Classifications

• • 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
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/54—No clear coat specified
  • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
• • 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
• • 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
  • C08J7/0427—Coating with only 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
  • C08J7/12—Chemical modification
• • 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
• • 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
  • B05D3/14—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 electrical means
  • B05D3/141—Plasma treatment
• • 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
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • 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
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Definitions

• the present invention relates to a method for producing a layer system comprising a substrate (S), a scratch-resistant layer (K) and a cover layer (D), and layer systems produced by the method.
• inorganic-organic hybrid materials by targeted hydrolysis and condensation of alkoxides, mainly silicon, aluminum, titanium and zirconium.
• 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. Due to the large number of possible combinations of both organic and inorganic components and the fact that the product properties can be greatly influenced by the manufacturing process, 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.
• the layers obtained are still relatively soft compared to pure inorganic materials. This is due to the fact that the inorganic components in the system have a strong crosslinking effect, but due to their very small size the mechanical properties such as. B. Hardness and abrasion resistance do not apply. So-called filled polymers allow the favorable mechanical properties of the inorganic components to be fully exploited, since particle sizes of several micrometers are present. However, the transparency of the materials is lost and applications in the field of optics are no longer possible. The use of small particles in nanometer size made of Si02 (e.g. Aerosile ® ), silica sol, Al 2 O 3 , Böh it, zirconium dioxide, titanium dioxide etc.
• Si02 e.g. Aerosile ®
• the achievable abrasion resistance is similar to that of the systems mentioned above.
• the upper limit of the amount of filler is determined by the high surface reactivity of the small particles, which results in agglomerations or intolerable increases in viscosity.
• DE 199 52 040 A1 discloses substrates with an 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 a coating sol of tetraethoxysilane (TEOS) and glycidyloxypropyltrimethoxysilane (GPTS) and curing the same at a temperature ⁇ 110 ° C.
• 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 at 50 ° C.
• a disadvantage of the coating sol described in this publication is its low storage stability (pot life), as a result of which the coating sol must be processed further within a few days after its production.
• Another disadvantage of the diffusion barrier layer systems described in this document is that they have unsatisfactory results after the Taber wear test for use in automotive glazing.
• US Pat. No. 4,842,941 discloses a plasma coating method in which a siloxane lacquer is applied to a substrate, the substrate coated in this way is introduced into a vacuum chamber and the surface of the coated substrate is activated in a vacuum with oxygen plasma. After activation, a dry chemical or physical overcoating is carried out with a silane in a high vacuum according to the CVD (Chemical Vapor Deposition) or PECVD (Physical Enhanced Chemical Vapor Deposition) process.
• CVD Chemical Vapor Deposition
• PECVD Physical Enhanced Chemical Vapor Deposition
• a disadvantage of the dry chemical or physical overcoating process described are the high investments which are required for a plasma coating system and the complex technical measures for generating and maintaining the vacuum.
• the plasma coating process described is also only suitable to a limited extent for coating large-area three-dimensional bodies.
• the present invention has for its object to provide a method for producing a scratch-resistant layer system comprising a substrate (S), a scratch-resistant layer (K) and a highly scratch-resistant cover layer (D), which has optimal adhesion properties between scratch-resistant (K) and cover layer (D) ensures and is also suitable for the uniform coating of three-dimensional substrates (S), in particular of automobile windows.
• 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) once produced can still be coated with the top layer (K) without any problems and even after a few weeks or months of storage ,
• the method is also intended to provide a coating with still further improved scratch resistance, adhesion, paint viscosity and elasticity, which has a lower tendency to gel and cloud compared to the compositions of the prior art.
• this object is achieved by a method for producing a layer system comprising a substrate (S), a scratch-resistant layer (K) and a cover layer (D) (a) applying a coating agent to a substrate (S), the coating agent comprising a polycondensate based on at least one silane produced by the sol-gel method and at least partially curing the same to form a scratch-resistant layer (K);
• step (b) of the process according to the invention results in a considerably improved abrasion resistance (Taber values) of the scratch-resistant coating system. It was also surprising that the surface treatment provided in step (b) enables the application of the top layer (D) to be decoupled from the application of the scratch-resistant layer (K) in a simple manner, which has significant process-economic advantages in the production of the layer systems. For example, after the scratch-resistant layer (K) has been applied, the layer systems can be temporarily stored and only then surface-treated at any time, first in accordance with step (b) and then overcoated with the top layer (D).
• the manufacturing method according to the invention is also simple and inexpensive to carry out.
• the at least partially hardened scratch-resistant layer (K) is surface-treated by flame treatment, corona treatment and / or plasma activation.
• Such surface treatment methods are generally known from coating technology and are used, for example, when painting, printing and gluing surfaces, in particular plastic surfaces, with printing inks, adhesives, etc.
• the surface treatment changes the surface characteristics of the material and increases its wettability without changing the material properties.
• the surface treatment increases the adhesion energy of the scratch-resistant layer (K). Particularly good results can be achieved if the adhesion energy of the scratch-resistant layer is brought to values> 70 mJ / m 2 , in particular> 80 mJ / m 2 , by the surface treatment.
• the surface treatment in step (b) is carried out by flaming.
• the oxidizing part of an open flame acts on the surface of the siloxane scratch-resistant layer (K).
• K siloxane scratch-resistant layer
• An exposure time of approx. 0.2 s is often sufficient. depending on the shape and mass of the molded part to be activated. An insufficient amount of heat prevents sufficient surface activation, while an exposure that is too long can deform or even melt the plastic.
• Flaming is essentially influenced by three parameters: flame setting (gas / air ratio), duration of exposure to flame and distance of the flame from the plastic (flame zone).
• the geometry of the flame is determined by the type of burner. It has proven to be particularly advantageous if the flame treatment is carried out in a continuous flame treatment system at a throughput speed of 1 to 20 m / min, in particular 2 to 10 m / min.
• the surface treatment in step (b) is carried out by corona treatment.
• the part to be treated is inserted directly into the discharge gap of a corona discharge.
• the gap is formed by the treatment roller, which guides the web, and a treatment electrode, which is located about 1.5 to 2.0 mm above the roller. With larger electrode spacings, an increased electrical voltage must be applied to ignite the discharge, so that the energy content of the individual discharge increases and increasingly hot arc discharges form.
• Typical power densities of these conventional electrodes are 1 W / mm for a single electrode rod.
• indirect corona systems electrical discharge takes place in front of the workpiece.
• An air stream deflects the discharge sparks onto the workpiece to be treated, so that there is only indirect contact with the discharge.
• a principle of indirect corona treatment is to let the discharge burn between two metallic pin electrodes.
• the current limitation necessary to form a corona discharge is carried out electronically.
• the discharge sparks are deflected with air. Thereby treatment distances are reached, which are in the range of 5 - 20 mm. Due to this large discharge width, it is absolutely necessary to minimize the energy content of the individual discharges through constructive measures.
• the discharge intensity can be reduced to 100 W through high operating frequencies of around 50 KHz and optimized discharge geometry and air flow. e.g. Corona-Gun CKG from Tigris. Single electrodes with a working width of approx. 20 mm are used.
• the arrangement can be adapted to 3-dimensional parts.
• the pretreatment takes place with cold corona discharges, so that the surfaces of thermally sensitive plastics are not optically changed. Streaks and clouds do not appear.
• LF low frequency
• HF high frequency
• spot generators which can be used depending on the product.
• Spot generators generate a high-voltage discharge, which is pressed onto the substrate with the help of air without using a counter electrode.
• a spot generator can be easily installed in existing production lines, is easy to use and is equipped with a timer and alarm function.
• the pretreatment width is 45-65 mm, with which a variety of products can be pretreated.
• the spot generator can also be supplied with two or more discharge heads.
• the high-frequency corona generates a high-voltage discharge with a frequency of 20 - 30 kHz, which forms a corona field between two electrodes in air.
• This corona activates the surface and thus creates greater adhesion and wettability.
• Corona activation of plates and simple 3-D geometries is possible at high speeds.
• a corona tunnel (eg from Tantec) is suitable for the pretreatment of complex-shaped parts, with which the entire surface of a body can be pretreated in the production line. Thanks to the special design of the electrodes, an absolutely homogeneous surface energy is achieved. Vertical side walls and 90 ° angles can also be treated.
• the Corona tunnel is designed specifically for the product and can also be integrated into existing systems. For example, it enables non-contact pretreatment of the entire top of parts up to 100 mm high and 2000 mm wide.
• the corona treatment is preferably carried out in a continuous corona system at a throughput speed of 1 to 20 m / min, in particular 2 to 10 m min and / or an output of 500 to 4000 W, in particular 1500 to 3500 W.
• the surface treatment in step (b) is carried out by plasma activation.
• the plasma treatment is preferably carried out in a chamber at a pressure of 1 to 10 " mbar, in particular 10 " to 10 "2 mbar and a power of 200 to 4000 W, in particular 1500 to 3500 W with a low-frequency generator and in particular air Process gas carried out (e.g. BPA 2000 standard system from Balzers).
• 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 prepared by the sol-gel method, and at least partially curing the same.
• a coating agent comprising a polycondensate based on at least one silane, which is prepared by the sol-gel method, and at least partially curing the same.
• 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, Kunststoff Taschenbuch, Carl Hanser Verlag, Kunststoff, Vienna 1992 ,
• the 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 if 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 produced by the sol-gel process, consisting essentially of 10 to 70% by weight of silica sol and 30 to 90% by weight. 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. 5,503,935, which, based on the weight:
• 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, primer-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 alkyl radical, 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 methyltri- methoxysilane, methyl trihydroxysilane or a mixture thereof which can form a partial condensate.
• thermosetting, primer-free silicone hard coating compositions are known to the person skilled in the art and are described in detail, for example, in US Pat. No. 5,503,935, the content of which is expressly incorporated by reference here.
• 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 group consisting of alkyl radicals with 1 to 3 carbon atoms and aryl radicals with 6 to 13 carbon atoms, and R is selected from the group consisting of alkyl radicals with 1 to 8 carbon atoms and aryl radicals with 6 up 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 agent.
• 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 agent.
• 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 polymethyl methacrylate (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 in detail, for example, in US Pat. No. 5,041,313, the content of which is expressly stated here. lent 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).
• colloidal silica sica sol
• Particularly suitable as 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
• index d is an integer with a value of (4-bc), or
• R and R are the same or different monovalent hydrocarbon radicals
• R 9 is a divalent hydrocarbon radical having 2 to 8 carbon atoms
• the index e is an integer with a value from 1 to 3
• the index f is an integer with a value from 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-methacryloxypropyl trimethoxysilane, 3-acryloxypropyltrimethonxysilane, 2-methacryloxyethyltrime thoxysilane, 2-acryloxyethyl trimethoxy silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysiloxyethyl 2-methoxysilane.
• Particularly suitable glycidoxy-functional silanes are, for example, 3-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyl trimethoxysilane, 3-glycidoxypropyltriethoxysilane and 2-glycidoxyethyltri-ethoxysilane. 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 Contain 500 parts by weight of additional 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 abovementioned constituents, also contain a UV absorber such as triazine or dibenzylresorcinol derivatives.
• Polycondensates based on silyl acrylates which contain nanoscale AlO (OH) particles, in particular nanoscale boehmite particles, as a further constituent can also be used as coating agents.
• Such coating compositions are described, for example, in the publications WO 98/51747 AI, WO 00/14149 AI, DE 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).
• 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 SiX a R 3 . a
• 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 is prepared by the sol-gel process and which has an epoxy group on a non-hydrolyzable substituent and, if appropriate, 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 epoxililanes 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, CI, Br and I, in particular CI and Br), alkoxy (in particular C 4 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 radicals are alkoxy groups, especially methoxy and ethoxy.
• non-hydrolyzable radicals without an epoxy group are hydrogen, alkyl, in particular C ⁇ .
• 4- alkyl such as methyl, ethyl, propyl and butyl
• alkenyl in particular C 2. 4 -alkenyl such as vinyl, 1-propenyl, 2-propenyl and butenyl
• alkynyl in particular C 2 - 4 -Alkynyl such as acetylenyl and propargyl
• aryl in particular C 6 - ⁇ 0 -aryl such as As phenyl and naphthyl
• 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-195 493, the disclosure of which is incorporated by reference into the present application.
• 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 group (preferably C - alkoxy and particular methoxy and ethoxy) and R 'represents a glycidyl or glycidyloxy (C ⁇ . 2 o) alkylene radical , in particular ß-glycidyloxyethyl-, ⁇ -glycidyloxypropyl, ⁇ -glycidyloxybutyl-, ⁇ -glycidyloxylpentyl-, ⁇ -glycidyloxyhexyl-, ⁇ -glycidyloxyoctyl-, co-
• GPTS ⁇ -glycidyloxypropyltrime thoxysilane
• 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 ran and their mixtures. 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, SiO 2, CeO 2 , ZnO, In 2 O 3 and TiO 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
• the principle of stabilizing nanoscale titanium nitride using guanidine propionic acid is described, for example, in German patent application P-43 34 639.1.
• 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 - 23 -
• hydrolyzable radicals examples include halogen (F, CI, Br and 1, in particular Ci and Br), alkoxy (in particular C - alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy, i-butoxy, sec-butoxy or tert-butoxy), aryloxy (especially C 6 -o-aryloxy, e.g. phenoxy), acyloxy (especially Ci-acyloxy such as acetoxy and propionyloxy) and alkylcarbonyl (e.g. acetyl) , Particularly preferred hydrolyzable radicals are alkoxy groups, especially methoxy and ethoxy.
• non-hydrolyzable radicals are hydrogen, alkyl, in particular C].
• Alkyl such as methyl, ethyl, propyl and n-butyl, i-butyl, sec-butyl and tert-butyl
• Alkenyl especially C 2 - 4 - alkenyl such as vinyl, 1-propenyl, 2-propenyl and butenyl.
• Alkynyl especially C 2 - 4 alkynyl such as acetylenyl and propargyl.
• Aryl in particular C 6 -o-aryl, such as phenyl and naphthyl), where the groups just mentioned may optionally have one or more substituents, such as halogen and alkoxy.
• substituents such as halogen and alkoxy.
• Methacrylic and methacryloxypropyl residues can also be mentioned in this connection.
• 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
• 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.
• CH 2 CH-CH 2 -Si (OOCCH 3 ) 3 ,
• CH 2 C (CH3) -COO-C 3 H 7 -Si (OCH 3 ) 3;
• CH2 C (CH 3 ) -COO-C 3 H 7 -Si (OC 2 H 5 ) 3,
• radicals R can be the same or different and stand for a hydrolyzable group, preferably for an alkoxy group having 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 C-C double or triple bond.
• the composition can also (preferably containing epoxy or hydroxyl groups) monomers such as.
• B. meth (acrylates) are incorporated (of course, these monomers can also have two or more functional groups of the same type, such as 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, CI, Br and I, in particular CI 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 (in particular C 6 .0 0 -aryloxy e.g. phenoxy), acyloxy (in particular such as Acetoxy and propionyloxy) and alkylcarbonyl (for example acetyl), or a C 1 -. 6 -alkoxy-C 2.
• alkyl group ie a group derived from C 6 alkyl ethylene glycol or propylene glycol, alkoxy having 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 additionally be used as a catalyst.
• a hydrolyzable silicon compound (F) with at least one non-hydrolyzable radical which has 5 to 30 fluorine atoms bonded directly to carbon atoms can also be used, these carbon atoms being separated from Si by at least 2 atoms.
• the use of such a 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. Is preferred to
• Hydrochloric acid used.
• boehmite is used as the particulate material (B)
• a clear sol is formed under these conditions.
• 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 chosen 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 cooled to about 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 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.
• the highly scratch-resistant top layer (D) is produced by applying a solvent-containing coating agent based on a silane to the surface-treated scratch-resistant layer (K) and curing it.
• the coating compositions for the top layer (D) can be, for example, the coating sols known from DE 199 52 040 A1 made of tetraethoxysilane (TEOS) and 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 a while with heating.
• Coating agents which can be used in the production process according to the invention for the top layer (D) are also those which are obtainable by (a) one or more compounds of the general formula I.
• M is an element or a compound selected from the group consisting of Si, Ti, Zr, Sn, Ce, Al, B, VO, In and Zn
• R ' represents a hydrolyzable radical and m is an integer from 2 to 4 , alone or together with
• R b SiR ' a (II) wherein the radicals R' and R are identical or different, R 'is as defined above, R is an alkyl group, an alkenyl group, an aryl group or a hydrocarbon group with one or more halogen groups, an epoxy group, a Glycidyloxy group represents an amino group, a mercapto group a methacryloxy group or a cyano group and a and b independently of one another have the values 1 to 3, the sum of a and b being four,
• the compounds of the formulas I and II can be used in any amount.
• the compound of the formula II is preferably used in an amount of less than 0.7 mol, in particular less than 0.5 mol, based on 1 mol of the compound of the formula I.
• the hydrolysis is preferably carried out in the presence of acids, in particular aqueous hydrochloric acid.
• a pH of the reaction mixture of 2.0 to 5.0 is particularly suitable.
• the hydrolysis reaction is slightly exothermic and is preferably supported by heating to 30 to 40 ° C.
• the reaction product is preferably cooled to room temperature and stirred at room temperature for some time, in particular 1 to 3 hours.
• the coating composition obtained is preferably stored at temperatures ⁇ 10 ° C., in particular at a temperature of approximately 4 ° C.
• All temperature information includes a deviation of ⁇ 2 ° C.
• a room temperature is understood to be a temperature of 20 to 23 ° C.
• the topcoat coating sol is prepared from 100 parts of a compound of formula I and / or a hydrolysis product thereof and a compound of formula II and / or a hydrolysis product thereof, the amount of compound II based on the 100 parts of compound I being less is less than 100 parts, preferably less than 70 parts, in particular less than 50 parts, or is completely omitted.
• the ready-to-apply top layer coating composition preferably has a solids content of 0.2 to 10%, in particular 0.5 to 5%.
• the compound of the formula I is preferably a compound
• M stands for a) Si +4 , Ti +4 , Zr +4 , Sn +4 , Ce +4 or b) Al +3 , B +3 , VO +3 , In +3 or c) Zn +2
• R represents a hydrolyzable radical and m is M [case a)] 4 in the case of tetravalent elements, M [case b)] 3 in the case of trivalent elements or compounds, and 2 in the case of divalent elements.
• Preferred elements for M are Si +4 , Ti +4 , Ce +4 and Al +3 , Si +4 is particularly preferred.
• hydrolyzable radicals examples include halogen (F, CI, Br and I, in particular CI and Br), alkoxy (in particular C-alkoxy such as, for example, methoxy, ethoxy, n- Propoxy, i-propoxy and n-butoxy, i-butoxy, sec-butoxy or tert-butoxy), aryloxy (especially C 6 - ⁇ 0 - aryloxy, for example phenoxy), acyloxy (e.g. in particular C ⁇ 4 acyloxy.. such as acetoxy and propionyloxy) and alkylcarbonyl (e.g. acetyl).
• Particularly preferred hydrolyzable radicals are alkoxy groups, especially methoxy and ethoxy.
• TiCl 4 Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 , Ti (OiC 3 H 7 ) 4 , Ti (OC 4 H 9 ) 4 , Ti (2-ethylhexoxy) 4 ;
• 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.
• Tetraethoxysilane (TEOS) is very particularly preferred.
• the compound of the formula II is preferably a compound
• R and R ' are identical or different (preferably identical), R' is a hydrolyzable group (preferably C M alkoxy and in particular methoxy and ethoxy) and R is an alkyl group, an alkenyl group, an aryl group or a hydrocarbon group with one or more halogen groups, an epoxy group, a glycidyloxy group, an amino group, a mer capto group is a methacryloxy group or a cyano group.
• R' is a hydrolyzable group (preferably C M alkoxy and in particular methoxy and ethoxy) and R is an alkyl group, an alkenyl group, an aryl group or a hydrocarbon group with one or more halogen groups, an epoxy group, a glycidyloxy group, an amino group, a mer capto group is a methacryloxy group or a cyano group.
• a can have the values 1 to 3 and b also the values 1 to 3
• Trialkoxysilanes triacyloxysilanes and Triphenoxysilane such as Methyltrimeth- oxysilane, silane methyltriethoxysilane, methyltrimethoxyethoxysilane, Methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, Phe nyltrimethoxysilan, phenyltriethoxysilane, phenyltriacetoxysilane, ⁇ -Chlorpropyltri- trimethoxysilane, ⁇ -chloropropyltriethoxysilane , ⁇ -Chlorpropyltriacetoxysilan, 3,3, 3 -Trifluorpropyltrimethoxy
• Preferred compounds of the formula II are methyltrialkoxysilane, dimethyldialkoxysilane, glycidyloxypropyltrialkoxysilane and or methacryloxypropyltrimethoxysilane.
• Particularly preferred compounds of the formula II are glycidyloxypropyltrimethoxysilane (GPTS), methyltriethoxysilane (MTS) and / or methacryloxypropyltrimethoxysilane (MPTS).
• water and inert solvents or solvent mixtures can optionally be added at any stage of the preparation, in particular during the hydrolysis.
• solvents are preferably alcohols which are liquid at room temperature and which are also formed during the hydrolysis of the alkoxides which are preferably used.
• Particularly preferred alcohols are C 8 alcohols, in particular methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, tert-butanol, n-pentanol, i-pentanol, n-hexanol, n-octanol.
• C are also preferred.
• compositions can furthermore contain customary additives such as dyes, leveling agents, UV stabilizers, IR stabilizers, photoinitiators, photosensitizers (if photochemical curing of the composition is intended) and / or thermal polymerization catalysts.
• leveling agents are in particular those based on polyether-modified polydimethylsiloxanes. It has proven to be particularly advantageous if the compositions contain leveling agents in an amount of about 0.005 to 2% by weight.
• the application to the substrate (S) coated with the scratch-resistant layer (K) is carried out by standard coating methods such as e.g. Dipping, flooding, brushing, brushing, knife coating, rolling, spraying, falling film application, spin coating and spinning.
• the coated substrate is cured.
• the curing preferably takes place thermally at temperatures in the range from 50 to 200 ° C., in particular 70 to 180 ° C. and particularly preferably 90 to 150 ° C. Under these conditions, the curing time should be 30 to 200 minutes, preferably 45 to 120 minutes.
• the layer thickness of the hardened cover layer should be 0.05 to 5 ⁇ m, preferably 0.1 to 3 ⁇ m.
• curing can also be carried out by irradiation, which may be followed by thermal post-curing.
• the top layer coating composition is applied at a relative humidity of 50 to 75%, in particular 55 to 70%.
• GPTS and TEOS are submitted and mixed.
• the amount of boehmite dispersion required for semi-stoichiometric pre-hydrolysis of the silanes (prepared analogously to Example 1) is slowly poured in with stirring. Then the reaction mixture stirred for 2 hours at room temperature. The solution is then cooled to 0 ° C using a cryostat. Aluminum tributoxyethanolate is then added dropwise via a dropping funnel. After the addition of the aluminate, the mixture is stirred at 0 ° C. for 1 hour. The rest of the boehmite dispersion is then added with cryostat cooling. After stirring for 15 minutes at room temperature, the cerium dioxide dispersion and BYK ® 306 are added as leveling agents.
• 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 PCT / EP01 / 03809.
• Example 4
• UV absorber 4- [ ⁇ - (tri- (methoxy / ethoxy) silyl) propoxy] -2-hydroxybenzophenone were 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.
• Test pieces were produced with the coating agents obtained as follows:
• the primer solution is dried and, in the case of the primer (example 3), then additionally subjected to a half-hour temperature treatment at 130 ° C.
• the primed polycarbonate sheets were then flooded with the scratch-resistant coating agent (Examples 1, 2, 4).
• the priming is omitted for the scratch-resistant coating agent of Example 6.
• the air drying time for dust drying was 30 minutes at 23 ° C and 63% 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 hardened scratch-resistant layer is then surface activated by flame treatment, corona treatment or plasma treatment.
• cover layer coating compositions (examples 7, 8, 9) were then also applied by flooding.
• the wet film was flashed off at 23 ° C. and 63% relative atmospheric humidity for 30 minutes and the plates were then heated at 130 ° C. for 120 minutes.
• the coated plates were stored for two days at room temperature and then subjected to the following defined tests.
• Example 3 Example 2
• Example 8 without 36 holes n b n b
• Example 3 Example 2
• Example 8 1 * Flame throughput 3 m / min 55 good 0/0 2.2
• Example 3 Example 2
• Example 8 1 * Flame throughput 3 m / min 66 good 0/0 2.5
• Example 3 Example 2 Example 7 without 34 holes n b n b
• Example 3 Example 2
• Example 3 Example 2
• Example 7 Corona l500 W 56 good 0/0 4.7
• Example 3 Example 2
• Example 3 Example 1 Example 8 without 24 many holes and craters n b n b
• Example 3 Example 1 Example 8 Corona 1000 W 48 good 0/0 4.1
• Example 3 Example 1 Example 8 Corona 1500 W 56 good 0/0 2.2
• Example 3 Example 1
• Example 5 Example 4
• Example 8 without 24 many holes and craters n b n b
• Example 5 Example 4
• Example 5 Example 4
• Example 8 without 24 large holes n b n b
• Example 5 Example 4
• Example 8 1 x flame pass 3 m min 64 good 0/0 8.0
• Example 5 Example.
• Example 8 2 x flaming pass 3 m min 56 good 0/0 3.4
• Example 3 Example 2 Example 9 without 33.7 craters and holes n b n b
• Example 3 Example 2 Example 9 1 * Flame throughput 6 m mm 48 good 0/0 2.3
• Example 3 Example 2
• Example 9 2 * Flame throughput 6 m / min 56 good 0/0 1.4
• Example 5 Example 4 Example 9 without 27 bad, pearls from n b n b
• Example 5 Example 4
• Example 9 1 x flaming pass 6 m / min 48 very good 0/0 2.6
• Example 5 Example 4 Example 9 2 x flaming pass 6 m / min 56 very good 0/0 2.2
• Lexan Margard MR5E is a transparent, UV-resistant and abrasion-resistant material for flat glazing from General Electric Plastics GmbH, Rüsselheim.
• the plate has a double tempered surface. 4

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• 2002
  • 2002-10-01 DE DE10245726A patent/DE10245726A1/de not_active Withdrawn
• 2003
  • 2003-09-27 AU AU2003271654A patent/AU2003271654A1/en not_active Abandoned
  • 2003-09-27 WO PCT/EP2003/010769 patent/WO2004031272A1/de not_active Application Discontinuation
  • 2003-09-27 EP EP03753472A patent/EP1549701A1/de not_active Withdrawn
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