WO2014021039A1 - Procédé permettant de produire un moule - Google Patents

Procédé permettant de produire un moule Download PDF

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Publication number
WO2014021039A1
WO2014021039A1 PCT/JP2013/067981 JP2013067981W WO2014021039A1 WO 2014021039 A1 WO2014021039 A1 WO 2014021039A1 JP 2013067981 W JP2013067981 W JP 2013067981W WO 2014021039 A1 WO2014021039 A1 WO 2014021039A1
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WO
WIPO (PCT)
Prior art keywords
layer
mold
electrodeposition
aluminum alloy
moth
Prior art date
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PCT/JP2013/067981
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English (en)
Japanese (ja)
Inventor
彰信 石動
箕浦　潔
藤井　暁義
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シャープ株式会社
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Application filed by シャープ株式会社 filed Critical シャープ株式会社
Priority to CN201380040620.1A priority Critical patent/CN104507655B/zh
Priority to JP2014528049A priority patent/JP5833763B2/ja
Publication of WO2014021039A1 publication Critical patent/WO2014021039A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—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
    • C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts

Definitions

  • the present invention relates to a mold manufacturing method, and more particularly to a mold having a porous alumina layer on the surface.
  • 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. Note that the two-dimensional size corresponds to the diameter when the shape of the convex portion when observed from a direction perpendicular to the surface on which the concave / convex pattern is formed approximates a circle.
  • 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, to the refractive index of the substrate.
  • the reflection in the wavelength region that is desired to be prevented from being reflected is suppressed by continuously changing the wavelength.
  • the moth-eye structure has an advantage that it can exhibit an antireflection effect with a small incident angle dependency over a wide wavelength range, can be applied to many materials, and can form an uneven pattern directly on a substrate. As a result, a low-cost and high-performance antireflection film (or antireflection surface) can be provided.
  • Patent Documents 2 to 4 As a method for producing a moth-eye structure, a method using an anodized porous alumina layer obtained by anodizing aluminum is attracting attention (Patent Documents 2 to 4).
  • anodized porous alumina layer obtained by anodizing aluminum will be briefly described.
  • a method for producing a porous structure using anodization has attracted attention as a simple method capable of forming regularly ordered nano-sized cylindrical pores (fine concave portions).
  • an acidic or alkaline electrolyte such as sulfuric acid, oxalic acid, or phosphoric acid
  • a voltage is applied using the aluminum substrate as an anode
  • oxidation and dissolution proceed simultaneously on the surface of the aluminum substrate.
  • An oxide film having pores can be formed. These cylindrical pores are oriented perpendicular to the oxide film and exhibit self-organized regularity under certain conditions (voltage, type of electrolyte, temperature, etc.). Is expected.
  • the porous alumina layer formed under specific conditions takes an array in which almost regular hexagonal cells are two-dimensionally filled with the highest density when viewed from the direction perpendicular to the film surface.
  • Each cell has a pore in the center, and the arrangement of the pores has periodicity.
  • the cell is formed as a result of local dissolution and growth of the film, and dissolution and growth of the film proceed simultaneously at the bottom of the pores called a barrier layer.
  • the distance between adjacent pores corresponds to approximately twice the thickness of the barrier layer and is approximately proportional to the voltage during anodization.
  • the diameter of the pores depends on the type, concentration, temperature, etc.
  • the pores of such porous alumina have an arrangement with high regularity (having periodicity) under a specific condition, an arrangement with irregularity to some extent or an irregularity (having no periodicity) depending on the conditions. ).
  • Patent Document 2 discloses a method of forming an antireflection film (antireflection surface) using a stamper having an anodized porous alumina film on the surface.
  • Patent Document 3 discloses a technique for forming a tapered concave portion in which the pore diameter continuously changes by repeating anodization of aluminum and pore diameter enlargement processing.
  • Patent Document 4 a technique for forming an antireflection film using an alumina layer in which fine concave portions have stepped side surfaces.
  • an antireflection film (antireflection surface) is provided by providing a concavo-convex structure (macro structure) larger than the moth eye structure in addition to the moth eye structure (micro structure). ) Can be given an anti-glare (anti-glare) function.
  • the two-dimensional size of the convex portion constituting the concave and convex that exhibits the antiglare function is 1 ⁇ m or more and less than 100 ⁇ m.
  • a mold for forming a moth-eye structure on the surface (hereinafter referred to as “moth-eye mold”) can be easily manufactured.
  • the surface of an anodized aluminum film is used as it is as a mold, the effect of reducing the manufacturing cost is great.
  • the surface structure of the moth-eye mold that can form the moth-eye structure is referred to as an “inverted moth-eye structure”.
  • a method using a photocurable resin is known. First, a photocurable resin is applied on the substrate. Subsequently, the uneven surface of the surface of the moth-eye mold is filled with the photocurable resin by pressing the uneven surface of the moth-eye mold subjected to the release treatment against the photocurable resin in a vacuum. Subsequently, the photocurable resin in the concavo-convex structure is irradiated with ultraviolet rays to cure the photocurable resin.
  • the moth-eye mold described above is formed on an aluminum substrate represented by a substrate formed of aluminum or a cylinder formed of aluminum, or a support formed of a material other than aluminum typified by a glass substrate. It can be manufactured using an aluminum film. However, when a moth-eye mold is manufactured using an aluminum film formed on a glass substrate or plastic film, the aluminum film (partially an anodized film) is bonded to the glass substrate or plastic film. May decrease.
  • the applicant of the present invention forms the inorganic underlayer (for example, SiO 2 layer) and the buffer layer (for example, AlO x layer) containing aluminum on the surface of the substrate formed of glass or plastic. It discovered that the fall of adhesiveness was suppressed and it is disclosing in patent document 5.
  • the present applicant has developed a method for efficiently producing an antireflection film by a roll-to-roll method using a cylindrical (roll-shaped) moth-eye mold.
  • a cylindrical moth-eye mold is formed, for example, by forming an organic insulating layer on the outer peripheral surface of a metal cylinder and alternately repeating anodization and etching on the aluminum film formed on the organic insulating layer. Is done.
  • the adhesiveness can be improved by forming the inorganic underlayer and the buffer layer disclosed in Patent Document 5.
  • Patent Documents 1, 2, 4, 5 and 7 All the disclosures of Patent Documents 1, 2, 4, 5 and 7 are incorporated herein by reference.
  • the present inventor examined the anion electrodeposition method as a method for forming an organic insulating layer on the outer peripheral surface of a metal cylinder. As shown in an optical microscope image in FIG. 12, foreign matter may be generated. It was. FIG. 12 shows a field of view of 482 ⁇ m ⁇ 688 ⁇ m, and the linear foreign matter extends to about 370 ⁇ m ⁇ about 250 ⁇ m. This foreign matter is not particularly problematic in general anion electrodeposition coating, but becomes a problem when forming a moth-eye mold having irregularities of the above-mentioned submicron order.
  • the moth-eye mold is formed by alternately repeating anodization and etching on the aluminum film formed on the organic insulating layer on which the above-mentioned foreign substance exists, the shape of the foreign substance is reflected on the surface of the moth-eye mold. Will be. As a result, a defect (abnormal shape) due to a foreign substance is formed on the antireflection surface formed using such a moth-eye mold, and the antireflection function may be locally degraded.
  • the present invention has been made to solve the above-mentioned problems, and its main object is to form an organic insulating layer on the surface of a metal substrate for forming a moth-eye mold by an anionic electrodeposition method. It is another object of the present invention to provide a method for manufacturing a moth-eye mold that suppresses the generation of foreign matter and thereby has few defects in the moth-eye structure having an inverted surface.
  • a mold manufacturing method includes a mold having an inverted moth-eye structure on the surface having a plurality of recesses having a two-dimensional size of 10 nm or more and less than 500 nm when viewed from the normal direction of the surface.
  • a step (a1) of preparing a metal substrate having a surface that diffusely reflects visible light, and a step of forming an organic insulating layer on the surface of the metal substrate by anion electrodeposition a step (a) of preparing a mold substrate, including a2) and a step (a3) of forming an aluminum alloy layer on the organic insulating layer, and partially anodizing the aluminum alloy layer (B) forming a porous alumina layer having a plurality of fine recesses, and contacting the porous alumina layer with an etching solution after the step (b).
  • the surface of the metal substrate has a diffuse reflectance of 10% to 45% for light having a wavelength of 550 nm incident on the surface at an incident angle of 8 °.
  • the voltage in the step (a2) is not less than 60V and not more than 120V.
  • the energization time in the step (a2) is 200 seconds or less.
  • the step (a2) is performed using a matte anion paint.
  • the step (a) further includes a step (a4) of forming an inorganic underlayer on the organic insulating layer after the step (a2) and before the step (a3).
  • the inorganic underlayer is, for example, a silicon oxide layer, a tantalum oxide layer, or a titanium oxide layer.
  • the thickness of the inorganic underlayer is, for example, not less than 50 nm and not more than 500 nm.
  • the step (a) includes a buffer layer containing aluminum and oxygen or nitrogen on the inorganic underlayer after the step (a4) and before the step (a3).
  • the step (a5) of forming is further included.
  • the buffer layer has a thickness of not less than 10 nm and not more than 500 nm, for example.
  • the aluminum content in the buffer layer has a higher profile on the aluminum alloy layer side than on the inorganic underlayer side.
  • the metal substrate is cylindrical, and the surface of the metal substrate is an outer peripheral surface of a cylinder of the metal substrate.
  • the metal substrate is a metal sleeve.
  • the metal sleeve is a nickel sleeve, a stainless steel sleeve, an aluminum sleeve or a copper sleeve.
  • the step (b) and the step (c) are further performed after the step (d).
  • the size and shape of the fine recesses can be adjusted by the number of times that the anodic oxidation and etching are repeated alternately. In addition, it is preferable to end by anodizing.
  • an embodiment of the present invention it is possible to suppress the generation of foreign matters when forming an organic insulating layer by an anionic electrodeposition method on the surface of a metal substrate for forming a moth-eye mold.
  • a method for manufacturing a moth-eye mold with few defects in the moth-eye structure formed is provided.
  • (A) is a schematic diagram which shows the mold base material 10 used for manufacture of the type
  • (b) is a schematic diagram which shows the mold 100 for moth eyes manufactured using the mold base material 10 It is.
  • (A)-(e) is a figure which shows the process of the manufacturing method of the roll type
  • (A)-(e) is a figure which shows the process of the manufacturing method of the type
  • (A) is a schematic diagram which shows the apparatus used for anion electrodeposition
  • (b) is a figure which shows the reaction in an electrode. It is a figure for demonstrating the relationship between the magnitude
  • (a) is the relationship between electrodeposition time (energization time) and film thickness.
  • (B) is a graph which shows the spectral diffuse reflectance of the electrodeposition film
  • the mold of the present embodiment is a moth-eye mold, and has an inverted moth-eye structure on the surface having a plurality of recesses having a two-dimensional size of 10 nm or more and less than 500 nm when viewed from the normal direction of the surface. .
  • a mold manufacturing method includes a metal base 72m, an organic insulating layer 13 formed on the metal base 72m, and an organic insulating layer 13 as shown in FIG. Including a step of preparing a mold base 10 having the aluminum alloy layer 18 formed.
  • the metal substrate 72m and the organic insulating layer 13 may be collectively referred to as the support 12.
  • the metal base material 72m has a surface that diffuses and reflects visible light, and an organic insulating layer 13 is formed on the surface by an anionic electrodeposition method, as will be described later in detail with an experimental example. Yes. As a result, the generation of linear foreign matters (see FIG. 12) on the surface of the organic insulating layer 13 is suppressed.
  • the thickness of the organic insulating layer 13 is, for example, 4 ⁇ m or more and 10 ⁇ m or less. If the thickness of the organic insulating layer 13 is less than 4 ⁇ m, sufficient insulation may not be obtained, and if it exceeds 10 ⁇ m, the productivity is lowered.
  • the aluminum alloy layer 18 is a layer containing aluminum as a main component, and includes a layer containing a metal element M other than aluminum and / or other non-metal elements.
  • the aluminum alloy layer 18 only needs to have a property as a valve metal layer (typically anodizing property), and is a layer made of pure aluminum (for example, a purity of 99.99 mass% or more). including.
  • the aluminum alloy layer 18 is formed by a known method (for example, an electron beam evaporation method or a sputtering method).
  • the thickness of the aluminum alloy layer 18 is preferably 100 nm or more, and preferably 3000 nm or less from the viewpoint of productivity, in order to obtain an anodized alumina layer having a surface structure serving as a moth-eye mold. Typically, it is about 1000 nm (1 ⁇ m).
  • the aluminum alloy layer 18 having a thickness of about 1 ⁇ m is deposited in a plurality of times rather than in a single deposition. That is, rather than continuously depositing to a desired thickness (for example, 1 ⁇ m), the process of interrupting the deposition to a certain thickness and restarting the deposition after a certain time has elapsed is repeated. It is preferable to obtain the aluminum alloy layer 18. For example, it is preferable to interrupt each time an aluminum alloy layer having a thickness of 50 nm is deposited and to obtain an aluminum alloy layer 18 having a thickness of about 1 ⁇ m by 20 aluminum alloy layers each having a thickness of 50 nm.
  • the quality (for example, chemical resistance and adhesiveness) of the finally obtained aluminum alloy layer 18 can be improved by dividing the deposition of the aluminum alloy into a plurality of times.
  • the continuous deposition of the aluminum alloy increases the temperature of the substrate (which has the surface on which the aluminum alloy layer is deposited), resulting in a distribution of thermal stress in the aluminum alloy layer 18 and the film This is considered to reduce the quality.
  • an inorganic underlayer 14 between the organic insulating layer 13 and the aluminum alloy layer 18 as in the mold base 10 shown in FIG.
  • the inorganic underlayer 14 is directly formed on the surface of the organic insulating layer 13 and functions to improve the adhesion between the organic insulating layer 13 and the aluminum alloy layer 18.
  • the inorganic underlayer 14 is preferably formed of an inorganic oxide or an inorganic nitride.
  • an inorganic oxide for example, a silicon oxide layer, a tantalum oxide layer, or a titanium oxide layer is preferable
  • an inorganic nitride for example, a silicon nitride layer is preferable.
  • the thermal expansion coefficient may be adjusted by adding impurities to the inorganic oxide layer or the inorganic nitride layer.
  • the thermal expansion coefficient can be increased by adding germanium (Ge), phosphorus (P), or boron (B).
  • the thickness of the inorganic underlayer 14 is preferably 40 nm or more, and more preferably 100 nm or more. If the thickness of the inorganic underlayer 14 is less than 40 nm, the effect of providing the inorganic underlayer 14 may not be sufficiently exhibited.
  • the thickness of the inorganic underlayer 14 is preferably 500 nm or less, and more preferably 200 nm or less. If the thickness of the inorganic underlayer 14 exceeds 500 nm, the formation time of the inorganic underlayer 14 becomes unnecessarily long. Also, the thicker the inorganic underlayer 14 formed on a curved surface or a flexible surface, the easier it is to crack.
  • the mold substrate 10 preferably further includes a buffer layer 16 between the inorganic base layer 14 and the aluminum alloy layer 18.
  • the buffer layer 16 acts to improve the adhesion between the inorganic underlayer 14 and the aluminum alloy layer 18.
  • a conductive layer preferably a valve metal layer
  • a conductive layer may be provided between the two.
  • the buffer layer 16 preferably contains aluminum (and metal element M) and oxygen or nitrogen. Although the oxygen or nitrogen content may be constant, it is particularly preferable that the aluminum (and metal element M) content has a higher profile on the aluminum alloy layer 18 side than on the inorganic underlayer 14 side. It is because it is excellent in matching of physical property values such as thermal expansion coefficient.
  • the thickness of the buffer layer 16 is preferably 10 nm or more, and more preferably 20 nm or more. Further, the thickness of the buffer layer 16 is preferably 500 nm or less, and more preferably 200 nm or less. If the thickness of the buffer layer 16 is less than 10 nm, sufficient adhesion may not be obtained between the inorganic underlayer 14 and the aluminum alloy layer 18. Further, if the thickness of the buffer layer 16 exceeds 500 nm, the formation time of the buffer layer 16 becomes unnecessarily long, which is not preferable.
  • the profile in the thickness direction of the aluminum content in the buffer layer 16 may change stepwise or may change continuously.
  • the buffer layer 16 is formed of aluminum, the metal element M, and oxygen, a plurality of aluminum oxide alloy layers whose oxygen content gradually decreases are formed, and the aluminum alloy layer 18 is formed on the uppermost layer.
  • the oxygen content of the buffer layer 16 is preferably 60 at% or less at the highest. The same applies to the case where the buffer layer 16 containing nitrogen instead of oxygen is formed.
  • a porous alumina layer 20 having a plurality of fine recesses 22 is formed by partially anodizing the aluminum alloy layer 18 using the mold base 10 shown in FIG.
  • the moth-eye mold 100 shown in FIG. 1 (b) can be obtained by performing the step of growing the minute recesses 22 of FIG.
  • the moth-eye mold 100 is suitably used for manufacturing an antireflection film (antireflection surface).
  • the shape of the fine recesses (pores) 22 of the porous alumina layer 20 used for manufacturing the antireflection film is generally conical.
  • the fine recess 22 may have a stepped side surface.
  • the two-dimensional size (opening diameter: D p ) of the fine recess 22 is preferably 10 nm or more and less than 500 nm, and the depth (D depth ) is preferably about 10 nm or more and less than 1000 nm (1 ⁇ m).
  • D p opening diameter
  • D depth is preferably about 10 nm or more and less than 1000 nm (1 ⁇ m).
  • the bottom part of the fine recessed part 22 is pointed (the bottom part is a point).
  • the fine concave portions 22 are closely packed, and assuming that the shape of the fine concave portions 22 when viewed from the normal direction of the porous alumina layer 20 is a circle, adjacent circles overlap each other, It is preferable that a brim is formed between the adjacent fine recesses 22.
  • the substantially conical minute concave portions 22 are adjacent so as to form a collar portion, the two-dimensional size D p of the fine concave portions 22 is assumed to be equal to the average adjacent distance D int .
  • the inverted moth-eye structure on the surface of the moth-eye mold 100 has few defects.
  • defects abnormal shapes due to foreign matters are prevented from being formed in the moth-eye structure on the anti-reflection surface. It is possible to form an antireflective surface with no increase in haze.
  • the roll mold was produced by the method described in Patent Document 7.
  • a nickel metal sleeve also referred to as a nickel sleeve
  • the metal sleeve refers to a metal cylinder having a thickness of 0.02 mm to 1.0 mm.
  • the metal sleeve is not limited to a nickel sleeve, and a metal sleeve made of stainless steel, aluminum, or copper can be used. These metal sleeves can be obtained from, for example, Dimco Corporation.
  • a metal sleeve 72m is prepared.
  • the metal sleeve 72m has a surface (outer peripheral surface) that diffuses and reflects visible light.
  • the surface of the metal sleeve 72m preferably has a diffuse reflectance of 10% to 45% for light having a wavelength of 550 nm incident on the surface at an incident angle of 8 °.
  • the metal sleeve is generally formed by electrodeposition of metal. The surface roughness of the metal sleeve can be adjusted by controlling the electrodeposition conditions, for example, the growth rate of the metal film.
  • the organic insulating layer 13 is formed on the outer peripheral surface of the metal sleeve 72m by an anionic electrodeposition method (see FIG. 6).
  • an anionic electrodeposition method a known anion electrodeposition method can be used.
  • the metal sleeve 72m is washed.
  • the metal sleeve 72m is immersed in an electrodeposition tank in which an electrodeposition liquid containing an anion electrodeposition resin is stored. Electrodes are installed in the electrodeposition tank.
  • the insulating resin layer is formed by anion electrodeposition
  • the metal sleeve 72m is used as an anode
  • the electrode installed in the electrodeposition tank is used as a cathode
  • a current is passed between the metal sleeve 72m and the cathode
  • the metal sleeve 72m is used.
  • An insulating resin layer is formed by depositing an electrodeposition resin on the outer peripheral surface of the film.
  • the organic insulating layer 13 is formed by performing a washing
  • the electrodeposition resin for example, an acrylic resin or a mixture of an acrylic resin and a melamine resin can be used.
  • the organic insulating layer 13 has a high effect of flattening the surface, and can suppress the surface scratches of the metal sleeve 72m and the like from being reflected on the surface shape of the aluminum alloy layer 18. Conversely, by using a matte anionic paint, the organic insulating layer 13 having antiglare property can be formed on the surface.
  • a moth-eye mold is formed using the aluminum alloy layer 18 formed on the organic insulating layer 13 having antiglare property, a moth-eye mold capable of forming an antireflection surface having antiglare property can be obtained.
  • an inorganic underlayer 14 is formed on the organic insulating layer 13 as shown in FIG.
  • the SiO 2 layer 14 having a thickness of about 100 nm is formed.
  • the buffer layer 16 and the aluminum alloy layer 18 are formed continuously.
  • the buffer layer 16 is formed as necessary.
  • the same target is used to form the buffer layer 16 and the aluminum alloy layer 18.
  • the ratio of aluminum to the metal element M is constant in the buffer layer 16 and the aluminum alloy layer 18.
  • the buffer layer 16 has a thickness of, for example, about 100 nm, and the aluminum alloy layer 18 has a thickness of about 1 ⁇ m.
  • the formation from the inorganic underlayer 14 to the formation of the aluminum alloy layer 18 is preferably performed by a thin film deposition method (for example, sputtering), and is preferably performed in the same chamber.
  • the porous alumina layer 20 having a plurality of fine recesses is formed on the surface of the aluminum alloy layer 18 by alternately repeating anodic oxidation and etching.
  • the mold 100a is obtained.
  • FIG. 3 the mold base 10 is shown in which the aluminum alloy layer 18 is directly formed on the support 12.
  • the mold substrate 10 includes a metal substrate, an organic insulating layer 13 formed on the metal substrate, and an aluminum alloy layer 18 deposited on the organic insulating layer 13.
  • the porous alumina layer 20 includes a porous layer having fine concave portions 22 and a barrier layer.
  • the porous alumina layer 20 is formed, for example, by anodizing the surface 18s in an acidic electrolytic solution.
  • the electrolytic solution used in the step of forming the porous alumina layer 20 is, for example, an aqueous solution containing an acid selected from the group consisting of oxalic acid, tartaric acid, phosphoric acid, chromic acid, citric acid, and malic acid.
  • the pore spacing, the pore depth, the pore shape, and the like can be adjusted.
  • the thickness of the porous alumina layer can be changed as appropriate.
  • the aluminum alloy layer 18 may be completely anodized.
  • the porous alumina layer 20 is brought into contact with an alumina etchant to be etched by a predetermined amount, thereby enlarging the hole diameter of the fine recess 22.
  • an alumina etchant to be etched by a predetermined amount, thereby enlarging the hole diameter of the fine recess 22.
  • the amount of etching (that is, the size and depth of the fine recess 22) can be controlled by adjusting the type / concentration of the etching solution and the etching time.
  • the etching solution for example, an aqueous solution of 10% by mass of phosphoric acid, an organic acid such as formic acid, acetic acid or citric acid, or a mixed solution of chromium phosphoric acid can be used.
  • the aluminum alloy layer 18 is partially anodized again to grow the fine recesses 22 in the depth direction and to thicken the porous alumina layer 20.
  • the side surface of the fine recess 22 is stepped.
  • the porous alumina layer 20 is further etched by bringing the porous alumina layer 20 into contact with an alumina etchant to further expand the hole diameter of the fine recess 22.
  • an alumina etchant it is preferable to use the above-described etchant, and in practice, the same etch bath may be used.
  • a moth-eye mold 100A having a porous alumina layer 20 having a desired concavo-convex shape is obtained as shown in FIG.
  • the side surface of the fine recess 22 can be stepped, or can be a smooth curved surface or a slope.
  • the roll-shaped mold has an advantage that the surface structure of the mold can be continuously transferred to a work piece (having a surface on which an antireflection film is formed) by rotating the roll-shaped mold about an axis.
  • An antireflection film manufacturing method includes a step of preparing the mold, a step of preparing a workpiece, and applying a photocurable resin between the mold and the surface of the workpiece. In this state, it includes a step of curing the photocurable resin by irradiating the photocurable resin with light and a step of peeling the mold from the antireflection film formed of the cured photocurable resin.
  • an antireflection film can be produced by a roll-to-roll method.
  • the film preferably includes a base film and a hard coat layer formed on the base film, and the antireflection film is preferably formed on the hard coat layer.
  • the base film for example, a TAC (triacetyl cellulose) film can be suitably used.
  • the hard coat layer for example, an acrylic hard coat material can be used.
  • a mold 100A shown in FIG. 4 has a buffer layer 16 formed on the support 12.
  • FIG. 5 is a schematic cross-sectional view for explaining a method for producing an antireflection film by a roll-to-roll method.
  • the roll-shaped moth-eye mold 100A shown in FIG. 4 is prepared.
  • the ultraviolet curable resin 32 ′ is irradiated with ultraviolet rays (UV) in a state where the workpiece 42 having the ultraviolet curable resin 32 ′ applied to the surface thereof is pressed against the moth-eye mold 100 A.
  • the ultraviolet curable 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 62 and 64 as shown in FIG.
  • the support rollers 62 and 64 have a rotation mechanism and convey the workpiece 42. Further, the roll-shaped moth-eye mold 100A is rotated in a direction indicated by an arrow in FIG. 5 at a rotation speed corresponding to the conveyance speed of the workpiece 42.
  • a cured product layer 32 to which the uneven structure (inverted moth-eye structure) of the moth-eye mold 100A is transferred is formed on the surface of 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 metal sleeve is used as a metal base
  • a bulk metal base for example, a pipe
  • a nickel sleeve having a thickness of about 150 ⁇ m, a diameter of 300 mm, and a length of 1510 mm was used.
  • Nickel sleeves with different surface roughness were prepared.
  • Anion electrodeposition was performed using an apparatus schematically shown in FIG.
  • the electrodeposition tank (width 2220 mm, depth 860 mm, length 790 mm) was filled with about 1000 L of electrodeposition liquid, and the temperature of the electrodeposition liquid was adjusted to about 23 ° C.
  • the filter is provided to remove the gelled resin particles generated when the electrodeposition solution deteriorates. If necessary, the two cocks are opened and the electrodeposition solution is circulated through the filter. Let In this study, the two cocks are closed and the electrodeposition solution is not circulated.
  • the cleaned metal sleeve 72m is immersed in the electrodeposition liquid in the electrodeposition tank.
  • the electrodeposition solution contains an anion electrodeposition resin (solid content), pure water, butanol, isopropyl alcohol (IPA), a neutralizing agent (NH 4 + ), and butyl cellosolve (film-forming aid).
  • an anion electrodeposition resin a mixed system of acrylic resin and melamine resin (HEG Coat 2000 manufactured by Kansai Paint Co., Ltd.) was used.
  • This electrodeposition liquid is composed of 5.3 to 6.0% by mass of an acrylic resin as a main agent, 3.6 to 3.9% by mass of a melamine resin as a crosslinking agent, and 0.3% by mass of a neutralizing agent.
  • this electrodeposition liquid contains 0.1% by mass of additive aids for imparting properties, 5.0-7.5% by mass of solvent, and 82.2-85.7% by mass of deionized water.
  • gel particles (diameter is approximately 0.20 ⁇ m) in which an acrylic resin is crosslinked with a melamine resin are formed, and a matte resin layer is obtained.
  • a glossy resin layer can also be formed by reducing the compounding quantity of the acrylic resin and melamine resin in the said electrodeposition liquid.
  • the diameter of the gel particles formed at this time is approximately 0.15 ⁇ m or less.
  • known materials such as the anion electrodeposition paint described in JP-A-2003-49112 can be used.
  • a method of dispersing filler in the electrodeposition liquid is also known.
  • a direct current voltage is applied between the metal sleeve 72m and the cathode to pass a current.
  • the voltage is preferably 120 V or less in order to prevent so-called gas pins.
  • the energization time is preferably 200 seconds or less.
  • the anion electrodeposition resin having a negative charge moves to the anode, and the anode H + is received on the metal sleeve 72m, and the ionicity disappears and becomes insoluble, and precipitates on the metal sleeve 72m.
  • the deposited resin is fused by Joule heat to form the organic insulating layer 13.
  • the thickness of the organic insulating layer 13 is, for example, 4 ⁇ m or more and 10 ⁇ m or less. In the following experimental example, the organic insulating layer 13 having a thickness of about 6 ⁇ m was formed.
  • the film forming rate is increased.
  • the processing voltage is 40 V, it takes about 300 seconds to obtain a 6 ⁇ m film.
  • the processing voltage is 80 V, a 6 ⁇ m film can be obtained in about 100 seconds.
  • the surface shape of the electrodeposition film strongly depends on the film thickness of the electrodeposition film. Even if the processing voltage is different (even if the processing time is different), the surface shape is almost the same as long as the film thickness is the same. I found out.
  • FIG. 7B electrodeposition films having different thicknesses are formed, the respective surface shapes are transferred to the curable resin film, and the curable resin film having the transferred surface shape is fixed on the black acrylic plate.
  • the results of measuring the spectral diffuse reflectance are shown below.
  • the spectral diffuse reflectance was measured by the SCE method using CM2006 manufactured by Konica Minolta.
  • the incident angle of the light irradiating the sample is 8 °, and the intensity of the reflected light (that is, only the diffuse reflected light) is excluded from the total reflected light (including regular reflected light and diffuse reflected light).
  • the diffuse reflectance measured with an integrating sphere and obtained for each wavelength is shown in the graph of FIG.
  • the electrodeposition film formed using the above-mentioned electrodeposition resin has a larger diffuse reflectance as it becomes thicker.
  • the antiglare property desired for the antireflection film varies depending on the application.
  • FIG. 7B shows that the antiglare property can be adjusted by adjusting the thickness of the electrodeposition film.
  • the electrodeposition material exemplified here is used, an appropriate antiglare property can be obtained when the thickness of the electrodeposition film is in the range of 6 ⁇ m to 7 ⁇ m.
  • Table 1 below shows the results of forming an insulating resin layer on a commercially available nickel sleeve having a mirror surface (diameter 300 mm, length 1510 mm) by the above-described anion electrodeposition.
  • the treatment voltage during electrodeposition was 40 V and 80 V, and the thickness of the insulating resin layer was 6 ⁇ m.
  • Table 1 the surface of the obtained insulating resin layer was observed, and the number of foreign matters as shown in FIG. 12 was obtained. The number of foreign matters was determined for each of three levels of foreign matters of 1 mm or more, 500 ⁇ m or more and less than 1 mm, or 300 ⁇ m or more and 500 ⁇ m or less.
  • the size of the foreign matter was defined as an average (biaxial average) of lengths in two orthogonal directions of a region where the linear foreign matter spreads in the microscope image. However, one of the two orthogonal directions is a direction (short axis direction) in which the length of the region is minimized. According to this definition, the size of the foreign matter shown in FIG. 12 is 320 ⁇ m. As a result of infrared spectroscopic analysis, the foreign matter was confirmed to have the same composition as the electrodeposition film, and was found to be an abnormal precipitate of resin during electrodeposition.
  • the deposition rate depends on the deposition reaction rate (Ra) at which the anion electrodeposition resin receives H + and insolubilizes at the anode, and the rate (Re) at which the anion electrodeposition resin moves by electrophoresis near the anode.
  • the film formation rate when the processing voltage is 80 V is about three times the film formation rate when the processing voltage is 40 V, which is very large.
  • the moving speed (Re) is sufficiently larger than the deposition reaction speed (Ra) at the anode, and as shown in FIG. 8A, local fluctuations in the concentration of the electrodeposition resin are observed. Even after abnormal precipitation occurs, the anion electrodeposition resin (R—COO—) is uniformly supplied to the anode, so that electrodeposition proceeds and the abnormal precipitation shape is maintained.
  • the processing voltage is preferably higher than 40V, more preferably 80V or higher.
  • the number of occurrences of abnormal deposition when the processing voltage is 60 V is less than half of that when the processing voltage is 40 V, and the abnormal deposition is suppressed by setting the processing voltage to 60 V or more. can do.
  • the processing voltage is preferably 120 V or less.
  • FIG. 9 shows the measurement results of the spectral diffuse reflectance of five nickel sleeves.
  • the spectral diffuse reflectance was measured by the SCE method using CM2006 manufactured by Konica Minolta in the same manner as described above.
  • the incident angle of the light irradiating the sample is 8 °, and the intensity of the reflected light (that is, only the diffuse reflected light) is excluded from the total reflected light (including regular reflected light and diffuse reflected light).
  • the diffuse reflectance measured by an integrating sphere and obtained for each wavelength is shown in the graph of FIG.
  • Samples A, B and C in FIG. 9 are samples A, B and C having the mirror surfaces shown in Table 1.
  • Samples G and H in FIG. 9 are nickel sleeves having a rough surface and appear cloudy visually.
  • the diffuse reflectance of samples A to C having a mirror surface is as low as about 5% or less in the measurement wavelength range (360 nm to 740 nm).
  • the diffuse reflectance of samples G and H having a rough surface has a value of 10% or more in most of the measurement wavelength range.
  • a diffuse reflectance with respect to visible light a diffuse reflectance with respect to 550 nm light may be used as a representative value.
  • the diffuse reflectance with respect to light of 550 nm is 5% or less for samples A to C, and 10% or more for samples G and H.
  • Table 2 The results when an insulating resin layer is formed on the rough surface of each nickel sleeve by anionic electrodeposition in the same manner as described above are shown in Table 2 below.
  • the treatment voltage was 40 V during electrodeposition.
  • Table 2 shows the number of foreign matters obtained in the same manner as described above for Table 1. For comparison, the results of samples A to C are also shown.
  • the example which measured the surface roughness of this rough surface with the stylus type surface roughness meter (The stylus type surface roughness measuring device by JIS-B-0651-1976) is shown below.
  • the reference length was 250 ⁇ m.
  • FIG. 11 shows the measurement results of the spectral diffuse reflectance of samples I, J, and K having the rough surface used this time.
  • FIG. 11 also shows the measurement results of the spectral diffuse reflectance of the samples A to H thus far.
  • the diffuse reflectances of samples I, J, and K are higher than the diffuse reflectances of the previous samples G and H and exceed 20% over the entire measurement wavelength range.
  • Sample K has the highest diffuse reflectance, and the diffuse reflectance at 550 nm is more than 40% and 45% or less.
  • Table 4 The results when an insulating resin layer is formed on the rough surface of each nickel sleeve by anionic electrodeposition in the same manner as described above are shown in Table 4 below.
  • the processing voltage during electrodeposition was 80V.
  • Table 4 shows the number of foreign matters obtained in the same manner as described above for Table 1. For comparison, the results of samples A to C are also shown.
  • the antireflection film (or antireflection surface) formed using this has excellent reflection. Has a prevention function. Further, when the organic insulating layer is formed using a matte anion paint, an antireflection film (or an antireflection surface) that uniformly exhibits antiglare properties can be formed.
  • the present invention relates to a mold manufacturing method, and in particular, can be widely applied to a moth-eye mold manufacturing method.
  • the moth-eye mold can be used to form an antireflection film.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention se rapporte à un procédé permettant de produire un moule en œil de papillon (100) qui est un procédé permettant de produire un moule qui présente une structure en œil de papillon inversée sur la surface, ledit procédé comprenant : une étape (a) consistant à préparer une base de moule (10), qui comprend une étape (a1) consistant à préparer une base métallique (72m) qui comporte une surface qui diffuse et réfléchit la lumière visible, une étape (a2) consistant à former une couche isolante organique (13) sur la surface de la base métallique (72m) par un procédé d'électrodéposition anionique, et une étape (a3) consistant à former une couche d'alliage d'aluminium (18) sur la couche isolante organique (13) ; une étape (b) consistant à former une couche d'alumine poreuse (20) qui comporte une pluralité de fines parties évidées (22) par anodisation partielle de la couche d'alliage d'aluminium (18) ; une étape (c) consistant à élargir la pluralité de fines parties évidées (22) en mettant la couche d'alumine poreuse (20) en contact avec un liquide de gravure ; et une étape (d) consistant à augmenter la pluralité de fines parties évidées (22) au moyen d'une oxydation anodique supplémentaire.
PCT/JP2013/067981 2012-07-31 2013-07-01 Procédé permettant de produire un moule WO2014021039A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2016084745A1 (fr) * 2014-11-25 2016-06-02 シャープ株式会社 Moule, procédé de fabrication de moule, et pellicule antireflet
JPWO2015129857A1 (ja) * 2014-02-28 2017-03-30 シャープ株式会社 型のリサイクル方法
US9844145B2 (en) 2012-06-11 2017-12-12 Mc10, Inc. Strain isolation structures for stretchable electronics
JP2020076996A (ja) * 2018-11-06 2020-05-21 学校法人東京理科大学 モスアイ転写型及びモスアイ転写型の製造方法

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JPS61292820A (ja) * 1985-06-11 1986-12-23 三菱電線工業株式会社 有機高分子被覆金属体の製造方法
WO2011105206A1 (fr) * 2010-02-24 2011-09-01 シャープ株式会社 Outil, procédé de production d'outil et production d'un film antireflet

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CN101088030B (zh) * 2004-12-03 2013-11-06 夏普株式会社 抗反射材料、光学元件、显示器件及压模的制造方法和使用了压模的抗反射材料的制造方法
US8747683B2 (en) * 2009-11-27 2014-06-10 Sharp Kabushiki Kaisha Die for moth-eye, and method for producing die for moth-eye and moth-eye structure

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
JPS61292820A (ja) * 1985-06-11 1986-12-23 三菱電線工業株式会社 有機高分子被覆金属体の製造方法
WO2011105206A1 (fr) * 2010-02-24 2011-09-01 シャープ株式会社 Outil, procédé de production d'outil et production d'un film antireflet

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9844145B2 (en) 2012-06-11 2017-12-12 Mc10, Inc. Strain isolation structures for stretchable electronics
JPWO2015129857A1 (ja) * 2014-02-28 2017-03-30 シャープ株式会社 型のリサイクル方法
WO2016084745A1 (fr) * 2014-11-25 2016-06-02 シャープ株式会社 Moule, procédé de fabrication de moule, et pellicule antireflet
JPWO2016084745A1 (ja) * 2014-11-25 2017-09-07 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
JP2020076996A (ja) * 2018-11-06 2020-05-21 学校法人東京理科大学 モスアイ転写型及びモスアイ転写型の製造方法

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