EP2488590A1 - Revêtements à base de tio2 à réfraction élevée et résistants aux rayures dans des monocouches ou multicouches - Google Patents

Revêtements à base de tio2 à réfraction élevée et résistants aux rayures dans des monocouches ou multicouches

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Publication number
EP2488590A1
EP2488590A1 EP10763197A EP10763197A EP2488590A1 EP 2488590 A1 EP2488590 A1 EP 2488590A1 EP 10763197 A EP10763197 A EP 10763197A EP 10763197 A EP10763197 A EP 10763197A EP 2488590 A1 EP2488590 A1 EP 2488590A1
Authority
EP
European Patent Office
Prior art keywords
layer
coating
coated product
nanoparticles
product according
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Withdrawn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
EP10763197A
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German (de)
English (en)
Inventor
Karlheinz Hildenbrand
Friedrich-Karl Bruder
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.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer MaterialScience AG
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Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP2488590A1 publication Critical patent/EP2488590A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
    • G11B7/2545—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins containing inorganic fillers, e.g. particles or fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the invention relates to coated products comprising a substrate (S) provided with a coating consisting of a single, high-index and scratch-resistant layer (A) or provided with a multilayer Au, in which alternating layers (A) with lower refractive layers (B), wherein the layers (A) are characterized in that they contain particularly finely divided T1O 2 - nanoparticles.
  • the coatings comprising the layer (A) can be produced by a process which enables the agglomeration-free deposition of the nanoparticles.
  • a further subject of the invention is therefore also a process for the production of the products provided with a single layer or with multilayer and their use, for example as "cover layer” in optical data storage or as IR reflection coatings.
  • High refractive index (HRI) coatings also referred to as HRI coatings
  • HRI coatings are known from a variety of applications, such as optical or planar waveguides, where the term “refractive index” is synonymous with “Real part of the complex refractive index”, both terms are used interchangeably in the present application and denoted by n.
  • Coatings with high refractive indices can in principle be produced by various methods T1O 2 , Ta 2 0 5 , CeÜ 2 , Y 2 O 3 deposited in a high vacuum via plasma processes. While it is easy to achieve refractive indices of more than 2.0 in the visible wavelength range, the method is relatively complex and expensive.
  • US Pat. No. 6,777,070 B1 describes an antireflective material and a polarizing film, the antistain coating consisting of 3 components: 1. a fluorine-containing methacrylate polymer, 2. a polymer of urethane acrylate and ultrafine particles, and 3. a surface-treated titanium oxide particle resin.
  • a fluorine-containing methacrylate polymer 2. a polymer of urethane acrylate and ultrafine particles
  • 3. a surface-treated titanium oxide particle resin 3.
  • a mixture of titanium dioxide and zirconium dioxide is used.
  • the present coated product exclusively contains titanium dioxide nanoparticles in the scratch-resistant layer.
  • DE 1,982,3732 A1 describes a process for the production of optical multilayer systems, wherein, inter alia, the application of a nanoscale inorganic solid particles containing flowable composition takes place on a glass substrate.
  • the substrates are of polymeric material.
  • Chem. Mater 2001, 13, 1137 -1 142 describes the preparation of optical thin films of high-index trialkoxysilane-capped PMMA titanium hybrid and, inter alia, its transmission. It is a scratch resistant coating on potassium bromide pellets. Polycarbonate as a substrate material is not mentioned.
  • US Pat. No. 6,777,706 Bl describes an optical product which contains a layer of organic material, which contains translucent nanoparticles.
  • the content of nanoparticles, including T1O 2 , in the cured layer may be 0-50 vol.%.
  • the coated product of the present invention contains in the coating an amount of> 58% by weight of titanium dioxide.
  • EP 0964019 A1 and WO 2004/009659 A1 disclose organic polymers, for example sulfur-containing polymers or halogenated acrylates (tetrabromophenyl acrylate, Polyscience Inc.), which inherently have a higher refractive index than conventional polymers and which are prepared by simple methods from organic solutions Conventional coating methods can be applied to surfaces. However, the refractive indices are limited to values of up to about 1.7, measured in the visible wavelength range.
  • nanoparticle-polymer hybrid formulations can be applied in a simple manner at low cost, for example by means of spin coating, to various substrates.
  • the achievable refractive indices are usually between the first mentioned sputtering surfaces and the layers of high refractive index polymers. With increasing nanoparticle contents, increasing refractive indices can be achieved.
  • US 2002/176169 A1 discloses the preparation of nanoparticle-acrylate hybrid systems, wherein the high-index layers contain a metal oxide, such as titanium oxide, indium oxide or tin oxide, and a UV-crosslinkable binder, for example acrylate-based, in organic solvent. After spin coats, solvent evaporation and UV irradiation, appropriate coatings for optical films / foils containing a scratch resistant coating, an HRI layer (I) in a thickness of 30 to 120 nm and a desired refractive index of 1.70.
  • a metal oxide such as titanium oxide, indium oxide or tin oxide
  • a UV-crosslinkable binder for example acrylate-based
  • These films should be suitable as antireflection layers.
  • a target refractive index range of up to 1.95 is given for the HRI layer (I)
  • the layers with higher refractive indices claimed in this application are to be regarded as desideratum only, and the disclosure does not satisfy the need for a method of producing such high refractive index layers.
  • EP-A 2008/040439 describes coated products comprising a substrate (S) and a coating (A) produced from a water-containing nanoparticle suspension.
  • the coatings (A) are characterized by having a real part n of the complex refractive index of at least 1.70, an imaginary part k of the complex refractive index of at most 0.016, a surface roughness of Ra less than 20 nm, and a scratch resistance of less or 0.75 ⁇ m scratch depth, the real part and the imaginary part of the refractive index being measured at a wavelength of 400-40 ⁇ m (that is to say in the wavelength range of the blue laser) and the surface roughness being denoted as Ra value by means of AFM (FIG. atomic force microscopy).
  • Such HRI coatings can be used as the uppermost layer in optical data storage (ODS), whereby the high refractive index enables the coupling of light in the evanescent field of a near-field lens (solid immersion lens, SIL).
  • ODS optical data storage
  • SIL solid immersion lens
  • the k value is related to the decay constant of the light intensity ⁇ as follows: ⁇ - a
  • the decay constant ⁇ in turn depends on the absorption and scattering (scatter) in the refractive medium. Particularly in the case of nanoparticle-containing systems, k or ⁇ can be dominated by scattering (scatter) in the visible wavelength range of 400-800 nm if the primary nanoparticles are too large or agglomerate nanoparticles to form larger particles, even if no molecular mass is present in this spectral range Absorption is present. A low k value thus describes a medium in which light scattering and absorption are low and which has good transmission properties.
  • One step of the production process for such coatings from EP-A 2008/040439 is the partial replacement of the water of an aqueous nanoparticle suspension with organic solvent. If the water content is not adjusted precisely, this process leads to agglomeration of the nanoparticles and thus to layers with reduced transmission (higher k values). In the course of further investigations, it turned out that agglomerations can not be avoided, especially when solvent is exchanged for water against organic solvents of suspensions containing TiCV nanoparticles.
  • Layers with a real part n of the complex refractive index of at least 1.85 and an imaginary part k of the complex refractive index of at most 0.01 (measured at a wavelength of 400-410 nm) can therefore be combined with HRI according to EP-A 2008/040439. Not achieve layers.
  • HRI layers for substrates such as glass, quartz or organic polymers, which have even better complex refractive indices than the prior art, characterized in that at the same time the real part n of the complex refractive index is higher and the imaginary part k is lower, and simultaneously with the values for surface roughness ("Ra value", measured by AFM (atomic force microscopy) and scratch resistance (determined by measuring the resulting scratch depth when guiding a diamond needle with a tip radius of 50 ⁇ m at a feed rate of 1.5 cm / s and a coating weight of 40 g over the coating), at least at a comparable level.
  • the layers should also be made by a simple process.
  • the HRI layers according to the invention have a layer thickness of> 120 nm, in particular> 125 nm and> 150 nm. Even in larger layer thicknesses, for example> 200 nm,> 300 nm and greater than 500 nm, good properties are achieved.
  • the layer thickness is preferably ⁇ 1 ⁇ m, particularly preferably ⁇ 500 nm.
  • the HRI layers according to the invention have a value of the sum of light absorption and light scattering of ⁇ 1 0 at a layer thickness of about 1 ⁇ m and a light radiation having a wavelength of 405 nm % on.
  • such high-index lacquer layers are characterized by a very low roughness (surface roughness) of less than 20 nm, determined by AFM (atomic force microscopy) and surprisingly good scratch resistance of less than 0.75 ⁇ m scratch depth.
  • the present invention therefore relates to a coated article comprising a substrate (S) made of an organic polymer, and at least one coating comprising at least one layer (A), characterized in that it contains finely divided TiC nanoparticles in an amount of 58% by weight. to 95 wt.% Based on the coating (A).
  • the T1O 2 nanoparticles are particularly finely dispersed, which is shown by the low k value, their good transparency and the low value for the sum of light absorption and scattering.
  • the transmission of the layers (A) is in the visible wavelength range (400-800 nm) even in a thickness of about 1 ⁇ preferably more than 70%, more preferably more than 75% and most preferably more than 80%.
  • LRI layers (B) characterized in that their refractive index n (real part) is at least 0.3 units lower than in the high refractive index HRI coating, ie n (B) ⁇ 1.6 and in particular ⁇ 1.5
  • This layer (B) also referred to here as "LRI” (low refractive index)
  • LRI low refractive index
  • first and last layers on the substrate may independently be HRI layer (A) or LRI layer (B).
  • the material of the substrate (S) is selected from at least one of the group consisting of glass, quartz (which is preferably used for planar waveguides) and organic polymers. From this group, organic polymers, and among them, in particular, polycarbonate, poly (methyl) methacrylate, polyester or cycloolefin polymer, are preferred.
  • Polycarbonates for the compositions according to the invention are homopolycarbonates, copolycarbonates and thermoplastic polyestercarbonates.
  • the polycarbonates and copolycarbonates according to the invention generally have weight average molecular weights of 2,000 to 200,000, preferably 3,000 to 150,000, in particular 5,000 to 100,000, very particularly preferably 8,000 to 80,000, in particular 12,000 to 70,000 g / mol (determined by GPC with polycarbonate calibration ).
  • These or other suitable bisphenol compounds are carbonated, in particular phosgene or in the melt transesterification process, diphenyl carbonate or dimethyl carbonate, reacted to form the respective polymers.
  • CD polycarbonates are - quality used, for example, linear polycarbonate based on bisphenol A, for example, the polycarbonate Makrolon ® types DPI -1265 (linear bisphenol-A polycarbonate having a melt volume flow rate of 19.0 cm 3 / 10 min at 250 ° C and a load of 2.16 kg, measured according to ISO 1133) or OD 2015 (linear bisphenol-a polycarbonate having a melt volume flow rate of 16.5 cm 3/10 min at 250 ° C and a Load of 2.16 kg, measured to ISO 1133 and a Vicat softening temperature of 145 ° C at a load of 50 N and a heating rate of 50 ° C per hour according to ISO 306) from. Bayer MaterialScience AG.
  • the substrate (S) may have spirally arranged grooves, depressions and / or elevations and on the surface so-called information layers or
  • the HRI layer (A) is prepared from a casting solution containing the following components:
  • Nanoparticle suspension Anhydrous T1O 2 nanoparticle suspensions in an organic solvent, for example isopropanol, are used.
  • An important boundary condition with regard to optical requirements is the particle size of the T1O 2 nanoparticles. It has been found that their particle sizes should not exceed values of about 100 nm (dioo value, maximum diameter of 100% of the particles, measured by analytical ultracentrifugation, "AUZ")
  • the dioo values are below 70 nm and the d 50 values (maximum diameter of 50% of the particles) below 25 nm.
  • the method of analytical ultracentrifugation for determining the particle size is described, for example, in "Particle Characterization", Part. Part. Syst. Charact, 1995, 12, 148-157 and thus known to the skilled person.
  • the HRI layer does not contain any Z VP articles.
  • Such products are marketed, for example, by the Japanese company Tayca, Tokyo under the brand name "Micro Titanium”.
  • the solvent should advantageously be exchanged for a higher-boiling solvent, the solvent exchange advantageously taking place by distillation.
  • the higher-boiling solvent should have a boiling point greater than or equal to 100 ° C.
  • Very particularly preferred are higher-boiling alcohols such as Diacetoalcohol (DAA, bp 166 ° C), l-methoxy-2-propanol (MOP, bp 120 ° C) or propyl glycol (bp 150-152 ° C) or mixtures of these solvents.
  • Binders Preference is given to using UV-reactive monomer components which, after coating, can be converted by means of a photochemical reaction into highly crosslinked polymer matrices. For example, the crosslinking takes place with the aid of UV irradiation. Crosslinking by means of UV irradiation is particularly preferred in view of increased scratch resistance.
  • the reactive components are preferably UV-crosslinkable acrylate systems, as described, for example, in PG Garratt in "Strahlenhärtung” 1996, C. Vincentz Vlg., Hannover or BASF Handbuch, Lackiertechnik, A. Goldschmidt, H. Streitberger, Vincentz Verlag, 2002 , Acrylate Resins, page 119 et seq ..
  • binders are polyfunctional acrylates, for example diacrylates, such as hexanediol diacrylate (HDDA) or the tripropylene glycol diacrylate (TPGDA), triacrylates, such as pentaerythritol triacrylate, tetraacrylates, such as ditrimethylolpropane tetraacrylate (DTMPTTA), pentaacrylates, such as dipentaerythritol pentaacrylate or hexaacrylates, such as dipentaerythritol hexaacrylate (DPHA), in particular DPHA is used
  • oligomeric or polymeric (meth) acrylates for example urethane acrylates
  • Hers tell methods for urethane acrylates are basically known and described, for.
  • the solvents may be selected from the group consisting of alcohols, ketones, diketones, cyc lis ethers, Glyko le, glyco lether, Gly kel ester, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide and propylene carbonate used. Preference is given to using 1-methoxy-2-propanol (methoxy alcohol, MOP) and 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol, DAA), whereby mixtures of these two solvents are preferably used.
  • MOP methoxy alcohol
  • DAA diacetone alcohol
  • the components used are preferably at least one additive selected from the group of photoinitiators and thermal initiators. Based on the sum of the parts by weight of the components of the casting solution, up to 3 parts by weight of additives (A3) are used, preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.5 part by weight.
  • additives Typical photoinitiators (UV initiators) are ⁇ -hydroxy ketones (Irgacure ® 184, Fa. Ciba) or Monoacylphosphine (Darocure ® TPO, Fa. Ciba).
  • the amount of energy required to initiate the UV polymerization is in the range of about 0.5 to 4 J / cm 2 , more preferably in the range of 2.0 to 3.0 J / cm 2 coated area.
  • Coating additives as they are, for example, by the company. Byk / Altana (46483 Wesel, Germany) under the name BYK, for example. BYK 344®, available in question.
  • the casting solution for the high-index coatings according to the invention is prepared by dissolving at least one binder and optionally further additives in an organic solvent or solvent mixture.
  • the resulting solution (hereinafter referred to as binder solution) is mixed with the above-described nanoparticle suspension, for example with stirring, and optionally filtered and degassed.
  • the suspension contains the same organic solvent or solvent mixture as the binder solution.
  • the casting solution is optionally treated with ultrasound, for example up to 5 minutes, preferably 10 to 60 seconds, and / or filtered through a filter, preferably with a 0.2 ⁇ m membrane (for example an RC membrane from Sartorius).
  • ultrasound for example up to 5 minutes, preferably 10 to 60 seconds
  • a filter preferably with a 0.2 ⁇ m membrane (for example an RC membrane from Sartorius).
  • a preferred coating composition comprises 15 to 30 parts by weight, preferably 17 to 28 parts by weight, more preferably 22 to 27 parts by weight of the nanoparticles of the invention, 2 to 8 parts by weight, preferably 2.5 to 5 parts by weight of acrylate-containing binder, 0 to 3 parts by weight, preferably 0.05 to 1 parts by weight, more preferably 0.1 to 0.5 parts by weight of further additives, 40 to 80 parts by weight, preferably 45 to 75 parts by weight, particularly preferably 55 to 73 parts by weight of organic solvent, the sum of the parts by weight of the components being 100 normalized.
  • the solids content of the T1O 2 - nanoparticles in the cured layer is 58 to 95 wt.% Preferably 70 to 90 wt.%, In particular 80 to 90 wt.%.
  • the casting solution is applied to the surface of the substrate or the surface of the information and storage layer.
  • Suitable coating technology are the methods known per se, such as flooding, dipping, knife coating, spraying, spin coating and pouring via slot or cascade casters and curtain casters. These processes are described, for example, in BASF Handbuch, Lackiertechnik A., Goldschmidt, H. Streitberger, Vincenz-Verlag, 2002, Chapter Lack für p. 494 ff.
  • the solvent contained in the casting solution may be partially or wholly removed.
  • the subsequent crosslinking of the polymer components of the casting solution is preferably carried out by photochemical (for example UV light) methods.
  • the photochemical crosslinking can be carried out, for example, on a UV exposure system: For this purpose, the coated substrate is placed on a conveyor belt, which at a speed of about 1 m / min at the UV exposure source, (Hg lamp, 80W) is passed. This process can also be repeated to increase the radiant energy per cm 2 .
  • the coated substrate can still be thermally treated, preferably with hot air, for example, 5 to 30 minutes at 60 ° C - 120 ° C.
  • the present invention thus also provides a process for producing a product coated with layer (A) comprising the steps
  • Binder 100 nm in an organic solvent with a boiling point> 100 ° C, b. Binder,
  • the coating with a single layer (A) described above gives a product with the layer sequence (S) - (A) or, in the case of two-sided coating, a product with the layer sequence (A) - (S ) - (A). These products are also the subject of this invention.
  • these layers have a refractive index> 1.85, in particular> 1.90, measured in a wavelength range from 380 to 420 nm.
  • HRI high-index
  • the use of the mentioned T1O 2 nanoparticles and the procedure described here make it possible to prevent agglomeration of the nanoparticles. This ensures that the layers have a low k value.
  • the HRI layers according to the invention At a wavelength of about 405 nm and a layer thickness of 1 ⁇ the sum of the measured light scattering and absorption, which determines the height of the ⁇ value, the HRI layers according to the invention at a value of less than 10%.
  • the layers have high transparency with transmission values of> 70%, in particular> 75% and very particularly preferably> 80% in the visible spectral range.
  • TiC HRI high-index TiC layers
  • layers (B) consisting of coatings prepared from conventional, thermally or photochemically crosslinkable casting formulations whose refractive index Therefore, in addition to the products with the described single-layer, high-index layers (A), there are also substrates with multilayers, which alternately have layers with a high (HRI) and a low (LRI) refractive index content of the present application, wherein the previously described TiC-containing formulations for the layers (A) are used as the HRI layer.
  • HRI high
  • LRI low
  • Layer (B) For the so-called LRI layers (B), naturally those formulations are to be preferred whose refractive index is as low as possible and which can be coated and crosslinked as analogously as possible to the TiCVHRI formulation. In principle, all coating formulations which have a significantly lower refractive index n than the T1O 2 -HRI coating (about 1.90 at 405 nm) are suitable as the low-refractive index layer (LRI). The difference An should be greater than 0.2, preferably greater than 0.25 and particularly preferably greater than 0.3. Layer (B) has a refractive index ⁇ 1.70, preferably ⁇ 1.65, particularly preferably ⁇ 1.60, measured in a wavelength range from 380 to 420 nm.
  • the binders may be, for example, polycondensation resins, for example polyesters or polyaddition resins, such as polyurethanes, or
  • the LRI-layer formulations may contain further constituents, such as initiators, rheological additives, leveling agents, or flow control agents, such as poly (meth) acrylates Fillers, the latter must be such that highly transparent layers are created. Accordingly, suitable fillers are only those nanoparticles which, in addition to mechanical and rheological effects, also have refractive index-lowering properties, for example silica nanoparticles with particle sizes smaller than (d 2 s) ⁇ 25 nm.
  • Particularly preferred formulations for the LRI layer (B) comprise UV-crosslinkable acrylate or polyurethane acrylate binders which are dissolved in alcoholic solvents and contain, as further components, inter alia UV initiators and low-refractive silica nanoparticles.
  • silica-containing, UV-crosslinkable formulations and coatings thereof is described, for example, in WO-A 2009/010193.
  • the production of the coatings from the formulations mentioned for layer (A) and (B) can furthermore be carried out by the methods known to the person skilled in the art.
  • An overview of common manufacturing processes can be found, for example, in the BASF Handbook, Lackiertechnik, Vincentz-Verlag, 2002, chapter “The coating”, p.333 ff, "in the textbook of coating technology (Brock, Groteklaes, Mischke - Vincentz Verlag, 2. Edition 2000, page 229ff.) Or in the textbook of paints and coating materials, Volume 8 - Production of paints and coating materials (Kittel, Hirzel Verlag, 2nd edition 2005).
  • the production takes place with stirring.
  • all components are added in succession to a template and homogenized with constant stirring.
  • the mixtures can be heated.
  • the substrates are coated alternately, for example by spin-coating, with the coating composition for an HRI layer (A) and coating composition for an LRI layer (B), for example a silica-LRI formulation.
  • the present invention thus also provides a process for producing a coated product, wherein the substrate (S) is coated on one or more sides alternately or several times alternately with layers (A) and (B), wherein the layer (A) after the method described above.
  • Such multilayers can be used as reflection-reducing coatings, as described, for example, in "Vacuum Coating 4", Gerhard Kienel, VDI Verlag, 1993.
  • a product with the layer sequence (S) - (B) y - [(A) - (2) is obtained by mutual, single-sided or multilateral coating of the substrate (S).
  • These products are also the subject of this invention. Very effective IR reflection properties will be found on these products according to the invention.
  • the subject matter of the present application is therefore also a process for producing a coated product containing at least once the above-described steps i. - iv. for applying a layer (A) and additionally containing the step at least once
  • polycarbonate substrates are coated with an alternating sequence of T1O 2 -HRI / silica LRI multilayers.
  • planar waveguides can be used in addition to optical data memories.
  • a waveguide is an inhomogeneous medium that, by virtue of its physical nature, bundles a wave in such a way that it is guided therein. The functional principle is explained in more detail, for example, in AW Snyder and JD Love, Optical Waveguide Theory, Chapman and Hall, London (1983). Examples
  • the coating thickness determination is carried out by means of a white light interferometer (ETA SPB-T, ETA Optics GmbH).
  • the refractive index n and the imaginary part k of the complex refractive index (k value of the coating) were obtained from the transmission and reflection spectra.
  • approximately 100-300 nm thick films of the coating were spun onto quartz glass substrate from dilute solution.
  • the direct transmission and reflection of this layer package were measured excluding the transmitted and reflected scattered light with a spectrometer from STEAG ETA Optics, CD-Measurement System ETA-RT and then the layer thickness and the spectral course of n and k to the measured transmission and reflection spectra adjusted. This is done with the internal software of the spectrometer and additionally requires the n and k data of the quartz glass substrate, which were determined beforehand in a blind measurement.
  • K is related to the decay constant of the light intensity ⁇ as follows: ⁇ - a ⁇ is the wavelength of the light.
  • the direct transmission and reflection is determined, excluding the transmitted and reflected scattered light.
  • the decay constant ⁇ or k also contains the components which, by scattering, lead to the attenuation of the light intensity and not only the portions of the pure molecular absorption.
  • the sum of absorption and scattering can also be determined via the measuring arrangement, which is dominated by the scattering (scattering) in the spectral range (400-800 nm) visible in the nanoparticle-containing systems in question if the primary nanoparticles are too large or Nanoparticles agglomerate to larger particles, even if there is no molecular absorption in this spectral range.
  • n and the imaginary part k were determined as a function of the wavelength, with a high wavelength dependence expected for high refractive indices (n: 1.88 to 1.93 in the range 380 to 420 nm, n: approx. 1.84 to 1.85 in the range 550 nm and n: about 1, 820 to 1, 825 in the range greater than 800 nm - the scatter of the measured values results from multiple determinations).
  • the surface roughness was determined by atomic force microscopy (AFM) according to standard ASTM E-42.14 STM / AFM, where R a values in the range of 15-18 nm were determined.
  • Scratch resistance To determine the scratch resistance, a diamond needle with a tip radius of 50 ⁇ m was guided onto the coating at a feed rate of 1.5 cm / s and a coating weight of 40 g, and the resulting scratch depth was measured. The measured values were in the range of about 0.58 to 0.65.
  • the nanoparticle suspension was concentrated on a rotary evaporator at 15-25 mbar at a temperature of 35-40 ° C, with isopropanol (bp. 82 ° C) was distilled off.
  • the decreasing volume was replaced by diacetone alcohol (DAA, 4-hydroxy-4-methyl-2-pentanone, acros, bp .: 166 ° C).
  • DAA diacetone alcohol
  • a UV-curable formulation with a high content of silica nanoparticles was prepared. Such formulations are content of application WO-A 2009/010193.
  • DPHA dipentaerythritol penta / hexaacrylate, Aldrich, 407283
  • PETA pentaerythritol triacrylate
  • Irgacure 184 ((1-hydroxycyclohexylbenzophenone, CIBA),
  • Darocure TPO diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide
  • the nanoparticle-containing suspension was homogenized by stirring. Before use, the nanoparticle-containing suspension was homogenized with an ultrasound finger and filtered through a 0.45 ⁇ filter.
  • the nanoparticle suspensions described in the above examples were each applied to a 2.5 ⁇ 2.5 cm glass substrate (quartz glass slide) at a rotation speed of 10000 min -1 (revolutions per minute) ) and then crosslinked with UV light (Hg lamp, about 3 J / cm 2 ).
  • Example 4 Optical Properties and Layer Thickness of the T1O 2 - HRI Coating from Example 2
  • Example 2 To determine the scratch resistance of the coating on plastic substrates and to determine the sum of absorption and scattering of the inventive coating of Example 2 in a coating layer thickness of about 1 ⁇ (accuracy +/- 10%) were the formulations described in Example 2 and 3 at the following spin-coat conditions on CD substrates from Makroion® OD2015 (linear bisphenol A polycarbonate with a melt volume flow rate of 16.5 cm 3/10 min at 250 ° C and a load of 2.16 kg, measured according to ISO 1133 and a Vicat softening temperature of 145 ° C at a load of 50 N and a heating rate of 50 ° C per hour according to ISO 306) coated:
  • Makroion® OD2015 linear bisphenol A polycarbonate with a melt volume flow rate of 16.5 cm 3/10 min at 250 ° C and a load of 2.16 kg, measured according to ISO 1133 and a Vicat softening temperature of 145 ° C at a load of 50 N and a heating rate of 50 ° C per hour according to ISO
  • the coating was cross-linked with a Hg lamp at 5.5 J / cm 2 .
  • Example 2 The formulation described in Example 2 was applied via a metering syringe to the CD substrate (Makroion OD 2015) using a fully automatic spin coater from the company Steag Hamatech, equipped with a pressure-operated metering device EFD 2000 XL.
  • the spin conditions (centrifugation of the excess lacquer) were selected so that a layer thickness of about 125 nm resulted.
  • the rotational speed of the substrate for 2.1 s at 240 min "1 (revolutions per minute), for 3 s to 1000 min " 1 (revolutions per minute) and then for 17 s to 7200 min "1 (revolutions per minute)
  • the mixture was then crosslinked with a Hg lamp at 5.5 J / cm 2 UV.
  • the S1O 2 -LRI formulation described in Example 3 was coated analogously to a) and UV crosslinked, although the coating conditions were aligned to layer thicknesses of about 190 nm. In detail, the following conditions were observed for centrifuging: 1.2 sec at 240 min -1 (revolutions per minute), 1.5 sec at 1000 min -1 (revolutions per minute) and 13 sec at 7000 min -1 (revolutions per minute) ).

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  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne des produits revêtus contenant un substrat (S) doté d'un revêtement se composant d'une couche individuelle, à réfraction élevée et résistante aux rayures (A) ou doté d'une structure multicouches, dans laquelle alternent des couches (A) avec des couches à faible réfraction (B), les couches (A) étant caractérisées par le fait qu'elles contiennent des nanoparticules de TiO2 réparties particulièrement finement.
EP10763197A 2009-10-16 2010-10-11 Revêtements à base de tio2 à réfraction élevée et résistants aux rayures dans des monocouches ou multicouches Withdrawn EP2488590A1 (fr)

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PCT/EP2010/065204 WO2011045275A1 (fr) 2009-10-16 2010-10-11 Revêtements à base de tio2 à réfraction élevée et résistants aux rayures dans des monocouches ou multicouches

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DE102011088154A1 (de) * 2011-12-09 2013-06-13 CFC Europe GmbH Schichtförmiges Produkt, insbesondere zur Verstärkung von optischen Effekten, und Verfahren zu seiner Herstellung
CN103730601A (zh) * 2013-12-26 2014-04-16 京东方科技集团股份有限公司 分布布拉格反射镜结构及制备方法和有机发光二极管结构
US10319878B2 (en) * 2014-10-31 2019-06-11 eLux, Inc. Stratified quantum dot phosphor structure

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WO2011045275A1 (fr) 2011-04-21
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