WO2018212359A1 - 反射防止部材 - Google Patents
反射防止部材 Download PDFInfo
- Publication number
- WO2018212359A1 WO2018212359A1 PCT/JP2018/019479 JP2018019479W WO2018212359A1 WO 2018212359 A1 WO2018212359 A1 WO 2018212359A1 JP 2018019479 W JP2018019479 W JP 2018019479W WO 2018212359 A1 WO2018212359 A1 WO 2018212359A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- convex
- antireflection member
- convex portion
- portions
- concave
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
Definitions
- the present invention relates to an antireflection member.
- a method of forming a nano-order fine uneven structure on the surface of a display is known.
- a fine uneven structure called “moth eye structure” has attracted attention.
- innumerable fine projections having a circular or polygonal bottom having a circular or polygonal bottom smaller than the wavelength of visible light are arranged at a pitch smaller than the wavelength of visible light.
- the refractive index in the thickness direction of the microstructure is determined by the area occupied by the material in each cross section in the thickness direction, the refractive index in the thickness direction of the moth-eye structure does not change abruptly.
- the refractive index in the thickness direction changes gently and continuously from the refractive index of air 1.0 to the refractive index of the substrate material of the display.
- the light incident on the surface of the display goes straight without almost any diffraction or reflection.
- the moth-eye structure on the surface it becomes possible to effectively reduce the reflectance of light on the incident surface.
- Patent Document 2 describes a concavo-convex pattern forming sheet used as an antireflection body.
- the antireflection body is formed by forming a hard layer made of a metal or a metal compound on a resin layer and causing the hard layer to meander and deform by contracting the resin layer.
- the moth-eye structure as described in Patent Document 1 has low mechanical strength, the convex part of the concavo-convex structure falls down due to friction or the like, and the effect of reducing the reflectance (that is, the antireflection effect) is likely to be impaired. .
- the antireflection body formed by the shrinkage of the resin layer as described in Patent Document 2 has a large in-plane variation in the unevenness depth, whereby light is easily scattered. Therefore, such an antireflective body has a problem that haze (cloudiness) is high.
- An object of the present invention is to provide an antireflection member having a high antireflection effect and wear resistance.
- an antireflection member having an uneven surface defined by convex portions and concave portions
- a Fourier transform image obtained by performing a two-dimensional fast Fourier transform process on the observation image of the concavo-convex surface shows a circular or annular pattern having an approximate center at the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1
- the convex portion and the concave portion extend in a random direction in plan view, In the cross section of the convex portion cut by a plane perpendicular to the extending direction of the convex portion, the width of the convex portion decreases from the bottom portion to the top portion of the convex portion, and 0.95D (D Is the height W of the protrusion), and the width W2 of the protrusion at a height of 0.05D from the bottom is 0.04P ⁇ W1 ⁇ 0.21P, 0
- An antireflection member satisfying .79P ⁇ W2 ⁇ 0.96P and 4.0
- an antireflection member having an uneven surface defined by convex portions and concave portions
- a Fourier transform image obtained by performing a two-dimensional fast Fourier transform process on the observation image of the concavo-convex surface shows a circular or annular pattern having an approximate center at the origin where the absolute value of the wave number is 0 ⁇ m ⁇ 1 ,
- the width of the convex portion decreases from the bottom portion to the top portion of the convex portion,
- the average pitch of the irregularities on the irregular surface is in the range of 150 to 250 nm,
- the average depth of the irregularities on the irregular surface is in the range of 90 to 300 nm
- an antireflection member having an aspect ratio of the convex portion within a range of 0.4-2.
- the antireflection member of the present invention has a high antireflection effect and wear resistance. Therefore, the antireflection member of the present invention can be suitably used for various applications.
- FIG. 1 is a schematic cross-sectional view of an antireflection member according to an embodiment.
- FIG. 2 shows an example of a planar structure of the uneven surface of the antireflection member according to the embodiment.
- FIG. 3 is an example of a Fourier transform image of the planar observation image of the uneven surface of the antireflection member according to the embodiment.
- FIG. 4 (a) is a schematic perspective view of a convex portion having a shape extending long and having a substantially triangular cross section cut by a plane perpendicular to the extending direction
- FIG. FIG. 5 is a diagram conceptually showing a concavo-convex surface having a convex portion shown in FIG. 4A and a refractive index n (z) in the vicinity thereof.
- FIG. 5A is a schematic perspective view of a convex portion having a shape extending long and having a parabolic outer shape cut in a plane perpendicular to the extending direction
- FIG. FIG. 6 is a diagram conceptually showing a concavo-convex surface having a convex portion shown in FIG. 5A and a refractive index n (z) in the vicinity thereof.
- FIG. 6A is a schematic perspective view of a convex portion having a substantially triangular cross section cut along a plane parallel to the height direction in the conventional moth-eye structure, and FIG. It is a figure which represents conceptually the refractive index n (z) in the uneven
- FIG. 7A is a schematic perspective view of a convex portion having a parabolic parabolic outer shape cut in a plane parallel to the height direction in the conventional moth-eye structure
- FIG. It is a figure which represents conceptually the refractive index n (z) in the uneven
- FIGS. 8A to 8G are diagrams conceptually showing each process of the manufacturing method of the antireflection member.
- FIG. 9A is a graph showing the calculation result of the transmittance when the uneven pitch is 160 nm
- FIG. 9B is a graph showing the calculation result of the transmittance when the uneven pitch is 200 nm.
- the antireflection member 100 includes a base material 40 and a concavo-convex structure layer 50 formed thereon.
- the concavo-convex structure layer 50 has a convex portion 60 and a concave portion 70 defined by the convex portion 60.
- the uneven structure layer 50 has an uneven surface 80.
- the base material 40 may be any translucent base material.
- base materials made of transparent inorganic materials such as glass, polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc.), acrylic resins (polymethyl methacrylate, etc.), polycarbonate, polyvinyl chloride, styrene resins (ABS resin etc.), Cellulosic resin (Triacetyl cellulose etc.), Polyimide resin (Polyimide resin, Polyimide amide resin etc.), Substrates which consist of resin, such as a cycloolefin polymer, are mentioned.
- the uneven structure layer 50 includes a protrusion 60. A portion sandwiched or surrounded by the convex portion 60 becomes the concave portion 70.
- the concavo-convex structure layer 50 may be made of a translucent material, for example, a Si-based material such as silica, SiN, or SiON, a Ti-based material such as TiO 2, or an ITO (indium tin oxide) -based material.
- inorganic materials such as ZnO, ZnS, ZrO 2 , Al 2 O 3 , BaTiO 3 , Cu 2 O, MgS, AgBr, CuBr, BaO, Nb 2 O 5 , SrTiO 2 , or described in WO2016 / 056277
- a resin material such as a thermoplastic resin and an ultraviolet curable resin may be used.
- the inorganic material may be a xerogel obtained by curing a precursor (sol) of an inorganic material by a sol-gel method. Xerogel has a three-dimensional network composed of strong covalent bonds such as Si—O bonds, and has sufficient mechanical strength.
- the uneven structure layer 50 may be composed of a composite material of the resin material and the inorganic material.
- the inorganic material, the resin material, or the composite material thereof may contain known fine particles and fillers.
- the inorganic material, the resin material, or a composite material thereof may contain an ultraviolet absorbing material.
- the ultraviolet absorbing material has an action of suppressing deterioration of the concavo-convex structure layer 50 by absorbing ultraviolet rays and converting light energy into a harmless form such as heat.
- an ultraviolet absorber arbitrary things, such as an ultraviolet absorber illustrated by WO2016 / 056277, can be used.
- the difference between the refractive index of the material constituting the concavo-convex structure layer 50 and the refractive index of the material constituting the substrate 40 may be ⁇ 0.1 or less. Thereby, reflection of light at the interface between the substrate 40 and the concavo-convex structure layer 50 is suppressed.
- FIG. 2 shows an example of a planar structure of the uneven surface 80.
- the uneven surface 80 is defined by a plurality of convex portions 60 (white portions) and a concave portion (black portion) 70 surrounding the convex portions 60.
- the plurality of convex portions 60 includes a plurality of extending portions 60e and a plurality of point portions 60d.
- the extending portion 60e has an elongated shape that extends in a random (non-uniform) direction in a straight line or by being bent (wound).
- the extending direction, the bending direction (swelling direction), and the extending length of the extending part 60e are not uniform. Some or all of the plurality of extending portions 60e may be branched in the middle.
- the point 60d has a circular or elliptical shape.
- the circular or elliptical shape includes a substantially circular or elliptical shape.
- the some convex part 60 may be comprised only from the some extension part 60e. That is, the point part 60d is not essential.
- the concave portion 70 extends in a random direction so as to surround each convex portion 60, and is continuous (connected) two-dimensionally as a whole.
- the concave portion 70 may include an independent portion surrounded by the annular convex portion 60.
- the concave portion 70 and the convex portion 60 are isotropically disposed as a whole.
- the concavo-convex surface 80 having such concave portions 70 and convex portions 60 is clearly different from the concavo-convex surface composed of regularly oriented convex portions such as stripes, wavy stripes, and zigzags, and dot-shaped convex portions.
- the concave and convex surface 80 in which the concave portions 70 and the convex portions 60 are arranged isotropic in this manner has less effect of confining light of a specific wavelength as compared with a surface on which a regular pattern such as a stripe is formed, The rainbow appearance of the antireflection member 100 (appearing colored according to the viewing angle) is suppressed.
- the concavo-convex structure layer 50 having such an isotropic concavo-convex surface 80 is cut along an arbitrary plane orthogonal to the surface of the substrate 40, the concavo-convex cross section appears repeatedly.
- the uneven surface may be one obtained by inverting the concave and convex portions shown in FIG.
- the uneven surface is defined by the plurality of recesses and the protrusions surrounding the recesses.
- the plurality of recesses are composed of a plurality of extending portions and a plurality of point portions, but the point portions are not essential.
- the convex portions 60 are continuous (connected) as a whole, even if the surface of the antireflection member 100 is rubbed, the convex portions 60 are not easily collapsed, and the antireflection member 100 has high wear resistance.
- many of the plurality of convex portions 60 are convex portions having a long extension length, and the proportion of the convex portions having a short extension length or a substantially dotted shape is small. preferable.
- the sum of the peripheral lengths of the convex portions 60 having a peripheral length (contour) that is 7 times or less the average pitch P of the unevenness described later is the circumference of the plurality of convex portions 60. It may be 10% or less of the total.
- the convex portion having a circumferential length of 7 times or less of the average pitch P of the unevenness has an extension length of about 3 times or less of the average pitch P and a short extension length.
- the ratio of such convex portions is 10% or less, the haze of the antireflection member 100 is less than 0.5%.
- “Sum of peripheral lengths of a plurality of convex portions” and “Sum of peripheral lengths of convex portions having a peripheral length not more than 7 times the average pitch P of unevenness among a plurality of convex portions” are obtained as follows. Can do. From the planar SEM image of the concavo-convex surface, a square region whose one side is 40 times or more the average pitch P of the concavo-convex is cut out. Using the image processing analysis software, the clipped image is binarized. Furthermore, using the image processing analysis software, the circumferences of the white portions that are not in contact with the outer circumference of the image are obtained.
- a value obtained by adding all the obtained perimeters is “the sum of the perimeters of the plurality of convex portions”.
- a value obtained by adding all of the obtained peripheral lengths that are 7 times or less of the average pitch P of unevenness is “a convex portion having a peripheral length of 7 times or less of the average pitch P of unevenness among a plurality of convex portions. Is the total perimeter of
- the sum of the peripheral lengths of the concave portions having a peripheral length equal to or less than seven times the average pitch P of the concave and convex portions among the plurality of concave portions It may be 10% or less of the total circumference of the plurality of recesses.
- the “total sum of the perimeters of the plurality of recesses” and the “total sum of the perimeters of the recesses having a perimeter not more than 7 times the average pitch P of the unevenness among the plurality of recesses” can be obtained as follows.
- a value obtained by adding all of the obtained circumferences that are 7 times or less of the average pitch P of the unevenness is “the circumference of the recess having a circumference of 7 times or less of the average pitch P of the unevenness among the plurality of recesses. The sum of the length.
- corrugated surface 80 may be comprised from the several extension part which has the elongate shape bent and extended. Also in this case, since the convex portion 60 is continuous (connected) for a long time, even if the surface of the antireflection member 100 is rubbed, the convex portion 60 is not easily collapsed, and the antireflection member 100 has high wear resistance.
- a Fourier transform image showing a circular or annular pattern as the center is obtained.
- the circular or annular pattern may exist in a region where the absolute value of the wave number is in the range of 4.0 to 6.7 ⁇ m ⁇ 1 .
- the circular pattern of the Fourier transform image is a pattern that is observed when bright spots are gathered in the Fourier transform image.
- the “circular shape” means that a pattern in which bright spots are gathered appears to have a substantially circular shape, and includes a concept in which a part of the outer shape appears to be convex or concave.
- “annular” means that a pattern of bright spots appears to be almost circular, and includes an outer circle of the ring or an inner circle that appears to be substantially circular, and It is a concept including what appears to be a convex shape or a concave shape in a part of the outer circle or the outer circle.
- a circular or annular pattern exists in a region where the absolute value of the wave number is in the range of 4.0 to 6.7 ⁇ m ⁇ 1 ” means that among the bright spots constituting the Fourier transform image 30% or more (more preferably 50% or more, still more preferably 80% or more, particularly preferably 90% or more) bright point is an area where the absolute value of the wave number is in the range of 4.0 to 6.7 ⁇ m ⁇ 1 It means to exist.
- the following is known about the relationship between the irregular shape in plan view and the Fourier transform image.
- the Fourier transform image is also Random pattern (no pattern).
- the arrangement and the extending direction of the projections and depressions are isotropic as a whole, but when the intervals between the adjacent convex portions or the adjacent concave portions are concentrated within a certain value range, a Fourier transform image Is circular or circular.
- interval of adjacent convex parts or adjacent recessed parts is uniform (constant), a Fourier-transform image becomes a sharp annular shape.
- 2D fast Fourier transform processing of planar observation images can be easily performed by electronic image processing using a computer equipped with 2D fast Fourier transform processing software.
- the average pitch P of the irregularities on the irregular surface 80 may be in the range of 150 to 250 nm.
- the average pitch average pitch P is 150 nm or more, the reflectance of visible light can be sufficiently reduced.
- the average pitch P of the unevenness is 250 nm or less, the scattering of visible light by the uneven surface 80 is suppressed, and it is possible to prevent the antireflection member 100 from appearing colored according to the viewing angle (rainbow appearance).
- the average pitch P of the unevenness means that the top portions 60t of the adjacent protrusions 60 or adjacent recesses in the cross section of the uneven surface 80 cut by a plane perpendicular to the extending direction of the protrusions 60 and / or the recesses 70.
- the average pitch P of the unevenness can be obtained using a scanning probe microscope, an electron microscope or the like.
- the average value of the concavo-convex depth (convex height or concavo-convex depth) D of the concavo-convex surface 80 may be in the range of 90 to 300 nm, and in the range of 200 to 300 nm. Within a range of 250 to 300 nm.
- the average depth of the unevenness is 90 nm or more, the reflectance of visible light can be sufficiently reduced.
- a transmittance of 98.5% or more can be achieved at all wavelengths in the visible light region, as shown in examples described later.
- the antireflection member 100 can have high wear resistance.
- the “concave / convex depth D” means that of the concave portion 70 and the convex portion 60 adjacent to each other in the cross section of the concave / convex surface 80 cut by a plane perpendicular to the extending direction of the convex portion 60 and / or the concave portion 70. It means the difference in height between the lowest point (bottom 70b) and the highest point (top 60t).
- the unevenness depth (convex height or concave depth) D of the uneven surface 80 may be 5% or less.
- the variation in the unevenness depth D is a value obtained by dividing the standard deviation of the unevenness depth D by the average value of the unevenness depth D.
- the unevenness depth D of the uneven surface 80 is 5% or less, light scattering on the uneven surface 80 is suppressed, the haze (cloudiness) of the antireflection member 100 is sufficiently small, and the transparency is high. Become.
- Such an uneven surface 80 with a small variation in the uneven depth D can be formed by a manufacturing method described later.
- the width of the convex portion 60 of the uneven surface 80 decreases toward the top portion 60 t of the convex portion 60.
- the width of the recess 70 decreases toward the bottom 70 b of the recess 70.
- vertical to the extending direction is a substantially triangle.
- substantially triangular means that the width W1 of the projection 60 at the height of 0.95D (D is the height of the projection) from the bottom 70b is 0.04P ⁇ W1 ⁇ 0.21P (P is the average pitch of the projections and depressions) ), The width W2 of the projection 60 at a height of 0.05D from the bottom 70b satisfies 0.79P ⁇ W2 ⁇ 0.96P, and W2 / W1 satisfies 4.0 ⁇ W2 / W1 ⁇ 19. Means shape.
- the shape of the cross section of the convex portion is a substantially triangular shape, a sufficient antireflection effect cannot be obtained, but in the case where the convex portion extends long like the antireflection member according to the embodiment, A high antireflection effect can be obtained when the shape of the cross section of the convex portion is substantially triangular. This is what the inventors of the present application have found after extensive research. This will be described below.
- the refractive index n (z) at each z coordinate is proportional to the cross-sectional area S (z) of the convex portion cut by a plane perpendicular to the z axis at each z coordinate. Therefore, the refractive index n (z) is proportional to z. Therefore, the refractive index n (z) is expressed as shown in FIG. In FIG. 4B, n 0 represents the refractive index of air, and n 1 represents the refractive index of the material of the concavo-convex structure layer. Thus, since the refractive index continuously changes in proportion to the coordinate in the height direction of the convex portion, a higher antireflection effect can be obtained.
- the refractive index n is expressed as shown in FIG.
- the convex portion has a circular shape or a polygonal shape in plan view, and is not a shape that extends long.
- the cross-sectional shape of the convex portion cut by a plane parallel to the height direction (z-axis direction) is substantially triangular.
- the cross-sectional area of the projection taken along a plane perpendicular to the z-axis S (z) is proportional to z 2.
- the refractive index n (z) is proportional to the cross-sectional area of the convex portion S (z)
- the refractive index n (z) is proportional to z 2.
- the refractive index n (z) is expressed as shown in FIG.
- FIG. 7A in the case where the outer shape of the convex portion cut along a plane parallel to the height direction (z-axis direction) of the convex portion is a parabola, the convex portion cut along a plane perpendicular to the z-axis.
- the sectional area S (z) of the part is proportional to z. Therefore, the refractive index n (z) is also proportional to z. Therefore, the refractive index n (z) is expressed as shown in FIG.
- the refractive index n (z) is expressed as shown in FIG.
- the convex portion having the shape as shown in FIG. 7A is preferable to the convex portion having the shape as shown in FIG.
- the concavo-convex aspect ratio D / d of the concavo-convex surface 80 may be within a range of 0.4-2.
- the “concave / concave aspect ratio D / d” means the ratio of the concave / convex depth D of the concave / convex surface 80 to the concave / convex pitch d.
- the concavo-convex aspect ratio D / d is 0.4 or more, the antireflection member 100 has a low reflectance.
- the unevenness aspect ratio D / d is 2 or less, the antireflection member 100 has high wear resistance.
- the manufacturing method of the antireflection member 100 mainly includes a step of producing a mold and a step of producing an antireflection member.
- a block copolymer solution composed of at least first and second polymer segments is prepared (solution preparation step), and the block copolymer solution is converted into an oxide film as shown in FIG.
- the block copolymer film 5 is formed by coating on the silicon substrate 1 with 3 (application process).
- the block copolymer in the block copolymer film 5 is phase-separated into a first polymer segment 5a and a second polymer segment 5b (phase separation step).
- Preparation, application, and phase separation of the block copolymer solution can be performed using materials and methods described in WO2013 / 161454.
- the block copolymer in the phase separation step, may be phase separated by self-organization of the block copolymer under a solvent atmosphere described in WO2013 / 161454.
- the micro phase separation structure formed by the phase separation process may be a vertical lamellar structure.
- one of the first polymer segment 5a and the second polymer segment 5b is selectively removed by etching (first etching step).
- etching a method described in WO2012 / 096368 such as an ultraviolet etching method can be used.
- the oxide film 3 is etched using the other of the first and second polymer segments 5a, 5b (first polymer segment 5a) as a mask (second etching step), and
- the silicon substrate 1 is etched into a tapered shape using the oxide film 3 as a mask (third etching step).
- the etching may be performed by a dry etching method.
- irregularities are formed on the surface of the silicon substrate 1, and the mold 2 is obtained.
- the uneven taper shape formed on the surface of the silicon substrate 1 can be controlled by the ratio of the etching rate between the oxide film 3 and the silicon substrate 1 in the third etching step. Therefore, the mold 2 having irregularities with an arbitrary cross-sectional shape can be formed.
- the unevenness of the mold 2 is transferred to the resin layer 51 (transfer process). Specifically, a resin layer 51 is formed by applying a curable resin on the substrate 40, the mold 2 is pressed against the resin layer 51 as shown in FIG. It hardens
- an inorganic material layer may be formed instead of the resin layer 51 by applying a solution of a precursor of an inorganic material on the substrate 40 instead of the curable resin.
- a precursor of an inorganic material for example, alkoxides (metal alkoxides) such as Si, Ti, Sn, Al, Zn, Zr, and In described in WO2016 / 056277, polysilazane, and the like can be used.
- the antireflection member may be produced by using the uneven structure layer 50 as the second mold and transferring the unevenness of the uneven structure layer 50 to another material.
- the mold 2 produced by using the self-organization of the block copolymer since the mold 2 produced by using the self-organization of the block copolymer is used, the area of the uneven surface is not limited as compared with the case of producing the mold by photolithography or the like. Therefore, the antireflection member 100 having a large area can be easily manufactured.
- the unevenness of the mold 2 is formed by etching the silicon substrate 1 using the oxide film 3 as a mask, the unevenness depth of the mold 2 is determined by the etching conditions. Therefore, the variation in the uneven depth of the mold 2 is small. Since the unevenness of the antireflection member 100 is an inversion of the unevenness of the mold 2, the unevenness of the unevenness depth of the antireflection member 100 is small.
- W1 and W2 satisfy 0.04P ⁇ W1 ⁇ 0.21P, 0.79P ⁇ W2 ⁇ 0.96P, 4.0 ⁇ W2 / W1 ⁇ 19.
- Calculation examples 11 and 12 do not satisfy any of 0.04P ⁇ W1 ⁇ 0.21P, 0.79P ⁇ W2 ⁇ 0.96P, and 4.0 ⁇ W2 / W1 ⁇ 19.
- the calculation example 13 does not satisfy 0.04P ⁇ W1 ⁇ 0.21P and 0.79P ⁇ W2 ⁇ 0.96P, and satisfies 4.0 ⁇ W2 / W1 ⁇ 19.
- the reflectance was 0.4% or less at any wavelength of 400 nm, 600 nm, and 800 nm, and the average reflectance at 400 nm to 800 nm was less than 0.4%.
- the reflectance exceeded 0.4% at a wavelength of 400 nm and / or 600 nm, and the average reflectance was 0.4% or more.
- the transmittance of a member having an uneven surface at a wavelength of 400 to 800 nm was determined by simulation.
- the shape of the cross section cut by a plane perpendicular to the extending direction of the convex portions formed on the uneven surface was an isosceles triangle having a base of 120 to 240 nm and a height of 100 to 300 nm.
- the uneven pitch on the uneven surface is equal to the bottom of the cross-sectional shape of the protrusion, and is 120 to 240 nm.
- FIG. 9A shows the transmittance when the uneven pitch (the bottom of the cross-sectional shape of the convex portion) is 160 nm
- FIG. 9B shows the transmittance when the uneven pitch is 200 nm.
- the legends in FIGS. 9 (a) and 9 (b) indicate the height of the convex portion (concave / convex depth).
- Example 1 A random copolymer (manufactured by Polymer Source) consisting of polystyrene (hereinafter abbreviated as “PS” where appropriate) and polymethyl methacrylate (hereinafter abbreviated as “PMMA” where appropriate) and having a hydroxyl group at the terminal was prepared. . The random copolymer was dissolved in toluene to obtain a random copolymer solution.
- PS polystyrene
- PMMA polymethyl methacrylate
- a block copolymer (manufactured by Polymer Source) consisting of PS and PMMA as described below was prepared.
- the block copolymer was dissolved in toluene to obtain a block copolymer solution.
- Mn of block copolymer 1,010,000
- Volume ratio of PS segment to PMMA segment (PS: PMMA) 53.9: 46.1
- Molecular weight distribution (Mw / Mn) 1.18
- the volume ratio of PS segment and PMMA segment in the block copolymer has a polystyrene density of 1.05 g / cm 3 and a polymethyl methacrylate density of 1.19 g / cm 3.
- Mn number average molecular weight
- Mw weight average molecular weight
- a random copolymer solution was spin-cast on an Si wafer with an oxide film and heated to 170 degrees under vacuum for 2 days. Thereafter, the Si wafer was ultrasonically cleaned in toluene, and the Si wafer was dried. The block copolymer solution was spin cast on a Si wafer and dried on a hot plate. Thereby, a block copolymer film was formed on the Si wafer.
- the Si wafer on which the block copolymer film was formed was placed in a petri dish, and the petri dish was placed in a sealed container with a glass window filled with tetrahydrofuran (THF) solution. While measuring the thickness of the block copolymer film through an interference type film thickness meter through the glass window, nitrogen gas was circulated in the sealed container so that the thickness of the block copolymer film was kept constant. In this way, the solvent annealing treatment was performed while the swelling degree of the block copolymer film was controlled to be constant.
- THF tetrahydrofuran
- the PMMA is selectively cut by irradiating the block copolymer film with ultraviolet rays, and the Si wafer is immersed in acetone to remove the PMMA. Dissolved.
- Each of the convex portion formed of PS and the concave portion formed by removing PMMA had an elongated shape that was bent and extended in an irregular direction.
- the surface of this Si wafer was demolded with an OPTOOL (manufactured by Daikin Industries). Thereafter, the first resin (fluorine-containing acrylic UV curable resin) was drop cast on the Si wafer, and the first resin was sandwiched between the Si wafer and a PET film (Tosyobo Co., Ltd., Cosmo Shine A4300). The first resin was cured by irradiation with UV light. Thereafter, the first resin was peeled from the Si wafer. Thereby, the unevenness
- a second resin fluorine-containing acrylic UV curable resin
- a second resin fluorine-containing acrylic UV curable resin
- ultraviolet rays are applied while pressing the uneven surface of the first resin against the second resin.
- the second resin was cured by irradiation.
- the first resin was peeled from the second resin.
- corrugation of 1st resin was formed in the surface of 2nd resin.
- Example 2 A precursor solution (sol) of silica was prepared and applied on the surface of a glass substrate to form a precursor solution film.
- the uneven surface of the first resin produced in the same manner as in Example 1 was pressed against the precursor solution film. Thereafter, the precursor solution film was heated with a hot plate to cure the precursor solution film to form silica. Thereafter, the first resin was peeled from the silica. Thereby, the unevenness
- an antireflection member composed of a glass substrate and an uneven structure layer made of silica was produced.
- Example 3 An antireflective member was produced in the same manner as in Example 2 except for the heating conditions for curing the precursor solution film to form silica.
- Example 4 An antireflection member was produced in the same manner as in Example 3 except that the solvent annealing treatment time and swelling degree of the block copolymer film were changed.
- a master mold having a concave and convex surface in which conical convex portions having a height of 350 nm are arranged in a regular triangular lattice at a pitch of 290 nm was prepared.
- the first resin was drop cast on the original mold, and the first resin was sandwiched between the mold and the PET film.
- the first resin was cured by irradiation with UV light. Thereafter, the first resin was peeled from the original mold. Thereby, the unevenness
- a precursor solution film was formed on the glass substrate in the same manner as in Example 2. After pressing the uneven surface of the first resin against the precursor solution film, the precursor solution film was heated with a hot plate to cure the precursor solution to form silica. Thereafter, the first resin was peeled from the silica. Thereby, the unevenness
- the variation of the unevenness depth D of the antireflection members of Examples 3 and 4 was determined.
- the variation of the uneven depth D was determined by measuring the uneven depth D at 10 locations from the cross-sectional STEM image, obtaining the average value and standard deviation of the uneven depth D, and dividing the standard deviation by the average value.
- Table 2 shows the variation of the unevenness depth D. In any case, the variation in the unevenness depth D was 5% or less.
- the uneven surface of the antireflection member of Examples 3 and 4 was observed with a flat SEM.
- a square region having a side of 40 ⁇ m was cut out from the planar SEM image.
- the cut out image was binarized using image processing analysis software (ImageJ).
- imageJ image processing analysis software
- the circumference of the white part (convex part) which is not contacting the outer periphery of an image was each calculated
- Antireflection Examples 1-4 and Comparative Examples 1 member had an average reflectance R 1 none sufficiently low.
- Example 2 In Comparative Example 1, R 2 / R 1 was 1.1, and the reflectance changed due to friction. In addition, the surface was scratched visually. It is considered that the antireflection member of Comparative Example 1 has a low mechanical strength (abrasion resistance) on the uneven surface, and the uneven shape collapsed due to friction. On the other hand, in Example 2, R 2 / R 1 was 1.0, and the reflectance did not change due to friction. No scratches were confirmed visually. The antireflection member of Example 2 is considered to have a high mechanical strength (abrasion resistance) on the uneven surface, and the uneven shape hardly changed even when rubbed.
- the antireflection member of Example 3 had a haze of 0.45%.
- the antireflection member of Example 4 had a relatively high value of 0.85% haze.
- Antireflection member of Example 3 is less than 10% P B / P A, while the ratio of the long convex portion of the extending length was large, the anti-reflection member of Example 4 P B / P A This is considered to be because the ratio of convex portions having a short extension length was relatively large.
- the antireflection member of the present invention has a high antireflection effect and high wear resistance.
- it can be used for various applications such as displays, window glass for buildings, glass for other building materials, and films for application to the surfaces of these articles. Can be used.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
Description
前記凹凸表面の観察画像に2次元高速フーリエ変換処理を施すことにより得られるフーリエ変換像が、波数の絶対値が0μm-1である原点を略中心とする円状又は円環状の模様を示し、
前記凸部及び前記凹部が、平面視上ランダムな方向に延在し、
前記凸部の延在方向に垂直な面で切断した前記凸部の断面において、前記凸部の幅が前記凸部の底部から頂部に向かって小さくなっており、前記底部から0.95D(Dは前記凸部の高さ)の高さにおける前記凸部の幅W1、及び、前記底部から0.05Dの高さにおける前記凸部の幅W2が、0.04P<W1<0.21P、0.79P<W2<0.96P及び4.0<W2/W1≦19(Pは前記凹凸表面の凹凸の平均ピッチ)を満たす反射防止部材が提供される。
前記凹凸表面の観察画像に2次元高速フーリエ変換処理を施すことにより得られるフーリエ変換像が、波数の絶対値が0μm-1である原点を略中心とする円状又は円環状の模様を示し、
前記凸部の幅が前記凸部の底部から頂部に向かって小さくなっており、
前記凹凸表面の凹凸の平均ピッチが150~250nmの範囲内であり、
前記凹凸表面の凹凸の平均深さが90~300nmの範囲内であり、
前記凸部のアスペクト比が0.4~2の範囲内である反射防止部材が提供される。
本実施形態に係る反射防止部材100は、図1に示すように、基材40と、その上に形成された凹凸構造層50を有する。凹凸構造層50は凸部60と、凸部60により画成される凹部70を有する。それにより、凹凸構造層50は凹凸表面80を有する。
反射防止部材100の製造方法の一例を、図8(a)~(g)を参照しながら説明する。反射防止部材100の製造方法は、主に、モールドを作製する工程と、反射防止部材を作製する工程を有する。
まず、少なくとも第1及び第2のポリマーセグメントからなるブロック共重合体溶液を調整し(溶液調製工程)、図8(a)に示すようにブロック共重合体溶液を酸化膜3付きのシリコン基板1に塗布して、ブロック共重合体膜5を形成する(塗布工程)。次いで、図8(b)に示すように、ブロック共重合体膜5中のブロック共重合体を、第1のポリマーセグメント5aと第2のポリマーセグメント5bに相分離させる(相分離工程)。ブロック共重合体溶液の調製、塗布、及び相分離は、WO2013/161454号に記載される材料及び方法を用いて行うことができる。特に、相分離工程では、WO2013/161454号に記載の溶媒雰囲気下におけるブロック共重合体の自己組織化によって、ブロック共重合体を相分離させてよい。相分離工程により形成されるミクロ相分離構造は、垂直ラメラ構造であってよい。
モールド2の凹凸を樹脂層51に転写する(転写工程)。具体的には、基材40上に硬化性樹脂を塗布して樹脂層51を形成し、図8(f)に示すように樹脂層51にモールド2を押圧し、次いで、樹脂層51を紫外線照射、加熱等により硬化させ、その後、図8(g)に示すように樹脂層51からモールド2を剥離する。それにより、基材40上に凹凸構造層50が形成された反射防止部材100が得られる。
凹凸表面を有する部材の、波長400~800nmにおける反射率をシミュレーションにより求めた。凹凸深さDを250nm、凹凸ピッチPを180nmとし、凸部の延在方向に垂直な面で切断した断面の形状を、表1に記載される形状とした。表1中のW1は、底部から0.95Dの高さにおける凸部の幅であり、W2は、底部から0.05Dの高さにおける凸部の幅である。波長400nm、600nm、800nmにおける反射率、及び波長400nm~800nmにおける平均反射率を表1中に示す。
凹凸表面を有する部材の、波長400~800nmにおける透過率をシミュレーションにより求めた。凹凸表面に形成されている凸部の延在方向に垂直な面で切断した断面の形状は、底辺120~240nm、高さ100~300nmの二等辺三角形とした。また、凹凸表面の凹凸ピッチは、凸部の断面形状の底辺と等しく、120~240nmとした。
ポリスチレン(以下、適宜「PS」と略する)とポリメチルメタクリレート(以下、適宜「PMMA」と略する)とからなり、末端にヒドロキシル基を有するランダム共重合体(Polymer Source社製)を用意した。ランダム共重合体をトルエンに溶解させて、ランダム共重合体溶液を得た。
ブロック共重合体のMn=1,010,000、
PSセグメントとPMMAセグメントの体積比(PS:PMMA)=53.9:46.1、
分子量分布(Mw/Mn)=1.18
シリカの前駆体溶液(ゾル)を調製し、ガラス基板表面に塗布して前駆体溶液膜を形成した。該前駆体溶液膜に実施例1と同様にして作製した第1樹脂の凹凸表面を押し付けた。その後、前駆体溶液膜をホットプレートで加熱し、前駆体溶液膜を硬化させてシリカを形成した。その後、第1樹脂をシリカから剥離した。それにより、シリカの表面に、第1樹脂の凹凸を反転した凹凸が形成された。以上のようにして、ガラス基板とシリカからなる凹凸構造層とから構成される反射防止部材を作製した。
前駆体溶液膜を硬化させてシリカを形成する時の加熱条件以外は実施例2と同様にして、反射防止部材を作製した。
ブロック共重合体膜の溶媒アニール処理の時間及び膨潤度を変更したこと以外は実施例3と同様にして、反射防止部材を作製した。
高さ350nmの円錐状の凸部が、290nmピッチで正三角格子配置されている凹凸表面を有する元型を用意した。当該元型に第1樹脂をドロップキャストし、第1樹脂をモールドとPETフィルムで挟み込んだ。第1樹脂にUV光を照射して硬化させた。その後、元型から第1樹脂を剥離した。それにより、第1樹脂の表面に、元型の凹凸を反転した凹凸が形成された。
実施例1-4の反射防止部材の中央部から集光イオンビーム(FIB)により薄片を切り出し、凹凸構造層の断面形状をSTEMにより観察した。実施例1-4の反射防止部材はいずれも、凸部の幅が底部から頂部に向かって小さくなっていた。比較例1の反射防止部材についても同様に観察したところ、円錐形状の凸部が観察された。実施例1-4及び比較例1について、断面STEM像から求めた凹凸表面の凹凸の平均ピッチ及び平均深さ、並びに凸部のアスペクト比を表2に示す。
実施例1-4および比較例1の反射防止部材を10cm角に切り出し、ガラス基板の裏面(凹凸構造層を形成した面の反対面)に黒染スプレーを塗布し乾燥させた。分光光度計(日立ハイテクサイエンス製U4100)を用いて、凹凸構造層の表面の入射角5°の反射率を波長400nm~780nmの範囲で測定した。測定した反射率をJIS Z 8722に準拠して視感度補正し、平均した値を平均反射率R1として表3に示す。
表面性測定機(新東科学株式会社製、トライボギアTYPE:38)の平面圧子(φ12mm)にアルファ10(テックスワイプ社製)を取り付け、実施例2,3及び比較例1の反射防止部材の凹凸表面を摩擦した。摩擦は以下の条件で行った。移動速度=1800mm/分、移動距離=25.0mm、荷重150g、往復回数=5回。摩擦後、反射防止部材の入射角5°の反射率を測定し、視感度補正して平均反射率R2を求めた。平均反射率R2の値及びR2/R1の値を表3に示す。また、目視により、摩擦後の反射防止部材の傷の有無を調べた。結果を表3に示す。
実施例3,4の反射防止部材のヘーズをヘーズメーター(日本電色工業製、NDH 7000SP、JIS K7136)にて測定した。結果を表3に示す。
80 凹凸表面、100 反射防止部材
Claims (7)
- 凸部及び凹部から画成される凹凸表面を有する反射防止部材であって、
前記凹凸表面の観察画像に2次元高速フーリエ変換処理を施すことにより得られるフーリエ変換像が、波数の絶対値が0μm-1である原点を略中心とする円状又は円環状の模様を示し、
前記凸部及び前記凹部が、平面視上ランダムな方向に延在し、
前記凸部の延在方向に垂直な面で切断した前記凸部の断面において、前記凸部の幅が前記凸部の底部から頂部に向かって小さくなっており、前記底部から0.95D(Dは前記凸部の高さ)の高さにおける前記凸部の幅W1、及び、前記底部から0.05Dの高さにおける前記凸部の幅W2が、0.04P<W1<0.21P、0.79P<W2<0.96P及び4.0<W2/W1≦19(Pは前記凹凸表面の凹凸の平均ピッチ)を満たす反射防止部材。 - 前記凹凸表面の凹凸の平均深さが200~300nmの範囲内である、請求項1に記載の反射防止部材。
- 前記凹凸表面が、複数の凸部と前記複数の凸部の各々を取り囲む凹部から画成され、
前記複数の凸部のうち前記凹凸表面の凹凸の平均ピッチの7倍以下の周長を有する凸部の周長の合計が、前記複数の凸部の周長の合計の10%以下である、請求項1または2に記載の反射防止部材。 - 前記凹凸表面が、複数の凹部と前記複数の凹部の各々を取り囲む凸部から画成され、
前記複数の凹部のうち前記凹凸表面の凹凸の平均ピッチの7倍以下の周長を有する凹部の周長の合計が、前記複数の凹部の周長の合計の10%以下である、請求項1または2に記載の反射防止部材。 - 前記凹凸表面の凹凸の平均ピッチが150~250nmの範囲内である、請求項1~4のいずれか一項に記載の反射防止部材。
- 凸部及び凹部から画成される凹凸表面を有する反射防止部材であって、
前記凹凸表面の観察画像に2次元高速フーリエ変換処理を施すことにより得られるフーリエ変換像が、波数の絶対値が0μm-1である原点を略中心とする円状又は円環状の模様を示し、
前記凸部の幅が前記凸部の底部から頂部に向かって小さくなっており、
前記凹凸表面の凹凸の平均ピッチが150~250nmの範囲内であり、
前記凹凸表面の凹凸の平均深さが90~300nmの範囲内であり、
前記凸部のアスペクト比が0.4~2の範囲内である反射防止部材。 - 前記凸部のアスペクト比が0.8~2の範囲内である請求項6に記載の反射防止部材。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201880031968.7A CN110622045A (zh) | 2017-05-19 | 2018-05-21 | 抗反射构件 |
JP2019518907A JPWO2018212359A1 (ja) | 2017-05-19 | 2018-05-21 | 反射防止部材 |
KR1020197029549A KR20200008545A (ko) | 2017-05-19 | 2018-05-21 | 반사 방지 부재 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017100040 | 2017-05-19 | ||
JP2017-100040 | 2017-05-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018212359A1 true WO2018212359A1 (ja) | 2018-11-22 |
Family
ID=64274003
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/019479 WO2018212359A1 (ja) | 2017-05-19 | 2018-05-21 | 反射防止部材 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPWO2018212359A1 (ja) |
KR (1) | KR20200008545A (ja) |
CN (1) | CN110622045A (ja) |
TW (1) | TW201907183A (ja) |
WO (1) | WO2018212359A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022515936A (ja) * | 2016-12-07 | 2022-02-24 | アメリカ合衆国 | 三次元的エッチングマスクを用いて形成される反射防止表面構造体 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008158293A (ja) | 2006-12-25 | 2008-07-10 | Nissan Motor Co Ltd | 親水性反射防止構造 |
JP2008279597A (ja) | 2006-05-10 | 2008-11-20 | Oji Paper Co Ltd | 凹凸パターン形成シートおよびその製造方法、反射防止体、位相差板、工程シート原版ならびに光学素子の製造方法 |
WO2010074191A1 (ja) * | 2008-12-26 | 2010-07-01 | ソニー株式会社 | 光学素子、表示装置、反射防止機能付き光学部品、および原盤 |
WO2012096368A1 (ja) | 2011-01-14 | 2012-07-19 | Jx日鉱日石エネルギー株式会社 | 微細パターン転写用のモールドの製造方法及びそれを用いた回折格子の製造方法、並びに該回折格子を有する有機el素子の製造方法 |
WO2013161454A1 (ja) | 2012-04-26 | 2013-10-31 | Jx日鉱日石エネルギー株式会社 | 微細パターン転写用のモールドの製造方法及びそれを用いた凹凸構造を有する基板の製造方法、並びに該凹凸構造を有する基板を有する有機el素子の製造方法 |
WO2016056277A1 (ja) | 2014-10-10 | 2016-04-14 | Jx日鉱日石エネルギー株式会社 | 光学位相差部材、光学位相差部材を備える複合光学部材、及び光学位相差部材の製造方法 |
JP2016128867A (ja) * | 2015-01-09 | 2016-07-14 | 東ソー株式会社 | 反射防止膜及びその製造方法 |
-
2018
- 2018-05-21 JP JP2019518907A patent/JPWO2018212359A1/ja active Pending
- 2018-05-21 WO PCT/JP2018/019479 patent/WO2018212359A1/ja active Application Filing
- 2018-05-21 CN CN201880031968.7A patent/CN110622045A/zh active Pending
- 2018-05-21 KR KR1020197029549A patent/KR20200008545A/ko unknown
- 2018-05-21 TW TW107117444A patent/TW201907183A/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008279597A (ja) | 2006-05-10 | 2008-11-20 | Oji Paper Co Ltd | 凹凸パターン形成シートおよびその製造方法、反射防止体、位相差板、工程シート原版ならびに光学素子の製造方法 |
JP2008158293A (ja) | 2006-12-25 | 2008-07-10 | Nissan Motor Co Ltd | 親水性反射防止構造 |
WO2010074191A1 (ja) * | 2008-12-26 | 2010-07-01 | ソニー株式会社 | 光学素子、表示装置、反射防止機能付き光学部品、および原盤 |
WO2012096368A1 (ja) | 2011-01-14 | 2012-07-19 | Jx日鉱日石エネルギー株式会社 | 微細パターン転写用のモールドの製造方法及びそれを用いた回折格子の製造方法、並びに該回折格子を有する有機el素子の製造方法 |
WO2013161454A1 (ja) | 2012-04-26 | 2013-10-31 | Jx日鉱日石エネルギー株式会社 | 微細パターン転写用のモールドの製造方法及びそれを用いた凹凸構造を有する基板の製造方法、並びに該凹凸構造を有する基板を有する有機el素子の製造方法 |
WO2016056277A1 (ja) | 2014-10-10 | 2016-04-14 | Jx日鉱日石エネルギー株式会社 | 光学位相差部材、光学位相差部材を備える複合光学部材、及び光学位相差部材の製造方法 |
JP2016128867A (ja) * | 2015-01-09 | 2016-07-14 | 東ソー株式会社 | 反射防止膜及びその製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022515936A (ja) * | 2016-12-07 | 2022-02-24 | アメリカ合衆国 | 三次元的エッチングマスクを用いて形成される反射防止表面構造体 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2018212359A1 (ja) | 2020-03-19 |
TW201907183A (zh) | 2019-02-16 |
CN110622045A (zh) | 2019-12-27 |
KR20200008545A (ko) | 2020-01-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5187495B2 (ja) | 反射防止膜、反射防止膜の製造方法、反射防止膜用鋳型、反射防止膜用鋳型を用いて得られた反射防止膜及びレプリカ膜を用いて得られた反射防止 | |
JP5163943B2 (ja) | 防眩フィルム、防眩性偏光板および画像表示装置 | |
US20130236697A1 (en) | Microstructured articles comprising nanostructures and method | |
KR20180063259A (ko) | 광학 시트, 편광판, 광학 시트의 선별 방법 및 광학 시트의 제조 방법, 그리고 표시 장치 | |
JP2010181862A (ja) | 光学素子およびその製造方法、原盤およびその製造方法、ならびに表示装置 | |
US10444407B2 (en) | Optical element including a plurality of concavities | |
JP2011107297A (ja) | 防眩性フィルムおよび表示装置 | |
CN116699738B (zh) | 防眩膜和图像显示装置 | |
JP2011100027A (ja) | 防眩性フィルム、およびその製造方法 | |
JP2009042714A (ja) | 撥水性反射防止構造及びその製造方法 | |
JP2007322763A (ja) | 反射防止構造、反射防止構造体及びその製造方法 | |
JP2011169961A (ja) | 親水性反射防止構造及びその製造方法 | |
JP2009294341A (ja) | 撥水性反射防止構造及び撥水性反射防止成形体 | |
JP2011123380A (ja) | 防眩性フィルム、およびその製造方法 | |
WO2018212359A1 (ja) | 反射防止部材 | |
CN110651201B (zh) | 防雾构件 | |
JP7468600B2 (ja) | 防眩フィルム及び画像表示装置 | |
JP2010032739A (ja) | レンズフィルムおよびこれを備えた光学表示用バックライトユニット | |
JP2010176133A (ja) | 光学フィルム及びこれを備えた光学表示用バックライトユニット | |
JP2015197462A (ja) | ランダムな凹凸構造による低反射フィルムおよびその作製方法 | |
CN118068461A (zh) | 基于微纳结构的增透、疏水、防眩、耐磨光学膜及其制备方法 | |
JP2016209816A (ja) | 凹凸構造体の製造方法 | |
JP6759528B2 (ja) | 凹凸構造体及び反射防止膜 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18802095 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019518907 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20197029549 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2018802095 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2018802095 Country of ref document: EP Effective date: 20191219 |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18802095 Country of ref document: EP Kind code of ref document: A1 |