CN107635740B - Mold release treatment method, the manufacturing method of antireflection film and demoulding processing unit - Google Patents
Mold release treatment method, the manufacturing method of antireflection film and demoulding processing unit Download PDFInfo
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- CN107635740B CN107635740B CN201680033863.6A CN201680033863A CN107635740B CN 107635740 B CN107635740 B CN 107635740B CN 201680033863 A CN201680033863 A CN 201680033863A CN 107635740 B CN107635740 B CN 107635740B
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- mold
- moth
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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
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
-
- 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
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/58—Applying the releasing agents
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Abstract
Mold release treatment method comprises the following steps: (a) preparing the release agent containing fluorine system compound and solvent with release property and surface has the cylindric or columned mold (100) of porous alumina layer (14)；(b) release agent is assigned to the surface of mold；And (c) make the release agent assigned in step (b) dry.The step of including air-flow (105) flowed to the Surface Creation of mold in the direction parallel with the axis of mold (100z) in step (c) and the step of rotate mold centered on the axis of mold.
Description
Technical field
The present invention relates to mold release treatment method, the manufacturing method of antireflection film and demoulding processing units." mould mentioned here
Tool " includes the mold for various processing methods (punching press or casting), otherwise referred to as pressing mold.Furthermore, it can also be used to print (packet
Include nano impression).
Background technique
For optical elements such as display device used in television set or mobile phone etc. or camera lens, it will usually implement
Antireflection technique improves the transit dose of light to reduce surface reflection.The reason is that for example, when being incident on air as light
It is such with the interface of glass, when light passes through the interface of the different medium of refractive index, because the reasons such as Fresnel reflection make the transmission of light
Amount is reduced, On The Deterioration of Visibility Over.
In recent years, as antireflection technique, the wavelength (λ of visible light is controlled in the period that substrate surface forms bumps
=380nm~780nm) method of fine relief pattern below attracts attention (referring to patent document 1~4).It constitutes and embodies
The two-dimentional size of the protrusion of the relief pattern of anti-reflective function is 10nm or more and does not reach 500nm.
The principle of so-called moth eye (Motheye) structure is utilized in the method, by the folding for making the light for being incident on substrate
It penetrates rate continuously to change along concave-convex depth direction, from the refractive index of incident medium to the refractive index of substrate, to inhibit to be intended to prevent
The reflection of the wavelength region only reflected.
Moth ocular structure can play the small antireflection effect of incident angle-dependent in extensive wavelength region, in addition to this, also
Have many advantages, such as to be applicable to multiple material, can directly form relief pattern on substrate.As a result, low cost and height can be provided
The antireflection film (or antireflective surfaces) of performance.
As the manufacturing method of moth ocular structure, using by making anodic oxidation porous alumina layer obtained by alumilite process
Method attract attention (patent document 2~4).
Here, for by the way that anodic oxidation porous alumina layer obtained by alumilite process is briefly described.In the past,
As the simple and easy method for the cylindric pore of nanoscale (fine recess portion) that can arrange to formation rule, the more of anodic oxidation are utilized
The manufacturing method of pore structure body attracts attention.If substrate is impregnated in the acidic electrolysis baths such as sulfuric acid, oxalic acid or phosphoric acid or alkaline electro
It solves in liquid, and applies voltage as anode, then aoxidized and dissolved simultaneously in substrate surface, so as to form its table
The punctulate oxidation film of mask.This columned pore orientation in a manner of perpendicular to oxidation film, it is (electric under certain conditions
Pressure, the type of electrolyte, temperature etc.) systematicness itself organized is shown, it is therefore contemplated that being applied to various functional materials.
For the porous alumina layer formed under given conditions, when from the direction perpendicular to film surface, be formed as
As the unit of substantially regular hexagon to be arranged made of the filling of most high-density two dimension.The center of each unit has pore, pore
Arrangement have periodically.Unit is formed by the dissolution and growth of the epithelium of part, in the pore of referred to as barrier layer
Bottom, while carrying out the dissolution and growth of epithelium.At this time, it was known that the interval (between center of the size of unit, i.e. adjacent pore
Distance) substantially 2 times of thickness of barrier layer are equivalent to, and it is substantially directly proportional to voltage when anodic oxidation.Furthermore it is known that pore
Although diameter depend on electrolyte type, concentration, temperature etc., usually the size of unit is (from the side perpendicular to film surface
To observation when, be unit the cornerwise length of longest) 1/3 or so.The pore of such porous aluminas is formed as specific
Under the conditions of the arrangement with high systematicness (with periodically) and be that the mixed of systematicness to a certain degree is had according to condition
Disorderly arrangement or the arrangement of irregular (not having periodically).
Patent document 2, which is disclosed, using surface there is the pressing mold of anodic oxidation multiaperture pellumina to form antireflection film
The method of (antireflective surfaces).
In addition, being disclosed in patent document 3 thin to be formed by the way that anodizing of aluminium and borehole enlargement processing is repeated
The technology for the tapered recess that aperture continuously changes.
Patent Document 4 discloses have the alumina layer of stair-stepping side come shape using fine concave portions by the applicant
At the technology of antireflection film.
In addition, other than being equipped with moth ocular structure (microstructure), being additionally provided with ratio such as the record in patent document 1,2 and 4
The big concaveconvex structure of moth ocular structure (macrostructure), thus, it is possible to assign anti-dazzle (anti-to antireflection film (antireflective surfaces)
Glare) function.Constituting and playing the two-dimentional size of the concave-convex protrusion of anti-dazzle function is 1 μm or more and not up to 100 μm.By patent
The complete disclosure of document 1,2 and 4 is continued to use for reference in this manual.
By utilizing anodic oxidation multiaperture pellumina, the mold to form moth ocular structure on surface can be easily manufactured
(hereinafter referred to as " the ophthalmically acceptable mold of moth ").Especially as described in patent document 2 and 4, if the surface of anodizing of aluminium film is directly used
Make mold, then the effect for reducing manufacturing cost is big.The structure that the surface of the ophthalmically acceptable mold of moth of moth ocular structure will be formed is known as " instead
The moth ocular structure turned ".
Manufacturing method as the antireflection film for using the ophthalmically acceptable mold of moth, it is known to use the method for photocurable resin.
Firstly, assigning photocurable resin on substrate.Then, by the convex-concave surface of the ophthalmically acceptable mold of moth by demoulding processing in vacuum
In press on photocurable resin, photocurable resin is filled in as a result, in the concaveconvex structure on the surface of the ophthalmically acceptable mold of moth.It connects
, ultraviolet light is irradiated to the photocurable resin in concaveconvex structure, hardens photocurable resin.Thereafter, make the ophthalmically acceptable mold of moth
It is separated from substrate, thus forms the hardening of the photocurable resin of the concaveconvex structure transferred with the ophthalmically acceptable mold of moth on the surface of the substrate
Nitride layer.It is recorded in such as patent document 4 using the manufacturing method of the antireflection film of photocurable resin.
The applicant develops the ophthalmically acceptable mold of moth using roll, and antireflection film is expeditiously manufactured in the way of roll-to-roll
Method (such as patent document 5).Patent document 5, which discloses, to have the surface of the mold of porous alumina layer to assign to surface
Release agent is without making it generate uneven mold release treatment method.The complete disclosure edge of patent document 5 is used for this explanation
It is for reference in book.
Existing technical literature
Patent document
Patent document 1: Japanese patent special table 2001-517319 bulletin
Patent document 2: Japanese patent special table 2003-531962 bulletin
Patent document 3: Japanese Patent Laid-Open 2005-156695 bulletin
Patent document 4: International Publication No. 2006/059686
Patent document 5: International Publication No. 2011/111669
Summary of the invention
The technical problems to be solved by the invention
However, being generated sometimes after present inventor carries out demoulding processing to the ophthalmically acceptable mold of moth on the surface of the ophthalmically acceptable mold of moth
It is uneven.Even if the mold release treatment method using patent document 5 assigns release agent, uneven situation can be also generated sometimes.By this
The research of inventor is learnt, after assigning release agent to the surface of the ophthalmically acceptable mold of moth, is generated in the step for keeping release agent dry
It is uneven.Details will be in described below.
This problem is not limited to the ophthalmically acceptable mold of moth, but has the porous of the fine concave portions comprising submicron order for surface
The mold of alumina layer is common problem.
The main purpose of the present invention is to provide a kind of pair of surfaces, and there is the surface of the mold of porous alumina layer to take off
Mould processing is without making it there is uneven method.
The means solved the problems, such as
Mold release treatment method involved in embodiments of the present invention, comprises the following steps: (a) preparing containing with demoulding
Property fluorine system compound and solvent release agent and surface have porous alumina layer cylindric or columned mold；(b)
The release agent is assigned to the surface of the mold；And (c) drying steps, make to assign in the step (b) described
Release agent is dry, and includes the air-flow flowed to the Surface Creation of the mold in the direction parallel with the axis of the mold
The step of and the step of rotate the mold centered on the axis of the mold.
In a certain embodiment, the rotation speed of the mold in the step (c) be 0.5rpm or more and 10rpm with
Under.
In a certain embodiment, if the diameter of the mold on the section vertical with the axis of the mold is set as D
(m), then the flow velocity of the air-flow in the step (c) be 0.05D (m/s) more than and 0.52D (m/s) below.
In a certain embodiment, the step of generation air-flow in the step (c) includes gas of the supply containing solvent
The step of body, the solvent make the fluorine compounds dissolution contained in the release agent.
In a certain embodiment, contain and solvent phase contained in the release agent in the gas containing the solvent
Same solvent.
In a certain embodiment, the surface of the porous alumina layer has the moth ocular structure of reversion, the moth eye of the reversion
Two-dimentional size when structure has from normal to a surface direction is 50nm or more and does not reach multiple recess portions of 500nm.
The manufacturing method of antireflection film involved in embodiments of the present invention, comprises the following steps: prepare by with
Upper any mold release treatment method implements the mold of demoulding processing；Prepare machined object；To the mold and the quilt
In the state of assigning light-hardening resin between the surface of machining object, keep the light hard and to the light-hardening resin irradiation light
Change hardening of resin；And the antireflection film formed by the light-hardening resin after hardening is removed from the mold.
Demoulding processing unit involved in embodiments of the present invention includes cylindric cover, has the 1st opening and the
2 openings；And rotatable support structure body, by cylindric or columned mold, with substantially parallel with the axis of the cover and can be around
The mode of the axis rotation of the mold is supported between the 1st opening of the cover and the 2nd opening.
In a certain embodiment, the demoulding processing unit also has the institute for supplying to give the cover from the 1st opening
State the air-flow feedway of the substantially parallel air-flow of axis.
In a certain embodiment, the air-flow feedway has the filter for being located at the 1st opening.
In a certain embodiment, the rotatable support structure body has motor and in conjunction with the drive shaft of the motor
Pedestal, at least part of the pedestal are located between the 1st opening and the 2nd opening.
Invention effect
Embodiment according to the present invention can have the surface of the mold of porous alumina layer to carry out demoulding processing to surface
It is uneven without generating it.
Detailed description of the invention
(a) of Fig. 1~(e) is for illustrating at mold release treatment method involved in embodiments of the present invention one and demoulding
Manage the schematic diagram of device 50.
(a) of Fig. 2 and (b) be for illustrate carry out experimental example after demoulding processing unit schematic diagram.
Fig. 3 is the investigation for the relationship for illustrating the rotation speed of the flow velocity and ophthalmically acceptable mold 100 of moth for air-flow 105
Figure.
(a) of Fig. 4~(e) is the schematic cross sectional views for illustrating the manufacturing method of the ophthalmically acceptable mold of moth.
Fig. 5 is the schematic cross sectional views for illustrating to manufacture the method for antireflection film in the way of roll-to-roll.
(a) of Fig. 6~(c) is for illustrating to compare used in previous mold release treatment method and the mold release treatment method
The schematic diagram of the demoulding processing unit 90 of example.
Specific embodiment
It is ophthalmically acceptable in moth after present inventor carries out demoulding processing to the ophthalmically acceptable mold of moth of roll (such as cylindric or cylindric)
The surface of mold generates unevenness sometimes.Research according to the present invention learns that unevenness is resulted from the table to the ophthalmically acceptable mold of moth
Face assign it is after the step of release agent, make to have assigned to the dry step of the release agent on the surface of the ophthalmically acceptable mold of moth (sometimes
Referred to as " release agent drying steps ") in.Hereinafter, will illustrate details.
Referring to (a)~(c) of Fig. 6, illustrate previous mold release treatment method.(a) of Fig. 6~(c) is previous for illustrating
Mold release treatment method and the mold release treatment method used in comparative example demoulding processing unit 90 schematic diagram.(a) of Fig. 6
It is the schematic diagram of the demoulding processing unit 90 of comparative example, (b) of Fig. 6 is the schematic sectional of the demoulding processing unit 90 of comparative example
Figure, (c) of Fig. 6 are the schematic diagrames for illustrating to investigate the method for the uneven reason generated in previous mold release treatment method.
As shown in (a) of Fig. 6, the demoulding processing unit 90 of comparative example has the cover 92 of square tube shape, the cover of the square tube shape
Body 92 has the 1st opening 92a and the 2nd opening 92b.The demoulding processing unit 90 of comparative example is ophthalmically acceptable by cylindric or columned moth
Mold 100 is maintained in cover 92 in the mode for keeping the long axis direction of mold 100 substantially parallel with the long axis direction of cover 92
Side.The ophthalmically acceptable mold 100 of moth for example erects configuration with long axis direction and the substantially parallel mode of vertical direction.On typical case, it is configured to
The long axis direction of the ophthalmically acceptable mold 100 of moth and the long axis direction and vertical direction of cover 92 are substantially uniform.
In release agent drying steps, to the ophthalmically acceptable mold of moth 100, surface with the moth ocular structure inverted (that is, circle
The side of cylinder or cylinder), supply the air-flow 105 ' flowed in the direction parallel with the central axis of the ophthalmically acceptable mold 100 of moth.Fig. 6's
(a) in example shown in, the air-flow 105 ' flowed from the 1st opening 92a of cover 92 to the 2nd opening 92b is supplied.105 ' example of air-flow
Such as it is fed in cover 92 via HEPA filter 94.
(b) of Fig. 6 is schematic cross sectional views when observing the demoulding processing unit 90 of comparative example from vertical direction.Air-flow
It is flowed in the 105 ' whole region between cover 92 and the ophthalmically acceptable mold 100 of moth.As shown in (b) of Fig. 6, the ophthalmically acceptable mold 100 of moth
Section (bottom surface) it is substantially round, in contrast, the section (bottom surface) of cover 92 is rectangular-shaped.In general, cover 92 is cut
Face is shape identical with the 1st opening 92a and the 2nd opening 92b.For example, it is 300mm that the bottom surface of the ophthalmically acceptable mold 100 of moth, which is diameter,
Circle, the section of cover 92 be side length be 600mm square.The ophthalmically acceptable mold 100 of moth is for example by the cylinder of the aluminium of thickness 15mm
It is formed, the length of the long axis direction of cylinder is 1600mm.
The step of assigning release agent is for example using the method and device recorded in patent document 5.Remember according in patent document 5
The method and/or device of load can prevent release agent from generating crawling.That is, release agent can be assigned in a manner of there is no unevenness.
The demoulding processing unit 90 of comparative example also has the motor for rotating the ophthalmically acceptable mold 100 of moth centered on axis
97.As the record of patent document 5 can also be such that the ophthalmically acceptable mold 100 of moth rotates in the step of assigning release agent.For example, when utilizing
When spray coating method (spray coating method) assigns the situation of release agent, if using in the long axis side of the ophthalmically acceptable mold 100 of moth
It, then can be and rotating the ophthalmically acceptable mold 100 of moth centered on axis to the entire side of the ophthalmically acceptable mold 100 of moth to mobile nozzle
Assign release agent.In contrast, not making the ophthalmically acceptable mold of moth in previous mold release treatment method, in release agent drying steps
100 rotations.In release agent drying steps, as previously discussed, air-flow 105 ' is entire between cover 92 and the ophthalmically acceptable mold 100 of moth
It is flowed in region.The reason is that, even if rotating the ophthalmically acceptable mold 100 of moth, air-flow 105 ' can also be spread by the mode
The entire side of the ophthalmically acceptable mold 100 of moth.
Implement demoulding processing (the step of including to assign release agent and release agent in the demoulding processing unit 90 using comparative example
Drying steps) after roll the ophthalmically acceptable mold 100 of moth surface, produce uneven 101a, 101b.Research according to the present invention
It learns, according to the difference for generating place, unevenness mainly can probably be divided into 2 kinds.In this specification, uneven 101a refers to main generation
The unevenness of end in the side of the ophthalmically acceptable mold 100 of moth, on long axis direction.Uneven 101a fecund is born in the ophthalmically acceptable mold of moth
Moth in example shown in the both ends of 100 side, the especially air-flow 105 ' end in downstream side, i.e. (a) of Fig. 6 is ophthalmically acceptable
Near the lower end 100e of mold 100.Uneven 101b refers in the side for occurring mainly with the ophthalmically acceptable mold 100 of moth, long axis direction
On center portion, part i.e. other than both ends unevenness.Uneven 101a is mostly strip.As shown in (a) of Fig. 6, generate not
The range 102a of equal 101a is the length on the long axis direction of the ophthalmically acceptable mold 100 of moth, from the lower end 100e of the ophthalmically acceptable mold 100 of moth
Spend the range of L102a.Implement in demoulding treated the ophthalmically acceptable mold 100 of moth in the demoulding processing unit 90 using comparative example,
Sometimes having length L102a is the situation of such as 200mm or more, 300mm or more.
As previously discussed, in the step of assigning release agent, using the method and device recorded in patent document 5, therefore
It can inhibit release agent and generate crawling.That is, unevenness 101a, 101b be considered being generated in the step of assigning release agent
's.
Present inventor utilizes smoke-wire method (Smoke-Wire method) to investigate the producing cause of uneven 101a, 101b
Investigate the flowing of the air-flow 105 ' in the demoulding processing unit 90 of comparative example.As shown in (c) of Fig. 6, height is equipped in cover 92
The filament (resistive conductor) 110 of resistance.It is coated with atoleine on resistive conductor 110, electric current is passed through and generates white cigarette, make air-flow 105 '
Flowing it is visible.The cigarette beam generating apparatus MS-405 manufactured in smoke-wire method using Co., Ltd., Jian Yuan research institute.By investigation
As a result, the position of the movement disorder of air-flow 105 ' is consistent with the unevenness position of 101a, 101b is generated.That is, in the ophthalmically acceptable mold 100 of moth
Surface (side) in, the end on long axis direction and the center portion on long axis direction, there are generate air-flow 105 ' not
(inhomogeneities) the case where.Inventor appreciates that the unevenness (inhomogeneities) of air-flow 105 ' encourages the production of unevenness 101a, 101b
It is raw, to find out the present invention.
Uneven 101a, 101b of the ophthalmically acceptable mold 100 of moth visual observations can be arrived immediately below fluorescent lamp.In addition, if moth is ophthalmically acceptable
Mold 100 has unevenness 101a, 101b, then is also formed with moth on the surface of the antireflection film made using the ophthalmically acceptable mold 100 of moth
The inhomogeneities (unevenness) of ocular structure.
It is the investigation of present inventor above, does not limit the present invention.
Hereinafter, illustrating mold release treatment method involved in embodiments of the present invention referring to attached drawing.In addition, the present invention is simultaneously
It is not limited to the embodiment of following example.Hereinafter, being carried out in case where the ophthalmically acceptable mold of the moth to roll carries out demoulding processing
Explanation." the ophthalmically acceptable mold of the moth of roll " includes the cylindric ophthalmically acceptable mold of moth and the ophthalmically acceptable mold of columned moth.Attached drawing below
In, identical reference marks is marked for the constituent element with substantially the same function, and the description thereof will be omitted sometimes.
(embodiment one)
(a) referring to Fig.1~(e) illustrates at mold release treatment method involved in embodiments of the present invention one and demoulding
Manage device.(a) of Fig. 1~(e) is for illustrating at mold release treatment method involved in embodiments of the present invention one and demoulding
Manage the schematic diagram of device 50.(a) of Fig. 1 is the schematic diagram for demoulding processing unit 50, and (b) of Fig. 1 is demoulding processing unit 50
Schematic cross sectional views.It (c) of Fig. 1 and is (d) figure for schematically showing the ophthalmically acceptable mold 100 of moth.(e) of Fig. 1 is schematically
Indicate the figure of an example of pedestal 56 specifically constituted.
Mold release treatment method involved in embodiments of the present invention one has following steps: step (A), prepares containing tool
There are the fluorine system compound of release property and the release agent of solvent and surface that there is the cylindric or columned of porous alumina layer 14
Mold 100；Step (B) assigns release agent to the surface of mold 100；And step (C), keep the release agent assigned in step (B) dry
It is dry.Step (C) includes: step (C1), generates the air-flow 105 flowed in the direction parallel with the axis 100z of mold 100；And step
(C2), mold 100 is rotated centered on the axis 100Z of mold 100.
Mold release treatment method involved in embodiment according to the present invention one can be to table as shown in experimental example below
There is the surface of the mold of porous alumina layer to carry out demoulding processing and it will not be made to there is unevenness for face.It especially, can anti-anti-avulsion
It is generated in mould agent drying steps uneven.
Hereinafter, illustrating the details of mold release treatment method involved in embodiments of the present invention one.
Firstly, prepare as Fig. 1 (c) and (d) shown in roll the ophthalmically acceptable mold 100 of moth and release agent (not shown).In
The surface (i.e. the side of cylinder or cylinder) of the ophthalmically acceptable mold 100 of moth has porous alumina layer 14.If the moth using roll is ophthalmically acceptable
Mold 100, then have the advantages that for example can in the way of roll-to-roll expeditiously volume production antireflection film.
Such as Fig. 1 (d) shown in, the ophthalmically acceptable mold 100 of moth have roll supporter 12 (such as pipe of stainless steel making),
The aluminium film 18 being formed on the surface of the supporter 12 of roll and the porous alumina layer 14 being formed in aluminium film 18.In addition, figure
In 1 (d), to ask easy, mold 100 ophthalmically acceptable for moth only shows a part of the supporter 12 of roll, one of aluminium film 18
Point and porous alumina layer 14 a part.Porous alumina layer 14 has multiple fine recess portion (pore) 14p.It is multiple micro-
Thin recess portion 14p, from normal to a surface direction when two-dimentional size be 50nm or more and do not reach 500nm.It is such as following detailed
It states, the ophthalmically acceptable mold 100 of moth can be by carrying out anodic oxidation and etching to the aluminium film 18 on the supporter 12 for being formed in roll repeatedly
To make.When making the ophthalmically acceptable mold 100 of moth, the method recorded in such as above patent document 3 and 4 can be used.
Then, the imparting of release agent is carried out.As release agent, using including fluorine system compound and solvent with release property
Fluorine system releasing agent.As fluorine system releasing agent, well known type can be widely used.For example, Fluoro Technology can be used
The FLUOROSURF of company's manufacture.As FLUOROSURF, such as FLUOROSURF FG-5010Z130-0.1 can be used.
In FLUOROSURF FG-5010Z130-0.1, contain perfluorooctylethyl group acrylate as fluorine system compound
The homopolymer of (Perfluorooctyl ethyl acrylate) contains diluent ZV (hydrofluoroether) as solvent.For example,
The concentration of the homopolymer of the perfluorooctylethyl group acrylate of FLUOROSURF FG-5010Z130-0.1 is 0.1%.
It is sometimes also molten including, for example, noninflammability fluorine series solvent or petroleum other than above-mentioned solvent as solvent in FLUOROSURF
Agent.As noninflammability fluorine series solvent, other than hydrofluoroether, also it can be mentioned, for example, perfluoropolyether, perfluoro alkane, hydrogen perfluoroalkyl polyether,
Hydrofluorocarbon etc..These noninflammability fluorine series solvents can be used alone a kind of or be use mixing two or more.It is molten as petroleum
Agent can be used for example, the solvent that normal heptane, acetone or normal heptane and acetone mix.
As fluorine system releasing agent, other than the type, the OPTOOL DSX of for example big King Company's manufacture also can be used.
Furthermore, it is possible to use the CLEAR COAT of three fluorine chemistry companies, well Du Pont manufacture.In addition, the solvent as fluorine system releasing agent, excellent
Choosing uses the solvent of fluorine system.But can also suitably select water-based solvent or well known organic solvent and be subject to using.In addition, molten
Agent can be not only the type that fluorine system compound can be made to dissolve, and can also be to make the type of fluorine system compound dispersion in a solvent.
Fluorine system releasing agent has compared with the release agent such as silicone release agent other than fluorine system releasing agent for being used for
The advantages of manufacturing the high mold release of the uv-hardening resin of antireflection film.In addition, fluorine system releasing agent has to ultraviolet light
The high advantage of resistance.In addition, the layer of fluorine system releasing agent is easy filming.
In the imparting of release agent, such as can be as described below, using the method and device recorded in patent document 5.It is logical
It crosses using the method and/or device recorded in patent document 5, the crawling of release agent can be prevented.In addition, such as patent document 5
Record, before the step of assigning release agent, can also carry out clean step, make the step of dry tack free, surface dried
The step of roasting (bake) etc..
Firstly, assigning solvent to the surface of the ophthalmically acceptable mold 100 of moth.Here the solvent assigned is in general institute in release agent
The solvent contained, but it is not limited to this, as long as it is molten that the fluorine system compound contained in release agent with release property can be made to dissolve
Agent.Solvent can be assigned for example using nozzle and using spraying method.Then, it is assigned to the surface of the ophthalmically acceptable mold 100 of moth de-
Mould agent.Release agent can be assigned for example using nozzle and using spraying method.
Then, make to assign dry to the release agent on the surface of the ophthalmically acceptable mold 100 of moth.In release agent drying steps, for moth
The surface of ophthalmically acceptable mold 100 generates the air-flow 105 flowed up in the side parallel with the axis 100z of the ophthalmically acceptable mold 100 of moth, and,
Rotate the ophthalmically acceptable mold 100 of moth centered on axis 100z.Axis 100z is the central axis of the ophthalmically acceptable mold 100 of moth.Air-flow 105 for example may be used
It can also be other gases (such as inert gas (such as nitrogen, Ar gas etc.), carbon dioxide gas (CO for air stream2), oxygen
Gas etc.).
The release agent drying steps of mold release treatment method involved in embodiment according to the present invention can inhibit previous
The generation of uneven 101a, the 101b that can be generated in mold release treatment method.At demoulding involved in embodiment according to the present invention
The release agent drying steps of reason method, can improve end in the side of the ophthalmically acceptable mold 100 of moth and central portion this two side, in moth
The homogeneity of the air-flow 105 flowed on the surface of ophthalmically acceptable mold 100.
The rotation speed of the ophthalmically acceptable mold 100 of moth as described in referring to experimental example, for example, it is preferable to for 0.5rpm or more and
10rpm is hereinafter, more preferably 1rpm or more and 10rpm or less.The flow velocity of air-flow 105 is for example preferably 0.05 × 100d (m/s)
Above and 0.52 × 100d (m/s) below.Here, the diameter of the bottom surface of the ophthalmically acceptable mold 100 of moth is 100d (m).The ophthalmically acceptable mold of moth
100 bottom surface is the section vertical with the axis 100z of the ophthalmically acceptable mold 100 of moth.If the above range of the flow velocity of air-flow 105 is scaled
Rotation speed is then equivalent to 1rpm or more and 10rpm range below.The reason is that because rpm is turn for indicating each minute
Several units, therefore, 1rpm are equivalent to (π × 100d)/60 (m/s).Flow velocity and the ophthalmically acceptable mold 100 of moth about air-flow 105
The relationship of rotation speed, referring to experimental example in described below.
Then, illustrate to demould processing unit 50 involved in present embodiment.According to demoulding processing unit 50, this can be implemented
Mold release treatment method involved in embodiment.But demoulding processing unit and unlimited involved in embodiments of the present invention
In the device of following example.
As shown in (a) of Fig. 1, demoulding processing unit 50 has the cylindrical shape of the 1st opening 52a and the 2nd opening 52b
Cover 52 and rotatable support structure body 58.Rotatable support structure body 58 by cylindric or columned mold 100, with cover
52 axis 52z it is substantially parallel and can around the axis 100z of mold 100 rotate mode, be supported on cover 52 the 1st opening 52a with
Between 2nd opening 52b.
According to demoulding processing unit 50, can to surface have porous alumina layer mold surface carry out demoulding processing and
It will not be made to generate uneven.It can especially prevent from generating in release agent drying steps uneven.
(b) of Fig. 1 is the schematic cross sectional views for demoulding processing unit 50.The ophthalmically acceptable mold 100 of moth and cover 52 for example configure
It is substantially parallel with vertical direction at long axis direction.That is, can be configured to the direction axis 100z of the ophthalmically acceptable mold 100 of moth and the axis of cover 52
The direction 52z and vertical direction are substantially uniform.The ophthalmically acceptable mold 100 of moth can also for example utilize the suspention for being installed on the ophthalmically acceptable mold 100 of moth
Component 69 ((a) referring to Fig.1) suspends in midair from top.Cover 52 can also for example be located at the (ginseng of imparting room 62 of corner post shape or square tube shape
According to (b) of Fig. 1) inside.
The demoulding processing unit 90 of comparative example has the cover 92 of square tube shape, therefore, from the surface of the ophthalmically acceptable mold 100 of moth
The distance of each point to cover 92 is inhomogenous.This reason will cause the inhomogeneities of air-flow 105 '.
In contrast, in demoulding processing unit 50 involved in embodiments of the present invention, as shown in (b) of Fig. 1, cover
52 section and the section of the ophthalmically acceptable mold 100 of moth are substantially round.In general, the 1st opening 52a and the 2nd opening of cover 52
The shape of 52b is the circle with mutually the same diameter.On typical case, it is arranged to when observing from vertical direction, cover 52 and moth
The center of ophthalmically acceptable mold 100 is consistent.At this point, each point being equidistant to cover 52 on the surface of the ophthalmically acceptable mold 100 of moth.The present invention
Embodiment involved in demoulding processing unit 50 in, on each point on the surface of the ophthalmically acceptable mold 100 of moth, the flow velocity of air-flow 105
It is all variable uniform.This effect may be embodied in the surface (side) of the ophthalmically acceptable mold 100 of moth, end on long axis direction and long axis
Center portion this two side on direction.Therefore, the unevenness that can be generated in the demoulding processing unit 90 of such as comparative example can be inhibited
The generation of 101a, 101b (referring to (a) of Fig. 6).
For example, the section of cover 52 is the circle of diameter 500mm.The bottom surface of the ophthalmically acceptable mold 100 of moth is the circle of diameter 300mm,
The ophthalmically acceptable mold 100 of moth is for example formed by the cylinder of the aluminium with a thickness of 15mm, and the length of the long axis direction of cylinder is 1600mm.Cover
52 such as metal (such as stainless steel, Al plate for processing through anodic oxidation) or resin (such as acrylic resin, polycarbonate
Resin, BS system resin etc.) it is formed.The semicircular cylinder formed by different materials can also be combined and form cover 52.Such as in
Here, the semicircular cylinder formed by stainless steel and acrylic resin is combined and forms cover 52.If with acrylic resin etc.
Transparent material forms at least part of cover 52, then is for example easy to observe the air-flow 105 in cover 52 using smoke-wire method.
Pedestal 56 of the rotatable support structure body 58 for example with motor 57 and in conjunction with the drive shaft 57d of motor 57.Pedestal
56 at least part is located between the 1st opening 52a and the 2nd opening 52b.Rotatable support structure body 58 can also Jin mono- Walk have will
Bonded block (not shown) of the pedestal 56 in conjunction with the drive shaft 57d of motor 57.
Motor 57 rotates the ophthalmically acceptable mold 100 of moth centered on the axis 100z of the ophthalmically acceptable mold 100 of moth.Release agent drying steps
In, the ophthalmically acceptable mold 100 of moth can be made to rotate centered on axis 100z using motor 57.As a result, as shown in following experimental example, it can press down
The generation of uneven 101a, the 101b (referring to (a) of Fig. 6) that can be generated in the demoulding processing unit 90 of comparative example processed.About generation
Uneven one of reason, is to keep the rate of drying of release agent uneven because of the inhomogeneities of air-flow 105.If making the ophthalmically acceptable mold of moth
100 rotations, then can be such that air-flow 105 homogenizes, so as to inhibit uneven generation.About the flow velocity of air-flow 105 and the ophthalmically acceptable mould of moth
The preferred range of the rotation speed of tool 100, will be referring to experimental example in described below.In the step of assigning release agent, certainly
Motor 57 can also be used rotate the ophthalmically acceptable mold 100 of moth.
If at least part of pedestal 56 is located between the 1st opening 52a of cover 52 and the 2nd opening 52b, can increase perpendicular
Histogram is upward, the distance between the lower end 100e of cover 52 the 2nd opening 52b and the ophthalmically acceptable mold 100 of moth L.Here, vertical
On direction, the 2nd opening 52b of cover 52 is located at the lower end 100e of the ophthalmically acceptable mold 100 of moth further below.In addition, demoulding processing step
In rapid, the ophthalmically acceptable mold 100 of moth can be steadily supported.
In the previous mold release treatment method using the demoulding processing unit 90 of comparative example, sometimes in the ophthalmically acceptable mold of moth
In 100 surface (side), unevenness 101a is generated centered on the end (especially lower end) on long axis direction (referring to Fig. 6
(a)).In the demoulding processing unit 90 of comparative example, even if the 2nd opening 52b of cover 52 is located at the lower end of the ophthalmically acceptable mold 100 of moth
The more top of 100e or further below, since distance L is small, the air-flow near the lower end 100e of the side of the ophthalmically acceptable mold 100 of moth
105 ' generate disorder, and generate unevenness 101a.In demoulding processing unit 50 involved in embodiments of the present invention, due to distance
L is big, therefore the air-flow 105 on the lower end periphery 100e of the side of the ophthalmically acceptable mold 100 of moth can be inhibited to generate disorder, so as to inhibit not
The generation of equal 101a.Distance L is for example preferably 200mm or more, more preferably 300mm or more.
Even if in the generation that cannot completely inhibit uneven 101a, but the range 102a that unevenness 101a is generated is (referring to Fig. 6's
(a)) it in the case of small, can use without problems in practical sometimes.When using the ophthalmically acceptable Mold Making film of moth (such as antireflection
Film) when, sometimes using the part other than part in the film produced, corresponding with the effective coverage of mold as remaining space
Processing.The length on long axis direction from the lower end 100e of the ophthalmically acceptable mold 100 of moth is the range within such as 20mm~50mm,
Sometimes it is not comprised in the effective coverage of mold.Therefore, in the ophthalmically acceptable mold 100 of moth, as long as the range that unevenness 101a is generated
Length L102a (referring to (a) of Fig. 6) on 102a, long axis direction from the 100e of lower end is, for example, 20mm hereinafter, then practical
On can use without problems.
Pedestal 56 is for example, cylindric, and the axis direction of pedestal 56 is set as substantially uniform with the direction axis 100z of mold 100.
For example, the face perpendicular to the sectional area of the pedestal 56 on the face of the axis 100z of mold 100, with the axis 100z perpendicular to mold 100
On mold 100 sectional area it is substantially uniform.
Pedestal 56 can also for example have the structure as shown in (e) of Fig. 1.(e) of Fig. 1 schematically shows pedestal 56
The figure of an example specifically constituted.
As exemplified by (e) of Fig. 1, pedestal 56 includes platen (mounting plate) 56a, for installing, fixing mould 100；Liquid
Bearing plate 56b accepts the liquid to drip down from the surface of mold 100；And connecting component 56z, these plates are connected with each other.Platen
56a and liquid bearing plate 56b, cross sectional shape when observing from vertical direction, it is respectively roughly circular on typical case.
The diameter in section when observing from vertical direction of platen 56a is observed with the slave long axis direction of the ophthalmically acceptable mold 100 of moth
When section diameter it is roughly the same.The center in the section of platen 56a observed from vertical direction, such as positioned at the ophthalmically acceptable mold of moth
On 100 long axis.
The diameter in section when observing from vertical direction of liquid bearing plate 56b, greater than the slave long axis of the ophthalmically acceptable mold 100 of moth
The diameter in section when direction is observed.The center in section when observing from vertical direction of liquid bearing plate 56b, such as positioned at moth
On the long axis of ophthalmically acceptable mold 100.Liquid bearing plate 56b has the side of cone cell.Upper surface (the platen 56a of liquid bearing plate 56b
The face of side) diameter, the diameter of the lower surface (face with platen 56a opposite side) less than liquid bearing plate 56b.Liquid bearing plate
The diameter of the upper surface of 56b, for example, it is roughly the same with the diameter in section when the observation of the slave long axis direction of the ophthalmically acceptable mold 100 of moth.
The diameter of the lower surface of liquid bearing plate 56b is greater than the straight of section when the slave long axis direction observation of the ophthalmically acceptable mold 100 of moth
Diameter.
If center and the diameter in section when observing from vertical direction of platen 56a, the slave long axis with the ophthalmically acceptable mold 100 of moth
The center in section when direction is observed and diameter are substantially uniform, then the liquid for being attached to the surface of the ophthalmically acceptable mold 100 of moth can be made suitable
It flows sharply.Jin mono- Walk, the disorder of the air-flow 105 near the lower end 100e of the ophthalmically acceptable mold 100 of moth can be inhibited.
If the side of liquid bearing plate 56b is cone cell, can prevent from dropping to the liquid storing part for being located at ophthalmically acceptable 100 lower section of mold of moth
Liquid splash in 59 and be attached to the ophthalmically acceptable mold 100 of moth.
If the diameter of the lower surface (face with platen 56a opposite side) of liquid bearing plate 56b is greater than the ophthalmically acceptable mold 100 of moth
The diameter in section when from long axis direction then can be reduced the gas invaded in cover 52 below the ophthalmically acceptable mold 100 of moth
Or dust.
When observing from vertical direction, connecting component 56z is completely Chong Die with the ophthalmically acceptable mold 100 of moth.Connecting component 56z from perpendicular
Sectional area of the histogram to sectional area when observation, when the slave long axis direction less than the ophthalmically acceptable mold 100 of moth is observed.As a result, in platen
Space is formed between 56a and liquid bearing plate 56b.The solvent and/or release agent that gasification can be detained are being formed by space.Energy
Prevent the release agent drying from the lower end side 100e of the ophthalmically acceptable mold 100 of moth for being coated on ophthalmically acceptable 100 surface of mold of moth.By making to take off
The dry speed of mould agent is uniform, can inhibit uneven generation.
Demoulding processing unit 50 also has air-flow feedway 55, which for example supplies from the 1st opening 52a
Give the substantially parallel air-flow 105 of the axis 52z of cover 52.The air-flow 105 supplied by air-flow feedway 55 is from the 1st opening 52a
Flow to the 2nd opening 52b.
Air-flow feedway 55 is for example with the filter 53 for being located at the 1st opening 52a.Air-flow feedway for example can also be into
Yi Walk has the HEPA filter 54 for being located at filter 53, the 1st opening 52a outside.
Air-flow is imported from air supplying part for example (not shown) to air-flow feedway 55.Air supplying part is independently of demoulding processing
Device 50 and set.The air-flow imported from air supplying part passes through filter 53 and is homogenized.Parallel with the axis 100z of mold 100
The air-flow 105 of direction flowing is fed into cover 52.Filter 53 is, for example, perforated plate (punching plate) (perforation gold
Belong to).The thickness of perforated plate is, for example, 0.5mm~1.5mm.The opening diameter of perforated plate is, for example, 1.0mm~8.0mm.Perforated plate
The spacing of opening is, for example, 1mm~20mm.The aperture opening ratio of perforated plate is, for example, 20%~50%.Here, using such as 60 ° of circular hole
The perforated plate of interlaced pattern (pattern of the circular opening arrays in the grid point of positive triangle grid).The opening of this perforation pattern
Rate can be according to 90.6 × D2/P2(%) (P: spacing between hole, D: bore dia) is obtained.
It is not limited to the above example, air supplying part also can be used as a part of air-flow feedway 55 and be arranged.Air-flow supplies
It can also air supplying part (not shown) of the Jin mono- Walk with for example, blade, pressure fan, electric fan etc. to device 55.
Demoulding processing unit 50 can be used to carry out for the step of assigning release agent and release agent drying steps.If using altogether
Logical device, then without the mobile ophthalmically acceptable mold of moth between two steps, so as to improve manufacturing yield.The world of the applicant is public
It opens to disclose in No. 2012/133390 and a kind of improves holding for release property by carrying out the step of assigning release agent for 2 times or more
The mold release treatment method of continuous property.Every progress primary the step of assigning release agent, just carry out the step for keeping release agent dry.Cause
This, in the mold release treatment method recorded in International Publication No. 2012/133390, can also be come by using common device into
Row assigns the step of release agent and release agent drying steps the two steps to improve manufacturing yield.By International Publication No. 2012/
No. 133390 all disclosures are continued to use for reference in this manual.
(embodiment two)
To in embodiments of the present invention two mold release treatment method and demoulding processing unit be illustrated.Hereinafter, with this
Mold release treatment method in embodiment and the mold release treatment method in demoulding processing unit and embodiment one and demoulding are handled
It is illustrated centered on the difference of device.
In mold release treatment method involved in embodiment two, generate air-flow 105 the step of comprising supply contain solvent
The step of gas, the solvent can be such that fluorine compounds contained in release agent dissolve.The solvent of gasification be, for example, and institute in release agent
The identical solvent of the solvent contained.The solvent of gasification can also be the solvent different from solvent contained in release agent.The solvent of gasification
As long as such as the solvent that the fluorine system compound contained in release agent with release property can be made to dissolve.
Mold release treatment method involved in embodiment according to the present invention two can be to table as shown in experimental example below
It is uneven without generating it that there is the surface of the mold of porous alumina layer to carry out demoulding processing in face.It especially, can anti-anti-avulsion
It is generated in mould agent drying steps uneven.
In mold release treatment method involved in embodiments of the present invention two, due to containing the solvent of gasification in air-flow 105,
Therefore can have the effect of that the rate of drying for making release agent slows down.It, sometimes can be than embodiment one as shown in following experimental example
Mold release treatment method more efficiently prevents from uneven generation.
The air-flow feedway 55 of the demoulding processing unit of the carry out mold release treatment method of present embodiment also has for example
Container (such as flask (flask)).The mouth of container and the steam introducing port being located between HEPA filter 54 and filter 53 connect
Knot.If solvent is put into container, solvent meeting spontaneous vaporization, so as to supply the air-flow 105 of the solvent containing gasification.Alternatively,
Gas (such as nitrogen or air) is imported by the way that solvent is put into flask, in the solvent into flask and makes its blistering, can make gas
Solvent containing gasification in body.It can air-flow 105 of the supply containing the solvent to gasify.The steam introducing port for being linked to container can also be set
In the outside of HEPA filter 54 and filter 53.
Demoulding processing unit involved in embodiments of the present invention two is not limited to example described above.It can also be such as
Evaporating dish is arranged in the outside of filter 53.Solvent can also be put into evaporating dish and make its spontaneous vaporization, gasified using containing
The air of solvent generate air-flow 105.The container for being packed into solvent is not limited to evaporating dish, as long as inside is able to maintain liquid
Shape.The section of container can be such as U-shaped or V shape.The container for being packed into solvent can also be for example with the cover with cylindrical shape
The mode that the inside of body 52 connects is arranged.The container for being packed into solvent can also for example can be integrated with demoulding processing unit 50.For example,
When air-flow 105 flows to the situation of the 2nd opening 52b from the 1st opening 52a, the container for being packed into solvent is preferably located at cover 52
Near 1st opening 52a of inside.Alternatively, the solvent after gasification can also be made to spray from air nozzle (not shown) and be included in gas
In body.At this point, preferably making solvent become misty small particles and be sprayed to change the flowing of air-flow will not greatly
Mist.In turn, by passing through filter 53 after, it can get the air-flow 105 of homogenization.
(experimental example)
Hereinafter, indicating experimental example.It (a) of Fig. 2 and is shown for illustrating to carry out the demoulding processing unit after experimental example
It is intended to.As experimental example, implement demoulding processing using the mold release treatment method of the embodiment one or embodiment two.This
In, change the flow velocity of air-flow 105 and the presence or absence of the rotation speed of the ophthalmically acceptable mold 100 of moth and the solvent in air-flow 105, carries out
Demoulding processing.
The ophthalmically acceptable mold of moth used herein, such as be repeated by using the method recorded in above patent document 3 and 4
The anodic oxidation of aluminium base makes with etching.As aluminium base, the supporter (pipe of stainless steel making) in roll is used
The substrate for forming the aluminium film 18 with a thickness of 1 μm using sputtering method on surface and producing.The diameter of the bottom surface of aluminium base is
The length of 300mm, long axis direction are 1600mm, with a thickness of 15mm.
Using the substrate, first by carrying out anodic oxidation, and porous alumina layer is formed on the surface of aluminium film 18.Anode
In oxidation step, using oxalic acid aqueous solution (3 DEG C of concentration 0.05mol/L, liquid temperature), applies 80V and carry out 60 seconds.As electrode, make
With Pt plate.Electrode is 150mm at a distance from substrate.
Then, by being etched, porous alumina layer is completely removed.In etching step, phosphate aqueous solution (concentration is used
30 DEG C of 8mol/L, liquid temperature) it carries out 90 minutes.
Then, by anodization step and etching step alternately 5 times (anodic oxidation 5 times, etching 4 times).Anodic oxygen
Change in step, in the same manner as the above, using oxalic acid aqueous solution (3 DEG C of concentration 0.05mol/L, liquid temperature), applies 80V and carry out 60
Second.In etching step, carried out 20 minutes using phosphate aqueous solution (30 DEG C of concentration 8mol/L, liquid temperature).
The ophthalmically acceptable mold of the moth obtained by this method is formed with the multiple of depth 400nm or so, pore interval 180nm or so
Pore.
Then, as described below, carrying out moth eye using the mold release treatment method of above embodiment one or embodiment two
It is handled with the demoulding of mold.At this point, as described in Table 1, changing the flow velocity and moth eye of air-flow 105 in release agent drying steps
With the presence or absence of the solvent in the rotation speed and air-flow 105 of mold 100, implement demoulding processing.Here, the cover 52 used
The diameter of bottom surface be 500mm, the length of vertical direction is 2000mm.It is on vertical direction, cover 52 the 2nd opening 52b with
The distance between the lower end 100e of the ophthalmically acceptable mold 100 of moth L ((a) referring to Fig.1) is 200mm.
The flow velocity of air-flow 105 is to measure as follows.As Fig. 2 (a) and (b) shown schematically in, in cover 52
4 positions of inside be respectively set 2 kinds of current meters 120 (Beatrix Co., Ltd. manufacture, ultra micro air velocity transducer BS-03 and
BS-05).By the way that measurable flow rates 2 kinds of current meters different from each other are arranged, the flow velocity of wider scope can be measured.Fig. 2
(b) be from vertical direction observation demoulding processing unit 50 schematic cross sectional views.As shown in (b) of Fig. 2, in a circumferential direction
Equally spaced 4 positions, each 2 kinds of current meters 120 are set.4 positions of current meter 120, position on vertical direction are set
It sets mutually the same.The approximate centre of cover 52 is arranged in current meter 120 in the vertical direction.To the flow velocity of air-flow 105,4 are utilized
The current meter 120 at a position measures 3 times respectively, calculates its average value (that is, average value of total 12 data).
The flowing of air-flow 105 in release agent drying steps is observed using smoke-wire method, whether there is or not uneven for investigation air-flow 105
Property.As shown in (b) of Fig. 2, the high-resistance filament (resistive conductor) 110 of substantially semicircle shape is equipped in cover 52.In smoke-wire method
The cigarette beam generating apparatus MS-405 manufactured using Co., Ltd., Jian Yuan research institute.It is coated with atoleine on resistive conductor 110, is passed through
Electric current and generate white cigarette, make the flowing of air-flow 105 as it can be seen that the flowing of range estimation investigation air-flow 105 whether to generate inhomogeneities (disorderly
Disorderly).
To the surface of demoulding treated the ophthalmically acceptable mold 100 of moth, in the underface of fluorescent lamp, whether there is or not unevenness for range estimation investigation.
As a result as described in Table 1.
[table 1]
In table 1, " 〇 " indicates what the unevenness on the surface of the ophthalmically acceptable mold 100 of moth was suppressed to can to use without problems on practical
Degree.Specifically, indicating to generate length in uneven range, long axis direction from the 100e of lower end (in (a) of Fig. 6
L102a) be 20mm or less." ◎ " indicates not seeing the unevenness on the surface of the ophthalmically acceptable mold 100 of moth."×" and " △ " indicate to see
There is unevenness on to the surface of the ophthalmically acceptable mold 100 of moth, generates the length on long axis direction in uneven range, from the 100e of lower end
(L102a in (a) of Fig. 6) is spent more than 20mm." △ " compared to "×", the uneven degree on the surface of the ophthalmically acceptable mold of moth compared with
Gently.
By making the flowing of air-flow 105 as it can be seen that can confirm that the unevenness on the surface of the ophthalmically acceptable mold 100 of moth corresponds to air-flow
105 disorder and generate.Disorder is not generated in the flowing of the situation of " ◎ ", air-flow 105.In the situation of " 〇 ", the stream of air-flow 105
Though dynamic generate disorder, only the length on the long axis direction from the 100e of lower end (L102a in (a) of Fig. 6) be 20mm with
Under range in generate disorder.In "×" and the situation of " △ ", the flowing of air-flow 105 generates disorder, and generates the range of disorder
Length (L102a in (a) of Fig. 6) on long axis direction interior, from the 100e of lower end is more than 20mm.
According to table 1, the rotation speed of the ophthalmically acceptable mold 100 of moth is for example preferably 0.5rpm or more and 10rpm hereinafter, more
Preferably 1rpm or more and 10rpm or less.In table 1, in " rotation speed " column, while note have rotation speed (rpm) and by its
It is scaled speed (m/s) resulting value.As previously discussed, rpm be indicate each minute revolution unit, therefore, if by moth
The diameter of the bottom surface of ophthalmically acceptable mold 100 is set as 100d (m), then 1rpm is equivalent to (π × 100d)/60 (m/s).It is in rotation speed
In the experimental example of 30 (rpm), because rotation speed is big, so air-flow 105 generates disorder.
According to table 1, the flow velocity of air-flow 105 be for example preferably 0.016 (m/s) or more and 0.157 (m/s) below.When
When in air-flow 105 without the solvent to gasify, the flow velocity of air-flow 105 is for example more preferably 0.016 (m/s) or more and 0.126 (m/s)
Below.It is found that when the flow velocity of air-flow 105 is 0.157 (m/s), because of the solvent containing gasification in air-flow 105, so more effectively
Ground carries out the homogenization of the homogenization of air-flow 105 and the surface of the ophthalmically acceptable mold 100 of moth.It is 0.01 (m/s) in the flow velocity of air-flow 105
Experimental example in, be considered that flow velocity is small and air-flow 105 and it is unchanged uniformly.The experiment for being 0.471 (m/s) in the flow velocity of air-flow 105
In example, it is considered the generation disorder of air-flow 105 due to flow velocity is big.
If will be more than preferred range i.e. 0.016 (m/s) of the flow velocity with said flow 105 and 0.157 (m/s) following phase
The rotation speed (m/s) of the ophthalmically acceptable mold 100 of the moth of co-extensive is converted into rotation speed (rpm), then for 1rpm or more and 10rpm with
Under.If the diameter of the bottom surface of the ophthalmically acceptable mold 100 of moth is set as 100d (m), which is equivalent to (π × 100d)/60 (m/
S) more than and (π × 100d)/6 (m/s) below (that is, 0.05 × 100d (m/s) or more, 0.52 × 100d (m/s) or more).That is, can
Know, the rotation speed of the flow velocity of air-flow 105 and the ophthalmically acceptable mold 100 of moth is preferably the size of same levels.For example, air-flow 105
The rotation speed of flow velocity and the ophthalmically acceptable mold 100 of moth can also be same size.About its reason, present inventor is proceeded as follows
It investigates.
Consider the flow velocity v by air-flow 105f(m/s) with the rotation speed v of the ophthalmically acceptable mold 100 of mothr(m/s) general speed synthesized
vt(m/s).The flow velocity v of air-flow 105fWith the rotation speed v of the ophthalmically acceptable mold 100 of mothrDirection it is orthogonal.Therefore, vt 2=vf 2+
vr 2Relationship set up.The dry speed of release agent depends on vt(such as with vtIt is directly proportional).
Because considering the flow velocity v of air-flow 105fWith the rotation speed v of the ophthalmically acceptable mold 100 of mothrRelationship, so as extreme
Example, it is contemplated that two kinds of situations.In view of situation shown in (i) following formula (1-1)~(1-3) and (ii) following formula (2-1)~
Situation shown in (2-3).
[number 1]
vf=v (1-1)
vr=v (1-2)
[number 2]
vr=0 (2-2)
(i) and in (ii), so that vtThe identical mode of value, determine (ii) in vfCoefficient (formula (2-1)).At both
Under situation, for flow velocity vfGenerate when changing, general speed vtThe absolute value of variable quantity be compared.
Flow velocity vfVariation is avf.A is the real number for being more than 0.As 0 < a < 1, flow velocity v is indicatedfReduce, as a > 1, indicates stream
Fast vfIncrease.As a=1, flow velocity v is indicatedfIt is unchanged.About the general speed v under various situationstVariable quantity absolute value, when
To be indicated when (i) with following formula (3), indicated when for (ii) with following formula (4).
[number 3]
The chart of the difference of A and B is drawn out in expression in Fig. 3.As can be seen from FIG. 3, B is consistently greater than A (A is consistently less than B).Also
It is the general speed v in situation (i)tVariable quantity be consistently less than the situation of (ii).Therefore, the flow velocity v in situation (i)fIt produces
General speed v when changingtVariable quantity be less than the situation of (ii), the rate of drying of release agent is easy to keep uniform.
As previously discussed, the rotation speed of the flow velocity and the ophthalmically acceptable mold 100 of moth that can investigate out air-flow 105 is preferably mutually same
The reasons why size of grade.But it is above the investigation of present inventor, do not limit the present invention.
Then, the manufacturing step of the ophthalmically acceptable mold of moth is illustrated referring to Fig. 4.(a) of Fig. 4~(e) is for illustrating the ophthalmically acceptable mould of moth
The schematic cross sectional views of the manufacturing method of tool.In addition, in example below, by using with substrate 16 and being deposited on substrate 16
On the aluminium base 10 of aluminium film 18 carry out anodic oxidation and etching, to make the ophthalmically acceptable mold of flat moth.
Firstly, preparing aluminium base 10 as shown in (a) of Fig. 4.Aluminium base 10 has substrate 16 and is deposited on substrate 16
Aluminium film 18.
Then, as shown in (b) of Fig. 4, anodic oxidation is carried out to the surface (the surface 18s of aluminium film 18) of substrate 10, thus
Form the porous alumina layer 14 with multiple pore 14p (fine recess portion).Porous alumina layer 14 has with pore 14p
Porous layer and barrier layer.Porous alumina layer 14 for example by acidic electrolysis bath to surface 18s carry out anodic oxidation and
It is formed.Electrolyte used in the step of forming porous alumina layer 14, for example, containing from by oxalic acid, tartaric acid, phosphoric acid, chromium
The aqueous solution of the acid selected in the group that acid, citric acid and malic acid are constituted.For example, using oxalic acid aqueous solution (concentration
5 DEG C of 0.06wt%, liquid temperature), anodic oxidation in 30 seconds is carried out to apply voltage 80V to the surface 18s of aluminium film 18, is consequently formed porous
Alumina layer 14.By adjusting anodic oxidation condition (for example, type of electrolyte, apply voltage), pore interval, thin is adjusted
Depth, the shape of pore in hole etc..In addition, the thickness of porous alumina layer can be changed suitably.It can also make the sun completely of aluminium film 18
Pole oxidation.
Then, as shown in (c) of Fig. 4, with specified amount and making the etchant of 14 catalytic oxidation aluminium of porous alumina layer
It is etched, thus makes the borehole enlargement of pore 14p.It here, can substantially isotropism by using wet etching
(isotropic) porous wall and barrier layer are etched.By adjusting the type, concentration and etching period of etching solution, energy
It controls etch quantity (that is, size and depth of pore 14p).As etching solution, such as phosphoric acid of 10 mass % or ant can be used
The aqueous solution or chromium phosphoric acid mixed aqueous solution of the organic acids such as acid, acetic acid, citric acid.For example, by using phosphoric acid (concentration 1mol/
L, 30 DEG C of liquid temperature) etch within 25 minutes, expand pore 14p.
Then, as shown in (d) of Fig. 4, make the locally anodic oxidation of aluminium film 18 again, to make pore 14p in depth side
To growing up and porous alumina layer 14 made to thicken.Here, the growth of pore 14p be since the bottom of established pore 14p,
Therefore the side of pore 14p becomes ladder-like.
Followed by, as needed, by losing the etchant of 14 catalytic oxidation aluminium of porous alumina layer with further progress
It carves, thus makes the aperture further expansion of pore 14p.It is practical here preferably also to use above-mentioned etching solution as etching solution
On, as long as using identical etching solution.
As described, as shown in (e) of Fig. 4, can get by the way that above-mentioned anodization step and etching step is repeated
The ophthalmically acceptable mold 100 of moth with porous alumina layer 14, the porous alumina layer 14 have desired concaveconvex shape.Thereafter, moth
Ophthalmically acceptable mold 100 is used for after for example implementing demoulding processing using the mold release treatment method of embodiment one or embodiment two
Manufacture antireflection film.
In addition, being to use with substrate 16 and the aluminium base of the aluminium film being deposited on substrate 16 18 10 among the above
It is illustrated in case where making the ophthalmically acceptable mold of flat moth, but the ophthalmically acceptable mold of moth of roll can also be by using tool
The aluminium base of the supporter (such as pipe of stainless steel making) and the aluminium film being formed on the supporter of roll that have roll carries out
Anodic oxidation and etching are to make.In addition, the ophthalmically acceptable mold of the moth of roll can also make by the following method, that is, as substrate
16, using having flexible polymeric membrane, form aluminium film on polymeric membrane, carry out anodic oxidation to the surface of aluminium film, thus
It forms porous alumina layer and polymeric membrane is fixed on to the outer peripheral surface of the supporter of roll thereafter.
Then, referring to Fig. 5, illustrate the manufacturing method of the antireflection film of embodiment according to the present invention.Fig. 5 is to be used for
Illustrate the schematic cross sectional views that the method for antireflection film is manufactured in the way of roll-to-roll.
The manufacturing method of antireflection film involved in embodiments of the present invention, comprises the following steps: prepare by with
Upper any mold release treatment method implements the mold of demoulding processing；Prepare machined object；To the mold with it is described
In the state of assigning light-hardening resin between the surface of machined object, to the light-hardening resin irradiation light, thus make the light
Hardening resin hardening；And the antireflection film formed by the light-hardening resin after hardening is removed from the mold.
As machined object, if antireflection film can be manufactured in a manner of roll-to-roll using the film of roll.It is preferred that are as follows: film tool
The hard conating for having basilar memebrane and being formed on basilar memebrane, antireflection film are formed on hard conating.It, can be appropriate as basilar memebrane
Use such as TAC (Triafol T) film.As hard conating, the hard painting material of such as acrylic acid series can be used.
Firstly, preparing the ophthalmically acceptable mold 100 of moth of roll.For example, preparing to have passed through embodiment one or embodiment two
Mold release treatment method implements the ophthalmically acceptable mold 100 of moth of demoulding processing.
Then, as shown in figure 5, in the pressing of machined object 42 that surface is imparted to ultraviolet hardening resin 32 ' in moth eye
In the state of mold 100, ultraviolet light (UV) is irradiated to ultraviolet hardening resin 32 ', thus makes ultraviolet hardening resin 32 ' hard
Change.As ultraviolet hardening resin 32 ', such as acrylic resin can be used.Machined object 42 is, for example, that (three acetic acid are fine by TAC
Dimension element) film.Machined object 42 is rolled out from the roller (not shown) that rolls out, later, slit type coater is for example utilized to its surface
(slit coater) etc. assigns ultraviolet hardening resin 32 '.As shown in figure 5, machined object 42 is supported by support roller 46 and 48.
Support roller 46 and 48 has rotating mechanism, and transports machined object 42.In addition, the ophthalmically acceptable mold 100 of the moth of roll with be processed
The corresponding rotation speed of conveying speed of object 42, to being rotated with direction shown in arrow for Fig. 5.
Thereafter, the ophthalmically acceptable mold 100 of moth is separated into (removing) from machined object 42, as a result, in the surface shape of machined object 42
At the hardening nitride layer 32 of the concaveconvex structure (the moth ocular structure of reversion) transferred with the ophthalmically acceptable mold 100 of moth.Surface is formed with hardening thing
The machined object 42 of layer 32 is wound onto take-up roll (not shown).
In addition, in order to form the excellent antireflection film of antireflection property, the pore 14p of the ophthalmically acceptable mold 100 of moth from surface
Normal direction observation when two dimension be preferably sized to 10nm or more and not up to 500nm (above patent document 1,2 and 4), it is more excellent
It is selected as 50nm or more and not up to 500nm.
More than, it is to be illustrated for carrying out the situation of demoulding processing to the ophthalmically acceptable mold of moth, but it is involved in the present invention
The mold release treatment method of embodiment can be also used in the mold of other than the ophthalmically acceptable mold of moth, surface with porous alumina layer
In demoulding processing.For example, can be used in the demoulding processing for forming the mold of photonic crystal (photonic crystal).
In among the above, there is the film of moth ocular structure as surface, though antireflection film is illustrated, embodiments of the present invention
Related mold is not limited to this, and is widely portable in manufacture of the surface with the film of moth ocular structure.
In addition, among the above, though illustrate the ophthalmically acceptable mold of moth for being used to form moth ocular structure, embodiments of the present invention
Related mold is not limited to this, and can be widely used in such as being used to form the not sharp protrusion in end (such as nano-pillar)
In mold.That is, the shape of recess portion small possessed by the surface of mold involved in embodiments of the present invention is not limited to
Substantially circular cone, such as can also be the substantially frustum of a cone, it can also be substantially cylinder.The bottom of small recess portion is not limited to a little, such as
Fillet can also be had, can also be plane.The shape of the opening portion of small recess portion is not limited to justify, such as can also be rectangular-shaped.
In addition, multiple small recess portions both can be configured regularly, irregularly can also (randomly) configure.
[industrial availability]
Mold release treatment method according to the present invention can be used as the mold for being used to form antireflection film, photonic crystal etc.
Mold release treatment method.
Symbol description
14: porous alumina layer
50: demoulding processing unit
52: cover
52a: the 1 opening
52b: the 2 opening
53: filter
54:HEPA filter
55: air-flow feedway
56: pedestal
57: motor
57d: drive shaft
58: rotatable support structure body
100: the ophthalmically acceptable mold of moth
105: air-flow
Claims (10)
1. a kind of mold release treatment method, which is characterized in that comprise the following steps:
(a) preparing the release agent containing fluorine system compound and solvent with release property and surface has porous alumina layer
Cylindric or columned mold；
(b) surface of Xiang Suoshu mold assigns the release agent；And
(c) it is dry to make the release agent assigned in the step (b), and includes for drying steps: be by the mold arrangement,
Between the 1st opening and the 2nd opening of cylindric cover with the 1st opening and the 2nd opening, the axis of the mold
It is substantially parallel with the axis of the cover, and when from the axis direction of the mold, the center of the cover and the mold
In the state that center is substantially uniform, if the surface relative to the mold, in the section vertical with the axis of the mold
The diameter of the mold is D (m), then generates on one side in the direction parallel with the axis of the mold with the stream of at least 0.05D (m/s)
The air-flow of speed flowing, the step for rotating the mold centered on the axis of the mold with the rotation speed of at least 0.5rpm
Suddenly.
2. mold release treatment method as described in claim 1, which is characterized in that in the step (c), the rotation of the mold
Speed is 10rpm or less.
3. mold release treatment method as claimed in claim 1 or 2, which is characterized in that in the step (c), the air-flow
Flow velocity be 0.52D (m/s) below.
4. mold release treatment method as claimed in claim 1 or 2, which is characterized in that in the step (c), generate the gas
The step of the step of stream includes gas of the supply containing solvent, which can make the fluorine system chemical combination contained in the release agent
Object dissolution.
5. mold release treatment method as claimed in claim 4, which is characterized in that in the gas containing the solvent, contain and institute
State the identical solvent of the solvent contained in release agent.
6. mold release treatment method as claimed in claim 1 or 2, which is characterized in that the surface of the porous alumina layer has
The moth ocular structure of reversion, the two-dimentional size when moth ocular structure of the reversion has from normal to a surface direction are 50nm or more
And multiple recess portions of 500nm are not reached.
7. a kind of manufacturing method of antireflection film, which is characterized in that comprise the following steps:
Prepare the mold for implementing demoulding processing by mold release treatment method described in any one of claims 1 to 6；
Prepare machined object；
In the state of to light-hardening resin is assigned between the mold and the surface of the machined object, by hard to the light
Change resin irradiation light and hardens the light-hardening resin；And
The antireflection film formed by the light-hardening resin after hardening is removed from the mold.
8. a kind of demoulding processing unit comprising:
Cylindric cover, has the 1st opening and the 2nd opening, and surface has the cylindric or columned of porous alumina layer
When mold is with from the axis direction of the cover, the substantially uniform side with the center of the cover and the center of the mold
Between the 1st opening and the 2nd opening that formula configured in the cover；And
Rotatable support structure body, by the mold with the axis of the cover it is substantially parallel, can around the axis of the mold rotate, simultaneously
Constitute the mold in a manner of the rotation of the rotation speed of at least 0.5rpm；
Air-flow feedway, to be open from the described 1st for giving the substantially parallel air-flow of the axis of the cover, i.e. when described
When the diameter of the mold in the vertical section of the axis of mold is D (m), the air-flow of the flow velocity at least 0.05D (m/s)
Mode is constituted.
9. demoulding processing unit as claimed in claim 8, which is characterized in that the air-flow feedway, which has, is located at described the
The filter of 1 opening.
10. demoulding processing unit as claimed in claim 8 or 9, which is characterized in that the rotatable support structure body has horse
It reaches and the pedestal in conjunction with the drive shaft of the motor；
At least part of the pedestal is located between the 1st opening and the 2nd opening.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015116391 | 2015-06-09 | ||
| JP2015-116391 | 2015-06-09 | ||
| PCT/JP2016/066923 WO2016199764A1 (en) | 2015-06-09 | 2016-06-07 | Mold release method, method for manufacturing antireflective film, and mold release device |
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| Publication Number | Publication Date |
|---|---|
| CN107635740A CN107635740A (en) | 2018-01-26 |
| CN107635740B true CN107635740B (en) | 2019-11-19 |
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| JP (1) | JP6546992B2 (en) |
| CN (1) | CN107635740B (en) |
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| WO2012133390A1 (en) * | 2011-03-30 | 2012-10-04 | シャープ株式会社 | Mold release treatment method, and antireflective film production method |
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| JP2006213016A (en) * | 2005-02-07 | 2006-08-17 | Nitto Denko Corp | Manufacturing method of polyimide belt |
| JP2008238597A (en) * | 2007-03-27 | 2008-10-09 | Ricoh Co Ltd | Polyimide resin seamless belt, its manufacturing method and image forming device |
| JP2012169378A (en) * | 2011-02-10 | 2012-09-06 | Seiko Epson Corp | Composition for forming piezoelectric ceramics film, method for manufacturing piezoelectric element, and method for manufacturing liquid injection head |
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| Publication number | Publication date |
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| CN107635740A (en) | 2018-01-26 |
| WO2016199764A1 (en) | 2016-12-15 |
| JP6546992B2 (en) | 2019-07-17 |
| JPWO2016199764A1 (en) | 2018-03-29 |
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