WO2000015732A1 - Structurally ordered articles, fabrication method and applications of the same - Google Patents
Structurally ordered articles, fabrication method and applications of the same Download PDFInfo
- Publication number
- WO2000015732A1 WO2000015732A1 PCT/US1999/018381 US9918381W WO0015732A1 WO 2000015732 A1 WO2000015732 A1 WO 2000015732A1 US 9918381 W US9918381 W US 9918381W WO 0015732 A1 WO0015732 A1 WO 0015732A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- film structure
- film
- ordering
- molecular ordering
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3615—Organic materials containing polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
Definitions
- the present invention relates to structurally ordered films and more particularly to ordered films employing a novel preparation process for optics applications.
- Liquid crystals exist in a phase intermediate between a crystalline solid and an isotropic liquid.
- the molecules of these compounds are usually rod-shaped with long molecular axes called the directors.
- Liquid crystal phases are characterized by the long-range order (i.e. in the sense of a solid) of the molecules.
- the nematic phase is the simplest, having only orientational ordering such that their directors are approximately parallel.
- the cholesteric liquid crystal phase originates from the presence of chirality in the nematic phase.
- Liquid crystals have many applications. They are used as displays in digital wristwatches, calculators, panel meters, thermometers, computer displays and industrial products. They may be used to record, store, and display images which may be projected onto a large screen.
- films may be prepared from liquid crystals, in which the molecular ordering is frozen, i.e. by polymerization, to provide desired optical properties.
- nematic and cholesteric (chiral nematic) films may be prepared to exhibit wavelength- and circular-polarization-selective reflectance/transmission (for cholesteric liquid crystal (CLC) films), and phase-shift transmission (for nematic liquid crystal (NLC) films).
- CLC cholesteric liquid crystal
- NLC nematic liquid crystal
- polymerized LCs may address some of these drawbacks, such LCs may be undesirable for many applications, due to, for example, inadequate mechanical properties (rigidity) and/or optical properties, (indices of refraction, characteristic wavelengths, etc.).
- an ordered optical film structure is fabricated by the steps of: (a) providing a first material and a second material which are substantially non-reactive relative to one another, at least one of the first material and the second material being a liquid crystal;
- an ordered optical film structure comprises a substrate and a material disposed on the substrate, the material being a non-liquid crystal having a liquid crystal-like molecular ordering.
- an ordered optical film structure is fabricated by the steps of:
- Fig. 1 is a preferred embodiment of steps for preparing optical films of the present invention.
- Fig. 2A is a cross-sectional schematic view (across the film thickness) of a structure of an aligned nematic film blend of materials A and B fabricated according to the steps of Fig. 1.
- Fig. 2B is the same cross-sectional view illustrating schematically the structure for the film shown in Fig. 2A, after the material B is selectively removed, leaving only material A.
- Fig. 2C shows the same cross-sectional view illustrating schematically the structure for the film shown in Fig. 2B, after a material C is added by filling the void left by the material B.
- Fig. 2D shows the same cross-sectional view illustrating schematically the structure for the film shown in Fig. 2C, after the material A is selectively removed, leaving only material C.
- Fig. 2E shows the same cross-sectional view illustrating schematically the structure for the film shown in Fig. 2C, after a material D is added by filling the void left by the material A.
- Fig. 3 shows a top view of a layer of aligned nematic film schematically showing component molecules aligned in one direction.
- Fig. 4A shows experimental reflectance spectra of an illustrative CLC film sample, according to the inventive process.
- Fig. 4B shows experimental reflectance spectra of another illustrative CLC film sample, according to the inventive process.
- Fig. 4C shows experimental reflectance spectra of a third illustrative CLC film sample, according to the inventive process.
- Fig. 5A shows a nematic-like film with phase retardation varied over zones fabricated with the present invention.
- Fig. 5B is a cross-sectional view of a pixeled RGB color filter fabricated in accordance with the present invention.
- Fig. 6 shows a nematic-like film as an absorptive linear polarizer fabricated with the present invention.
- Fig. 7 illustrates a preferred embodiment of tunable notch filter fabricated with present invention.
- Fig. 8 illustrates a preferred embodiment of tunable dye laser fabricated with present invention.
- the present invention relates to film processing techniques.
- an 'ordered' structure for example, having nematic or cholesteric ordering, is obtained, as shown for example, in Figs. 2A - 3.
- the invention includes subtracting a constituent from a structure that includes a liquid crystal, to form a 'mold' (or polymer matrix if a polymer is used as the remaining component) on a molecular level.
- a liquid crystal-like structure may be obtained.
- This resulting structure is fabricated entirely, or at least partially, from non-LC material, while exhibiting some LC characteristics.
- the liquid crystal-like structure overcomes the drawbacks of LCs and may have some other advantageous properties.
- the term 'liquid crystal' or 'LC means the class of materials in which a liquid-like order exists in at least one direction of space and in which some degree of anisotropy is present, as defined by DeGennes and Prost in The Physics of Liquid Crystals, (2nded.), pp. 1-3, Clarendon Press, 1993.
- the term 'non-liquid crystal' or 'non- LC as used herein refers to substantially any material including monomers and/or polymers, which are not liquid crystals as defined herein. Suitable non-LC materials include substantially any materials capable of filling the voids as described herein.
- the non-LC material may be an organic or inorganic gas, liquid, a solution of small particles in a liquid or solid (after polymerization or other freezing.
- suitable non-LC materials include thermally or radiatively curable epoxies and acrylates.
- the term 'liquid crystal-like molecular ordering' is defined herein as the long range molecular order characteristic of liquid crystals, such as, for example, nematic, smectic, and columnar or cholesteric ordering.
- FIG. 1 a preferred embodiment of the fabrication process of the optical devices of the present invention is shown.
- materials A and B are substantially uniformly mixed.
- the material A is a liquid crystal, which may be either polymerizable or non-polymerizable.
- the material A itself may be a mixture of several materials.
- the materials B is a liquid crystal or a non- liquid crystal, which may be either polymerizable or non-polymerizable.
- the material B itself may be a mixture of several materials.
- materials capable of being polymerized in any convenient manner, such as photo and/or thermal-induced polymerization or other means may be utilized.
- a photo- polymerizable material a small amount of photo-initiator may be added to the blend. Typically, its concentration is a few percentage by weight.
- Materials A and B are 'non-reactive.' As used herein, the term 'non-reactive' has the same meaning as used by R.A.M Hikmet and B.H. Zwerver, in 'Cholesteric gels formed by LC molecules and their use in optical storage,' Liquid Crystals, 13, 561(1993), (the Hikmet/Zwerver paper) and others: no chemical reaction between the materials to form a different material.
- Step 2 an optical film is prepared with the blend, using well-known techniques for liquid crystals.
- the film is 'aligned' in the sense that the molecules of the blend are long- range ordered and the film exhibits its characteristic optical properties, for example, wavelength- and circular-polarization-selective reflectance for cholesteric liquid crystal (CLC) films, and phase-shift for nematic liquid crystal (NLC) films.
- Figure 2A illustrates schematically the ordering for a nematic liquid crystal film consisting of materials A and B, whose elongated molecules are represented by ellipsoids of two sizes, 2A2 for material A and 2 A3 for material B.
- the film is disposed on a substrate 2A1.
- the long axes of molecules are ordered more-or-less in parallel, resulting in a film that is optically birefringent.
- the refractive indices, taken along and perpendicular to the averaged direction of the molecular long axes, or the molecular director, are represented by ri e and ri o , respectively.
- the optical birefringence ⁇ n ri e - no.
- n av (n e + no)/2.
- At least one material of the blend (either material A or material B) is polymerizable, it may be advantageous to 'freeze' the molecular ordering by polymerization.
- the 'ordering' may be changed.
- the reflectance band after polymerization may exhibit a significantly increased bandwidth over the reflectance band before the polymerization. This is attributed to a local compositional non-uniformity (in terms of relative concentration of materials A and B) across the film thickness direction that results in a continuously varied pitch formed during polymerization.
- a film may be prepared with a blend consisting of materials A and B at a predetermined temperature. Additional film processing steps may be performed at a lower or higher temperature at which the ordered liquid crystal structure is maintained by one of the components, i.e., material A.
- Step 3 the material B is removed, either partially or completely, from the film by some means, for example, dissolving with a suitable solvent or vaporizing with heat or evaporation under vacuum.
- the sites occupied by the removed material become vacant.
- These voids are elongated in shape, not necessarily uniform in size but are spatially ordered in a certain manner.
- the voids are arranged such that the average direction of their long axes point parallel to the film plane (i.e., substantially parallel to the substrate surface plane) and perpendicular to the direction across the film (i.e., substantially perpendicular to the direction normal to the substrate).
- Fig. 2B shows schematically the same cross-sectional view of the structure for the film shown in Fig. 2A, after the material B is selectively removed, leaving only material A, with some residual material B (not shown).
- the film is on a substrate 2B1.
- One of the sites vacated by the material B is represented by dashed lines at 20.
- the distribution or 'density' of the sites or voids 20 is proportional to the local density of the material B (in Fig. 2A).
- the voids 20 are relatively small and they are expected to be of microscopic scale (1/30 wavelength of incident light or smaller) and are connected to one another.
- the voids are arranged such that the average direction of their long axes in a film plane parallel to the substrate plane traces in a helical fashion across the film direction (normal to the substrate surface).
- the average index of refraction is smaller due to the presence of voids or empty sites 20.
- Other optical characteristics of the resulting film are also modified. For example, the wavelength- and circular-polarization- selective reflectance band is shifted to a shorter wavelength, and bandwidth is reduced for CLC films.
- the phase-shift ⁇ that is equal to ⁇ nZ, where L is the thickness of the film, is reduced for nematic films.
- Step 4 may be optionally used to engineer desired properties, such as a particular operating temperature range, improved mechanical and/or chemical stability, etc., into the film structure.
- This step involves introducing a material C into the voids 20 of the film.
- This material C may be a liquid crystal or a non-liquid crystal that may be either polymerizable or non-polymerizable.
- the non-LC material C may be optically isotropic.
- the material C may be an organic or inorganic gas, liquid or solid, and it itself may be a mixture of several materials.
- the material C may be the component B, minus some of its constituents.
- the component C is of low viscosity to facilitate its infiltration into the voids by capillary action.
- Placing the film with its surface coated with the component C in a vacuum chamber substantially increases the filling speed, as the air in the voids 20 is evacuated. If the material C is polymerizable, either by light, heat or other means, the film is polymerized to freeze the molecular ordering.
- the resulting film consists of the original material A and the added material C, and possibly material B (either as a residue, due to incomplete removal or deliberately introduced as a component of C). The optical characteristics of the resulting films are again modified.
- the wavelength- and circular-polarization-selective reflectance band is shifted to a longer wavelength and bandwidth is modified (either broadened or narrowed) for CLC films, the phase-shift is modified (increased or reduced) for nematic films, depending on the material C.
- Step 5 is an additional optional step that may be used to further engineer desired properties, such as operating temperature range, and/or improved mechanical and/or chemical stability, etc., into the film structure.
- the material A is removed, either partially or completely, from the film by some means, for example, by selectively dissolving with a suitable solvent or etching with a suitable etchant.
- the sites occupied by the removed material A become vacant.
- These voids are elongated in shape, not necessarily uniform in size but are spatially ordered in a certain manner.
- the voids are arranged such that the average direction of their long axes in the particular film plane (parallel to the substrate) traces in a helical fashion across the film direction (normal to the substrate surface).
- the voids are arranged such that the average direction of their long axes in the particular film plane (parallel to the substrate surface) points in one direction across the film direction (normal to the substrate).
- the distribution or 'density' of the voids is proportional to the local density of the material A prior to removal.
- the resulting film is substantially of material C, which may be a non-liquid crystal but retains a liquid crystal-like structure that exhibits characteristic optical properties, for example, the wavelength- and circular-polarization- selective reflectance band for films initially having the so-called CLC ordering and the phase-shift for films initially having a nematic ordering.
- the resulting film thus may provide the desirable optical characteristics of CL films, without the disadvantages associated with LCs such as temperature sensitivity, etc.
- Alternate process (A + C) - A C
- a liquid crystal-like film of a non-liquid crystal material C may be obtained by first preparing a film with some materials A and C, then removing the material A from the film. For the purposes of step 5 above, it is assumed that an aligned liquid crystal film cannot be readily prepared directly from a blend of the particular materials A and C chosen.
- Step 6 is a still further optional step that may be used to further engineer desired properties, such as operating temperature range, and/or improved mechanical and/or chemical stability, etc., into the film structure.
- a material D is introduced in the voids of the film after the material A is removed.
- the component D may be a liquid crystal or a non-liquid crystal that may be either polymerizable or non-polymerizable.
- the material D may be a gas, liquid or solid and it itself may be a mixture of several materials.
- the component D is of low viscosity to facilitate its infiltration or permeation into the voids by capillary action.
- the film with its surface coated with the component D in a vacuum chamber substantially increases the filling speed, as the air in the voids is evacuated.
- the material D is polymerizable, either by light, heat or other means, the film is polymerized to 'freeze' the film structure.
- the resulting film consists of the materials C and D that may be either a liquid crystal or non-liquid crystal.
- the optical characteristics of the resulting film are again modified, for example, the center wavelength and the bandwidth of the wavelength- and circular-polarization-selective reflectance band is modified in the case of CLC-like films and birefringence is modified in the case of for nematic-like films.
- a liquid crystal-like film of materials C and D may be obtained by first preparing a film with materials A, C and D, then removing the material A from the film and filling the voids with C or D.
- a liquid crystal-like film of materials C and D may be obtained by first preparing a film with materials A, C and D, then removing the material A from the film and filling the voids with C or D.
- an aligned liquid crystal film cannot be readily prepared directly from a blend of materials C and D.
- Fig. 4A shows experimental reflectance spectra of film samples that were prepared in accordance of the invented process.
- Curve 4A1 is the reflectance spectrum of a planar CLC film of a blend consisting of a BASF acrylate CLC polymer #181 (45% by weight), a chiral nematic (53% by weight) and a small amount of Ciba-Geigy photo-initiator Irgacure 184 (2% by weight).
- the chiral nematic itself consisted of Merck low-molecular-weight nematic liquid crystal E44 and chiral dopant R1011 (0.7% by weight with respect to the chiral nematic).
- the film was 20 ⁇ m thick and was prepared in a conventional manner, i.e., two glass substrates were first spin-coated with a thin polyimide alignment layer which are mechanically rubbed. Glass beads of 20 ⁇ m in diameter were then dispersed between the two glass substrates, with the coated sides facing each other. The CLC blend was then introduced between the substrates by capillary action. After mechanically shearing (relatively small sideways motions of the substrates to force the LC molecules to align), the film was annealed at room temperature for 30 minutes (a process of letting the sample sit undisturbed and letting the intrinsic molecular force further align the molecules). The film was then photo-polymerized with an UV lamp. One of the substrates was removed.
- the reflectance 4A1 was taken from the 'naked' film side (the side without the glass substrate).
- material A was the BASF 181 polymer and material B was the low-molecular chiral nematic.
- a film with the blend (A + B) was thus prepared.
- the B-component (the low-molecular-weight chiral nematic) was subsequently removed by dissolving with acetone, resulting in a CLC-like film with material component A only. It is interesting to note that by re-introducing the component B (the chiral nematic Merck E44 and R1011) the reflectance spectrum was nearly identical to that of the original film.
- Fig. 4B shows experimental reflectance spectra of film samples that were prepared in accordance with the invented process.
- Curve 4B1 was the spectrum of a planar CLC film of the blend consisting of a BASF acrylate CLC polymer #181 (26%) by weight), a chiral nematic (69% by weight) and a small amount of Ciba-Geigy photo-initiator Irgacure 184 (5% by weight).
- the chiral nematic itself consisted of Merck low-molecular- weight nematic liquid crystal E44 and chiral dopant CB15 (24.4% by weight with respect to the chiral nematic).
- the film was 20 ⁇ m thick and was prepared in a similar manner described above with respect to Example I. After the film sample was photo-polymerized with a UV lamp and one of the substrates was removed, the reflectance 4A1 was taken from the 'naked' film side.
- A was the BASF 181 polymer
- B was the low- molecular chiral nematic.
- a film with the blend (A + B) was prepared.
- the B-component (the low-molecular-weight chiral nematic) was subsequently removed by dissolving with acetone, resulting in a CLC-like film with material component A only.
- the film had helically ordered voids that were occupied by the component B.
- Fig. 4C shows experimental reflectance spectra of film samples prepared in accordance with the invented process.
- Curve 4C1 is the reflectance spectrum of a planar CLC film of the blend consisting of a BASF acrylate CLC polymer #181 (45% by weight), a chiral nematic (53% by weight) and a small amount of Ciba-Geigy photo-initiator Irgacure 184 (2% by weight).
- the chiral nematic itself consisted of Merck low-molecular-weight nematic liquid crystal E44 and chiral dopant R1011 (0.7% by weight).
- the film was 20 ⁇ m thick and was prepared in a similar manner described above.
- the reflectance 4A1 was taken from the 'naked' film side.
- A was the BASF 181 polymer
- B was the low-molecular chiral nematic.
- a film with the blend (A + B) was prepared.
- the B-component (the low-molecular-weight chiral nematic) was subsequently removed by dissolving with acetone, resulting in a CLC-like film with material component A only with the reflectance spectrum shown as curve 4C2. It is noted that center wavelength of the reflectance band was shifted from about 734nm to about 265nm. The reflectance of the processed film was reduced, due to material absorption in the UV spectral region.
- the aligned nematic film of the present invention may be used as a phase-retardation device.
- the quarter-wavelength retardation device is an optical device that changes a circularly polarized incident light into linearly polarized light after traversing the film and vice versa, in which a linearly polarized incident light is changed into circularly polarized after traversing.
- the phase retardation ⁇ is strongly dependent on the wavelength ⁇ , of incident light, so that a quarter-wavelength device 'perfectly' or optimally designed for ⁇ i is not a 'perfect' quarter- wavelength device for ⁇ 2 .
- the light ⁇ 2 transmitted from a quarter-wavelength device designed for ⁇ i is elliptically polarized, instead linearly or circularly polarized.
- circularly polarized incident light of wavelengths ⁇ ) and ⁇ 2 ⁇ ⁇ [ cannot be simultaneously transformed into linearly polarized light.
- linearly polarized incident light of wavelengths ⁇ ] and ⁇ 2 ⁇ ⁇ i cannot be simultaneously transformed into circularly polarized light.
- these devices are typically complex, and for example, tend to require several birefringent layers in a stack.
- a display may be divided into spatial regions, for which the phase retardation film of the present invention is optimized to a particular spectral band.
- Fig. 5A illustrates such an optical device 510 having plural zones in a 'checker board' fashion, having zones 511 for red-color subpixels, zones 512 for green-color subpixels, and zones 513 for blue-color subpixels.
- the visible range (400 - 700nm) may be divided into three so-called primary color bands: red (R) (607 - 700nm), green (G) (510 - 607nm) and blue (B) (400 - 510nm) for RGB color subpixels.
- the ⁇ I2 's are 650, 554 and 448nm, respectively, for the red, green and blue bands.
- ⁇ 12 's may be chosen, for example, to be the mean value over the band weighted by lamp intensity-dependent distribution.
- the planar cholesteric film of the present invention may be used as a spatially featured notch or rejection filter device.
- a color display utilizing a CLC color filter such a filter device has advantages over conventional absorptive color filter film used for liquid crystal displays, such as disclosed in Japanese reference No. 9-318807.
- the color filter film is divided into spatial regions, for which the filter of the present invention is optimized to a particular spectral band.
- the rejection filter it is more convenient to describe the rejection filter as a pass filter.
- a red-passing filter rejects the green and blue spectral components
- a green-passing filter rejects the red and blue spectral components
- a blue- passing filter rejects the red and green spectral components.
- the optical device 510 may have plural zones in a 'checker board' fashion, having zones 511 of a red-passing filter, zones 512 of green-passing filter, and zones 513 of a blue-passing filter. The neighboring red, green and blue-passing filters constituting a pixel.
- a pixeled color filter film may be easily fabricated for primary colors, by adding an appropriate material C for a subpixel such that the red-passing filter has two subregions, one rejecting the green spectral component and the other rejecting the blue spectral component.
- Fig. 5B shows a cross-sectional view of the pixeled RGB color filter.
- the red-passing subpixel filter includes two sublayers 511G and 51 IB, rejects the green and blue spectral components 515RG and 515RB, respectively, of the incident 'white' circularly polarized light 5151.
- the transmitted light is circularly polarized red component 515TR.
- the green-passing subpixel filters includes two sublayers 512R and 512B, and rejects the red and blue spectral components 515RR and 515RB, respectively, of the incident 'white' circularly polarized light 5151.
- the transmitted light is circularly polarized red component 515TG.
- the blue-passing subpixel filters consists of two sublayers 513R and 513G, rejects the red and green spectral components 515RR and 515RG, respectively, of the incident 'white' circularly polarized light 5151.
- the transmitted light is circularly polarized red component 515TB.
- the red-passing filter may be a single layer (i.e., no sublayers), if its rejection band is broad enough to cover both the green and blue.
- the filter instead of adding a different material C to opposite sides of the film, the filter may be fabricated as two distinct layers laminated together, each layer having subpixeled R-, G-, and B-rejection bands.
- the processes of the present invention may be utilized to fabricate dichroic polarizers using a nematic LC as the material A. It is known that films with aligned nematic LC doped with dichroic dyes may be used for an absorptive polarizer, due to its ability to absorb more strongly incident light of a particular polarization than the other, since the dye molecules are aligned in the film. Referring to Figs. 2C, 2D and 2E, one of the added materials C and/or D (for example, material C indicated by 2C3 in Fig. 2C, material C indicated by 2D2 in Fig. 2D, material C indicated by 2E2 and material D indicated by 2E3 in Fig.
- materials C and D may be chosen for their 'light fastness' (resistance to bleaching/decomposition as dichroic dyes do), broadband (a blend of absorptive materials showing a composite broadband absorption), wide spectral range (more absorptive materials over UV to IR spectral range are available, compared to special dichroic organic dyes) and high operating temperatures.
- Fig. 6 illustrates a dichroic polarizer 601, with a sectional view 501 showing the structure that includes material A 61 and material C 62.
- the director 63 is represented by an arrow.
- the incident light 64A is unpolarized and transmitted light 64B is substantially polarized perpendicular to the director, as the light component polarized in parallel to the director is substantially absorbed by material C.
- a single layer broadband circular polarizer may be obtained with certain cholesteric liquid crystal blends and polymerization, in the manner set forth in the above-referenced Li/Faris patent. Briefly described, such a polarizer may be fabricated with a CLC blend which includes a polymerizable CLC monomer and a non-reactive nematic liquid crystal or chiral nematic liquid crystal (a nematic liquid crystal with chiral dopant). The nematic liquid crystal or chiral nematic liquid crystal has limited temperature range as a liquid crystal phase. Thus, such a polarizer has a limited operating temperature range.
- nematic liquid crystal or chiral nematic liquid crystal (about 100°C) rather than by the polymer matrix itself (about 200°C).
- these nematic liquid crystal or chiral nematic liquid crystals are typically thermotropic, that is, the optical properties are strongly dependent on temperature.
- the characteristics of a polarizer using such a blend are relatively temperature sensitive.
- a polymerizable CLC monomer may be utilized as the material A and a non- reactive nematic liquid crystal or chiral nematic liquid crystal as the material B.
- the resulting film is fully polymeric which is CLC-like, that is, exhibits wavelength- and circular polarization-selective reflectance.
- the optical properties of the film are temperature-insensitive over a relatively large temperature range, particularly near the high limit.
- a further advantage of this process is that the removed material B may be recycled for subsequent use. This is particularly advantageous in the event a desired material B is available only from a limited number of suppliers and is thus relatively scarce and/or expensive.
- n av c ⁇ n av ⁇ + c 2 n av2
- ci and c 2 are weighted coefficients that are functions of the relative fractions of materials 1 and 2 and possibly of other material parameters.
- the variables n av ⁇ and n av2 are equal to (rL. + n o )/2 for each of the materials 1 and 2, respectively, as discussed hereinabove.) If material 2 is replaced by voids, then the weighted average will be smaller, as voids (air) has a refractive index of 1 (which is a minimum).
- the resulting film also has a smaller ⁇ n (due to the nulled contribution from material B after removal) and possibly smaller P 0 (due to film thickness shrinkage).
- a film with a broader bandwidth and a longer center wavelength is first prepared.
- materials and their percent concentrations may be selected to optimize the LC blend for a desired reflectance band.
- the particular process steps used may also be selected, i.e., one or more of optional process steps 4 - 6 may be utilized, to obtain desired properties. For example, by filling voids with material C, a 'dense' (that is, no voids) film may be obtained.
- Such films may have some advantages, such as being more mechanically stable (due to increased rigidity), and more resistant to moisture (due to less surface area), etc.
- Fig. 7 illustrates a preferred embodiment of a tunable notch filter, using the structure fabricated by the CLC-like film processing of the invention.
- the notch filter 700 consists of a CLC-like film 701 sandwiched between two substrates 702 and 703. The substrates are provided for convenience to transmit pressure represented by arrows 705 on the CLC-like film.
- a circularly polarized light beam 7041 is incident on the film. If the wavelength of the incident beam is within the reflectance band, the incident light is substantially reflected. The reflected beams is indicated by 704R. If the wavelength of the incident beam is outside the reflectance band, the incident light is substantially transmitted.
- the transmitted beam is indicated by 704T.
- the handedness of the CLC-like film is the same as the circular polarized state of the incident beam.
- the pitch changes and the reflectance band shifts and narrows.
- the transmission of the incident light (either transmitted or reflected) by the device may be controlled.
- tunable notch filters may also be used as pressure sensors. For example, shifts in the reflectance band of the filter may be used to determine changes in pressure being applied to the filter. It should be clear to one skilled in the art that stacking left-handed and right- handed CLC-like films with similar reflectance bands may form a switchable mirror that reflects or transmits unpolarized light.
- Fig. 8 illustrates a preferred embodiment of a tunable dye laser, using the structure fabricated by the CLC-like film processing of the present invention.
- the dye laser 800 consists of the dye-doped gain medium 801 sandwiched between two substrates 802 and 803. The substrates are provided for convenience to transmit pressure represented by arrows 805 on the dye-doped CLC-like film.
- the pump beam 804P is incident on the film and the stimulated emission emits in two directions normal to the film surface, represent by 804A and 804B.
- this device By changing the pitch of film (via pressure), the edge of the reflectance band changes, to change the output wavelength of the dye laser.
- this device also may be used as a pressure sensor.
- the output wavelength of the laser emission may be monitored to indicate the pressure applied to the device in a manner similar to the tunable notch filter described hereinabove.
- An added advantage of utilizing the tunable dye laser in this manner is that the monitored signal (the wavelength of the laser emission) is independent of the angle at which the pump beam is incident on the sensor.
- the reflectance band depends on the angle between the observer and film normal. A 'blue' shifting (a shorter center wavelength) is observed as the incidence angle increases.
- Hikmet and Zwerver utilize a chiral nematic material consisting of a polymerizable monomer nematic material and a non-reactive chiral dopant to prepare an aligned CLC film with a first center wavelength of a characteristic reflectance band.
- the chiral dopant is then locally removed by thermal evaporation at a high temperature (about 200°C) using a focused laser beam, resulting in a reflectance band having a second center wavelength.
- the shifting in the reflectance band may thus be utilized to store digital data represented by binary states.
- the data storage layers may have lower operating temperature and/or narrower reflectance bandwidth which results in more storage capacity when wavelength division multiplexing is used in a multilayer structure in the manner described in commonly assigned U.S. Patent No. 5,353,247 to Faris entitled, “Optical Mass Storage System and Memory Cell Incorporated Therein” and U.S. Patent Application, Serial No. 08/539279 August 1995, by B. Fan and S. M. Faris, entitled “Multiple Layer Optical Recording Media and Method and System for Recording and Producing Information Using the Same” (as amended).
- the particular material C may be chosen to be relatively volatile (to lower evaporation temperature), to provide a narrower second reflectance bandwidth, and/or larger shift between the first and second center wavelengths (by changing ⁇ n and or n av after data recording).
- the particular process steps used may also be selected, i.e., one or more of optical process steps 4 - 6 may be utilized, to obtain desired properties.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000570261A JP2003517623A (en) | 1998-09-11 | 1999-08-12 | Manufacturing method of articles with arranged tissue and its application |
AU54817/99A AU5481799A (en) | 1998-09-11 | 1999-08-12 | Structurally ordered articles, fabrication method and applications of the same |
CA002343306A CA2343306A1 (en) | 1998-09-11 | 1999-08-12 | Structurally ordered articles, fabrication method and applications of the same |
EP99941099A EP1115809A4 (en) | 1998-09-11 | 1999-08-12 | Structurally ordered articles, fabrication method and applications of the same |
HK02100425.3A HK1042317A1 (en) | 1998-09-11 | 2002-01-18 | Structurally ordered articles, fabrication method and applications of the same |
HK02106037A HK1044558A1 (en) | 1998-09-11 | 2002-08-19 | structuraly ordered articles, fabrication method and application of the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/151,909 US6106743A (en) | 1998-09-11 | 1998-09-11 | Structurally ordered articles, fabrication method and applications of the same |
US09/151,909 | 1998-09-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000015732A1 true WO2000015732A1 (en) | 2000-03-23 |
Family
ID=22540762
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/018381 WO2000015732A1 (en) | 1998-09-11 | 1999-08-12 | Structurally ordered articles, fabrication method and applications of the same |
Country Status (9)
Country | Link |
---|---|
US (1) | US6106743A (en) |
EP (1) | EP1115809A4 (en) |
JP (1) | JP2003517623A (en) |
KR (1) | KR100763647B1 (en) |
CN (2) | CN100338176C (en) |
AU (1) | AU5481799A (en) |
CA (1) | CA2343306A1 (en) |
HK (2) | HK1042317A1 (en) |
WO (1) | WO2000015732A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002008828A2 (en) * | 2000-07-24 | 2002-01-31 | Reveo, Inc. | Composite nonlinear optical film, method of producing the same and applications of the same |
US7531081B2 (en) | 2001-02-13 | 2009-05-12 | Shell Oil Company | Base oil composition |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AUPP373698A0 (en) * | 1998-05-27 | 1998-06-18 | Commonwealth Scientific And Industrial Research Organisation | Molecular coatings |
US6870595B1 (en) * | 1998-09-22 | 2005-03-22 | Minolta Co., Ltd. | Optical filter device and method of making same |
US6577798B2 (en) * | 2000-07-18 | 2003-06-10 | Reveo, Inc. | Method for producing non-linear optical organic crystal film |
US7528904B2 (en) * | 2001-12-13 | 2009-05-05 | Sony Deutschland Gmbh | Method of forming a composite containing a matrix component and at least one liquid crystal component |
US7029729B2 (en) * | 2003-02-24 | 2006-04-18 | 3M Innovative Properties Company | Cholesteric liquid crystal additives |
US6913708B2 (en) * | 2003-02-24 | 2005-07-05 | 3M Innovative Properties Company | Cholesteric liquid crystal drying process and solvent |
US7068344B2 (en) * | 2003-02-24 | 2006-06-27 | 3M Innovative Properties Company | Cholesteric liquid crystal optical bodies and methods of manufacture and use |
KR101146521B1 (en) | 2004-07-19 | 2012-05-25 | 삼성전자주식회사 | Phase delay element, method for manufacturing thereof, substrate having the same and method for manufacturing thereof, and light providing method and liquid crystal display using the same |
TWI410476B (en) * | 2010-08-25 | 2013-10-01 | Univ Nat Cheng Kung | Polymer film without cholesteric liquid crystal, polymer film and reflective display module |
CN103926735A (en) * | 2013-06-28 | 2014-07-16 | 上海天马微电子有限公司 | Colored film substrate and manufacturing method thereof and display panel and display device |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5353247A (en) * | 1992-05-27 | 1994-10-04 | Faris Sadeg M | Optical mass storage system and memory cell incorporated therein |
WO1997032224A1 (en) * | 1996-02-29 | 1997-09-04 | Minnesota Mining And Manufacturing Company | An optical film |
US5691789A (en) * | 1995-10-30 | 1997-11-25 | Li; Le | Single-layer reflective super broadband circular polarizer and method of fabrication therefor |
JPH09318807A (en) * | 1996-05-27 | 1997-12-12 | Matsushita Electric Ind Co Ltd | Color filter and liquid crystal display device using the same |
US5731861A (en) * | 1995-05-02 | 1998-03-24 | Minolta Co., Ltd. | Composite material, display device using the same and process of manufacturing the same |
US5737044A (en) * | 1994-07-12 | 1998-04-07 | U.S. Philips Corporation | Illumination system using a broadband cholesteric polarizer having its surface of maximum helix pitch face the radiation source |
US5762823A (en) * | 1993-09-08 | 1998-06-09 | U.S. Philips Corporation | Switchable cholesteric filter and luminaire having such a filter |
US5793456A (en) * | 1993-01-11 | 1998-08-11 | U.S. Philips Corporation | Cholesteric polarizer and the manufacture thereof |
US5796454A (en) * | 1996-12-04 | 1998-08-18 | Advanced Display Systems, Inc. | Cholesteric liquid crystal display employing circular polarizer and methods of operation and manufacture therefor |
US5858268A (en) * | 1995-06-28 | 1999-01-12 | Ag Technology Co., Ltd. | Liquid crystal optical element, a liquid crystal display element and a projection type liquid crystal display apparatus |
US5891357A (en) * | 1995-09-27 | 1999-04-06 | Fuji Xerox Co., Ltd. | Optical element and method of manufacturing the same, and macromolecular liquid crystal for an optical element |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3060656B2 (en) * | 1990-11-26 | 2000-07-10 | セイコーエプソン株式会社 | Liquid crystal display device |
FR2702058B1 (en) * | 1993-02-23 | 1995-04-07 | Thomson Csf | Process for obtaining composite materials based on polymer and liquid crystals with dichroic dyes. |
DE4441651A1 (en) * | 1994-11-23 | 1996-04-25 | Basf Ag | Polymerisable material for coating and printing substrates |
JPH08248398A (en) * | 1995-03-13 | 1996-09-27 | Fuji Xerox Co Ltd | Liquid crystal display element |
JP3770974B2 (en) * | 1996-09-20 | 2006-04-26 | 松下電器産業株式会社 | Liquid crystal display |
DE19705497C2 (en) * | 1997-02-13 | 1999-01-28 | Max Planck Gesellschaft | Process for the preparation of mesoporous solids, solids obtainable by the process and their use |
-
1998
- 1998-09-11 US US09/151,909 patent/US6106743A/en not_active Expired - Fee Related
-
1999
- 1999-08-12 EP EP99941099A patent/EP1115809A4/en not_active Withdrawn
- 1999-08-12 KR KR1020017003196A patent/KR100763647B1/en not_active IP Right Cessation
- 1999-08-12 WO PCT/US1999/018381 patent/WO2000015732A1/en not_active Application Discontinuation
- 1999-08-12 CN CNB998132071A patent/CN100338176C/en not_active Expired - Fee Related
- 1999-08-12 JP JP2000570261A patent/JP2003517623A/en active Pending
- 1999-08-12 CA CA002343306A patent/CA2343306A1/en not_active Abandoned
- 1999-08-12 AU AU54817/99A patent/AU5481799A/en not_active Abandoned
- 1999-08-12 CN CNB2004100694061A patent/CN1306283C/en not_active Expired - Fee Related
-
2002
- 2002-01-18 HK HK02100425.3A patent/HK1042317A1/en unknown
- 2002-08-19 HK HK02106037A patent/HK1044558A1/en not_active IP Right Cessation
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5353247A (en) * | 1992-05-27 | 1994-10-04 | Faris Sadeg M | Optical mass storage system and memory cell incorporated therein |
US5793456A (en) * | 1993-01-11 | 1998-08-11 | U.S. Philips Corporation | Cholesteric polarizer and the manufacture thereof |
US5762823A (en) * | 1993-09-08 | 1998-06-09 | U.S. Philips Corporation | Switchable cholesteric filter and luminaire having such a filter |
US5737044A (en) * | 1994-07-12 | 1998-04-07 | U.S. Philips Corporation | Illumination system using a broadband cholesteric polarizer having its surface of maximum helix pitch face the radiation source |
US5731861A (en) * | 1995-05-02 | 1998-03-24 | Minolta Co., Ltd. | Composite material, display device using the same and process of manufacturing the same |
US5858268A (en) * | 1995-06-28 | 1999-01-12 | Ag Technology Co., Ltd. | Liquid crystal optical element, a liquid crystal display element and a projection type liquid crystal display apparatus |
US5891357A (en) * | 1995-09-27 | 1999-04-06 | Fuji Xerox Co., Ltd. | Optical element and method of manufacturing the same, and macromolecular liquid crystal for an optical element |
US5691789A (en) * | 1995-10-30 | 1997-11-25 | Li; Le | Single-layer reflective super broadband circular polarizer and method of fabrication therefor |
WO1997032224A1 (en) * | 1996-02-29 | 1997-09-04 | Minnesota Mining And Manufacturing Company | An optical film |
JPH09318807A (en) * | 1996-05-27 | 1997-12-12 | Matsushita Electric Ind Co Ltd | Color filter and liquid crystal display device using the same |
US5796454A (en) * | 1996-12-04 | 1998-08-18 | Advanced Display Systems, Inc. | Cholesteric liquid crystal display employing circular polarizer and methods of operation and manufacture therefor |
Non-Patent Citations (3)
Title |
---|
GENNES DE P G, PROST J: "LIQUID CRYSTALS: MAIN TYPES AND PROPERTIES THE PHYSICS OF LIQUID CRYSTALS", PHYSICS OF LIQUID CRYSTALS, X, XX, vol. ED-02, 1 January 1993 (1993-01-01), XX, pages 01 - 03, XP002922842 * |
HIKMET ET AL.: "Cholesteric Gels formed by LC molecules and their use in optical storage", LIQUID CRYSTALS, vol. 13, no. 4, 1993, pages 561 - 570, XP002922843 * |
See also references of EP1115809A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002008828A2 (en) * | 2000-07-24 | 2002-01-31 | Reveo, Inc. | Composite nonlinear optical film, method of producing the same and applications of the same |
WO2002008828A3 (en) * | 2000-07-24 | 2002-07-18 | Reveo Inc | Composite nonlinear optical film, method of producing the same and applications of the same |
US7531081B2 (en) | 2001-02-13 | 2009-05-12 | Shell Oil Company | Base oil composition |
Also Published As
Publication number | Publication date |
---|---|
KR20010075059A (en) | 2001-08-09 |
CN1591043A (en) | 2005-03-09 |
HK1042317A1 (en) | 2002-08-09 |
CN1342191A (en) | 2002-03-27 |
HK1044558A1 (en) | 2002-10-25 |
JP2003517623A (en) | 2003-05-27 |
KR100763647B1 (en) | 2007-10-05 |
CN100338176C (en) | 2007-09-19 |
EP1115809A4 (en) | 2007-05-02 |
EP1115809A1 (en) | 2001-07-18 |
US6106743A (en) | 2000-08-22 |
CA2343306A1 (en) | 2000-03-23 |
AU5481799A (en) | 2000-04-03 |
CN1306283C (en) | 2007-03-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Mitov et al. | From selective to wide-band light reflection: a simple thermal diffusion in a glassy cholesteric liquid crystal | |
US7324180B2 (en) | Laminated retardation optical element, process of producing the same, and liquid crystal display | |
US6106743A (en) | Structurally ordered articles, fabrication method and applications of the same | |
Binet et al. | Switchable broadband light reflection in polymer-stabilized cholesteric liquid crystals | |
JP2007241071A (en) | Transflective liquid crystal display device | |
US6303056B1 (en) | Composite nonlinear optical film, method of producing the same and applications of the same | |
Lin et al. | Widely tunable photonic bandgap and lasing emission in enantiomorphic cholesteric liquid crystal templates | |
US7352422B2 (en) | Retardation optical element and method of producing the same, and polarization element and liquid crystal display, each including retardation optical element | |
Binet et al. | Bragg reflections in cholesteric liquid crystals: from selectivity to broadening and reciprocally | |
WO2004019085A1 (en) | Retardation optical device, its manufacturing method, and liquid crystal display | |
Li et al. | Fabrication and application of 1D micro-cavity film made by cholesteric liquid crystal and reactive mesogen | |
Nevskaya et al. | Liquid-crystal-based microlasers | |
JP4748806B2 (en) | Optical multilayer | |
JP4377633B2 (en) | Phase difference optical element, manufacturing method thereof, and liquid crystal display device | |
Yoshida et al. | Tunable single photonic defect-mode in cholesteric liquid crystals with laser-induced local modifications of helix | |
Mitov et al. | Glassy cholesteric broadband reflectors with a pitch gradient: material design, optical properties and microstructure | |
Takezoe | Liquid crystal lasers | |
Watanabe et al. | Thermotropic Polypeptides. 6. On Cholesteric Mesophase with Grandjean Texture and its Solidification | |
Relaix et al. | The effect of geometric and electric constraints on the performance of polymer-stabilized cholesteric liquid crystals with a double-handed circularly polarized light reflection band | |
US6961106B2 (en) | Retardation optical element having the function of reflecting ultraviolet light, and liquid crystal display comprising the same | |
Toriumi et al. | Optical properties of lyotropic poly (γ-benzyl L-glutamate) liquid crystals | |
JP2019139080A (en) | Wavelength selection film, video source unit, and display | |
US20060170859A1 (en) | Method of patterning cholesteric film and optical element having the cholesteric film patterned by the method | |
Zhou et al. | Broadband Circular Polarizer based on Cholesteric Liquid Crystal and Cholesteric Polymer Composite Films | |
Zhou | Cholesteric liquid crystal photonic crystal lasers and photonic devices |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 99813207.1 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 2343306 Country of ref document: CA Ref document number: 2343306 Country of ref document: CA Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2000 570261 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020017003196 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999941099 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1999941099 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020017003196 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1999941099 Country of ref document: EP |