EP1633805A1 - Procede de realisation de systemes de couches antirayures sans formation de buee - Google Patents

Procede de realisation de systemes de couches antirayures sans formation de buee

Info

Publication number
EP1633805A1
EP1633805A1 EP04734514A EP04734514A EP1633805A1 EP 1633805 A1 EP1633805 A1 EP 1633805A1 EP 04734514 A EP04734514 A EP 04734514A EP 04734514 A EP04734514 A EP 04734514A EP 1633805 A1 EP1633805 A1 EP 1633805A1
Authority
EP
European Patent Office
Prior art keywords
scratch
layer
fog
coating agent
resistant
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Withdrawn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
EP04734514A
Other languages
German (de)
English (en)
Inventor
Peter Bier
Peter Capellen
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1633805A1 publication Critical patent/EP1633805A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/08—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by flames
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • C08J7/054—Forming anti-misting or drip-proofing coatings
    • 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
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1233—Organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1245—Inorganic substrates other than metallic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a method for producing layer systems containing a substrate (S), one or more scratch-resistant layers (K) and a fog-free top layer (D), and to layer systems produced by the method and their use.
  • inorganic-organic hybrid materials by targeted hydrolysis and condensation of alkoxides, mainly silicon, aluminum, titanium and zircon.
  • This process creates an inorganic network.
  • additional organic groups can be incorporated, which can be used on the one hand for functionalization and on the other hand for the formation of defined organic polymer systems.
  • this material system offers a very wide range of variation. This means that coating systems in particular can be maintained and tailored to a wide variety of requirement profiles.
  • Such coating systems are preferably used to make plastics and glass scratch-resistant. Coating agents of this type are described in more detail in the chapter “Production of the scratch-resistant layers”.
  • DE 199 52 040 A1 discloses substrates with a particularly abrasion-resistant diffusion barrier layer system, the diffusion barrier layer system comprising a hard base layer based on hydrolyzable epoxysilanes and a cover layer arranged above it.
  • the top layer is obtained by applying and curing a coating sol based on tetraethoxysilane.
  • Activation takes place in a dry chemical or physical overcoating with a silane in a high vacuum according to the CVD (Chemical Vapor Deposition). This forms a highly scratch-resistant layer of silicon oxide on the substrate.
  • CVD Chemical Vapor Deposition
  • top cover layers consist essentially of silicon oxide, they are not fogging-free.
  • the parts equipped with it are fog-free, but their scratch resistance and the durability of the anti-fog properties under extreme conditions such as boiling steam water or aggressive chemicals are limited.
  • the present invention is therefore based on the object of providing a method for producing a fog-free scratch-resistant layer system comprising a substrate (S), one or more scratch-resistant layers (K) and a fog-free top layer (D), which has optimum adhesion properties between the scratch-resistant layer (K ) and cover layer (D) and is also suitable for the uniform coating of three-dimensional substrates (S).
  • the method is also intended to decouple the production of the scratch-resistant layer (K) and the top layer (D) and to ensure that a scratch-resistant layer (K) which has been produced once is coated with the top layer (D) without any problems and even after a storage period of a few weeks or months can be.
  • this object is achieved by a method for producing a layer system comprising a substrate (S), one or more scratch-resistant layers (K) and a fog-free top layer (D)
  • the fog-free cover layer (D) which essentially consists of an oxidic compound of silicon, aluminum, titanium, indium, zirconium, tin and / or cerium, by adding silicon, aluminum, titanium, zirconium, tin and / or cerium compounds in the fuel gas-air mixture.
  • the layer systems can also be temporarily stored and then surface-treated at any time initially in accordance with step (b) and overcoated with the top layer (D).
  • the manufacturing method according to the invention can be carried out simply and inexpensively.
  • the surface treatment of the upper scratch-resistant layer (K) with simultaneous production of the fog-free cover layer (D) in step (b) by flame treatment with the addition of silicon, aluminum, titanium, zirconium, tin and / or cerium compounds in the fuel gas / air mixture.
  • the metering of the additives for producing the fog-free top layer (D) works according to the principle of metered admixture of an organic precursor or an aerosol into the air stream.
  • the dosing is carried out by process-controlled evaporation or by spray mist.
  • Suitable devices include the burner SMB22 in combination with the control units of the FTS series from Arcogas GmbH Rötweg 24 in Mönsheim, Germany. Easily evaporable organometallic compounds, in particular alcoholates or acetates of the above metals, are suitable as organic precursors. Silicon tetraalkoxides have proven to be particularly favorable.
  • Aqueous dispersions of metal oxide nanoparticles which are injected into the air stream and deposited, are particularly suitable for the production of aerosols.
  • No. 5,008,148 describes the coating of polycarbonate or polyphenylene sulfide articles with metal oxide layers using a low-pressure plasma process for UV protection.
  • the articles manufactured according to US 5,008,148 are not fogging-free.
  • an open flame preferably its oxidizing part, acts on the surface of the molded plastic body.
  • An exposure time of approx. 0.2 s is usually sufficient. depending on the shape and mass of the molded part to be activated.
  • the air-gas mixture supplied also has a strong influence on the characteristics of the flame, for example a flame operated with a "rich” mixture (high gas content) is just as unstable as a flame operated with a “lean” mixture (low gas content).
  • the burner setting and the burner spacing are crucial for effective flame treatment.
  • the burner output influences the entire flame characteristic (temperature, ion distribution, size of the active zone).
  • the flame length changes, which in turn results in the distance from the burner to the product.
  • the burner output is directly proportional to the amount of gas currently flowing (liters per minute). Too little power leads to poor treatment, i.e. the surface energy is not increased sufficiently. With higher power, the ion concentration increases and the treatment is intensified. Too high an output leads to a high material temperature and thus to the melting of the surface. This can be seen from the fact that the surface is shiny or matt after flame treatment.
  • the working speed and thus the possible contact time is usually specified by the user, which results in the requirement for the burner output.
  • the working speed and the burner output should always be optimally coordinated with one another in tests.
  • the flame treatment is carried out in a continuous flame treatment system at a continuous speed of 1 to 20 m / min, in particular 2 to 10 m / min.
  • the surface treatment increases the adhesion energy of the scratch-resistant layer (K), resulting in very good adhesion of the fog-free top layer (D).
  • the fog-free cover layer (D) preferably has a water contact angle below 40 degrees below 20 degrees and the polar portion of the surface tension of the cover layer (D) is above 20%, preferably above 30%.
  • the scratch-resistant layer (K) is produced in step (a) by applying a coating agent to a substrate (S), the coating agent comprising a polycondensate based on at least one silane, which is produced by the sol-gel method, and at least partially curing thereof.
  • a coating agent comprising a polycondensate based on at least one silane, which is produced by the sol-gel method, and at least partially curing thereof.
  • the choice of substrate materials (S) for coating is not restricted.
  • the coating compositions are preferably suitable for coating wood, textiles, paper, stone goods, metals, glass, ceramics and plastics, and in particular are particularly suitable for coating thermoplastics, as described in Becker / Braun, Plastic Pocket Book, Carl Hanser Verlag, Kunststoff, Vienna 1992 ,
  • the coating compositions are particularly suitable for coating transparent thermoplastics and preferably polycarbonates.
  • Spectacle lenses, optical lenses, automobile lenses and plates in particular can be coated with the compositions obtained according to the invention.
  • the scratch-resistant layer (K) is preferably formed in a thickness of 0.5 to 30 ⁇ m.
  • a primer layer (P) can also be formed between the substrate (S) and the scratch-resistant layer (K).
  • any silane-based polycondensates produced by the sol-gel process can be used as the coating agent for the scratch-resistant layer (K).
  • Particularly suitable coating agents for the scratch-resistant layer (K) are in particular
  • Known polycondensates based on methylsilane can be used as coating agents for the scratch-resistant layer (K).
  • Polycondensates based on methyltrialkoxysilanes are preferably used.
  • the substrate (S) can be coated, for example, by applying a mixture of at least one methyltrialkoxysilane, a water-containing organic solvent and an acid, evaporating the solvent and curing the silane to form a highly crosslinked polysiloxane under the influence of heat.
  • the solution of the methyltrialkoxysilane preferably consists of 60 to 80% by weight of the silane.
  • Methyltrialkoxysilanes which hydrolyze rapidly are particularly suitable, which is particularly the case when the alkoxy group contains no more than four carbon atoms.
  • Strong inorganic acids such as sulfuric acid and perchloric acid are particularly suitable as catalysts for the condensation reaction of the silanol groups formed by hydrolysis of the alkoxy groups of methyltrialkoxysilane.
  • the concentration of the acidic catalyst is preferably about 0.15% by weight, based on the silane.
  • Alcohols such as methanol, ethanol and isopropanol or ether alcohols such as ethyl glycol are particularly suitable as inorganic solvents for the system consisting of methyltrialkoxysilane, water and acid.
  • the mixture preferably contains 0.5 to 1 mole of water per mole of silane.
  • Polycondensates based on methylsilane and silica sol can also be used as the coating agent for the scratch-resistant layer (K).
  • Particularly suitable coating compositions of this type are polycondensates prepared by the sol-gel process, consisting essentially of 10 to 70% by weight of silica sol and 30 to 90% by weight of a partially condensed organoalkoxysilane in an aqueous / organic solvent mixture.
  • Particularly suitable coating compositions are the thermosetting, primer-free silicone hard coating compositions described in US Pat. No.
  • an acrylated polyurethane adhesion promoter with an M n of 400 to 1,500 and selected from an acrylated polyurethane and a methacrylated polyurethane and
  • Organoalkoxysilanes which can be used in the preparation of the dispersion of the thermosetting, hardness-free silicone hard coating compositions in aqueous / organic solvent preferably fall under the formula
  • R is a monovalent C ⁇ . 6 -hydrocarbon radical, in particular a C ⁇ -4 -ATkylrest
  • R 1 is an R or a hydrogen radical and a is an integer from 0 to 2 inclusive.
  • the organoalkoxysilane of the aforementioned formula is preferably methyltrimethoxysilane, methyltrihydroxysilane or a mixture thereof which can form a partial condensate.
  • Polycondensates based on methylsilanes and silica sol with a solids content of 10 to 50% by weight dispersed in a water / alcohol mixture can also be used as the coating agent for the scratch-resistant layer (K).
  • the solids dispersed in the mixture comprise silica sol, in particular in an amount of 10 to 70% by weight, and a partial condensate derived from organotrialkoxysilanes, preferably in an amount of 30 to 90% by weight, the partial condensate preferably having the formula R ' Si (OR) 3 , wherein R 'is selected from the Grappe, consisting of alkyl radicals having 1 to 3 carbon atoms and Aryl residues with 6 to 13 carbon atoms, and R is selected from the group consisting of alkyl residues with 1 to 8 carbon atoms and aryl residues with 6 to 20 carbon atoms.
  • the coating composition preferably has an alkaline pH, in particular a pH of 7.1 to about 7.8, which is achieved by a base which is volatile at the curing temperature of the coating composition.
  • alkaline pH in particular a pH of 7.1 to about 7.8, which is achieved by a base which is volatile at the curing temperature of the coating composition.
  • Suitable primer compositions are, for example, polyacrylate primers.
  • Suitable polyacrylate primers are those based on polyacrylic acid, polyacrylic esters and copolymers of monomers with the general formula
  • the polyacrylate resin can be thermoplastic or thermosetting and is preferably dissolved in a solvent.
  • a solution of polymethyltriethacrylate (PMMA) in a solvent mixture of a rapidly evaporating solvent such as propylene glycol methyl ether and a slower evaporating solvent such as diacetone alcohol can be used as the acrylate resin solution.
  • Particularly suitable acrylate primer solutions are thermoplastic primer compositions containing
  • thermoplastic primer compositions are known to the person skilled in the art and are described, for example, in US 5 041 313, the content of which is expressly incorporated by reference.
  • the primer layer is arranged between the substrate (S) and the scratch-resistant layer (K) and serves to promote adhesion between the two layers.
  • silyl acrylate can also be used as the coating agent for the scratch-resistant layer (K).
  • these coating compositions preferably contain colloidal silica (silica sol).
  • Particularly suitable silyl acrylates are acryloxy-functional silanes of the general formula
  • R 3 and R 4 are identical or different monovalent hydrocarbon radicals
  • R 5 is a divalent hydrocarbon radical with 2 to 8 carbon atoms
  • R 6 is hydrogen or a monovalent hydrocarbon radical
  • the index b is an integer with a value from 1 to 3
  • the index c is an integer with a value of 0 to 2
  • the index d is an integer with a value of (4-bc), or
  • R 7 and R 8 are the same or different monovalent hydrocarbon radicals
  • R 9 is a divalent hydrocarbon radical with 2 to 8 coblene atoms
  • the index e is an integer with a value from 1 to 3
  • the index f is an integer with a value of 0 to 2
  • the index g is an integer with a value of (4-ef), and mixtures thereof.
  • Particularly suitable acryloxy-functional silanes are, for example, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethonxysilane, 2-methacryloxyethytrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxy-silane, 3-acryloxypropyltriethoxysiloxysilane-methoxy-siloxysilane-3-methoxy-siloxysilane-3-methoxysiloxysilane.
  • Particularly suitable glycidoxy-functional silanes are, for example, 3-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 2-glycidoxyethyltriethoxysilane. These compounds are also described in DE 31 26 662 AI. As a further constituent, these coating compositions can contain further acrylate compounds, in particular hydroxyacrylates.
  • acrylate compounds that can be used are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy-3-methacryloxypropyl acrylate, 2-hydroxy-3-acryloxypropyl acrylate, 2-hydroxy-3-methacryloxypropyl methacrylate, diethyl acrylate , Triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, tetrahydrofurfuryl methacrylate and 1,6-hexanediol diacrylate.
  • Particularly preferred coating compositions of this type are those which contain 100 parts by weight of colloidal silica, 5 to 500 parts by weight of silyl acrylate and 10 to 500 parts by weight of further acrylate.
  • such coating compositions can be cured after application to a substrate (S) by UV radiation to form a scratch-resistant layer (K), as described in DE 31 26 662 A1.
  • the coating compositions can also contain conventional additives.
  • Particularly suitable are the radiation-curable scratch-resistant coatings described in US Pat. No. 5,990,188, which, in addition to the aforementioned components, also contain a UV absorber such as triazine or dibenzylresorcinol derivatives.
  • Polycondensates based on silyl acrylates which contain nanoscale A10 (OH) particles, in particular nanoscale boehmite particles, as a further constituent can also be used as coating agents.
  • Coating agents of this type are described, for example, in the printed publications WO 98/51747 AI, WO 00/14149 AI, DE-A 197 46 885, US 5 716 697 and WO 98/04604 AI, the content of which is expressly incorporated by reference here.
  • these coating compositions can be hardened after application to a substrate (S) by UV rays, with the formation of a scratch-resistant layer (K).
  • S substrate
  • K scratch-resistant layer
  • Polycondensates based on multifunctional cyclic organosiloxanes can also be used as coating agents for the scratch-resistant layer (K).
  • Such multifunctional, cyclic organosiloxanes include, in particular, those of the following formula
  • n and R within the molecule can be the same or different, preferably the same, and the further radicals have the following meaning:
  • the production and properties of such multifunctional cyclic organosiloxanes and their use in scratch-resistant coating compositions are accordingly Generally known to a person skilled in the art and described, for example, in Drackschrift DE 196 03 241 Cl, the content of which is expressly incorporated by reference here.
  • compositions based on cyclic organosiloxanes are described, for example, in the publications WO 98/52992, DE 197 11 650, WO 98/25274 and WO 98/38251, the content of which is also expressly referred to here.
  • Preferred scratch-resistant layers (K) are those which are obtainable by curing a coating composition comprising a polycondensate based on at least one silane which has been prepared by the sol-gel process and which has an epoxide group on a non-hydrolyzable substituent and optionally a curing catalyst selected from Lewis Bases and alcoholates from titanium, zircon or aluminum.
  • a curing catalyst selected from Lewis Bases and alcoholates from titanium, zircon or aluminum.
  • Preferred coating compositions for scratch-resistant layers based on expoxylilanes and nanoparticles are those which
  • Such coating compositions result in highly scratch-resistant coatings that adhere particularly well to the material.
  • the compounds (A) to (D) are explained in more detail below.
  • the compounds (A) to (D) can be contained not only in the composition for the scratch-resistant layer (K), but also as an additional component (s) in the composition for the cover layer (D).
  • the silicon compound (A) is a silicon compound which has 2 or 3, preferably 3, hydrolyzable radicals and one or 2, preferably one, non-hydrolyzable radical. The only or at least one of the two non-hydrolyzable residues has an epoxy group.
  • hydrolyzable radicals examples include halogen (F, Cl, Br and I, in particular Cl and Br), alkoxy (in particular. -Alkoxy such as, for example, methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy, i -butoxy, sec-butoxy and tert-butoxy), aryloxy (especially C 6 - ⁇ o-aryloxy e.g. phenoxy), acyloxy (especially C ⁇ . -acyloxy such as acetoxy and propionyloxy) and alkylcarbonyl (e.g. acetyl) , Particularly preferred hydrolyzable residues are alkoxy groups, especially methoxy and ethoxy.
  • non-hydrolyzable radicals without an epoxy group are hydrogen, alkyl, in particular C 1-4 -alkyl (such as methyl, ethyl, propyl and butyl), alkenyl (in particular C 2 -alkenyl such as vinyl, 1-propenyl, 2-propenyl and butenyl), alkynyl (especially C 2 -. 4 alkynyl such as acetylenyl and propargyl), and aryl, in particular . ⁇ 0 aryl such.
  • the groups just mentioned optionally one or more substituents such.
  • B. may have halogen and alkoxy. Methacrylic and methacryloxypropyl residues can also be mentioned in this connection.
  • non-hydrolyzable radicals with an epoxy group are, in particular, those which have a glycidyl or glycidyloxy group.
  • silicon compounds (A) which can be used according to the invention can, for. B. pages 8 and 9 of EP-A-195493.
  • Silicon compounds (A) which are particularly preferred according to the invention are those of the general formula
  • radicals R are the same or different (preferably identical) and represent a hydrolyzable grappa (preferably C 1 -C alkoxy and special methoxy and ethoxy) and R 'represents a glycidyl or glycidyloxy (C 2 O 2) alkylene radical , especially ß-glycidyl oxyethyl-, ⁇ -glycidyloxypropyl, ⁇ -glycidyl-oxybutyl-, ⁇ -glycidyloxylpentyl-, ⁇ -glycidyl-oxyhexyl-, ⁇ -glycidyloxyoctyl-, ⁇ -glycidyl-oxynonyl-, ⁇ -glycidyloxydylidyl-, 2- (3,4-epoxycyclohexyl) ethyl.
  • GPTS ⁇ -glycidyloxypropyltrimethoxysilane
  • the particulate materials (B) are an oxide, hydrated oxide, nitride or carbide of Si, Al and B and of transition metals, preferably Ti, Zr and Ce, with a particle size in the range from 1 to 100, preferably 2 to 50 nm and particularly preferably 5 to 20 nm and mixtures thereof. These materials can be used in the form of a powder, but are preferably used in the form of a (in particular acid-stabilized) sol.
  • Preferred particulate materials are boehmite, Si0 2 , Ce0 2 , ZnO, rn 2 0 3 and Ti0 2 . Nanoscale boehmite particles are particularly preferred.
  • the particulate materials are commercially available in the form of powders and the production of (acid stabilized) sols therefrom is also known in the art.
  • the principle of stabilizing nanoscale titanium nitride using guanidine propionic acid is e.g. B. described in German patent application DE-A 43 34639.
  • the variation of the nanoscale particles is usually accompanied by a variation in the refractive index of the corresponding materials.
  • cerium dioxide can be used as the particulate material. This preferably has a particle size in the range from 1 to 100, preferably 2 to 50 nm and particularly preferably 5 to 20 nm.
  • This material can be used in the form of a powder, but is preferably used in the form of a (in particular acid-stabilized) sol.
  • Particulate cerium oxide is commercially available in the form of sols and powders, and the production of (acid-stabilized) sols therefrom is also known in the art.
  • Compound (B) is preferably used in the composition for the scratch-resistant layer (K) in an amount of 3 to 60% by weight, based on the solids content of the coating agent for the scratch-resistant layer (K).
  • silicon compounds (A) In addition to the silicon compounds (A), other hydrolyzable compounds of elements from the group consisting of Si, Ti, Zr, Al, B, Sn and V are also used to produce the scratch-resistant coating composition, and preferably with the silicon compound (s) (A) hydrolyzed.
  • the compound (C) is a compound of Si, Ti, Zr, B, Sn and V of the general formula
  • R represents a hydrolyzable radical
  • R ' represents a non-hydrolyzable radical represents and x in the case of tetravalent metal atoms M (case a)) 1 to 4 and in the case of trivalent metal atoms M (case b)) 1 to 3.
  • X is preferably greater than 1. That is, the compound (C) has at least one, preferably a plurality of hydrolyzable radicals.
  • hydrolyzable radicals examples include halogen (F, Cl, Br and 1, in particular and Br), alkoxy (in particular such as methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy, i-butoxy, sec-butoxy or tert-butoxy), aryloxy (in particular C 6 .0 0 -aryloxy, e.g. phenoxy), acyloxy (in particular ⁇ -acyloxy such as acetoxy and propionyloxy) and alkylcarbonyl (e.g. acetyl).
  • Particularly preferred hydrolyzable residues are alkoxy groups, especially methoxy and ethoxy.
  • non-hydrolyzable radicals are hydrogen, alkyl, in particular C 4 alkyl (such as methyl, ethyl, propyl and n-butyl, i-butyl, sec-butyl and tert-butyl),
  • Alkenyl in particular C 2 -alkenyl such as, for example, vinyl, 1-propenyl, 2-propenyl and butenyl
  • alkynyl in particular C 1 -C -alkynyl such as, for example, acetylenyl and propargyl
  • alkenyl in particular C 2 -alkenyl such as, for example, vinyl, 1-propenyl, 2-propenyl and butenyl
  • alkynyl in particular C 1 -C -alkynyl such as, for example, acetylenyl and propargyl
  • Aryl especially C 6 ⁇ o-aryl, such as phenyl and naphthyl), wherein the above-mentioned groups optionally have one or up more substituents such as halogen and alkoxy, can point.
  • substituents such as halogen and alkoxy
  • CH 2 CH-Si (OOCCH 3 ) 3 ,
  • CH 2 CH-SiCl 3
  • CH 2 CH-Si (OCH 3 ) 3
  • CH 2 CH-Si (OC 2 H 5 ) 3
  • CH 2 CH-Si (OC 2 H 4 OCH 3 ) 3
  • CH 2 CH-CH 2 -Si (OCH3) 3
  • CH 2 CH-CH 2 -Si (OOCCH 3 ) 3 ,
  • radicals R can be the same or different and stand for a hydrolyzable group, preferably for an alkoxy group with 1 to 4 carbon atoms, in particular for methoxy, ethoxy, n-propoxy, i-propoxy, n -Butoxy, i-butoxy, sec-butoxy or tert-butoxy.
  • these compounds (C) can also have non-hydrolyzable radicals which have a CC double or triple bond.
  • the composition can also contain (preferably epoxy or hydroxyl group-containing) monomers such as, for. B. meth (acrylates) are incorporated (self- Of course, these monomers can also have two or more functional groups of the same type, such as. B. poly (meth) acrylates of organic polyols; the use of organic polyepoxides is also possible).
  • the organic species is polymerized in addition to the structure of the organically modified inorganic matrix, as a result of which the crosslinking density and thus also the hardness of the corresponding coatings and moldings increase.
  • compound (C) is preferably used in an amount of 0.2 to 1.2 mol, based on 1 mol of silicon compound (A).
  • the hydrolyzable compound (D) is a compound of Ti, Zr or Al of the following general formula
  • hydrolyzable groups examples include halogen (F, Cl, Br and I, in particular Cl and Br), alkoxy (in particular C 6 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy , i-butoxy, sec-butoxy or tert-butoxy, n-pentyloxy, n-hexyloxy), aryloxy (especially C 6 -o-aryloxy e.g.
  • halogen F, Cl, Br and I, in particular Cl and Br
  • alkoxy in particular C 6 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy , i-butoxy, sec-butoxy or tert-butoxy, n-pentyloxy, n-hexyloxy
  • alkoxy in particular C 6 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy and n
  • alkoxy has the same meaning as mentioned above.
  • M is particularly preferred aluminum and R '"ethanolate, sec-butanolate, n-propanolate or n-butoxyethanolate.
  • compound (D) is preferably used in an amount of 0.23 to 0.68 mol, based on 1 mol of silicon compound (A).
  • a Lewis base (E) can optionally also be used as a catalyst.
  • a hydrolyzable silicon compound (F) with at least one non-hydrolyzable radical which has 5 to 30 directly on carbon atoms can optionally be used has bound fluorine atoms, these carbon atoms being separated from Si by at least 2 atoms.
  • fluorinated silane means that the corresponding coating is additionally given hydrophobic and dirt-repellent properties.
  • compositions for the scratch-resistant layer (K) can be produced by the process described in more detail below, in which a sol of the material (B) has a pH in the range from 2.0 to 6.5, preferably 2.5 to 4.0 , is reacted with a mixture of the other components.
  • sols are even more preferably produced by a process which is also defined below, in which the sol as defined above is added in two portions to the mixture of (A) and (C), with certain temperatures preferably being maintained, and the addition of (D. ) between the two portions of (B), also preferably at a certain temperature.
  • the hydrolyzable silicon compound (A) can optionally be prehydrolyzed together with the compound (C) using an acidic catalyst (preferably at room temperature) in aqueous solution, preferably using about 1/2 mole of water per mole of hydrolyzable group.
  • Hydrochloric acid is preferably used as the catalyst for the pre-hydrolysis.
  • the particulate materials (B) are preferably suspended in water and the pH is adjusted to 2.0 to 6.5, preferably to 2.5 to 4.0. Acidification is preferred
  • the compound (C) is mixed with the compound (A).
  • the first portion of the particulate material (B) suspended as described above is then added.
  • the amount is preferably selected so that the water contained therein is sufficient for the semi-stoichiometric hydrolysis of the compounds (A) and (C). It is 10 to 70% by weight of the total amount, preferably 20 to 50% by weight.
  • the reaction is slightly exothermic. After the first exothermic reaction has subsided, the temperature is adjusted to about 28 to 35 ° C., preferably about 30 to 32 ° C. by tempering, until the reaction starts and an internal temperature is reached which is higher than 25 ° C., preferably higher than 30 ° C and more preferably higher than 35 ° C. After the end of the addition of the first portion of the material (B), the temperature is maintained for 0.5 to 3 hours, preferably 1.5 to 2.5 Hours and then cools down to approx. 0 ° C. The remaining material (B) is preferably added slowly at a temperature of 0 ° C.
  • the compound (D) and, if appropriate, the Lewis base (E) are also preferably added slowly after the addition of the first portion of the material (B) at about 0 ° C.
  • the temperature is then kept at about 0 ° C. for 0.5 to 3 hours, preferably for 1.5 to 2.5 hours, before adding the second portion of the material (B).
  • the remaining material (B) is slowly added at a temperature of approx. 0 ° C.
  • the added dropwise solution is preferably pre-cooled to approximately 10 ° C. immediately before being added to the reactor.
  • the cooling is preferably removed so that the reaction mixture is warmed up to a temperature of more than 15 ° C. (to room temperature) slowly without additional temperature control.
  • inert solvents or solvent mixtures can optionally be added at any stage of the preparation. These solvents are preferably the solvents described for the top layer composition.
  • the scratch-resistant layer compositions can contain the usual additives described for the top layer composition.
  • the application and hardening of the scratch-resistant layer composition takes place after drying, preferably thermally at 50 to 200 ° C., preferably 70 to 180 ° C. and in particular 110 to 130 ° C. Under these conditions, the curing time should be less than 120, preferably less than 90, in particular less than 60 minutes.
  • the layer thickness of the hardened scratch-resistant layer (K) should be 0.5 to 30 ⁇ m, preferably 1 to 20 ⁇ m and in particular 2 to 10 ⁇ m.
  • a highly scratch-resistant layer (SK) is produced by applying a solvent-based coating agent based on a silane to the surface-treated scratch-resistant layer (K) and curing it.
  • the coating compositions for the highly scratch-resistant layer can be, for example, the coating sols made of tetraethoxysilane (TEOS) and known in DE 19952040 A1 Act glycidyloxypropyltrimethoxysilane (GPTS).
  • the coating sol is prepared by prehydrolyzing and condensing TEOS with ethanol as the solvent in HCL acidic aqueous solution. GPTS is then stirred into the thus pre-hydrolyzed TEOS and the sol is stirred for some time with heating.
  • Other variants are described in DE 10245 729, DE 10245 725 and DE 102 52421.
  • the primer solution is prepared by dissolving 6 g of Araldit PZ 3962 and 1.3 g of Araldit PZ 3980 in 139.88 g of diacetone alcohol at room temperature in accordance with patent application EP-A 1282 673.
  • UV absorber 4- [ ⁇ - (tri- (methoxy / ethoxy) silyl) propoxy] -2-hydroxybenzophenone was added. The mixture was stirred at room temperature for two weeks. The composition had a solids content of 20% by weight and contained 11% by weight of the UV absorber, based on the solids. The coating composition had a viscosity of about 5 cSt at room temperature.
  • Example 4 0.4% by weight of a silicone leveling agent and 0.3% by weight of an acrylate polyol, namely Joncryl 587 (M n 4300) from SC Johnson Wax Company in Racine, Wisconsin, were stirred into the coating sol prepared according to Example 4. To accelerate the polycondensation reaction, 0.2% by weight of tetra-n-butylammonium acetate were mixed in homogeneously, as in Example 4 before the application.
  • Sheets measuring 100 * 150 * 3.2 mm were injection molded from polycarbonate (Makrolon 3103 ® and Makrolon AL 2647 ® from Bayer AG) on the FH160 injection molding machine from Klöckner.
  • the polycarbonate granules were dried for twelve hours at 120 ° C. in a circulating air drying cabinet to a residual moisture below 0.01% before processing.
  • the melt temperature was 300 ° C.
  • the tool was tempered to 90 ° C.
  • the closing pressure was 770 and the after-pressure 700 bar.
  • the total cycle time of the injection molding process was 48.5 seconds.
  • Makrolon 3103 is a UV-stabilized bisphenol A polycarbonate with an average molecular weight M w (weight average) of approx. 31000 g / mol.
  • Makrolon AL 2647 also a bisphenol A polycarbonate, contains an additive package consisting of UV stabilizer, mold release agent and thermal stabilizer. Its average molecular weight M w is approximately 26500 g / mol.
  • Test pieces were produced with the coating compositions obtained as follows:
  • the injection molded polycarbonate sheets were cleaned with isopropanol and, if necessary, primed by flooding with a primer solution.
  • the primer solution was dried and, in the case of the primer of Example 3, then additionally subjected to a heat treatment at 130 ° C. for half an hour.
  • the primed polycarbonate sheets were then flooded with the scratch-resistant coating agent (Examples 1, 2, 4).
  • the primer rank is omitted for the scratch-resistant coating agent of Example 6.
  • the air drying time for dust drying is 30 minutes at 23 ° C and 53% relative Humidity.
  • the dust-dry plates were heated in an oven at 130 ° C for 30 to 60 minutes and then cooled to room temperature.
  • the coated plates were stored at room temperature for two days.
  • the fog-free top layer is then applied by flaming with the FTS 401 device from Arcotec, Mönsheim, Germany.
  • the belt speed was 20 m / min, the amount of air 120 and the amount of gas 5.5 1 min.
  • the device combination FTS 201D / 99900017 was used for the silicate coating.
  • the coated polycarbonate sheets were attached at an angle of 60 ° with the coated side down on the ceiling of a model greenhouse, so that the water-spreading effect could be compared by observing the formation of droplets.
  • water was evaporated with a heating source, so that a temperature of 50 ° C and a humidity of 100% was established.
  • the plates were left under these conditions for 6 hours and then heated in a dry heating cabinet at 40 ° C. for 4 hours. The procedure was then repeated alternately in the model greenhouse and in the heating cabinet until the water-spreading effect disappeared (evident from the droplet formation on the plate). As a criterion for the Durability of the fog-free layer was given the number of cycles before droplet formation occurs.
  • the steam test was carried out as a further test.
  • the coated polycarbonate sheets were exposed to a closed water vapor atmosphere at 100 ° C. It was observed when the water-spreading effect disappeared and the first drop formation occurred.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

La présente invention concerne un procédé de réalisation de systèmes de couches contenant un substrat (S), au moins une couche (K) et une couche de couverture (D) sans formation de buée. L'invention concerne également des systèmes de couches réalisés selon ledit procédé et leur utilisation.
EP04734514A 2003-06-05 2004-05-24 Procede de realisation de systemes de couches antirayures sans formation de buee Withdrawn EP1633805A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003125436 DE10325436A1 (de) 2003-06-05 2003-06-05 Verfahren zur Herstellung von beschlagsfreien Kratzfest-Schichtsystemen
PCT/EP2004/005557 WO2004108801A1 (fr) 2003-06-05 2004-05-24 Procede de realisation de systemes de couches antirayures sans formation de buee

Publications (1)

Publication Number Publication Date
EP1633805A1 true EP1633805A1 (fr) 2006-03-15

Family

ID=33482559

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04734514A Withdrawn EP1633805A1 (fr) 2003-06-05 2004-05-24 Procede de realisation de systemes de couches antirayures sans formation de buee

Country Status (10)

Country Link
US (1) US20040247899A1 (fr)
EP (1) EP1633805A1 (fr)
JP (1) JP2006526494A (fr)
KR (1) KR20060015336A (fr)
CN (1) CN1798797A (fr)
CA (1) CA2528063A1 (fr)
DE (1) DE10325436A1 (fr)
IL (1) IL172099A0 (fr)
TW (1) TW200512237A (fr)
WO (1) WO2004108801A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018054847A1 (fr) 2016-09-22 2018-03-29 Covestro Deutschland Ag Pièces moulées transparentes de faible épaisseur

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004053708A1 (de) * 2004-11-03 2006-05-04 Schott Ag Verfahren zur Herstellung eines Erzeugnisses mit Antibeschlag-Beschichtung, sowie verfahrensgemäß herstellbares Erzeugnis
US7651560B2 (en) * 2004-12-20 2010-01-26 Koenig & Bauer Ag Abhesive layer of cross-linked nanoparticles
DE102006029617A1 (de) * 2006-06-23 2007-12-27 Verein zur Förderung von Innovationen durch Forschung, Entwicklung und Technologietransfer e.V. (Verein INNOVENT e.V.) Verfahren zur Modifizierung der Oberflächeneigenschaften von Glas
DE102007009512A1 (de) * 2007-02-27 2008-08-28 Friedrich-Schiller-Universität Jena Optisches Element mit einer Antibeschlagsschicht und Verfahren zu dessen Herstellung
DE102007015450A1 (de) * 2007-03-30 2008-10-02 Siemens Ag Beschichtung für Dampfkondensatoren
DE102007038314A1 (de) * 2007-08-14 2009-04-16 Evonik Degussa Gmbh Verfahren zur kontrollierten Hydrolyse und Kondensation von Epoxy-funktionellen Organosilanen sowie deren Condensation mit weiteren organofunktionellen Alkoxysilanen
US20090130447A1 (en) * 2007-11-16 2009-05-21 Nth Tech Corporation Hydrophilic systems and methods thereof
EP2488590A1 (fr) * 2009-10-16 2012-08-22 Bayer MaterialScience AG Revêtements à base de tio2 à réfraction élevée et résistants aux rayures dans des monocouches ou multicouches
KR101135182B1 (ko) * 2009-11-20 2012-04-16 성지산업 주식회사 유리 표면 보호 코팅제 및 그 제조방법
US8802202B2 (en) * 2010-03-05 2014-08-12 Suneeta S. Neogi Method for imparting tarnish protection or tarnish protection with color appearance to silver, silver alloys, silver films, silver products and other non precious metals
DE102011010718B4 (de) * 2010-03-12 2022-07-07 Heidelberger Druckmaschinen Ag Verfahren zum Herstellen einer strukturierten, Bedruckstoff kontaktierenden Oberfläche
US8758894B2 (en) * 2010-04-09 2014-06-24 Nanofilm, Ltd. Fog and abrasion resistant hardcoat for plastics having hydrophilic surfactant rich surface portion with surfactant concentration gradient
US9254506B2 (en) * 2010-07-02 2016-02-09 3M Innovative Properties Company Moisture resistant coating for barrier films
TR201809809T4 (tr) * 2011-02-02 2018-07-23 Advenira Entpr Inc Solüsyon ile türetilen nanokompozit prekursör solüsyonlar.
US10131793B2 (en) 2011-02-02 2018-11-20 Advenira Enterprises, Inc. Modified hybrid sol-gel solutions and compositions formed from such solutions
JP5629033B1 (ja) * 2013-01-23 2014-11-19 デクセリアルズ株式会社 親水性積層体、及びその製造方法、防汚用積層体、物品、及びその製造方法、並びに防汚方法
US10652394B2 (en) 2013-03-14 2020-05-12 Apple Inc. System and method for processing voicemail
KR101806803B1 (ko) * 2017-09-01 2017-12-08 (주)도은 유기용제를 함유하지 않는 안경렌즈용 하드 코팅액 조성물
BE1025655B1 (fr) * 2017-10-23 2019-05-21 Mecar Sa Matériau de masquage et utilisation du matériau pour masquage d'un objectif et munition permettant de disperser un tel matériau de masquage
US11203677B2 (en) * 2017-11-03 2021-12-21 American Biltrite (Canada) Ltd. Resilient surface coverings and methods of making and using thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3400079A1 (de) * 1984-01-03 1985-07-11 Röhm GmbH, 6100 Darmstadt Wasserspreitendes kunststoffmaterial, verfahren zu seiner herstellung u. verwendung als verglasungs- und bedachungsmaterial
US4842941A (en) * 1987-04-06 1989-06-27 General Electric Company Method for forming abrasion-resistant polycarbonate articles, and articles of manufacture produced thereby
DE3821131A1 (de) * 1988-06-23 1989-12-28 Bayer Ag Verfahren zur herstellung von kunststofformkoerpern mit verbesserter witterungsbestaendigkeit
US5104732A (en) * 1988-12-22 1992-04-14 General Electric Company Thermoplastic sheet having enhanced water wetting and spreading characteristics
US4994318A (en) * 1989-01-17 1991-02-19 General Electric Company Thermoplastic substrates having improved water spreading characteristics
DE19952040A1 (de) * 1999-10-28 2001-05-03 Inst Neue Mat Gemein Gmbh Substrat mit einem abriebfesten Diffusionssperrschichtsystem
ATE320318T1 (de) * 2000-06-30 2006-04-15 Ngimat Co Verfahren zur abscheidung von materialien
DE10245726A1 (de) * 2002-10-01 2004-04-15 Bayer Ag Verfahren zur Herstellung eines Kratzfest-Schichtsystems

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004108801A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018054847A1 (fr) 2016-09-22 2018-03-29 Covestro Deutschland Ag Pièces moulées transparentes de faible épaisseur

Also Published As

Publication number Publication date
JP2006526494A (ja) 2006-11-24
WO2004108801A1 (fr) 2004-12-16
TW200512237A (en) 2005-04-01
CA2528063A1 (fr) 2004-12-16
CN1798797A (zh) 2006-07-05
KR20060015336A (ko) 2006-02-16
DE10325436A1 (de) 2004-12-23
IL172099A0 (en) 2011-08-01
US20040247899A1 (en) 2004-12-09

Similar Documents

Publication Publication Date Title
EP1633805A1 (fr) Procede de realisation de systemes de couches antirayures sans formation de buee
EP0728164B1 (fr) Procede de preparation de compositions a base de silanes contenant des groupes epoxy
DE3786864T3 (de) Beschichtungszusammensetzungen auf der Basis von Siloxanen und Metalloxiden.
EP0967253B1 (fr) Agents antisalissure, leur préparation, leur emploi et des compositions de revêtement antisalissure
EP2385076B1 (fr) Procédé de fabrication d'un matériau de revêtement
EP1012212B1 (fr) Composition de recouvrement a base de silanes contenant des groupes epoxyde
DE3751856T2 (de) Organisch-anorganisches Hybridpolymer
DE60122636T2 (de) Beschichtungszusammensetzungen, deren Herstellung und Verwendung, beschichtete Gegenstände
EP1565768A1 (fr) Systeme stratifie, composition de revetement et procede de production de ladite composition
EP2484732B1 (fr) Matériau composite et son procédé de fabrication
EP1549700B1 (fr) Systeme stratifie et procede de fabrication dudit systeme
EP1549701A1 (fr) Procede de fabrication d'un systeme stratifie resistant aux rayures
WO1992021729A1 (fr) Compositions d'enduction a base de polycondenses anorganiques fluores, leur preparation et leur utilisation
DE19952040A1 (de) Substrat mit einem abriebfesten Diffusionssperrschichtsystem
WO2009151664A2 (fr) Matières de revêtement transparentes hybrides composites sol-gel en nanoparticule
EP1150782B1 (fr) Substrats laques par poudrage, pourvus d'une couche de finition a base de silane contenant des groupe epoxyde
WO1993003088A1 (fr) Procede d'enduction de substrats en matieres plastiques et laque utilisee pour mettre en ×uvre ce procede
EP1282673A2 (fr) Revetement resistant aux rayures
EP0947520A1 (fr) Mélanges contenant du bore et/ou d'aluminium matériaux hybrides et revêtements
EP1012213B1 (fr) Compositions de recouvrement a base de silanes contenant des groupes epoxyde
DE3917535A1 (de) Verfahren zur herstellung kratzfester materialien und zusammensetzung hierfuer
EP1192225B8 (fr) Utilisation de composes exempts d'azote comme agents adhesifs pour des revetements resistant a l'abrasion a base de silicium appliques sur du polycarbonate
WO2000037577A1 (fr) Compositions de revetement renfermant du dioxyde de cerium
EP0849332A1 (fr) Procédé de fabrication des rêvetements sur substrats et une composition de rêvetement correspondante

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: 20060105

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 IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20070222

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: 20101201