EP1778598A2 - Abrieb- und kratzfeste beschichtungen mit niedriger brechzahl auf einem substrat - Google Patents

Abrieb- und kratzfeste beschichtungen mit niedriger brechzahl auf einem substrat

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Publication number
EP1778598A2
EP1778598A2 EP05752553A EP05752553A EP1778598A2 EP 1778598 A2 EP1778598 A2 EP 1778598A2 EP 05752553 A EP05752553 A EP 05752553A EP 05752553 A EP05752553 A EP 05752553A EP 1778598 A2 EP1778598 A2 EP 1778598A2
Authority
EP
European Patent Office
Prior art keywords
substrate
metal
coating
precursor
magnesium
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Withdrawn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
EP05752553A
Other languages
German (de)
English (en)
French (fr)
Inventor
Heike Arndt
Mohammad Jilavi
Martin Mennig
Peter William Oliveira
Helmut Schmidt
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.)
LEIBNIZ-INSTITUT fur NEUE MATERIALIEN GEMEINNUETZ
Original Assignee
Leibniz Institut fuer Neue Materialien Gemeinnuetzige 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 Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH filed Critical Leibniz Institut fuer Neue Materialien Gemeinnuetzige GmbH
Publication of EP1778598A2 publication Critical patent/EP1778598A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • 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
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/284—Halides
    • C03C2217/285—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/29—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes

Definitions

  • the invention relates to a substrate with an abrasion and scratch-resistant coating with a low refractive index, comprising magnesium fluoride and at least one metal or semimetal oxide, a process for its production and its use and the coating composition used for the process and its production.
  • magnesium fluoride MgF 2
  • MgF 2 magnesium fluoride
  • These materials are used both as components in multilayer systems and as single layers.
  • Magnesium fluoride is used in particular as the ⁇ / 4 anti-reflective single layer.
  • thin MgF 2 layers are produced using complex and expensive PVD and CVD processes or sputtering.
  • the disadvantage of this method is that the coating of large substrates becomes very tedious and expensive and curved substrates cannot be coated homogeneously. In addition, good abrasion resistance cannot be achieved.
  • the transmission of the coated glasses is only 94.05% (550 nm) compared to 91.61% (550 nm) for the uncoated glass.
  • the inadequate antireflection effect of these layers is a disadvantage.
  • JP-A-2026824 produces magnesium fluoride brine.
  • aqueous magnesium salt solutions are mixed with aqueous fluoride solutions and heated.
  • by-product salts have to be removed by means of ultrafiltration.
  • thin layers with a refractive index of n 1.16 (193 nm) on optical substrates lead to a transmission loss of less than 0.5%.
  • the layers are produced by applying an MgF 2 sol.
  • the MgF 2 sol is obtained by reacting magnesium acetate with hydrofluoric acid in methanol and then autoclaved.
  • magnesium is dissolved in an anhydrous solvent and converted to the fluoroalkoxide with fluorinated alcohols. After filtering the solution, the Mg alkoxides are hydrolysed.
  • this process has the advantage that non-toxic, harmless starting materials are assumed, starting materials such as anhydrous solvents and fluorinated alcohols are expensive.
  • this patent application does not contain any information about the optical or mechanical properties of layers which can be obtained by immersion application, for example on glass of the brine described above.
  • Magnesium fluoride layers are produced there by the thermal disproportionation of fluorine-containing magnesium compounds such as magnesium trifluoroacetate, magnesium t ⁇ ' fluoroacetylacetonate or magnesium hexafluoroacetylacetonate.
  • fluorine-containing magnesium compounds such as magnesium trifluoroacetate, magnesium t ⁇ ' fluoroacetylacetonate or magnesium hexafluoroacetylacetonate.
  • the compounds mentioned are dissolved in organic solvents such as butyl acetate or ethylene glycol monoethyl ether, applied to substrates (glass, quartz glass) by spinning, spraying or dipping and cured at at least 300 ° C. for at least 1 min.
  • the layers obtained in this way have a refractive index of 1.36 to 1.38 and are therefore in the range of the bulk material. Glass substrates coated in this way nevertheless show a residual reflection of 0.5%.
  • Magnesium fluoride layers are produced in a similar manner according to S. Fujihara et al., Journal of Sol-Gel-Science and Technology 19 (2000) 311-314.
  • One route includes the conversion of magnesium acetate with trifluoroacetic acid (TFA) and water in 2-propanol.
  • TFA trifluoroacetic acid
  • n 1.2
  • magnesium ethanolate (Mg (OEt) 2 ) is reacted with trifluoroacetic acid (TFA) in 2-propanol to magnesium trifluoroacetate
  • TFA trifluoroacetic acid
  • the brine produced in this way was applied by spinning onto quartz glass and cured at temperatures from 300 ° C. to 600 ° C. for 10 minutes.
  • the substrates coated in this way have a relatively low transmission of a maximum of approximately 96.6%. Information on the refractive index of these layers is missing.
  • sols of metal or semi-metal oxides for layers made of metal or semi-metal oxides such as ZrO 2 , Al 2 O 3, TiO 2 , Ta 2 O 5 or SiO 2 layers, give coatings with good optical quality can, but their refractive index is significantly higher (1.46 to 2.3) than that of MgF 2 layers.
  • the object of the invention was to provide a wet-chemical synthesis route for low-refractive optical layers using non-toxic or only slightly toxic starting materials, which are characterized by good optical quality and in particular a low refractive index.
  • these layers should have an abrasion resistance that goes beyond the state of the art.
  • the object was achieved by a coating composition comprising magnesium fluoride or a precursor thereof and at least one metal or semimetal oxide or a precursor thereof.
  • the coating composition according to the invention can easily be applied wet-chemically to a substrate and hardened or compacted by heat treatment.
  • the invention thus also provides a substrate with an abrasion and scratch resistant coating with a low refractive index, comprising magnesium fluoride and at least one metal or semimetal oxide.
  • the coating composition comprises magnesium fluoride or a precursor thereof and at least one metal or semimetal oxide or a precursor thereof.
  • the at least one metal or semimetal oxide or a precursor thereof is present in the coating composition as a sol, i.e. the coating composition is preferably a coating sol.
  • the magnesium fluoride or a precursor thereof can be in the form of a sol or as a solution.
  • the coating composition is preferably prepared by mixing a sol or a solution of magnesium fluoride or a precursor thereof and a sol of at least one metal or semimetal oxide or a precursor thereof.
  • the sol or solution of magnesium fluoride or a precursor thereof can be prepared in any manner known in the art, some of which have been listed above.
  • the sol or solution is preferably obtained from the reaction of a magnesium compound, preferably a hydrolyzable magnesium compound, with a fluorinated organic compound, the reaction usually being carried out in an organic solvent.
  • Hydrolyzable here also means the hydration ability of the Mg compound.
  • a preliminary stage here means, in particular, compounds of magnesium which can be converted into MgF 2 , in particular under the conditions for producing the substrate according to the invention, such as in the heat treatment.
  • magnesium compounds or complexes of fluorinated organic compounds can be converted into magnesium fluoride by a thermal disproportionation reaction. If necessary, disproportionation reactions or the conversion into MgF 2 take place already at room temperature, so that MgF 2 can already be contained in the sol or the solution.
  • the mixture of magnesium compound and fluorinated compound can also be heated, for example in order to promote the conversion into MgF 2 in the sol or the solution.
  • All compounds which can be reacted with a fluorinated organic compound, in particular hydrolyzable magnesium compounds, are suitable as the magnesium compound.
  • examples are magnesium alkoxides.
  • the alkoxy group of the magnesium alkoxide preferably has 1 to 12 carbon atoms, with magnesium methoxide, magnesium ethoxide, magnesium propoxide and magnesium butoxide being preferred.
  • the most preferred compound is magnesium ethanolate (Mg (OEt) 2 ).
  • the alkoxide can be linear or branched, for example n-propanolate or isopropanolate.
  • Any suitable solvent may be used as the solvent, e.g. one of those listed below for the manufacture of the metal or semimetal oxides.
  • Alcohols examples are ethanol, n-propanol, 2-propanol or butanol.
  • a preferred production route for the sol or the solution with magnesium fluoride or a precursor thereof can be described as follows.
  • a hydrolyzable magnesium compound preferably magnesium alcoholate, particularly preferably magnesium ethylate
  • an organic solvent preferably an alcohol, particularly preferably 2-propanol
  • ketones and carboxylic acid, in particular trifluoroacetic acid, containing CF 3 groups are preferably used. Any undissolved constituents that may be present are then filtered off.
  • All oxides of metals or semimetals can be used as metal or semimetal oxides.
  • Preferred metals or semimetals M for the metal or semimetal oxides are, for example, B, Al, Ga, In, Si, Ge, Sn, Pb, Y, Ti, Zr, V, Nb, Ta, Mo, W, Fe, Cu, Ag , Zn, Cd, Ce and La or mixed oxides thereof.
  • a type of oxide or a mixture of oxides can be used.
  • oxides which can optionally be hydrated are ZnO, CdO, SiO 2 , GeO 2 , TiO 2 , ZrO 2 , CeO 2 , SnO 2 , Al 2 O 3 (boehmite, AIO (OH), also as aluminum hydroxide), B 2 O 3l ln 2 O 3 , La 2 O 3 , Fe 2 O 3 , Fe 3 O, Cu 2 O, Ta 2 O 5 , Nb 2 O 5 , V 2 O 5 , M0O3 or WO 3 .
  • silicates, zirconates, aluminates, stannates of metals or semimetals, and mixed oxides such as indium tin oxide (ITO), antimony tin oxide (ATO), fluorine-doped tin oxide (FTO), luminous pigments with Y or Eu- containing compounds, spinels, ferrites or mixed oxides with a perovskite structure such as BaTi ⁇ 3 and PbTiO 3 can be used.
  • ITO indium tin oxide
  • ATO antimony tin oxide
  • FTO fluorine-doped tin oxide
  • luminous pigments with Y or Eu- containing compounds such as spinels, ferrites or mixed oxides with a perovskite structure such as BaTi ⁇ 3 and PbTiO 3
  • a perovskite structure such as BaTi ⁇ 3 and PbTiO 3
  • semimetal or metal oxides which are optionally hydrated (oxide hydrate), of Si, Ge, Al, B, Zn, Cd, Ti, Zr, Ce, Sn, In, La, Fe, Cu, Ta, Nb, V, Mo or W.
  • SiO 2 , Al 2 O 3 , Ta 2 Os, ZrO 2 and TiO 2 are particularly preferred.
  • the sol of at least one semimetal or metal oxide can be produced by dispersing produced particles, in particular nanoscale particles, in a solvent or in situ.
  • the particles can usually be made in various ways, e.g. through flame pyrolysis, plasma processes, colloid techniques, sol-gel processes, controlled germination and growth processes, MOCVD processes and emulsion processes. These methods are described in detail in the literature.
  • the sol of at least one semimetal or metal oxide is preferably produced by a sol-gel process.
  • hydrolyzable compounds are usually hydrolyzed with water, if appropriate with acidic or basic catalysis, and, if appropriate, at least partially condensed.
  • the Hydrolysis and / or condensation reactions lead to the formation of compounds or condensates with hydroxyl, oxo groups and / or oxo bridges, which serve as precursors.
  • the sol containing the oxides or precursors can be obtained by suitably setting the parameters, for example degree of condensation, solvent, temperature, water concentration, duration or pH.
  • the precursors of the oxides mean in particular the condensation products mentioned.
  • sol-gel process Further details of the sol-gel process are available, for example, from CJ Brinker, GW Scherer: "Sol-Gel Science - The Physics and Chemistry of Sol-Gel-Processi ⁇ g", Academic Press, Boston, San Diego, New York, Sydney (1990) described.
  • the hydrolysis and condensation can be carried out in a solvent, but they can also be carried out without a solvent, with the hydrolysis being able to form solvents or other liquid constituents.
  • Suitable solvents are both water and organic solvents or mixtures. These are the usual solvents used in the field of coating.
  • suitable organic solvents are alcohols, preferably lower aliphatic alcohols (Ci-Cs alcohols), such as methanol, ethanol, 1-propanol, isopropanol and 1-butanol, ketones, preferably lower dialkyl ketones, such as acetone and methyl isobutyl ketone, ethers, preferably lower Dialkyl ethers, such as diethyl ether, or diol monoethers, amides, such as dimethylformamide, tetrahydrofuran, dioxane, sulfoxides, sulfones or butyl glycol and mixtures thereof. Alcohols are preferably used. High-boiling solvents can also be used. In the sol-gel process, the solvent can optionally be an alcohol formed from the alcoholate compounds during the hydrolysis.
  • hydrolyzable metal or semimetal compounds for example the metals and semimetals M listed above, are suitable as hydrolyzable compounds.
  • One or more hydrolyzable compounds can be used.
  • the hydrolyzable metal or semimetal compound is preferably a compound of the general formula MX n (1), in which M is the metal or semimetal defined above, X is a hydrolyzable group which can be identical or different, two groups X being by a bidentate hydrolyzable group or an oxo group can be replaced or three groups X can be replaced by a tridentate hydrolyzable group, and n corresponds to the valence of the element when X has a charge of 1 and is often 3 or 4.
  • the hydrolyzable compound can also have non-hydrolyzable groups which partially replace the hydrolyzable groups.
  • hydrolyzable groups X which can be identical or different, are hydrogen, halogen (F, Cl, Br or I, in particular Cl or Br), alkoxy (for example C 1-6 alkoxy, for example methoxy, ethoxy, n-propoxy, i-propoxy and n-, i-, sec.- or tert-butoxy), aryloxy (preferably C ⁇ -io-aryloxy, such as phenoxy), alkaryloxy, e.g. benzoyloxy, acyloxy (e.g.
  • C ⁇ -6 - Acyloxy preferably -C -4 -acyloxy, such as acetoxy or propionyloxy
  • amino and alkylcarbonyl eg C 2-7 alkylcarbonyl such as acetyl
  • complexing agents such as ß-dicarbonyls (eg acetyl acetonato).
  • the groups mentioned can optionally contain substituents, such as halogen or alkoxy.
  • Preferred hydrolyzable radicals X are halogen, alkoxy groups and acyloxy groups, with alcoholates being particularly preferred.
  • the compounds can also be stabilized with additional complexing compounds.
  • titanium compounds of the formula 1X 4 are TiCl 4 , Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (pentoxy) 4 , Ti (hexoxy), Ti (2-ethylhexoxy), Ti (n-OC 3 H 7 ) or Ti (i-OC 3 H 7 ) 4 .
  • ⁇ -diketone and (meth) acrylic residues are examples of usable hydrolyzable compounds of elements M.
  • usable hydrolyzable compounds of elements M are AI (OCH 3 ) 3 , AI (OC 2 H 5 ) 3 , AI (OnC 3 H 7 ) 3 , AI (OiC 3 H 7 ) 3 , AI (OnC 4 H 9 ) 3 , AI (O-sec.-C 4 H 9 ) 3 , AICI 3 , AICI (OH) 2 , AI (OC 2 H 4 OC 4 H 9 ) 3 , ZrCI 4 , Zr (OC 2 H 5 ) 4 , Zr (OnC 3 H 7 ) 4 , Zr (0-iC 3 H 7 ) 4 , Zr (OC Hg), ZrOCI, Zr (pentoxy) 4 , Zr (hexoxy) 4 , Zr (2-ethylhexoxy) 4 , and Zr compounds that have complexing residues, such as, for example,
  • silanes of the formula SiX 4 are Si (OCH 3 ), Si (OC 2 H 5 ) 4, Si (0-n- or -iC 3 H 7 ) 4 , Si (OC 4 H 9 ) 4 , SiCl 4 , HSiCI 3 , Si (OOCCH 3 ) 4 .
  • Si (OCH 3 ) 4 is preferred tetraalkoxysilanes, with those having CC alkoxy being particularly preferred, in particular tetramethoxysilane and tetraethoxysilane (TEOS).
  • the semimetal or metal oxides can also be prepared in the presence of a complexing agent.
  • suitable complexing agents are e.g. unsaturated carboxylic acids and ß-dicarbonyl compounds, e.g. (Meth) acrylic acid, acetylacetone and ethyl acetoacetate.
  • an adhesion promoter can be used, which usually interacts or is bound or complexed with the particle of semimetal or metal oxide or the precursor thereof and thereby surface-modifies the particle and thereby promotes adhesion to the substrate.
  • the adhesion promoter preferably has another functional group.
  • Complexing agents can also be suitable as adhesion promoters.
  • an adhesion promoter examples include unsaturated carboxylic acids such as (meth) acrylic acid and a hydrolyzable silane with at least one non-hydrolyzable group, the silane being particularly suitable for sols of SiO 2 .
  • hydrolyzable silanes with at least one non-hydrolyzable group as adhesion promoters are compounds of the formula RSiX 3 (II), in which X is as defined in formula (I).
  • the non-hydrolyzable radical R can be non-hydrolyzable radicals R without a functional group or preferably with a functional group.
  • Examples of the functional groups of the radical R are the epoxy, hydroxy, ether, amino, monoalkylamino, dialkylamino, amide, carboxy, vinyl, acryloxy, Methacryloxy, cyano, halogen, aldehyde, alkylcarbonyl, and phosphoric acid groups. These functional groups are bonded to the silicon atom via alkylene, alkenylene or arylene bridge groups, which can be interrupted by oxygen or -NH groups.
  • the bridge groups mentioned are derived, for example, from the alkyl, alkenyl or aryl radicals mentioned above.
  • the radicals R having a functional group preferably contain 1 to 18, in particular 1 to 8, carbon atoms.
  • silanes of the formula (II) are hydrolyzable silanes with a glycidyloxy group, amino group or (meth) acryloxy groups, such as ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -glycidyloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri (m) ethoxysilane, 3- (meth ) acryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, trimethoxysilylpropyldiethylenetriamine.
  • a glycidyloxy group, amino group or (meth) acryloxy groups such as ⁇ -glycidyloxypropyltrimethoxysilane, ⁇ -glycidyloxypropyltriethoxysilane, 3- (meth
  • (Meth) acrylic stands for methacrylic or acrylic. Further specific examples of hydrolyzable silanes with non-hydrolyzable groups can e.g. can be found in EP-A-195493.
  • the surface modification of nanoscale particles is a known method, as described by the applicant e.g. in WO 93/21127 (DE 4212633) or WO 96/31572.
  • the semimetal or metal oxide sol is thus preferably synthesized from the corresponding hydrolyzable compound, preferably from the metal alkoxide, by hydrolysis, optionally in the presence of a catalyst and / or complexing agent.
  • ZrO 2 sols are preferably used, the z. B. from zirconium tetra- ⁇ -propylate can be prepared by reaction with hydrochloric acid in the presence of acetylacetone.
  • the sol from the at least one metal or semimetal oxide or its precursors are then mixed with the solution or the sol of magnesium fluoride or its precursors.
  • the ratio can vary widely. In general, however, the amounts are chosen such that the molar ratio of the amount of magnesium (Mg) in magnesium fluoride or its precursors to metal or semimetal (M) in the at least one metal or semimetal oxide or its precursors Mg / M in the coating composition in the range of 1: 0.01 to 1: 1.8, more preferably in the range from 1: 0.05 to 1: 0.5 or 1: 0.1 to 1: 0.5 and particularly preferably from 1: 0.1 to 1 : 0.2 lies.
  • the coating composition preferably comprises essentially no further components. However, it is conceivable to add other additives.
  • magnesium fluoride or its precursors and the at least one metal or semimetal oxide or its precursors preferably make up at least 80% by weight, more preferably at least 90% by weight and particularly preferably at least 95% by weight of the solids content of the coating composition.
  • the proportion of magnesium fluoride or its precursors is preferably at least 10% by weight, more preferably at least 20% by weight and particularly preferably at least 30% by weight, based on the solids content of the coating composition.
  • the coating composition is applied to a substrate.
  • substrates come into consideration.
  • a suitable substrate are substrates made of metal, semiconductor, glass, ceramic, glass ceramic, plastic, crystalline substrates or inorganic-organic composite materials.
  • substrates are used which are stable to a thermal treatment of the coating.
  • the substrates can be pretreated, e.g. for cleaning, through a corona treatment or with a pre-coating (e.g. a paint or a metallized surface).
  • the layers obtained are used in particular for optical coatings or optical or optoelectronic applications.
  • Preferred substrates are in particular those which are translucent at least in a certain region or in certain regions of the light spectrum from UV light to visible light to infrared light.
  • Transparent substrates with translucency in the range of visible light are particularly useful.
  • plastic substrates are polycarbonate, polymethyl methacrylate, polyacrylate, polyethylene terephthalate.
  • Transparent plastics, glasses e.g. silicate glasses, such as window glass or optical glasses, silica glass, quartz glass, borosilicate glass or soda lime silicate glass, chalcogenide and halide glasses etc.
  • crystalline substrates e.g. sapphire, silicon or lithium niobate
  • Suitable substrates for optical applications are e.g. Flat glasses, watch glasses, instrument covers, lenses and other optical elements, plastic films or transparent containers.
  • All common wet chemical methods for producing optical layers such as, for. B. dipping, spinning, spraying, roll coating techniques or combinations of these, as well as common printing processes, eg. B. screen printing, flexographic printing or pad printing can be used.
  • Other coating processes are knife coating, casting, brushing, flood coating, slot coating, meniscus coating or curtain coating.
  • the coating is subjected to a thermal aftertreatment, for example above 50 ° C.
  • the temperature used can vary within wide ranges, preferably a heat treatment in the temperature range from 100 ° C. and 600 ° C., more preferably from 300 to 500 ° C., particularly preferably from 400 to 450 ° C.
  • the optical properties (eg reflection, refractive index) and the mechanical properties can be controlled by the choice of temperature. They depend on the optical properties of the substrate (refractive index), on the intended optical purpose (anti-reflective coating, interference layer package), on the thermal resistance of the substrate and on the desired application (outdoor application, indoor application).
  • the heat treatment can, for example, harden or densify and / or convert the precursors into MgF 2 or the oxide.
  • the ratio of Mg to metal or semimetal in the finished view corresponds at least approximately to the ratio in the coating composition.
  • the ratio can vary widely.
  • the material Quantity ratio of magnesium (Mg) in magnesium fluoride to metal or semimetal (M) in the at least one metal or semimetal oxide in the coating in the range from 1: 0.01 to 1: 1.8, more preferably in the range from 1: 0.05 to 1: 0.5 or 1: 0.1 to 1: 0.5 and particularly preferably from 1: 0.1 to 1: 0.2.
  • the layers preferably consist essentially of MgF 2 and the at least one semimetal or metal oxide. If necessary, the above-mentioned complexing agents or adhesion promoters or other additives can be contained in the finished coating in relatively small amounts. Organic components used, such as complexing agents or from the adhesion promoter, can optionally be volatile during the heat treatment or burned out. It is usually mostly or essentially inorganic layers.
  • Magnesium fluoride and the at least one metal or semimetal oxide preferably make up at least 80% by weight, more preferably at least 90% by weight and particularly preferably at least 95% by weight of the coating.
  • the proportion of magnesium fluoride in the coating is preferably at least 10% by weight, more preferably at least 20% by weight and particularly preferably at least 30% by weight.
  • the layer thickness can vary within wide ranges, but is usually in the range from 20 nm to 1 ⁇ m, preferably 30 to 500 nm and particularly preferably 50 to 250 nm.
  • the coating according to the invention can be used as a single layer or as a layer from a multi-layer package.
  • the other layers can be the same, possibly with different ratios, or different, usually also optical layers. Accordingly, further layers can be applied to the substrate in a conventional manner before and / or after the coating.
  • the coating is used as an optical coating.
  • the coating is particularly suitable for anti-reflective coatings, in particular as a single layer, and for interference layer packages. These antireflective and interference boundary layers are preferably used on transparent substrates or substrates which are translucent in at least one region of the wavelength range from UV light to IR light.
  • MgF 2 sol The solution or sol with MgF 2 or its precursors is simply called MgF 2 sol, even if it is a solution of MgF 2 precursors.
  • MgF 2 sol At room temperature, 25.396 g (0.22 mol) of magnesium ethylate are added to 522.810 g of 2-propanol. 51.016 g (0.35 mol) of trifluoroacetic acid (TFA) are added to the stirred dispersion and the mixture is stirred at room temperature. A slight warming of the reaction mixture is observed at the start of the reaction. As the reaction progresses, the reaction mixture becomes increasingly clear. After 2 hours, any insoluble constituents present are separated off using a syringe filter (1.2 ⁇ m) and the reaction mixture is then left to stand at room temperature. A colorless precipitate forms overnight, which is separated off using a pleated filter. The filtrate is filtered again through a 1.2 ⁇ m syringe filter and a yellow solution results. The coating composition is stable in storage at room temperature for at least 4 weeks.
  • TFA trifluoroacetic acid
  • SiO 2 sol At room temperature, 13.29 g (87.3 mmol) of tetramethoxysilane (TMOS) are dissolved in 11.80 g of ethanol. A mixture of 13.40 g (744.4 mmol) of water, 0.30 g of hydrochloric acid (37%) and 11.80 g of ethanol is added with stirring. The mixture is stirred at room temperature for at least 2 h (brief heating of the reaction mixture after addition) and diluted with 130 g of 2-propanol.
  • TMOS tetramethoxysilane
  • Al 2 O 3 sol 40 g (0.16 mol) of aluminum tri-sec-butoxide are dissolved in 240 g of 2-propanol at room temperature with stirring. 8 g (0.08 mol) of acetyl acetone and 3.2 g (0.18 mol) of water are added with stirring. The mixture is stirred at room temperature for 1 h and filtered through a 0.45 ⁇ m syringe filter. The result is a yellow, clear sol.
  • Zr0 2 sol 24 g (51.3 mmol) of zirconium tetra-n-propylate (70% by weight in 1-propanol) are dissolved in 240 g of 2-propanol at room temperature. 2.553 g (25.5 mmol) of acetylacetone are added with stirring and the mixture is stirred for 10 min. Then 1.8 g of concentrated salsic acid are added and the mixture is stirred at room temperature for 1 h. Filtration through a 5 ⁇ m syringe filter results in a yellow, clear sol.
  • MgF 2 composite sols are produced.
  • Lime sodium silicate glass panes are cleaned by rubbing them with ethanol and coated with the respective sol using the immersion process (3.5 mm / s). The coating is cured at 450 ° C. for 30 minutes.
  • the scratch resistance is tested with a steel wool test (steel wool 0000, 250 g / 1 cm 2 , 10 cycles).
  • the damage (number of scratches generated) is assessed using light microscopy.
  • the reflectivity is determined spectroscopically.
  • a significant improvement in scratch resistance is achieved with a mixing ratio of MgF 2 sol / SiO 2 sol of 50/60.
  • the transmission is higher than in the case of the uncoated glass and also higher than in the case of a pure SiO 2 layer.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
EP05752553A 2004-06-08 2005-06-07 Abrieb- und kratzfeste beschichtungen mit niedriger brechzahl auf einem substrat Withdrawn EP1778598A2 (de)

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JP2008501557A (ja) 2008-01-24
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US20140017399A1 (en) 2014-01-16
US20080261053A1 (en) 2008-10-23
WO2005120154A3 (de) 2006-03-16

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