WO2018143370A1 - 反射防止膜、反射防止膜の製造方法、型および型の製造方法 - Google Patents

反射防止膜、反射防止膜の製造方法、型および型の製造方法 Download PDF

Info

Publication number
WO2018143370A1
WO2018143370A1 PCT/JP2018/003480 JP2018003480W WO2018143370A1 WO 2018143370 A1 WO2018143370 A1 WO 2018143370A1 JP 2018003480 W JP2018003480 W JP 2018003480W WO 2018143370 A1 WO2018143370 A1 WO 2018143370A1
Authority
WO
WIPO (PCT)
Prior art keywords
antireflection film
mold
aluminum
less
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/003480
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
林　秀和
登喜生 田口
幸男 島村
智之 北川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sharp Corp filed Critical Sharp Corp
Priority to CN201880009997.3A priority Critical patent/CN110268102B/zh
Priority to US16/483,100 priority patent/US20200241172A1/en
Publication of WO2018143370A1 publication Critical patent/WO2018143370A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • 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
    • C25D11/16—Pretreatment, e.g. desmutting
    • 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G02B1/116—Multilayers including electrically conducting layers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2905/00—Use of metals, their alloys or their compounds, as mould material
    • B29K2905/02—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • 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
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • 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
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids

Definitions

  • the present invention relates to an antireflection film, an antireflection film manufacturing method, a mold, and a mold manufacturing method.
  • 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.
  • the two-dimensional size of the convex portions constituting the concavo-convex pattern exhibiting the antireflection function is 10 nm or more and less than 500 nm.
  • 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.
  • 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 and 3 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 and 3).
  • 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 the anodized aluminum film is used as a mold as it is, 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”.
  • an anti-glare (anti-glare) function is imparted to the anti-reflection film (or anti-reflection surface) by providing an uneven structure larger than the moth-eye structure. be able to.
  • the two-dimensional size of the convex portion or the concave portion constituting the concavo-convex structure exhibiting the anti-glare function (sometimes referred to as “anti-glare structure”) is, for example, not less than 200 nm and less than 100 ⁇ m.
  • the surface structure of the mold that can form an antiglare structure is referred to as an “inverted antiglare structure”.
  • the entire disclosure of Patent Documents 1 to 4 is incorporated herein by reference.
  • a method for efficiently producing a mold for forming an antireflection film (or antireflection surface) having a desired antiglare function has been studied.
  • clear images tend to be preferred. That is, there is a tendency to demand an antireflection film that exhibits antiglare properties while maintaining clearness without degrading high-definition images when pasted on a high-definition display panel.
  • an antireflection film that exhibits antiglare properties while maintaining clearness without degrading high-definition images when pasted on a high-definition display panel.
  • the present invention provides an antireflection film (or an antireflection surface) that maintains anti-glare properties, exhibits antiglare properties, and is suppressed from appearing cloudy when viewed from an oblique viewing angle. It is an object of the present invention to provide a method for producing such an antireflection film, to provide a mold for forming such an antireflection film, and to provide a method for efficiently producing such a mold. .
  • a mold manufacturing method includes a step (a) of preparing an aluminum base material that has been subjected to mechanical mirror finishing, and the surface of the aluminum base material is substantially spherical and includes alumina particles.
  • the average particle diameter of the projection material is 10 ⁇ m or more and less than 35 ⁇ m.
  • the particle size distribution of the projection material has a peak within a range of ⁇ 10% from the average particle size.
  • the manufacturing method further includes a step (g) of performing electropolishing on the surface of the aluminum substrate between the step (b) and the step (c).
  • the mold according to the embodiment of the present invention is a mold manufactured by any one of the above-described mold manufacturing methods.
  • the mold according to another embodiment of the present invention has a plurality of first recesses having a two-dimensional size of 1 ⁇ m or more and 12 ⁇ m or less when viewed from the normal direction of the surface, and when viewed from the normal direction of the surface.
  • a surface structure having a plurality of second recesses having a two-dimensional size of 10 nm or more and less than 500 nm is provided, and a distance between adjacent ones of the plurality of first recesses is 2 ⁇ m or more and 10 ⁇ m or less.
  • An antireflection film manufacturing method includes a step of preparing any of the above molds, a step of preparing a workpiece, and photocuring between the mold and the surface of the workpiece.
  • the antireflection film according to the embodiment of the present invention is an antireflection film manufactured by the above-described method for manufacturing an antireflection film.
  • the antireflection film according to another embodiment of the present invention has a plurality of first protrusions having a two-dimensional size of 1 ⁇ m or more and 12 ⁇ m or less when viewed from the normal direction of the surface, and the normal direction of the surface.
  • a surface structure having a plurality of second convex portions having a two-dimensional size of 10 nm or more and less than 500 nm, and assuming that the 60 ° specular gloss is 1, the 20 ° specular gloss is 0.01 or more and 0. .1 or less.
  • the 20-degree specular gloss is 0.01 or more and 1.0 or less
  • the 60-degree specular gloss is 1.0 or more and 10.0 or less.
  • the 20 degree specular gloss is 0.001 or more and 0.005 or less.
  • the 85 degree specular gloss is 50.0 or more and 75.0 or less.
  • the common logarithm of relative diffuse reflectance (%) is plotted on the vertical axis, with the incident angle being 5 °, the light receiving angle on the horizontal axis, and the maximum value of diffuse reflected light intensity being normalized to 80%.
  • the light distribution distribution curve is 3% or more in a range where the light receiving angle is 5 ° to 7 °, the light receiving angle is 8 ° to 10 °, and the relative diffuse reflectance (%) is 2% or more. Including points within a range of 8% or less, a light receiving angle of 10 ° to 15 °, and the relative diffuse reflectance (%) within a range of 0.9% to 1.1% including.
  • the haze value is 2% or more and 40% or less.
  • a method of manufacturing an antireflection film includes a step (a) of preparing an aluminum base material subjected to mechanical mirror finishing, and a surface of the aluminum base material is substantially spherical.
  • a step of manufacturing a mold by a mold manufacturing method including the step (f) of growing a recess, a step of preparing a workpiece, and a photocurable resin between the mold and the surface of the workpiece. Including the step of curing the photocurable resin by irradiating the photocurable resin with light in the applied state, and the step of peeling the mold from the antireflection film formed of the cured photocurable resin. And a plurality of first protrusions having a two-dimensional size of 1 ⁇ m or more and 5 ⁇ m or less when viewed from the normal direction of the surface, and a two-dimensional size of 10 nm when viewed from the normal direction of the surface. More than 500nm An antireflection film having a surface structure having two convex portions and having a 60 ° specular glossiness of 1 and a 20 ° specular glossiness of 0.01 or more and 0.1 or less is manufactured.
  • a method of manufacturing an antireflection film includes a step (a) of preparing an aluminum base material that has been subjected to mechanical mirror finishing, and a surface of the aluminum base material is substantially spherical. Yes, a step (b) of forming a plurality of first recesses on the surface of the aluminum substrate by spraying a projection material containing alumina particles and having an average particle size of 10 ⁇ m or more and 40 ⁇ m or less; and the step (b) After the step (c), an inorganic material layer is formed on the surface of the aluminum substrate, and an aluminum film is formed on the inorganic material layer, thereby producing a mold substrate (c) and the step (c).
  • step (d) of forming a porous alumina layer having a plurality of second recesses by anodizing the surface of the aluminum film and after the step (d) A step (e) of enlarging the plurality of second recesses of the porous alumina layer by bringing the mina layer into contact with an etching solution; and further anodizing after the step (e); A step of producing a mold by a mold production method including a step (f) of growing a second recess, a step of preparing a workpiece, and photocuring between the mold and the surface of the workpiece.
  • An antireflection film having a surface structure having a number of second convex portions and having an 85 degree specular gloss of 1 and a 20 degree specular gloss of 0.001 to 0.005 is manufactured.
  • an antireflection film (or an antireflection surface) that exhibits antiglare properties while maintaining clarity and is suppressed from appearing cloudy when viewed from an oblique viewing angle,
  • a method for producing such an antireflection film a mold for forming such an antireflection film, and a method for efficiently producing such a mold.
  • FIG. 5 is a schematic diagram for explaining a process of forming an inverted anti-glare structure by spraying a projection material onto the surface of an aluminum substrate 12 in the manufacturing process of the moth-eye mold 100 according to the embodiment of the present invention. . It is a figure for demonstrating the manufacturing method of the anti-reflective film using the type
  • (A) And (b) is the SEM image (full scale 20.0 micrometer in a SEM image) of the surface of the aluminum piece which has the inverted anti-glare structure formed by spraying a projection material.
  • FIG. (A) and (b) are SEM images of the antireflection film according to the embodiment of the present invention, and (a) is an SEM image (a full image in the SEM image when the surface of the antireflection film is observed from the vertical direction).
  • (B) is a cross-sectional SEM image of the antireflection film (full scale 3.0 ⁇ m in the SEM image), and (c) is a cross-sectional SEM image of the antireflection film (in the SEM image). Full scale of 500 nm).
  • (A) to (c) are SEM images of the antireflection film according to the reference example, and (a) is an SEM image when the surface of the antireflection film is observed from the vertical direction (full scale 10.
  • (B) is a cross-sectional SEM image of the antireflection film (full scale 3.0 ⁇ m in the SEM image), and (c) is a cross-sectional SEM image of the antireflection film (full scale in the SEM image).
  • (A) And (b) is typical sectional drawing of the antireflection film which has an anti-glare function
  • (a) is typical sectional drawing of the antireflection film 50 which has an anti-glare structure on the surface
  • b) is a schematic cross-sectional view of an antireflection film 950 having a layer having an antiglare function inside the surface.
  • (A) shows the bright contrast ratio when the antireflection films of Comparative Examples 2 to 7 and Comparative Example 10 are viewed from the front
  • (b) shows Comparative Examples 2 to 7 and Comparative Example. The luminance of the white display state when the antireflection film of Example 10 is viewed from the front direction is shown.
  • (C) is the antireflection film of Comparative Examples 2 to 7 and Comparative Example 10 when viewed from the front direction. The brightness of the black display state is shown.
  • (A) is a graph showing the measurement result of the light distribution of diffuse reflection by the antireflection films of Comparative Examples 3 to 7, and (b) shows the measurement system of the light distribution of diffuse reflection. It is a schematic diagram.
  • (A) and (b) are graphs showing the results of measuring the luminance of the anti-reflection films of Comparative Examples 2 to 7 in the white display state while changing the polar angle. It is a figure which expands and shows a part of ().
  • (A) And (b) is a figure which shows typically the relationship of the magnitude
  • FIG. 1A to 1D are schematic cross-sectional views for explaining a method for manufacturing a moth-eye mold 100 according to an embodiment of the present invention.
  • FIG. 1A is a schematic cross-sectional view of the aluminum base 12
  • FIG. 1B is a cross-sectional view schematically showing the surface structure of the aluminum base 12 having an inverted antiglare structure.
  • FIG. 1C is a schematic cross-sectional view of the mold base 10 obtained by forming the inorganic material layer 16 and the aluminum film 18 on the surface of the aluminum base 12, and
  • FIG. 2 is a schematic cross-sectional view of a moth-eye mold 100 having an inverted antiglare structure and an inverted motheye structure superimposed on the inverted antiglare structure.
  • FIG.1 (d) is sectional drawing corresponding to a part (area
  • the mold base means an object to be anodized and etched in the mold manufacturing process.
  • the aluminum substrate means bulk aluminum that can be self-supported.
  • FIG. 1 shows an enlarged part of the moth-eye mold 100, but the moth-eye mold 100 according to the embodiment of the present invention has, for example, a cylindrical shape (roll shape).
  • a cylindrical shape roll shape
  • an antireflection film can be efficiently produced by a roll-to-roll method.
  • the entire disclosure of WO 2011/105206 is incorporated herein by reference.
  • a cylindrical mold will be described below as an example, the mold according to the embodiment of the present invention is not limited to a cylindrical shape.
  • a cylindrical substrate 12 is prepared.
  • the cylindrical substrate 12 is made of aluminum, for example.
  • the aluminum base material 12 is demonstrated.
  • the aluminum base 12 is mechanically mirror-finished.
  • the cylindrical aluminum substrate 12 is made of, for example, an Al—Mg—Si based aluminum alloy.
  • a relatively rigid aluminum substrate having an aluminum purity of 99.50 mass% or more and less than 99.99 mass% is used.
  • impurities contained in the aluminum substrate 12 iron (Fe), silicon (Si), copper (Cu), manganese (Mn), zinc (Zn), nickel (Ni), titanium (Ti), lead (Pb) It is preferable that at least one element selected from the group consisting of tin (Sn) and magnesium (Mg) is included, and Mg is particularly preferable.
  • the mechanism by which pits (dents) are formed in the etching process is a local cell reaction, and therefore ideally contains no noble elements than aluminum and is a base metal, Mg (standard electrode potential ⁇ It is preferable to use an aluminum substrate 12 containing 2.36V) as an impurity element. If the content of an element nobler than aluminum is 10 ppm or less, it can be said that the said element is not included substantially from an electrochemical viewpoint.
  • the Mg content is preferably 0.1% by mass or more, and more preferably in the range of about 3.0% by mass or less. If the Mg content is less than 0.1 mass%, sufficient rigidity cannot be obtained. On the other hand, when the content rate increases, Mg segregation easily occurs.
  • Mg forms an anodic oxide film having a form different from that of aluminum, which causes defects.
  • the content rate of an impurity element according to the rigidity required according to the shape of the aluminum base material 12, thickness, and a magnitude
  • an appropriate Mg content is about 3.0 mass%, and the aluminum substrate 12 having a three-dimensional structure such as a cylinder is produced by extrusion.
  • the content rate of Mg is 2.0 mass% or less. If the Mg content exceeds 2.0 mass%, extrusion processability generally decreases.
  • Byte cutting is preferred as the mechanical mirror finish. If, for example, abrasive grains remain on the surface of the aluminum base 12, electrical conduction between the aluminum film 18 and the aluminum base 12 is facilitated in a portion where the abrasive grains exist. In addition to the abrasive grains, where there are irregularities, local conduction between the aluminum film 18 and the aluminum substrate 12 is likely to occur. When local conduction is made between the aluminum film 18 and the aluminum base 12, there is a possibility that a battery reaction occurs locally between the impurities in the aluminum base 12 and the aluminum film 18.
  • the cylindrical aluminum substrate 12 is typically formed by a hot extrusion method.
  • the hot extrusion method includes a mandrel method and a porthole method, and it is preferable to use an aluminum substrate 12 formed by the mandrel method.
  • a seam (weld line) is formed on the outer peripheral surface of the cylindrical aluminum substrate 12 formed by the porthole method, and the seam is reflected in the moth-eye mold 100. Therefore, depending on the accuracy required for the moth-eye mold 100, it is preferable to use the aluminum substrate 12 formed by the mandrel method.
  • the problem of a seam can be eliminated by performing cold drawing processing on the aluminum base material 12 formed by the porthole method.
  • cold drawing may be applied to the aluminum substrate 12 formed by the mandrel method.
  • an inverted antiglare structure is formed on the surface 12 s of the aluminum base 12 as shown in FIG.
  • the inverted anti-glare structure formed by spraying the projection material has a plurality of first recesses 12a.
  • FIG. 2 shows a process of forming an inverted antiglare structure by spraying a projection material onto the surface of the aluminum base 12 in the manufacturing process of the moth-eye mold 100 according to the embodiment of the present invention (referred to as a spraying process process). It is a schematic diagram for explaining.
  • an aluminum substrate 12 shown in FIG. 1 (a) is prepared.
  • the cylindrical aluminum base material is arranged so that the major axis direction is substantially parallel to the vertical direction.
  • an anti-glare structure that is inverted on the surface of the aluminum base 12 is formed by spraying a projection material from the nozzle 82 toward the surface of the aluminum base 12.
  • the projection material is substantially spherical, the projection material contains alumina particles, and the average particle size of the projection material is 10 ⁇ m or more and 40 ⁇ m or less.
  • the shape of the inverted anti-glare structure formed on the surface of the aluminum base 12 can be changed.
  • the aluminum base 12 may be rotated about the major axis of the aluminum base 12.
  • a projection material can be sprayed uniformly on the surface (side surface of the cylindrical aluminum base material 12) of the aluminum base material 12, and the anti-glare structure reversed evenly on the surface of the aluminum base material 12 can be formed.
  • the aluminum substrate 12 indicates the speed of rotation about the longitudinal axis of the aluminum substrate 12 as v r.
  • the nozzle 82 may be moved along the long axis direction of the aluminum base 12. In FIG. 2, the speed at which the nozzle 82 moves along the long axis direction of the aluminum base 12 is indicated as v v .
  • the conditions for spraying the projection material include, for example, the distance d from the nozzle 82 to the surface of the aluminum base 12, the discharge pressure of the projection material, and the moving speed v v of the nozzle 82.
  • Time of blowing speed v r and the projection member of the aluminum substrate 12, (of the surface of the aluminum substrate 12, the area subjected to blasting treatment) treated area is appropriately adjusted in accordance with the.
  • the average particle diameter of the projection material may be 10 ⁇ m or more and less than 35 ⁇ m.
  • the particle size distribution of the projection material may have a peak within a range of ⁇ 10% from the average particle size.
  • an inorganic material layer 16 is formed on the surface of the aluminum substrate 12, and an aluminum film 18 is formed on the inorganic material layer 16, thereby producing the mold substrate 10. To do.
  • a structure reflecting an inverted antiglare structure formed by spraying the surface of the aluminum base 12 is formed on the surface of the aluminum film 18.
  • the inverted antiglare structure formed on the surface 18s of the aluminum film 18 is gentler than the inverted antiglare structure formed on the surface 12s of the aluminum base 12.
  • the structure formed in the aluminum film 18 is also called an inverted antiglare structure.
  • the inverted antiglare structure formed on the surface of the aluminum film 18 has a plurality of third recesses 18a. Details of the plurality of third recesses 18a and the plurality of first recesses 12a will be described later with reference to FIG.
  • the inorganic material layer 16 for example, tantalum oxide (Ta 2 O 5 ) or silicon dioxide (SiO 2 ) can be used.
  • the inorganic material layer 16 can be formed by sputtering, for example.
  • the thickness of the tantalum oxide layer is, for example, 200 nm.
  • the thickness of the inorganic material layer 16 is preferably 100 nm or more and less than 500 nm. If the thickness of the inorganic material layer 16 is less than 100 nm, defects (mainly voids, that is, gaps between crystal grains) may occur in the aluminum film 18 in some cases. Further, when the thickness of the inorganic material layer 16 is 500 nm or more, the aluminum base 12 and the aluminum film 18 are easily insulated from each other depending on the surface state of the aluminum base 12. In order to anodize the aluminum film 18 by supplying current to the aluminum film 18 from the aluminum substrate 12 side, it is necessary that a current flow between the aluminum substrate 12 and the aluminum film 18.
  • the aluminum film 18 can be uniformly anodized over the entire surface without causing a problem that it is difficult to be supplied.
  • the thick inorganic material layer 16 it is generally necessary to lengthen the film formation time.
  • the film formation time is lengthened, the surface temperature of the aluminum base 12 is unnecessarily increased. As a result, the film quality of the aluminum film 18 is deteriorated, and defects (mainly voids) may occur. If the thickness of the inorganic material layer 16 is less than 500 nm, the occurrence of such a problem can be suppressed.
  • the aluminum film 18 may be a film formed of aluminum having a purity of 99.99 mass% or more (hereinafter referred to as “high-purity aluminum film”). ).
  • the aluminum film 18 is formed using, for example, a vacuum deposition method or a sputtering method.
  • the thickness of the aluminum film 18 is preferably in the range of about 500 nm or more and about 1500 nm or less, for example, about 1 ⁇ m.
  • the entire disclosure of WO 2011/125486 is incorporated herein by reference.
  • an aluminum alloy film described in International Publication No. 2013/183576 may be used instead of the high-purity aluminum film.
  • the aluminum alloy film described in International Publication No. 2013/183576 includes aluminum, a metal element other than aluminum, and nitrogen.
  • the “aluminum film” includes not only a high-purity aluminum film but also an aluminum alloy film described in International Publication No. 2013/183576.
  • the entire disclosure of WO2013 / 183576 is incorporated herein by reference.
  • the average grain size of the crystal grains constituting the aluminum alloy film as viewed from the normal direction of the aluminum alloy film is, for example, 100 nm or less, and the maximum surface roughness Rmax of the aluminum alloy film is 60 nm or less.
  • the content rate of nitrogen contained in the aluminum alloy film is, for example, not less than 0.5 mass% and not more than 5.7 mass%.
  • the absolute value of the difference between the standard electrode potential of a metal element other than aluminum contained in the aluminum alloy film and the standard electrode potential of aluminum is 0.64 V or less, and the content of the metal element in the aluminum alloy film is 1.0 mass. % Or more and 1.9 mass% or less is preferable.
  • the metal element is, for example, Ti or Nd.
  • the metal element is not limited to this, and other metal elements whose absolute value of the difference between the standard electrode potential of the metal element and the standard electrode potential of aluminum is 0.64 V or less (for example, Mn, Mg, Zr, V, and Pb).
  • the metal element may be Mo, Nb, or Hf.
  • the aluminum alloy film may contain two or more of these metal elements.
  • the aluminum alloy film is formed by, for example, a DC magnetron sputtering method.
  • the thickness of the aluminum alloy film is also preferably in the range of about 500 nm to about 1500 nm, for example, about 1 ⁇ m.
  • anodic oxidation and etching are alternately repeated to form the inverted moth-eye structure, whereby the moth-eye mold 100 shown in FIG. 1D is obtained. That is, in the process of forming the inverted moth-eye structure, the surface of the aluminum film 18 is anodized to form a porous alumina layer 14 having a plurality of second recesses 14p, and then the porous alumina layer 14 Including a step of enlarging the plurality of second recesses 14p of the porous alumina layer 14 by contacting with an etching solution, and then a step of growing the plurality of second recesses 14p by further anodizing. To do.
  • the electrolytic solution used for anodization is, for example, an aqueous solution containing an acid selected from the group consisting of oxalic acid, tartaric acid, phosphoric acid, sulfuric acid, chromic acid, citric acid, and malic acid.
  • an aqueous solution of an organic acid such as formic acid, acetic acid, or citric acid or an aqueous solution of sulfuric acid, a mixed aqueous solution of chromic phosphoric acid, or an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide can be used.
  • the series of steps of repeating anodization and etching end with the anodization step.
  • the subsequent etching process is not performed
  • the bottom of the second recess 14p can be reduced.
  • a method for forming such an inverted moth-eye structure is disclosed in Patent Document 3, for example.
  • an anodic oxidation step electrolytic solution: oxalic acid aqueous solution (concentration 0.3 mass%, liquid temperature 10 ° C.), applied voltage: 80 V, application time: 55 seconds
  • etching step etching solution: phosphoric acid aqueous solution (10 mass%, 30 ° C.) ), Etching time: 20 minutes
  • 5 times: 5 times of anodization and 4 times of etching as shown in FIG.
  • the moth-eye mold 100 having the porous alumina layer 14 is obtained.
  • the second recess 14p has a substantially conical shape and is adjacent to form a flange.
  • a barrier layer is formed under the second recess 14p.
  • the porous alumina layer 14 includes a porous layer having the second recess 14p and a barrier layer (under the aluminum film side) (on the aluminum film side). The bottom of the recess 14p). It is known that the interval (center-to-center distance) between the adjacent second recesses 14p corresponds to approximately twice the thickness of the barrier layer and is approximately proportional to the voltage during anodic oxidation. Under the porous alumina layer 14, an aluminum remaining layer 18 r that has not been anodized in the aluminum film 18 is present.
  • the inverted moth-eye structure constituted by the second recesses 14p is formed so as to be superimposed on the inverted anti-glare structure.
  • the “two-dimensional size” of the second recess 14p refers to the area equivalent circle diameter of the recess when viewed from the normal direction of the surface.
  • the two-dimensional size of the recess corresponds to the diameter of the bottom surface of the cone.
  • the second concave portions (fine concave portions) 14p are densely arranged, and there is no gap between the adjacent second concave portions 14p (for example, the bottom surface of the cone is partially overlapping) case, the average distance between adjacent D int of the two second recesses 14p adjacent to each other (distance between centers of adjacent second recesses 14p) includes a 2-dimensional size D p of the second recess 14p Almost equal.
  • the moth-eye mold 100 can be manufactured.
  • the anti-glare property is exhibited while maintaining the clearness, and the appearance of cloudiness when viewed from an oblique viewing angle is suppressed.
  • An antireflection film can be formed.
  • the antireflection film that exhibits antiglare properties while maintaining the clearness and is suppressed from appearing cloudy when viewed from an oblique viewing angle.
  • a mold for forming can be efficiently obtained.
  • Anti-reflective film appears cloudy when viewed from an oblique viewing angle means that the anti-reflective film appears whitish when viewed from an oblique viewing angle (oblique white-brown), and / or It may indicate that it looks whitish when viewed from an oblique viewing angle.
  • Patent Document 5 discloses a mold manufacturing method by blasting the surface of an aluminum base material and then anodizing the surface of the blasted aluminum base material.
  • the object to be anodized in the method for producing a mold of Patent Document 5 is an aluminum substrate, and does not have an inorganic material layer and an aluminum film on the aluminum substrate.
  • a spherical projecting material having no sharp shape is used as the projecting material (referred to as “abrasive material used for blasting” in Patent Document 5).
  • a mold for forming an antireflection film having antireflection properties and antiglare properties and suppressing the occurrence of glare can be obtained.
  • glass beads are used as a spherical projection material that does not have a sharp shape.
  • Patent Document 5 describes that the center particle size of the projection material is preferably 35 ⁇ m to 150 ⁇ m.
  • the obtained antireflection film suppresses white turbidity when viewed from an oblique viewing angle. It turns out not to be.
  • the present inventor has produced anti-glare properties while maintaining clearness by producing a mold by the following method, and suppresses appearing cloudy when viewed from an oblique viewing angle. It has been conceived that a mold for forming the antireflection film formed can be obtained.
  • the surface of the aluminum substrate 12 is reversed to the surface of the aluminum substrate 12 by performing a spraying process using a projection material that is substantially spherical, contains alumina particles, and has an average particle size of 10 ⁇ m or more and 40 ⁇ m or less. Then, an anti-glare structure is formed, and then an aluminum film 18 is formed on the aluminum substrate 12. As a result, a gently inverted anti-glare structure can be formed on the surface of the aluminum film 18 (that is, the surface of the mold base 10), so that the anti-glare property is exhibited while maintaining the clearness, and the oblique viewing angle. Thus, it is possible to obtain a mold for forming an antireflection film that is suppressed from appearing cloudy when viewed from above.
  • the average particle size of the projection material used for the spraying treatment of the surface of the aluminum base 12 is smaller than that of the manufacturing method of Patent Document 5. Therefore, by forming the aluminum film 18 on the surface of the aluminum substrate 12, the effect of smoothing the inverted anti-glare structure on the surface of the mold substrate 10 is prominent.
  • the moth-eye mold 100 has the following advantages. As described above, seams (weld lines) and cutting marks may be formed on the surface of the aluminum base 12. For example, a seam can be formed on the surface of a cylindrical aluminum substrate formed by the porthole method. In addition, cutting traces may be formed on the surface of the aluminum base material that has been subjected to mirror finishing (for example, bite cutting) that involves the formation of a work-affected layer. In the moth-eye mold 100 according to the embodiment of the present invention, the aluminum film 18 is formed on the aluminum substrate 12.
  • the surface of the aluminum film 18 can reflect seams and cutting marks formed on the surface of the aluminum base material 12, but the seam and cutting marks reflected on the surface of the aluminum film 18 (that is, the surface of the mold base material 10). Is gentler than that formed on the surface of the aluminum base 12 and is not noticeable. Moreover, in the method for manufacturing the moth-eye mold 100 according to the embodiment of the present invention, since the projection material is not sprayed on the surface of the aluminum film 18, the aluminum film 18 is not locally broken by the projection material. Therefore, the thickness of the aluminum film 18 can be reduced (for example, about 500 nm or more and about 1500 nm or less).
  • FIG. 3 is a schematic cross-sectional view for explaining a method for producing an antireflection film by a roll-to-roll method.
  • a cylindrical moth-eye mold 100 is prepared.
  • the cylindrical moth-eye mold 100 is manufactured by the above-described manufacturing method.
  • ultraviolet light is applied to the ultraviolet curable resin 32 ′ by irradiating the ultraviolet curable resin 32 ′ with the workpiece 42 having the ultraviolet curable resin 32 ′ pressed against the moth-eye mold 100.
  • the cured resin 32 ′ is cured.
  • an acrylic resin can be used as the ultraviolet curable resin 32 ′.
  • the workpiece 42 is, for example, a TAC (triacetyl cellulose) film.
  • the workpiece 42 is unwound from an unillustrated unwinding roller, and then an ultraviolet curable resin 32 ′ is applied to the surface by, for example, a slit coater.
  • the workpiece 42 is supported by support rollers 46 and 48 as shown in FIG.
  • the support rollers 46 and 48 have a rotation mechanism and convey the workpiece 42.
  • the cylindrical moth-eye mold 100 is rotated in the direction indicated by the arrow in FIG. 3 at a rotational speed corresponding to the transport speed of the workpiece 42.
  • the cured product layer 32 to which the concavo-convex structure (inverted moth-eye structure and inverted anti-glare structure) of the moth-eye mold 100 has been transferred is transferred to the workpiece 42.
  • the workpiece 42 having the cured product layer 32 formed on the surface is wound up by a winding roller (not shown).
  • a release agent is applied to the surface of the moth-eye mold 100 to release the moth-eye mold 100. May be applied.
  • the release agent is preferably a compound having a (per) fluoropolyether group, a hydrolyzable group (for example, an alkoxy group), and an Si atom. Further, the release agent may contain a perfluoroalkyl compound in addition to at least one compound (perfluoropolyether compound). Examples of the perfluoroalkyl compounds include C 8 F 17 CH 2 CH 2 Si (OMe) 3, C 6 F 13 CH 2 CH 2 Si (OMe) 3, and C 4 F 9 CH 2 CH 2 Si (OMe). 3 etc. are mentioned. When such a release agent is applied to the surface of the moth-eye mold 100, the moth-eye mold 100 can be easily peeled from the cured product layer 32 after the ultraviolet curable resin 32 'is irradiated with ultraviolet rays.
  • a UV curable resin containing a solvent for example, acrylic resin
  • a solvent for example, acrylic resin
  • a solvent that dissolves the surface of the TAC film for example, a ketone
  • the solvent dissolves the surface of the TAC film, a region where TAC and the ultraviolet curable resin are mixed is formed.
  • the solvent is removed, and the TAC film is wound so that the ultraviolet curable resin is in close contact with the outer peripheral surface of the moth-eye mold.
  • ultraviolet rays are irradiated to cure the ultraviolet curable resin.
  • the temperature of the ultraviolet curable resin is maintained at 30 ° C. to 70 ° C.
  • the TAC film is peeled off from the moth-eye mold, and again irradiated with ultraviolet rays as necessary.
  • the material for forming the hard coat layer may contain a solvent that dissolves the surface of the TAC film. Good. In this case, it is not necessary to add a solvent to the ultraviolet curable resin for forming the antireflection film.
  • an aqueous primer for example, a polyester resin or an acrylic resin
  • FIGS. 4A and 4B are SEM images (full scale 20.0 ⁇ m in SEM image) of the surface of an aluminum piece having an inverted antiglare structure formed by spraying a projection material.
  • FIGS. 4A and 4B show an inverted antiglare structure formed on the surface of a mirror-finished aluminum piece.
  • An inverted antiglare structure was formed on the surface of an aluminum piece corresponding to the aluminum substrate 12 in FIG.
  • an Al—Mg—Si-based aluminum alloy a small piece of aluminum having a thickness of 15 mm and a square of about 5 cm was used.
  • JIS A6063 has the following composition (mass%). Si: 0.20 to 0.60%, Fe: 0.35% or less, Cu: 0.10% or less, Mn: 0.10% or less, Mg: 0.45 to 0.9%, Cr: 0. 10% or less, Zn: 0.10% or less, Ti: 0.10% or less, Other: Individual is 0.05% or less, the whole is 0.15% or less, the balance: Al
  • Table 6 shows the conditions of the spraying process performed to obtain the inverted antiglare structure shown in FIGS. 4A and 4B (the conditions for spraying the projection material and the type of the projection material). Table 6 collectively shows the conditions of the spraying process of the experimental example in the specification and the type of aluminum of the target (that is, the aluminum substrate 12) on which the spraying process was performed.
  • the inverted antiglare structure formed by spraying the projection material onto the surface of the aluminum base 12 has a plurality of first recesses 12a. There is no regularity in the arrangement of the plurality of first recesses 12a. It can also be seen that the two-dimensional size distribution of the plurality of first recesses 12a is wide. Here, the “two-dimensional size” of the first recess 12a refers to the area circle equivalent diameter. From the SEM image of FIG.
  • the two-dimensional size of the plurality of first recesses 12a ranges from 2 ⁇ m to 10 ⁇ m, and the average of the two-dimensional size of the plurality of first recesses 12a is 5 ⁇ m,
  • the distance between the adjacent first recesses 12a (the distance between the centers of the adjacent first recesses 12a) can be estimated to be 2 ⁇ m or more and 10 ⁇ m or less. From the SEM image of FIG.
  • the two-dimensional size of the plurality of first recesses 12a ranges from 5 ⁇ m to 20 ⁇ m, and the average of the two-dimensional size of the plurality of first recesses 12a is 10 ⁇ m,
  • the distance between the adjacent first recesses 12a (the distance between the centers of the adjacent first recesses 12a) can be estimated to be 1 ⁇ m or more and 10 ⁇ m or less.
  • the two-dimensional size of the plurality of first recesses 12a included in the inverted anti-glare structure in FIG. 4A is smaller than the average particle size of the projection material.
  • the average of the two-dimensional sizes of the plurality of first recesses 12a is smaller than the average particle diameter of the projection material.
  • the first recesses 12a are densely and irregularly arranged, for example as schematically shown in FIG. 1B, and the inverted antiglare structure does not have a flat portion between the first recesses 12a.
  • the arithmetic average roughness Ra of the surface 12s having an inverted antiglare structure formed by spraying a projection material on the surface of the aluminum base 12 is, for example, 0.05 ⁇ m or more and 0.3 ⁇ m or less.
  • the inorganic material layer 16 is formed on the surface of the aluminum base 12 having the inverted antiglare structure, and the aluminum film 18 is formed on the inorganic material layer 16.
  • the aluminum film 18 has an inverted antiglare structure including a plurality of third recesses 18a. Since the plurality of third recesses 18a reflect the plurality of first recesses 12a, the shape of the plurality of third recesses 18a (for example, two-dimensional size, depth, distance between adjacent portions, etc.) is plural. It may be the same as that of the first recess 12a.
  • the inverted antiglare structure formed on the surface 18 s of the aluminum film 18 is gentler than the inverted antiglare structure formed on the surface 12 s of the aluminum substrate 12.
  • the ridge lines included in the plurality of third recesses 18a are gentler (not pointed) than the ridge lines included in the plurality of first recesses 12a. Therefore, the surface 18s of the aluminum film 18 having an inverted antiglare structure is gentler than the surface 12s of the aluminum substrate 12 having an inverted antiglare structure.
  • the surface roughness of the surface 18 s of the aluminum film 18 may be smaller than the surface roughness of the surface 12 s of the aluminum substrate 12.
  • the two-dimensional size of the plurality of third recesses 18a also refers to the area circle equivalent diameter. The same applies to the “two-dimensional size” of the convex portion in which the third concave portion 18a is inverted.
  • the two-dimensional size of the plurality of third recesses 18a is, for example, 1 ⁇ m to 12 ⁇ m, and may be 3 ⁇ m to 12 ⁇ m, for example.
  • the depth of the plurality of third recesses 18a is, for example, not less than 1 ⁇ m and not more than 4 ⁇ m.
  • the aspect ratio of the depth to the two-dimensional size of the plurality of third recesses 18a is, for example, not less than 0.05 and not more than 0.5.
  • the aluminum substrate 12 having an antiglare structure inverted on the surface was manufactured by performing a spraying treatment process on the surface of the aluminum substrate 12.
  • a mold sample was produced without forming an inorganic material layer and an aluminum film on the aluminum substrate 12.
  • a mold sample was manufactured by changing the conditions of the spraying process applied to the surface of the aluminum substrate 12, and a mold release treatment was applied to the surface of the mold sample by applying a release agent.
  • the mold release treatment was performed as follows. First, a dilute solution was prepared by diluting a release agent (Optool DSX manufactured by Daikin Industries, Ltd.) with “S-135” manufactured by Fluoro Technology. The concentration of the release agent in the diluted solution was 0.1%.
  • the mold release agent was provided to the surface of the mold sample by immersing the mold sample in the diluent of the mold release agent for 3 minutes. Thereafter, the mold sample coated with the release agent was annealed at 150 ° C. for 1 hour and rinsed with “S-135” manufactured by Fluoro Technology for 3 minutes. After the mold release treatment, an acrylic ultraviolet curable resin was applied to the surface of the mold sample, and cured by irradiating with ultraviolet rays while being transferred onto the TAC film. Sample film No. having the antiglare structure obtained was obtained. 1-No. For 4, the antiglare function was evaluated.
  • Anti-glare film No. 1-No. Table 6 shows the conditions of the spraying process applied to the mold sample to obtain 4.
  • Table 1 shows anti-glare film No. 1-No. 4 shows the results of evaluating the antiglare function.
  • “Glitter”, “Moire” and “White turbidity” in Table 1 indicate that the antireflection film is applied to the surface of the viewer side of the display panel of a liquid crystal television (AQUAS LC-60UD1, Sharp Corporation, 60 inches). It is the result of pasting and visual subjective evaluation. Subjective evaluation was conducted by listening to 10 people. “Glitter” indicates a result of evaluating whether or not the display surface is glaring when viewed from the normal direction of the surface. “Moire” indicates the result of evaluating whether or not moire has occurred on the display surface when viewed from the normal direction of the surface. The “white turbidity” is a result of evaluating whether or not the antireflection film appears cloudy (discolored) when viewed from a polar angle of 80 ° from the normal direction of the surface.
  • the “haze value of the antireflection film” in Table 1 is a result of measuring the haze value of the antireflection film 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.
  • Anti-glare film No. 3 is an anti-glare film No. 3; 1 and no. It had a haze value greater than 2, and appeared cloudy when viewed from an oblique viewing angle.
  • Anti-glare film No. 3 and anti-glare film no Compared with 4, the difference in the effect of suppressing the occurrence of glare was observed despite the fact that the arithmetic mean roughness Ra of the mold surface was comparable.
  • the average particle diameter of the projection material used here is compared, since glass beads have a larger average particle diameter than alumina particles, there is a possibility that the occurrence of glare could not be suppressed.
  • the antiglare film No. The average particle size of the alumina particles used for producing the mold samples for forming 1-3 was 17 ⁇ m
  • the average particle diameter of the glass beads used for producing the mold sample for forming 4 was 23 ⁇ m.
  • anti-glare film No. using alumina particles as a projection material No. using alumina particles as a projection material. 1-No. From the result of 3, it was found that there is a correlation between the haze value of the antireflection film and the arithmetic average roughness Ra of the mold surface.
  • FIGS. 5A and 5B show the antireflection film (center) of Example 1, the antireflection film of Reference Example 1 (right), and the antireflection film of Comparative Example 1 (left) attached to the surface.
  • FIG. 5A is an optical image of a display panel (liquid crystal television, product name: AQUAS LC-60UD1, Sharp Corporation, 60 inches) attached
  • FIG. 5A is an optical image viewed from the normal direction of the surface.
  • FIG. 5B is a diagram showing an optical image viewed from an oblique viewing angle (polar angle 60 °).
  • the antireflection films of Example 1 and Reference Example 1 were formed by the method described with reference to FIG. 3 using the moth-eye mold 100 manufactured by the method described with reference to FIGS.
  • the moth-eye mold for forming the antireflection film of Example 1 is the antiglare film No. described above.
  • the moth-eye mold for forming the antireflection film of Reference Example 1 is obtained by performing the spraying process under the same conditions as the spraying process applied to the mold sample for forming the anti-glare film No. described above. . It was obtained by performing a spraying process under the same conditions as the spraying process applied to the mold sample for forming 3.
  • Example 1 and the antireflection film of Reference Example 1 have the same structure as the antireflection film 50 shown in FIG. That is, the antireflection film of Example 1 and Reference Example 1 has a base film (TAC film), a hard coat layer formed on the base film, and an antireflection film having an antiglare structure and a motheye structure on the surface. .
  • TAC film base film
  • a hard coat layer formed on the base film
  • an antireflection film having an antiglare structure and a motheye structure on the surface.
  • the antireflection film of Comparative Example 1 is an antireflection film having an antireflection function and an antiglare function that is currently commercially available.
  • the antireflection film of Comparative Example 1 does not have a moth-eye structure.
  • Table 2 shows the results of evaluating the antireflection function and antiglare function of the antireflection film of Example 1, the antireflection film of Reference Example 1, and the antireflection film of Comparative Example 1.
  • “Blur of reflected image” in Table 2 is to visually evaluate the blurring of the outline of the image reflected on the antireflection film when the antireflection film is viewed from the front direction (normal direction of the surface). This is the result of evaluating the antiglare property of the antireflection film. “ ⁇ ” indicates that the image outline is moderately blurred and a clear image can be obtained. “ ⁇ ” indicates that the outline of the image is excessively blurred for the purpose of obtaining a clear image. However, as a matter of course, there is a case where the antireflection film “ ⁇ ” can be suitably used as the antireflection film having a higher antiglare function.
  • the “white turbidity” in Table 2 is a result of visual evaluation of whether or not the antireflection film appears clouded (white brown).
  • the “front direction” is the result when viewed from the normal direction of the surface, and the “oblique viewing angle” is the result when viewed from a polar angle of 80 ° from the normal direction of the surface.
  • the haze values in Table 2 were 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 total light transmitted light, and the ratio of the diffuse transmitted light to the total light transmitted light was defined as the haze value.
  • the 20-degree specular gloss, 60-degree specular gloss, and 85-degree specular gloss were measured using a gloss meter (manufactured by Suga Test Instruments Co., Ltd., product name: GS-4K) after the film was attached to a black acrylic plate. .
  • the antireflection film of Example 1 and Reference Example 1 has the same structure as the antireflection film 50 shown in FIG. That is, the surface structure of the antireflection film 32 included in the antireflection film 50 exhibits an antireflection function and an antiglare function. Therefore, the evaluation results of the antireflection function and antiglare function shown in Table 2 for the antireflection films of Example 1 and Reference Example 1 are the results of the antireflection function and antiglare function of the antireflection film of Example 1 and Reference Example 1. It can be considered equivalent to evaluation.
  • the antireflection film of Example 1 has a moderate degree of blurring of the outline of the reflected image when viewed from the front direction, whereby a clear image can be obtained.
  • the antireflection film of Example 1 has a low haze value.
  • the antireflection film of Example 1 is cloudy and invisible when viewed from the front and when viewed from an oblique viewing angle. Furthermore, since the antireflection film of Example 1 has a moth-eye structure, the antireflection function is sufficiently exhibited even when viewed from an oblique viewing angle. Since the antireflection film of Example 1 has a moth-eye structure, it achieves excellent black display quality (that is, low brightness in the black display state).
  • the antireflection film of Reference Example 1 since the antireflection film of Reference Example 1 has a high haze value, it appears cloudy when viewed from the front. In addition, the antireflection film of Reference Example 1 appears cloudy even when viewed from an oblique viewing angle (oblique white brown). In the antireflection film of Reference Example 1, the outline of the reflected image when viewed from the front direction is excessively blurred for the purpose of obtaining a clear image.
  • the antireflection film of Comparative Example 1 has a lower haze value than the antireflection film of Example 1, and is suppressed from appearing cloudy when viewed from the front direction and from an oblique viewing angle.
  • the black display quality is lower than the antireflection film of Example 1 (that is, the luminance in the black display state is high).
  • the antireflection film of Comparative Example 1 does not have a moth-eye structure, the antireflection effect when viewed from an oblique viewing angle is not sufficient.
  • the antireflection film according to the embodiment of the present invention exhibits antiglare properties while maintaining clearness, and can suppress the appearance of cloudiness when viewed from an oblique viewing angle.
  • the antireflection film of Example 1 has a 60-degree specular gloss of 4.0, an 85-degree specular gloss of 68.4, and a 20-degree specular gloss of 0.1.
  • the antireflection film of Example 1 has a 60 ° specular glossiness and an 85 ° specular glossiness smaller than the antireflection film of Comparative Example 1.
  • the antireflection film of Example 1 is superior to the antireflection film of Comparative Example 1 in antiglare properties when viewed from an oblique viewing angle.
  • FIG. 5B also shows that the antireflection film of Example 1 suppresses reflection when viewed from an oblique viewing angle as compared to the antireflection film of Comparative Example 1.
  • the antireflection film of Reference Example 1 also has a 60 ° specular glossiness and an 85 ° specular glossiness smaller than the antireflection film of Comparative Example 1.
  • the antireflection film of Reference 1 is superior to the antireflection film of Comparative Example 1 in antiglare properties when viewed from an oblique viewing angle.
  • the 20-degree specular gloss of the antireflection film of Reference Example 1 is 0.05, which is smaller than the antireflection film of Example 1.
  • the antireflection film of Reference Example 1 is inferior to the antireflection film of Example 1 from the viewpoint of clearness.
  • the 60 degree specular gloss of the antireflection film according to the embodiment of the present invention is preferably 1.0 or more and 10.0 or less, and the 20 degree specular gloss is preferably 0.01 or more and 1.0 or less. .
  • the 85 degree specular gloss of the antireflection film according to the embodiment of the present invention is preferably 50.0 or more and 75.0 or less.
  • the antireflection film according to the embodiment of the present invention for example, if the 60 ° specular gloss is 1, the 20 ° specular gloss is preferably 0.01 or more and 0.1 or less.
  • the 20 ° specular gloss is preferably 0.001 or more and 0.005 or less.
  • Such an antireflection film exhibits antiglare properties while maintaining clearness, and can suppress appearing cloudy when viewed from an oblique viewing angle.
  • the haze value of the antireflection film according to the embodiment of the present invention is preferably 5 or more and 30 or less.
  • the haze value of the antireflection film may be, for example, 2 or more and 40 or less.
  • an antireflection film According to the method for manufacturing an antireflection film according to the embodiment of the present invention, a film that exhibits antiglare properties while maintaining clearness and that can be prevented from appearing cloudy when viewed from an oblique viewing angle. It can be produced efficiently.
  • the manufacturing method of the antireflection film according to the embodiment of the present invention is excellent in mass productivity.
  • the mold for forming the antireflection film of Example 1 and the antireflection film of Reference Example 1 is an antiglare film No. 2 and anti-glare film No. 2 3 was obtained by performing a spraying process step under the same conditions as the mold sample for forming 3.
  • the haze value of 2 is different from that of the moth-eye structure.
  • the haze value of the antireflection film of Reference Example 1 and the antiglare film No. The same applies to the reason why the haze value of 3 is different.
  • FIG. 6 and 7 show SEM images of the antireflection film of Example 1 and the antireflection film of Reference Example 1.
  • FIG. 6A to 6C are SEM images of the antireflection film of Example 1, and FIG. 6A is an SEM image when the surface of the antireflection film of Example 1 is observed from the vertical direction.
  • FIG. 6B is a cross-sectional SEM image of the antireflection film of Example 1 (full scale 3.0 ⁇ m in the SEM image), and FIG. ) Is a cross-sectional SEM image of the antireflection film of Example 1 (full scale 500 nm in the SEM image).
  • 7A to 7C are SEM images of the antireflection film of Reference Example 1, and FIG.
  • FIG. 7A is an SEM image of the surface of the antireflection film of Reference Example 1 observed from the vertical direction.
  • FIG. 7B is a cross-sectional SEM image of the antireflection film of Reference Example 1 (full scale 3.0 ⁇ m in the SEM image), and
  • FIG. ) Is a cross-sectional SEM image of the antireflection film of Reference Example 1 (full scale 500 nm in the SEM image).
  • the moth-eye structure is formed so as to overlap the anti-glare structure.
  • the antiglare structure is formed by inverting an inverted antiglare structure having a plurality of third recesses 18a. That is, the anti-glare structure is configured by the first convex portion in which the plurality of third concave portions 18a are inverted.
  • the two-dimensional size of the first protrusion is 1 ⁇ m or more and 5 ⁇ m or less, and the distance between adjacent first protrusions (adjacent to each other). It can be seen that the distance between the centers of the first protrusions is about 10 ⁇ m.
  • the two-dimensional size of the first protrusions is 0.1 ⁇ m or more and 2 ⁇ m or less, and the distance between adjacent first protrusions is 1 ⁇ m or more and 5 ⁇ m or less. It turns out that it is.
  • the distance between adjacent first protrusions of the antireflection film of FIG. 7 is smaller than the distance between adjacent first protrusions of the antireflection film of FIG.
  • the two-dimensional size of the second convex portion and the distance between adjacent portions are about 200 nm, and the height (corresponding to the depth of the second concave portion 14p). The average of is 236 nm.
  • the two-dimensional size of the plurality of first protrusions is, for example, 1 ⁇ m or more and 12 ⁇ m or less.
  • the height of the plurality of first protrusions is, for example, 1 ⁇ m or more and 4 ⁇ m or less.
  • the aspect ratio of the depth with respect to the two-dimensional size of the plurality of first protrusions is, for example, 0.05 or more and 0.5 or less.
  • the antireflection film according to the embodiment of the present invention exhibits antiglare properties while maintaining clearness, and can suppress the appearance of cloudiness when viewed from an oblique viewing angle. It will be described below that such an effect cannot be obtained with a conventional antireflection film (or antireflection film).
  • Table 3 shows the results of evaluating the antireflection function and antiglare function of the antireflection films of Comparative Examples 2 to 9.
  • the “white turbidity” in the “front direction” is the result when viewed from the front direction of the antireflection film, “ ⁇ ” indicates that there is no white turbidity, and “ ⁇ ” indicates that there is a slight cloudiness. “X” indicates that there is a clear cloudiness.
  • Type in Table 3 indicates the type (type) of the antireflection film structure of Comparative Examples 2 to 9. As described with reference to FIG. 8, antireflection films having an antiglare function are roughly classified into “external haze type (or non-filler type)” and “internal haze type (or filler type)” depending on the structure. Can do.
  • FIGS. 8A and 8B are schematic cross-sectional views of an antireflection film having an antiglare function, respectively.
  • FIG. 8A is a schematic cross-sectional view of an antireflection film 50 having an antiglare structure on the surface
  • FIG. 8B shows an antireflection film 950 having a layer having an antiglare function inside the surface. It is typical sectional drawing.
  • the “haze value” in Table 3 was measured by attaching the antireflection film 50 of FIG. 8A or the antireflection film 950 of FIG. 8B to a glass plate.
  • the antireflection film 50 includes a base film (for example, a TAC film) 42, a hard coat layer 43, and an antireflection film 32 having a moth-eye structure and an antiglare structure on the surface.
  • the antireflection film 50 is provided on the viewer side of a polarizing layer (for example, PVA) 212 disposed on the viewer side of the display panel 200. Due to the antiglare structure of the antireflection film 32 on the surface, the antireflection film 50 exhibits antiglare properties.
  • An antireflection film having an antiglare structure on the surface may be referred to as an “external haze type”.
  • the antireflection film according to the embodiment of the present invention constitutes an external haze type antireflection film.
  • the polarizing layer 212 is protected by a base film (for example, TAC film) 42 and a protective layer (for example, TAC) 214.
  • the display panel having the antireflection film 50 is not limited to the illustrated configuration, and may have the following configuration.
  • a polarizing plate having a polarizing layer and protective layers provided on both sides of the polarizing layer is provided on the viewer side of the display panel 200, and an antireflection film 50 is further provided on the viewer side of the polarizing plate via an adhesive layer. It may be pasted.
  • the antireflection film 950 includes an internal haze layer 933, a base film (for example, a TAC film) 42, a hard coat layer 43, and an antireflection film 932 having a moth-eye structure on the surface.
  • the internal haze layer 933 has a scattering property.
  • the internal haze layer 933 is formed of, for example, an adhesive containing particles having scattering properties.
  • the antireflection film 950 is provided further on the viewer side of the polarizing layer (for example, PVA layer) 212 disposed on the viewer side of the display panel 200. Due to the internal haze layer 933, the antireflection film 950 exhibits antiglare properties.
  • An antireflection film having a scattering layer inside the surface of the antireflection film may be referred to as an “internal haze type”.
  • the polarizing layer 212 is held by holding layers (for example, TAC) 214 and 216.
  • the polarizing layer 212 and the holding layers 214 and 216 are sometimes referred to as polarizing plates.
  • An adhesive layer may be provided between the polarizing plate 212 and the polarizing plate having the holding layers 214 and 216 and the antireflection film 950.
  • the antireflection films of Comparative Examples 2 and 3 are external haze types, and the antireflection films of Comparative Examples 5 to 9 are internal haze types.
  • the antireflection films of Comparative Examples 2 and 3 have the same structure as the antireflection film 50 shown in FIG. 8A, and the antireflection films of Comparative Examples 5 to 9 are shown in FIG.
  • the antireflection film of Comparative Example 4 does not have an antiglare function.
  • the internal haze-type antireflection film has an internal haze layer having an antiglare function on the inner side of the surface, so that it appears cloudy particularly when viewed from an oblique viewing angle rather than when viewed from the surface normal direction. The problem is likely to occur.
  • the external haze type antireflection film has an antiglare structure on the surface, so that such a problem hardly occurs.
  • the inventor of the present invention has come up with an antireflection film capable of solving the above-described problems and a method for producing such an antireflection film.
  • an antireflection film and a method for manufacturing the same have been developed that have the same degree of blurring of the outline of an image reflected on the antireflection film as that of the antireflection film of Comparative Example 5.
  • the reason for using the antireflection film of Comparative Example 5 as a guide is that the clearness of the antireflection film of Comparative Example 5 is preferred in at least a part of the market.
  • the degree of blurring of the contour of the image reflected on the antireflection film (that is, the degree of antiglare property of the antireflection film) is not limited to this, and may be changed according to the purpose and form of use of the antireflection film. Of course.
  • FIG. 9A shows the contrast ratio under high illuminance (100 Lux) when the antireflection films of Comparative Examples 2 to 7 and Comparative Example 10 are viewed from the front direction
  • FIG. 9C shows the brightness in the white display state when the antireflection films of Comparative Examples 2 to 7 and Comparative Example 10 are viewed from the front
  • FIG. 9C shows Comparative Examples 2 to 7 and Comparative Example 10.
  • the luminance of the black display state when the antireflection film is viewed from the front is shown.
  • the antireflection film of Comparative Example 10 is a low reflection film (LR film) having no antiglare function.
  • the brightness in the white display state and the brightness in the black display state were measured as follows, and the bright place contrast ratio was calculated as follows from the ratio of the brightness in the white display state and the brightness in the black display state.
  • the following measurement method is based on ARIB TR-B28 of the Japan Radio Industry Association. Brightness of the white display state, Y level 940 (100% white), C B, inputs signals -C R level 512, luminance colorimeter: using (product name BM-5A, mfd Techno House) The luminance was measured in a dark room.
  • the display was adjusted using a PLUGE signal or the like, and the luminance of the Y level 940 (white 100%) portion was adjusted to 100 cd / m 2 .
  • the backlight intensity (light intensity) adjustment function does not operate either automatically or manually.
  • the antireflection film of Comparative Example 3 is compared with the antireflection film of Comparative Example 2 that does not have a moth-eye structure, it can be seen that the luminance in the white display state is increased by having the moth-eye structure. This is because the transmittance of light emitted from the backlight is improved. Further, it can be seen that the moth-eye structure reduces the luminance in the black display state and improves the quality of the black display.
  • the antireflection film of Comparative Example 3 is compared with the antireflection film of Comparative Example 4 that does not have an antiglare structure, the brightness in the white display state is lowered and the brightness in the black display state is increased by having the antiglare structure. I understand. As a result, the photopic contrast ratio is lowered due to the antiglare structure.
  • the antireflection film of Comparative Example 3 is compared with the antireflection film of Comparative Example 5 having clearness.
  • the antireflection film of Comparative Example 3 has lower white display state and black display state luminance than the antireflection film of Comparative Example 5.
  • the antireflection film of Comparative Example 3 is superior to the antireflection film of Comparative Example 5 in the bright place contrast ratio.
  • FIG. 10A is a graph showing a measurement result of the light distribution of diffuse reflection by the antireflection films of Comparative Examples 3 to 7, and FIG. 10B shows the light distribution of diffuse reflection. It is a schematic diagram which shows a measurement system. The diffuse reflected light does not specifically exclude scattered light.
  • the light distribution of the diffuse reflected light is such that the antireflection film is irradiated with light at an incident angle of 5 °, and the diffuse reflected light is distributed at a light receiving angle of 0 ° to 25 °.
  • the light distribution was measured.
  • each antireflection film was attached to a glass plate, and the light distribution was measured with a goniophotometer.
  • a goniophotometer As a goniophotometer, GP-200 manufactured by Murakami Color Research Laboratory was used.
  • the light distribution with the common logarithm of relative diffuse reflectance (%) normalized with the incident angle of 5 °, the light receiving angle on the horizontal axis, and the maximum value of diffuse reflected light intensity at 80% is plotted on the vertical axis.
  • a distribution curve is shown. The same applies to the light distribution curves shown below unless otherwise specified.
  • the light distribution curve has a peak value at a light receiving angle of 5 °.
  • the antireflection film according to the embodiment of the present invention has a relative diffuse reflectance (%) of 3% or more, for example, in the range of the light receiving angle of 5 ° to 7 °. Including a point where the light receiving angle is 8 ° to 10 ° and the relative diffuse reflectance (%) is in the range of 2% to 8%, the light receiving angle is 10 ° to 15 °, and The relative diffuse reflectance (%) includes a point in the range of 0.9% to 1.1%. Details will be described later with reference to FIG.
  • FIG. 11 (a) and 11 (b) are graphs showing the results of measuring the luminance of the white display state of the antireflection films of Comparative Examples 2 to 7 while changing the polar angle.
  • FIG.11 (b) is a figure which expands and shows a part of Fig.11 (a).
  • the antireflection film of Comparative Example 2 having no moth-eye structure has the lowest luminance. That is, the brightness of the antireflection films of Comparative Examples 3 to 7 is higher than the brightness of the antireflection film of Comparative Example 2 that does not have a moth-eye structure. For example, at a polar angle of 70 °, the luminance of the antireflection film of Comparative Example 4 having no antiglare structure is about 30% higher than the luminance of the antireflection film of Comparative Example 2.
  • the luminance of the antireflection film of Comparative Example 3 is about 15% higher than the luminance of the antireflection film of Comparative Example 2.
  • the reflectance at the surface of light incident on the display panel increases as the incident angle increases. Therefore, the antireflection film having a moth-eye structure on the surface has a great effect of reducing surface reflection when viewed from an oblique viewing angle (particularly a large polar angle).
  • the brightness of the antireflection film of Comparative Example 3 tends to be lower than the brightness of the antireflection film of Comparative Example 4 that does not have an antiglare structure, but the antireflection films of Comparative Examples 5 to 7 that are internal haze types. The brightness is comparable.
  • the present inventor forms an antireflection film that exhibits antiglare properties while maintaining clearness, and is suppressed from appearing cloudy when viewed from an oblique viewing angle.
  • the manufacturing method of the mold was examined.
  • the antireflection film (or antireflection film) according to the embodiment of the present invention has an antiglare structure on the surface
  • the mold for forming such an antireflection film has an inverted antiglare structure on the surface.
  • the present inventor has studied various methods for forming an inverted antiglare structure on the surface of a mold, and has come up with a mold manufacturing method according to an embodiment of the present invention.
  • Table 4 shows the results of evaluating the antireflection function and the antiglare function of the antireflection film of Example 2, Comparative Example 6, and the antireflection films of Comparative Examples 11 to 13.
  • the antireflection films of Example 2 and Comparative Examples 11 to 13 are external haze type antireflection films having the same structure as the antireflection film 50 shown in FIG. As already described, the evaluation results of the antireflection function and the antiglare function of the external haze type antireflection film are considered to be equivalent to the evaluation of the antireflection function and the antiglare function of the antireflection film of the antireflection film. be able to.
  • the antireflection film of Example 2 was formed using the moth-eye mold manufactured by the method described above.
  • Table 6 shows the conditions of the spraying process in the process of manufacturing the moth-eye mold for forming the antireflection film of Example 2.
  • the antireflection film of Comparative Example 11 was formed using a moth-eye mold manufactured as follows. Differences from the mold manufacturing method according to the embodiment of the present invention will be mainly described. The same applies to the following.
  • an inorganic material is formed on the surface of the aluminum base 12.
  • Layer 16 was formed by electrodeposition.
  • a matting agent was mixed with the electrodeposition resin.
  • a matting agent for example, a surface on which a convex portion having a two-dimensional size of about 20 ⁇ m and a height of less than 1 ⁇ m as viewed from the normal direction is formed.
  • a structure reflecting the inverted antiglare structure of the surface of the inorganic material layer 16 is formed on the surface of the aluminum film 18.
  • the two-dimensional size of the convex portions constituting the antiglare structure included in the antireflection film of Comparative Example 11 was approximately 30 ⁇ m.
  • the electrodeposition method for example, a known electrodeposition coating method can be used. For example, first, the substrate 12 is washed. Next, the base material 12 is immersed in an electrodeposition tank in which an electrodeposition liquid containing an electrodeposition resin is stored. Electrodes are installed in the electrodeposition tank. When the curable resin layer is formed by cationic electrodeposition, the substrate 12 is used as a cathode, the electrode installed in the electrodeposition tank is used as an anode, and a current is passed between the substrate 12 and the anode. A curable resin layer is formed by precipitating an electrodeposition resin on the outer peripheral surface.
  • the curable resin layer is formed by anion electrodeposition
  • the curable resin layer is formed by passing an electric current using the base material 12 as an anode and the electrode installed in the electrodeposition tank as a cathode. Then, an organic insulating layer is formed by performing a cleaning process, a baking process, and the like.
  • the electrodeposition resin for example, a polyimide resin, an epoxy resin, an acrylic resin, a melamine resin, a urethane resin, or a mixture thereof can be used.
  • the antireflection film of Comparative Example 12 was formed using a moth-eye mold manufactured as follows. In the manufacturing process of the mold for forming the antireflection film of Comparative Example 12, the surface of the aluminum substrate 12 subjected to mirror finishing was treated with hydrogen fluoride and ammonium as described in International Publication No. 2015/159797. The anti-glare structure inverted on the surface of the aluminum substrate 12 was formed by performing a satin treatment with an aqueous solution containing a salt of For reference, the entire disclosure of WO2015 / 1599797 is incorporated herein by reference.
  • the aluminum substrate 12 an Al—Mg—Si-based aluminum alloy, particularly one formed of JIS A6063 was used as the aluminum substrate 12.
  • alkaline cleaning step The step of etching the surface of the aluminum base 12 using an alkaline etching solution (hereinafter sometimes referred to as “alkaline cleaning step”) was performed before the step of treating the surface of the aluminum base 12 with a matte finish.
  • alkali cleaning step at least a part of the work-affected layer of the aluminum substrate 12 that may cause cutting marks can be removed.
  • the alkali cleaning step also serves as a degreasing step for the aluminum base 12.
  • an alkaline etchant As an alkaline etchant, an aqueous solution containing an organic alkaline detergent (product name: Semi-clean LC-2, manufactured by Yokohama Oil & Fat Co., Ltd.) at a concentration of 16 mass%, a corrosion inhibitor (Cilesbit AL, Kirest Co., Ltd.) as an acidic additive. Using an aqueous solution to which 10 vol% of a product made by company was added, an alkali washing step was performed at 40 ° C. for 40 minutes.
  • an organic alkaline detergent product name: Semi-clean LC-2, manufactured by Yokohama Oil & Fat Co., Ltd.
  • a corrosion inhibitor Cilesbit AL, Kirest Co., Ltd.
  • a cleaning step with pure water After the alkali cleaning step, a cleaning step with pure water, a pretreatment step, a satin treatment step, a post-treatment step, and a cleaning step with pure water were performed in this order.
  • an aqueous solution containing 2.5 mass%, 1 mass%, and 1 mass% of ammonium fluoride, ammonium sulfate, and ammonium dihydrogen phosphate, respectively, is used as an etching solution for the satin treatment.
  • the satin treatment was performed for a minute.
  • the satin treatment process was performed while rotating around the long axis of the aluminum base 12 (rotation speed: 5 rpm), and the etchant for the satin treatment was circulated in the etching tank.
  • the etching solution is diluted 2.5 times (that is, ammonium fluoride, ammonium sulfate, and ammonium dihydrogen phosphate are 1 mass%, 0.4 mass%, and 0.2%, respectively).
  • the surface treatment of the aluminum substrate 12 was performed at room temperature for 3 minutes using an aqueous solution containing 4 mass%.
  • the pretreatment step and the posttreatment step were performed while rotating around the long axis of the aluminum base 12 (rotation speed: 5 rpm). At this time, the pretreatment etchant and the posttreatment etchant were not circulated in the etching bath.
  • a bar-type shower unit was used in combination.
  • the washing process with pure water was performed using a hand shower.
  • a two-fluid nozzle was used in combination.
  • the two-dimensional size of the convex portions constituting the antiglare structure included in the antireflection film of Comparative Example 12 was approximately 10 ⁇ m.
  • the antireflection film of Comparative Example 13 was formed using a moth-eye mold manufactured as follows.
  • the inverted antiglare structure was formed on the surface of the aluminum film 18 by setting the thickness of the aluminum film 18 to 1.0 ⁇ m.
  • Patent Document 4 by forming an aluminum film 18 having a thickness of 0.5 ⁇ m or more and 5 ⁇ m or less, a plurality of convex portions having an average two-dimensional size of 200 nm or more and 5 ⁇ m or less can be obtained.
  • a moth-eye mold having an inverted anti-glare structure can be produced.
  • the antireflection film of Example 2 exhibited antiglare properties while maintaining clearness, and was suppressed from appearing cloudy when viewed from an oblique viewing angle.
  • an anti-glare structure is formed on the surface of the aluminum substrate 12 by spraying a projection material on the surface of the aluminum substrate 12 and then the surface of the aluminum substrate 12 is electropolished, when viewed from an oblique viewing angle. Can be further suppressed from appearing cloudy.
  • the anti-glare structure inverted on the surface of the aluminum substrate 12 becomes gentle, thereby effectively suppressing the appearance of cloudiness when viewed from an oblique viewing angle. It is considered possible.
  • the antireflection film of Example 2 can reduce the manufacturing cost by using the moth-eye mold manufactured by the method as described above. That is, when a mold is manufactured by a method in which an antiglare film having an antiglare function is provided on the substrate 12 and the aluminum film 18 is formed on the antiglare film, the manufacturing cost tends to increase. In the mold manufacturing method according to the embodiment of the present invention, since the projection material is sprayed on the surface of the base material 12 and the aluminum film 18 is deposited on the base material 12, the manufacturing cost can be reduced.
  • the antireflection film of Comparative Example 11 appears cloudy when viewed from an oblique viewing angle. Furthermore, the antireflection film of Comparative Example 11 cannot sufficiently suppress the occurrence of glare.
  • the antireflection film of Comparative Example 12 appears cloudy when viewed from an oblique viewing angle.
  • the antireflection film of Comparative Example 13 is not sufficiently blurred in the reflected image. That is, the antiglare property is not sufficient.
  • the antireflection film of Comparative Example 6 appears cloudy when viewed from an oblique viewing angle. Furthermore, the antireflection film of Comparative Example 6 cannot sufficiently suppress the occurrence of glare. Moreover, the antireflection film of Comparative Example 6 is inferior to the antireflection film of Example 2 in terms of the bright spot contrast ratio when viewed from the front direction.
  • the occurrence of glare depends on the size relationship between the concavo-convex structure constituting the antiglare structure and the dot pitch Px in the row direction.
  • FIGS. 12A and 12B are diagrams schematically showing the relationship between the size of the concavo-convex structure constituting the antiglare structure and the dot pitch Px in the row direction
  • FIG. 12A shows the antiglare structure
  • FIG. 12B shows a case where the concavo-convex structure constituting the anti-glare structure is smaller than the dot pitch Px.
  • the dots refer to R, G, and B dots that constitute pixels in a typical color liquid crystal display panel. That is, when the pixel in the color liquid crystal display panel is composed of three dots (R dot, G dot, and B dot) arranged in the row direction, the pixel pitch in the row direction is equal to the dot pitch Px in the row direction. Tripled. Note that the pixel pitch in the column direction is equal to the dot pitch Py in the column direction.
  • the surface 28s having the concavo-convex structure constituting the antiglare structure may have a continuous corrugated surface shape having no flat portion.
  • a concavo-convex structure having a continuous corrugated surface shape is characterized by the average value of the distance between adjacent recesses (average inter-adjacent distance AD int ) or the two-dimensional size AD p of the recesses.
  • AD int average inter-adjacent distance
  • AD p two-dimensional size
  • the average distance AD int between the concave portions AD int (considered to be equal to the two-dimensional size AD p of the concave portion) is, for example, a dot pitch Px in the row direction (the pixel has three dots ( In the case of R, G, B), if the pixel pitch in the row direction is larger than 3 times the dot pitch), a sufficient anti-glare function cannot be obtained.
  • the average adjacent distance AD int (two-dimensional size AD p ) of the recesses is substantially equal to each other, and the dot pitch Is preferably smaller.
  • Example 5 the antireflection films of Example 2, Comparative Example 5 and Comparative Example 11 are attached to the surface on the viewer side of the four types of display panels having different dot pitches, and whether or not the display surface glare occurs.
  • the result of visual evaluation was shown.
  • “ ⁇ ” indicates that there is glare regardless of whether the entire green display or the entire white display is performed, and “ ⁇ ” indicates that the glare is not noticeable in the entire white display, but the entire green display is displayed. When it is done, it indicates that there is glare. “ ⁇ ” indicates that there is no glare in the entire white display, but when the entire green display is performed, it indicates that there is a slight glare, and “ ⁇ ” indicates no glare. Indicates that there is no.
  • “Glitter” in Table 4 indicates that the display in Table 5 has a diagonal of 9.7 inches, the dot pitch in the row direction (Px in FIG. 12) is about 32 ⁇ m, and the dot pitch in the column direction (equal to the pixel pitch). ) Shows the results of evaluation using about 96 ⁇ m and about 264 ppi. Although not described in Table 5, Comparative Example 6 was similarly evaluated.
  • 2-dimensional size AD p of the first projecting portion having antireflection film constituting the antiglare structure having on the surface of Example 2 is 5 ⁇ m or less. In order to suppress the occurrence of glare, it is preferable that the two-dimensional size AD p of the first protrusion is sufficiently smaller than the dot pitch in the row direction.
  • the two-dimensional size of the convex portions constituting the antiglare structure of the antireflection film of Comparative Example 11 is about 30 ⁇ m. Since the two-dimensional size of the convex portion constituting the antiglare structure of the antireflection film of Comparative Example 11 is larger than the two-dimensional size of the convex portion constituting the antiglare structure of the antireflection film of Example 2, In suppressing the occurrence of glare, the antireflection film of Comparative Example 11 is inferior to the antireflection film of Example 2.
  • the antireflection film of Comparative Example 5 is an internal haze type, it does not have an antiglare structure on the surface.
  • the antireflection film of Example 2 is superior to the antireflection film of Comparative Example 5 in suppressing the occurrence of glare.
  • FIG. 13 is a graph showing the measurement results of the light distribution of diffuse reflection by the antireflection films of Example 3, Reference Example 2, Comparative Example 3, Comparative Example 5, Comparative Example 12, Comparative Example 12 and Comparative Example 13.
  • FIG. 13 also shows the relative diffuse reflectance (%) normalized by setting the incident angle to 5 °, the light receiving angle to the horizontal axis, and the maximum value of diffuse reflected light intensity to 80%.
  • the light distribution curve is shown with the common logarithm on the vertical axis.
  • the antireflection film of Example 3 and Reference Example 2 is an external haze type antireflection film having the same structure as the antireflection film 50 shown in FIG.
  • the antireflection films of Example 3 and Reference Example 2 were manufactured by the method described above.
  • Table 6 shows the conditions of the spraying process in the process of manufacturing the moth-eye mold for forming the antireflection film of Example 3 and Reference Example 2.
  • the light distribution distribution curve of the antireflection film of Example 3 takes a peak value at a light receiving angle of 5 °, the peak width is relatively narrow, a range of a light receiving angle of 2 ° to 3 °, and a range of a light receiving angle of 7 ° to 8 °.
  • the inclination is gradually inflected and falls within a range up to a light receiving angle of 20 °.
  • the antireflection film of Example 3 exhibits antiglare properties while maintaining clearness, and is suppressed from appearing cloudy when viewed from an oblique viewing angle.
  • the light distribution curve of the antireflection film of Reference Example 2 does not fall within the range up to a light receiving angle of 25 °.
  • the antireflection film of Reference Example 2 tends to appear cloudy when viewed from an oblique viewing angle.
  • the antireflection film according to the embodiment of the present invention has a relative diffuse reflectance (%) of 3% or more and a light reception angle of 8 ° or more and 10 ° or less, for example, in the range of the light reception angle of 5 ° or more and 7 ° or less. And a point where the relative diffuse reflectance (%) is in the range of 2% to 8%, the light receiving angle is 10 ° to 15 °, and the relative diffuse reflectance (%) is 0.9. % And 1.1% or less is included.
  • the peak width is relatively narrow, and the light distribution distribution curve It is preferable not to have a point where the slope changes discontinuously. In addition, outside the peak, it is preferable to attenuate faster as the distance from the peak center (5 °) increases.
  • Table 6 shows the conditions of the spraying process step of the experimental example in the specification (conditions for spraying the projection material and the type of the projection material) and the type of target aluminum subjected to the spraying process. Specifically, the type of aluminum forming the aluminum substrate 12, the type of projection material, the average particle size of the projection material, the pressure at which the projection material is discharged from the nozzle 82, and between the nozzle 82 and the surface of the mold substrate 10 And a speed v v for moving the nozzle 82 along the long axis direction of the mold substrate 10.
  • Embodiments of the present invention include, for example, an antireflective film for high-definition display panels, a method of manufacturing such an antireflective film, a mold for forming such an antireflective film, and the efficiency of such a mold. It is preferably used in a method that can be manufactured well.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
PCT/JP2018/003480 2017-02-03 2018-02-01 反射防止膜、反射防止膜の製造方法、型および型の製造方法 Ceased WO2018143370A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880009997.3A CN110268102B (zh) 2017-02-03 2018-02-01 防反射膜、防反射膜的制造方法、模具及模具的制造方法
US16/483,100 US20200241172A1 (en) 2017-02-03 2018-02-01 Antireflective film, method for manufacturing antireflective film, mold, and method for manufacturing mold

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-018555 2017-02-03
JP2017018555A JP6854660B2 (ja) 2017-02-03 2017-02-03 反射防止膜の製造方法および型の製造方法

Publications (1)

Publication Number Publication Date
WO2018143370A1 true WO2018143370A1 (ja) 2018-08-09

Family

ID=63039823

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/003480 Ceased WO2018143370A1 (ja) 2017-02-03 2018-02-01 反射防止膜、反射防止膜の製造方法、型および型の製造方法

Country Status (4)

Country Link
US (1) US20200241172A1 (enExample)
JP (1) JP6854660B2 (enExample)
CN (1) CN110268102B (enExample)
WO (1) WO2018143370A1 (enExample)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3628758A1 (en) * 2018-09-27 2020-04-01 Apple Inc. Textured surface for titanium parts
JP7663838B2 (ja) * 2019-07-31 2025-04-17 ソニーグループ株式会社 医療用観察システム及び表示装置
US12085734B1 (en) * 2020-04-20 2024-09-10 Apple Inc. Electronic devices with low-reflectance coatings
CN112589686A (zh) * 2021-01-05 2021-04-02 贵阳方盛汽车饰件有限公司 一种关于汽车行业皮纹塑料件去除亮斑方法
CN113802163B (zh) * 2021-08-18 2023-02-17 陕西师范大学 一种氧化铝微米阶梯与纳米孔复合结构的制备方法
TWI821864B (zh) 2021-12-29 2023-11-11 大立光電股份有限公司 成像鏡頭、遮光片及電子裝置
TWI850085B (zh) * 2022-01-28 2024-07-21 大立光電股份有限公司 成像鏡頭及電子裝置
JP7800286B2 (ja) * 2022-04-28 2026-01-16 株式会社Ｊｖｃケンウッド モニターケース
CN114890658B (zh) * 2022-06-06 2024-02-27 浙江晶泰玻璃科技有限公司 一种防眩光玻璃及其制备工艺
US20250329302A1 (en) * 2024-04-19 2025-10-23 Innolux Corporation Display device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013142802A (ja) * 2012-01-11 2013-07-22 Dainippon Printing Co Ltd 反射防止フィルム、反射防止フィルムの作製に用いられる型、および、型の製造方法
WO2016084745A1 (ja) * 2014-11-25 2016-06-02 シャープ株式会社 型および型の製造方法ならびに反射防止膜

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5194486B2 (ja) * 2007-02-28 2013-05-08 住友化学株式会社 液晶表示装置
US9416461B2 (en) * 2009-10-14 2016-08-16 Sharp Kabushiki Kaisha Die and method for manufacturing die, and anti-reflection coating
WO2011052652A1 (ja) * 2009-10-28 2011-05-05 シャープ株式会社 型および型の製造方法ならびに反射防止膜
WO2011055757A1 (ja) * 2009-11-06 2011-05-12 シャープ株式会社 型の製造方法および型
CN107002272B (zh) * 2014-11-21 2021-10-26 夏普株式会社 模具、模具的制造方法、防反射膜及防反射膜的制造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013142802A (ja) * 2012-01-11 2013-07-22 Dainippon Printing Co Ltd 反射防止フィルム、反射防止フィルムの作製に用いられる型、および、型の製造方法
WO2016084745A1 (ja) * 2014-11-25 2016-06-02 シャープ株式会社 型および型の製造方法ならびに反射防止膜

Also Published As

Publication number Publication date
CN110268102A (zh) 2019-09-20
US20200241172A1 (en) 2020-07-30
JP6854660B2 (ja) 2021-04-07
CN110268102B (zh) 2021-10-08
JP2018123403A (ja) 2018-08-09

Similar Documents

Publication Publication Date Title
JP6854660B2 (ja) 反射防止膜の製造方法および型の製造方法
CN101004456B (zh) 防眩膜及其制造方法、制造用于其的金属模具的方法及显示装置
JP5163943B2 (ja) 防眩フィルム、防眩性偏光板および画像表示装置
CN101484829B (zh) 防眩膜及图像显示装置
JP5135871B2 (ja) 防眩フィルム、防眩性偏光板及び画像表示装置
US9366785B2 (en) Mold, method for manufacturing a mold, and antireflective film
JP5615971B2 (ja) 型の製造方法
JP6322294B2 (ja) 型の製造方法および反射防止膜の製造方法
WO2011125486A1 (ja) 型および型の製造方法ならびに反射防止膜の製造方法
JP2007237541A (ja) 表面に微細な凹凸形状を有する金型、その金型の製造方法及びその金型を用いた防眩フィルムの製造方法
JP2010118396A (ja) 光学フィルタ及びその製造方法
JP6309081B2 (ja) 型の製造方法および反射防止膜の製造方法
WO2014021039A1 (ja) 型の製造方法
JP6626898B2 (ja) 基材の表面処理方法および型の製造方法
TW202012158A (zh) 覆蓋膜和圖像顯示裝置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18747841

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18747841

Country of ref document: EP

Kind code of ref document: A1