CN102628969A - Sheet having uneven pattern formed thereon and method for production thereof - Google Patents
Sheet having uneven pattern formed thereon and method for production thereof Download PDFInfo
- Publication number
- CN102628969A CN102628969A CN2012101098436A CN201210109843A CN102628969A CN 102628969 A CN102628969 A CN 102628969A CN 2012101098436 A CN2012101098436 A CN 2012101098436A CN 201210109843 A CN201210109843 A CN 201210109843A CN 102628969 A CN102628969 A CN 102628969A
- Authority
- CN
- China
- Prior art keywords
- relief pattern
- sheet
- resin
- hard layer
- relief
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229920005989 resin Polymers 0.000 claims abstract description 252
- 239000011347 resin Substances 0.000 claims abstract description 252
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- 238000013459 approach Methods 0.000 claims description 91
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- 238000000034 method Methods 0.000 description 176
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
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- 239000002184 metal Substances 0.000 description 29
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 20
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- 239000002671 adjuvant Substances 0.000 description 4
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- 229910052732 germanium Inorganic materials 0.000 description 4
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0006—Arrays
- G02B3/0037—Arrays characterized by the distribution or form of lenses
- G02B3/005—Arrays characterized by the distribution or form of lenses arranged along a single direction only, e.g. lenticular sheets
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0006—Arrays
- G02B3/0037—Arrays characterized by the distribution or form of lenses
- G02B3/0043—Inhomogeneous or irregular arrays, e.g. varying shape, size, height
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0221—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Abstract
Disclosed is a sheet having an uneven pattern formed thereon, which comprises a base material comprising a resin and a hard layer formed on one surface of the base material and comprising a resin, wherein an uneven pattern is formed on the surface of the hard layer. In the sheet, the difference between the glass transition temperature (Tg2) of the resin constituting the hard layer and the glass transition temperature (Tg1) of the resin constituting the base material (Tg2 - Tg1) is 10 DEG C or more, and the average depth of the bottoms of the uneven pattern is 10% or more when the modal pitch is set as 100%. Also disclosed is a method for producing the sheet.
Description
The application be that on November 7th, 2007 (priority date is on February 21st, 2007 the earliest), application number are 200780051495.9 the applying date, denomination of invention divides an application for the application of " relief pattern forms sheet and manufacturing approach thereof ".
Technical field
The present invention relates to be disposed at the relief pattern formation sheet and the manufacturing approach thereof of diffuser.In addition, also relate to the diffuser of using relief pattern to form sheet.In addition, also relate to the diffuser manufacturing with operation sheet master, it is used as makes the surperficial mould use that is formed with the diffuser of relief pattern.Further, the manufacturing approach that also relates to diffuser.
The present invention relates to optical sheet and light diffusing patch as uses such as light diffusing patch.
The present invention relates to light diffusing diffusion light conductor that light source is sent.In addition, also relate to the back light unit that is disposed at liquid crystal indicator.
The present invention relates to be provided to the relief pattern formation sheet and the manufacturing approach thereof of optical elements such as antireflection object, polarizer.In addition, relate to antireflection object, the polarizer that uses relief pattern to form sheet.In addition, relate to the optical element manufacturing and use the operation sheet, it is used as the mould of making the optical element with relief pattern and uses.
The present invention requires the right of priority of following invention: on February 21st, 2007 spy in japanese publication be willing on June 7th, 2007-040694 number 1 the spy in japanese publication be willing on June 7th, 2007-151676 number 1 the spy in japanese publication be willing on June 7th, 2007-151677 number 1 the spy in japanese publication be willing to 2007-151795 number and on October 4th, 2007 spy in japanese publication be willing to the 2007-261176 patent, quote its content here.
Background technology
Usually the relief pattern that utilizes the surface to be formed with wavy relief pattern forms sheet as diffuser.
For example; In patent documentation 1; Disclose as the material that is formed with the diffuser of relief pattern, it is formed with a plurality of projection bodies at least one face of light transmission base material, and the height of projection body is 2～20 μ m; Be spaced apart 1～10 μ m between projection body summit, the length breadth ratio of projection body is more than 1.In addition, in patent documentation 1, also disclose, carried out method for processing through surface irradiation KrF PRK homenergic bundle to the light transmission base material as the method that forms the projection body.
In patent documentation 2, the diffuser that on a face, is formed with by the wavy concavo-convex anisotropic diffusion pattern that constitutes is disclosed.In addition; In patent documentation 2; Disclose as forming the anisotropy method of patterning, carried out laser radiation through film and make public, develop, formed and form irregular main hologram on the face photoresist; This main hologram is transferred to mould, utilizes this mould to come the method for shaping resin.
Patent documentation 1: japanese kokai publication hei 10-123307 communique
Patent documentation 2: TOHKEMY 2006-261064 communique
As the optical sheet with diffuse etc., known have the surface to form irregular.For example, in patent documentation 3, the light diffusing patch that is formed with a plurality of point-like protuberances at substrate surface is disclosed.Patent documentation 3 described optical sheets spray ink through ink-jet on substrate, form the protuberance of point-like through making the ink set.
Patent documentation 3: TOHKEMY 2004-157430 communique
The mode spacing (modal pitch) that known surface is formed with by the fine wavy concavo-convex relief pattern that constitutes, relief pattern is that the following relief pattern of wavelength of visible light forms sheet, can be used as optical elements such as antireflection object, polarizer and uses (with reference to non-patent literature 1).
Relief pattern forms sheet and can be used as the antireflection object utilization, is owing to following reason.
When the sheet surface is not provided with relief pattern,,, refractive index causes producing reflection because sharply changing at the interface of sheet and air.But on the surface of sheet, be that the layout setting of sheet and air is when having wavy relief pattern; In the relief pattern part; Refractive index be shown as air refraction and relief pattern form value between the refractive index of sheet (below; Be called middle refractive index), and this middle refractive index changes along the depth direction of relief pattern continuously.Particularly, the position is dark more, forms the refractive index of sheet more near relief pattern.Because middle refractive index changes like this continuously, rapid variation can not take place in the refractive index at above-mentioned such interface, can suppress reflection of light.In addition, the spacing of relief pattern is wavelength of visible light when following, partly is difficult for taking place visible diffraction of light at relief pattern, promptly by visible interference of light cause painted.
In addition, relief pattern form sheet can be used as the polarizer utilization be because, in the part of relief pattern, the mutually different air of refractive index disposes with relief pattern formation sheet alternately, the result manifests optical anisotropy to light.Further, the spacing of relief pattern identical with wavelength of visible light or be its when following, appear at the phenomenon that wide visible wavelength region shows equal phase differential.
Form the instantiation of sheet as such relief pattern; For example; In non-patent literature 2; Gold evaporation is to form metal level on a face of the warmed-up sheet that is made up of dimethyl silicone polymer in proposition, and cooling makes the sheet that is made up of dimethyl silicone polymer shrink then, obtains having formed at layer on surface of metal the sheet of wavy relief pattern.
In addition, in patent documentation 4, propose to form basalis and metal level successively, make the thermal shrinkage of heat-shrinkable film of synthetic resin then, obtain being formed with the sheet of wavy relief pattern at layer on surface of metal on the surface of heat-shrinkable film of synthetic resin.
In patent documentation 5, propose to form by meeting because the layer that exposure-processed causes the material of volumetric contraction to constitute through this layer is carried out exposure-processed, obtains forming irregular on the surface.
Yet the relief pattern that patent documentation 4,5 and non-patent literature 2 are put down in writing forms sheet, does not show excellent properties as optical element.Particularly, can't fully reduce reflectivity when using, in addition, when using, can't fully increase phase differential, can not produce equal phase differential in wide wavelength region may in addition as polarizer as antireflection object.
In addition, as making the method that relief pattern forms sheet, the known photoetching process of utilizing visible light that the use pattern mask is arranged.Yet this method can't be made the relief pattern with the spacing below the light wavelength that can be used as optical element and form sheet.Therefore, need utilization can carry out more ultraviolet laser interferometric method, the electron ray photoetching process of microfabrication.These methods are resist layer exposures of utilizing ultraviolet laser interference light, electron ray to make to form on the substrate, develop, and form the corrosion-resisting pattern layer, as mask, form concaveconvex shape through dry etching method etc. with this corrosion-resisting pattern layer.Yet, when being suitable for ultraviolet laser interferometric method, electron ray photoetching process, be difficult to the wide zone that surpasses 10cm is processed, there is the mass-produced problem that is not suitable for.
In addition, in patent documentation 6, propose on substrate, to dispose stratum granulosum, as etching mask, substrate surface is carried out the method for dry etching with stratum granulosum.Yet this method also is difficult to the wide zone that surpasses 30cm is processed, and has the mass-produced problem that is not suitable for.
Patent documentation 4: japanese kokai publication sho 63-301988 communique
Patent documentation 5: TOHKEMY 2003-187503 communique
Patent documentation 6: TOHKEMY 2005-279807 communique
Non-patent literature 1: chrysanthemum Tian Jiuxiong, rock Tagayasu Den one work, " optics ", and Japanese optics can be issued, the 27th volume, and No. 1,1998, p.12～17
Work such as non-patent literature 2:Ned Bowden, " Nature ", No. 393,1998, p.146
Summary of the invention
The problem that invention will solve
The diffuser that patent documentation 1,2 is put down in writing has enough diffuse.Yet patent documentation 1 is put down in writing passes through the method that energy beam shines, and patent documentation 2 is put down in writing passes through the problem that there is the method more complicated in method that laser makes public, develops the film of photoresist.In addition, the anisotropy of the diffusion of the diffuser of patent documentation 1,2 is insufficient.
In view of the foregoing, the object of the present invention is to provide can easy manufacturing the relief pattern that diffuser utilizes that can be used as form sheet.In addition, the object of the present invention is to provide the relief pattern that can easy manufacturing utilizes to form the manufacturing approach that the sheet relief pattern forms sheet as diffuser.In addition, the object of the present invention is to provide the excellent diffuser of anisotropy of diffusion.Further; The object of the present invention is to provide and can make the manufacturing approach of the diffuser manufacturing of diffuser with operation sheet and diffuser easy and in a large number, said diffuser is formed with relief pattern and forms the equal mode spacing of sheet and the relief pattern of mean depth.
Attempting through concavo-convex diffusion of light, the reflex time controlled; When if being spaced apart between jog is suitable with the light wavelength degree; Can produce because interference causes painted problem, in addition, during the exceedance 10 μ m of this interval; May produce can visual identification bright line etc., therefore expect being spaced apart below the 20 μ m between jog.Yet the optical sheet that patent documentation 3 is put down in writing if be spaced apart several 10 μ m～several 100 μ m between jog, can form stable interval, but want to obtain the interval below the 20 desired μ m, then difficulty relatively.
In addition,, make optical characteristics such as diffuse inhomogeneous sometimes, thereby its position in regulation is uprised or step-down becomes inhomogeneous for optical sheet.For example, employed LGP in the back light unit of liquid crystal indicator is in order to prevent to mirror on the LGP surface image of the linear light source that is configured in its side end face, with near the diffuse raising of the bright dipping side surface this linear light source of LGP.In addition, in liquid crystal indicator, use have a plurality of linear light sources, point source of light under during the type back light unit, it is improved from the diffuse directly over it between linear light source, the point source of light gradually.
Form irregular optical sheet for the surface; Inhomogeneous for its optical characteristics is adjusted into, consider to change the interval between jog according to the position, but the optical sheet of being put down in writing in the patent documentation 3; Interval between jog is made as below the 20 μ m; Then be difficult to changing at interval, therefore, thereby the optical sheet that patent documentation 3 is put down in writing is difficult to make optical characteristics to uprise or step-down becomes inhomogeneous at assigned position.
Therefore, the object of the present invention is to provide objective optics characteristic (diffuse etc.) excellence, and be easy to make the uneven optical sheet of optical characteristics.In addition, the object of the present invention is to provide the target light diffusive excellent, and be easy to make the uneven light diffusing patch of diffuse.
Because the light diffusion anisotropy of the diffusion light conductor put down in writing of patent documentation 1,2 is insufficient, the light that sends from the light source of the back light unit that possesses these diffusion light conductors can not be by anisotropic diffusion fully.Therefore, the brightness of the emergent light that penetrates from the diffusion light conductor is according to the position and difference, and the brightness meeting of the image of liquid crystal indicator is inhomogeneous.
The object of the present invention is to provide and to make the light that sends from light source the diffusion light conductor and the back light unit of anisotropic diffusion fully.
The object of the present invention is to provide the relief pattern that shows excellent properties when using to form sheet as optical elements such as antireflection object, polarizers.In addition, the object of the present invention is to provide the relief pattern that to make this relief pattern formation sheet in large area easy, and in large quantities to form the manufacturing approach of sheet.In addition, the object of the present invention is to provide the antireflection object of antiradar reflectivity, produce the polarizer of equal phase differential in wide wavelength region may.Further, the object of the present invention is to provide the optical element manufacturing of can be easy and making in large quantities use the operation sheet, said optical element is formed with mode spacing and the equal relief pattern of mean depth with relief pattern formation sheet.
The scheme that is used to deal with problems
The present invention comprises following scheme.
[1] a kind of relief pattern forms sheet; It is characterized in that; Said relief pattern forms sheet and has the resin system hard layer on resin base material and the face that is arranged on said base material; Be formed with along the relief pattern of a direction on said hard layer surface, constitute the glass transition temperature Tg of the resin of hard layer
2Glass transition temperature Tg with the resin that constitutes base material
1Poor (Tg
2-Tg
1) be more than 10 ℃, the mode spacing of relief pattern is for surpassing 1 μ m and below 20 μ m, being 100% o'clock with said mode spacing, and the mean depth of relief pattern bottom is more than 10%.
[2] a kind of relief pattern forms the manufacturing approach of sheet; It is characterized in that; Have on a face of resin base material, be provided with surface smoothing, thickness be to surpass the operation of 0.05 μ m and the resin system hard layer cambium layer compressing tablet below 5.0 μ m and makes the operation of the folded deformation of hard layer at least of said laminate, hard layer is made up of than the high resin more than 10 ℃ of the resin that constitutes base material glass transition temperature.
[3] form the manufacturing approach of sheet according to [2] described relief pattern, it uses single shaft direction heat shrink property film as resin base material, in the operation that makes the hard layer folded deformation, and zone of heating compressing tablet and single shaft direction heat shrink property film is shunk.
[4] a kind of diffuser, it possesses [1] described relief pattern and forms sheet, and base material and hard layer that said relief pattern forms sheet are transparent.
[5] a kind of relief pattern forms sheet; It is characterized in that said has resin base material and the hard layer that is arranged on the face of said base material, be formed with along the relief pattern of a direction on said hard layer surface; Hard layer is made up of metal or metallic compound; The mode spacing of relief pattern is for surpassing 1 μ m and below 20 μ m, with said mode spacing as 100% o'clock, the mean depth of relief pattern bottom is more than 10%.
[6] form sheet according to [5] described relief pattern, its hard layer is made up of metal.
[7] form sheet according to [5] described relief pattern, said metal is at least a kind of metal that is selected from the group of being made up of gold, aluminium, silver, carbon, copper, germanium, indium, magnesium, niobium, palladium, lead, platinum, silicon, tin, titanium, vanadium, zinc, bismuth.
[8] a kind of relief pattern forms sheet; It is characterized in that; Have on a face of resin base material, be provided with surface smoothing, thickness be to surpass the operation of 0.01 μ m and metallic below 0.2 μ m or metallic compound system hard layer cambium layer compressing tablet and makes the operation of the folded deformation of hard layer at least of said laminate, hard layer is made up of metal or metallic compound.
[9] a kind of [8] described relief pattern forms the manufacturing approach of sheet, and it uses single shaft direction heat shrink property film as resin base material, in the operation that makes the hard layer folded deformation, and zone of heating compressing tablet and single shaft direction heat shrink property film is shunk.
[10] a kind of diffuser manufacturing is with operation sheet master; It uses as the mould of making diffuser; It possesses the described relief pattern in [1], [5], [8] and forms sheet, and said diffuser is formed with on the surface and the equal mode spacing of said relief pattern and the relief pattern of mean depth.
[11] a kind of manufacturing approach of diffuser, it has following operation: on the face that be formed with relief pattern of [10] described diffuser manufacturing with operation sheet master, be coated with the operation of uncured curable resin; After said curable resin is solidified, with the operation of filming and peeling off after solidifying from operation sheet master.
[12] a kind of manufacturing approach of diffuser, it has following operation: the operation that the described diffuser manufacturing of sheet thermoplastic resin and claim 10 is contacted with the face that is formed with relief pattern of operation sheet master; Said sheet thermoplastic resin is pressed on the operation sheet master, and heating makes its softening, as to cool off then operation; With the operation that cooled sheet thermoplasticity resin is peeled off from operation sheet master.
[13] a kind of manufacturing approach of diffuser, it has following operation: on the face that be formed with relief pattern of the described diffuser manufacturing of claim 10 with operation sheet master, the transfer printing of lamination relief pattern is with the operation of material; Thereby peel off from aforementioned operation sheet master with material and make 2 operations operation with the shaping thing with being laminated to relief pattern transfer printing on the relief pattern; Contact on the face of a side at the relief pattern with said operation sheet master of said 2 operations, be coated with the operation of uncured curable resin with the shaping thing; After said curable resin is solidified, the operation that filming of solidifying peeled off with the shaping thing from 2 operations.
[14] a kind of manufacturing approach of diffuser is characterized in that, it comprises following operation: in [10] described diffuser manufacturing with the face laminated relief pattern transfer printing that is formed with relief pattern of operation sheet master operation with material; Thereby peel off from aforementioned operation sheet master with material and make 2 operations operation with the shaping thing with being laminated to relief pattern transfer printing on the relief pattern; Make sheet heat-curing resin and said 2 operations contact the operation of the face contact of a side with the relief pattern with aforementioned operation sheet master of shaping thing; Said sheet thermoplastic resin is pressed on 2 operations with on the shaping thing, and heating makes its softening, as to cool off then operation; With the operation that cooled sheet thermoplastic resin is peeled off with the shaping thing from 2 operations.
[15] a kind of optical sheet is characterized in that, on smooth one side or two sides, decentralized configuration has and has concavo-convex relief region.
According to [15] described optical sheet, it is characterized in that [16] its relief region is by configuration unevenly.
[17] a kind of light diffusing patch, it possesses [15] described optical sheet.
[18] according to [17] described light diffusing patch, the concavo-convex mode spacing A in its relief region is above 1 μ m and below 20 μ m, with respect to mode spacing A, the ratio (B/A) of concavo-convex mean depth B is 0.1～3.0.
According to [18] described light diffusing patch, it is characterized in that [19] its relief region is point-like and disperses.
[20] a kind of diffusion light conductor; It is characterized in that; This diffusion light conductor is made up of the transparent resin layer that on a face, is formed with the wavy relief pattern that crawls; The mode spacing of its relief pattern is above 1.0 μ m and below 20 μ m, with respect to mode spacing A, the ratio (B/A) of concavo-convex mean depth B is 0.1～3.0.
[21] a kind of back light unit; It is characterized in that; It has [20] described diffusion light conductor, reflecting plate and light source; The face of the opposite side of the face with being formed with relief pattern of said reflecting plate and this diffusion light conductor sets in opposite directions, and said light source is equipped between said diffusion light conductor and the said reflecting plate.
[22] a kind of back light unit; It is characterized in that; It has [20] described diffusion light conductor, reflecting plate and light source, and the face of the opposite side of the face with being formed with relief pattern of said reflecting plate and this diffusion light conductor sets in opposite directions, and any side of said light source and said diffusion light conductor is adjacent.
[23] a kind of relief pattern forms sheet; It is characterized in that; Said has resin base material and the resin system hard layer that is arranged at least a portion of said base material outside surface; Said hard layer is that the relief pattern with wavy relief pattern forms in the replacement page or leaf, constitutes the glass transition temperature Tg of the resin of hard layer
2Glass transition temperature Tg with the resin that constitutes base material
1Poor (Tg
2-Tg
1) be more than 10 ℃, the mode spacing of relief pattern is below the 1 μ m, is being 100% o'clock with said mode spacing, the mean depth of relief pattern bottom is more than 10%.
[24] a kind of relief pattern forms the manufacturing approach of sheet; It is characterized in that; Have the crawl operation of distortion of operation and the hard layer at least that makes the aforementioned layers compressing tablet that at least one part at the resin base material outside surface is provided with resin system hard layer and the cambium layer compressing tablet of surface smoothing, hard layer is made up of than the high resin more than 10 ℃ of the resin that constitutes base material glass transition temperature.
[25] a kind of antireflection object, it possesses [23] described relief pattern and forms sheet.
[26] a kind of polarizer, it possesses [23] described relief pattern and forms sheet.
[27] a kind of optical element sheet for manufacturing, it uses as mould of making optical element, and it possesses the characteristic that [23] described relief pattern forms sheet, and said optical element has and the equal mode spacing of said relief pattern and the relief pattern of mean depth.
The invention effect
Concavo-convex of formation of the present invention can be used as diffuser and uses, and can make easily.
Through the manufacturing approach of relief pattern formation sheet of the present invention, can make the relief pattern that uses as diffuser easily and form sheet.
The diffusion anisotropy of diffuser of the present invention is excellent.
Through the manufacturing approach of diffuser manufacturing of the present invention with operation sheet and diffuser, can make diffuser easy and in large quantities, it is formed with and the equal mode spacing of relief pattern sheet and the relief pattern of mean depth.
The objective optics excellent of optical sheet of the present invention, and be easy to make its optical characteristics inhomogeneous.
The target light diffusive of light diffusing patch of the present invention is excellent, and is easy to make its diffuse inhomogeneous.
Through diffusion light conductor of the present invention and back light unit, can make the light that sends from light source anisotropic diffusion fully.
Relief pattern of the present invention forms sheet, suits to use as optical elements such as antireflection object, polarizers.In addition, relief pattern of the present invention forms the manufacturing of also suitable do of sheet element and uses the operation sheet, is used to make the mould of the optical element with wavy relief pattern.
The manufacturing approach that relief pattern of the present invention forms sheet can easily form fine relief pattern in large area on the surface, therefore can make suitable relief pattern as optical element etc. easy and in large quantities and form sheet.
Antireflection object reflectivity of the present invention is low, excellent performance.
Polarizer of the present invention can produce equal phase differential, excellent performance in wide wavelength coverage.
The operation sheet is used in the optical element manufacturing of the application of the invention, can make optical element easy and in large quantities, and it has with relief pattern and forms the equal mode spacing of sheet and the relief pattern of mean depth.
Description of drawings
Fig. 1 shows the amplification stereogram that a part that relief pattern of the present invention is formed an embodiment of sheet has been amplified.
Fig. 2 is the sectional view after the relief pattern formation sheet edge direction vertical with the formation direction of relief pattern of Fig. 1 cut off.
Fig. 3 is to the take a picture greyscale transformation image of the image that obtains of the surface of relief pattern through the surface optics microscope.
Fig. 4 is that the image with Fig. 3 carries out the image that obtains behind the Fourier transform.
Fig. 5 is the chart that obtains with respect to the distance mapping from circle ring center with brightness in the image of Fig. 4.
Fig. 6 is to the boost line L in the image of Fig. 4
3On the chart that obtains of brightness mapping.
Fig. 7 representes that relief pattern of the present invention forms the sectional view of laminate of an embodiment of the manufacturing approach of sheet.
Fig. 8 is a figure that instance describes to the manufacturing approach of the diffuser of using relief pattern formation sheet of the present invention.
Fig. 9 is to the take a picture greyscale transformation image of the image that obtains of the surface of the relief pattern of comparative example 4 through the surface optics microscope.
Figure 10 is that the image with Fig. 9 carries out the image that obtains behind the Fourier transform.
Figure 11 is the figure that obtains with respect to the distance mapping from circle ring center with brightness in the image of Figure 10.
Figure 12 is to the boost line L in the image of Figure 10
5On the chart that obtains of brightness mapping.
Figure 13 is the stereographic map of the 1st embodiment of expression optical sheet of the present invention.
Figure 14 is the sectional view of the printed sheet used when making optical sheet shown in Figure 13 of expression.
Figure 15 is the transmission electron microscope photo on printed sheet surface.
Figure 16 is the transmission electron microscope photo on optical sheet surface.
Figure 17 is the stereographic map of the 2nd embodiment of expression optical sheet of the present invention.
Figure 18 is the stereographic map of the 3rd embodiment of expression optical sheet of the present invention.
Figure 19 is the stereographic map of the 4th embodiment of expression optical sheet of the present invention.
Figure 20 is the sectional view of other embodiments of expression diffusion light conductor of the present invention.
Figure 21 is the sectional view of the 1st embodiment of expression back light unit of the present invention.
Figure 22 is the sectional view of the 2nd embodiment of expression back light unit of the present invention.
Figure 23 is the amplification stereogram after the part of an embodiment of relief pattern formation sheet of the present invention is amplified in expression.
Figure 24 is the greyscale transformation image of the image that obtains not taking a picture along the surface of the relief pattern of specific direction through atomic force microscope.
Figure 25 is that the image to Figure 24 carries out the image that obtains behind the Fourier transform.
Figure 26 is the figure that brightness obtains with respect to the distance mapping from circle ring center in the image of Figure 25.
Reference numeral
10 relief patterns form sheet; The 10a laminate; 11 base materials (transparent resin layer); 11a heat shrink property film; 12 hard layers; The 12a relief pattern; The 12b bottom; The resin system hard layer of 13 surface smoothings (surface smoothing hard layer); 210a, 210b, 210c, 210d optical sheet; 211 smooth one sides; 212,215,216,217 relief region; 213 heat shrink property films; 214 relief region form uses protuberance; 100,200 back light units; 310 diffusion light conductors; 315 surfaces; 316 the insides; 320 reflecting plates; 330 light sources; 340 diffusion films; 350 prismatic lenses; 360 brightness rising films
Embodiment
1. relief pattern forms sheet
(relief pattern forms sheet-1)
An embodiment that relief pattern of the present invention is formed sheet describes.
The relief pattern that Fig. 1 and Fig. 2 show this embodiment forms sheet.The relief pattern of this embodiment forms sheet 10 and has the hard layer 12 on base material 11 and the face that is arranged at base material 11, and hard layer 12 has relief pattern 12a.
The relief pattern 12a that relief pattern forms sheet 10 has along roughly unidirectional wavy concavo-convex, and this is wavy concavo-convex for crawling.In addition, the top of the protuberance of the relief pattern 12a of this embodiment has slyness.
Constitute hard layer 12 resin (below be called the 2nd resin.) glass transition temperature Tg
2With the resin that constitutes base material 11 (below be called the 1st resin.) glass transition temperature Tg
1Poor (Tg
2-Tg
1) be more than 10 ℃, be preferably more than 20 ℃, more preferably more than 30 ℃.Through making (Tg
2-Tg
1) difference be more than 10 ℃, can be at Tg
2With Tg
1Between temperature under easily process.With Tg
2With Tg
1Between temperature during as processing temperature, can process under the Young modulus of base material 11 is than the high condition of the Young modulus of hard layer 12 making, the result forms relief pattern 12a easily on hard layer 12.
In addition, owing to consider, there is no need to use Tg from the economy aspect
2Surpass 400 ℃ resin, do not have Tg
1Be lower than-150 ℃ resin, therefore, preferred (Tg
2-Tg
1) be below 550 ℃, more preferably below 200 ℃.
Consider that from can easily forming relief pattern 12a under the processing temperature when making relief pattern formation sheet 10, the difference of the Young modulus of base material 11 and hard layer 12 is preferably 0.01～300GPa, more preferably 0.1～10GPa.
Here said processing temperature is meant, for example, after the relief pattern stated form the heating-up temperature when carrying out thermal shrinkage in the manufacturing approach of sheet.In addition, Young modulus is based on the value that JIS K 7113-1995 records.
The glass transition temperature Tg of the 1st resin
1Be preferably-150～300 ℃, more preferably-120～200 ℃.Because there is not glass transition temperature Tg
1Be lower than-150 ℃ resin, the glass transition temperature Tg of the 1st resin
1Be below 300 ℃ the time, processing temperature (Tg that can be when making relief pattern and form sheet 10
2With Tg
1Between temperature) under easily heat.
Under the processing temperature when making relief pattern formation sheet 10, the Young modulus of the 1st resin is preferably 0.01～100MPa, more preferably 0.1～10MPa.The Young modulus of the 1st resin is 0.01MPa when above, has to can be used as the hardness that base material 11 uses, and is 100MPa when following, has and can when hard layer 12 deforms, follow the pliability that it deforms.
As the 1st resin; For example can enumerate; Polyester such as polyethylene terephthalate; Polyolefin such as tygon, polypropylene, gathers resins such as cycloolefin at organic siliconresins such as polystyrene resins such as styrene-butadiene block copolymer, PVC, polyvinylidene chloride, dimethyl silicone polymer, fluororesin, ABS resin, polyamide, acrylic resin, polycarbonate.
The glass transition temperature Tg of the 2nd resin
2Be preferably 40～400 ℃, more preferably 80～250 ℃.Because, the glass transition temperature Tg of the 2nd resin
2Be more than 40 ℃ the time, can the processing temperature when making relief pattern and form sheet 10 be made as room temperature or more than the room temperature, thus useful, consider from the economy aspect, there is no need to use glass transition temperature Tg
2The resin that surpasses 400 ℃ is as the 2nd resin.
Under the processing temperature when making relief pattern and form sheet 10, the Young modulus of the 2nd resin is preferably 0.01～300GPa, 0.1～10GPa more preferably.Because; The Young modulus of the 2nd resin is that 0.01GPa is when above; Can obtain than the hardness more fully of the Young modulus under the processing temperature of the 1st resin; Have the enough hardness that is used to keep relief pattern after forming relief pattern 12a, consider that from the economy aspect resin that there is no need to use Young modulus to surpass 300GPa is as the 2nd resin.
As the 2nd resin; Though also the difference with the kind of the 1st resin can be used for example polyvinyl alcohol (PVA), polystyrene, acrylic resin, styrene-propene acid copolymer, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, PEN, polycarbonate, polyethersulfone, fluororesin etc.Wherein, consider preferred fluororesin from having antifouling property concurrently.
The thickness of base material 11 is preferably 0.3～500 μ m.The thickness of base material 11 is 0.3 μ m when above, and relief pattern forms sheet 10 and is difficult for brokenly, is 500 μ m when following, the slimming easily of relief pattern formation sheet 10.
In addition, thickness also can be set is that the resin system supporter of 5～500 μ m is used for support base material 11.In addition, higher in order to make diffuse as diffuser the time, can on base material 11, attach the film that contains micro air bubble.
When relief pattern is formed sheet 10 and uses as diffuser; With further raising light diffusion effect is purpose; The organic light diffusing agent that in base material 11, contains the light diffusing agent that is made up of mineral compound, is made up of organic compound can not arranged in the scope of big infringement optical characteristics such as light transmissions.
As inorganic light diffuser, can enumerate monox, white carbon, talcum, magnesium oxide, zinc paste, titanium dioxide, lime carbonate, hydrate of aluminium, barium sulphate, glass, mica etc.
As organic light diffusing agent, can enumerate styrenic particle, acrylic acid series polymeric compounds particle, siloxane-based polymers particle etc.These light diffusing agents can use separately, perhaps make up more than 2 kinds and use.
Never be prone to the infringement light transmission and consider that with respect to 100 mass parts the 1st resin, the content of light diffusing agent is preferably below 10 mass parts.
In addition, when relief pattern is formed sheet 10 as diffuser, be purpose with further raising diffusion effect, can in base material 11, contain micro air bubble not having in the scope of big infringement to optical characteristics such as light transmissions.Micro air bubble is difficult for reducing light transmission less to the absorption of light.
As the formation method of micro air bubble, be useful in the method (for example, japanese kokai publication hei 5-212811 communique, the disclosed method of japanese kokai publication hei 6-107842 communique) of sneaking into gas-development agent in the base material 11; The acrylic acid series Foamex is carried out foaming treatment make its method that contains micro air bubble (for example, the disclosed method of TOHKEMY 2004-2812 communique) etc.Further, consider, preferably make foam unevenly in the certain location method of (for example, the disclosed method of TOHKEMY 2006-124499 communique) of micro air bubble from carrying out more face irradiation uniformly.
In addition, can make up use aforementioned lights diffusion agent and micro air bubble.
The thickness of hard layer 12 is preferably above 0.05 μ m and below 5 μ m, more preferably 0.1～2 μ m.The thickness of hard layer is for surpassing 0.05 μ m and when 5 μ m are following, easily as after state such manufacturing relief pattern formation sheet.
In addition, be purpose to improve adaptation, to form finer structure, can between base material 11 and hard layer 12, form prime coat.
The mode spacing A that relief pattern forms the relief pattern 12a of sheet 10 is above 1 μ m and below 20 μ m, is preferably above 1 μ m and below 10 μ m.When mode spacing A is lower than 1 μ m, transmittance, when surpassing 20 μ m, the diffuse variation.
Be 100% o'clock with mode spacing A, the mean depth B of the bottom 12b of relief pattern 12a is (that is, length breadth ratio is more than 0.1) more than 10%, is preferably (that is, length breadth ratio is more than 0.3) more than 30%.With mode spacing A is 100%, and mean depth B is lower than at 10% o'clock, uses with operation sheet master as the diffuser manufacturing even relief pattern is formed sheet 10, also is difficult to obtain the high diffuser of diffuse.
In addition, considering from the viewpoint of easy formation relief pattern 12a, is being 100% o'clock with mode spacing A, and mean depth B is preferably (that is, length breadth ratio is below 3.0) below 300%, more preferably (that is, length breadth ratio is below 2.0) below 200%.
Here said bottom 12b is meant the minimum value of the recess of relief pattern 12a; Mean depth B is meant; When observing the cross section (with reference to Fig. 2) along its length relief pattern is formed after sheet 10 cuts off, from forming the whole parallel datum line L of face direction of sheet 10 with relief pattern
1Length B to each protuberance top
1, B
2, B
3... mean value (B
AV), and from datum line L
1Arrive the length b of the bottom of each recess
1, b
2, b
3... mean value (b
AV) poor (b
AV-B
AV).
The top of aforementioned protuberance and the bottom of aforementioned recess are the parts that the opposition side with base material 11 sides at hard layer 12 joins.
As the method for measuring mean depth B, adopt the image in the cross section of the relief pattern that obtains through the atomic force microscope photograph to measure the respectively degree of depth of bottom, try to achieve the method for their mean value.
From obtaining the viewpoint of the high diffuser of light diffusing anisotropy, preferred relief pattern 12a is crawling to a certain degree, and the spacing between adjacent protuberance is disperseed along the direction of relief pattern 12a.Here, the dispersion of the orientation of relief pattern 12a is called the degree of orientation.The degree of orientation is big more, is orientated overstepping the bounds of propriety loosing.This degree of orientation is tried to achieve through following method.
At first, through of the top photograph of surface optics microscope, be gray scale file (for example, tiff form etc.) with this image transformation to relief pattern.In the image (with reference to Fig. 3) of gray scale file, whiteness is low more, the bottom of expression recess darker (whiteness is high more, and the top of expression protuberance is high more).Then, the image to the gray scale file carries out Fourier transform.Fig. 4 shows the image behind the Fourier transform.The white portion that expands both sides from the center of the image of Fig. 4 to comprised relief pattern 12a spacing and towards information.
Then, the picture centre along continuous straight runs from Fig. 4 draws boost line L
2, to the mapping of the brightness on this boost line (with reference to Fig. 5).The transverse axis of the figure of Fig. 5 is represented the inverse of spacing, and the longitudinal axis is represented frequency, and the 1/X reciprocal of the value X that frequency is maximum representes the mode spacing of relief pattern 12a.
Then, in Fig. 4, draw and boost line L
2Boost line L perpendicular to value X part
3, to this boost line L
3On brightness mapping (with reference to Fig. 6).Wherein, for can more various concaveconvex structures, the transverse axis of Fig. 6 be divided by the numerical value after the value of X.The transverse axis of Fig. 6 is the index (orientation) of expression with respect to the inclined degree of concavo-convex formation direction (above-below direction among Fig. 3), and the longitudinal axis is represented frequency.In the mapping of Fig. 6, the half breadth W of peak value
1The degree of orientation of (frequency is the peak width on the height of a peaked half) expression relief pattern.Half value broadband W
1Big more, the spacing that expression is crawled is overstepping the bounds of propriety looses.
The above-mentioned degree of orientation is preferably 0.3～1.0.Owing to the degree of orientation is 0.3～1.0 o'clock, the dispersion of the spacing of relief pattern 12a is big more, this relief pattern is formed sheet become higher with the diffuse of using this relief pattern formation sheet as the diffuser of operation sheet master use.Because the degree of orientation surpasses at 1.0 o'clock, it is unordered that the direction of relief pattern becomes to a certain extent, though therefore diffuse can uprise, anisotropy has the tendency of step-down.
In order to make the degree of orientation is 0.3～1.0, when making relief pattern formation sheet, selects suitable method, makes it receive the effect of necessary compression stress.
Constitute the glass transition temperature Tg of the 2nd resin of hard layer 12
2Glass transition temperature Tg with the 1st resin that constitutes base material 11
1Poor (Tg
2-Tg
1) be that relief pattern of the present invention more than 10 ℃ forms sheet 10, can through after the relief pattern the stated manufacturing approach that forms sheet make, therefore can make easily.
In addition; The result found after the inventor etc. studied, and when base material 11 and hard layer 12 were all transparent, the mode spacing A that relief pattern of the present invention forms the relief pattern 12a of sheet 10 was above 1 μ m and below 20 μ m; With aforementioned mode spacing A is 100% o'clock; The mean depth B of the bottom 12b of relief pattern 12a is more than 10%, and it has sufficient diffuse, therefore can be used as diffuser and uses.
But relief pattern of the present invention forms the qualification that sheet does not receive above-mentioned embodiment.For example, the top of the protuberance of the relief pattern of relief pattern formation sheet of the present invention also can be sharp.Yet, consider that from the viewpoint that the anisotropy that makes diffusion becomes higher the shape of the protuberance of relief pattern is preferably the top and has slyness.
(relief pattern forms sheet-2)
Further; Research such as the inventor is the back result find, is below the 1 μ m through the mode spacing A that makes relief pattern 12a, below 0.04 μ m; With mode spacing A is 100% o'clock; The mean depth B of the bottom 12b of relief pattern 12a is more than 10%, when above, can bring into play excellent performance as optical element in particular for 100%.Particularly, reflectivity can be lower when finding relief pattern formed sheet 10 and uses as antireflection object, in addition, and can be when using at the wide equal phase differential of scope generation as polarizer.
This be because, the mode spacing A of relief pattern 12a is short like this below the 1 μ m, and is 100% o'clock with mode spacing A, mean depth B is dark like this more than 10%.That is, mode spacing A is short, and is identical with wavelength of visible light or be below it, is difficult for producing owing to concavo-convex visible diffraction of light, the diffusion that causes.And, elongated because mean depth B is dark along the middle refractive index continually varying part of thickness direction, can significantly bring into play the effect that suppresses the light reflection.In addition, because mode spacing A is short, mean depth B is dark, and along thickness direction, the part that mutually different air of refractive index and relief pattern formation sheet dispose each other is elongated, and the anisotropic part of display optical is elongated, therefore can produce phase differential.Further, roughly the same in wide scope by the phase differential of such relief pattern 12a generation.
At this moment, with respect to base material 11, the refractive index of hard layer 12 is low, but because can obtain high preventing reflection characteristic, so preferred.
Further, the thickness of hard layer 12 is preferably 1～100nm.The thickness of hard layer 12 is 1nm when above, and hard layer 12 is difficult for producing defectives, and thickness is 100nm when following, can fully guarantee the light transmission of hard layer 12.
In addition, the thickness of hard layer 12 more preferably below the 50nm, is preferably below the 20nm especially.The thickness of hard layer 12 is 50nm when following, states such relief pattern after making easily and forms sheet.
In addition, be purpose to improve adaptation, to form finer structure, can between base material 11 and hard layer 12, form prime coat.
Further, also can on hard layer 12, resin bed be set.
The mode spacing A that relief pattern forms the relief pattern 12a of sheet 10 is below the 1 μ m, is preferably below the 0.4 μ m.In addition, consider that from the viewpoint that can easily form relief pattern 12a mode spacing A is preferably more than the 0.05 μ m.
Each spacing A of relief pattern 12a
1, A
2, A
3... all be preferably mode spacing A ± 60% scope, in the scope more preferably ± 30%.Each spacing be mode spacing A's ± 60% scope in the time, spacing becomes evenly, can bring into play the more performance of excellence as optical element.
In addition, be under the condition below the 1 μ m satisfying mode spacing A, each spacing A
1, A
2, A
3... can change continuously.
Each depth B of relief pattern 12a
1, B
2, B
3... all be preferably mean depth B ± 60% scope in, in the scope more preferably ± 30%.Each spacing be mean depth B's ± 60% scope in the time, the degree of depth becomes evenly, can bring into play the more performance of excellence as optical element.
In addition, be that 100% o'clock mean depth B is under the condition more than 10% with mode spacing A, each depth B
1, B
2, B
3... can change continuously.
Of the back, relief pattern forms sheet 10 except going for optical element, optical element manufacturings such as antireflection object, polarizer with the operation sheet, can also be as utilizations such as super-hydrophobic or ultra hydrophilic sheet.
In addition, relief pattern forms the qualification that sheet does not receive above-mentioned embodiment.For example; In the above-mentioned embodiment; Hard layer has periodic wavy relief pattern along the Width that this relief pattern forms sheet, but except this relief pattern, also can have the periodic wavy relief pattern that forms the length direction of sheet along relief pattern.Further, in most cases, hard layer also can have not the wavy relief pattern along specific direction.Under these situations, because the mode spacing of relief pattern is below the 1 μ m, the former mode spacing of stating is 100% o'clock, and the mean depth of relief pattern bottom is more than 10%, shows excellent performance as optical element.
Consider that from the viewpoint of refractive index the top of protuberance is preferably sharp, but the top also can have slyness.
Relief pattern is tried to achieve the mode spacing through following method for not along specific direction the time.At first, through the top photograph of atomic force microscope, be gray scale file (for example, tiff form etc.) with this image transformation to relief pattern.
In the image (with reference to Figure 24) of gray scale file, whiteness is low more, the bottom of expression recess darker (whiteness is high more, and the top of expression protuberance is high more).Then, the image to the gray scale file carries out Fourier transform.Figure 25 shows the image behind the Fourier transform.In the image behind Fourier transform, the directivity of the direction indication gray scale of observing from the center of white portion, in addition, the inverse of the distance from the center to the white portion is represented the cycle of gray level image.Relief pattern becomes the image of white annulus shown in figure 25 during not along specific direction.Then, the boost line L that on the image behind the Fourier transform, draws linearity laterally from circle ring center
2, with brightness (Y axle) with respect to excentric distance (X axle) mapping (with reference to Figure 26).Then, read the value r that shows peaked X axle among this figure.The inverse of this r (1/r) is the mode spacing.
(relief pattern forms sheet-3)
The relief pattern that is easy to get calmly forms the viewpoint of sheet 10 to be considered, when hard layer 12 is made up of metal or metallic compound, and preferable alloy.
Do not become too high from Young modulus; The viewpoint that forms relief pattern 12a is more easily considered; As metal, be preferably at least a kind of metal that is selected from the group of forming by gold, aluminium, silver, carbon, copper, germanium, indium, magnesium, niobium, palladium, lead, platinum, silicon, tin, titanium, vanadium, zinc, bismuth.Here said metal also comprises semimetal.
Because same reason; As metallic compound, be preferably at least a kind of metallic compound that is selected from the group of forming by titanium dioxide, aluminium oxide, zinc paste, magnesium oxide, tin oxide, cupric oxide, indium oxide, cadmium oxide, massicot, monox, barium fluoride, calcium fluoride, magnesium fluoride, zinc sulphide, gallium arsenide.
In addition, when hard layer 12 was made up of metal, laminar surface can oxidation by air form the air oxidation film, but in the present invention, the layer after such layer on surface of metal oxidation by air is also regarded the layer that is made up of metal as.
The thickness of hard layer 12 be preferably surpass 0.01 μ m and below 0.2 μ m, 0.02～0.1 μ m more preferably.The thickness of hard layer is for above 0.01 μ m and when 0.2 μ m is following, and is of the back, makes relief pattern easily and form sheet.
In addition, be purpose to improve adaptation, to form finer structure, can between base material 11 and hard layer 12, form prime coat.
The mode spacing A that relief pattern forms the relief pattern 12a of sheet 10 is above 1 μ m and below 20 μ m, is preferably above 1 μ m and below 10 μ m.When mode spacing A is lower than 1 μ m, and when surpassing 20 μ m, though with relief pattern form sheet 10 as the diffuser manufacturing with the use of operation sheet master, also be difficult to obtain the high diffuser of diffuse.
2. relief pattern forms the manufacturing approach of sheet
An embodiment that relief pattern of the present invention is formed the manufacturing approach of sheet describes.
The manufacturing approach that the relief pattern of this embodiment forms sheet comprises following operation: as shown in Figure 7, the hard layer 13 that surface smoothing is set on the face as the heat shrink property film 11a of resin base material (below, be called surface smoothing hard layer 13.), the operation of cambium layer compressing tablet 10a (below, be called the 1st operation.) and make heat shrink property film 11a heat shrink, make laminate 10a the hard layer of surface smoothing at least 13 folded deformations operation (below, be called the 2nd operation.)。
Here, surface smoothing hard layer 13 is meant that the described center line average roughness of JIS BO601 is the layer below the 0.1 μ m.
The 1st operation-1
In the 1st operation; Resinous surface smoothing hard layer 13 is set and the method for cambium layer compressing tablet 10a on the face of heat shrink property film 11a; For example can enumerate; Be coated with machine etc. through spin coater, rod and be coated with the solution or the dispersion liquid of the 2nd resin, make the method for solvent seasoning then at the face of heat shrink property film 11a; Press the method for the surface smoothing hard layer of making in advance 13 etc. at the surface layer of heat shrink property film 11a.
As heat shrink property film 11a, for example can using, polyethylene terephthalate is shrinkable film, polystyrene shrinkable film, polyolefin shrinkable film, polyvinyl chloride shrinkable film etc.
In shrinkable film, preferably shrink 50～70% film.Use when shrinking 50～70% shrinkable film; Deformation rate can be for more than 50%; Can easily make relief pattern and form sheet 10; Make the mode spacing A of its relief pattern 12a be to surpass 1 μ m and below 20 μ m, be that the mean depth B of the bottom 12b of relief pattern 12a is more than 10% at 100% o'clock with mode spacing A.Further, also can easily make relief pattern and form sheet 10, make that it is with mode spacing A at 100% o'clock, the mean depth B of the bottom 12b of relief pattern 12a is more than 100%.
The deformation rate here is meant, (length before the distortion-distortion back length)/(length before the distortion) * 100 (%).Perhaps, (distortion back length)/(length before the distortion) * 100 (%).
In addition, through following operation, can make with mode spacing A is 100% o'clock, and the mean depth B of relief pattern 12a is 300%.
The coated glass transition temperature is lower than the primer resin layer of heat shrink property film 11a on heat shrink property film 11a, is formed on the laminate that is provided with surface hard smooth layer 13 on this primer resin layer.Thereby make this laminate heat shrink form relief pattern and form sheet.
Heat shrink property film 11a after the heat shrink is peeled off other the heat shrink property film of fitting again, cambium layer compressing tablet from laminate.Compare with making 1 heat shrink property film heat shrink,, can make mean depth B become big through making this laminate heat shrink.Through repeatedly repeating this operation, can be 100% o'clock with mode spacing A, the mean depth B of relief pattern 12a is 300%.
The thickness of surface smoothing hard layer 13 of the present invention is for surpassing 0.05 μ m and below 5.0 μ m, being preferably 0.1～1.0 μ m.Through the thickness that makes surface smoothing hard layer 13 is in the aforementioned range, can guarantee that the mode spacing A of relief pattern 12a is in above 1 μ m and the scope below 20 μ m really.
Yet the thickness of surface smoothing hard layer 13 is 0.05 μ m when following, and mode spacing A may become below the 1 μ m, and when surpassing 5 μ m, mode spacing A may surpass 20 μ m.
In addition, surface smoothing hard layer 13 of the present invention is made up of than the high resin (the 2nd resin) more than 10 ℃ of the resin that constitutes heat shrink property film (the 1st resin) glass transition temperature.The glass transition temperature through making the 1st resin and the glass transition temperature of the 2nd resin are aforementioned relation, the mode spacing A of relief pattern 12a is in really surpasses 1 μ m and the scope below 20 μ m.
The thickness of surface smoothing hard layer 13 also can change continuously.When the thickness of surface smoothing hard layer 13 was variation continuously, the spacing of the relief pattern 12a that the compression back forms and the degree of depth were variation continuously.
In order more easily to form relief pattern 12a, the Young modulus of the surface smoothing hard layer 13 of this manufacturing approach is preferably 0.01～300GPa, more preferably 0.1～10GPa.
When making laminate 10a distortion, preferably make 13 distortion of surface smoothing hard layer with the deformation rate more than 5%.When making 13 distortion of surface smoothing hard layer with the deformation rate more than 5%, can be 100% o'clock with mode spacing A easily, the mean depth B of the bottom 12b of relief pattern 12a be more than 10%.
Further, more preferably make 13 distortion of surface smoothing hard layer with the deformation rate more than 50%.When making 13 distortion of surface smoothing hard layer with the deformation rate more than 50%, can be 100% o'clock with mode spacing A easily, the mean depth B of the bottom 12b of relief pattern 12a be more than 100%.
The 1st operation-2
In addition, when hard layer 12 is made up of metal or metallic compound,, for example can enumerate the method for evaporation metal, metallic compound on the face of heat shrink property film 11a as the method for cambium layer compressing tablet 10a; Press the method for the surface smoothing hard layer of making in advance 13 etc. at the surface layer of heat shrink property film 11a.
In order to make this manufacturing approach can more easily form relief pattern 12a, the Young modulus of surface smoothing hard layer 13 is preferably 0.1～500GPa, more preferably 1～150GPa.
For the Young modulus that makes surface smoothing hard layer 13 in aforementioned range, surface smoothing hard layer 13 preferably is made up of the a kind of metal that is selected from the group that gold, aluminium, silver, carbon, copper, germanium, indium, magnesium, niobium, palladium, lead, platinum, silicon, tin, titanium, vanadium, zinc, bismuth form at least.Perhaps, surface smoothing hard layer 13 preferably is made up of the a kind of metallic compound that is selected from the group that titanium dioxide, aluminium oxide, zinc paste, magnesium oxide, tin oxide, cupric oxide, indium oxide, cadmium oxide, massicot, monox, barium fluoride, calcium fluoride, magnesium fluoride, zinc sulphide, gallium arsenide form at least.
Here, Young modulus is based on " the high temperature Young modulus test method of metal material " of JIS Z 2280-1993, is the value that records under 23 ℃ with temperature change.When hard layer is made up of metallic compound too.
The thickness of surface smoothing hard layer 13 is for surpassing 0.01 μ m and below 0.2 μ m, being preferably 0.02～0.1 μ m.Through the thickness that makes surface smoothing hard layer 13 is in the aforementioned range, can guarantee that the mode spacing A of relief pattern 12a is in above 1 μ m and the scope below 20 μ m really.Yet when the thickness of surface smoothing hard layer 13 was lower than 0.01 μ m, mode spacing A became below the 1 μ m, and when surpassing 0.2 μ m, mode spacing A surpasses 20 μ m.
In addition, the thickness of surface smoothing hard layer 13 also can change continuously.When the thickness of surface smoothing hard layer 13 was variation continuously, the spacing of the relief pattern 12a that the compression back forms and the degree of depth were variation continuously.
When making laminate 10a distortion, preferably make 13 distortion of surface smoothing hard layer with the deformation rate more than 5%.When making 13 distortion of surface smoothing hard layer with the deformation rate more than 5%, can be 100% o'clock with mode spacing A easily, the mean depth B of the bottom 12b of relief pattern 12a be more than 10%.
Further, more preferably make 13 distortion of surface smoothing hard layer with the deformation rate more than 50%.When making 13 distortion of surface smoothing hard layer with the deformation rate more than 50%, can be 100% o'clock with mode spacing A easily, the mean depth B of the bottom 12b of relief pattern 12a be more than 100%.
The 2nd operation-1
In the 2nd operation, through making heat shrink property film 11a thermal shrinkage, on surface smoothing hard layer 13, form wavy relief pattern 12a along the direction vertical with shrinkage direction, obtain hard layer 12.
Heating means when making heat shrink property film 11a heat shrink can be enumerated hot blast, steam or the method in hot water, passed through etc., wherein, consider the method for preferably in hot water, passing through from the viewpoint that film is evenly shunk.
Heating-up temperature when making heat shrink property film 11a thermal shrinkage is preferably according to kind and the spacing of target relief pattern 12a and the appropriate depth selection of bottom 12b of the heat shrink property film that uses.
In this manufacturing approach, the thickness of surface smoothing hard layer 13 is thin more, and the Young modulus of surface smoothing hard layer 13 is low more, and then the mode spacing A of relief pattern 12a becomes more little, and the deformation rate of base material is high more, and it is dark more that mean depth B becomes.Therefore, in order to make mode spacing A, the mean depth B of relief pattern 12a, need the suitable aforementioned condition of selecting for regulation.
More than the relief pattern of explanation forms the manufacturing approach of sheet; Because the glass transition temperature of the 2nd resin of formation surface smoothing hard layer 13 is higher more than 10 ℃ than the 1st resin that constitutes heat shrink property film 11a; Under the temperature between the glass transition temperature of the glass transition temperature of the 1st resin and the 2nd resin, it is higher than heat shrink property film 11a that the Young modulus of surface smoothing hard layer 13 becomes.And; Because the thickness of surface smoothing hard layer 13 is above 0.05 μ m and below 5.0 μ m; Under the temperature between the glass transition temperature of the glass transition temperature of the 1st resin and the 2nd resin, add man-hour, along with the increase of thickness, surface smoothing hard layer 13 also takes place folding.Further, owing to surface smoothing hard layer 13 is laminated on the heat shrink property film 11a, so the stress that the contraction of heat shrink property film 11a produces is distributed in whole equably.Therefore,, surface smoothing hard layer 13 folded deformations can be made, relief pattern formation sheet 10 can be made easy and in large area as the excellent performance of diffuser through the present invention.
And, through this manufacturing approach, can easily make the mode spacing A of relief pattern 12a surpass 1 μ m and below 20 μ m, make with mode spacing A to be at 100% o'clock, the mean depth B of the bottom 12b of relief pattern 12a is more than 10%.
In addition, as the manufacturing approach of relief pattern formation sheet, the method for following (1)～(4) also can be suitable for.
(1) whole at base material 11 is provided with surface smoothing hard layer 13, cambium layer compressing tablet 10a, the method that a laminate 10a integral body direction is surfacewise compressed.
When the glass transition temperature of base material 11 is lower than room temperature; The compression of laminate 10a is at room temperature carried out; The glass transition temperature of base material 11 is room temperature when above, and being compressed in the glass transition temperature that is higher than base material 11 and being lower than under the temperature of glass transition temperature of surface smoothing hard layer 13 of laminate 10a carried out.
(2) whole at base material 11 is provided with surface smoothing hard layer 13; Cambium layer compressing tablet 10a; Along a direction tensile layer compressing tablet 10a, its vertical direction along draw direction is shunk, thus the method that makes surface smoothing hard layer 13 a direction compression surfacewise.
When the glass transition temperature of base material 11 is lower than room temperature; The stretching of laminate 10a is at room temperature carried out; The glass transition temperature of base material 11 is room temperature when above, and being stretching in the glass transition temperature that is higher than base material 11 and being lower than under the temperature of glass transition temperature of surface smoothing hard layer 13 of laminate 10a carried out.
(3) at the base material that forms by uncured ionization radial line curable resin 11 laminated surface smoothing hard layers 13; Cambium layer compressing tablet 10a; Come curing substrate 11 through the irradiation ionization radial line; Base material 11 is shunk, thereby make the method for surface smoothing hard layer 13 at least one direction compression surfacewise of base material 11 laminated.
(4) through solvent swell and on the dilated base material 11; The level and smooth hard layer 13 of laminating surface; Cambium layer compressing tablet 10a, the solvent of removing in the base material 11 through drying shrinks laminate 10a, thereby makes surface smoothing hard layer 13 at least one the direction compression surfacewise that is laminated on the base material 11.
In method (1), as the method for cambium layer compressing tablet 10a, for example can enumerate, be coated with the solution or the dispersion liquid of coating resin on a face of base material 11 such as machine through spin coater, rod, make the method for solvent seasoning again; Method of the surface smoothing hard layer of making in advance in a face laminated of base material 11 13 etc.
As the method that makes direction compression surfacewise of laminate 10a integral body, for example can enumerate, with end of holding sheet compressing tablet 10a such as vice and with the end of its opposition side, make the method for its compression etc.
In method (2), as along the method for a direction tensile layer compressing tablet 10a, for example, with the method for the end of the end of drawing machine tensile layer compressing tablet 10a and its opposition side etc.
In method (3), can enumerate ultraviolet curing resin, electron ray curing type resin etc. as the ionization radial line curable resin.
In method (4), solvent is according to suitable selection of kind of the 1st resin.Select the The suitable solvent baking temperature according to solvent types.
Surface smoothing hard layer 13 in method (2)～(4) can use and the middle identical composition of material that uses of method (1), can be identical thickness.In addition, the formation method of laminate 10a can be the same with method (1), is useful in the face coating resin solution or the dispersion liquid of base material 11, makes the method for solvent seasoning again; The method of the surface smoothing hard layer of making in advance in a face laminated of base material 11 13.
The 2nd operation-2
The mode spacing A of relief pattern 12a is 1 μ m when following, and for method (1), the thickness of surface smoothing hard layer 13 is preferably below the 50nm, more preferably below the 20nm.The thickness of surface smoothing hard layer 13 is 50mm when following, and the mode spacing A of relief pattern 12a can be below the 1 μ m really.
In addition, the viewpoint consideration that the hard layer 12 after compression is difficult for producing defective, surface smoothing hard layer 13 is preferably more than the 1nm.
At this moment, surface smoothing hard layer 13 is made up of than high the 2nd resin more than 10 ℃ of the 1st resin glass transition temperature.Through surface smoothing hard layer 13 is made up of than high the 2nd resin more than 10 ℃ of the 1st resin glass transition temperature; When compression, make base material 11 distortion; And make surface smoothing hard layer 13 form the distortion of crawling of wavy bending, can easily form relief pattern 12a.
Relief pattern in above explanation forms in the manufacturing approach of sheet; Because the glass transition temperature of the 2nd resin of formation surface smoothing hard layer 13 is higher more than 10 ℃ than the 1st resin that constitutes base material 11; Under the temperature between the glass transition temperature of the glass transition temperature of the 1st resin and the 2nd resin, the Young modulus of surface smoothing hard layer 13 becomes than base material 11 height.Therefore, under the temperature between the glass transition temperature of the glass transition temperature of the 1st resin and the 2nd resin, add man-hour, along with the increase of thickness, surface smoothing hard layer 13 also takes place folding.Further, because surface smoothing hard layer 13 is laminated on the base material 11, be distributed in integral body equably owing to compress, shrink the stress that produces.Therefore,, can easily make its distortion of crawling, make relief pattern and form sheet 10, can make relief pattern formation sheet 10 easy and in large area as the excellent performance of optical element through the present invention.
And,, can easily make the mode spacing A of relief pattern 12a shorten, and make mean depth B deepen through this manufacturing approach.Particularly, can make easily that the mode spacing A of relief pattern 12a is below the 1 μ m, be 100% o'clock with mode spacing A, and the mean depth B of the bottom 12b of relief pattern 12a is more than 10%.
Further, through this manufacturing approach, can easily make each spacing A among the relief pattern 12a
1, A
2, A
3... with each depth B
1, B
2, B
3... evenly.
The 2nd operation-3
As making the surface smoothing hard layer; When using metal or metallic compound to make, in the 2nd operation, through making heat shrink property film 11a thermal shrinkage; On the direction vertical of surface smoothing hard layer 13, form wavy relief pattern 12a, obtain hard layer 12 with shrinkage direction.
Heating means when making heat shrink property film 11a heat shrink can be enumerated hot blast, steam or the method in hot water, passed through etc., wherein, consider the method for preferably in hot water, passing through from making its viewpoint of evenly shrinking.
Heating-up temperature when making heat shrink property film 11a thermal shrinkage is preferably according to kind and the spacing of target relief pattern 12a and the appropriate depth selection of bottom 12b of the heat shrink property film that uses.
In this manufacturing approach, the thickness of surface smoothing hard layer 13 is thin more, and the Young modulus of surface smoothing hard layer 13 is low more, and then the mode spacing A of relief pattern 12a becomes more little, and the deformation rate of base material is high more, and then mean depth B becomes dark more.Therefore, in order to make mode spacing A, the mean depth B of relief pattern 12a, need the suitable aforementioned condition of selecting for regulation.
Relief pattern in above explanation forms in the manufacturing approach of sheet; Because the Young modulus of the surface smoothing hard layer 13 that is made up of metal or metallic compound is much larger than heat shrink property film 11a; Hot compression is during than the hard surface smoothing hard layer 13 of heat shrink property film 11a; It also takes place folding when thickness increases.Further, because surface smoothing hard layer 13 is laminated on the heat shrink property film 11a, heat shrink property film 11a shrinks the stress that produces and is distributed in integral body equably.Therefore,, can make surface smoothing hard layer 13 folded deformations through the present invention, can be easy and the relief pattern of making the excellent performance of the engineering sheet that is used to make diffuser in large area form sheet 10.
And, through this manufacturing approach, can easily make the mode spacing A of relief pattern 12a surpass 1 μ m and below 20 μ m, make to be at 100% o'clock with mode spacing A, the mean depth B of the bottom 12b of relief pattern 12a is more than 10%.
In addition, all the time, form the method with sheet as making relief pattern, known have nano impression with the relief pattern of mould by after being pressed on the thermoplastic sheet thermoplastic resin, makes the hot nano impression method of its cooling; After being covered with uncured ionization radial line curable resin constituent on the relief pattern of nano impression with mould, the irradiation ionization radial line makes the light nano impression method of its curing.
Hot nano impression method need apply uniform pressure to mold integral, on thermoplastic resin, pushes the mould with relief pattern, in such method; When the area of mould becomes big; The mould applied pressure is become inhomogeneous, and the result can cause the transfer printing of relief pattern to become inhomogeneous.Therefore, be inappropriate for the production that employed large-area relief pattern in the display screen etc. of LCD TV forms sheet.
In addition, in light nano impression method,, cause the transfer printing of relief pattern to become incomplete because the release property of mould and cured resin is not enough.And the reusable number of times of mould is many more, and this tendency is obvious more.
With respect to these nano impression methods, above-mentioned relief pattern forms the manufacturing approach of sheet because therefore the transfer printing that can omit relief pattern can solve the problems referred to above that the nano impression method exists.
In addition; Though above-mentioned embodiment is whole at base material hard layer is set; But also can hard layer be set, can hard layer all be set, can also hard layer be set in the part on the two sides of base material at the whole face on the two sides of base material in the part of a face of base material.
3. diffuser
Diffuser of the present invention has mode spacing A for surpassing 1 μ m and the above-mentioned relief pattern formation sheet 10 below 20 μ m.
For diffuser of the present invention, also can form face of sheet 10 or the layer that the two sides has other at relief pattern.For example, form at relief pattern on the face that is formed with relief pattern 12a one side of sheet 10, containing in order to prevent that this face is contaminated with fluororesin or organic siliconresin is that the thickness of principal ingredient is the stain-proofing layer about 1～5nm.
In addition, also can on the face of base material 11 1 sides of diffuser, possess transparent resin system or glass supporter.
Further, also can on the face of base material 11 1 sides, form bond layer, suitable functional for it is had, also can contain pigment.
Above-mentioned have the diffuser of the present invention that relief pattern that the surface is formed with relief pattern forms sheet 10 and have sufficient diffuse.
4. the diffuser manufacturing is with the manufacturing approach of operation sheet master and diffuser
Diffuser manufacturing of the present invention with operation sheet master (below, be called operation sheet master.) possess above-mentioned relief pattern and form sheet 10; Through method shown in following; 12a is transferred to other materials with relief pattern; As can being used for large tracts of land and making the mould of diffuser in large quantities, this diffuser is formed with on the surface and the equal mode spacing of this operation sheet master and the relief pattern of mean depth.
Operation sheet master can further possess resin system or the metallic supporter that is used to support relief pattern formation sheet 10.
As using operation sheet master to make the concrete grammar of diffuser, for example can enumerate the method for following (a)～(c).
(a) has the method for following operation: on the face that is formed with relief pattern of operation sheet master; Be coated with the operation of uncured ionization radial line curable resin; And the irradiation ionization radial line, make aforementioned curable resin solidify the operation of filming and peeling off that will solidify then from operation sheet master.Here, ionization radial line typically refers to ultraviolet ray or electron ray, but the present invention also comprises luminous ray, X ray, ion irradiation etc.
(b) has the method for following operation: on the face that is formed with relief pattern of operation sheet master; Be coated with the operation of uncured liquid thermosetting resin; And heating makes aforementioned liquid thermosetting resin solidification, the operation of filming and peeling off from operation sheet master that will solidify then.
(c) has the method for following operation: the operation that the face that is formed with relief pattern of operation sheet master is contacted with the sheet thermoplastic resin; With this sheet thermoplastic resin is pressed on operation sheet master, and heating makes it softening, then the operation of cooling; And the operation peeled off from operation sheet master of the sheet thermoplastic resin that will cool off.
In addition, also can use 2 operations of operation sheet mastered to use the shaping thing, re-use these 2 operations and make diffuser with the shaping thing.Use the shaping thing as 2 operations, for example can enumerate, 2 operation sheets.In addition, use the shaping thing, can enumerate: operation sheet master is reeled, be attached at the inboard of cylinder, be inserted with in this cylinder inboard under the state of roller and carry out plating, roller is taken out from cylinder, obtain the plating roller as 2 operations.
As the concrete grammar of 2 operations of use, can enumerate the method for following (d)～(f) with the shaping thing.
(d) has the method for following operation: on the face that is formed with relief pattern of operation sheet master, thereby carry out the operation of metal deposition lamination coating layers (material is used in the relief pattern transfer printing) such as nickel; Thereby this coating layer is peeled off the operation of 2 operations of making metallic with the shaping thing from operation sheet master, then, on the face of 2 operations, be coated with the operation of uncured ionization radial line curable resin with a side that contacts with relief pattern of shaping thing; The irradiation ionization radial line solidifies aforementioned curable resin, the operation of filming and peeling off with the shaping thing from 2 operations after will solidifying then.
(e) have the method for following operation: on the face that is formed with relief pattern of operation sheet master, the operation of lamination coating layer (material is used in the relief pattern transfer printing); Thereby this coating layer is peeled off the operation of 2 operations of making metallic with the shaping thing from operation sheet master; And on the face of these 2 operations, be coated with the operation of uncured liquid thermosetting resin with a side that contacts with relief pattern of shaping thing; After making this resin solidification through heating, with the operation of filming and peeling off with the shaping thing after solidifying from 2 operations.
(f) have the method for following operation: on the face that is formed with relief pattern of operation sheet master, the operation of lamination coating layer (material is used in the relief pattern transfer printing); Thereby this coating layer is peeled off the operation of 2 operations of making metallic with the shaping thing from operation sheet master; The operation that these 2 operations are contacted with the sheet thermoplastic resin with the face of a side that contacts with relief pattern of shaping thing; This sheet thermoplastic resin is pressed on 2 operations with on the shaping thing, and heating makes its softening, as to cool off then operation; And the operation peeled off with the shaping thing from 2 operations of the sheet thermoplastic resin that will cool off.
Instantiation to method (a) describes.As shown in Figure 8, at first, on the face that is formed with relief pattern 112a of netted operation sheet master 110, through the uncured aqueous ionization radial line curable resin 112c of spreader 120 coatings.Then, roller 130 is pushed through the operation sheet master 110 that is coated with this curable resin, made aforementioned curable resin be filled into the inside of the relief pattern 112a of operation sheet master 110.Afterwards, through ionising radiation beam irradiating apparatus 140 irradiation ionization radial lines, make crosslinked, the curing of curable resin.Then, the ionization radial line curable resin after solidifying is peeled off from operation sheet master 110, thereby can be made network diaphragm diffuser 150.
For method (a); To give release property is purpose; Can be before the uncured ionization radial line curable resin of coating, it is the layer about 1～10nm that the thickness that is made up of organic siliconresin, fluororesin etc. is set on the face that is formed with relief pattern of operation sheet master.
As the spreader of the uncured ionization radial line curable resin of coating on the face that is formed with relief pattern of operation sheet master, can enumerate T die head spreader, roll coater, rod and be coated with device etc.
As uncured ionization radial line curable resin, can enumerate and contain the material of composition more than a kind that is selected from the following monomer: the acrylic ester of prepolymers such as epoxy acrylate, epoxidized oil acrylic ester, acrylic acid urethane ester, unsaturated polyester (UP), polyester acrylate, polyether acrylate, ethene/acrylic ester, polyene/acrylic ester, organic silicon acrylic ester, polybutadiene, polystyrene-based methyl acrylic ester, aliphatic acrylate, ester ring type acrylic ester, aromatic series acrylic ester, hydroxyl, contain allylic acrylic ester, contain monomers such as the acrylic ester of glycidyl ether, carboxylic acrylic ester, halogen-containing acrylic ester.Uncured ionization radial line curable resin preferably dilutes with solvent etc.
In addition, in uncured ionization radial line curable resin, also can add fluororesin, organic siliconresin etc.
When uncured ionization radial line curable resin being cured, preferably in uncured ionization radial line curable resin, add acetophenones, Photoepolymerizationinitiater initiaters such as benzophenone through ultraviolet ray.
Behind the uncured aqueous ionization radial line curable resin of coating, shine ionization radial line again behind the base material that constitutes by resin, glass etc. of can fitting.The irradiation of ionization radial line can be shone from any side with ionization radial line permeability of base material, operation sheet master.
The thickness of the sheet of the ionization radial line curable resin after the curing is preferably about 0.1～100 μ m.The thickness of the sheet of the ionization radial line curable resin after the curing is 0.1 μ m when above, can guarantee to obtain full intensity, is 100 μ m when following, can guarantee to obtain flexible fully.
In above-mentioned method shown in Figure 8, operation sheet master is netted, but also can be thin slice.When using thin slice, the stamped method that is suitable for thin slice is used as the tabular mould, rolls of sheets is invested roller stamped method that roller uses as cylindric mould etc.In addition, also can be at the inboard operation sheet master that disposes thin slice of the mould of injection (mo(u)lding) machine.
Yet,,, need repeatedly repeat to form the operation of relief pattern for the method for using these thin slices for a large amount of production diffuser.When the release property of ionization radial line curable resin and operation sheet master hangs down, after repeatedly repeating, have to produce and block relief pattern, the incomplete tendency of relief pattern transfer printing.
With respect to this, as shown in Figure 8, because operation sheet master is netted, can form large-area continuous relief pattern, even the repeated use number of times of relief pattern formation sheet is few, also can make the diffuser of requirement in the short time.
In method (b), (e),, for example can enumerate uncured melamine resin, urethane resin, epoxy resin etc. as the liquid thermosetting resin.
In addition, the solidification temperature in the method (b) preferably is lower than the glass transition temperature of operation sheet master.Because solidification temperature is when to be the glass transition temperature of operation sheet master above, the relief pattern of operation sheet master might be out of shape during curing.
As the thermoplastic resin among method (c), (f), can enumerate for example acrylic resin, polyolefin, polyester etc.
Pressure when the sheet thermoplastic resin is pressed on 2 operations with the shaping thing is preferably 1～100MPa.Pressure when pushing is 1MPa when above, and transfer printing relief pattern accurately is 100MPa when following, can prevent excessive pressurization.
In addition, in the method (c), the heating-up temperature of thermoplastic resin preferably is lower than the glass transition temperature of operation sheet master.Heating-up temperature is the glass transition temperature of operation sheet master when above, and the relief pattern of operation sheet master might be out of shape during heating.
From the viewpoint consideration of transfer printing relief pattern accurately, the chilling temperature after the heating is preferably the glass transition temperature that is lower than thermoplastic resin.
In method (a)～(c), consider from the viewpoint that the relief pattern that can prevent operation sheet master is out of shape, preferably can omit heating, use the method (a) of ionization radial line curable resin.
In method (d)～(f), 2 operations of metallic are preferably about 50～500 μ m with the thickness of shaping thing.It is 50 μ m when above that 2 operations of metallic are used the thickness of shaping thing, and 2 times operation has enough intensity with the shaping thing, is 500 μ m when following, can guarantee to obtain enough flexible.
In the method (d)～(f),, can use any one of ionization radial line curable resin, heat-curing resin, thermoplastic resin because the less metal film-making of the distortion of having used heat to cause forms the material that sheet is used as the operation sheet as relief pattern.
In method (a)～(f); When the relief pattern formation sheet that makes is used as diffuser; With further raising light diffusion effect is purpose, the organic light diffusing agent or the micro air bubble that can contain the light diffusing agent that is made up of aforementioned mineral compound, be made up of organic compound.
In addition, in (d)～(f), obtained 2 operations on the metal and used the shaping thing though the relief pattern of operation sheet master is transferred to,, also can be transferred to resin and obtain 2 operations and use the shaping thing.At this moment, as operable resin, for example can enumerate employed ionization radial line curable resin etc. in polycarbonate, polyacetal, polysulfones, the method (a).When using the ionization radial line curable resin, (a) is the same with method, carry out successively the ionization radial line curable resin coating, solidify, peel off, obtain 2 operations and use the shaping thing.
Also can bond layer be set at the face of the opposite side of the face that is formed with relief pattern of the above-mentioned diffuser that obtains like this.In addition, also can further form relief pattern at the face of the opposite side of the face that is formed with relief pattern.
In addition, also can not peel off as relief pattern formation sheet or 2 operations of operation sheet master and it used as protective seam, can before using diffuser, peel off protective seam immediately with the shaping thing.
Because the diffuser that makes through above-mentioned manufacturing approach, be formed with above-mentioned relief pattern and form the identical relief pattern of sheet 10, thereby concavo-convex orientation to disperse, the anisotropy of diffusion is excellent.
For diffuser, also can form face of sheet or the layer that the two sides is provided with other at relief pattern.For example, can form sheet, be formed with on the face of relief pattern one side, be provided with in order to prevent that this face is contaminated that to contain with fluororesin or organic siliconresin be that the thickness of principal ingredient is the stain-proofing layer about 1～5nm at relief pattern.
In addition, also can transparent resin system or glass supporter be set at the face that does not form relief pattern one side of diffuser.
5. optical sheet
5-1. the 1st embodiment
The 1st embodiment to optical sheet of the present invention describes.
Figure 13 shows the optical sheet of this embodiment.In addition, in order to be easy to explanation, the relief region 212 of Figure 13 is amplified, and expression sparsely should configuration.
The light diffusing patch that the end α that the optical sheet 210a of this embodiment is used as at length direction disposes light source 330 uses; On smooth one side 11; It is the pattern of the relief region 212 of elliptical shape that the point-like decentralized configuration has profile, and its length direction along optical sheet 210a becomes close gradually from an end α to other end β.In addition, in the present invention, the center line average roughness of the smooth JIS of being meant BO601 record is below the 0.1 μ m.In addition, relief region is meant that the center line average roughness of JIS BO601 record is above 0.1 μ m, particularly surpasses more than the 0.5 μ m.
Relief region
For the optical sheet 210a of this embodiment that is used for light diffusing patch, the mode spacing A of its relief pattern 12a is preferably above 1 μ m and below 20 μ m, more preferably above 1 μ m and below 10 μ m.When mode spacing A was lower than 1 μ m, below wavelength of visible light, refraction did not take place and sees through light at relief pattern 12a in visible light, and when surpassing aforementioned higher limit, the anisotropy step-down of diffusion is easy to generate the unbalanced tendency of brightness.
With respect to the ratio of the mean depth B of the relief pattern of the mode spacing A of relief pattern 12a (B/A, below, be called length breadth ratio.) be preferably 0.1～3.0.Length breadth ratio is lower than at 0.1 o'clock, can not obtain the objective optics characteristic.On the contrary, length breadth ratio in the manufacturing of optical sheet 210a, had the tendency that is difficult to form relief pattern 12a greater than 3.0 o'clock.
Here, mean depth B is meant, the mean depth of the bottom 12b of relief pattern 12a.
In addition, bottom 12b is the minimum point of the recess of relief pattern 12a, and mean depth B is following value: when observing the cross section (with reference to Fig. 2) after short-axis direction cuts off relief region 12, from the parallel datum line L of whole direction of optical sheet 10a
1Length B to each protuberance top
1, B
2, B
3... mean value (B
AV), and from datum line L
1Arrive the length b of the bottom of each recess
1, b
2, b
3... mean value (b
AV) poor (b
AV-B
AV).
As the method for measuring mean depth B, adopt through the take a picture image in cross section of the relief pattern 12a that obtains of atomic force microscope and measure the degree of depth of each bottom 12b, try to achieve the method etc. of their mean value.
As this embodiment, relief pattern 12a is meant along crawling of a direction, and the degree of orientation of the relief pattern of trying to achieve through following method is more than 0.3.This degree of orientation is the index of dispersion of the orientation of relief pattern, and this value is big more, and the expression orientation is overstepping the bounds of propriety looses.
The above-mentioned degree of orientation is lower than at 0.3 o'clock, because the dispersion of the orientation of relief pattern 12a diminishes, so diffusion of light property diminishes.
In addition, the degree of orientation is preferably below 1.0.The degree of orientation surpasses at 1.0 o'clock, because the direction of relief pattern 12a becomes unordered to a certain extent, though diffuse uprises, anisotropy has the tendency of step-down.
In order to make the degree of orientation is more than 0.3, for example, after in the manufacturing stated, can suit to select heat shrink property film and relief region to form and use protuberance.
In addition, can use also that on a surface, to be formed with the degree of orientation be the be shaped method of transparent resin of the mould of the relief pattern more than 0.3.
With respect to the area of the face of optical sheet 210a, though the ratio of the area of relief region 212 is according to the target light diffusive and difference is preferably 30～100%.The area ratio of relief region 212 is 30% when above, can bring into play sufficient diffuse.
The constituent material of optical sheet
In addition, with improve thermotolerance, photostability is a purpose, in can not be to the hurtful scope of optical characteristics such as light transmission, can in optical sheet 10a, contain adjuvant.Can enumerate light stabilizer, ultraviolet light absorber, anti-oxidant, lubricant, light diffusing agent etc. as adjuvant.Wherein, preferably add light stabilizer, with respect to 100 mass parts transparent resins, its addition is preferably 0.03～2.0 mass parts.The addition of light stabilizer is 0.03 mass parts when above, can give full play to its additive effect, but when surpassing 2.0 mass parts, becomes excessive, causes unnecessary cost to increase.
In addition; With further raising light diffusion effect is purpose; In can not be to the hurtful scope of optical characteristics such as light transmission, organic light diffusing agent that can in optical sheet 210a, contain the inorganic light diffuser that constitutes by mineral compound, constitute by organic compound.
As inorganic light diffuser, can enumerate silicon dioxide, white carbon, talcum, magnesium oxide, zinc paste, titanium dioxide, lime carbonate, hydrate of aluminium, barium sulphate, calcium silicate, magnesium silicate, alumina silicate, lagoriolite, zinc silicate, glass, mica etc.
As organic light diffusing agent, can enumerate polystyrene aggregated particles, acrylic acid series aggregated particles, siloxane-based aggregated particles, polyamide-based aggregated particles etc.These light diffusing agents can be distinguished independent use or make up more than 2 kinds and use.
In addition, in order to obtain excellent light diffusion characteristic, these light diffusing agents can be porous structures such as petal-shaped or spherocrystal shape.
The viewpoint that never is prone to the infringement light transmission considers that with respect to 100 mass parts transparent resins, the content of light diffusing agent is preferably below 10 mass parts.
Further, be purpose with further raising light diffusion effect, can not have in the scope of big infringement optical characteristics such as light transmissions, can in optical sheet 210a, contain micro air bubble.Because micro air bubble is few to the absorption of light, be difficult to cause therefore that light transmission reduces.
Formation method as micro air bubble; Can be useful in sneak into gas-development agent among the optical sheet 210a method (for example; Japanese kokai publication hei 5-212811 communique; The disclosed method of japanese kokai publication hei 6-107842 communique), the acrylic acid series Foamex bubble of setting out is handled, make its method that contains micro air bubble (for example, the disclosed method of TOHKEMY 2004-2812 communique) etc.Further, consider the method (for example, the disclosed method of TOHKEMY 2006-124499 communique) that micro air bubble is foamed in certain location unevenly from carrying out face irradiation more uniformly.
In addition, can aforementioned lights diffusion agent and fine foaming combination be used.
The thickness of optical sheet
The thickness of optical sheet 10a be preferably 0.02～3.0mm, more preferably 0.05～2.5mm, be preferably 0.1～2.0mm especially.When the thickness of optical sheet 10a is lower than 0.02mm, because its degree of depth than relief pattern 12a is also little, thus improper, when thicker,, the tendency that is difficult for handling is arranged because the quality of optical sheet 10a becomes big than 3.0mm.
Method of application
Above-mentioned optical sheet 210a can be used as light diffusing patch and uses.Specifically, make an end α and light source 330 adjacent uses of optical sheet 210a.Through at the end α of optical sheet 210a configuration light source 330, light is propagated in optical sheet 210a.In addition, can make the light in optical sheet 210a, propagated in relief region 212 by diffusion, then from being formed with the face outgoing of relief region 212 1 sides.Further, because relief region 212 is to become close pattern successively from an end α to other end β to be configured, can make at the exit dose of the light of other end β outgoing more.Usually, far away more from light source 330, a little less than the light intensity of in optical sheet 210a, propagating becomes more, but because more near other end β, it is many more that the exit dose of light becomes, and can make from the light intensity of optical sheet 210a outgoing even.
When using optical sheet 120a,, preferably reflecting plate is set at the face that does not have relief region 212 in order to improve the light utilization ratio of light source 330.
More than the optical sheet 210a of the 1st embodiment of explanation brings into play diffuse through the relief pattern 12a that the surface in relief region 212 forms.In addition, configuration relief region 212 make to become close along the pattern of other end β one side of the length direction of optical sheet 210a, thereby the diffuse of other end β one side that makes at length direction uprises.Like this, can adjust the diffuse of optical sheet 210a through the interval between the adjustment relief region 212, the diffuse that obtains expecting in the position of expectation easily.
Manufacturing approach
Example to the method for making optical sheet 210a describes.
(the 1st manufacturing approach)
The 1st manufacturing approach is to use the method for heat shrink property thin film fabrication optical sheet 210a.
Promptly; The 1st manufacturing approach is to make the method that the relief pattern that constitutes optical sheet 210a forms sheet; It possesses following operation: on a face of heat shrink property film, thereby the level and smooth resin system relief region of print surface form operation with protuberance formation printed sheet (below, be called the 1st operation.); Thereby make heat shrink property film heat shrink make the relief region at least of printed sheet form operation with the protuberance folded deformation (below, be called the 2nd operation.)。
The 1st operation
Like Figure 14 and shown in Figure 15, in the 1st operation, form method with protuberance 14 as printing relief region on a face of heat shrink property film 13, can be suitable for for example serigraphy, intaglio printing, offset lithography, ink jet printing etc.
As heat shrink property film 13, for example can using, polyethylene terephthalate is shrinkable film, polystyrene shrinkable film, polyolefin shrinkable film, polyvinyl chloride shrinkable film etc.
In heat shrink property film 213, preferably shrink 50～70% film.When use shrinking 50～70% shrinkable film, deformation rate can be for more than 50%, the mode spacing A that can easily make relief pattern 12a for surpass 1 μ m and below 20 μ m and length breadth ratio be the relief pattern formation sheet 0.1 or more.
Here, deformation rate is meant, (length before the distortion-distortion back length)/(length before the distortion) * 100 (%).Perhaps refer to (distortion back length)/(length before the distortion) * 100 (%).
From being easy to form the wavy relief pattern 12a consideration of crawling, relief region forms with protuberance 214 and is made up of than the high resin (the 2nd resin) more than 10 ℃ of the resin that constitutes heat shrink property film 213 (the 1st resin) glass transition temperature.
As the 2nd resin, can use for example polyvinyl alcohol (PVA), polystyrene, acrylic resin, styrene-propene acid copolymer, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, PEN, polycarbonate, polyethersulfone, fluororesin etc.
Consider that from the relief pattern 12a of easy formation expectation form the surface with protuberance 214 in relief region, the center line average roughness described in the JIS BO601 is below the 0.1 μ m.
In addition, the thickness that relief region forms with protuberance 214 is preferably 0.05～5.0 μ m, more preferably 0.1～1.0 μ m.Relief region forms the thickness during as aforementioned range uses protuberance 214, the mode spacing A of relief pattern 12a can be really for above 1 μ m and below 20 μ m.And when relief region formed thickness with protuberance 214 and is lower than 0.05 μ m, mode spacing A was below the 1 μ m, and when surpassing 5.0 μ m, mode spacing A is above 20 μ m.
Further, relief region forms uses the thickness of protuberance 214 also can not be certain value, for example, can along a continuous thickening of direction, also can attenuation.
In addition, consider that from forming the wavy relief pattern 12a that crawls more easily the Young modulus that relief region forms with protuberance 214 is preferably 0.01～300GPa, more preferably 0.1～10GPa.
The 2nd operation
In the 2nd operation, through making 213 thermal shrinkages of heat shrink property film,, relief region forms wavy relief pattern 12a on forming with the direction vertical with shrinkage direction of protuberance 214, obtain relief region 212 (with reference to Figure 16).
Heating means when making heat shrink property film 213 heat shrink can be set forth in hot blast, steam or the method in hot water, passed through etc., wherein, consider the method for preferably in hot water, passing through from making its viewpoint of evenly shrinking.
In this manufacturing approach; Relief region forms thin more with the thickness of protuberance 214, and relief region forms low more with the Young modulus of protuberance 214, and then the mode spacing A of relief pattern 12a becomes more little; The deformation rate of heat shrink property film is high more, and then mean depth B becomes dark more.
In above-mentioned the 1st manufacturing approach, under the temperature between the glass transition temperature of the glass transition temperature of the 1st resin and the 2nd resin, the Young modulus that relief region forms with protuberance 214 becomes than heat shrink property film 213 height.Therefore, under the temperature between the glass transition temperature of the glass transition temperature of the 1st resin and the 2nd resin, add man-hour, relief region forms with protuberance 214 and folds more than thickness increase.Further,, relief region is laminated on the heat shrink property film 213 with protuberance 214 because forming, therefore, because the stress that the contraction of heat shrink property film 213 produces is distributed in integral body equably.Therefore, shrink, make relief region form, can form relief region 212 with protuberance 214 folded deformations through making heat shrink property film 213.Therefore, through above-mentioned manufacturing approach, can obtain constituting the relief pattern formation sheet of optical sheet 210a.
The above-mentioned relief pattern that obtains like this forms sheet and can directly use as optical sheet 210a.At this moment, formation has formed optical sheet 210a with protuberance 214 with relief region through heat shrink property film 213.
(the 2nd manufacturing approach)
The 2nd manufacturing approach is that the relief pattern that the 1st manufacturing approach obtains is formed sheet as operation sheet master, makes the method for optical sheet 210a.
Operation sheet master also can be laminar, can also be the netted of continuous sheet.
As the concrete grammar of the 2nd manufacturing approach, for example can enumerate the method for following (a)～(c).
(a) has the method for following operation: on the face that is formed with relief region of operation sheet master, be coated with the operation of uncured ionization radial line curable resin; And the irradiation ionization radial line, make aforementioned curable resin solidify the operation of filming and peeling off that will solidify then from operation sheet master.Here, ionization radial line generally is meant ultraviolet ray or electron ray, but the present invention also comprises luminous ray, X ray, ion irradiation etc.
(b) has the method for following operation: on the face that is formed with relief region of operation sheet master, be coated with the operation of uncured liquid thermosetting resin; And heating makes aforementioned liquid thermosetting resin solidification, the operation of filming and peeling off from operation sheet master that will solidify then.
(c) has the method for following operation: the operation that the face that is formed with relief region of operation sheet master is contacted with the sheet transparent thermoplastic resin; This sheet transparent thermoplastic resin is pressed on operation sheet master, and heating makes its softening, as to cool off then operation; And the operation peeled off from operation sheet master of the sheet transparent thermoplastic resin that will cool off.
In addition, can use 2 operations of operation sheet mastered to use the shaping thing, re-use these 2 operations and make optical sheet 10a with the shaping thing.As the concrete grammar of 2 operations of use, can enumerate the method for following (d)～(f) with the shaping thing.
(d) has the method for following operation: on the face that is formed with relief region of operation sheet master, thereby carry out the operation of metal deposition lamination coating layers such as nickel; Thereby coating layer is peeled off the operation of 2 operations of making metallic with the shaping thing from operation sheet master; Then, with the contacting with relief region on the face of a side of shaping thing, be coated with the operation of uncured ionization radial line curable resin 2 operations; And the irradiation ionization radial line solidifies aforementioned curable resin, the operation of filming and peeling off with the shaping thing from 2 operations that will solidify then.
(e) has the method for following operation: in the operation of the face laminated coating layer that is formed with relief region of operation sheet master; Thereby this coating layer is peeled off the operation of 2 operations of making metallic with the shaping thing from operation sheet master; With the contacting with relief region on the face of a side of shaping thing, be coated with the operation of uncured liquid thermosetting resin in these 2 operations; And make this resin solidification through heating, the operation of filming and peeling off with the shaping thing that will solidify then from 2 operations.
(f) has the method for following operation: in the operation of the face laminated coating layer that is formed with relief region of operation sheet master; Thereby this coating layer is peeled off the operation of 2 operations of making metallic with the shaping thing from operation sheet master; The operation that these 2 operations are contacted with the sheet transparent thermoplastic resin with the face that contacts a side with relief region of shaping thing; This sheet transparent thermoplastic resin is pressed on 2 operations use the shaping thing, and heating makes its softening, as to cool off then operation; And the operation peeled off with the shaping thing from 2 operations of the sheet transparent thermoplastic resin that will cool off.
Instantiation to method (a) describes.As shown in Figure 8, at first, on the face that is formed with netted relief region 112a of operation sheet master 110, through the uncured aqueous ionization radial line curable resin 112c of spreader 120 coatings.Then, roller 130 is pushed through the operation sheet master 110 that is coated with this curable resin, made aforementioned curable resin be filled into the inside of the relief pattern 112a of operation sheet master 110.Afterwards, through ionising radiation beam irradiating apparatus 140 irradiation ionization radial lines, make crosslinked, the curing of curable resin.Then, the ionization radial line curable resin after solidifying is peeled off from operation sheet master 110, can be made netted optical sheet 210a.
For method (a); To give release property is purpose; Can be before the uncured ionization radial line curable resin of coating, it is the layer of 1～10nm degree that the thickness that is made up of organic siliconresin, fluororesin etc. is set on the face that is formed with relief region of operation sheet master.
As the spreader of the uncured ionization radial line curable resin of coating on the face that is formed with relief region of operation sheet master, can enumerate T die head spreader, roll coater, rod and be coated with device etc.
Can enumerate as uncured ionization radial line curable resin and to contain the material of composition more than a kind that is selected from the following monomer: epoxy acrylate; The epoxidized oil acrylic ester; Urethane acrylate; Unsaturated polyester (UP); Polyester acrylate; Polyether acrylate; Ethene/acrylic ester; Polyene/acrylic ester; Organic silicon acrylic ester; Polybutadiene; Prepolymers such as polystyrene-based methyl acrylic ester; Aliphatic acrylate; The ester ring type acrylic ester; The aromatic series acrylic ester; The acrylic ester of hydroxyl; Contain allylic acrylic ester; The acrylic ester that contains glycidyl ether; Carboxylic acrylic ester; Monomers such as halogen-containing acrylic ester.Uncured ionization radial line curable resin preferably dilutes with solvent etc.
In addition, uncured ionization radial line curable resin also can add fluororesin, organic siliconresin etc.
When uncured ionization radial line curable resin being cured, preferably in uncured ionization radial line curable resin, add acetophenones, the Photoepolymerizationinitiater initiater of benzophenone etc. through ultraviolet ray.
As the concrete grammar of (d), except the operation sheet master in the method (a) is become use this operation sheet mastered 2 operations with the shaping thing, (a) is the same with said method.
As the liquid thermosetting resin among method (b), (e), can enumerate for example uncured, melamine resin, urethane resin, epoxy resin etc.
In addition, the solidification temperature in the method (b) preferably is lower than the glass transition temperature of operation sheet master.Because solidification temperature is when to be the glass transition temperature of operation sheet master above, the relief pattern of operation sheet master might be out of shape during curing.
As the transparent thermoplastic resin among method (c), (f); For example can enumerate styrene-methylmethacrylate copolymer (MS), polymethylmethacrylate (PMMA), polystyrene (PS), cyclic olefin polymer (COP), polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET), PET-G, polyethersulfone (PES), PVC (PVC), polyethylene terephthalate resins such as (PET) etc.Wherein, consider that preferred MS, PMMA, PS, COP, PC consider that from the viewpoint of hydroscopicity and cost more preferably the styrene containing ratio is the MS of 30～90 quality % from the shaping processing view.
These transparent thermoplastic resins can be individual layer or sandwich construction.For example, can use the transparent thermoplastic resin etc. of the 3-tier architecture that all is provided with the PMMA layer on the two sides of PS layer.
Further, also can use the resin that is provided with high refractive index resins on aforementioned transparent thermoplastic resin's surface.As the resin of high index of refraction, for example can to enumerate fluorenes and be epoxy compound, fluorenes and be acrylate compounds, fluorenes be polyester (OKP), polymethyl-benzene base silane (PMPS), gather diphenyl silane (PDPS) etc.
In method (c), the pressure when the sheet thermoplastic resin is pressed on operation sheet master and in method (f), the pressure when the sheet thermoplastic resin is pressed on 2 operations with the shaping thing all is preferably 1～100MPa.Pressure when pushing is 1MPa when above, and transfer printing relief pattern accurately is 100MPa when following, can prevent excessive pressurization.
In addition, in the method (c), the heating-up temperature of thermoplastic resin preferably is lower than the glass transition temperature of operation sheet master.Heating-up temperature is the glass transition temperature of operation sheet master when above, and the relief pattern of operation sheet master might be out of shape during heating.
From transfer printing relief pattern consideration accurately, the chilling temperature after the heating is preferably the glass transition temperature that is lower than thermoplastic resin.
(the 3rd manufacturing approach)
The 3rd manufacturing approach is relief pattern formation sheet that the surface with resinous layer is provided with metallic or metallic compound system relief region is made optical sheet 210a as operation sheet master a method.
The relief pattern that is provided with metallic or metallic compound system relief region forms sheet; Replace the formation of resin system relief region to use protuberance except forming with protuberance with metallic or metallic compound system relief region; Replace printing to form relief region with vapor deposition and form with beyond the protuberance, can be through obtaining with the identical method of the 1st manufacturing.
That is the manufacturing approach that the relief pattern that, is provided with metallic or metallic compound system relief region forms sheet has following operation: thus thereby form with the operation of protuberance formation vapor deposition sheet and make heat shrink property film heat shrink make the operation of the formation of relief region at least of vapor deposition sheet with the protuberance folded deformation in face vacuum evaporation metallic of heat shrink property film or metallic compound system relief region.
Form in the manufacturing approach of sheet at this relief pattern, because the relief region of metallic or metallic compound system forms with the Young modulus of the protuberance Young modulus much larger than heat shrink property film, when hot compression, it folds than thickness increase more.As a result, can obtain being provided with the relief pattern formation sheet of relief region.In addition, the relief region of this relief pattern formation sheet is the same with optical sheet 210a.
Consider from more easily forming relief pattern 12a; Form metal as constituting relief region in the 3rd manufacturing approach, be preferably at least a kind of metal that is selected from the group of forming by gold, aluminium, silver, carbon, copper, germanium, indium, magnesium, niobium, palladium, lead, platinum, silicon, tin, titanium, vanadium, zinc, bismuth with protuberance.Here said metal also comprises semimetal.
Because same reason; As metallic compound, be preferably at least a kind of metallic compound that is selected from the group of forming by titanium dioxide, aluminium oxide, zinc paste, magnesium oxide, tin oxide, cupric oxide, indium oxide, cadmium oxide, massicot, monox, barium fluoride, calcium fluoride, magnesium fluoride, zinc sulphide, gallium arsenide.
Consider that from the relief pattern 12a of easy formation expectation form the surface with protuberance in relief region, the center line average roughness of putting down in writing among the JIS BO601 is below the 0.1 μ m.
The thickness that metallic or metallic compound system relief region form with protuberance is preferably 0.01～0.2 μ m, more preferably 0.05～0.1 μ m.Relief region forms the thickness during as aforementioned range uses protuberance, the mode spacing A of relief pattern 12a, can be really for above 1 μ m and below 20 μ m.Yet when relief region formed thickness with protuberance and is lower than 0.01 μ m, mode spacing A became below the 1 μ m, and when surpassing 0.2 μ m, mode spacing A is above 20 μ m.
Further, relief region forms uses the thickness of protuberance also can not be certain value, for example, can along a continuous thickening of direction, also can attenuation.
Evaporation metal or metallic compound system relief region form when using protuberance on heat shrink property film, can on the surface of heat shrink property film, put the mask with the identical pattern openings of protuberance with the relief region that will form.
Heating means when making heat shrink property film heat shrink can be set forth in the method passed through in hot blast, steam or the hot water etc., wherein, consider the method for preferably in hot water, passing through from it is evenly shunk.
As the concrete grammar of the 3rd manufacturing approach, can be set forth in and employedly in the method (a)～(f) with the 2nd manufacturing approach form sheet as operation sheet master with the relief pattern that is provided with relief region of metallic or metallic compound system and replace the 2nd resinous relief pattern that is provided with relief region to form the method for sheet.
(the 4th manufacturing approach)
The 4th manufacturing approach is, use possess mould, the heating cooling unit of this mould of heating cooling and to the building mortion of the presser unit of this mould pressurization, make the method for optical sheet 10a by unfashioned transparent thermoplastic resin.As the transparent thermoplastic resin that the 4th manufacturing approach is used, can enumerate and use and the identical resin of the employed transparent thermoplastic resin of the 2nd manufacturing approach.
Particularly, in the 4th manufacturing approach, at first, in mould, fill transparent thermoplastic resin's bead or powder, through the heating cooling unit to mold heated, and through presser unit to pressurizeing in the mould.Then, make in the mould and cool off, stop pressurization, obtain optical sheet 210a through the heating cooling unit.
In this manufacturing approach,, use the mould that on optical sheet 210a and face that exit facet contacts, is formed with the wavy relief pattern that crawls as mould.For example, as mould, can use the additional mould that mould that relief pattern forms sheet is arranged, formed the wavy relief pattern that crawls through laser radiation etc. at a face on a face in the 1st～the 3rd manufacturing approach.
As the manufacturing process of the 4th manufacturing approach, for example can be suitable for press forming method, injection molding method.
The optical sheet 210a that obtains through above-mentioned the 1st～the 4th manufacturing approach can directly use, and also can fit in transparent resin system or glass through bonding agent and strengthen with using as final optical sheet on the substrate.
More than the manufacturing approach of the optical sheet 210a of explanation can dispose relief region 212 and make its other end β side pattern along the length direction of optical sheet 210a become close gradually easily on smooth one side.Therefore, can easily obtain the high optical sheet 210a of diffuse of the other end β side of length direction.
5-2. the 2nd embodiment
The 2nd embodiment to optical sheet of the present invention describes.
Figure 17 shows the optical sheet of this embodiment.In addition, in order to be easy to explanation, in Figure 17, relief region 215 is amplified, and expression sparsely should configuration.
The light diffusing patch that the end α that the optical sheet 210b of this embodiment is used as at length direction disposes light source 330 uses; Decentralized configuration has along the Width of optical sheet 210b and forms banded relief region 215 on smooth one side 211, makes its length direction along optical sheet 210b become close from an end α gradually to other end β pattern.
The same with the optical sheet 210a of the 1st embodiment, through disposing such relief region 215, can be so that the diffuse of the other end β side of optical sheet 210b be high.
The relief pattern of the relief region 215 of the 2nd embodiment is identical with the relief pattern 12a of the relief region 12 of the 1st embodiment.Also the area ratio with the 1st embodiment is identical with respect to the area ratio of the relief region 215 of the area of the face of optical sheet 210b.
The optical sheet 210b of the 2nd embodiment can be through making with the identical manufacturing approach of manufacturing approach of the optical sheet 210a of the 1st embodiment.
5-3. the 3rd embodiment
The 3rd embodiment to optical sheet of the present invention describes.
Figure 18 shows the optical sheet of this embodiment.In addition, in order to be easy to explanation, in Figure 18, also relief region 216 is amplified, and expression sparsely should configuration.
The light diffusing patch that the end α that the optical sheet 210c of this embodiment is used as at length direction disposes light source 330 uses; On smooth one side 211; Decentralized configuration has netted relief region 216, and it is by constituting along the band-like portions 216a of optical sheet 210c length direction with along the band-like portions 216b of Width.The part 216b along optical sheet 210c Width of relief region 216 is become thickly configuration gradually by the length direction along optical sheet 210c from an end α to other end β.
The relief pattern of the relief region 216 of the 3rd embodiment is identical with the relief pattern 12a of the relief region 212 of the 1st embodiment.With respect to the area ratio of the relief region 216 of the area of the face of optical sheet 210c, also the area ratio with the 1st embodiment is identical.
The optical sheet 210c of the 3rd embodiment can be through making with the identical manufacturing approach of manufacturing approach of the optical sheet 210a of the 1st embodiment.
5-4. the 4th embodiment
The 4th embodiment to optical sheet of the present invention describes.
Figure 19 shows the optical sheet of this embodiment.In addition, in order to be easy to explanation, in Figure 19, relief region 217 is amplified, and expression sparsely should configuration.
The optical sheet 210d of this embodiment is used as the light diffusing patch use of disposing linear light source 330 at the face C that is not formed with relief region 217 sides.In addition, near more from light source 330 on the smooth one side 211 of this optical sheet 210d, the relief region 217 of elliptical shape is got over thickly decentralized configuration.
In this embodiment, the light that sends from light source 330 incides optical sheet 210d unevenly, but because the part that strong more light arrives, relief region 217 can be made light by diffusion and outgoing by more thickly configuration.Therefore, can make from the light intensity homogenising of optical sheet 210d outgoing.
The relief pattern of the relief region 217 of the 4th embodiment is identical with the relief pattern 12a of the relief region 212 of the 1st embodiment.Also the area ratio with the 1st embodiment is identical with respect to the area ratio of the relief region 217 of the area of the face of optical sheet 210d.
The optical sheet 210d of the 4th embodiment can be through making with the identical manufacturing approach of manufacturing approach of the optical sheet 210a of the 1st embodiment.
5-5. other embodiments
In addition, optical sheet of the present invention does not receive the restriction of above-mentioned embodiment.
For example, for above-mentioned the 1st embodiment, the 4th embodiment, the profile of relief region is an elliptical shape, but also can be circle, rectangle etc.
In addition, for optical sheet of the present invention, relief region also can randomly form.
In addition, the relief pattern of relief region also can be for not crawling, for straight line also can.
In addition, also can form relief region on the two sides of optical sheet.
In addition, also can strengthen optical sheet with base material with strengthening.
6. diffusion light conductor
Embodiment to diffusion light conductor of the present invention describes.
Fig. 1 shows the diffusion light conductor of this embodiment.The diffusion light conductor 10 of this embodiment is to be made up of the transparent resin layer 11 that is formed with the wavy relief pattern 12a that crawls in one side.Other face (the inside) of the transparent resin layer 11 of this embodiment is not for forming the level and smooth face of relief pattern.
The mode spacing A of relief pattern 12a is for surpassing 1 μ m and below 20 μ m, being preferably above 1 μ m and below 10 μ m.When mode spacing A was lower than 1 μ m, below wavelength of visible light, refraction did not take place and sees through light in visible light at concavo-convex place, and when surpassing 20 μ m, the anisotropy step-down of diffusion is easy to generate brightness irregularities.
With respect to the ratio of the concavo-convex mean depth B of the mode spacing A of relief pattern 12a (B/A, below, be called length breadth ratio.) be 0.1～3.0.Length breadth ratio is lower than at 0.1 o'clock, and the anisotropy step-down of diffusion is easy to generate brightness irregularities.On the contrary, length breadth ratio in the manufacturing of diffusion light conductor 10, was difficult to form relief pattern 12a greater than 3.0 o'clock.
Here, mean depth B is the mean depth of the bottom 12b of relief pattern 12a.In addition, bottom 12b is the minimum value of the recess of relief pattern 12a, and mean depth B is meant, when observing the cross section (with reference to Fig. 2) after along its length diffusion light conductor 10 being cut off, from the datum line L parallel with 10 whole directions of diffusion light conductor
1Length B to each protuberance top
1, B
2, B
3... mean value (B
AV), and from datum line L
1Arrive the length b of the bottom of each recess
1, b
2, b
3... mean value (b
AV) poor (b
AV-B
AV).
As the method for measuring mean depth B, adopt through the take a picture image in cross section of the relief pattern 12a that obtains of atomic force microscope and measure the degree of depth of each bottom 12b, try to achieve the method etc. of their mean value.
Of the present invention crawling be meant, the degree of orientation of the relief pattern of trying to achieve through following method is more than 0.3.This degree of orientation is the index of dispersion of the orientation of relief pattern, and this value is big more, and the expression orientation is overstepping the bounds of propriety looses.
In order to try to achieve the degree of orientation, at first,, be gray scale file (for example, tiff form etc.) with this image transformation through of the top photograph of surface optics microscope to relief pattern.In the image (with reference to Fig. 3) of gray scale file, whiteness is low more, the bottom of expression recess darker (whiteness is high more, and the top of expression protuberance is high more).Then, the image to the gray scale file carries out Fourier transform.Fig. 4 shows the image behind the Fourier transform.The white portion that expands to both sides from the center of the image of Fig. 4 comprised relief pattern 12a spacing and towards information.
Then, draw boost line L2 from the center along continuous straight runs of the image of Fig. 4, to the mapping of the brightness on this boost line (with reference to Fig. 5).The transverse axis of scheming among Fig. 5 is the inverse of expression spacing, and the longitudinal axis is represented frequency, and the 1/X reciprocal of the value X when frequency is maximum representes the mode spacing of relief pattern 12a.
Then, in Fig. 4, draw and boost line L
2Boost line L perpendicular to value X part
3, to this boost line L
3On brightness mapping (with reference to Fig. 6).But, for can more various concaveconvex structures, the numerical value after the transverse axis of Fig. 6 is removed by the value of X.The transverse axis of Fig. 6 is the index (orientation) that shows with respect to the inclined degree of concavo-convex formation direction (above-below direction among Fig. 3), and the longitudinal axis is represented frequency.In the mapping of Fig. 6, the half breadth W of peak value
1The degree of orientation of (frequency is the peak width on the height of a peaked half) expression relief pattern.Half value broadband W
1Big more, the spacing that expression is crawled is overstepping the bounds of propriety looses.
Because the above-mentioned degree of orientation is lower than at 0.3 o'clock, the dispersion of the orientation of relief pattern 12a diminishes, so diffusion of light property diminishes.
In addition, the degree of orientation is preferably below 1.0.The degree of orientation surpasses at 1.0 o'clock, because the direction of relief pattern 12a becomes unordered to a certain extent, though diffuse uprises, anisotropy has the tendency of step-down.
In order to make the degree of orientation is more than 0.3, for example after state in the manufacturing, suitable heat shrink property film and the surface smoothing hard layer selected gets final product.For example, the shrinkage factor of heat shrink property film is high more, and perhaps the Young modulus of surface smoothing hard layer is more little, and it is big more that orientation becomes.The diffusion light conductor 10 that obtains through this manufacturing approach is made up of 2 layers of resin bed.
In addition, can use also that be formed with the degree of orientation on a surface be the be shaped method of transparent resin of the mould of the relief pattern more than 0.3.The diffusion light conductor 10 that obtains through this manufacturing approach is made up of 1 layer of resin bed.
In addition, it is equal that above-mentioned that kind is utilized the mode spacing and the average headway of the relief pattern that Fourier transform tries to achieve.
In addition, with improve thermotolerance, photostability is a purpose, can in can not be to the hurtful scope of optical characteristics such as light transmission, in transparent resin layer 11, contain adjuvant.Can enumerate light stabilizer, ultraviolet light absorber, anti-oxidant, lubricant, light diffusing agent etc. as adjuvant.Wherein, preferably add light stabilizer, with respect to 100 mass parts transparent resins, its addition is preferably 0.03～2.0 mass parts.The addition of light stabilizer is 0.03 mass parts when above, can give full play to its additive effect, but when surpassing 2.0 mass parts, becomes excessive, causes unnecessary cost to increase.
In addition; With further raising light diffusion effect is purpose; Can not cause in the scope of big infringement the organic light diffusing agent that in transparent resin layer 11, contains the inorganic light diffuser that constitutes by mineral compound, constitutes by organic compound to optical characteristics such as light transmissions.
As inorganic light diffuser, can enumerate silicon, white carbon, talcum, magnesium oxide, zinc paste, titanium dioxide, lime carbonate, hydrate of aluminium, barium sulphate, calcium silicate, magnesium silicate, alumina silicate, lagoriolite, zinc silicate, glass, mica etc.
As organic light diffusing agent, can enumerate polystyrene aggregated particles, acrylic acid series aggregated particles, siloxane-based aggregated particles, polyamide-based aggregated particles etc.These light diffusing agents can be distinguished independent use, perhaps make up more than 2 kinds and use.
In addition, in order to obtain excellent light diffusion characteristic, these light diffusing agents can be the porous structure of petal-shaped or spherocrystal shape etc.
Never be prone to the infringement light transmission and consider that with respect to 100 mass parts transparent resins, the content of light diffusing agent is preferably below 10 mass parts.
Further, be purpose with further raising light diffusion effect, can in transparent resin layer 11, contain micro air bubble not causing in the scope of big infringement to optical characteristics such as light transmissions.Micro air bubble is few to the absorption of light, is difficult to cause therefore that light transmission reduces.
As the formation method of micro air bubble, can be useful in the method (for example, japanese kokai publication hei 5-212811 communique, the disclosed method of japanese kokai publication hei 6-107842 communique) of sneaking into gas-development agent in the transparent resin layer 11; The acrylic acid series Foamex bubble of setting out is handled, made its method that contains micro air bubble (for example, the disclosed method of TOHKEMY 2004-2812 communique) etc.Further, consider the method (for example, the disclosed method of TOHKEMY 2006-124499 communique) that micro air bubble is foamed in certain location unevenly from the viewpoint that can carry out face irradiation more uniformly.
In addition, can aforementioned lights diffusion agent and fine foaming combination be used.
The thickness of transparent resin layer 11 be preferably 0.02～3.0mm, more preferably 0.05～2.5mm, be preferably 0.1～2.0mm especially.When the thickness of transparent resin layer 11 is lower than 0.02mm, because of its degree of depth than relief pattern is also little, thus improper, when being thicker than 3.0mm,, the tendency that is difficult for handling is arranged because the quality of diffusion light conductor 10 becomes big.
Manufacturing approach
Can make with the manufacturing approach identical with the manufacturing approach of aforementioned optical sheet.
Function
Above-mentioned diffusion light conductor 10 has the anisotropic diffusion property of light.Particularly, when light source was set, the light that sends from light source incided diffusion light conductor 10 by the inside at the face that does not form relief pattern 12a one side (the inside) of diffusion light conductor 10, in the diffusion light conductor 10 through arriving male and fomale(M&F) then.Here, the light that the incident angle of the angle at and subcritical angle above with 0 degree arrives reflects, and shines the outside surface of diffusion light conductor 10.Because from the diffusion light conductor 10 interior directions of light of passing through not is a direction, the male and fomale(M&F) of diffusion light conductor 10 and the angle of light are not definite value, and light reflects at wide angular range.And because concavo-convex for disperseing orientation, the anisotropy of diffusion uprises with crawling.
In addition, with respect to male and fomale(M&F), after the light generation total reflection that arrives with the angle more than the critical angle again through in the diffusion light conductor, afterwards, outgoing during with the angle arrival male and fomale(M&F) at subcritical angle.In addition, the light that arrives with the incident angle of the angle of 0 degree does not reflect, and directly shines the outside surface of diffusion light conductor.
In addition, when a side of diffusion light conductor 10 is provided with light source, also with above-mentioned the same, in diffusion light conductor 10, pass through, refraction takes place and shines the outside surface of diffusion light conductor in the light that the incident angle of the angle at and subcritical angle above with 0 degree arrives.Here, concavo-convex is that dispersion is orientated with crawling, thereby the anisotropy of diffusion uprises.
In addition, diffusion light conductor of the present invention does not receive the restriction of above-mentioned embodiment.For example, when side disposes light source in the inside of transparent resin layer,, preferably have the fine wavy concavo-convex of anti-reflective function in the formation of the inside of transparent resin layer in order to improve the incident efficient of light.Here, fine wavy concavo-convex mode spacing is preferably below the 1 μ m, and length breadth ratio is preferably more than 0.1.This is because when the mode spacing surpassed 1 μ m, perhaps length breadth ratio surpassed at 0.1 o'clock, can not obtain anti-reflective function.
Aforementioned fine wavy concavo-convex, also can be with forming the inside that relief pattern that light diffusion uses be formed at transparent resin layer.For example; Through press forming, when injection moulding is made the diffusion light conductor; As mould; Can use at the face that joins with exit facet (surface) side of transparent resin layer to be formed with the relief pattern that light diffusion is used, and be formed with the method for the mould of fine wavy relief pattern at the face that joins with the plane of incidence (the inside) side of transparent resin layer.
In addition, aforementioned fine wavy concavo-convex, also can be formed in the inside of transparent resin layer with the relief pattern different terrain that light diffusion is used.For example, can be attached to the inside side of transparent resin layer through the film that bonding agent will be formed with fine wavy relief pattern.
In addition, in order further to improve light diffusing anisotropy, can contain the film of micro air bubble in plane of incidence side or exit facet side apposition.Shown in figure 20, when plane of incidence side apposition contains the film 317 of micro air bubble, in order effectively to utilize the light that sends from light source 330; Preferably at the part 317a of the strong irradiation of light intensity of light source 330, the content of micro air bubble is many, at other part 317b; The content of micro air bubble is few, perhaps, does not contain.
Diffusion light conductor of the present invention also can be the thickness wedge shape of attenuation gradually that passes through, and light source is disposed at a thick side of the diffusion light conductor of wedge shape.
Diffusion light conductor of the present invention must be formed with the wavy relief pattern that crawls on a face, but is not limited to only be formed with relief pattern at a face.That is, on the another side of transparent resin layer, also can be formed with the wavy relief pattern that crawls.
7. back light unit
7-1. the 1st embodiment
The 1st embodiment for back light unit of the present invention describes.
Figure 21 shows the back light unit of this embodiment.The back light unit 100 of this embodiment be so-called under type; Possess diffusion light conductor 310, reflecting plate 320 and a plurality of light source 330,330......; Wherein, The opposing face (the inside 316) of the face that is formed with relief pattern of diffusion light conductor 310 (surface 315) sets with reflecting plate 320 in opposite directions, and a plurality of light sources 330 are equipped between diffusion light conductor 310 and the reflecting plate 320.In addition, on the surface of diffusion light conductor 310 315 1 sides successively lamination diffusion film 340, prismatic lens 350, brightness rising film 360 are arranged.
As light source 330, for example can enumerate cold-cathode tube, light emitting diode etc.
As reflecting plate 320, for example can enumerate, the surface is the sheet metal of mirror-like, perhaps possesses the laminate of such sheet metal etc.
As diffusion film 340, for example can enumerate, contain the resin molding of transparent grain etc.Diffusion film 340 makes by the further diffusion of light of diffusion light conductor outgoing.
As prismatic lens 350, for example can enumerate, the resin sheet (for example, Sumitomo 3M Limited makes, and commodity are called Vikuiti BEFIII) of the coniform or pyramidal projection of a plurality of rules etc. is arranged at a mask.Prismatic lens 350 makes that from the working direction of the light of diffusion film 340 outgoing be the vertical direction with respect to face.
As brightness rising film 360, for example can enumerate, the compressional wave (P ripple) of light is passed through, and make the sheet (for example, Sumitomo 3M Limited makes, trade name Vikuiti DBEF-D400) etc. of shear wave (S ripple) reflection.
7-2. the 2nd embodiment
The 2nd embodiment to back light unit of the present invention describes.
Figure 22 shows the back light unit of this embodiment.The back light unit 200 of this embodiment; It is so-called edge-light type; Possess diffusion light conductor 310, reflecting plate 320 and a plurality of light source 330; The opposing face (the inside 316) of the face that is formed with relief pattern of diffusion light conductor 310 (surface 315) sets with reflecting plate 320 in opposite directions, and a plurality of light sources 330 are equipped on a side of diffusion light conductor 310.In addition, on the surface of diffusion light conductor 310 315 1 sides successively lamination diffusion film 340, prismatic lens 350, brightness rising film 360 are arranged.
The employed diffusion light conductor of this embodiment 310, reflecting plate 320, light source 330, diffusion film 340, prismatic lens 350 are identical with the 1st embodiment with brightness rising film 360.
The back light unit 100 that possesses the above-mentioned embodiment of the diffusion light conductor 310 that is formed with the wavy relief pattern that crawls, the light that sends from light source 330 at the male and fomale(M&F) of diffusion light conductor 310 with high anisotropic diffusion.Therefore, the difficult brightness irregularities that image takes place of liquid crystal indicator that possesses back light unit 100,200.
8. antireflection object
Antireflection object of the present invention possesses the relief pattern formation sheet 10 that above-mentioned mode spacing A is the relief pattern 12a below the 1 μ m.
For antireflection object of the present invention, also can have other layers on face or the two sides that relief pattern forms sheet 10.For example, can form on the face that is formed with relief pattern 12a one side of sheet 10 at relief pattern, having containing of being provided with in order to prevent that this face is contaminated is that the thickness of principal ingredient is the stain-proofing layer about 1～5nm with fluororesin or silicones.
The relief pattern of antireflection object of the present invention forms the wavy relief pattern 12a part of sheet 10, the middle refractive index between the refractive index (refractive index of base material 11) of demonstration air refraction and relief pattern formation sheet 10, and this middle refractive index changes continuously.And the mode spacing A of relief pattern 12a is below the 1 μ m, and is 100% o'clock with mode spacing A, and the mean depth B of the bottom 12b of relief pattern 12a is more than 10%.Owing to these reasons, the reflection of light rate can be low especially, and particularly, reflectivity can be almost 0%.This be because; As stated; The mode spacing A that relief pattern forms the relief pattern 12a of sheet 10 is so short below the 1 μ m, is 100% o'clock with mode spacing A, and mean depth B is so dark more than 10%; It is elongated to change part continuously along the middle refractive index of thickness direction, can significantly bring into play the effect that suppresses the light reflection.
Such antireflection object for example can be installed in, image display devices such as LCD panel, PDP, the illuminating part top of light emitting diode, the surface of solar panel etc.
When being installed on image display device, owing to can prevent the reflection of throwing light on, thus can improve the visuality of image.When being installed on the illuminating part top of light emitting diode, can improve the outgoing efficient of light.When being installed on solar panel surperficial, owing to make that the incident quantitative change of light is many, thus can improve the generating efficiency of solar cell.
9. polarizer
Polarizer of the present invention possesses the above-mentioned relief pattern formation sheet 10 that mode spacing A is the relief pattern 12a below the 1 μ m.But, concavo-convex direction is not random, but along a direction.
The same with above-mentioned antireflection object, for polarizer of the present invention, also can possess other layers on face or the two sides that relief pattern forms sheet 10, for example, can be equipped with stain-proofing layer at the mask that is formed with relief pattern 12a one side that relief pattern forms sheet 10.
Polarizer of the present invention can significantly be brought into play the effect that produces phase differential.This be because; As stated, the mode spacing A that relief pattern forms the relief pattern 12a of sheet 10 is so short below the 1 μ m, and is 100% o'clock with mode spacing A; Mean depth B is so dark more than 10%; Along thickness direction, it is elongated that mutually different air of refractive index and relief pattern form sheet 10 mutual configuration sections, and the anisotropic part of display optical is elongated.Further, the spacing of relief pattern be with the wavelength of visible light same degree or for its when following, can in wide visible wavelength range, produce equal phase differential.
(the operation sheet is used in the optical element manufacturing)
Optical element manufacturing of the present invention with the operation sheet (below; Abbreviate the operation sheet as); Possessing above-mentioned mode spacing A is the relief pattern formation sheet 10 of the relief pattern 12a below the 1 μ m; Method through shown in following is transferred to relief pattern on the other materials; Can be used as mould and use, be used for making in large quantities the relief pattern that optical elements such as can be used as antireflection object, polarizer in large area uses and form sheet, this relief pattern forms sheet to have and the equal mode spacing of this operation sheet and the relief pattern of mean depth.
Use the concrete grammar of operation sheet manufacturing optical element identical with the method for aforementioned optical sheet.
Embodiment 1
The value that the Young modulus of following example is to use tension test appearance (TESTER SANGYO CO., the TE-7001 that LTD. makes) and records based on JIS K 7113-1995.When temperature not being put down in writing especially, be the value under 23 ℃.
(embodiment 1)
Thickness along the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate system heat shrink property film (the Mitsubishi Plastic of 3GPa; Inc. the HISHIPET LX-60S that makes; Glass transition temperature is 70 ℃) a face on; Use rod to be coated with polymethylmethacrylate (the Port リ マ one ソ one ス Co., Ltd. system P4831-MMA of device coating with dilution with toluene; Glass transition temperature is 100 ℃), making its thickness is 200nm, obtains laminate thereby form hard layer.
Then; This laminate was heated 1 minute down at 80 ℃; Make its thermal shrinkage before the heating length 40% (promptly; The deformation rate that makes its distortion is 60%), obtain hard layer and form sheet (diffuser) at the relief pattern that has periodic wavy relief pattern along the direction vertical with respect to shrinkage direction.
In addition, polyethylene terephthalate system heat shrink property film is respectively 50Mpa, lGPa with the Young modulus of this polymethylmethacrylate under 80 ℃.
(embodiment 2)
Except coating with the polystyrene of dilution with toluene (the system PS of Port リ マ one ソ one ス Co., Ltd., glass transition temperature is 100 ℃) in addition, the same with embodiment 1, obtain relief pattern formation sheet (diffuser).
In addition, polyethylene terephthalate system heat shrink property film is respectively 50Mpa, 1GPa with the Young modulus of this polystyrene under 80 ℃.
(embodiment 3)
Except the coating thickness of polystyrene is the 1 μ m, the same with embodiment 2, obtain relief pattern and form sheet (diffuser).
(embodiment 4)
Except laminate was heated 1 minute down at 70 ℃, make its thermal shrinkage in addition to 90% (that is, the deformation rate that makes its distortion is 10%) of heating preceding length, the same with embodiment 2, obtain relief pattern and form sheet (diffuser).
(embodiment 5)
The relief pattern that use is obtained by embodiment 1 forms sheet (diffuser) and uses as operation sheet master, according to following method, obtains diffuser.
That is, the face coating that is formed with relief pattern at the operation sheet master that is obtained by embodiment 1 contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that does not join with operation sheet master of filming of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, and pushes.
Then, irradiation ultraviolet radiation above cellulose triacetate film solidifies uncured ultra-violet solidified resin composition, and this solidfied material is peeled off from operation sheet master, obtains diffuser.
(embodiment 6)
The relief pattern that use is obtained by embodiment 1 forms sheet (diffuser) and uses as operation sheet master, obtains optical element according to following method.
That is, on the face that is formed with relief pattern of the operation sheet master that is obtained by embodiment 1, implement the nickel plating, this nickel coating is peeled off, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that film, that do not join with 2 operation sheets of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, and pushes.
Then, irradiation ultraviolet radiation above cellulose triacetate film solidifies uncured ultra-violet solidified resin composition, and this solidfied material is peeled off from 2 operation sheets, obtains diffuser.
(embodiment 7)
Except using heat-curable epoxy resin to replace ultra-violet solidified resin composition, the use heating replaces the ultraviolet ray irradiation to make this beyond heat-curing resin curing, and is the same with embodiment 6, obtains diffuser.
(embodiment 8)
The same with embodiment 6, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, superimposed thickness is the polymethyl methacrylate film of 50 μ m, and heating.Push thermoplastic polymethyl methacrylate film and 2 operation sheets from both sides, make its cooling curing then, again it is peeled off from 2 operation sheets, obtain diffuser.
(comparative example 1)
Except the coating thickness of polystyrene is the 6 μ m, the same with embodiment 2, obtain relief pattern and form sheet (diffuser).
(comparative example 2)
Except the coating thickness of polystyrene is the 40nm, the same with embodiment 2, obtain relief pattern and form sheet (diffuser).
(comparative example 3)
Except with Mitsubishi Plastic; Inc. the HISHIPET LX-60S that makes uses with HI SHIPET LX-10S (Young modulus is 3GPa) and replaces; And with this laminate 70 ℃ of down heating 1 minute, make its 97% (that is, making the deformation rate of its distortion is 3%) that is punctured into length before the heating in addition; The same with embodiment 1, obtain relief pattern and form sheet (diffuser).
(comparative example 4)
Use the manufacturing approach of the anisotropic diffusion pattern shown in the patent documentation 2 to obtain relief pattern formation sheet.
Promptly; Shield and photosensitive film plate are provided with in parallel to each other; And make each other the 1m that is spaced apart, and it is 1mm that said shield has width, length is the slit of 10cm; Embedding in the slit has the such diffusing panel of ground glass to make the laser diffusion and sees through, and said photosensitive film plate is coated with the commercially available photoresist of thickness 100 μ m.
Then, use wavelength to shine from aforementioned shield side,,, make that the photoresist on the photosensitive film plate makes public then by the argon laser of ground glass diffusion through aforementioned slots as the argon laser of 514nm.
Repeat aforementioned shown in exposure, make the photoresist exposure of whole of photosensitive film plate.Then, the photosensitive film after the exposure is developed, obtain relief pattern and form sheet (diffuser).
In addition, the gray scale file changing image of comparative example 4 is shown in Fig. 9, and the Fourier transform image of gray scale document image is shown in Figure 10.In addition, draw boost line L4 along horizontal direction, be illustrated in Figure 11 with what the brightness on this boost line mapping obtained from the picture centre of Figure 10.Further, in Figure 10, draw the boost line L5 perpendicular to value Y part, be illustrated in Figure 12 with what the mapping of the brightness on this boost line L5 obtained with boost line L4.
(comparative example 5)
Except used thickness is that 50 μ m, Young modulus are 2 stretching polyethylene terephthalate thin film (Teijin Ltd makes G2) replacement heat shrink property film of 5GPa, the same with embodiment 1, attempt to obtain relief pattern and form sheet (diffuser).Yet, fail to form wavy relief pattern, do not obtain relief pattern and form sheet (diffuser).
(comparative example 6)
At the thickness along the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate system heat shrink property shrinkable film (the Mitsubishi Plastic of 3GPa; Inc. the HISHIPET LX-10S that makes; Glass transition temperature is 70 ℃) a face on, adopt excellent rubbing method, the Young modulus that coating is diluted in toluene is dimethyl silicone polymer (the KS 847T of Shin-Etsu Chemial Co., Ltd of 2MPa; Glass transition temperature is-120 ℃) and the dispersion liquid of platinum catalyst (CAT-PL-50T of Shin-Etsu Chemial Co., Ltd); Making its thickness is 200mm, forms hard layer, thereby obtains laminate.
Then, this laminate was heated 1 minute down at 100 ℃, make its thermal shrinkage, attempt to obtain relief pattern and form sheet, but fail to make the hard layer folded deformation, do not form wavy relief pattern.
Through atomic force microscope (Veeco Instruments make NanoScopeIII) from the relief pattern of embodiment 1～8 and comparative example 1～6 form sheet diffuser above photograph.
The relief pattern that utilizes the image of atomic force microscope to measure embodiment 1～8 and comparative example 1～4 forms the degree of depth of relief pattern at 10 places of sheet, and these values are average, tries to achieve mean depth.
In addition, the degree of orientation of relief pattern is tried to achieve through following method.
At first, through of the top photograph of surface optics microscope, be gray scale file (with reference to Fig. 3) with this image transformation to relief pattern.Then, the image with the gray scale file carries out Fourier transform.Fig. 4 shows the image behind the Fourier transform.Then, draw boost line L from the picture centre of Fig. 4 along horizontal direction
2, with the mapping of the brightness on this boost line (with reference to Fig. 5).Then, in Fig. 5, draw and boost line L
2Boost line L perpendicular to value X part (inverse of mode spacing)
3, with this boost line L
3On brightness mapping (with reference to Fig. 6).Then, the half breadth W through the peak value in Fig. 6 mapping
1Try to achieve the degree of orientation of relief pattern.These values are shown in table 1.
In addition, based on following benchmark, estimate well-formedness as diffuser through the mode spacing of relief pattern and the mean depth of bottom.This evaluation result is shown in table 1.
Zero: the mode spacing of relief pattern is for surpassing 1 μ m and below 20 μ m, being 100% o'clock with the mode spacing, and mean depth is more than 10%, and the degree of orientation is 0.3～1.0, and is suitable to diffuser.
△: the mode spacing of relief pattern is below the 1 μ m or surpasses 20 μ m, perhaps, is 100% o'clock with the mode spacing, and mean depth is lower than 10%, and perhaps the degree of orientation is lower than 0.3, not necessarily is fit to as diffuser.
*: can not form relief pattern
Table 1:
Make the embodiment 1～8 of the surface smoothing hard layer folded deformation of laminate, can easily make relief pattern and form sheet.
Further, the mode spacing that the relief pattern of embodiment 1～8 forms the relief pattern of sheet is above 1 μ m and below 20 μ m, is 100% o'clock with aforementioned mode spacing, and the mean depth of bottom is more than 10%, is suitable as diffuser.Mode spacing and the mean depth that embodiment 1～4 can obtain above-mentioned that kind be because the thickness of surface smoothing hard layer for surpass 0.05 μ m and below 5 μ m, deformation rate is more than 10%.
In addition; Form the manufacturing approach of sheet (diffuser) through the relief pattern that embodiment 1 is obtained as the embodiment 5～8 of operation sheet; Can make diffuser easily, it had with relief pattern form the equal mode spacing of sheet (diffuser) and the relief pattern of mean depth.
With respect to this, in comparative example 1 and 2, because the thickness of surface hard smooth layer is below the 0.05 μ m or surpasses 5 μ m that the mode spacing that the relief pattern that obtains forms the relief pattern of sheet (diffuser) is below the 1 μ m or surpasses 20 μ m.In addition, because the deformation rate of comparative example 3 is 3%, the relief pattern that obtains forms sheet, is 100% o'clock with the mode spacing, and the mean depth of relief pattern bottom is lower than 10%.In addition, the degree of orientation of comparative example 4 is lower than 0.3.These comparative examples 1～4 not necessarily are fit to as diffuser.
In addition; Use the comparative example 5 of 2 stretching polyethylene terephthalate thin film as resin bed; And the manufacturing approach of the comparative example 6 of the glass transition temperature that uses the 2nd resin laminate lower than the 1st resin, because the surface smoothing hard layer is failed folded deformation, do not form relief pattern.
Young modulus in following examples; Be to use tension test appearance (ORIENTEC Co.; LTD. the TENSILON RT C-1210 that makes), adopt " the high temperature Young modulus test method of metal material " of JIS Z2280-1993, temperature is changed into the value that records after 23 ℃.When hard layer is made up of metallic compound too.
(embodiment 9)
At the thickness along the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate system heat shrink property film (the Mitsubishi Plastic of 3GPa; Inc. on the face HISHIPET LX-10S that makes); The vacuum evaporation Young modulus is the aluminium of 70GPa; Making its thickness is 0.05 μ m, has obtained forming the laminate of surface smoothing hard layer.
Then; This laminate was heated 1 minute down at 100 ℃; 40% (that is, the deformation rate of distortion is 60%) of length before making its thermal shrinkage for heating obtains hard layer and forms sheet for the relief pattern that has periodic wavy relief pattern along the direction vertical with respect to shrinkage direction.
Then, relief pattern is formed sheet as operation sheet master,, obtain diffuser according to following method.
That is, on the face that is formed with relief pattern of operation sheet master, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that does not join with operation sheet master of filming of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, pushes then.
Then, irradiation ultraviolet radiation above cellulose triacetate film solidifies uncured uv curing resin, and this solidfied material is peeled off from operation sheet master, obtains diffuser.
(embodiment 10)
The relief pattern that will obtain through the method for embodiment 9 forms sheet and uses as operation sheet master, obtains diffuser according to following method.
That is, on the face that is formed with relief pattern of the operation sheet master that embodiment 9 obtains, implement the nickel plating, this nickel coating is peeled off, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that film, that do not join with 2 operation sheets of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, pushes then.
Then, irradiation ultraviolet radiation above cellulose triacetate film solidifies uncured curable resin, and this solidfied material is peeled off from 2 operation sheets, obtains diffuser.
(embodiment 11)
Except using heat-curable epoxy resin replacement ultra-violet solidified resin composition, replace the ultraviolet ray irradiation to make this beyond heat-curable epoxy resin curing through heating, the same with embodiment 10, obtain diffuser.
(embodiment 12)
The same with embodiment 10, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, superimposed thickness is the polymethyl methacrylate film of 50 μ m, then heating.Push thermoplastic polymethyl methacrylate film and 2 operation sheets from both sides, make its cooling curing then, the polymethyl methacrylate film after solidifying is peeled off from 2 operation sheets, obtain diffuser.
(comparative example 7)
Except the thickness of the aluminium of vacuum evaporation is the 0.3 μ m, the same with embodiment 9, obtain diffuser.
(comparative example 8)
Except the thickness of the aluminium of vacuum evaporation is the 0.01 μ m, the same with embodiment 9, obtain diffuser.
(comparative example 9)
At the thickness along the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate system heat shrink property film (the Mitsubishi Plastic of 3GPa; Inc. make HISHIPET LX-10S) a face on; The vacuum evaporation Young modulus is the aluminium of 70GPa; Making its thickness is 0.05 μ m, has obtained forming the laminate of surface smoothing hard layer.
Then,, make its 97% (that is, the deformation rate of distortion is 3%) that is retracted to the preceding length of heating in addition except this laminate was heated 1 minute down at 70 ℃, the same with embodiment 9, obtain diffuser.
Through atomic force microscope (Veeco Instruments make NanoScopeIII) from the relief pattern of embodiment 9～12 and comparative example 7～9 form sheet diffuser above photograph.
The relief pattern that utilizes the image of atomic force microscope to measure embodiment 9～12 and comparative example 7～9 forms the degree of depth of relief pattern at 10 places of sheet, and these values are average, tries to achieve mean depth.
In addition, the degree of orientation of relief pattern is tried to achieve through following method.
At first, through of the top photograph of surface optics microscope, be gray scale file (with reference to Fig. 3) with this image transformation to relief pattern.Then, the image with the gray scale file carries out Fourier transform.Fig. 4 shows the image behind the Fourier transform.Then, draw boost line L from the picture centre of Fig. 4 along horizontal direction
2, with the mapping of the brightness on this boost line (with reference to Fig. 5).In Fig. 5, draw and boost line L
2Boost line L perpendicular to value X part (inverse of mode spacing)
3, with this boost line L
3On brightness mapping (with reference to Fig. 6).Then, the half breadth W through the peak value in the pattern of Fig. 6
1Try to achieve the degree of orientation of relief pattern.
These values are shown in table 2.
In addition, based on following benchmark,, estimate well-formedness as diffuser through the mode spacing of relief pattern and the mean depth of bottom.This evaluation result is shown in table 2.
Zero: the mode spacing of relief pattern is for surpassing 1 μ m and below 20 μ m, being 100% o'clock with the mode spacing, and mean depth is more than 10%, and the degree of orientation is 0.3～1.0, and is suitable to diffuser.
△: the mode spacing of relief pattern is below the 1 μ m or surpasses 20 μ m, perhaps, is 100% o'clock with the mode spacing, and mean depth is lower than 10%, and perhaps the degree of orientation is lower than 0.3, not necessarily is suitable as diffuser.
*: can not form relief pattern
Table 2
The relief pattern that the surface smoothing hard layer folded deformation that makes laminate is obtained forms sheet as the embodiment 9～12 that operation sheet master uses, and can easily make the diffuser with relief pattern.Especially, the mode spacing of the relief pattern of the diffuser that is obtained by embodiment 9～12 is for surpassing 1 μ m and below 20 μ m, being 100% o'clock with aforementioned mode spacing, and the mean depth of bottom is more than 10%, and is suitable to diffuser.In embodiment 9～12, can access the mode spacing and the mean depth of above-mentioned that kind, this is because the thickness of surface smoothing hard layer is above 0.01 μ m and below 0.2 μ m, deformation rate is more than 10%.
With respect to this, in comparative example 7 and 8, because the thickness of surface hard smooth layer is below the 0.01 μ m or surpasses 0.2 μ m that the mode spacing of the relief pattern of the diffuser that obtains is below the 1 μ m or surpasses 20 μ m.In addition, in comparative example 9,, be that the mean depth of the relief pattern bottom of the diffuser that obtained in 100% o'clock is lower than 10% with the mode spacing because deformation rate is 3%.In addition, the degree of orientation of comparative example 10 is lower than 0.3.They not necessarily are suitable as diffuser.
(embodiment 13)
Thickness in the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate system heat shrink property film (the Mitsubishi Plastic of 3GPa; Inc. make HISHIPET LX-60S; Glass transition temperature is 70 ℃) a face on; Coating is with polystyrene (the system PS of Port リ マ one ソ one ス Co., Ltd. of dilution with toluene; Glass transition temperature is 100 ℃), utilizing intaglio press (the K プ リ Application テ イ Application グ Block Le one Off ア one that Matsuo Sangyo Co., Ltd. makes) printing diameter is that 50 μ m, thickness are the point-like of 500mm, obtains printed sheet.
Dot pattern is meant, in width 5cm * length 10cm scope, from the end to end of this length direction, the some area ratio is in 0～100% scope, and every 1cm increases by 10% gradient pattern.In addition, some area ratio 0% expression not printing fully, whole printing of 100% expression.
Then, through this printed sheet was heated 1 minute down at 80 ℃, make 40% (that is, the deformation rate of distortion be 60%) of its thermal shrinkage for the preceding length of heating.Under 80 ℃, the Young modulus of polystyrene (1GPa) is than Young modulus (50MPa) height of polyethylene terephthalate system heat shrink property film.Therefore, at thermal shrinkage time point folded deformation, has periodic wavy relief pattern along the direction formation vertical with respect to shrinkage direction.Thus, obtain on smooth one side, being formed with the relief pattern formation sheet of relief region.
The mode spacing of relief pattern that forms the relief region of sheet at this relief pattern is 5 μ m, and length breadth ratio is 1, and the degree of orientation is 0.3.
The diffuse that the relief pattern that obtains is formed sheet is discovered, the direction vertical with respect to shrinkage direction has in parallel direction and to make the light anisotropic diffusion property of diffusion more consumingly.In addition, diffuse also increases along the big direction of area ratio change of relief region gradually.The relief pattern of such embodiment 13 forms sheet can be used as light diffusing patch.
(embodiment 14)
Except using along two direction of principal axis heat shrink; Thickness is that 25 μ m, Young modulus are polyethylene terephthalate shrinkable film (the Mitsubishi Plastic of 3GPa; Inc. the HISHIPET PX-40S that makes) replace Mitsubishi Plastic; Inc. beyond the HI SHIPET PX-60S that makes, the same with embodiment 13, obtain relief pattern and form sheet.Form at this relief pattern on the face of sheet, form not wavy relief pattern along specific direction.
The mode spacing of the relief pattern of the relief region of this relief pattern formation sheet is 5 μ m, and length breadth ratio is 1.
The optical characteristics that the relief pattern of embodiment 14 is formed sheet is studied, and it has isotropic diffuse.Therefore, the relief pattern of embodiment 14 forms sheet and can be used as the light diffusing patch utilization.
(embodiment 15)
Except utilizing ink-jet printer (the Dimatix Materials Printer DMP-2831 of FUJIFILM Corporation) the printing points, the same with embodiment 13, obtain relief pattern and form sheet.The mode spacing of the relief pattern of the relief region of this relief pattern formation sheet is 5 μ m, and length breadth ratio is 1, and the degree of orientation is 0.3.
The optical characteristics that the relief pattern that obtains is formed sheet is studied, and it has the anisotropic diffusion property identical with embodiment 13.Therefore, the relief pattern of embodiment 15 forms sheet and can be used as light diffusing patch.
(embodiment 16)
The relief pattern that the method for use through embodiment 13 obtains forms sheet as operation sheet master, obtains light diffusing patch according to following method.
Promptly; On the face that is formed with relief pattern of the operation sheet master that is obtained by embodiment 13, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the one side that film, that do not join with operation sheet master of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, pushes then.
Then, above cellulose triacetate film, carry out the ultraviolet ray irradiation, uncured uv curing resin is solidified, this solidfied material is peeled off from operation sheet master, obtain light diffusing patch.
The light diffusing patch that obtains has identical relief region, identical diffuse with the light diffusing patch of embodiment 13.
(embodiment 17)
The relief pattern that the method for use through embodiment 13 obtains forms sheet as operation sheet master, obtains light diffusing patch according to following method.
That is, on the face that is formed with relief pattern of the operation sheet master that obtains through embodiment 13, implement the nickel plating, this nickel coating is peeled off, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that does not join with 2 operation sheets of filming at uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, pushes then.
Then, above cellulose triacetate film, carry out the ultraviolet ray irradiation, uncured curable resin is solidified, this solidfied material is peeled off from 2 operation sheets, obtain light diffusing patch.
The light diffusing patch that obtains has identical relief region, identical diffuse with the light diffusing patch of embodiment 13.
(embodiment 18)
Except using heat-curable epoxy resin to replace ultra-violet solidified resin composition, the utilization heating replaces the ultraviolet ray irradiation to make this beyond heat-curable epoxy resin curing, and is the same with embodiment 17, obtains light diffusing patch.
The light diffusing patch that obtains has identical relief region, identical diffuse with the light diffusing patch of embodiment 13.
(embodiment 19)
The same with embodiment 17, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, superimposed thickness is the polymethyl methacrylate film of 50 μ m, then heating.Push thermoplastic polymethyl methacrylate film and 2 operation sheets from both sides, make its cooling curing then, the polymethyl methacrylate film after solidifying is peeled off from 2 operation sheets, obtain light diffusing patch.
The light diffusing patch that obtains has identical relief region, identical diffuse with the light diffusing patch of embodiment 13.
(embodiment 20)
Thickness in the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate system heat shrink property film (the Mitsubishi Plastic of 3GPa; Inc. the HI SHIPET LX-10S that makes; Glass transition temperature is 70 ℃) a face on, place the mask be formed with a plurality of point-like peristomes (aperture 50 μ m).
The pattern of mask open portion is in width 5cm * length 10cm scope, and from the end to end of this length direction, the peristome area ratio is in 0～100% scope, and every 1cm increases by 10% gradient pattern.In addition, the peristome area ratio is that 0% expression does not have opening, is whole opening of 100% expression.
Then, on a face of heat shrink property film, be placed with under the state of mask, the vacuum evaporation Young modulus is the aluminium of 70GPa, and making its thickness is 0.05 μ m, obtains the vapor deposition sheet.
At this moment, on a face of heat shrink property film, form the aluminium point.This dot pattern is, in width 5cm * length 10cm scope, from the end to end of this length direction, the some area ratio is in 0～100% scope, and every 1cm increases by 10% gradient pattern.In addition, 0% expression of some area ratio does not have vapor deposition fully.Whole vapor deposition of 100% expression.
Then, through this vapor deposition sheet was heated 1 minute down at 100 ℃, make 40% (that is, the deformation rate of distortion be 60%) of its thermal shrinkage for the preceding length of heating.At thermal shrinkage time point folded deformation, has periodic wavy relief pattern along the direction formation vertical with respect to shrinkage direction.Thus, obtain on a face, being formed with the relief pattern formation sheet of relief region.
The mode spacing of relief pattern that forms the relief region of sheet at this relief pattern is 3 μ m, and length breadth ratio is 1, and the degree of orientation is 0.3.
Then, the relief pattern that obtains is formed sheet use, obtain light diffusing patch according to following method as operation sheet master.
That is, on the face that is formed with relief pattern of the operation sheet master that obtains, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the one side of not joining with operation sheet master of filming of uncured ultra-violet solidified resin composition, superimposed thickness is to push then behind the cellulose triacetate film of 50 μ m.
Then, above cellulose triacetate film, carry out the ultraviolet ray irradiation, uncured uv curing resin is solidified, this solidfied material is peeled off from operation sheet master, obtain light diffusing patch.
Light diffusing patch to obtaining discovers, it has the anisotropy diffuse identical with embodiment 13.
(embodiment 21)
Except using along the thickness of two direction of principal axis heat shrink is 25 μ m, Young modulus polyethylene terephthalate shrinkable film (the Mitsubishi Plastic as 3GPa; Inc. the HISHIPET PX-40S that makes) replace Mitsubishi Plastic; Inc. beyond the HISHIPET LX-60S that makes; The same with embodiment 20, obtain relief pattern and form sheet.The mode spacing of relief pattern that forms the relief region of sheet at this relief pattern is 3 μ m, and length breadth ratio is 1.
Then, use this relief pattern to form sheet, the same with embodiment 20, obtain light diffusing patch.Optical characteristics to the light diffusing patch of embodiment 21 discovers that it has isotropic diffuse.
(embodiment 22)
The relief pattern that will obtain through the method for embodiment 20 forms sheet and uses as operation sheet master, obtains light diffusing patch according to following method.
That is, on the face that is formed with relief pattern of the operation sheet master that obtains through embodiment 20, implement the nickel plating, this nickel coating is peeled off, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that film, that do not join with 2 operation sheets of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, pushes then.
Then, above cellulose triacetate film, carry out the ultraviolet ray irradiation, uncured curable resin is solidified, this solidfied material is peeled off from 2 operation sheets, obtain light diffusing patch.
The light diffusing patch that obtains has identical relief region, identical diffuse with the light diffusing patch of embodiment 20.
(embodiment 23)
Except using heat-curable epoxy resin to replace ultra-violet solidified resin composition, the use heating replaces the ultraviolet ray irradiation to make this beyond heat-curable epoxy resin curing, and is the same with embodiment 22, obtains light diffusing patch.
The light diffusing patch that obtains has identical relief region, identical diffuse with the light diffusing patch of embodiment 20.
(embodiment 24)
The same with embodiment 22, obtaining thickness is 2 operation sheets of 200 μ m.On the face that is formed with relief pattern of these 2 operation sheets, superimposed thickness is the polymethyl methacrylate film of 50 μ m, then heating.Push thermoplastic polymethyl methacrylate film and 2 operation sheets from both sides, make its cooling curing then, the polymethyl methacrylate film that solidifies is peeled off from 2 operation sheets, obtain light diffusing patch.
The light diffusing patch that obtains has the relief region identical with the light diffusing patch of embodiment 20, has identical diffuse.
Be mixed with the optical sheet of the embodiment 13～24 of relief region for a face, because the relief pattern of relief region makes light generation diffusion, so diffuse is excellent.In addition and since the relief region of above-mentioned optical sheet at the other end of length direction by compact configuration, the diffuse of the other end of length direction is high.
The Young modulus of following examples is to use tension test appearance (TE-7001 that TESTER SANGYO CO., LTD make), the value that records based on JIS K 7113-1995 benchmark.When temperature not being put down in writing especially, be the value under 23 ℃.
(embodiment 25)
Thickness in the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate shrinkable film (the Mitsubishi Plastic of 3GPa; Inc. the HISHIPET LX-60S that makes; Glass transition temperature is 70 ℃) a face on, through spin-coating method coating polymethylmethacrylate (Port リ マ one ソ one ス Co., Ltd. makes P4831-MMA, and glass transition temperature is 100 ℃) with dilution with toluene; Making its thickness is 12nm, has obtained forming the laminate of hard layer.
Then; This laminate was heated 1 minute down at 80 ℃; Make its 40% (that is, the deformation rate of distortion is 60%) that is punctured into the preceding length of heating, obtain hard layer and form sheet at the relief pattern that the direction vertical with respect to shrinkage direction has periodic wavy relief pattern.
In addition, the polyethylene terephthalate shrinkable film is respectively 50Mpa, 1GPa with the Young modulus of this polymethylmethacrylate under 80 ℃.
(embodiment 26)
Thickness in the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate shrinkable film (the Mitsubishi Plastic of 3GPa; Inc. make HISHIPETLX-61S, glass transition temperature is 70 ℃) a face on, the coating dilute with water polyvinyl alcohol (PVA) (KURARAY CO.; The PVA 105 that L TD. makes; Glass transition temperature is 85 ℃), making its thickness is 12nm, has obtained forming the laminate of hard layer.
Then; This laminate was heated 1 minute down at 75 ℃; Make its 50% (that is, the deformation rate of distortion is 50%) that is punctured into the preceding length of heating, obtain hard layer and form sheet at the relief pattern that the direction vertical with respect to shrinkage direction has periodic wavy relief pattern.
In addition, the polyethylene terephthalate shrinkable film is respectively 50Mpa, 1GPa with the Young modulus of this polymethylmethacrylate under 75 ℃.
(embodiment 27)
Thickness in the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate shrinkable film (the Mitsubishi Plastic of 3GPa; Inc. the HISHIPET LX-61S that makes; Glass transition temperature is 70 ℃) a face on; Vapor deposition fluororesin (the NANOS B that T&K Inc. makes) also solidifies, and making its thickness is 12 μ m, obtains forming the laminate of hard layer.
Then; This laminate was heated 1 minute down at 75 ℃; Thereby make its 50% (that is, the deformation rate of distortion is 50%) that is punctured into the preceding length of heating, obtain hard layer and have the relief pattern formation sheet that has periodic wavy relief pattern in the direction vertical with respect to shrinkage direction.
(embodiment 28)
Utilizing stretching device, will be that 2MPa, thickness are the sheet stretching of 5mm by the Young modulus that dimethyl silicone polymer constitutes, and make its length become 2 times, be fixed in then under this state.Then, under this state, on a face of this sheet; Coating is with polymethylmethacrylate (the system P4831-MMA of Port リ マ one ソ one ス Co., Ltd. of dilution with toluene; Glass transition temperature is 100 ℃), making its thickness is 12nm, has obtained forming the laminate of hard layer.
Then, stop to stretch, make this laminate be returned to the length before stretching, make hard layer, obtain hard layer and have the relief pattern formation sheet that has periodic wavy relief pattern in the direction vertical with respect to compression direction with deformation rate 50% compression.
(embodiment 29)
On a face of the sheet of the Young modulus 2MPa that constitutes by dimethyl silicone polymer, thickness 5mm; Coating is with polymethylmethacrylate (the system P4831-MMA of Port リ マ one ソ one ス Co., Ltd. of dilution with toluene; Glass transition temperature is 100 ℃); Making its thickness is 12nm, obtains forming the laminate of hard layer.
Then; Through stretching device the length of laminate is stretched to 5 times length; Length along the normal direction of draw direction is shunk 50% (that is, the deformation rate of distortion is 50%), obtains hard layer and has the relief pattern that has a periodic wavy relief pattern along draw direction and form sheet.
(comparative example 10)
Except the coating polymethylmethacrylate, making its thickness is beyond the 60nm, the same with embodiment 25, obtains relief pattern and forms sheet.
(comparative example 11)
Except used thickness is that 50 μ m, Young modulus are 2 stretching polyethylene terephthalate thin film (Teijin Ltd makes G2) replacement shrinkable film of 5GPa, the same with embodiment 25, attempt to obtain relief pattern and use the operation sheet.Yet, fail to form wavy relief pattern, do not obtain relief pattern and use the operation sheet.
(comparative example 12)
Thickness in the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate shrinkable film (the Mitsubishi Plastic of 3GPa; Inc. the HISHIPET LX-10S that makes; 70 ℃ of glass transition temperatures) on the face, coating is with the polymethylmethacrylate (the system P4831-MMA of Port リ マ one ソ one ス Co., Ltd., glass transition temperature is 100 ℃) of dilution with toluene; Making its thickness is 12nm, has obtained forming the laminate of surface smoothing hard layer.
Then, this laminate was heated 1 minute down at 70 ℃, make it be retracted to 97% (that is, the deformation rate of distortion is 3%) of the preceding length of heating, obtain the relief pattern operation with beyond the sheet, the same with embodiment 25, obtain relief pattern and form sheet.
(comparative example 13)
Thickness in the thermal shrinkage of single shaft direction is that 50 μ m, Young modulus are polyethylene terephthalate shrinkable film (the Mitsubishi Plastic of 3GPa; Inc. the HISHIPET LX-10S that makes; Glass transition temperature is 70 ℃) a face on; Adopt spin-coating method, coating uses the Young modulus of dilution with toluene to be the dimethyl silicone polymer (the KS 847T of Shin-Etsu Chemial Co., Ltd, glass transition temperature are-120 ℃) of 2MPa and the dispersion liquid of platinum catalyst (PS-1 of Shin-Etsu Chemial Co., Ltd); Making its thickness is 12nm, has obtained forming the laminate of hard layer.
Then, 100 ℃ of down heating 1 minute, attempt forms sheet through making its heat shrink obtain relief pattern with this laminate, but fails to make the hard layer distortion of crawling, and fails to form wavy relief pattern.
(embodiment 30)
To form sheet by the relief pattern that embodiment 25 obtains and use, obtain optical element according to following method as the operation sheet.
That is, on the face that is formed with relief pattern of the operation sheet that is obtained by embodiment 25, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that film, that do not join with the operation sheet of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, pushes then.
Then, above cellulose triacetate film, carry out the ultraviolet ray irradiation, uncured curable resin is solidified, this solidfied material is peeled off from the operation sheet, obtain optical element.
(embodiment 31)
To form sheet by the relief pattern that embodiment 25 obtains as the operation sheet, obtain optical element according to following method.
That is, on the face that is formed with relief pattern of the operation sheet that is obtained by embodiment 25, implement the nickel plating, this nickel coating is peeled off, obtaining thickness is the nickel plating sheet of 200 μ m.On the face that is formed with relief pattern of this nickel plating sheet, coating contains the uncured ultra-violet solidified resin composition that epoxy acrylate is prepolymer, 2-ethylhexyl acrylate and benzophenone series Photoepolymerizationinitiater initiater.
Then, on the face that film, that do not join with the operation sheet of uncured ultra-violet solidified resin composition, superimposed thickness is the cellulose triacetate film of 50 μ m, pushes then.
Then, above cellulose triacetate film, carry out the ultraviolet ray irradiation, uncured curable resin is solidified, this solidfied material is peeled off from the operation sheet, obtain optical element.
(embodiment 32)
Except using heat-curable epoxy resin to replace ultra-violet solidified resin composition, the use heating replaces the ultraviolet ray irradiation to make this beyond heat-curing resin curing, and is the same with embodiment 31, obtains optical element.
(embodiment 33)
The same with embodiment 11, obtaining thickness is the nickel plating sheet of 200 μ m.On the face that is formed with relief pattern of this nickel plating sheet, superimposed thickness is the polymethyl methacrylate film of 50 μ m, and heating.Push thermoplastic polymethyl methacrylate film and nickel plating sheet from both sides, make its cooling curing then, it is peeled off from nickel plating sheet, obtain relief pattern and form sheet.
Through atomic force microscope (Veeco Instruments make NanoScopeIII), from the relief pattern of embodiment 25～33, comparative example 10～13 form sheet optical element above photograph.
The relief pattern that utilizes the image of atomic force microscope to measure embodiment 25～33, comparative example 10～13 forms the degree of depth of relief pattern at 10 places of the optical element of sheet, and these values are average, tries to achieve mean depth.
These values are shown in table 3.
In addition, based on following benchmark, estimate well-formedness as diffuser through the mode spacing of relief pattern and the mean depth of bottom.This evaluation result is shown in table 3.
Zero: the mode spacing of relief pattern is below the 1 μ m, is 100% o'clock with the mode spacing, and mean depth is more than 10%, and is suitable to optical element.
*: the mode spacing of relief pattern surpasses below the 1 μ m, perhaps, is 100% o'clock with the mode spacing, and mean depth is lower than 10%, is not suitable for as optical element.
Table 3
The laminate that makes a face of the 1st resinous base material be provided with the hard layer that is made up of than high the 2nd resin more than 10 ℃ of the 1st resin glass transition temperature the crawl embodiment 25～29 of distortion, the manufacturing approach of comparative example 10,12 can easily be made relief pattern and form sheet.In addition, the mode spacing that the relief pattern that is obtained by embodiment 25～29 forms the relief pattern of sheet is below the 1 μ m, is 100% o'clock in aforementioned mode spacing, and the mean depth of bottom is more than 10%, and is suitable to optical element.In embodiment 25～29, can obtain the mode spacing and the mean depth of above-mentioned that kind, this is that deformation rate is more than 50% because the thickness of surface smoothing hard layer is below the 50nm.
In addition,, can make optical element easily, it had with relief pattern form the equal mode spacing of sheet and the relief pattern of mean depth through forming the manufacturing approach of sheet by the relief pattern that embodiment 25 obtains as the embodiment 30～33 of operation sheet.
In addition, in comparative example 10, because the thickness of surface hard smooth layer surpasses 50nm, the mode spacing that the relief pattern that therefore obtains forms the relief pattern of sheet surpasses 1 μ m.In addition, because the deformation rate of comparative example 12 is 3%, be 100% o'clock with the mode spacing, the mean depth that the relief pattern that obtains forms the relief pattern bottom of sheet is lower than 10%.Therefore, they not necessarily are suitable for as optical element.
With respect to this; As resin bed; The manufacturing approach of using the comparative example 11 of 2 stretching polyethylene terephthalate thin film and using the comparative example 13 of the glass transition temperature of the 2nd resin laminate lower than the 1st resin; Therefore the distortion because the surface smoothing hard layer does not crawl does not form relief pattern.
Utilizability on the industry
Relief pattern of the present invention forms sheet can be used as diffuser, can make easily.Through the manufacturing approach of relief pattern formation sheet of the present invention, the relief pattern that can make easily as diffuser forms sheet.
The anisotropy of the diffusion of diffuser of the present invention is excellent.Through the manufacturing approach of diffuser manufacturing of the present invention with operation sheet and diffuser, can make diffuser easy and in large quantities, make it be formed with to have and form the equal mode spacing of sheet and the relief pattern of mean depth with relief pattern.
The objective optics excellent of optical sheet of the present invention, and can easily make optical characteristics inhomogeneous.The target light diffusive of light diffusing patch of the present invention is excellent, and can easily make diffuse inhomogeneous.
Through diffusion light conductor of the present invention and back light unit, can make the light that sends from light source anisotropic diffusion fully.
Relief pattern of the present invention forms sheet, suits to use as optical elements such as antireflection object, polarizers.In addition, relief pattern of the present invention forms sheet and also suits to use with the operation sheet as the optical element manufacturing, and it is reserved as the mould of making the optical element with wavy relief pattern.
Claims (7)
1. a relief pattern forms the manufacturing approach of sheet; It is characterized in that; Have on a face of resin base material, be provided with surface smoothing, thickness be to surpass the operation of 0.05 μ m and the resin system hard layer cambium layer compressing tablet below 5.0 μ m and makes the operation of the folded deformation of hard layer at least of said laminate
Hard layer is made up of than the high resin more than 10 ℃ of the resin that constitutes base material glass transition temperature.
2. relief pattern according to claim 1 forms the manufacturing approach of sheet, and it uses single shaft direction heat shrink property film as resin base material, in the operation that makes the hard layer folded deformation, and zone of heating compressing tablet and single shaft direction heat shrink property film is shunk.
3. a relief pattern forms sheet, it is characterized in that, said relief pattern forms sheet and has the resin system hard layer on resin base material and at least a portion that is arranged at said base material outside surface, and said hard layer has wavy relief pattern,
Constitute the glass transition temperature Tg of the resin of hard layer
2Glass transition temperature Tg with the resin that constitutes base material
1Difference be Tg
2-Tg
1Be more than 10 ℃,
The mode spacing of relief pattern is below the 1 μ m, is being 100% o'clock with said mode spacing, and the mean depth of relief pattern bottom is more than 10%.
4. a relief pattern forms the manufacturing approach of sheet; It is characterized in that; It has resin system hard layer that surface smoothing is set at least a portion of resin base material outside surface and the operation of cambium layer compressing tablet is crawled distortion so that the degree of orientation of said relief pattern is 0.3～1.0 operation with the hard layer at least that makes the aforementioned layers compressing tablet
Hard layer is made up of than the high resin more than 10 ℃ of the resin that constitutes base material glass transition temperature.
5. antireflection object, it possesses the described relief pattern of claim 3 and forms sheet.
6. polarizer, it possesses the described relief pattern of claim 3 and forms sheet.
7. the operation sheet is used in an optical element manufacturing; It uses as the mould of making optical element; It possesses the characteristic that the described relief pattern of claim 3 forms sheet, and said optical element has with said relief pattern and forms the equal mode spacing of sheet and the relief pattern of mean depth.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007040694A JP5211506B2 (en) | 2007-02-21 | 2007-02-21 | Convex and concave pattern forming sheet and manufacturing method thereof, antireflection body, retardation plate and optical element manufacturing process sheet. |
| JP2007-040694 | 2007-02-21 | ||
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| JP2007-151795 | 2007-06-07 | ||
| JP2007261176A JP5391539B2 (en) | 2007-10-04 | 2007-10-04 | Optical sheet and manufacturing method thereof |
| JP2007-261176 | 2007-10-04 |
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| CN2007800514959A Division CN101611332B (en) | 2007-02-21 | 2007-11-07 | Sheet having uneven pattern formed thereon and method for production thereof |
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| CN102628969B CN102628969B (en) | 2014-10-08 |
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| CN201410354369.2A Expired - Fee Related CN104122612B (en) | 2007-02-21 | 2007-11-07 | Sheet having uneven pattern formed thereon and method for production thereof |
| CN201210109843.6A Expired - Fee Related CN102628969B (en) | 2007-02-21 | 2007-11-07 | Sheet having uneven pattern formed thereon and method for production thereof |
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| KR (5) | KR101456522B1 (en) |
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- 2007-11-07 KR KR1020157003702A patent/KR101541288B1/en active IP Right Grant
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| CN108476562A (en) * | 2015-12-10 | 2018-08-31 | 王子控股株式会社 | The manufacturing method of substrate, optical element, mold, organic illuminating element, organic thin film solar cell and substrate |
| CN108476562B (en) * | 2015-12-10 | 2020-01-21 | 王子控股株式会社 | Substrate, optical element, mold, organic light-emitting element, organic thin-film solar cell, and method for manufacturing substrate |
| CN109791248A (en) * | 2016-09-29 | 2019-05-21 | 迪睿合株式会社 | Optical body, the manufacturing method of optical body and light emitting device |
| US10883676B2 (en) | 2016-09-29 | 2021-01-05 | Dexerials Corporation | Optical body having a concave-convex structure, method for manufacturing the optical body, and light emitting device |
| TWI731228B (en) * | 2017-03-29 | 2021-06-21 | 日商大日本印刷股份有限公司 | Optical film and image display device |
| WO2019127856A1 (en) * | 2017-12-29 | 2019-07-04 | 珠海迈时光电科技有限公司 | Diffractive optical element and optical device comprising same diffractive optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI536048B (en) | 2016-06-01 |
| TW201418785A (en) | 2014-05-16 |
| TW201418786A (en) | 2014-05-16 |
| TW201631332A (en) | 2016-09-01 |
| TWI448736B (en) | 2014-08-11 |
| KR20120085940A (en) | 2012-08-01 |
| TW201418783A (en) | 2014-05-16 |
| KR101193615B1 (en) | 2012-10-26 |
| KR101456522B1 (en) | 2014-11-04 |
| KR101541287B1 (en) | 2015-08-03 |
| TWI598638B (en) | 2017-09-11 |
| WO2008102487A1 (en) | 2008-08-28 |
| TWI518376B (en) | 2016-01-21 |
| CN104122612A (en) | 2014-10-29 |
| KR20140027530A (en) | 2014-03-06 |
| TW201418784A (en) | 2014-05-16 |
| KR20090125061A (en) | 2009-12-03 |
| TWI530713B (en) | 2016-04-21 |
| CN104122612B (en) | 2017-04-12 |
| TW201447389A (en) | 2014-12-16 |
| TW200912388A (en) | 2009-03-16 |
| TWI536047B (en) | 2016-06-01 |
| TWI545351B (en) | 2016-08-11 |
| CN102628969B (en) | 2014-10-08 |
| KR20150027304A (en) | 2015-03-11 |
| CN102176079A (en) | 2011-09-07 |
| CN102176079B (en) | 2013-01-23 |
| KR101541288B1 (en) | 2015-08-03 |
| KR20140027529A (en) | 2014-03-06 |
| KR101414004B1 (en) | 2014-08-05 |
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