EP1565768A1 - Systeme stratifie, composition de revetement et procede de production de ladite composition - Google Patents

Systeme stratifie, composition de revetement et procede de production de ladite composition

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Publication number
EP1565768A1
EP1565768A1 EP03810971A EP03810971A EP1565768A1 EP 1565768 A1 EP1565768 A1 EP 1565768A1 EP 03810971 A EP03810971 A EP 03810971A EP 03810971 A EP03810971 A EP 03810971A EP 1565768 A1 EP1565768 A1 EP 1565768A1
Authority
EP
European Patent Office
Prior art keywords
layer
scratch
coating agent
layer system
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Withdrawn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
EP03810971A
Other languages
German (de)
English (en)
Inventor
Peter Bier
Reiner Meyer
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 EP1565768A1 publication Critical patent/EP1565768A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material

Definitions

  • the present invention relates to a layer system comprising a substrate (S), a scratch-resistant layer (K) and a cover layer (DE) as well as a method for producing these layer systems.
  • This process creates an inorganic network.
  • additional organic groups can be incorporated, which can be used for functionalization on the one hand, and for the formation of defined organic polymer systems on the other.
  • 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 5 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 cross-linking effect, but due to their very small size, the mechanical properties such as Hardness and abrasion resistance do not come into play. So-called filled polymers allow the beneficial 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 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-A 199 52 040 discloses substrates with an abrasion-resistant diffusion barrier system, the diffusion barrier system comprising a hard base layer based on hydrolyzable epoxysilanes and a cover layer arranged above it.
  • the top layer is made by applying a coating sol of tetraethoxysilane (TEOS) and glycidyloxypropyl trimethoxysilane (GPTS) and curing it at a temperature ⁇ 110 ° C.
  • the coating sol is produced by pre-hydrolyzing 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. for 5 hours.
  • 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 systems described in this document is that they have unsatisfactory results after the Taber wear test for use in automotive glazing.
  • the adhesion between the base and top layers is only guaranteed if the top layer is immediate, i.e. must be applied and cured within a few hours after the base layer has hardened. There is no possibility of decoupling the top coat overcoat and the base coat application. Rather, the substrates coated with the base layer have to be processed immediately and not, as would often be desirable from the point of view of process economics, first stored temporarily and only provided with the cover layer when necessary.
  • US Pat. No. 4,842,941 discloses a plasma coating process 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 introduced into a vacuum chamber and the surface of the coated substrate is activated in a vacuum with oxygen plasma becomes.
  • 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 method described is also only suitable to a limited extent for coating large-area three-dimensional bodies.
  • the object of the present invention is to provide a scratch-resistant layer system and a method for producing this layer system comprising a substrate (S), a scratch-resistant layer (K) and a highly scratch-resistant cover layer (DE), which have optimal adhesion properties between scratch-resistant (K) and top layer (DE) are guaranteed and are also suitable for the uniform coating of three-dimensional substrates (S), in particular of automotive slices, suitable.
  • the method is also intended to enable decoupling of the production of the scratch-resistant layer (K) and the top layer (DE) and to ensure that a scratch-resistant layer (K) which has been produced once is still problem-free and problem-free with the top layer (K) even after a storage period of a few weeks or months. can be coated.
  • the layer system and method are also intended to provide a coating with even more 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.
  • the scratch-resistant layer (K) is preferably 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, prepared by the sol-gel process, and at least partially curing the same ,
  • a coating agent comprising a polycondensate based on at least one silane, prepared by the sol-gel process, and at least partially curing the same .
  • substrate materials (S) for coating is not restricted. Wood, textiles, paper, stone goods, metals, glass, ceramics and plastics are particularly suitable, and in particular thermoplastics, as described in Becker / Braun, Plastic Pocket Book, Carl Hanser Verlag, Kunststoff, Vienna 1992. Transparent thermoplastics and preferably polycarbonates are particularly suitable. In particular injection molded parts, foils, spectacle lenses, optical lenses, automobile windows and plates can be coated with the layer system 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 compositions for scratch resistance (K) are in particular (1) methyl silane systems,
  • 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.
  • Ammonium compounds or, in particular, strong inorganic acids such as sulfuric acid and perchloric acid are 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.
  • the production, application and curing of such coating compositions are known to the person skilled in the art and are described, for example, in the publications DE-A 2 136 001, DE-A 2 113 734 and US-A 3 707 397.
  • Polycondensates based on methylsilane and silica sol can also be used as coating agents for the scratch-resistant layer (K).
  • Particularly suitable coating compositions of this type are polycondensates produced by the sol-gel process from essentially 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. 5,503,935, which, based on the weight:
  • an acrylated polyurethane adhesion promoter with an M n of 400 to 1500 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 solvents preferably fall under the formula
  • R is a monovalent Ci.g hydrocarbon radical, in particular a Ci .4 alkyl radical,
  • a is an integer from 0 to 2 inclusive.
  • the organoalkoxysilane of the aforementioned formula is preferably methyltrimethoxysilane, methyltriethoxysilane or a mixture thereof which can form a partial condensate.
  • the preparation, properties and curing of such 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.
  • 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 ' 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 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.
  • 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
  • R is a C ⁇ .i2 alkyl group
  • 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, for example, in US Pat. No. 5,041,313.
  • the primer compositions can also contain conventional constituents, in particular UV absorbers such as triazine, dibenzoylresorcinol, benzophenone, benzotriazole, oxalanilide, malonic acid ester and cyanoacrylate derivatives.
  • UV absorbers such as triazine, dibenzoylresorcinol, benzophenone, benzotriazole, oxalanilide, malonic acid ester and cyanoacrylate derivatives.
  • Nanoscale inorganic particles such as cerium oxide, titanium dioxide and zinc oxide have also proven themselves as UV absorbers.
  • 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
  • R3 and R ⁇ are the same or different types of monovalent hydrocarbon radicals
  • R5 is a divalent hydrocarbon radical with 2 to 8 carbon atoms
  • R represents hydrogen or a monovalent hydrocarbon radical
  • b is an integer with a value from 1 to 3
  • c is an integer from 0 to 2
  • d is an integer with a value of (4-b-c), or
  • R ⁇ and R are the same or different types of monovalent hydrocarbon radicals
  • R9 represents a divalent hydrocarbon radical with 2 to 8 carbon atoms
  • e is an integer with a value from 1 to 3
  • f is an integer from 0 to 2
  • g is an integer with a value of (4-ef)
  • Particularly suitable acryloxy-functional silanes are, for example, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxy-silane, 3-acrylicoxypropyltriethoxysiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxilyl
  • Particularly suitable glycidoxy-functional silanes are, for example, 3-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 2-glycidoxyethyltriethoxysilane. These compounds are also described in DE-A 3 126 662.
  • these coating compositions can contain further acrylate compounds, in particular hydroxyacrylates.
  • Other 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, diethylene glycol , 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-A 3 126 662.
  • 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 dibenzyl-resorcinol derivatives. Further coating compositions based on silyl acrylates and silica sol are described in US Pat. Nos. 5,468,789, 5,466,491, 5,318,850, 5,242,719 and 4,455,205.
  • 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.
  • Such coating compositions are described, for example, in WO 98/51747, WO 00/14149, DE-A 197 46 885, US-A 5 716 697 and WO 98/04604.
  • 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
  • Ri C ⁇ -Cg alkyl or Cg-C 14 aryl, preferably methyl or ethyl,
  • R2 is hydrogen, alkyl or aryl when b is 1, or alkyl or aryl when b is 2 or 3, and
  • R3 is alkyl or aryl, preferably methyl.
  • Examples of compounds of the formula (II) are: cyclo- ⁇ OSiCH 3 [(CH2) 2Si (OH) (CH3) 2] ⁇ 4, cyclo- ⁇ OS ⁇ CH3 [(CH2) 2Si (OCH3) (CH 3 ) 2 ] ⁇ 4, cyclo- ⁇ OSiCH 3 [(CH2 ) 2Si (OCH3) 2 (CH3)] ⁇ 4, cyclo- ⁇ OSiCH3 [(CH2) 2Si (OC 2 H5) (CH 3 )] ⁇ 4; cyclo- ⁇ OSiCH3 [(CH2) 2Si (OC 2 H5) 3] ⁇ 4.
  • 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 1 -C alcohols, in particular methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, tert-butanol, n-pentanol, i-pentanol, n-hexanol, n-octanol and n-butoxy ethanol.
  • Ci .g-Glycol ether, in particular n-butoxy ethanol are also preferred. Isopropanol, butanol, ethanol and / or water are particularly suitable as solvents.
  • compositions may further contain conventional additives such as e.g. 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 0.01 to 3% by weight.
  • the coating composition thus produced can be used for coating different substrates.
  • the choice of substrate materials for coating is not limited.
  • the 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 are described.
  • the compositions are particularly suitable for coating transparent thermoplastics and preferably polycarbonates. In particular injection molded parts, foils, glasses, optical lenses, automotive discs and plates can be coated with the compositions obtained according to the invention.
  • the application to the substrate is preferably carried out by Stodard inspection methods such as Dipping, flooding, brushing, brushing, knife coating, rolling, spraying, falling film application, spin coating and spinning.
  • the coating agent can only be dried on the substrate or, if necessary after prior drying, the coated substrate is cured at room temperature.
  • the curing preferably takes place thermally at temperatures in the range from> 20 to 200 ° C., in particular 70 to 180 ° C. and particularly preferably 90 to 150 ° C. Under these conditions, the curing time should be 15 to 200 minutes, preferably 45 to 120 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.
  • curing can also be carried out by irradiation, which may be followed by thermal post-curing.
  • the coating compositions according to the invention are particularly suitable for the production of cover layers (DE) in scratch-resistant coating systems.
  • top layers (DE) based on hydrolyzable silanes with epoxy groups are suitable for application to scratch-resistant layers (K).
  • Preferred cover layers 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 epoxy 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.
  • Covering layers (DE) are preferably those which contain a coating composition
  • Such coating compositions result in highly scratch-resistant coatings that adhere particularly well to the material.
  • the silicon compound (A) is preferably 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-hydrolysable residues has an epoxy group.
  • hydrolyzable radicals examples include halogen (F, Cl, Br and I, in particular Cl and Br), alkoxy (in particular C 1.4 alkoxy such as, for example, methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy, i-butoxy , sec-butoxy and tert-butoxy), aryloxy (especially Cg.i o-aryloxy, for example phenoxy), acyloxy (in particular C ⁇ _4-acyloxy, such as acetoxy and propionyloxy) and acylcarbonyl (eg acetyl).
  • Particularly preferred hydrolyzable radicals are alkoxy groups, especially methoxy and ethoxy.
  • non-hydrolyzable radicals without an epoxy group are hydrogen, alkyl, especially C1.4-alkyl (such as methyl, ethyl, propyl and butyl), alkenyl (especially C2.4-alkenyl such as vinyl, 1-propenyl, 2-propenyl) and butenyl), alkynyl (in particular Cg.i Q-aryl such as phenyl and naphthyl), the groups just mentioned optionally having one or more substituents such as Halogen and alkoxy may have.
  • 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 be found, for example, on pages 8 and 9 of EP-A 0 195 493. 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 1.4 alkoxy and particular methoxy and ethoxy) and R 'represents a glycidyl or glycidyloxy (C ⁇ _2 ⁇ ) alkylene radical, in particular ß-glycidyl-oxyethyl-, ⁇ -glycidyloxypropyl, ⁇ -glycidyl-oxybutyl-, ⁇ -glycidyloxylpentyl-, co-glycidyloxy-hexyl-, ⁇ -glycidyloxyoctyl-, ⁇ -glycidyloxynonyl, ⁇ -glycidyloxydoxydyloxydoxydyl - (3, 4-epoxycyclohexyl) ethyl.
  • GPTS ⁇ -glycidyloxypropyltrimethoxysilane
  • the particulate materials (B) are preferably an oxide, oxide hydrate, 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, SiO 2, CeO 2, ZnO, 2O3 and TiO 2. Nanoscale boehmite particles are particularly preferred.
  • the particulate materials are commercially available in the form of powders and the manufacture of (acid stabilized) sols therefrom is also known in the art. In addition, reference can be made to the manufacturing examples given below.
  • the principle of stabilizing nanoscale titanium nitride using guanidine propionic acid is e.g. described in DE-A 43 34 639.
  • the variation of the nanoscale particles is usually accompanied by a variation in the refractive index of the corresponding materials.
  • the replacement of boehmite particles by CeO2, ZrO2 or TiO2 particles leads to materials with higher refractive indices, the refractive index according to the Lorentz-Lorenz equation additively results from the volume of the high refractive index component and the matrix.
  • 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 an amount of 0.2 to 1.2 moles based on 1 mole of silicon compound (A).
  • 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 (I)
  • Al represents +3 , B +3 or (VO) +3 ,
  • R represents a hydrolyzable radical
  • R ' represents a non-hydrolyzable residue
  • M (case b)) can be 1 to 3. If several radicals R and / or R 'are present in a compound (C), these can in each case be the same or different. 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 Cl and Br), alkoxy (in particular O4 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy and n-butoxy, i-butoxy, sec-butoxy or tert-butoxy), aryloxy (in particular Cg-I Q- aryloxy, for example phenoxy), acyloxy (in particular Ci. 4-acyloxy such as acetoxy and propionyloxy) and alkylcarbonyl (eg acetyl).
  • Particularly preferred hydrolyzable radicals are alkoxy groups, especially methoxy and ethoxy.
  • non-hydrolyzable radicals are hydrogen, alkyl, in particular Cl ⁇ _4-alkyl (such as methyl, ethyl, propyl and n-butyl, i-butyl, sec-butyl and tert-butyl), alkenyl (especially C2_4-alkenyl such as Vinyl, 1-propenyl, 2-propenyl and butenyl), alkynyl (especially C2.4-alkynyl such as acetylenyl and propargyl) and aryl (especially Cg.i Q- aryl such as phenyl and naphthyl), the groups just mentioned may optionally have one or more 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
  • CH 2 CH-Si (OC 2 H 4 OCH 3 ) 3
  • CH 2 CH-CH 2 -Si (OCH 3 ) 3
  • CH 2 CH-CH2-Si (OC 2 H5) 3
  • CH 2 CH-CH 2 -Si (OOCCH 3 ) 3
  • CH2 C (CH 3 ) -COO-C 3 H 7 -Si (OCH 3 ) 3,
  • these compounds (C), in particular the silicon compounds), can also have non-hydrolyzable radicals which have a C-C double or C-C triple bond.
  • monomers preferably epoxy or hydroxyl group-containing
  • 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, polysiloxanes, etc., 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 preferably a compound of Ti, Zr or Al of the following general formula
  • M stands for Ti, Zr or AI and
  • radicals R '" can be the same or different and stand for a hydrolyzable group
  • hydrolyzable groups examples include halogen (F, Cl, Br and I, in particular Cl and
  • alkoxy especially C1.g-alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy and n-
  • M is particularly preferred aluminum and R '"ethanolate, sec-butanolate, n-propanolate, n-butoxy, n-propoxy, 2-propoxy, ethoxy and / or methoxyethanolate.
  • compound (D) is preferably used in an amount of 01 to 0.7 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) can be used with at least one non-hydrolyzable radical which has 5 to 30 fluorine atoms bonded directly to carbon atoms, the 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 top layer (DE) 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, together with the compound (C), using an acid catalyst (preferably at room temperature) in aqueous
  • Prehydrolyzed solution preferably about X A moles of water per mole of hydrolyzable
  • 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. Hydrochloric acid is preferably used for acidification. When 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 obtained 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 approximately 28 to 35 ° C., preferably approximately 30 to 32 ° C., 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 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 optionally the Lewis base (E) are also preferably added slowly after the addition of the first portion of the material (D) 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.
  • solvents or solvent mixtures can optionally be added at any stage of production.
  • These solvents are preferably the solvents already described at the beginning for the scratch-resistant coating composition.
  • Preferred solvents are water, alkoxy alcohols and / or alcohols, especially water.
  • the top layer compositions can contain the usual additives already described at the beginning for the scratch-resistant layer composition.
  • the application and hardening of the top layer composition is preferably carried out 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 240, preferably less than 180, in particular less than 120 minutes. If additional photoinitiators are used, curing can also be carried out by irradiation, which may be followed by thermal curing.
  • the layer thickness of the hardened cover layer (DE) should be 0.1 to 30 ⁇ m, preferably 0.5 to 10 ⁇ m and in particular 1.0 to 6 ⁇ m.
  • the invention also includes a layer system
  • the application to the substrate is preferably 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.
  • standard coating methods such as e.g. Dipping, flooding, brushing, brushing, knife coating, rolling, spraying, falling film application, spin coating and spinning.
  • the layer systems according to the invention can be produced by a method which comprises at least the following steps:
  • the scratch-resistant layer (K) only dries on after application or additionally thermally at temperatures in the range from> 20 to 200 ° C., in particular 70 to 180 ° C. and particularly preferably 90 to 150 ° C is dried. Under these conditions, the curing time should be 15 to 200 minutes, preferably 45 to 120 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. In the presence of unsaturated compounds, curing can also be carried out by irradiation, which may be followed by thermal post-curing.
  • the scratch-resistant coating agent contains leveling agents in an amount of 0.01 to 3% by weight.
  • the hardened or, in particular, fully hardened scratch-resistant layer (K) is activated before the top layer coating agent is applied.
  • Corona treatment, flame treatment, plasma treatment or chemical etching are preferred as activation processes. Flame treatment, normal pressure plasma and corona treatment are particularly suitable.
  • 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.
  • Aluminum tributoxyethanolate was then added dropwise via a dropping funnel.
  • Boehmite dispersion added under thermostatic cooling. After stirring for 15 minutes at room temperature, the cerium dioxide dispersion from Rhodia GmbH in Frankfurt / Main and
  • Test pieces were produced with the coating agents obtained as follows:
  • the primer solution (example 2) is only dried on.
  • the primed polycarbonate sheets were then flooded with the basecoat coating agent (example 1 or 3) (variant A).
  • 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 minutes and then cooled to room temperature.
  • top layer coating composition (example 4, 5 and 6) diluted with water and 2-propanol was also applied by flooding.
  • the wet film was flashed off at 23 ° C for 30 minutes and the plates were then heated at 130 ° C for 120 minutes.
  • a further variant (B) consists in that the plates, flooded with the scratch-resistant coating agent Examples 1, 2 and 3, are dried for one hour for 60 minutes at 21 ° C. and 39% relative atmospheric humidity and these dust-dry plates are dried directly with the diluted top layer coating agent Example 6 is also overcoated by flooding (wet on wet process). The wet film was flashed off at 21 ° C. and 39% atmospheric humidity for 30 minutes and the plates were then heated at 130 ° C. for 120 minutes.
  • the primer step is omitted.
  • the polycarbonate sheets are flooded with the coating agent of Example 3 directly after cleaning with isopropanol.
  • the other conditions are analog.
  • a surface activation of the hardened basecoat layer by flame treatment, corona or normal pressure plasma treatment, brushing or chemical etching etc. has proven to be particularly favorable for improving the adhesion and the course of the top layer coating agent.
  • the coated plates were stored for two days at room temperature and then subjected to the following defined tests.
  • the lacquered panels are cross-cut according to EN IS 2409: 1994 and stored in water at 65 ° C.
  • the storage time (days) from which the first loss of liability occurs in the tape test from 0 to 2 is recorded.
  • Table 1 shows the application parameters, the wear (Taber values) and adhesion properties when the layer systems are stored in water, depending on the scratch-resistant layer (K) with and without a top layer.
  • Table 2 shows the wear properties (Taber values) depending on the scratch-resistant layer (K), the lacquer application, the activation process and the top layer (D).
  • Table 3 shows the wear properties of commercially available scratch-resistant polycarbonate sheets which, after activation by flame treatment or corona treatment, were treated with the topcoat of the invention.
  • the topcoat is not liable for activation.
  • the Taber value of the Lexan-Margard® MR5E sheet without topcoat used was 15.1%.
  • Lexan Margard® MR 5 E is a transparent, UV-resistant and abrasion-resistant material for flat glazing
  • the plate has a double tempered surface.

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Abstract

La présente invention concerne un système stratifié comprenant un substrat (S), une couche anti-rayures (K) et une couche de protection (DE) ainsi qu'un procédé de fabrication dudit système stratifié.
EP03810971A 2002-11-12 2003-11-06 Systeme stratifie, composition de revetement et procede de production de ladite composition Withdrawn EP1565768A1 (fr)

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DE10252421A DE10252421A1 (de) 2002-11-12 2002-11-12 Beschichtungszusammensetzung und Verfahren zu deren Herstellung
DE10252421 2002-11-12
PCT/EP2003/012391 WO2004044627A1 (fr) 2002-11-12 2003-11-06 Systeme stratifie, composition de revetement et procede de production de ladite composition

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JP (1) JP2006505432A (fr)
KR (1) KR20050086508A (fr)
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JP5038893B2 (ja) * 2005-06-21 2012-10-03 日本板硝子株式会社 透明物品およびその製造方法
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ATE549097T1 (de) * 2007-05-01 2012-03-15 Exatec Llc Verfahren für einheitliche wetterbeständigkeit einer beschichtung
WO2009004986A1 (fr) * 2007-07-02 2009-01-08 Nitto Kasei Co., Ltd. Catalyseur de durcissement pour polymère organique et composition durcissable sous l'action de l'humidité contenant ce catalyseur
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JP5177809B2 (ja) * 2007-07-02 2013-04-10 日東化成株式会社 有機重合体用硬化触媒及びそれを含有する湿気硬化型組成物
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AU2003276262A1 (en) 2004-06-03
DE10252421A1 (de) 2004-05-19
JP2006505432A (ja) 2006-02-16
CN1711485A (zh) 2005-12-21
US20040126573A1 (en) 2004-07-01
KR20050086508A (ko) 2005-08-30
TW200418908A (en) 2004-10-01

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