film formed using a moth-eye mold produced using a mold substrate having an aluminum alloy layer having a thickness of 4 ⁇ m
  • FIG. 9 is a surface SEM image of an antireflection film formed by using a moth-eye mold produced using mold bases having different thicknesses of aluminum alloy layers, and FIG. 9A shows a thickness of 4 ⁇ m ( Example 3), FIG. 9B is a surface SEM image of an antireflection film formed using a moth-eye mold produced using a mold substrate having an aluminum alloy layer having a thickness of 3 ⁇ m (Example 4). It is.
  • FIG. 10 is a graph showing the relationship between the average diameter and the haze value of the region surrounded by the annular convex portions of the antireflection films of Examples 1 to 4 and Comparative Example.
  • a target region is selected so as not to include a region where a structure corresponding to abnormal particles is formed.
  • 10 are selected from the larger ones of the first areas, and the lengths of the major axis and the minor axis are measured.
  • the haze value of the antireflection film of Examples 2 and 3 is larger than the haze value of the antireflection film of Example 4.
  • the antireflection films of Examples 2 and 3 are compared with abnormal particles. This is presumably because there is a large structure (area circle equivalent diameter exceeds 1 ⁇ m), and the haze value increases accordingly.
  • the average value of the major axis and the minor axis of the first region is in the range of 500 nm to 600 nm, and the haze value is in the range of 2% to 6%.
  • the antireflection films of Examples 2 to 4 have clearness and exhibit antiglare properties, and are preferably used for high-definition display panels.
  • FIG. 11A shows a surface SEM image of the antireflection film of Example 1
  • FIG. 11B shows a surface SEM image of the antireflection film of Example 5.
  • an antireflection film was formed using a moth-eye mold produced in the same manner as in Example 1 (anodization time 33 seconds) except that the anodic oxidation time in the moth-eye mold manufacturing process was 45 seconds. Produced.
  • the height of the first protrusions in the antireflection film of Example 1 is 100 nm to 150 nm, and the height of the second protrusions in the region surrounded by the first protrusions. Is about 10 nm.
  • the height of the first convex portion in the antireflection film of Example 5 is 200 nm to 250 nm, and the second convex portion in the region surrounded by the first convex portion. The height is about 50 nm.
  • the first region surrounded by the first protrusions has an average value of the major axis and the minor axis of more than 300 nm and not more than 800 nm.
  • the antiglare property can be exhibited while having clearness.
  • the first convex portion and the second convex portion exhibit an antireflection function similarly to the conventional antireflection film having a moth-eye structure.
  • the present invention is used for an antireflection film, a mold suitably used for the production of such an antireflection film, and a method for manufacturing the mold.
  • the antireflection film is suitably used for a high-definition display panel.
  • Anti-reflective film 32s Support part 32a 1st convex part 32b 2nd convex part R1 1st area

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Abstract

La présente invention concerne une pellicule antireflet (32A) qui comporte une pluralité de premières excroissances (32a) dont, vues de la direction de la ligne normale de la surface, la taille bidimensionnelle est comprise entre 50 nm et moins de 300 nm, et la hauteur est comprise entre 50 et 300 nm. La pluralité de premières excroissances (32a) inclut une pluralité de groupes d'excroissances annulaires dans chacun desquels une pluralité des premières excroissances (32a) est alignée en une forme d'anneau à des distances interproximales comprises entre 50 nm et moins de 300 nm. Une pluralité de zones respectivement confinées par la pluralité de groupes d'excroissances annulaires inclut une pluralité de premières zones (R1) dans lesquelles la valeur moyenne du grand axe et du petit axe est comprise entre plus de 300 nm mais pas plus de 800 nm.
PCT/JP2015/082735 2014-11-25 2015-11-20 Moule, procédé de fabrication de moule, et pellicule antireflet WO2016084745A1 (fr)

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EP3459353A1 (fr) 2017-09-26 2019-03-27 Sharp Kabushiki Kaisha Film polymère synthétique dont la surface a une activité microbicide; composition de résine photodurcissable; méthode de préparation de film polymère synthétique et méthode de stérilisation par utilisation de surface de film polymère synthétique
US10934405B2 (en) 2018-03-15 2021-03-02 Sharp Kabushiki Kaisha Synthetic polymer film whose surface has microbicidal activity, plastic product which includes synthetic polymer film, sterilization method with use of surface of synthetic polymer film, photocurable resin composition, and manufacturing method of synthetic polymer film
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US10968292B2 (en) 2017-09-26 2021-04-06 Sharp Kabushiki Kaisha Synthetic polymer film whose surface has microbicidal activity, photocurable resin composition, manufacturing method of synthetic polymer film, and sterilization method with use of surface of synthetic polymer film
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US10934405B2 (en) 2018-03-15 2021-03-02 Sharp Kabushiki Kaisha Synthetic polymer film whose surface has microbicidal activity, plastic product which includes synthetic polymer film, sterilization method with use of surface of synthetic polymer film, photocurable resin composition, and manufacturing method of synthetic polymer film

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