EP2047302A1 - Matériaux flexibles pour applications optiques - Google Patents

Matériaux flexibles pour applications optiques

Info

Publication number
EP2047302A1
EP2047302A1 EP06778072A EP06778072A EP2047302A1 EP 2047302 A1 EP2047302 A1 EP 2047302A1 EP 06778072 A EP06778072 A EP 06778072A EP 06778072 A EP06778072 A EP 06778072A EP 2047302 A1 EP2047302 A1 EP 2047302A1
Authority
EP
European Patent Office
Prior art keywords
layer
porous
material according
layers
refractive index
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06778072A
Other languages
German (de)
English (en)
Inventor
Robert Beer
Gilbert Gugler
Marc Pauchard
Stefan Schuettel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wifag-Polytype Holding AG
Original Assignee
Ilford Imaging Switzerland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ilford Imaging Switzerland GmbH filed Critical Ilford Imaging Switzerland GmbH
Publication of EP2047302A1 publication Critical patent/EP2047302A1/fr
Withdrawn legal-status Critical Current

Links

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
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/285—Interference filters comprising deposited thin solid films

Definitions

  • the present invention relates to flexible materials for optical applications which have on a flexible support at least two thin layers in direct contact, the refractive indices of which differ by at least 0.20.
  • One of these layers is porous or nanoporous and contains inorganic nanoparticles, the other is a non-porous polymer layer.
  • Dielectric thin layers are thin, mostly transparent layers of different chemical compounds with layer thicknesses, which are typically in the micrometer and nanometer range.
  • dielectric thin films are used to alter the optical properties of surfaces and interfaces. Such interfaces help to partially reflect and partially transmit and refract incident light.
  • the targeted use of the right materials and layer thicknesses can effectively influence the refraction and reflection behavior.
  • the layer thicknesses of interest are all in the range of light wavelengths ⁇ i to ⁇ 2, which is of interest in a particular application.
  • ⁇ / 4 layers ie. H. Layers with a thickness of ⁇ / 4.
  • layer thicknesses which are twice or an integer multiple of ⁇ / 4
  • the desired effect is still present, but it decreases with increasing layer thickness more and more.
  • interference filters By a sequence of layers with high and low refractive indices and suitable layer thicknesses, it is possible, for example, to produce an interference filter which is permeable only for very specific wavelengths of light.
  • Such interference filters are widely used in spectroscopy as dielectric filters, for example.
  • Bragg reflectors which selectively and practically completely reflect certain wavelengths, with reflectivities of more than 99% being possible.
  • a Bragg reflector can be used, for example, to construct a polymer laser as described by N. Tessler, GJ Denton and RH Friend in "Lasing from conjugated-polymer microcavities", Nature 382, 695-697 (1996).
  • Such interference effects can also be used to create "physical colors,” which is exploited, for example, in the manufacture of colored sunglass lenses with high light stability.
  • physical colors are also used as optical security features on banknotes or labels for product security.
  • waveguide structures which are able to guide specific light wavelengths within these structures into precisely defined zones and to decouple them at another, desired location.
  • a high refractive index (core) layer is surrounded by lower refractive index (cladding) layers.
  • the light is transmitted in the core through total internal reflection.
  • the layer thickness of the core defines how many modes of a light wave can be passed on. Waveguides that can pass only the fundamental mode are called unimodal waveguides or single-mode waveguides.
  • the layer thickness of the core in these waveguides depends on the refractive indices of the materials used and the range of wavelengths of light ⁇ i to ⁇ £, which is of interest in a particular application, as described, for example, by X. Peng, L. Liu, J. Wu, Y. Li, Z. Hou, L. Xu, W. Wang, F. Li and M. Ye in "Wide-range amplified spontaneous emission wavelength-tuning in a solid-state dye waveguide", Optics Letters 25, 314-316 (US Pat. 2000).
  • the core layer thickness is about 2 to 6 wavelengths.
  • the layer thickness of the core for a single mode waveguide is below a wavelength when the difference in refractive indices of the layers is greater than 0.20. As the layer thickness of the core increases, an increasing number of higher modes are passed and a multimode waveguide is referred to.
  • Single-mode waveguides have a number of advantages over multimode waveguides and are therefore preferred in certain applications. It is therefore of great interest to be able to realize thin waveguide layers and high differences in the refractive indices. Interesting applications of such waveguides can be found, for example, on integrated optical chips for data transmission or on sensor chips for the analysis of samples by the interaction with light.
  • the number of ⁇ / 4 layers required in a dielectric mirror can be increased by increasing the difference in refractive indices of the layers used of the reflection behavior are drastically reduced, as described for example in the patent application US 2004 / 0'096'574.
  • the refractive index varies between 1.45 (silicate glass) and 3.40 (indium phosphide), as reported by N. Kambe, S. Kumar, S. Khirovolu, B. Chaloner-Gill, YD Blum, DB MacQueen and GW Faris in Refractive Index Engineering of Nano-Polymer Composites ", K. Kobayashi,” Optical Integrated Devices “, Kyoritsu Publications, Tokyo, pages 26-30 (1999).
  • the patent application EP1'116'966 describes how, by doping silicate glasses with B2O3 or P2O5, the refractive index of the pure silicate glass can be slightly lowered or slightly increased.
  • Table 1 summarizes the refractive indices of common or described organic polymers at a wavelength of 550 nm.
  • refractive indices above 1.76 are also accessible.
  • Y. Wang, T. Flaim, S. Fowler, D. Holmes, and C. Planje describe in "Hybrid High Refractive Index Polymer Coatings," Proceedings of SPIE 5724, 42-49 (2005), the preparation of a hybrid material of titanium dioxide and titanium organic polymer which has a refractive index of 1.94 at 400 nm.
  • Patent US Pat. No. 6,204,202 describes, for example, the preparation of porous SiO 2 layers with refractive indices between 1.10 and 1.40, which are obtained by a sol-gel method and the use of thermally decomposable polymers. Such polymer-containing coatings must be heated for 10 to 60 minutes to a temperature of at least 400 ° C, so that the polymer is decomposed and pure SiO 2 layers arise with the desired properties. Aerogels can also be used to prepare such porous, low refractive index layers as described, for example, by A. Köhler, J.S. Wilson and R.H. Friend in "Fluorescence and Phosphorescence in Organic Materials", Advanced Materials .14, 701 (2002).
  • Such layers are produced, for example, by vacuum evaporation or wet-chemical with a sol-gel process.
  • a combination of layers of Al 2 O 3 and GaP is described, which has a difference of the refractive indices of 1.87.
  • the difference in the refractive indices can be increased still further in some cases, but the amount of realizable layer combinations is limited by the limited compatibility of the compounds to be used and the possible coating methods.
  • porous layers which are used in optical applications, also do not have the appropriate mechanical properties and sometimes require inappropriate steps in the manufacturing process (high temperature treatment, supercritical drying, etc.) in order to be able to apply large-scale and cost on flexible support ,
  • the layers produced have a high mechanical flexibility.
  • Flexible layers can be obtained by applying solutions of suitable organic polymers or suitable melted polymers.
  • suitable organic polymers or suitable melted polymers For example, in the patent application JP 2005-055'543 a method is described how multiple polymer layers for optical applications can be produced.
  • the amount of layer combinations obtainable here too is limited by the limited combinability of the materials to be used (adhesion, solubility in various solvents, etc.) as well as the problem of precise multiple coating.
  • Fast drying recording materials for ink jet printing use porous or nanoporous ink receptive layers containing inorganic nanoparticles and a low level of binders. Such layers have a high mechanical flexibility.
  • Ink-jet recording materials having on a flexible support a flexible inorganic nanoparticle-containing porous or nanoporous ink-receiving layer and a polymer layer disposed thereover are also known.
  • Such recording materials with a nonporous polymer layer are described, for example, in the patent applications EP 1'188'572 and EP 1'591 '265, the layer thicknesses of the polymer layer normally being between 3 ⁇ m and 15 ⁇ m. The layer thickness of 3 ⁇ m must not be exceeded in order to obtain the desired ink absorption properties of the polymer film.
  • a recording material having a porous polymer layer is described, for example, in patent application EP 0761'459.
  • the recording material is thermally treated after printing to seal the porous polymer layer and thereby protect the underlying image.
  • the polymer film is formed only after the printing of the recording material by the application of a polymer solution or the polymer film is laminated thereon by means of an adhesion promoter.
  • such polymer layers should not be thicker than a quarter to about a whole wavelength ⁇ of the light used.
  • the patent application EP 1'492'389 describes an optical amplifier material which contains on a carrier a thin, transparent amplifier layer which contains nanocrystalline, nanoporous aluminum oxides or aluminum oxide / hydroxides and optionally a binder, and above that a luminescent layer, preferably consisting of tris- (8-hydroxyquinolino) -aluminum.
  • the luminescent compound is formed by vapor deposition. and the resulting luminescent layer has sufficient mechanical flexibility only at layer thicknesses below 200 nm.
  • FIG. 1 schematically shows the simplest structure of a material according to the invention for optical applications.
  • a porous or nanoporous layer (2) which contains inorganic nanoparticles and, arranged above, a nonporous polymer layer (4).
  • (3) denotes the boundary layer between the porous or nanoporous layer (2) and the non-porous polymer layer (4).
  • FIG. 2 shows schematically a further material according to the invention for optical applications.
  • two layer packages from FIG. 1 are arranged one above the other in the reverse order.
  • (3) and (3 ') denote the boundary layers between the porous or nanoporous layers (2) and (2') and the non-porous polymer layers (4) and (4 ').
  • the aim of the invention is the provision of flexible materials for optical applications, which consist of a flexible carrier and at least two layers applied thereto with a large difference in the refractive indices, which are in direct contact with each other. These materials have a high mechanical flexibility and can be produced inexpensively in large quantities. It has now surprisingly been found that this objective can be achieved by suitable combinations of porous or nanoporous layers having a low refractive index, which contain inorganic nanoparticles, with non-porous polymer layers having a high refractive index.
  • the difference between the refractive indices of the two layers is at least 0.20 in the range of wavelengths of interest ⁇ i to ⁇ £. But preferably higher values, preferably between 0.20 to 0.76 in the region of interest light wavelengths .lambda..sub.i to ⁇ 2 'm is further provided always that is .lambda..sub.i smaller than ⁇ 2.
  • the thickness of this boundary layer is extremely important in optical applications and has a great influence on the proportion of light which is reflected.
  • the wavelength of light plays a decisive role here.
  • An optically sharp boundary layer in the materials according to the invention is then used if the thickness of the boundary layer in the region of the wavelengths of interest ⁇ i to ⁇ £ is not greater than 1/5 of the wavelength of the light.
  • the application areas of the materials for optical applications are in the wavelength range between 200 nm ( ⁇ i) and 2500 nm ( ⁇ 2).
  • the visible spectral range of the light between 400 nm and 700 nm is interesting for all applications where directly visible optical effects are to be generated for humans. For example, this is the case in the production of physical colors for decorative purposes, for color effects in security features or for simple optical sensors based on a color change of a test strip.
  • the range of interesting wavelengths of light ⁇ i and ⁇ 2 for the materials according to the invention extends here, for example, over the entire visible spectral range between 400 nm and 700 nm.
  • Optically sharp boundary layers must not have a thickness greater than 140 nm for these applications. However, preference is given to a thickness of the boundary layer which is not greater than 70 nm.
  • the range of interesting wavelengths ⁇ i and ⁇ £ for the materials according to the invention extends over the range between 200 nm and 400 nm.
  • Optically sharp Boundary layers must not have a thickness greater than 80 nm for these applications. However, preference is given to a thickness of the boundary layer which is not greater than 40 nm.
  • the range of the interesting wavelengths ⁇ i and ⁇ 2 for the materials according to the invention extends over the range between 700 nm and 2500 nm.
  • Optically sharp boundary layers must not have a thickness greater than 500 nm for these applications. However, preference is given to a thickness of the boundary layer which is not greater than 250 nm.
  • a layer package consisting of a porous or nanoporous layer with a low refractive index and a non-contact layer in direct contact with it.
  • porous polymer layer with a high refractive index forms the smallest unit of the inventive materials.
  • the materials according to the invention contain at least one such layer package or a sequence of such layer packages, the differences of the refractive indices of the different layers, the order of the layers, the orientation of the layers, the composition of the layers and their thickness depending on the particular application.
  • the porous or nanoporous layer with the low refractive index, which contains inorganic nanoparticles, has in the material according to the invention a dry film thickness between 0.2 ⁇ m and 60.0 ⁇ m, preferably between 1.0 ⁇ m and 40.0 ⁇ m, particularly preferably between 2.0 ⁇ m and 20.0 ⁇ m.
  • the non-porous polymer layer with the high refractive index has a dry film thickness of between 0.05 ⁇ m and 2.5 ⁇ m, preferably between 0.2 ⁇ m and 2.0 ⁇ m, in the material according to the invention. Layer thicknesses between 0.3 ⁇ m and 0.8 ⁇ m are particularly preferred.
  • the materials according to the invention may, between the individual layer packages, if present between the layer packages and the support or on the layer packages, comprise one or more additional layers with different functions (for example luminescent layers, electrically conductive layers, reflective layers, protective layers, mechanical mechanical layers) Stabilization or release layers).
  • additional layers with different functions for example luminescent layers, electrically conductive layers, reflective layers, protective layers, mechanical mechanical layers
  • the material according to the invention consists of a flexible carrier on which a porous or nanoporous layer with a low refractive index, which contains inorganic nanoparticles, and above it a non-porous polymer layer with a high Refractive index are applied.
  • This embodiment is of interest, for example, for those applications in which the light propagating in the non-porous polymer layer having the high refractive index should be optically decoupled from the flexible support regardless of whether the light is coupled into the non-porous polymer layer having the high refractive index or was created there.
  • An example of such an application is described by T. Tsutsui, M. Yahiro, H.
  • a layer package consisting of a porous or nanoporous layer a deep refractive index, which contains inorganic nanoparticles, and a non-porous polymer layer with a high refractive index applied in reverse order.
  • non-porous polymer layer having the high refractive index functions as an optical waveguide and the porous or nanoporous deep refractive index layers containing inorganic nanoparticles shield the waveguide on both sides (cladding of the waveguide).
  • refractive index of the used non-porous layers 4 and 4 ' is identical, no additional optical boundary layer is formed between these layers.
  • the jacket of the waveguide also makes it possible, for example, for the flexible material according to the invention to be glued or transferred onto another carrier by means of an adhesive, without influencing the properties of the nonporous polymer layer having the high refractive index.
  • the porous or nanoporous layers having a low refractive index contain inorganic nanoparticles and optionally a small amount of binders and other additives. After drying, they have a specific, measurable pore volume.
  • the pore volume can be determine the BET method.
  • the BET method for pore volume determination has been described by S. Brunauer, PH Emmet and I. Teller in "Adsorption of Gases in Multimolecular Layers", Journal of the American Chemical Society 60, 309-319 (1938).
  • a simpler method is to fill the pores with a suitable solvent of known density and directly determine the pore volume by increasing the weight of the layer.
  • the porous or nanoporous layers according to the invention have a pore volume of between 0.1 ml / g and 2.5 ml / g, the reference value being the unit weight of the porous or nanoporous layer containing inorganic nanoparticles.
  • pore volumes of between 0.2 ml / g and 2.5 ml / g determined in this way are preferred; pore volumes between 0.4 ml / g and 2.5 ml / g are particularly preferred.
  • the refractive index of the porous or nanoporous layer containing inorganic nanoparticles is influenced by the porosity.
  • An increase in porosity leads to a decrease in the refractive index.
  • refractive indices between 1.00 (air) and that of the inorganic nanoparticles used, for example the value 1.45 when using SiO 2 as inorganic nanoparticles.
  • refractive indices between 1.05 to 1.40 can be achieved in this way.
  • the effective refractive index of such layers can be approximated by forming the volume weighted sum of the refractive index of the nanoparticle network and the refractive index of the gas filled pores.
  • such a porous or nanoporous layer with a porosity of 0.80 which mainly contains SiO 2 nanoparticles with a refractive index of 1.45 and air with a refractive index of 1.00, has an effective refractive index of 1.09.
  • a three-dimensional network of these nanoparticles gradually forms. The interstices of this network are filled with the solvent used or dispersants and, if appropriate, the other additives used. During further drying, the solvent used or dispersant is removed.
  • the remaining additives are unable to completely fill the interstices of the nanoparticles and release them. are in the network of nanoparticles filled with gas pores.
  • This consists of two phases, a solid and a gaseous, existing three-dimensional network has structures with dimensions in the submicron range.
  • the porous or nanosized layer has a transmission value for light of wavelength 550 nm between 60% and 99%.
  • the nanoporous layer has a transmission value between 80% and 95%.
  • the nanoporous layer has a transmission value between 85% to 95%.
  • inventive materials also solve the problems of brittleness and stiffness of the porous or nanoporous layers for optical applications described in the prior art.
  • the desired mechanical properties are achieved by the use of a suitable binder in the porous or nanoporous layers containing inorganic nanoparticles.
  • inorganic nanoparticles for producing the porous or nanoporous layers having a low refractive index for example, natural, precipitated or powdered metal oxides, metal oxide / hydroxide and natural or synthetic zeolites can be used.
  • metal oxides for example, SiO 2, Al 2 O 3, TiO 2, ZnO, ZrO 2 and SnO 2 or the mixed oxide indium-tin oxide can be used. It is also possible to use mixtures of all these compounds.
  • metal oxide / hydroxide for example, AIOOH can be used.
  • inorganic nanoparticles having a refractive index of less than 1.80 at a wavelength of 550 nm.
  • Particularly preferred inorganic nanoparticles are precipitated or dusty silica, alumina, alumina / hydroxide and the zeolites zeolite beta, ZSM-5, mordenite, LTA (Linde Type A ), Faujasites and LTL (Linde Type L).
  • the size of the inorganic nanoparticles can be determined by imaging techniques, such as high-resolution transmission electron microscopy or scanning electron microscopy.
  • the mean particle diameter of the inorganic nanoparticles is preferably between 5 nm and 200 nm, particularly preferably the size range between 10 nm and 60 nm.
  • the inorganic nanoparticles preferably have a narrow particle size distribution, with at least 90% of the primary particles having a smaller diameter have twice the above-mentioned average particle diameter and practically no primary particles have a larger diameter than three times the aforementioned average particle diameter.
  • the inorganic nanoparticles can also be present in the form of agglomerates (secondary particles) which have a measurable BET pore volume as the solid substance.
  • a precipitated silica prepared by a wet process and, secondly, a dusty silica produced by a gas phase process.
  • Precipitated silica can be prepared, for example, by wet process by metathesis of sodium silicate by an acid or by passing through a layer of ion exchange resin as silica sol, by heating and ripening this silica sol, or by gelling a silica sol.
  • Dust-form silica is generally prepared in a flame hydrolysis process, for example by combustion of silicon tetrachloride with hydrogen and oxygen.
  • Example of such dusty silica is Aerosil® 200 (SiO 2 having an isoelectric point at pH 2.0) available from DEGUSSA AG, Frankfurt / Main, Germany. According to its data sheet, this substance has a BET specific surface area of about 200 m 2 / g and a primary particle size of about 12 nm.
  • Aerosil® 200 SiO 2 having an isoelectric point at pH 2.0
  • this substance has a BET specific surface area of about 200 m 2 / g and a primary particle size of about 12 nm.
  • Another example is Cab-O-Sil® M-5 available from Cabot Corporation, Billerica, USA , According to its data sheet, this product has a BET specific surface area of about 200 m 2 / g and a size of the primary particles of about 12 nm.
  • the agglomerates are 0.2 ⁇ m to 0.3 ⁇ m long.
  • preferably dusty silica having an average size of the primary particles of at most 20 nm and a specific surface area of at least 150 m 2 / g as determined by the BET method is used.
  • the likewise preferred zeolite beta is available in the form of nanoparticles with a mean size of 30 nm from NanoScape AG, Kunststoff, Germany.
  • the other nanocrystalline zeolites (the size of the primary particles is given in parentheses) are ZSM-5 (70 nm - 100 nm), mordenites (500 nm), LTA (90 nm), faujasites (80 nm) and LTL (50 nm) available there.
  • metal oxide / hydroxide for example, alumina / hydroxide can be used. Particularly preferred is pseudoboehmite.
  • a preferred alumina is ⁇ -alumina.
  • the aluminas or alumina / hydroxides incorporated in the crystal lattice elements of rare earths.
  • Their preparation is described for example in the patent application EP 0'875'394.
  • Such aluminas or alumina / hydroxides contain one or more elements of atomic number 57 to 71 of the Periodic Table of the Elements, preferably in an amount between 0.4 and 2.5 mole percent based on Al2O3.
  • a preferred rare earth element is lanthanum.
  • the surface of the inorganic nanoparticles can be modified in order to break up the possibly present agglomerates of the primary particles during the dispersing process into smaller units and to stabilize them.
  • the size of the dispersed particles has a considerable influence on the transparency of the porous or nanoporous layer containing these nanoparticles.
  • the surface modification can also serve to improve the compatibility of the nanoparticle surfaces with the binders and / or solvents or dispersants used. In such a modification, an uncharged, a positively charged or a negatively charged surface can be generated.
  • a preferred type of surface modification for producing a positively charged surface of silicon dioxide is that with polyaluminum hydroxychloride, as proposed, for example, in patent application DE 10'020'346.
  • the patent application WO 00/202222 describes the surface modification of gas phase produced silica with aluminum chlorohydrate.
  • Another preferred type of surface modification of silica is that with aminoorganosilanes, as described for example in patent application EP 0'663'620.
  • a particularly preferred mode of surface modification of silica is described in European Patent Application EP 1'655'348 in which the surface of the silica is reacted with the reaction products of at least one aminoorganosilane and a trivalent aluminum compound.
  • Preferred compounds of the trivalent aluminum for surface modification with the reaction products of a compound of trivalent aluminum and an aminoorganosilane are aluminum chloride, aluminum nitrate, aluminum acetate, aluminum formate and aluminum chlorohydrate.
  • the amount of the compound of trivalent aluminum is typically between 0.1 percent by weight and 20 percent by weight based on the amount of silica. A value between 0.5% by weight and 10% by weight is preferred.
  • Particularly preferred aminoorganosilanes for surface modification with the reaction products of a compound of trivalent aluminum and an aminoorganosilane are 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, (3-triethoxysilylpropyl) -diethylenetriamine, 3-aminopropyltriethoxysilane, N - (2-aminoethyl) -3-aminopropyltriethoxysilane, (3-triethoxysilylpropyl) -diethylenetriamine and mixtures thereof.
  • the total amount of Aminoorganosilans or the mixture of Aminoorganosilanen is typically between 0.1 weight percent and 10 weight percent based on the amount of silica. A value between 0.5% by weight and 20% by weight is preferred.
  • the weight ratio between the compound of trivalent aluminum (for example aluminum chlorohydrate) and the aminoorganosilanes is advantageously chosen so that the desired pH is achieved when the two components of the two reagents are mixed. Preference is given to a molar ratio between 0.1 and 2.0, more preferably a molar ratio of between 0.4 and 1.5, based on the number of aluminum atoms and the number of amino groups of the aminoorganosilane.
  • Particularly preferred for the surface modification with the reaction products of a compound of trivalent aluminum and at least one Aminoorganosilane is dusty silica having a primary particle size of at most 20 nm.
  • the dispersion at high shear rates gives a uniform distribution of the reaction products on the silica. Furthermore, the theological behavior of the dispersion is improved.
  • the inorganic nanoparticles are in amounts between 0.2 g / m ⁇ and 60.0 g / m ⁇ , preferably between 1.0 g / m ⁇ and 40.0 g / m2, more preferably between 2.0 g / m2 and 20.0 g / m2 available.
  • the amount of binder present in the porous or nanoporous layer should be sufficiently small to achieve the desired porosity, but also high enough to produce stable, well-bonded coatings on the flexible support without brittleness.
  • Amounts up to 60% by weight of the binder based on the total amount of the inorganic nanoparticles may be used, but preferred are amounts between 0.5% and 40.0% by weight of the binder based on the total amount of the inorganic nanoparticles in the porous or nanoporous layer having the low refractive index.
  • Particular preference is given to amounts between 10.0% by weight and 30.0% by weight, based on the total amount of the inorganic nanoparticles in the porous or nanoporous layer with the low refractive index.
  • Suitable binders for the porous or nanoporous deep refractive index layer containing inorganic nanoparticles are generally water-soluble hydrophilic polymers.
  • Synthetic, natural or modified natural water-soluble polymers such as fully or partially hydrolyzed polyvinyl alcohol or copolymers of vinyl acetate and other monomers; modified polyvinyl alcohols; Polyvinylpyrrolidone, polyethylene oxides; Homopolymers or copolymers of (meth) acrylamide; Polyvinyl pyrrolidones, polyvinyl acetals, polyurethanes and starch or modified starch, cellulose or modified cellulose such as hydroxyethyl cellulose, carboxymethyl cellulose and gelatin can be used as well as mixtures of these polymers.
  • conductive polymers such as polythiophene, polyaniline, polyacetylene, poly (3,4-ethylene) dioxythiophene, mixtures of poly (3,4-ethylene) dioxythiophene-poly (styrenesulfonate), polyfluorene, polyphenylene, polyphenylene and Polyphenylenevinylene in double strand form and block copolymers of different conductive polymers or block copolymers of conductive and non-conductive polymers.
  • Poly (3,4-ethylene) dioxythiophene is preferred.
  • Particularly preferred synthetic binders for the porous or nanoporous deep refractive index layer containing inorganic nanoparticles are modified and unmodified polyvinyl alcohol, polyvinylpyrrolidone or their mixtures.
  • the above-mentioned binders having crosslinkable groups can be converted to practically water-insoluble layers with the aid of a crosslinker or hardener.
  • Such crosslinks can be covalent or ionic.
  • Crosslinking or curing of the layers permits a change in the physical layer properties, such as, for example, liquid absorption, dimensional stability under the action of liquids, vapors or temperature changes, or resistance to layer damage and brittleness.
  • the crosslinkers and hardeners are selected on the basis of the water-soluble polymers to be crosslinked.
  • Organic crosslinkers and hardeners include, for. B. aldehydes (such as formaldehyde, glyoxal or glutaraldehyde); N-methylol compounds (such as dimethylolurea or methylol-dimethylhydantoin); Dioxanes (such as 2,3-dihydroxydioxane); reactive vinyl compounds (such as 1,3,5-trisacryloyl-hexahydro-s-triazine or bis (vinylsulfonyl) ethyl ether), reactive halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine) ; epoxides; aziridines; CarbamoylpyridinENSen or mixtures of two or more of these crosslinkers mentioned.
  • aldehydes such as formaldehyde, glyoxal or glutaraldehyde
  • N-methylol compounds such as dimethylolurea or
  • Inorganic crosslinkers and hardeners include, for example, chrome alum, aluminum alum, boric acid, zirconium compounds or titanocenes.
  • the layers may also contain reactive substances which crosslink the layers under the influence of UV light, electron beams, X-rays or heat.
  • the polymers may be blended with water-insoluble natural or synthetic high molecular weight compounds, especially acrylic latices or styrene acrylic latices.
  • the nanoporous layers with the low refractive index may also contain compounds which absorb light in the wavelength range of interest between 200 nm and 2500 nm. In a preferred embodiment of the invention, it is organic compounds which absorb light in the range between 200 nm and 700 nm. In another embodiment of the invention, the nanoporous layers having the low refractive index may also contain luminescent organic molecules, luminescent organic pigments, luminescent organic polymers, luminescent inorganic nanoparticles and organic or inorganic nanoparticles with luminescent compounds contained therein which emit light in the wavelength range of interest between 200 nm and 2500 nm.
  • the non-porous polymer layer having the high refractive index consists of synthetic, natural or modified natural water-soluble polymers such as fully or partially hydrolyzed polyvinyl alcohol or
  • (Meth) acrylamide Polyvinylpyrrolidone, polyvinyl acetals, polyurethanes and starch or modified starch, cellulose or modified cellulose such as hydroxyethyl cellulose, carboxymethyl cellulose and gelatin or mixtures thereof.
  • Preferred synthetic polymers are modified polyvinyl alcohol, polyurethane, (meth) acrylated polybutadiene, copolymers of (meth) acrylamide and polyacrylonitriles or their mixtures.
  • Conductive polymers such as polythiophene, polyanilines, polyacetylene, poly (3,4-ethylene) dioxythiophene, mixtures of poly (3,4-ethylene) dioxythiophene-poly (styrenesulfonate), polyfluorene, polyphenylene, polyphenylene and polyphenylenevinylene in double-stranded form, and Block copolymers of different conducting polymers or block copolymers of conducting and non-conducting polymers can also be used. Poly (3,4-ethylene) dioxythiophene is preferred.
  • Polyelectrolytes such as salts of polystyrenesulfonic acid, salts of polyvinylsulfonic acid, salts of poly-4-vinylbenzylammonium cation, salts of polyallylamine, salts of polyethyleneimine, salts of poly (dimethyldiallyl) -ammonium cation, poly (allylamine) hydrochloride, Chitosan, polyacrylic acids and their salts, dextran sulfates, alginates, salts of poly (I - [4- (3-carboxyl-4-hydroxyphenylazo) benzenesulfonamido] -1,2-ethane, salts of poly (dimethyldiallylammonium) cations , Block copolymers and their mixtures can also be used.
  • This layer can also be crosslinked or hardened, as previously described for the layer with the deep refractive index.
  • the non-porous polymer layer having the high refractive index may also consist of water-dispersible thermoplastic polymers.
  • the polymer film is produced in an additional step after the application of the layer by a heat treatment under pressure. This subsequent heat treatment under pressure is not necessary, for example, if the layer during the drying phase reaches or exceeds the glass transition temperature of the thermoplastic polymer for a certain time.
  • the water-dispersible thermoplastic polymers include, for example, particles, latices or waxes of polyethylene, polypropylene, polytetrafluoroethylene, polyamides, polyesters, polyurethanes, acrylonitriles, polymethacrylates such as methyl methacrylates, polyacrylates, polystyrenes, polyvinyl chloride, polyethylene terephthalate, copolymers of ethylene and acrylic acid and paraffin waxes (such as Polysperse, available from Lawter Int., Belgium). Mixtures of these compounds or polymers such as polystyrene and acrylates, ethylene-acrylate copolymers, copolymers of styrene and acrylonitrile may also be used.
  • the particle size of the latices can be between 20 nm and 5 1 000 nm, preferably between 40 nm and 1000 nm, and more preferably between 50 nm and 500 nm.
  • the glass transition temperature is between 30 ° C. and 170 ° C., preferably between 50 ° C and 110 ° C, more preferably between 60 ° C and 90 0 C.
  • the latex particles may be fused into a film having the facilities and conditions known to those skilled in the art, such as are common in the lamination of photographic and inkjet printing paper.
  • the laminator GBC 3500 Pro available from GBC European Films Group, Mercuriusstraat 9, Kerkrade, Holland, may be used. This device is particularly suitable for a heat treatment at a temperature of 120 ° C at a flow rate of about 27 cm / min.
  • the water-dispersible thermoplastic polymers can also be composed of several shells, wherein, for example, the core and an outer shell can have a different swellability or a different glass transition temperature.
  • the polymer particles or polymer latices may have an uncharged surface or a positive or negative surface charge.
  • the polymer particles can be mixed with water-soluble binders, such as the aforementioned binders, preferably with polyvinyl alcohol or mixtures of different polyvinyl alcohols. Preference is given to polyvinyl alcohols having a viscosity of at least 26 mPasec and a degree of hydrolysis of at least 70%.
  • the non-porous polymer layer is produced in an additional step by heat treatment under pressure and / or UV exposure, as described by MMG Antonisse, PH Binda and S. Udding-Louwrier in "Application of UV Curable Powder Coatings on Paperlike Substrates", American Ink Maker 79 (5). 22-26 (2001).
  • the nonporous polymer layers with the high refractive index may additionally contain, in addition to the polymers, non-porous inorganic compounds which may further increase the refractive index.
  • non-porous inorganic compounds which may further increase the refractive index.
  • inorganic compounds are used which have a higher refractive index in the wavelength range of interest between 200 nm and 2500 nm than the polymer used in the non-porous polymer layer. The refractive index of the nonporous polymer layer is then increased by adding the inorganic compound.
  • the proportion of inorganic compounds in relation to the polymer used in the non-porous polymer layer is kept so low that no porosity can arise because the presence of gas-filled pores otherwise the refractive index would reappear.
  • a layer in which the ratio of the pore volume to the total volume is less than 4% is defined as "nonporous".
  • the achievable effective refractive indices of the resulting non-porous layer are always between the refractive index of the non-porous starting layer and the refractive index of the added inorganic compound.
  • the average particle diameter of these inorganic nanoparticles is preferably between 5 nm and 200 nm, more preferably the size range between 10 nm and 60 nm.
  • the inorganic nanoparticles preferably have a narrow particle size distribution, wherein at least 90 % of the primary particles have a smaller diameter than twice the aforementioned average particle diameter and practically no primary particles have a diameter larger than three times the aforementioned average particle diameter.
  • Examples of such preferred nanoparticles in the nonporous polymer layer are PbS, TiO 2, SiO 2, Al 2 O 3, ZrO 2, ZnO and SnO 2.
  • the inorganic compounds are polymers such as poly (dibutyl titanate).
  • the non-porous polymer layers with the high refractive index may also contain, in addition to the polymers, compounds which absorb light in the wavelength range of interest between 200 nm and 2500 nm.
  • organic compounds absorb light between 200 nm and 700 nm.
  • the non-porous polymer layers with the high refractive index may also contain luminescent organic molecules, luminescent organic pigments, luminescent organic polymers, luminescent inorganic nanoparticles and organic or inorganic nanoparticles with luminescent compounds contained therein, which in the wavelength range of interest 200 nm and 2500 nm emit light.
  • Flexible carriers for the novel materials are a large variety of flexible carriers, such as those used in the photographic industry, among others.
  • transparent carriers of cellulose esters such as cellulose triacetate, cellulose acetate, cellulose propionate or cellulose acetate / butyrate
  • polyesters such as polyethylene terephthalate or polyethylene naphthalate, polyamides, polycarbonates , Polyimides, polyolefins, polyvinyl acetals, polyethers, polyvinyl chloride and polyvinylsulfones.
  • polyesters in particular polyethylene terephthalate such as, for example, Cronar® from Du-Pont Tejin Films or polyethylene naphthalate, because of their excellent dimensional stability.
  • baryta paper, polyolefin-coated papers, white opaque polyesters such as Melinex® from Du-Pont Tejin Films can be used in the opaque supports used in the photographic industry.
  • Particularly preferred are polyolefin-coated papers or white opaque polyester.
  • carriers consisting of acrylonitrile-butadiene-styrene, polycarbonate, polyetherinide, polyether ketone, polymethyl methacrylate, polyoxymethylene and polystyrene can also be used.
  • subbing layers are well known in the photographic industry and contain e.g. As terpolymers of vinylidene chloride, acrylonitrile and acrylic acid or vinylidene chloride, methyl acrylate and itaconic acid.
  • the adhesion of the layers to the support can also be improved, for example, by a corona or corona / aerosol treatment of the support before the casting. All of these flexible carriers can also be provided with an electrically conductive layer. Preference is given to metals or indium tin oxide coated plastic carrier.
  • Flexible metal foils for example made of aluminum, can also be used. All of these supports can also have three-dimensional surface structures.
  • the layers according to the invention are generally prepared from aqueous solutions or dispersions containing all the necessary components on the flexible layer
  • wetting agents are added as casting aids in order to improve the casting behavior and the uniformity of the
  • plasticizers for example glycerol.
  • the novel materials comprise at least one layer package which contains a porous or nanoporous layer with a low refractive index and a non-porous polymer layer with a high refractive index, or several such layer packages, the differences in the refractive indices of the different layers, the sequence of the layers, the orientation of the layers , the composition of the layers and their thickness depend on the particular application. In the case of several layer packages, these can be applied successively or also together to the flexible carrier.
  • the porous or nanoporous layer with the low refractive index which contains inorganic nanoparticles and a binder and optionally further additives
  • the flexible carrier For this purpose, aqueous, colloidal dispersions of these inorganic nanoparticles, together with the binder and optionally further additives, at temperatures between 0 ° C and 100 ° C, preferably between 15 ° C and 60 ° C on flexible metal, paper or Plastic support, which may also be coated with indium tin oxide or metals, applied and the molded flexible carrier is then dried.
  • the nonporous polymer layer with the high refractive index is then applied thereto by adding aqueous solutions of the polymer, which optionally contain further additives, or, when using water-dispersible thermoplastic polymers, colloidal dispersions of these thermoplastic polymers, optionally together with an additional binder temperatures ren between 0 ° C and 100 ° C, preferably between 15 ° C and 60 ° C are applied and the coated flexible carrier is then dried.
  • the non-porous high refractive index polymer layer and then the low refractive index porous or nanoporous layer containing inorganic nanoparticles and a binder and optionally further additives are applied to the applied flexible carrier.
  • further layer packages can be applied to the already coated with a layer package flexible carrier by one of the methods described above.
  • either the non-porous polymer layer with the high refractive index or the porous or nanoporous layer with the low refractive index can be in direct contact with the carrier in the first layer package.
  • two layer packages are applied to the flexible support, the layer order being as follows: flexible support, a porous or nanoporous layer having a low refractive index, a nonporous layer having a high refractive index, then a second nonporous layer having a high refractive index and on it again a second porous or nanoporous layer with a low refractive index.
  • the layer packages each containing a porous or nanoporous layer with a low refractive index, which contains inorganic nanoparticles, and a non-porous polymer layer with high refractive index, simultaneously in one step on flexible metal, paper or plastic substrates, which also with Indium tin oxide or metals can be coated, applied. Subsequently, the molded in this way flexible carrier is dried.
  • the layer packages each containing a porous or nanoporous layer with low refractive index, which contains inorganic nanoparticles, and a non-porous polymer layer with high refractive index, are applied successively in two separate coating steps on the flexible support.
  • the drying can be done, for example, with air, with IR rays, with microwave radiation, by contact drying (the drying energy is introduced by pure heat conduction in contact with the surface of a heated material in the material to be dried) or a combination of these methods.
  • the drying is preferably carried out with a gas mixture, preferably air, wherein the layer temperature during drying does not exceed 100 ° C, preferably 60 ° C.
  • the casting solutions can be applied to the flexible carrier in various ways.
  • the casting processes include various well-known casting methods such as gravure coating, roll coating, bar brushing, slot casting, extrusion casting, doctor blade casting, cascade casting, curtain casting or other customary casting methods. If the flexible support is fixed on a firm base, dipping or centrifugal casting can also be used.
  • the casting speed depends on the method used and can be changed within wide limits.
  • the curtain casting at speeds between 30 m / min and 2000 m / min, preferably between 50 m / min and 500 m / min.
  • All of the above-mentioned layer packages may optionally contain further additives in one or more of the layers, such as, for example, luminescent or light-absorbing compounds. All of the above-mentioned layer packages may optionally contain inorganic compounds for increasing the refractive index in the non-porous polymer layer having the high refractive index.
  • one or more additional layers with other functions are applied between the individual layer packages, if several are present, between the layer packages and the carrier or on the layer packages.
  • additional layers with other functions for example luminescent layers, electrically conductive layers, reflective layers, protective layers, Layers for mechanical stabilization or release layers.
  • a structure can be applied to the individually applied layers.
  • a structure can be produced by means of inkjet printing, photolithography, offset printing, laser marking or hot stamping.
  • a porous or nanoporous layer having a low refractive index and the composition listed in Table 1 (in the dried state) was applied to a subbed Cronar® 742 transparent polyester support available from DuPont Teijin Films, Germany.
  • the surface-modified SiO 2 was prepared by the method of Example 1 of patent application EP 1'655'348.
  • Polyvinyl alcohol C is available as Mowiol 40-88 from Omya AG, Oftringen, Switzerland.
  • the hardener is boric acid, available from Schweizerhall Chemie AG, Basel, Switzerland.
  • a non-porous polymer layer of high refractive index consisting of polyvinyl alcohol B having a dry film thickness of about 0.24 ⁇ m was applied.
  • Polyvinyl alcohol B is also available as Mowiol 56-98 from Omya AG, Oftringen, Switzerland.
  • Example 2
  • a porous or nanoporous layer having a low refractive index and the composition listed in Table 2 (in the dried state) was applied to the subbed transparent polyester support of Example 1.
  • Polyvinyl alcohol D is available as Gohsefimer K-210 from Nippon Synthetic Chemical Industry Ltd., Osaka, Japan.
  • the latex is Jonrez E2001, available from MeadWestvaco Corporation, Stamford, USA.
  • This layer was sealed with the GBC 3500 Pro laminator at a temperature of 120 ° C at a speed of about 27 cm / min.
  • a porous or nanoporous layer having a low refractive index and the composition listed in Table 4 (in the dried state) was applied to the subbed transparent polyester support of Example 1.
  • the lanthanum-containing alumina / hydroxide was prepared by the method of Example 1 of patent application EP 0O67O86.
  • Polyvinylpyrrolidone is Luviskol * K 90, available from BASF AG Wädenswil, Switzerland.
  • visible interference colors which are visible to the eye occur when viewed in daylight. These interference colors are due to the multiple reflection of the incident light at the interface between the porous or nanoporous deep refractive index layer containing inorganic nanoparticles and the non-porous polymer layer having the high refractive index. They are only clearly visible if the boundary layer is optically sufficient is sharp and the refractive index difference of the layers is at least 0.20.
  • the visual assessment in the visible region of the spectrum (400 nm - 700 nm) is very meaningful.
  • the interference colors could in principle also be recorded by means of a spectrometer. However, this method would be advantageous only where interference colors occur which are below or above the range visible to the human eye, or where multiple interferences overwhelm the spectral resolution of the human eye.
  • Table 6 summarizes the evaluations of the interference colors of the test samples under the experimental conditions given above.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

L'invention concerne un matériau flexible pour des applications optiques dans une gamme d'ondes comprise entre ?<SUB>1</SUB> et ?<SUB>2</SUB>, ?<SUB>1</SUB> étant inférieure à ?<SUB>2</SUB>. Ce matériau est constitué d'un support flexible et d'au moins un empilement de couches appliqué sur ledit support, lequel empilement est composé d'une couche poreuse ou nanoporeuse à bas indice de réfraction, qui contient des nanoparticules inorganiques et au moins un liant, et d'une couche polymère non poreuse à haut indice de réfraction, en contact direct avec la couche poreuse ou nanoporeuse. L'invention se caractérise en ce que les épaisseurs des couches limites entre les couches poreuses ou nanoporeuses et les couches polymères en contact direct avec ces dernières, couches dont l'indice de réfraction varie d'une valeur à une autre, équivalent au maximum à 1/5 de la longueur d'onde ?<SUB>2</SUB>. La différence entre les indices de réfraction des couches poreuses ou nanoporeuses et des couches polymères non poreuses équivaut au moins à 0,20, 200 nm et 2 500 nm étant des valeurs typiques pour ?<SUB>1</SUB> et ?<SUB>2</SUB>.
EP06778072A 2006-07-28 2006-07-28 Matériaux flexibles pour applications optiques Withdrawn EP2047302A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2006/064823 WO2008011919A1 (fr) 2006-07-28 2006-07-28 Matériaux flexibles pour applications optiques

Publications (1)

Publication Number Publication Date
EP2047302A1 true EP2047302A1 (fr) 2009-04-15

Family

ID=37903621

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06778072A Withdrawn EP2047302A1 (fr) 2006-07-28 2006-07-28 Matériaux flexibles pour applications optiques

Country Status (5)

Country Link
US (1) US20100208349A1 (fr)
EP (1) EP2047302A1 (fr)
JP (1) JP2009544491A (fr)
CN (1) CN101501533B (fr)
WO (1) WO2008011919A1 (fr)

Families Citing this family (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2164302A1 (fr) * 2008-09-12 2010-03-17 Ilford Imaging Switzerland Gmbh Elément optique et son procédé de fabrication
TWI491930B (zh) 2009-04-15 2015-07-11 ３Ｍ新設資產公司 光學膜
JP5727460B2 (ja) 2009-04-15 2015-06-03 スリーエム イノベイティブ プロパティズ カンパニー 光結合を防止するための光学フィルム
TWI605276B (zh) 2009-04-15 2017-11-11 ３Ｍ新設資產公司 光學結構及包含該光學結構之顯示系統
US9291752B2 (en) 2013-08-19 2016-03-22 3M Innovative Properties Company Retroreflecting optical construction
WO2010120845A2 (fr) 2009-04-15 2010-10-21 3M Innovative Properties Company Rétroéclairage et système d'affichage l'incorporant
US9464179B2 (en) 2009-04-15 2016-10-11 3M Innovative Properties Company Process and apparatus for a nanovoided article
FR2949775B1 (fr) * 2009-09-10 2013-08-09 Saint Gobain Performance Plast Substrat de protection pour dispositif collecteur ou emetteur de rayonnement
FR2949776B1 (fr) 2009-09-10 2013-05-17 Saint Gobain Performance Plast Element en couches pour l'encapsulation d'un element sensible
CN102576101B (zh) 2009-10-24 2015-01-14 3M创新有限公司 空隙化扩散体
JP5932652B2 (ja) 2009-10-24 2016-06-08 スリーエム イノベイティブ プロパティズ カンパニー 光学構造物
US8922733B2 (en) 2009-10-24 2014-12-30 3M Innovative Properties Company Light source and display system incorporating same
KR101781661B1 (ko) 2009-10-24 2017-09-25 쓰리엠 이노베이티브 프로퍼티즈 컴파니 구배 나노공극형 물품을 위한 방법
US8950924B2 (en) 2009-12-08 2015-02-10 3M Innovative Properties Company Optical constructions incorporating a light guide and low refractive index films
US9791604B2 (en) 2010-04-15 2017-10-17 3M Innovative Properties Company Retroreflective articles including optically active areas and optically inactive areas
MX341955B (es) 2010-04-15 2016-09-08 3M Innovative Properties Co Articulos retrorreflectantes que incluyen areas opticamente activas y areas opticamente inactivas.
EP2558290B1 (fr) 2010-04-15 2019-01-23 3M Innovative Properties Company Objets rétroréfléchissants comprenant des zones optiquement actives et des zones optiquement inactives
JP5593916B2 (ja) * 2010-07-24 2014-09-24 コニカミノルタ株式会社 近赤外反射フィルム及びそれを設けた近赤外反射体
WO2012014644A1 (fr) * 2010-07-24 2012-02-02 コニカミノルタホールディングス株式会社 Procédé de fabrication d'un film réfléchissant proche de l'infrarouge, et corps réfléchissant proche de l'infrarouge le comportant
EP2597496A4 (fr) * 2010-07-24 2015-11-11 Konica Minolta Holdings Inc Film réfléchissant proche de l'infrarouge, et corps réfléchissant proche de l'infrarouge le comportant
KR101420115B1 (ko) * 2010-07-30 2014-07-21 주식회사 잉크테크 투명 도전막의 제조방법 및 이로부터 제조되는 투명 도전막
JP6247534B2 (ja) 2010-10-20 2017-12-13 スリーエム イノベイティブ プロパティズ カンパニー 光学拡散性低屈折率要素
JP6001545B2 (ja) 2010-10-20 2016-10-05 スリーエム イノベイティブ プロパティズ カンパニー ナノ空隙ポリマー層を組み込んだ広帯域半鏡面ミラーフィルム
TWI534458B (zh) 2010-10-20 2016-05-21 ３Ｍ新設資產公司 經保護之低折射率光學元件
CN103154777B (zh) 2010-10-20 2015-11-25 3M创新有限公司 具有互连空隙的低折射率漫射体元件
US9470827B2 (en) 2010-10-27 2016-10-18 Konica Minolta, Inc. Near-infrared reflective film, method for producing same, and near-infrared reflector provided with near-infrared reflective film
US9804308B2 (en) 2010-12-09 2017-10-31 Konica Minolta, Inc. Near-infrared reflective film and near-infrared reflector provided with the same
JP5724413B2 (ja) * 2011-02-02 2015-05-27 コニカミノルタ株式会社 近赤外反射フィルム、その製造方法及び近赤外反射体
WO2012112624A2 (fr) 2011-02-15 2012-08-23 Svaya Nanotechnologies, Inc. Procédés et matériaux pour espèces polyioniques fonctionnelles, et leur dépôt
JP5703855B2 (ja) * 2011-03-07 2015-04-22 コニカミノルタ株式会社 近赤外反射フィルム、近赤外反射フィルムの製造方法及び近赤外反射体
FR2973939A1 (fr) 2011-04-08 2012-10-12 Saint Gobain Element en couches pour l’encapsulation d’un element sensible
JP5644667B2 (ja) * 2011-05-17 2014-12-24 コニカミノルタ株式会社 赤外遮蔽フィルム、赤外遮蔽フィルムの製造方法、および赤外遮蔽体
JP5724621B2 (ja) * 2011-05-20 2015-05-27 コニカミノルタ株式会社 赤外線遮蔽フィルム及びそれを用いた赤外線遮蔽体
WO2012161096A1 (fr) * 2011-05-20 2012-11-29 コニカミノルタホールディングス株式会社 Film formant écran aux infrarouges
JP5729144B2 (ja) * 2011-06-02 2015-06-03 コニカミノルタ株式会社 赤外遮蔽フィルムおよび赤外遮蔽体
JP5724620B2 (ja) * 2011-05-20 2015-05-27 コニカミノルタ株式会社 赤外線遮蔽フィルム及びそれを用いた赤外線遮蔽体
JP5811626B2 (ja) * 2011-06-23 2015-11-11 コニカミノルタ株式会社 光学反射フィルム及びそれを用いた光学反射体
US20130027766A1 (en) * 2011-07-28 2013-01-31 Kiyoshi Itoh Infrared reflection films
WO2013052931A2 (fr) 2011-10-07 2013-04-11 Svaya Nanotechnologies, Inc. Synthèse de solutions d'oxydes métalliques et de solutions d'oxydes métalliques mixtes
WO2013052927A2 (fr) * 2011-10-07 2013-04-11 Svaya Nanotechnologies, Inc. Film de contrôle solaire à large bande
US9664831B2 (en) * 2011-10-12 2017-05-30 Konica Minolta, Inc. Near-infrared shielding film and near-infrared shielding body
EP2775328B1 (fr) * 2011-10-31 2021-03-31 Konica Minolta, Inc. Film de réflexion optique, et corps de réflexion optique mettant en uvre celui-ci
KR20140105449A (ko) * 2011-10-31 2014-09-01 다우 코닝 인디아 프라이빗 리미티드 광 확산 열가소성 수지 조성물 및 광 확산 부재
DE102011119598A1 (de) 2011-11-29 2013-05-29 Ovd Kinegram Ag Optisch variables Element
JP6099236B2 (ja) * 2011-12-09 2017-03-22 コニカミノルタ株式会社 反射防止膜
WO2013089066A1 (fr) * 2011-12-12 2013-06-20 コニカミノルタ株式会社 Film optique stratifié, film de protection contre l'infrarouge et corps de protection contre l'infrarouge
JP5708504B2 (ja) * 2012-01-06 2015-04-30 コニカミノルタ株式会社 誘電体多層膜構造を有する顔料およびそれを含む塗料
JP5817553B2 (ja) * 2012-01-23 2015-11-18 コニカミノルタ株式会社 赤外遮蔽フィルムおよび赤外遮蔽体
EP2808710A4 (fr) * 2012-01-25 2016-04-06 Konica Minolta Advanced Layers Film optique
EP2626447A1 (fr) 2012-02-07 2013-08-14 ILFORD Imaging Switzerland GmbH Couches nanoporeuses pour applications optiques
JP5994849B2 (ja) * 2012-05-08 2016-09-21 コニカミノルタ株式会社 合わせガラス
WO2013179902A1 (fr) * 2012-05-31 2013-12-05 コニカミノルタ株式会社 Objet de protection contre les infrarouges
US8834004B2 (en) 2012-08-13 2014-09-16 3M Innovative Properties Company Lighting devices with patterned printing of diffractive extraction features
US8944662B2 (en) 2012-08-13 2015-02-03 3M Innovative Properties Company Diffractive luminaires
CN104704145B (zh) 2012-09-17 2017-06-09 伊士曼化工公司 用于提高叠层过程的控制和效率的方法、材料和设备
WO2014073291A1 (fr) * 2012-11-08 2014-05-15 コニカミノルタ株式会社 Film de réflexion optique et réflecteur optique l'utilisant
WO2014073379A1 (fr) * 2012-11-08 2014-05-15 コニカミノルタ株式会社 Film optique stratifié, film de protection contre l'infrarouge et corps de protection contre l'infrarouge
US9784902B2 (en) 2013-03-25 2017-10-10 3M Innovative Properties Company Dual-sided film with split light spreading structures
US9261641B2 (en) 2013-03-25 2016-02-16 3M Innovative Properties Company Dual-sided film with compound prisms
WO2015034896A1 (fr) 2013-09-05 2015-03-12 3M Innovative Properties Company Film optique double face à micro-lentilles et groupes de prismes
DE102013221324A1 (de) 2013-10-21 2015-04-23 Bundesdruckerei Gmbh Mit mindestens einem Druckmerkmal versehenes Druckprodukt, Verfahren zu dessen Herstellung und Transferfolie
ES2536827B1 (es) * 2013-11-27 2015-12-18 Indo Optical S.L. Lente oftálmica que comprende una base de material polimérico con un recubrimiento con una estructura multicapa interferencial antireflejante, antiiridiscente y con filtro IR
KR20210134835A (ko) * 2014-09-12 2021-11-10 세키스이가가쿠 고교가부시키가이샤 합판유리용 중간막 및 합판유리
US9817166B2 (en) 2014-12-15 2017-11-14 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9453949B2 (en) 2014-12-15 2016-09-27 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891357B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
US9891347B2 (en) 2014-12-15 2018-02-13 Eastman Chemical Company Electromagnetic energy-absorbing optical product and method for making
EP3323864A1 (fr) 2016-11-22 2018-05-23 BASF Coatings GmbH Revêtement optique à faible indice de réfraction
JP6627828B2 (ja) 2017-07-19 2020-01-08 日亜化学工業株式会社 薄膜の製造方法、薄膜形成材料、光学薄膜、及び光学部材
US10338287B2 (en) 2017-08-29 2019-07-02 Southwall Technologies Inc. Infrared-rejecting optical products having pigmented coatings
US11747532B2 (en) 2017-09-15 2023-09-05 Southwall Technologies Inc. Laminated optical products and methods of making them
EP3710548B1 (fr) * 2017-11-17 2023-06-07 Imerys USA, Inc. Revêtements thermoscellables
WO2019121650A1 (fr) * 2017-12-21 2019-06-27 Lumileds Holding B.V. Dispositif d'éclairage
US10627555B2 (en) 2018-04-09 2020-04-21 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
US10613261B2 (en) 2018-04-09 2020-04-07 Southwall Technologies Inc. Selective light-blocking optical products having a neutral reflection
EP4031496A1 (fr) 2019-09-17 2022-07-27 Basf Se Nanoparticules d'oxyde métallique
JP2020030435A (ja) * 2019-11-14 2020-02-27 日亜化学工業株式会社 薄膜形成材料、光学薄膜、及び光学部材
WO2021187453A1 (fr) * 2020-03-19 2021-09-23 三菱ケミカル株式会社 Composition de résine, préimprégné, article moulé et procédé de fabrication de préimprégné
US12613366B2 (en) * 2020-04-06 2026-04-28 Viavi Solutions Inc. Article including a stack of alternating layers
US12504571B2 (en) * 2020-04-06 2025-12-23 Viavi Solutions Inc. Article including two external layers of absorbing nanoparticles
CN115867614A (zh) 2020-08-21 2023-03-28 巴斯夫欧洲公司 具有高折射率的可uv固化涂层
US12216310B2 (en) * 2021-08-06 2025-02-04 Battelle Memorial Institute Mixed-matrix composite integrated fiber optic CO2 sensor
EP4234641A1 (fr) 2022-02-25 2023-08-30 Basf Se Compositions comprenant des nanoparticules de dioxyde de titane modifiées et leurs utilisations
CN119731276A (zh) 2022-07-11 2025-03-28 巴斯夫欧洲公司 具有高折射率的可uv固化涂层

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62196175A (ja) * 1986-02-24 1987-08-29 Canon Inc 被記録材および記録画像の形成方法
JPS62271781A (ja) * 1986-05-21 1987-11-26 Canon Inc 画像形成方法
CN1008558B (zh) * 1987-02-20 1990-06-27 天津市光学精密机械研究所 冷光片
JP3204966B2 (ja) * 1990-08-08 2001-09-04 松下電器産業株式会社 薄膜光学素子の製造方法
US5667880A (en) * 1992-07-20 1997-09-16 Fuji Photo Optical Co., Ltd. Electroconductive antireflection film
JP3315515B2 (ja) * 1994-01-07 2002-08-19 旭硝子株式会社 インクジェット記録物の製造方法およびインクジェットプリンター用記録シート
US6383559B1 (en) * 1995-12-07 2002-05-07 Fuji Photo Film Co., Ltd. Anti-reflection film and display device having the same
US5919555A (en) * 1996-11-06 1999-07-06 Fuji Photo Film Co., Ltd. Anti-reflection film and display device having the same
JP4161387B2 (ja) * 1997-01-23 2008-10-08 株式会社ニコン 多層反射防止膜
US6210858B1 (en) * 1997-04-04 2001-04-03 Fuji Photo Film Co., Ltd. Anti-reflection film and display device using the same
JP3967822B2 (ja) * 1997-04-04 2007-08-29 富士フイルム株式会社 反射防止膜およびそれを用いた画像表示装置
US6207260B1 (en) * 1998-01-13 2001-03-27 3M Innovative Properties Company Multicomponent optical body
DE69937764T2 (de) * 1998-09-22 2008-11-27 Fujifilm Corp. Verfahren zur Herstellung eines Antireflektionsfilms
JP2001083316A (ja) * 1999-09-09 2001-03-30 Fuji Photo Film Co Ltd 光学フィルターおよび反射防止膜
US6861115B2 (en) * 2001-05-18 2005-03-01 Cabot Corporation Ink jet recording medium comprising amine-treated silica
JP3953829B2 (ja) * 2002-02-20 2007-08-08 大日本印刷株式会社 表面が強化された反射防止層、反射防止材、および反射防止体
DE10336041A1 (de) * 2003-08-01 2005-02-17 Merck Patent Gmbh Optisches Schichtsystem mit Antireflexeigenschaften
JP4120932B2 (ja) * 2003-03-24 2008-07-16 日本ゼオン株式会社 積層体及び光学部材
JP2006088615A (ja) * 2004-09-27 2006-04-06 Fuji Photo Film Co Ltd 積層型ガスバリアフィルム
US7615283B2 (en) * 2006-06-13 2009-11-10 3M Innovative Properties Company Fluoro(meth)acrylate polymer composition suitable for low index layer of antireflective film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008011919A1 *

Also Published As

Publication number Publication date
WO2008011919A1 (fr) 2008-01-31
JP2009544491A (ja) 2009-12-17
CN101501533A (zh) 2009-08-05
CN101501533B (zh) 2012-02-15
US20100208349A1 (en) 2010-08-19

Similar Documents

Publication Publication Date Title
EP2047302A1 (fr) Matériaux flexibles pour applications optiques
EP2164302A1 (fr) Elément optique et son procédé de fabrication
EP2801846B1 (fr) Élément optique doté d&#39;un revêtement à haute diffusivité
US6756120B2 (en) Colored articles and compositions and methods for their fabrication
DE69531705T2 (de) Feine Zinkoxid-Teilchen, Verfahren zu ihrer Herstellung und ihre Verwendung
EP2347452A2 (fr) Collecteur fluorescent et son utilisation
EP3740815B1 (fr) Verre de lunettes comprenant au moins une couche nanostructurée et/ou microstructurée
DE102007001168A1 (de) Staubdichtes, lichtdurchlässiges Element und dessen Verwendung sowie Bilderzeugungsgerät mit einem solchen Element
DE102007001686A1 (de) Optisches Element mit Antireflexbelag
EP3384329B1 (fr) Produit optique absorbant l&#39;énergie électromagnétique
EP3384330B1 (fr) Produit optique absorbant l&#39;énergie électromagnétique
DE102015122788A1 (de) Verfahren zur Herstellung von leitfähigen Strukturen
WO2018158114A1 (fr) Composant optoélectronique et procédé de fabrication d&#39;un composant optoélectronique
EP2067061A1 (fr) REVÊTEMENT TRANSPARENT EN SiO2 POREUX POUR UN MATÉRIAU DE SUBSTRAT TRANSPARENT
WO2009037073A1 (fr) Procédé d&#39;application d&#39;un revêtement transparent sur un substrat avec du plasma sous pression atmosphérique
KR101072865B1 (ko) 광학적 응용을 위한 가요성 재료
EP2130408A1 (fr) Élément stratifié électroluminescent
DE102016206319A1 (de) Antireflektierende Beschichtung und Verfahren zur Herstellung einer antireflektierenden Beschichtung
JP2026053416A (ja) ハイブリッド・ディフューザー及びその製造方法
DE2406598A1 (de) Anorganische infrarotabschwaecher mit transparenz im sichtbaren bereich
EP1492389A1 (fr) Matériaux à amplification optique

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080320

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

17Q First examination report despatched

Effective date: 20091221

DAX Request for extension of the european patent (deleted)
19U Interruption of proceedings before grant

Effective date: 20131209

19W Proceedings resumed before grant after interruption of proceedings

Effective date: 20150803

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: WIFAG-POLYTYPE HOLDING AG

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20160203