EP1446455A2 - Scratch-resistant coating method for optical storage media - Google Patents

Scratch-resistant coating method for optical storage media

Info

Publication number
EP1446455A2
EP1446455A2 EP02801907A EP02801907A EP1446455A2 EP 1446455 A2 EP1446455 A2 EP 1446455A2 EP 02801907 A EP02801907 A EP 02801907A EP 02801907 A EP02801907 A EP 02801907A EP 1446455 A2 EP1446455 A2 EP 1446455A2
Authority
EP
European Patent Office
Prior art keywords
coating
optical data
radiation
acrylate
dvd
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Withdrawn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
EP02801907A
Other languages
German (de)
French (fr)
Inventor
Helmut Steinberger
Rainer Vesper
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
Momentive Performance Materials GmbH
Original Assignee
GE Bayer Silicones GmbH and Co KG
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 GE Bayer Silicones GmbH and Co KG, Bayer MaterialScience AG filed Critical GE Bayer Silicones GmbH and Co KG
Publication of EP1446455A2 publication Critical patent/EP1446455A2/en
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins
    • G11B7/2545—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins containing inorganic fillers, e.g. particles or fibres

Definitions

  • the invention relates to a method for transparent scratch-resistant coating of optical data carrier and data recording materials.
  • Optical data recording materials have recently come into increasing use as a variable recording and / or archiving medium for large amounts of data.
  • the recording materials are subject to a localized change in the optical properties, such as the absorption maximum, the light reflection properties or the extinction coefficient, when they are exposed to radiation, for example from a laser beam.
  • the local change can be used to record information.
  • Fault compensation software can compensate for such reading errors caused by surface defects to a certain extent, but it is known that they are not suitable for the compensation of larger surface defects.
  • thermoplastic materials such as polycarbonate, polymethyl methacrylate and chemical modifications thereof are typically used for optical storage media. These thermoplastics have excellent mechanical stability against dimensional changes, have high transparency and impact resistance, but also a certain sensitivity to scratches. As a result, polycarbonate substrates are sensitive against destruction by scratches, wear and mechanical erosion. The known scratch sensitivity of the recording substrates used made it worthwhile to look for technical processes which in particular reduce this sensitivity on the reading side.
  • the transparent, scratch-resistant coating has to meet a number of requirements with regard to applicability, curing speed, its technical properties and last but not least its optical and electrical properties.
  • methods for applying certain coating materials have hitherto been proposed, which give the substrate a certain protection against scratching.
  • These coating materials consist of a UV or electron beam curable acrylate binder which can optionally be mixed with a slip additive and / or other additives and which is optionally applied to the substrate with a layer thickness of 0.004 to 10 microns by the centrifugal casting coating method.
  • the coating materials shown there provide some protection against scratching; however, these systems have so far not been able to establish themselves due to an insufficient protection effect. Furthermore, the systems described tend, after weathering, i.e. Storage under certain climatic conditions, becoming cloudy or reducing or losing their adhesion to the substrate.
  • the object of the present invention is to provide an economically producible, scratch-resistant coating which adheres to the substrate surface on the reading side of optical storage media and which, on account of its film hardness, protects the substrate surface from mechanical scratching after curing and which protects against external environmental influences under the term "weathering" (so-called . climate test) is stable and does not have any disadvantages of a technical nature such as, for example, increasing birefringence, signal attenuation, or bending of the panes, discoloration or clouding of the surface, changes in legibility or writeability by a focused laser beam.
  • the known systems based on organic photocurable acrylates provide coatings with a layer thickness of between 7 and 12 microns, which shrink strongly during curing and distort the polycarbonate plate as shrinkage occurs, with the result that the information carriers are not playable or writable / readable.
  • the acrylate resin compositions used according to the invention contain alkoxysilylacrylate-modified metal oxides, which are formed by reacting hydrolysis products of alkoxysilylacrylates with metal oxides.
  • the present invention thus provides optical data storage devices which are provided with a coating which is obtained by radiation curing a radiation-curable coating composition which comprises at least one colloidal metal oxide, at least one hydrolysis product of at least one alkoxysilyl acrylate, at least one acrylate monomer and at least one photoinitiator.
  • the radiation-curable coating agents appropriately contain:
  • (D) Q 01% to 15% by weight of at least one photoinitiator, based on the total mass of the coating composition.
  • Colloidal metal oxides (A) suitably include: silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide and zinc oxide.
  • colloidal silicon dioxide is preferred.
  • the colloidal metal oxides are advantageously used as a dispersion of submicron metal oxide particles in an aqueous and / or organic solvent medium.
  • Such colloidal dispersions of metal oxide particles can be obtained either by hydrolysis of the corresponding metal alkoxides or, starting from aqueous solutions of the corresponding alkali metalates, by removing the alkali metal ions with the aid of ion exchangers.
  • colloidal aqueous or alcoholic-aqueous dispersions of the metal oxides with a particle size distribution between 1 and 1000 nm are obtained.
  • the particle sizes should preferably not exceed 100 nm.
  • a typical particle size distribution of the silicon dioxide particles is between 5 and 40 nm.
  • the particle size distribution can be determined either by means of scanning electron microscopy by optical measurement of a counted number of particles or by electronic counting devices (e.g. Coulter-Multisizer. 3, Beckman Coultert Inc. or Laser Diffraction Sizer CDA 500, Malvern Instruments, Ltd. UK). In the case of very small particles ( ⁇ 100 nm), the use of zeta civers for measuring particle sizes has proven to be the most accurate method.
  • the metal oxides in particular the SiO 2 particles, contain tetrafunctional (Q) metal or silicon atoms and deliver the hardness into the coating compositions. These colloidal metal oxides have hydroxyl functions on their surface in the sol state.
  • Dispersions of colloidal silicon dioxide can be obtained, for example, from various manufacturers such as DuPont, Nalco Chemical Company or Bayer AG. Colloidal dispersions of silicon dioxide are available in either acidic or alkaline form. The acidic form is preferably used for the production of the coating materials, since these provide better properties of the coatings than the alkaline forms.
  • Naicoag 1034A.RTM. is an example of a colloidal silica with satisfactory properties. It contains approx. 34% by weight of SiO 2 . In the examples, the values given also include the water content. Thus, for example, 520 grams represent Naicoag 1034A.RTM. about 177 grams of SiO 2 .
  • the coating compositions according to the invention preferably contain 1 to 60% by weight of colloidal metal oxides, particularly preferably 5 to 40% by weight, in each case based on the total amount of the coating composition.
  • Component (B) used according to the invention is preferably a hydrolysis product of a silyl acrylate of the general formula (I):
  • a is an integer from 0 to 2, preferably 0,
  • b is an integer from 1 to 3, preferably 1, and
  • the sum of a + b is 1 to 3, preferably 1.
  • the straight-chain or branched alkyl radical having 1 to 8 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, etc.
  • R Preferred radicals for R are methyl, ethyl, propyl, cyclohexyl, hexyl, octyl, isopropyl and isobutyl.
  • the alkyl radicals are preferred.
  • R particularly preferably represents methyl and ethyl.
  • the optionally substituted aryl radical having 6 to 10 carbon atoms includes, for example, phenyl or naphthyl radicals which can be substituted by one or more, preferably one to three, substituents selected from the group of alkyl groups having 1 to 6 carbon atoms and
  • Halogen atoms such as fluorine, chlorine, bromine or iodine are selected, e.g.
  • a preferred aryl radical for R is phenyl.
  • R 1 in general formula (I) represents hydrogen, a straight-chain or branched alkyl radical with 1 to 8 carbon atoms, a cycloalkyl radical with 3 to 8 carbon atoms or an optionally substituted aryl radical with 6 to 10 carbon atoms in the aryl part, and when a plurality of groups R 1 is present (a + b> 1) these can be the same or different from one another.
  • R 1 in general formula (I) represents hydrogen, a straight-chain or branched alkyl radical with 1 to 8 carbon atoms, a cycloalkyl radical with 3 to 8 carbon atoms or an optionally substituted aryl radical with 6 to 10 carbon atoms in the aryl part, and when a plurality of groups R 1 is present (a + b> 1) these can be the same or different from one another.
  • R 1 in general formula (I) represents hydrogen, a straight-chain or branched alkyl radical with 1 to 8 carbon atoms, a cycloalky
  • R 1 is preferably methyl or ethyl.
  • R 2 in the general formula (I) represents hydrogen, a straight-chain or branched alkyl radical having 1 to 8 carbon atoms or an optionally substituted aryl radical having 6 to 10 carbon atoms, and the groups R 2 can be identical or different from one another.
  • R 2 is preferably hydrogen and / or methyl, and in particular the carbon atom adjacent to the carbonyl carbon atom can also carry a methyl group as R 2 (methacrylates).
  • the substituents R 2 are therefore preferably all hydrogen, and the substituent R 2 which is located on the carbon atom in the vicinity of the carbonyl carbon atom can also be methyl.
  • R 3 in the general formula (I) represents a single bond or a straight-chain or branched, optionally substituted alkylene radical (alkanediyl radical) having 1 to 8 carbon atoms in the alkylene radical or an optionally substituted arylene radical (aryldiyl radical) having 6 to 10 carbon atoms in the arylene radical the alkylene radical is preferably substituted with one to three, more preferably one, substituent selected from the group consisting of halogen and hydroxy.
  • the arylene radical is preferably substituted by one to three, more preferably one radical which is selected from the group of alkyl groups having 1 to 6 carbon atoms, halogen atoms, such as fluorine, chlorine, bromine or iodine, and hydroxy.
  • R 3 include:
  • Linear alkylene residues such as methylene, ethylene, trimethylene, tetramethylene, etc., preferably unbranched residues, optionally branched halogenated alkylene residues with 2 to 8 carbon atoms, optionally branched hydroxylated alkylene residues with 2 to 8 carbon atoms, arylene radicals with 6 to 10 carbon atoms e.g. phenylene (1 , 2-, 1, 3- and 1,4-phenylene), tolylene, naphthylene, etc., halogenated arylene radicals having 6 to 10 carbon atoms in the arylene part, etc.
  • R 3 is a single bond, methylene or ethylene.
  • the silyl acrylates of the general formula (I) used according to the invention are known per se and are described, for example, in US Pat. No. 4,491,508, to which reference is made in this respect.
  • silyl acrylates of the formula (I) preferably contain acrylate or methacrylate compounds, such as:
  • CH 2 CCH 3 CO 2 - CH 2 -Si (OCH 2 CH3) 3
  • CH 2 CCH 3 CO 2 - CH 2 -Si (OCH 3 ) 3
  • CH 2 CCH 3 CO 2 - CH 2 CH ⁇ Si (OCH 2 CH 3 ) 3
  • CH 2 CCH 3 CO 2 - CH 2 CH ⁇ Si (OCH 3 ) 3 .
  • CH 2 CHCO 2 - CH 2 CH 2 - Si (OCH 2 CH 3 ) 3
  • CH 2 CHCO 2 - CH2CH2 - Si (OCH 3 ) 3
  • CH 2 CCH 3 CO 2 - CH 2 CH 2 CH 2 - Si (OCH 2 CH 3 ) 3
  • CH 2 CCH 3 CO 2 - CH2CH2CH2 - Si (OCH 3 ) 3 .
  • CH 2 CHCO 2 - CH 2 CH 2 CH 2 - Si (OCH 2 CH 3) 3
  • CH 2 CHC ⁇ 2- CH2CH2CH2- Si (OCH 3) 3
  • CH2 CCH 3 CO 2 - CH 2 CH 2 CH 2 CH 2 - Si (OCH2CH 3 ) 3
  • CH 2 CCH 3 CO 2 - CH2CH2CH2CH2 - Si (OCH 3 ) 3
  • CH 2 CHCO 2 - CH 2 CH 2 CH 2 CH 2 - Si (OCH 2 CH 3 ) 3
  • CH 2 CHCO 2 - CH2CH2CH2CH2 - Si (OCH 3 ) 3l etc.
  • hydrolysis products (B) of the alkoxysilyl acrylates, preferably of the formula (I), contained in the coating agent used according to the invention are produced by contacting the alkoxysilyl acrylates with water.
  • alkoxysilyl acrylates These are partially or fully hydrolyzed alkoxysilyl acrylates.
  • the corresponding hydroxysilylacrylates are formed by the hydrolysis and can react with one another and with the hydroxyl groups of the colloidal metal oxides with condensation.
  • the hydrolysis products are believed to react with the colloidal metal oxides to form Si-O-metal bonds.
  • the hydrolysis products of the silyl acrylates can be formed before or during the production of the coating compositions used according to the invention.
  • the amount of material (B) used according to the invention in the coating agent used according to the invention is advantageously 0.1 to 50% by weight, preferably 1 to 15% by weight, in each case based on the total amount of the coating agent.
  • the acrylate monomers (C) used according to the invention preferably have the general formula (II):
  • R represents hydrogen, a straight-chain or branched alkyl radical having 1 to 8 carbon atoms or an optionally substituted aryl radical having 6 to 10 carbon atoms in the aryl part, and the substituents R 4 can be identical or different from one another, and R 5 represents an optionally substituted mono- to hexavalent organic radical.
  • n is preferably an integer from 1 to 4, particularly preferably from 2 to 4.
  • R is preferably hydrogen and / or methyl, where in particular the carbon atom adjacent to the carbonyl carbon atom can also carry a methyl group as R 4 (methacrylates).
  • the substituents R 4 are therefore preferably all hydrogen (acrylates), the substituent R 4 being the methyl (methacrylates) can also be located on the carbon atom in the position adjacent to the carbonyl carbon atom.
  • R 5 includes mono- to hexavalent, preferably di- to tetravalent organic radicals, which can be optionally substituted.
  • the valency corresponds to the number of acrylate groups n.
  • R 5 preferably includes optionally substituted straight-chain or branched aliphatic or aromatic hydrocarbon radicals having 1 to 20, preferably 1 to 10, carbon atoms.
  • divalent radicals reference can be made to the radicals mentioned above for R 3 .
  • R 5 optionally has one to three substituents, such as halogen or hydroxy.
  • the acrylate monomers of formula (II) include mono- and polyfunctional acrylate monomers.
  • Monoacrylates optionally include hydroxy substituted alkyl acrylates and alkyl methacrylates such as e.g. Hydroxyethyl acrylate, etc.
  • the acrylate monomers of the formula (II) are present in the preparations according to the invention in a proportion of at least 5% by weight to 25% by weight, preferably 5 to 10% by weight, in order to ensure increased adhesion to the substrates used ,
  • the coating agent used according to the invention preferably contains at least one acrylate with at least two ethylenically unsaturated groups, optionally in combination with a monofunctional or polyfunctional acrylate.
  • polyfunctional acrylates of formula (II) examples include:
  • the coating agent used according to the invention preferably contains a mixture of two or more polyfunctional acrylate monomers of the formula (II), more preferably a diacrylate and a higher-functionality acrylate.
  • Coating compositions which contain a mixture of diacrylates and higher-functional acrylates advantageously have a weight ratio of diacrylate and higher-functional acrylate of from 0.5: 99 to about 99: 0.5, particularly preferably from 1: 99 to 99: 1.
  • a mixture a di- and a tri-acrylate of the general formula (II) can be used.
  • Exemplary mixtures of diacrylate and polyfunctional acrylate include hexanediol diacrylate with trimethylolpropane triacrylate (TMPTA), hexanediol diacrylate with pentaerythritol tetraacrylate, diethylene glycol diacrylate with pentaerythritol triacrylate and diethylene glycol diacrylate
  • Trimethylolpropane Coating agents which contain two polyfunctional acrylate monomers of the formula (II) are particularly preferred.
  • the amount of the acrylate monomer (C) in the coating agent used according to the invention is advantageously 25 to 90% by weight, preferably 40 to 85% by weight, in each case based on the total amount of the composition.
  • the photocrosslinkable coating compositions used according to the invention contain an amount of at least one photoinitiator (D) required for photosensitization, ie an amount which is suitable for effecting UV photocuring.
  • this required amount is in a range between 0.01 to 15% by weight, preferably 0.1 to 10% by weight, 1 to 8% by weight, more preferably 1.5 to 7% by weight on the sum of all components in the coating composition.
  • Using Larger quantities of photoinitiator give coating agents which harden faster.
  • photoinitiators (D) for example, those mentioned in US Patents 4,491, 508 and 4,455,205 can be used.
  • Photoinitiators such as Methylbenzoyl formate which are suitable for the use according to the invention are available under various trade names.
  • the UV-curing coating compositions used according to the invention preferably consist essentially of components (A) to (D).
  • further additives known per se can be added to the coating compositions used according to the invention in a proportion which does not impair the achievement of the object according to the invention, such as e.g. soluble salts, soaps, amines, non-ionic and anionic surfactants, acids, bases, as well as substances that counteract gelling.
  • Various flow control agents as well as wetting agents, light stabilizers and dyes can also be added.
  • non-acrylic monomers such as N-methylpyrrolidone or styrenes are used like some monoacrylates, for example isobornyl acrylate, phenoxyethyl acrylate or Hydroxyethyl methacrylate both improve the properties of the cured product film by increasing its flexibility and improve its adhesion to the substrate materials. They also reduce the viscosity of the mixture preparation.
  • the UV-curable coating compositions used according to the invention can be produced by mixing components (A) to (D) together and any further components which may be present.
  • the silyl acrylate can be hydrolyzed in the presence of the aqueous colloidal metal oxide and the water-miscible alcohol.
  • the aqueous colloidal metal oxide can be added to the silyl acrylate which has been hydrolyzed in aqueous-alcoholic solution either at room temperature or at the reflux temperature of the solvent used.
  • Suitable solvents include, for example, all water-miscible alcohols and alcohol-solvent azeotropes.
  • solvents examples include isopropyl alcohol, 4-methoxypropanol, n-butanol, 2-butanol, ethanol and similar alcohols.
  • an azeotropic mixture of water and alcohol is distilled off from the formulation. In cases where no alcohol was used in the original hydrolysis mixture, the alcohol required for the azeotropic distillation must be added subsequently in order to completely remove the water contained in the mixture.
  • the present invention further relates to a method for coating optical data carriers such as CD, SuperAudio-CD, CD -R, CD -RW, DVD, DVD-R, DVD-RW and DVR on the reading side.
  • optical data carriers such as CD, SuperAudio-CD, CD -R, CD -RW, DVD, DVD-R, DVD-RW and DVR.
  • CD-ROM data from data not construction
  • DVD-ROM manufacturer can be erased information storage specified analog CD-DA (digital audio)
  • DVD-RW user data storage layer based on writable rewritable - Magneto-Optical
  • CD-DA Compact Disk-Digital Audio
  • CD-ROM Compact Disk - Read Only Memory
  • DVD-ROM Digital Versatile Disk - Read Only Memory
  • CD-R Compact Disk - Recordable
  • DVD-R Digital Versatile Disk - Recordable
  • CD-RW Compact Disk - ReWritable
  • DVD-RW Digital Versatile Disk - ReWritable
  • the optical data storage devices coated according to the invention generally consist of transparent thermoplastics such as polycarbonate based on bisphenol-A (BPA-PC), polycarbonate based on trimethyl-cyclohexyl Bisphenol polycarbonate (TMC-PC), fluorenyl polycarbonate,
  • BPA-PC bisphenol-A
  • TMC-PC trimethyl-cyclohexyl Bisphenol polycarbonate
  • fluorenyl polycarbonate fluorenyl polycarbonate
  • the UV-curable coating agents are expediently applied to the individual panes when coating disk-shaped optical data carriers, such as CD, DVD and DV-R, and then cured by the action of UV rays.
  • disk-shaped optical data carriers such as CD, DVD and DV-R
  • the disc which is either kept in a dust-free chamber within a production line or, if it was manufactured in a preceding step, after pretreatment with deionized air, in a centrifugal casting chamber with the amount of the coating material required for the process in the form of a liquid ring or coated in a spiral and then distributed evenly on the substrate surface within 1, 0 to 10 seconds by increasing the number of rotations of the substrate to revolutions of 1000 to 10000 per minute and the excess is thrown off. It is possible to design the spinning process using a speed program so that the radial layer thickness distribution is largely constant.
  • This process creates a uniform liquid film on the substrate surface with a layer thickness between 0.001 and 100 microns.
  • the layer thickness that can be achieved depends on the rheological properties of the coating material, such as the viscosity, the number of revolutions of the spin plate and the duration of exposure to high numbers of revolutions during the spinning process.
  • the uncured film on the surface of the substrate should immediately after spinning with the help of a suitable type of radiation such as UV or Electron beams are cured, but preferably by ultraviolet radiation; expedient at room temperature up to about 45 ° Celsius.
  • Suitable UV radiation sources are, for example, unpulsed radiation sources. Pulsed radiation sources are not used here in the practice of UV radiation curing.
  • electron radiation (EB) can be used for curing radiation-crosslinkable coating materials, but in practice EB curing devices have proven to be too large or too slow in terms of process time.
  • the radiation power of the UV lamps used in the system used is variable from 1000 to 20,000 watts, preferably approx. 1600 to 2200 watts (for CD, CD-R, CD-RW and DVD).
  • the UV lamp used (manufacturer: Singulus; type: 200 BTZ / DF) is a high-pressure mercury lamp with a variable power consumption from 1000 to 20000 watt h.
  • other standard mercury lamps can also be used if they deliver a corresponding output in the curing-relevant UV range (250 to 400 nm, but preferably in the range from 360 to 380 nm).
  • the thickness of the resulting hardened coating should preferably be at most 100 microns in order to ensure adequate hardening. Higher layer thicknesses can lead to deformation (dishing) of the optical data carriers due to shrinkage during hardening, so that they can no longer be read or written. Preferred layer thicknesses are in a range between 100 and 1 micron. Particularly preferred layer thicknesses are in a range between 10 and 3 microns.
  • the coating agent used according to the invention generally represents the outer layer of the writing and reading side, ie the side of the coated side optical data carrier, which the laser beam penetrates ,. However, it can also be used both for coating the writing and reading side and for coating the opposite side.
  • the coatings produced according to the invention offer a number of advantages over the prior art.
  • the coatings produced according to the invention also have improved hardness and scratch resistance compared to the coatings used in the prior art.
  • the coatings produced according to the invention in the case of the CD or DVD either cause no “electronic noise” or no additional errors which can have a negative effect on the reading accuracy or the writeability.
  • the coated CD or DVD is stored under certain artificially set climatic conditions (temperature: 70 ° Celsius; relative humidity: 50%; storage time: 96 hours; in a more stringent variant of these tests, the CD or DVD is stored under other conditions: Temperature: 80 ° Celsus; relative humidity: 95%, storage time: 96 hours; in a further tightened variant of this test the CD or DVD are stored under different conditions: temperature: 70 ° Celsius; relative humidity: 90%; Storage time: 500 hours).
  • the CD or DVD is left in a standard atmosphere for 24 hours and the deviation from the planarity is then measured.
  • the condition of the coating is also examined by eye. No spots with peeling of the coating may be visible.
  • the cross-cut test checks the adhesion of the coating before and after the climatic test.
  • the above-mentioned cross-cut test is carried out by making parallel incisions in the CD / DVD material with the aid of a multiple knife. The disc is then rotated 90 ° and the operation repeated. This creates a cross-hatch pattern with 1 mm 2 patterns on the coating.
  • the cross cut is briefly covered with an adhesive tape, for example of the type 3M Scotch 710, and the tape is then pulled off.
  • a sample does not pass the cross-cut test if one of the squares produced is detached from the substrate by the adhesive tape. This experiment is repeated three times for each sample.
  • the scratch resistance is determined using the pencil hardness method and the “Taber
  • Abrader "method determined.
  • the Taber Abrader Test uses round disks with a hole in the middle.
  • the Taber Abrader is equipped with CS-1 OF wheels that are reconditioned every 500 cycles by running them on an S-111 disc for 15 cycles.
  • the weights used are 500 g.
  • the turbidity is measured at 4 points of future abrasion using a GARDNER turbidity meter.
  • the sample is abraded over a certain number of cycles and cleaned of adhering particles.
  • the turbidity difference is determined from the turbidity value determined using the same procedure minus the initial turbidity as delta haze. Each measurement is carried out on 5 samples.
  • a mixture of 50 parts t-butanol, 16.6 parts Naicoag 1034A, a product of the Nalco Company, Oak Brook, Illinois and 1 part gamma methacryloxypropyltrimethoxysilane (MAPTMS) was heated to reflux for 5 minutes. After cooling to room temperature, 13.2 parts of a 1: 1 mixture of hexanediol diacrylate and trimethylolpropane triacrylate were added. The solvent was then distilled off under reduced pressure. After about half of the solvent was distilled off, an additional 30 parts of t-butanol were added. All of the solvent and water were distilled off. A clear solution was obtained. 1.5 parts of alpha, alpha-diethoxyacetophenone were added to 100 parts of this solution.
  • the UV-curable coating agent obtained in this way was coated in an automatic coating system from STEAG-Hamatech, type DVD-R2500, on CD-R disks which come from its own production, coated and for 2 seconds at 2200 watt / h power consumption the UV lamp hardened.
  • the properties of the coating obtained are shown in Table 1.
  • the application to the substrate was carried out under the same conditions as when the lacquers according to the invention were applied.
  • the spin coater was spun off at 3000 rpm for 2 seconds. A layer thickness of 8.5 microns ( ⁇ m) was obtained.
  • Example 4 comparative example
  • a varnish specially recommended for CD coating (type: Daicure Clear SD-715, manufacturer: Dainippon Ink & Chemicals, Inc., Japan) was applied to CD-R in the manner shown in Example 3. After curing, measured a layer thickness of 5 microns ( ⁇ m).
  • Table 2 shows the electrical properties and the climate resistance of the coated substrates.
  • BLER Block Error Rate; Change from uncoated product; Correction units / sec required for reading correction.
  • BLER is given as the rate of errors per second.
  • the specification limit is 220 errors per second, whereby a specification of 50 errors per second as the maximum average value and 100 errors per second as the maximum peak value is recommended for CD-ROM.
  • BLER is critical in that the number of errors that occur should be kept as low as possible to ensure data integrity.
  • Radial Noise (RN) measured track change according to ISO / IEC 10 149, has a limit of 30 nanometers within a bandwidth of 500 to 2500 Hz. RN occurs when the track is damaged. At high RN peaks, the servo control can skip tracks. A high average RN level is an indication of poorly defined pits.
  • Deviation (DEV) deviation (height) measured in angular degrees (°) from the plane from the view of the metallized top.
  • DEV deviation (height) measured in angular degrees (°) from the plane from the view of the metallized top.
  • DEV is measured on 10 different diameters, distributed over the disk surface. It results from the angle between the center of the disc and the surface of the disc that deviates from the plane.
  • the specification for the DEV allows a height deviation of +/- 0.5 mm to the plane for both recorded and unrecorded CD-Rs. Excessive values for the deviation cause problems with the focusing and thus the loss of the RF signal.

Abstract

The invention relates to optical data storage media which are provided with a coating and which are obtained by radiation curing of a radiation-curable covering material comprising at least one colloidal metal oxide, at least one hydrolysis product of at least one alkoxy silyl acrylate, at least one acrylate monomer and, optionally, at least one UN photoinitiator. The invention also relates to a method for the production thereof.

Description

VERFAHREN ZUR KRATZFESTBESCHICHTUNG VON OPTISCHEN SPEICHERMEDIENMETHOD FOR THE SCRATCH-PROOF COATING OF OPTICAL STORAGE MEDIA
Gegenstand der Erfindung ist ein Verfahren zur transparenten Kratzfestbeschichtung von optischen Datenträger- und Datenaufzeichnungsmaterialien.The invention relates to a method for transparent scratch-resistant coating of optical data carrier and data recording materials.
Hintergrund der ErfindungBackground of the Invention
Optische Datenaufzeichnungsmaterialien sind in der letzten Zeit in wachsendem Maße als ein variables Aufzeichnungs- und/oder Archivierungsmedium für große Datenmengen in Gebrauch gekommen. In diesen Aufzeichnungsmedien sind die Aufzeichnungsmaterialien einem örtlich begrenzten Wechsel der optischen Eigenschaften unterworfen wie dem Absorptionsmaximum, der Lichtreflexionseigenschaften oder dem Extinktionskoeffizienten, wenn diese der Strahlung zum Beispiel eines Laserstrahls ausgesetzt sind. Die örtliche Veränderung kann zur Informationsaufzeichnung nutzbar gemacht werden.Optical data recording materials have recently come into increasing use as a variable recording and / or archiving medium for large amounts of data. In these recording media, the recording materials are subject to a localized change in the optical properties, such as the absorption maximum, the light reflection properties or the extinction coefficient, when they are exposed to radiation, for example from a laser beam. The local change can be used to record information.
Da aber auch Kratzer auf der Leseseite des optischen Datenträgers für den Leselaser eine örtliche Veränderung darstellt, führen diese zu Falschinformationen und damit zu Störungen des Einleseprozesses. Fehlerkompensationssoftware kann solche durch Oberflächenstörungen verursachten Einlesefehler zwar bis zu einem bestimmten Umfang ausgleichen, sind aber für die Kompensation stärkerer Oberflächenstörungen bekanntlich nicht geeignet.However, since scratches on the reading side of the optical data carrier represent a local change for the reading laser, this leads to incorrect information and thus to disturbances in the reading process. Fault compensation software can compensate for such reading errors caused by surface defects to a certain extent, but it is known that they are not suitable for the compensation of larger surface defects.
Für optische Speichermedien werden typischerweise transparente thermoplastische Kunststoffe eingesetzt wie zum Beispiel Polycarbonat, Polymethylmethacrylat und chemische Modifikationen hiervon. Diese thermoplastischen Kunststoffe verfügen über eine ausgezeichnete mechanische Stabilität gegenüber Dimensionsveränderungen, haben eine hohe Transparenz und Schlagzähigkeit, jedoch auch eine gewisse Empfindlichkeit gegenüber Verkratzungen. Dem zufolge sind Polycarbonatsubstrate empfindlich gegen Zerstörung durch Kratzer, Abnutzung und mechanische Erosion. Die bekannte Kratzempfindlichkeit der verwendeten Aufzeichnungssubstrate machte es sinnvoll, nach technischen Verfahren zu suchen, die insbesondere diese Empfindlichkeit auf der Leseseite reduziert.Transparent thermoplastic materials such as polycarbonate, polymethyl methacrylate and chemical modifications thereof are typically used for optical storage media. These thermoplastics have excellent mechanical stability against dimensional changes, have high transparency and impact resistance, but also a certain sensitivity to scratches. As a result, polycarbonate substrates are sensitive against destruction by scratches, wear and mechanical erosion. The known scratch sensitivity of the recording substrates used made it worthwhile to look for technical processes which in particular reduce this sensitivity on the reading side.
Um das Substrat vor physikalischer Abnutzung zu schützen, ist es vorteilhaft, einen Überzug, bestehend aus einem kratzfesten Material, auf das Substratmaterial aufzubringen. Dabei hat der transparente, kratzfeste Überzug eine Reihe von Anforderungen in Bezug auf die Applizierbarkeit, die Aushärtungsgeschwindigkeit, seine technischen Eigenschaften und nicht zuletzt seine optischen und elektrischen Eigenschaften zu erfüllen. Hierzu wurden bisher Verfahren zum Auftrag bestimmter Beschichtungsmaterialien vorgeschlagen, die für das Substrat einen gewissen Schutz vor Verkratzung ergaben.In order to protect the substrate from physical wear, it is advantageous to apply a coating consisting of a scratch-resistant material to the substrate material. The transparent, scratch-resistant coating has to meet a number of requirements with regard to applicability, curing speed, its technical properties and last but not least its optical and electrical properties. For this purpose, methods for applying certain coating materials have hitherto been proposed, which give the substrate a certain protection against scratching.
So wird beispielsweise in US Patenten 4,455,205 und US 4,491 ,508 und in US 4,198,465 vorgeschlagen, photohärtbare Acrylate als kratzfesten Schutzüberzug von Kunststoffen zu verwenden. Als beschichtbare Substrate werden verschiedene Kunststoffe, Metalle und metallisierte Thermoplaste erwähnt. Die Beschichtung transparenter Substrate wird nicht hervorgehoben. Für den Fachmann war es nicht naheliegend die dort beschriebenen Überzugsmittel bei optischen transparenten Datenträgern zu verwenden, da diese Überzugsmittel kolloidales Siliziumdioxid enthalten. Optische Datenträger erfordern nämlich eine besonders hohe Transparenz (> 80% Transmission) im verwendeten Wellenlängenbereich der Lese- und Schreibe-Laser, zumal der Lichtstrahl bei beiden Vorgängen das Substrat zweimal durchläuft. Der Wellenlängebereich des Lasers soll dabei nicht nur sichtbares Licht bis 750 nm, sondern auch den ultravioletten Bereich bis 300 nm umfassen.For example, it is proposed in US Patents 4,455,205 and US 4,491, 508 and in US 4,198,465 to use photocurable acrylates as a scratch-resistant protective coating for plastics. Various plastics, metals and metallized thermoplastics are mentioned as coatable substrates. The coating of transparent substrates is not emphasized. It was not obvious to a person skilled in the art to use the coating agents described there for optical transparent data carriers, since these coating agents contain colloidal silicon dioxide. Optical data carriers require a particularly high level of transparency (> 80% transmission) in the wavelength range used by the read and write lasers, especially since the light beam passes through the substrate twice in both processes. The wavelength range of the laser should not only include visible light up to 750 nm, but also the ultraviolet range up to 300 nm.
Ferner werden verschiedene Schutzüberzüge für optische Speichermedien in der Fachliteratur beschrieben (siehe dort in Zech, Spie „Review of Optical Storage Media" Optical Information Storage, Vol. 177, 1979, pp 56 ff, oder z.B. US 5,176,943, JP 02-260145).Various protective coatings for optical storage media are also described in the specialist literature (see there in Zech, Spie “Review of Optical Storage Media "Optical Information Storage, Vol. 177, 1979, pp 56 ff, or for example US 5,176,943, JP 02-260145).
Diese Beschichtungsmaterialien bestehen aus einem UV- oder Elektronenstrahl-härtbaren Acrylatbindemittel, das gegebenenfalls mit einem Slip-Additiv und/oder weiteren Additiven versetzt werden kann und das gegebenenfalls mit einer Schichtdicke von 0,004 bis 10 Mikron auf das Substrat durch das Schleuderguß-Beschichtungsverfahren aufgebracht wird.These coating materials consist of a UV or electron beam curable acrylate binder which can optionally be mixed with a slip additive and / or other additives and which is optionally applied to the substrate with a layer thickness of 0.004 to 10 microns by the centrifugal casting coating method.
Maßnahmen zum Schutz vor Verkratzungen von CD und DVD sind beispielsweise in der US 5,939,163 beschrieben, die einen Acrylatüberzug offenbart, der in Schichtdicken von 0.01 - 30 Micron, vorzugsweise von 0,05 - 10 Mikron aufgetragen wird.Measures to protect CD and DVD from scratches are described, for example, in US Pat. No. 5,939,163, which discloses an acrylate coating which is applied in layer thicknesses of 0.01-30 microns, preferably 0.05-10 microns.
Die dort dargestellten Überzugsmaterialien liefern zwar einen gewissen Schutz vor Verkratzung; jedoch konnten sich diese Systeme bisher wegen eines zu geringen Schutzeffektes nicht durchsetzen. Ferner neigen die beschriebenen Systeme dazu, nach Bewitterung, d.h. Lagerung unter bestimmten klimatischen Bedingungen, trübe zu werden oder ihre Haftung zum Substrat zu mindern oder zu verlieren.The coating materials shown there provide some protection against scratching; however, these systems have so far not been able to establish themselves due to an insufficient protection effect. Furthermore, the systems described tend, after weathering, i.e. Storage under certain climatic conditions, becoming cloudy or reducing or losing their adhesion to the substrate.
Aufgabe der vorliegenden Erfindung ist die Schaffung eines wirtschaftlich herstellbaren kratzfesten und auf der Substratoberfläche haftenden Überzuges auf der Leseseite von optischen Speichermedien, der aufgrund seiner Filmhärte nach erfolgter Aushärtung die Substratoberfläche vor mechanischer Verkratzung schützt und der gegen äußere Umwelteinwirkungen unter dem Begriff „Bewitterung" ( sog. Klimatest ) beständig ist und der keine Nachteile technischer Natur einbringt wie z.B die Erhöhung der Doppelbrechung, Signaldämpfung, oder das Verbiegen der Scheiben, Verfärbung oder Trübung der Oberfläche, Veränderung der Lesbarkeit oder der Beschreibbarkeit durch einen fokussierten Laserstrahl. Die bekannten Systeme auf Basis organischer photohärtbarer Acrylate liefern Überzüge mit einer Schichtdicke zwischen 7 und 12 Mikron, die während der Härtung stark schrumpfen und die Polycarbonatplatte durch den eintretenden Schrumpf verziehen, was dazu führt, daß die Informationsträger nicht spielbar oder schreibbar / lesbar werden.The object of the present invention is to provide an economically producible, scratch-resistant coating which adheres to the substrate surface on the reading side of optical storage media and which, on account of its film hardness, protects the substrate surface from mechanical scratching after curing and which protects against external environmental influences under the term "weathering" (so-called . Climate test) is stable and does not have any disadvantages of a technical nature such as, for example, increasing birefringence, signal attenuation, or bending of the panes, discoloration or clouding of the surface, changes in legibility or writeability by a focused laser beam. The known systems based on organic photocurable acrylates provide coatings with a layer thickness of between 7 and 12 microns, which shrink strongly during curing and distort the polycarbonate plate as shrinkage occurs, with the result that the information carriers are not playable or writable / readable.
Durch geeignete Maßnahmen kann zwar erreicht werden, daß die Schichtdicke reduziert werden kann, jedoch sinkt hierdurch die Kratzfestigkeit erheblich.Appropriate measures can be taken to reduce the layer thickness, but this significantly reduces the scratch resistance.
Es wurde nun überraschend gefunden, daß unter Verwendung spezieller UV- härtbarer anorganischer Lacksysteme sowohl eine gute Haftung des Überzuges auf den Substratmaterialien, eine ausreichende Transparenz als auch eine überlegene Kratzfestigkeit bei niedrigen Schichtdicken des Überzuges erreicht wird, durch die die Geometrie der optischen Datenträger nicht oder nur im Rahmen der zulässigen Toleranzen verändert wird.It has now surprisingly been found that, using special UV-curable inorganic lacquer systems, both good adhesion of the coating to the substrate materials, sufficient transparency and superior scratch resistance are achieved at low layer thicknesses of the coating, by means of which the geometry of the optical data carriers does not or is only changed within the permissible tolerances.
Die erfindungsgemäß verwendeten Acrylatharzzusammensetzung enthalten alkoxysilylacrylatmodifizierte Metalloxide, die durch Umsetzung von Hydrolyseprodukten von Alkoxysilylacrylaten mit Metalloxiden gebildet werden.The acrylate resin compositions used according to the invention contain alkoxysilylacrylate-modified metal oxides, which are formed by reacting hydrolysis products of alkoxysilylacrylates with metal oxides.
Die vorliegende Erfindung stellt somit optische Datenspeicher bereit, die mit einer Beschichtung versehen sind, die durch Strahlungshärtung eines strahlungshärtbaren Überzugsmittels, dass mindestens ein kolloidales Metalloxid, mindestens ein Hydrolyseprodukt mindestens eines Alkoxysilylacrylates, mindestens ein Acrylat-Monomer sowie mindestens einen Photoinitiator umfaßt, erhalten wird.The present invention thus provides optical data storage devices which are provided with a coating which is obtained by radiation curing a radiation-curable coating composition which comprises at least one colloidal metal oxide, at least one hydrolysis product of at least one alkoxysilyl acrylate, at least one acrylate monomer and at least one photoinitiator.
Die strahlungshärtbaren Überzugsmittel enthalten zweckmäßig:The radiation-curable coating agents appropriately contain:
(A) 1 % bis 60 Gew.-% mindestens eines kolloidalen Metalloxides,(A) 1% to 60% by weight of at least one colloidal metal oxide,
(B) 0,1% bis 50 Gew.-% mindestens eines Materials, das durch Hydrolyse von mindestens einem Alkoxysilylacrylat, bevorzugt der Formel (I) entsteht, (C) 25 % bis 90 Gew.-% mindestens eines Acrylatmonomers, bevorzugt der Formel (II) und(B) 0.1% to 50% by weight of at least one material which is formed by hydrolysis of at least one alkoxysilylacrylate, preferably of the formula (I), (C) 25% to 90% by weight of at least one acrylate monomer, preferably of the formula (II) and
(D) Q,01 % bis 15 Gew.-% mindestens eines Photoinitiators, bezogen auf die Gesamtmasse des Überzugsmittels.(D) Q, 01% to 15% by weight of at least one photoinitiator, based on the total mass of the coating composition.
Kolloidale Metalloxide (A) schließen zweckmäßig ein: Siliziumdioxid, Zirconiumdioxid, Titandioxid, Aluminiumoxid und Zinkoxid.Colloidal metal oxides (A) suitably include: silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide and zinc oxide.
Bevorzugt ist kolloidales Siliziumdioxid. Die kolloidalen Metalloxide werden zweckmäßig als Dispersion von Metalloxidteilchen im Submikronbereich in einem wäßrigen und/oder organischen Lösungsmittelmedium verwendet. Solche kolloidalen Dispersionen von Metalloxidteilchen sind entweder durch Hydrolyse der entsprechenden Metallalkoxide oder, ausgehend von wäßrigen Lösungen der entsprechenden Alkalimetallate durch Entfernung der Alkalimetallionen mit Hilfe von Ionenaustauschern erhältlich. Man erhält, abhängig von den Verfahrensbedingungen, kolloidale wäßrige oder alkoholischwäßrige Dispersionen der Metalloxide mit einer Teilchengrößenverteilung zwischen 1 und 1000 nm. Für die Verwendung in den erfindungsgemäßen Beschichtungsmitteln sollten die Partikelgrößen bevorzugt nicht über 100 nm liegen. Eine typische Teilchengrößenverteilung der Siliziumdioxidpartikel liegt zwischen 5 und 40 nm.Colloidal silicon dioxide is preferred. The colloidal metal oxides are advantageously used as a dispersion of submicron metal oxide particles in an aqueous and / or organic solvent medium. Such colloidal dispersions of metal oxide particles can be obtained either by hydrolysis of the corresponding metal alkoxides or, starting from aqueous solutions of the corresponding alkali metalates, by removing the alkali metal ions with the aid of ion exchangers. Depending on the process conditions, colloidal aqueous or alcoholic-aqueous dispersions of the metal oxides with a particle size distribution between 1 and 1000 nm are obtained. For use in the coating compositions according to the invention, the particle sizes should preferably not exceed 100 nm. A typical particle size distribution of the silicon dioxide particles is between 5 and 40 nm.
Die Bestimmung der Teilchengrößenverteilung kann entweder mit Hilfe der Rasterelektronenmikroskopie durch Optische Vermessung einer ausgezählten Teilchenmenge oder durch elektronische Zählgeräte (z.B. Coulter-Multisizer.3, Beckman Coultert Inc. oder Laser Diffraction Sizer CDA 500, Malvern Instruments, Ltd. UK) erfolgen. Bei sehr kleinen Teilchen (< 100 nm) hat sich der Einsatz von Zeta-Civern zur Vermessung der Partikelgrößen als genaueste Methode bewährt.The particle size distribution can be determined either by means of scanning electron microscopy by optical measurement of a counted number of particles or by electronic counting devices (e.g. Coulter-Multisizer. 3, Beckman Coultert Inc. or Laser Diffraction Sizer CDA 500, Malvern Instruments, Ltd. UK). In the case of very small particles (<100 nm), the use of zeta civers for measuring particle sizes has proven to be the most accurate method.
Die Metalloxide, insbesondere die SiO2-Partikel beinhalten tetrafunktionelle (Q) Metall- bzw. Siliziumatome und liefern die Härte in die Beschichtungsmassen. Diese kolloidalen Metalloxide besitzen im Solzustand auf ihrer Oberfläche Hydroxylfunktionen.The metal oxides, in particular the SiO 2 particles, contain tetrafunctional (Q) metal or silicon atoms and deliver the hardness into the coating compositions. These colloidal metal oxides have hydroxyl functions on their surface in the sol state.
Diese Funktionen können durch Kondensationsreaktion mit den beispielsweise trifunktionellen Acrylatsilantriolen der Formel (I) (gebildet durch Hydrolyse aus trialkoxysilan-modifizierten Acrylaten „siliconmodifizierten Acrylaten") unter Bildung von Partikeln mit einer „core-shell"-Struktur reagieren.These functions can react by condensation reaction with, for example, trifunctional acrylatesilanetriols of the formula (I) (formed by hydrolysis from trialkoxysilane-modified acrylates “silicon-modified acrylates”) to form particles with a “core-shell” structure.
Dispersionen von kolloidalem Siliziumdioxid sind beispielsweise von verschiedenen Herstellern wie DuPont, Nalco Chemical Company oder der Bayer AG zu beziehen. Kolloidale Dispersionen von Siliziumdioxid sind entweder in saurer oder alkalischer Form erhältlich. Für die Herstellung der Beschichtungsmaterialien wird vorzugsweise die saure Form verwendet, da diese bessere Eigenschaften der Beschichtungen liefern als die alkalischen Formen.Dispersions of colloidal silicon dioxide can be obtained, for example, from various manufacturers such as DuPont, Nalco Chemical Company or Bayer AG. Colloidal dispersions of silicon dioxide are available in either acidic or alkaline form. The acidic form is preferably used for the production of the coating materials, since these provide better properties of the coatings than the alkaline forms.
Naicoag 1034A.RTM. ist ein Beispiel für ein kolloidales Siliziumdioxid mit befriedigenden Eigenschaften. Es enthält ca. 34 Gew.-% an SiO2. In den Beispielen beinhalten die angegebenen Werte auch den Wasseranteil. Somit repräsentieren beispielsweise 520 Gramm Naicoag 1034A.RTM. ungefähr 177 Gramm SiO2.Naicoag 1034A.RTM. is an example of a colloidal silica with satisfactory properties. It contains approx. 34% by weight of SiO 2 . In the examples, the values given also include the water content. Thus, for example, 520 grams represent Naicoag 1034A.RTM. about 177 grams of SiO 2 .
Bevorzugt enthalten die erfindungsgemäßen Überzugsmittel 1 bis 60 Gew.-% kolloidale Metalloxide, besonders bevorzugt 5 bis 40 Gew.-%, jeweils auf die Gesamtmenge des Überzugsmittel bezogen.The coating compositions according to the invention preferably contain 1 to 60% by weight of colloidal metal oxides, particularly preferably 5 to 40% by weight, in each case based on the total amount of the coating composition.
Die erfindungsgemäß eingesetzte Komponente (B) stellt bevorzugt ein Hydrolyseprodukt eines Silylacrylates der allgemeine Formel (I) dar: Component (B) used according to the invention is preferably a hydrolysis product of a silyl acrylate of the general formula (I):
worinwherein
a eine ganze Zahl von 0 bis 2, bevorzugt 0 ist,a is an integer from 0 to 2, preferably 0,
b ist eine ganze Zahl von 1 bis 3, bevorzugt 1 ist, undb is an integer from 1 to 3, preferably 1, and
die Summe von a+b 1 bis 3, bevorzugt 1 beträgt.the sum of a + b is 1 to 3, preferably 1.
In der Formel (I) stellt R einen geradkettigen oder verzweigten Alkylrest mit 1 bis 8 Kohlenstoffatomen, einen Cycloalkylrest mit 3 bis 8 Kohlenstoffatomen oder einen gegebenenfalls substituierten Arylrest mit 6 bis 10 Kohlenstoffatomen im Arylteil dar. Wenn eine Mehrzahl von Gruppen R vorliegt (a=2), können die Reste R gleich oder verschieden voneinander sein. Der geradkettige oder verzweigte Alkylrest mit 1 bis 8 Kohlenstoffatomen schließt beispielsweise ein Methyl, Ethyl, Propyl, Butyl, usw.In formula (I), R represents a straight-chain or branched alkyl radical with 1 to 8 carbon atoms, a cycloalkyl radical with 3 to 8 carbon atoms or an optionally substituted aryl radical with 6 to 10 carbon atoms in the aryl part. If a plurality of groups R are present (a = 2), the radicals R may be the same or different from one another. The straight-chain or branched alkyl radical having 1 to 8 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, etc.
Bevorzugte Reste für R sind Methyl, Ethyl, Propyl, Cyclohexyl, Hexyl, Octyl, Isopropyl und Isobutyl. Bevorzugt sind die Alkylreste. Besonders bevorzugt stellt R Methyl und Ethyl dar.Preferred radicals for R are methyl, ethyl, propyl, cyclohexyl, hexyl, octyl, isopropyl and isobutyl. The alkyl radicals are preferred. R particularly preferably represents methyl and ethyl.
Der gegebenenfalls substituierte Arylrest mit 6 bis 10 Kohlenstoffatomen schließt beispielsweise Phenyl- oder Naphthylreste ein, die durch einen oder mehrere, bevorzugt ein bis drei Substituenten substituiert sein können, die aus der Gruppe von Alkylgruppen mit 1 bis 6 Kohlenstoffatomen undThe optionally substituted aryl radical having 6 to 10 carbon atoms includes, for example, phenyl or naphthyl radicals which can be substituted by one or more, preferably one to three, substituents selected from the group of alkyl groups having 1 to 6 carbon atoms and
Halogenatomen, wie Fluor, Chlor, Brom oder lod, ausgewählt sind, wie z.B.Halogen atoms such as fluorine, chlorine, bromine or iodine are selected, e.g.
Phenyl, Toluyl, Xylyl, Naphthyl, Chlorophenyl usw. Ein bevorzugter Arylrest für R ist Phenyl.Phenyl, toluyl, xylyl, naphthyl, chlorophenyl, etc. A preferred aryl radical for R is phenyl.
R1 in der allgemeinen Formel (I) stellt Wassserstoff, einen geradkettigen oder verzweigten Alkylrest mit 1 bis 8 Kohlenstoffatomen, einen Cycloalkylrest mit 3 bis 8 Kohlenstoffatomen oder einen gegebenenfalls substituierten Arylrest mit 6 bis 10 Kohlenstoffatomen im Arylteil dar, und wenn eine Mehrzahl von Gruppen R1 vorliegt (a+b >1) können diese gleich oder verschieden voneinander sein. Bezüglich des geradkettigen oder verzweigten Alkylrestes mit 1 bis 8 Kohlenstoffatomen oder des gegebenenfalls substituierten Arylrestes mit 6 bis 10 Kohlenstoffatomen und deren bevorzugten Definitionen kann zu den Erläuterungen zum Substituenten R verwiesen werden.R 1 in general formula (I) represents hydrogen, a straight-chain or branched alkyl radical with 1 to 8 carbon atoms, a cycloalkyl radical with 3 to 8 carbon atoms or an optionally substituted aryl radical with 6 to 10 carbon atoms in the aryl part, and when a plurality of groups R 1 is present (a + b> 1) these can be the same or different from one another. With regard to the straight-chain or branched alkyl radical with 1 to 8 carbon atoms or the optionally substituted aryl radical with 6 to 10 carbon atoms and their preferred definitions, reference can be made to the explanations for the substituent R.
Bevorzugt stellt R1 Methyl oder Ethyl dar.R 1 is preferably methyl or ethyl.
R2 in der allgemeinen Formel (I) stellt Wasserstoff, einen geradkettigen oder verzweigten Alkylrest mit 1 bis 8 Kohlenstoffatomen oder einen gegebenenfalls substituierten Arylrest mit 6 bis 10 Kohlenstoffatomen dar, und die Gruppen R2 können gleich oder verschieden voneinander sein.R 2 in the general formula (I) represents hydrogen, a straight-chain or branched alkyl radical having 1 to 8 carbon atoms or an optionally substituted aryl radical having 6 to 10 carbon atoms, and the groups R 2 can be identical or different from one another.
Bezüglich des geradkettigen oder verzweigten Alkylrestes mit 1 bis 8 Kohlenstoffatomen oder des gegebenenfalls substituierten Arylrestes mit 6 bis 10 Kohlenstoffatomen und deren bevorzugten Definitionen kann zu den Erläuterungen zum Substituenten R verwiesen werden.With regard to the straight-chain or branched alkyl radical with 1 to 8 carbon atoms or the optionally substituted aryl radical with 6 to 10 carbon atoms and their preferred definitions, reference can be made to the explanations for the substituent R.
Bevorzugt stellt R2 Wasserstoff und/oder Methyl dar, wobei insbesondere auch das Kohlenstoffatom in Nachbarstellung zum Carbonylkohlenstoffatom eine Methylgruppe als R2 tragen kann (Methacrylate). Bevorzugt sind die Substituenten R2 also alle Wasserstoff, wobei der Substituent R2, der am Kohlenstoffatom in Nachbarstellung zum Carbonylkohlenstoffatom sitzt, auch Methyl sein kann. R3 in der allgemeinen Formel (I) stellt eine Einfachbindung oder einen geradkettigen oder verzweigten, gegebenenfalls substituierten Alkylenrest (Alkandiylrest) mit 1 bis 8 Kohlenstoffatomen im Alkylenrest oder einen gegebenenfalls substituierten Arylenrest (Aryldiylrest) mit 6 bis 10 Kohlenstoffatomen im Arylenrest dar. Gegebenenfalls ist der Alkylenrest bevorzugt mit ein bis drei, bevorzugter einem Substituenten substituiert, der aus der Gruppe aus Halogen und Hydroxy ausgewählt wird. Gegebenenfalls ist der Arylenrest bevorzugt mit ein bis drei, bevorzugter einem Rest substituiert, der aus der Gruppe von Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, Halogenatomen, wie Fluor, Chlor, Brom oder lod, und Hydroxy ausgewählt wird. Beispiele für R3 schließen ein:R 2 is preferably hydrogen and / or methyl, and in particular the carbon atom adjacent to the carbonyl carbon atom can also carry a methyl group as R 2 (methacrylates). The substituents R 2 are therefore preferably all hydrogen, and the substituent R 2 which is located on the carbon atom in the vicinity of the carbonyl carbon atom can also be methyl. R 3 in the general formula (I) represents a single bond or a straight-chain or branched, optionally substituted alkylene radical (alkanediyl radical) having 1 to 8 carbon atoms in the alkylene radical or an optionally substituted arylene radical (aryldiyl radical) having 6 to 10 carbon atoms in the arylene radical the alkylene radical is preferably substituted with one to three, more preferably one, substituent selected from the group consisting of halogen and hydroxy. If appropriate, the arylene radical is preferably substituted by one to three, more preferably one radical which is selected from the group of alkyl groups having 1 to 6 carbon atoms, halogen atoms, such as fluorine, chlorine, bromine or iodine, and hydroxy. Examples of R 3 include:
Lineare Alkylenreste, wie z.B. Methylen, Ethylen, Trimethylen, Tetramethylen, usw., bevorzugt unverzweigte Reste, gegebenenfalls verzweigte halogeriierte Alkylenreste mit 2 bis 8 Kohlenstoffatomen, gegebenenfalls verzweigte hydroxylierte Alkylenreste mit 2 bis 8 Kohlenstoffatomen, Arylenradikale mit 6 bis 10 Kohlenstoffatomen z.B. Phenylen (1 ,2-, 1 ,3- und 1,4-Phenylen), Tolylen, Naphthylen, usw., halogenierte Arylenradikale mit 6 bis 10 Kohlenstoffatomen im Arylenteil usw. Bevorzugt ist R3 eine Einfachbindung, Methylen oder Ethylen. Die erfindungsgemäß verwendeten Silylacrylate der allgemeinen Formel (I) sind an sich bekannt und sind beispielsweise u.a. in der US 4, 491 ,508 beschrieben, auf die insoweit in Bezug genommen wird.Linear alkylene residues, such as methylene, ethylene, trimethylene, tetramethylene, etc., preferably unbranched residues, optionally branched halogenated alkylene residues with 2 to 8 carbon atoms, optionally branched hydroxylated alkylene residues with 2 to 8 carbon atoms, arylene radicals with 6 to 10 carbon atoms e.g. phenylene (1 , 2-, 1, 3- and 1,4-phenylene), tolylene, naphthylene, etc., halogenated arylene radicals having 6 to 10 carbon atoms in the arylene part, etc. Preferably R 3 is a single bond, methylene or ethylene. The silyl acrylates of the general formula (I) used according to the invention are known per se and are described, for example, in US Pat. No. 4,491,508, to which reference is made in this respect.
Die Silylacrylate der Formel (I) beinhalten bevorzugt Acrylat- bzw. Methacrylat- Verbindungen, wie:The silyl acrylates of the formula (I) preferably contain acrylate or methacrylate compounds, such as:
CH2=CCH3CO2— CH2-Si(OCH2CH3)3, CH2=CCH3CO2— CH2-Si(OCH3)3,CH 2 = CCH 3 CO 2 - CH 2 -Si (OCH 2 CH3) 3 , CH 2 = CCH 3 CO 2 - CH 2 -Si (OCH 3 ) 3,
CH2=CCH3CO2— CH2CH^Si(OCH2CH3)3, CH2=CCH3CO2— CH2CH^Si(OCH3)3.CH 2 = CCH 3 CO 2 - CH 2 CH ^ Si (OCH 2 CH 3 ) 3 , CH 2 = CCH 3 CO 2 - CH 2 CH ^ Si (OCH 3 ) 3 .
CH2=CHCO2— CH2CH2— Si(OCH2CH3)3, CH2=CHCO2— CH2CH2— Si(OCH3)3,CH 2 = CHCO 2 - CH 2 CH 2 - Si (OCH 2 CH 3 ) 3, CH 2 = CHCO 2 - CH2CH2 - Si (OCH 3 ) 3 ,
CH2=CCH3CO2— CH2CH2CH2— Si(OCH2CH3)3, CH2=CCH3CO2— CH2CH2CH2— Si(OCH3)3.CH 2 = CCH 3 CO 2 - CH 2 CH 2 CH 2 - Si (OCH 2 CH 3 ) 3 , CH 2 = CCH 3 CO 2 - CH2CH2CH2 - Si (OCH 3 ) 3 .
CH2=CHCO2— CH2CH2CH2— Si(OCH2CH3)3, CH2=CHCθ2— CH2CH2CH2— Si(OCH3)3,CH 2 = CHCO 2 - CH 2 CH 2 CH 2 - Si (OCH 2 CH 3) 3, CH 2 = CHCθ2- CH2CH2CH2- Si (OCH 3) 3,
CH2=CCH3Cθ2 — CH2CH2CH2CH2 — Si(OCH2CH3)3, CH2=CCH3CO2— CH2CH2CH2CH2— Si(OCH3)3,CH2 = CCH 3 CO 2 - CH 2 CH 2 CH 2 CH 2 - Si (OCH2CH 3 ) 3 , CH 2 = CCH 3 CO 2 - CH2CH2CH2CH2 - Si (OCH 3 ) 3 ,
CH2=CHCO2— CH2CH2CH2CH2— Si(OCH2CH3)3, CH2=CHCO2— CH2CH2CH2CH2— Si(OCH3)3l etc.CH 2 = CHCO 2 - CH 2 CH 2 CH 2 CH 2 - Si (OCH 2 CH 3 ) 3 , CH 2 = CHCO 2 - CH2CH2CH2CH2 - Si (OCH 3 ) 3l etc.
Die in dem erfindungsgemäß verwendeten Uberzugsmittel enthaltenen Hydrolyseprodukte (B) der Alkoxysilylacrylate, vorzugsweise der Formel (I), werden durch Inkontaktbringen der Alkoxysilylacrylate mit Wasser erzeugt.The hydrolysis products (B) of the alkoxysilyl acrylates, preferably of the formula (I), contained in the coating agent used according to the invention are produced by contacting the alkoxysilyl acrylates with water.
Dabei handelt es sich um partiell oder vollständig hydrolysierte Alkoxysilylacrylate. Durch die Hydrolyse entstehen die entsprechenden Hydroxysilylacrylate, die untereinander und mit den Hydroxylgruppen der kolloidalen Metalloxide unter Kondensation reagieren können.These are partially or fully hydrolyzed alkoxysilyl acrylates. The corresponding hydroxysilylacrylates are formed by the hydrolysis and can react with one another and with the hydroxyl groups of the colloidal metal oxides with condensation.
Man nimmt an, dass die Hydrolyseprodukte mit den kolloidalen Metalloxiden unter Bildung von Si-O-Metall-Bindungen reagieren.The hydrolysis products are believed to react with the colloidal metal oxides to form Si-O-metal bonds.
Wie weiter unten genauer bei der Herstellung der erfindungsgemäßen Uberzugsmittel beschrieben, kann die Bildung der Hydrolyseprodukte der Silylacrylate vor oder während der Herstellung der erfindungsgemäß verwendeten Uberzugsmittel erfolgen. Die Menge des erfindungsgemäß verwendeten Materials (B) in dem erfindungsgemäß verwendeten Uberzugsmittel beträgt zweckmäßig 0,1 bis 50 Gew.-%, bevorzugt 1 bis 15 Gew.-%, jeweils bezogen auf die Gesamtmenge des Überzugsmittels.As described in more detail below in the production of the coating compositions according to the invention, the hydrolysis products of the silyl acrylates can be formed before or during the production of the coating compositions used according to the invention. The amount of material (B) used according to the invention in the coating agent used according to the invention is advantageously 0.1 to 50% by weight, preferably 1 to 15% by weight, in each case based on the total amount of the coating agent.
Die erfindungsgemäß verwendeten Acrylatmonomere (C) besitzen bevorzugt die allgemeine Formel (II):The acrylate monomers (C) used according to the invention preferably have the general formula (II):
worin n eine Zahl von 1 bis 6 ist, R Wasserstoff, einen geradkettigen oder verzweigten Alkylrest mit 1 bis 8 Kohlenstoffatomen oder einen gegebenenfalls substituierten Arylrest mit 6 bis 10 Kohlenstoffatomen im Arylteil darstellt, und die Substituenten R4 gleich oder verschieden voneinander sein können, und R5 einen gegebenenfalls substituierten ein- bis sechswertigen organischen Rest bedeutet.wherein n is a number from 1 to 6, R represents hydrogen, a straight-chain or branched alkyl radical having 1 to 8 carbon atoms or an optionally substituted aryl radical having 6 to 10 carbon atoms in the aryl part, and the substituents R 4 can be identical or different from one another, and R 5 represents an optionally substituted mono- to hexavalent organic radical.
n ist bevorzugt eine ganze Zahl von 1 bis 4, besonders bevorzugt von 2 bis 4.n is preferably an integer from 1 to 4, particularly preferably from 2 to 4.
Bezüglich des geradkettigen oder verzweigten Alkylrestes mit 1 bis 8 Kohlenstoffatomen oder des gegebenenfalls substituierten Arylrestes mit 6 bis 10 Kohlenstoffatomen für R4 und deren bevorzugten Definitionen kann zu den Erläuterungen zum Substituenten R der Formel (I) verwiesen werden.Regarding the straight-chain or branched alkyl radical having 1 to 8 carbon atoms or the optionally substituted aryl radical having 6 to 10 carbon atoms for R 4 and their preferred definitions, reference can be made to the explanations for the substituent R of the formula (I).
Bevorzugt stellt R Wasserstoff und/oder Methyl dar, wobei insbesondere auch das Kohlenstoffatom in Nachbarstellung zum Carbonylkohlenstoffatom eine Methylgruppe als R4 tragen kann (Methacrylate). Bevorzugt sind die Substituenten R4 also alle Wasserstoff (Acrylate), wobei der Substituent R4, der am Kohlenstoffatom in Nachbarstellung zum Carbonylkohlenstoffatom sitzt auch Methyl sein kann (Methacrylate).R is preferably hydrogen and / or methyl, where in particular the carbon atom adjacent to the carbonyl carbon atom can also carry a methyl group as R 4 (methacrylates). The substituents R 4 are therefore preferably all hydrogen (acrylates), the substituent R 4 being the methyl (methacrylates) can also be located on the carbon atom in the position adjacent to the carbonyl carbon atom.
R5 schließt ein- bis sechwertige, vorzugsweise zwei- bis vierwertige organische Reste ein, die gegebenenfalls substituiert sein können. Die Wertigkeit entspricht der Anzahl der Acrylatgruppen n. Bevorzugt schließt R5 gegebenenfalls substituierte geradkettige oder verzweigte aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 20, bevorzugt 1 bis 10 Kohlenstoffatomen ein. Bezüglich der zweiwertigen Reste kann zu den für R3 oben genannten Resten verwiesen werden.R 5 includes mono- to hexavalent, preferably di- to tetravalent organic radicals, which can be optionally substituted. The valency corresponds to the number of acrylate groups n. R 5 preferably includes optionally substituted straight-chain or branched aliphatic or aromatic hydrocarbon radicals having 1 to 20, preferably 1 to 10, carbon atoms. With regard to the divalent radicals, reference can be made to the radicals mentioned above for R 3 .
R5 weist gegebenenfalls bevorzugt ein bis drei Substituenten auf, wie Halogen oder Hydroxy.R 5 optionally has one to three substituents, such as halogen or hydroxy.
Die Acrylatmonomere der Formel (II) schließen mono- und polyfunktionelle Acrylatmonomere ein.The acrylate monomers of formula (II) include mono- and polyfunctional acrylate monomers.
Monoacrylate schließen gegebenenfalls Hydroxy-substituierte Alkylacrylate und - Alkylmethacrylate, wie z.B. Hydroxyethylacrylat etc. ein. Die Acrylatmonomere der Formel (II) sind in den erfindungsgemäßen Zubereitungen in einem Mengenanteil von mindestens 5 Gew.-% bis 25 Gew.-%, bevorzugt 5 bis 10 Gew.-%, enthalten, um eine erhöhte Haftung auf den verwendeten Substraten zu gewährleisten.Monoacrylates optionally include hydroxy substituted alkyl acrylates and alkyl methacrylates such as e.g. Hydroxyethyl acrylate, etc. The acrylate monomers of the formula (II) are present in the preparations according to the invention in a proportion of at least 5% by weight to 25% by weight, preferably 5 to 10% by weight, in order to ensure increased adhesion to the substrates used ,
Bevorzugt ist in dem erfindungsgemäß verwendeten Uberzugsmittel mindestens ein Acrylat mit mindestens zwei ethylenisch ungesättigten Gruppen, wahlweise in Kombination mit einem mono- oder polyfunktionellen Acrylat enthalten.The coating agent used according to the invention preferably contains at least one acrylate with at least two ethylenically unsaturated groups, optionally in combination with a monofunctional or polyfunctional acrylate.
Beispiele der polyfunktionellen Acrylate der Formel (II) schließen ein:Examples of the polyfunctional acrylates of formula (II) include:
Diacrylate der Formeln: H3? O I I O CH.Diacrylates of the formulas: H 3 ? OIIO CH.
II ' II '
H9C=C-C-O-C-O-C-C=CHP 2 H2 2 H 9 C = CCOCOCC = CH P 2 H 2 2
Triacrylate der Formeln:Triacrylates of the formulas:
Tetraacrylate der Formeln:Tetraacrylates of the formulas:
Derartige Acrylate sind an sich bekannt, und es kann z.B. auf diejenigen verwiesen werden, die in der US 4,491 ,508 sowie US 4,198,465 beschrieben sind, verwiesen werden. Bevorzugt enthält das erfindungsgemäß verwendete Uberzugsmittel eine Mischung aus zwei oder mehreren polyfunktionellen Acrylat-Monomeren der Formel (II), noch bevorzugter ein Diacrylat und ein höherfunktionelles Acrylat. Uberzugsmittel, die eine Mischung aus Diacrylaten und höherfunktionellen Acrylaten enthalten, haben zweckmäßig ein Gewichtsverhältnis aus Diacrylat und höherfunktionellem Acrylat von 0,5 : 99 bis etwa 99 : 0,5, besonders bevorzugt von 1 : 99 bis 99 : 1. Beispielsweise kann eine Mischung eines Di- und eines Tri-acrylates der allgemeinen Formel (II) verwendet werden. Beispielhafte Mischungen von Diacrylat und polyfunktionellem Acrylat beinhalten Hexandioldiacrylat mit Trimethylolpropan-triacrylat (TMPTA), Hexandioldiacrylat mit Pentaerythrit-tetraacrylat, Diethylenglycoldiacrylat mit Pentaerythrit-triacrylat und Diethylenglycoldiacrylat mitSuch acrylates are known per se, and reference can be made, for example, to those described in US Pat. Nos. 4,491,508 and 4,198,465. The coating agent used according to the invention preferably contains a mixture of two or more polyfunctional acrylate monomers of the formula (II), more preferably a diacrylate and a higher-functionality acrylate. Coating compositions which contain a mixture of diacrylates and higher-functional acrylates advantageously have a weight ratio of diacrylate and higher-functional acrylate of from 0.5: 99 to about 99: 0.5, particularly preferably from 1: 99 to 99: 1. For example, a mixture a di- and a tri-acrylate of the general formula (II) can be used. Exemplary mixtures of diacrylate and polyfunctional acrylate include hexanediol diacrylate with trimethylolpropane triacrylate (TMPTA), hexanediol diacrylate with pentaerythritol tetraacrylate, diethylene glycol diacrylate with pentaerythritol triacrylate and diethylene glycol diacrylate
Trimethylolpropantriacrylat. Uberzugsmittel, die zwei polyfunktionelle Acrylatmonomere der Formel (II) enthalten, sind besonders bevorzugt.Trimethylolpropane. Coating agents which contain two polyfunctional acrylate monomers of the formula (II) are particularly preferred.
Die Menge des Acrylatmonomers (C) in dem erfindungsgemäß verwendeten Uberzugsmittel beträgt zweckmäßig 25 bis 90 Gew.-%, bevorzugt 40 bis 85 Gew.-%, jeweils bezogen auf die Gesamtmenge der Zusammensetzung.The amount of the acrylate monomer (C) in the coating agent used according to the invention is advantageously 25 to 90% by weight, preferably 40 to 85% by weight, in each case based on the total amount of the composition.
In einer besonderen Ausführungsform der Erfindung beträgt der Anteil monofunktioneller Acrylate als Komponente (C) (n=1), bezogen auf die Gesamtmenge der Komponente (C) 5 bis 50 Gew.-%, bevorzugt 5 bis 25, noch bevorzugter 5 bis 10 Gew.-%.In a particular embodiment of the invention, the proportion of monofunctional acrylates as component (C) (n = 1), based on the total amount of component (C), is 5 to 50% by weight, preferably 5 to 25, more preferably 5 to 10% by weight .-%.
Die photovernetzbaren, erfindungsgemäß verwendeten Uberzugsmittel enthalten eine für die Photosensibilisierung erforderliche Menge mindestens eines Photoinitiators (D), d.h. eine Menge, die geeignet ist, die UV- Photohärtung zu bewirken. Im allgemeinen liegt diese erforderliche Menge in einem Bereich zwischen 0,01 bis 15 Gew-%, bevorzugt 0,1 bis 10 Gew.-%, 1 bis 8 Gew.-%, noch bevorzugter 1 ,5 bis 7 Gew.-% bezogen auf die Summe aller Bestandteile in der Beschichtungszusammensetzung. Bei Verwendung größerer Photoinitiatormengen erhält man Uberzugsmittel, die schneller aushärten.The photocrosslinkable coating compositions used according to the invention contain an amount of at least one photoinitiator (D) required for photosensitization, ie an amount which is suitable for effecting UV photocuring. In general, this required amount is in a range between 0.01 to 15% by weight, preferably 0.1 to 10% by weight, 1 to 8% by weight, more preferably 1.5 to 7% by weight on the sum of all components in the coating composition. Using Larger quantities of photoinitiator give coating agents which harden faster.
Als Photoinitiatoren (D) können beispielsweise die in den US-Patenten 4,491 ,508 sowie 4,455,205 genannten verwendet werden. Photoinitiatoren, wie z.B. Methylbenzoylformiat, die für den erfindungsgemäßen Einsatz geeignet sind, sind unter verschiedenen Handelsnamen erhältlich.As photoinitiators (D), for example, those mentioned in US Patents 4,491, 508 and 4,455,205 can be used. Photoinitiators such as Methylbenzoyl formate which are suitable for the use according to the invention are available under various trade names.
Die erfindungsgemäß verwendeten UV-härtenden Uberzugsmittel bestehen bevorzugt im wesentlichen aus den Komponenten (A) bis (D). Es ist dem Fachmann jedoch bekannt, dass den erfindungsgemäß verwendeten Überzugsmitteln gegebenenfalls noch weitere, an sich bekannte Zusatzstoffe in einem Anteil, der die Lösung der erfindungsgemäßen Aufgabe nicht beinträchtigt, hinzugefügt werden können, wie z.B. lösliche Salze, Seifen, Amine, nichtionische und anionische Tenside, Säuren, Basen, sowie Substanzen, die der Vergelung entgegenwirken. Ferner können verschiedene Verlaufshilfsmittel sowie Benetzungsmittel, Lichtstabilisatoren und Farbstoffe zugesetzt werden.The UV-curing coating compositions used according to the invention preferably consist essentially of components (A) to (D). However, it is known to the person skilled in the art that, if appropriate, further additives known per se can be added to the coating compositions used according to the invention in a proportion which does not impair the achievement of the object according to the invention, such as e.g. soluble salts, soaps, amines, non-ionic and anionic surfactants, acids, bases, as well as substances that counteract gelling. Various flow control agents as well as wetting agents, light stabilizers and dyes can also be added.
Derartige Zusatzstoffe sind beispielsweise in den US-Patenten 4,491 ,508 und 4,455,205 beschrieben.Such additives are described, for example, in US Patents 4,491, 508 and 4,455,205.
Die verschiedenen grenzflächenaktiven Hilfsmittel, die den Beschichtungs- zusammensetzungen zugesetzt werden können, sind an sich bekannt und bedürfen keiner weiteren Erklärung. Sie sind beispielsweise in:The various surface-active auxiliaries that can be added to the coating compositions are known per se and do not require any further explanation. For example, you are in:
Kirk-Othmer „Encyclopedia of Chemical Technology", Vol. 19, Interscience Publishers, New York, 1969, s. 507 - 593, und der "Encyclopedia of Polymer Science and Technology", Vol. 13, Interscience Publishers, New York, 1970, s. 477 - 486 beschrieben.Kirk-Othmer "Encyclopedia of Chemical Technology", Vol. 19, Interscience Publishers, New York, 1969, pp. 507-593, and "Encyclopedia of Polymer Science and Technology", Vol. 13, Interscience Publishers, New York, 1970 , pp. 477-486.
Weitere Nicht-Acrylmonomere wie N-Methylpyrrolidon oder Styrole dienen wie einige Monoacrylate z.B. Isobornylacrylat, Phenoxyethylacrylat oder Hydroxyethylmethacrylat sowohl der Verbesserung der Eigenschaften des ausgehärteten Produktfilmes, indem sie deren Flexibilität steigern, als auch ihre Haftung auf den Substratmaterialien verbessern. Ferner wirken sie viskositätssenkend auf die Mischungszubereitung.Other non-acrylic monomers such as N-methylpyrrolidone or styrenes are used like some monoacrylates, for example isobornyl acrylate, phenoxyethyl acrylate or Hydroxyethyl methacrylate both improve the properties of the cured product film by increasing its flexibility and improve its adhesion to the substrate materials. They also reduce the viscosity of the mixture preparation.
Die Herstellung der erfindungsgemäß verwendeten UV-härtbaren Überzugs- mittel kann durch Zusammenmischen der Komponenten (A) bis (D) und der gegebenenfalls vorhandenen weiteren Komponenten erfolgen. In einem Mischvogang kann das Silylacrylat in Gegenwart des wäßrig kolloidalen Metalloxids und des mit Wasser mischbaren Alkohols hydrolysiert werden. In einem, weiteren Verfahrensschritt kann das wässrige kolloidale Metalloxid zu dem Silylacrylat gegeben werden, das in wäßrig-alkoholischer Lösung entweder bei Raumtemperatur oder bei Refluxtemperatur des verwendeten Lösungsmittels hydrolysiert wurde. Geeignete Lösungsmittel schließen zum Beispiel alle wassermischbaren Alkohole sowie Alkohol-Lösungsmittel-Azeotrope ein. Beispiele solcher Lösungsmittel sind Isopropylalkohol, 4-Methoxypropanol, n-Butanol, 2-Butanol, Ethanol und ähnliche Alkohole. Um ein lösungsmittelfreies Produkt zu erhalten, wird ein azeotropes Gemisch aus Wasser und Alkohol aus der Formulierung abdestilliert. In solchen Fällen, wo kein Alkohol in der ursprünglichen Hydrolysemischung eingesetzt wurde, ist der für die azeotrope Destillation erforderliche Alkohol nachträglich zuzusetzen, um das in der Mischung enthaltene Wasser vollständig zu entfernen.The UV-curable coating compositions used according to the invention can be produced by mixing components (A) to (D) together and any further components which may be present. In a mixing process, the silyl acrylate can be hydrolyzed in the presence of the aqueous colloidal metal oxide and the water-miscible alcohol. In a further process step, the aqueous colloidal metal oxide can be added to the silyl acrylate which has been hydrolyzed in aqueous-alcoholic solution either at room temperature or at the reflux temperature of the solvent used. Suitable solvents include, for example, all water-miscible alcohols and alcohol-solvent azeotropes. Examples of such solvents are isopropyl alcohol, 4-methoxypropanol, n-butanol, 2-butanol, ethanol and similar alcohols. To obtain a solvent-free product, an azeotropic mixture of water and alcohol is distilled off from the formulation. In cases where no alcohol was used in the original hydrolysis mixture, the alcohol required for the azeotropic distillation must be added subsequently in order to completely remove the water contained in the mixture.
Die vorliegende Erfindung bezieht sich weiterhin auf ein Verfahren zur Beschichtung von optischen Datenträgern wie beispielsweise CD, SuperAudio-CD, CD -R, CD -RW, DVD , DVD - R, DVD - RW und DVR auf der Leseseite. Eine systematische Übersicht über die derzeit bekannten optischen und magnetooptischen Datenträgersysteme ist in der nachstehenden Tabelle gegeben. Bevorzugte Systeme sind: CD-R, CD-RW, DVD, DVD-R, DVD-RW und DVR. Typen Dateneingabe Eigenschaften AusführungsbeispieleThe present invention further relates to a method for coating optical data carriers such as CD, SuperAudio-CD, CD -R, CD -RW, DVD, DVD-R, DVD-RW and DVR on the reading side. A systematic overview of the currently known optical and magneto-optical data carrier systems is given in the table below. Preferred systems are: CD-R, CD-RW, DVD, DVD-R, DVD-RW and DVR. Types of data entry Properties Examples
CD-ROM Daten vom Daten nicht Aufbau undCD-ROM data from data not construction and
DVD-ROM Hersteller löschbar Informationsspeicherung vorgegeben analog CD-DA(Digital- Audio)DVD-ROM manufacturer can be erased information storage specified analog CD-DA (digital audio)
CD-R Daten vom Daten nicht Polymersubstrat (PC) mitCD-R data from data not using polymer substrate (PC)
DVD-R Benutzer löschbar Speicherschicht aus einschreibbar Daten nicht - Metall/Polymer wiedereinschreibbar - Farbmittel/PolymerDVD-R user erasable storage layer from writable data not - metal / polymer rewritable - colorant / polymer
CD-RW Daten vom Daten löschbar Polymersubstrat (PC) mitCD-RW data from data erasable polymer substrate (PC) with
DVD-RW Benutzer Daten Speicherschicht auf Basis einschreibbar wiedereinschreibbar - Magneto-OpticalDVD-RW user data storage layer based on writable rewritable - Magneto-Optical
DVR Recording (MO-R)DVR Recording (MO-R)
- Phase-Change- phase change
Recording (PC-R)Recording (PC-R)
CD-DA = Compact Disk-Digital AudioCD-DA = Compact Disk-Digital Audio
CD-ROM = Compakt Disk - Read Only Memory , DVD-ROM = Digital Versatile Disk - Read Only MemoryCD-ROM = Compact Disk - Read Only Memory, DVD-ROM = Digital Versatile Disk - Read Only Memory
CD-R = Compakt Disk - Recordable ,CD-R = Compact Disk - Recordable,
DVD-R = Digital Versatile Disk - RecordableDVD-R = Digital Versatile Disk - Recordable
CD-RW = Compact Disk - ReWritable ,CD-RW = Compact Disk - ReWritable,
DVD-RW = Digital Versatile Disk - ReWritableDVD-RW = Digital Versatile Disk - ReWritable
DVR = High Density Disk - RecordableDVR = High Density Disk - Recordable
zur Erzielung kratzfester Überzüge auf diesen optischen Datenträgern unter Verwendung der vorstehend beschriebenen UV-härtbaren Uberzugsmittel.to achieve scratch-resistant coatings on these optical data carriers using the UV-curable coating agents described above.
Die erfindungsgemäß beschichteten optischen Datenspeicher bestehen im allgemeinen aus transparenten Thermoplasten wie Polycarbonat auf Basis von Bisphenol-A (BPA-PC), Polycarbonat auf Basis von Trimethyl-Cyclohexyl- Bisphenol-Polycarbonat (TMC-PC), Fluorenyl-Polycarbonat,The optical data storage devices coated according to the invention generally consist of transparent thermoplastics such as polycarbonate based on bisphenol-A (BPA-PC), polycarbonate based on trimethyl-cyclohexyl Bisphenol polycarbonate (TMC-PC), fluorenyl polycarbonate,
Polymethylmethacrylat, cyclisches Polyolefin-Copolymer COC 513 (Hersteller: Ticona GmbH, Nippon Zeon, Japan, Japan Synthetic Rubber, Japan), hydrierte Polystyrole (HPS) (Hersteller: Dow Chemical) sowie amorphe Polyolefine und Polyester (Hersteller: Kodak Corp., USA).Polymethyl methacrylate, cyclic polyolefin copolymer COC 513 (manufacturer: Ticona GmbH, Nippon Zeon, Japan, Japan Synthetic Rubber, Japan), hydrogenated polystyrene (HPS) (manufacturer: Dow Chemical) and amorphous polyolefins and polyester (manufacturer: Kodak Corp., USA ).
Die UV-härtbaren Uberzugsmittel werden dabei zweckmäßig bei Beschichtung scheibenförmiger optischer Datenträger, wie CD, DVD und DV-R, durch ein Schleudergußverfahren auf die einzelnen Scheiben aufgetragen und anschließend durch die Einwirkung von UV-Strahlen gehärtet.The UV-curable coating agents are expediently applied to the individual panes when coating disk-shaped optical data carriers, such as CD, DVD and DV-R, and then cured by the action of UV rays.
Hierzu wird vorzugsweise die Scheibe, die entweder in einer staubfrei gehaltenen Kammer innerhalb einer Fertigungslinie oder, wenn sie in einem vorgelagerten Schritt hergestellt wurde, nach Vorbehandlung mit entionisierter Luft, in einer Schleudergußkammer mit der für den Prozess erforderlichen Menge des Beschichtungsmaterials in Form eines Flüssigkeitsringes oder einer Spirale belegt und anschließend durch Erhöhung der Rotationszahl des Substrates auf Umdrehungszahlen von 1000 bis 10000 pro Minute innerhalb von 1 ,0 bis 10 Sekunden gleichmäßig auf der Substratoberfläche verteilt und der Überschuß abgeschleudert. Es ist möglich, den Abschleudervorgang mit Hilfe eines Drehzahlprogrammes so zu gestalten, daß die radiale Schichtdickenverteilung weitgehend konstant ist.For this purpose, the disc, which is either kept in a dust-free chamber within a production line or, if it was manufactured in a preceding step, after pretreatment with deionized air, in a centrifugal casting chamber with the amount of the coating material required for the process in the form of a liquid ring or coated in a spiral and then distributed evenly on the substrate surface within 1, 0 to 10 seconds by increasing the number of rotations of the substrate to revolutions of 1000 to 10000 per minute and the excess is thrown off. It is possible to design the spinning process using a speed program so that the radial layer thickness distribution is largely constant.
Dieser Vorgang erzeugt auf der Substratoberfläche einen gleichmäßigen Flüssigkeitsfilm mit einer Schichtdicke zwischen 0,001 und 100 Mikron. Die erzielbare Schichtdicke ist abhängig von den rheologischen Eigenschaften des Überzugmaterials wie der Viskosität, der Umdrehungszahl des Schleudertellers und der Einwirkungsdauer hoher Umdrehungszahlen während des Abschleudervorganges.This process creates a uniform liquid film on the substrate surface with a layer thickness between 0.001 and 100 microns. The layer thickness that can be achieved depends on the rheological properties of the coating material, such as the viscosity, the number of revolutions of the spin plate and the duration of exposure to high numbers of revolutions during the spinning process.
Der ungehärtete Film auf der Oberfläche des Substrates sollte unmittelbar nach dem Abschleudervorgang mit Hilfe einer geeigneten Strahlungsart wie UV oder Elektronenstrahlen ausgehärtet werden, vorzugsweise jedoch durch Ultraviolettstrahlung; zweckmäßig bei Raumtemperatur bis etwa 45° Celsius. Geeignete UV-Strahlungsquellen sind dabei beispielsweise ungepulste Strahlungsquellen. Gepulste Strahlungsquellen werden hier in der Praxis der UV-Srahlungshärtung nicht eingesetzt. Grundsätzlich läßt sich Elektronen- Strahlung (EB) für die Härtung von strahlungsvernetzbaren Beschichtungsmaterialien einsetzen, in der Praxis haben sich EB- Härtungseinrichtungen jedoch als zu groß oder zu langsam bezüglich der Prozeßzeit erwiesen. Die Strahlungsleistung der verwendeten UV-Lampen sind im eingesetzten System variabel von 1000 bis 20000 Watt, bevorzugt ca. 1600 bis 2200 Watt (für CD, CD-R, CD-RW und DVD). Die verwendete UV-Lampe (Hersteller: Fa. Singulus; Typ: 200 BTZ/DF) ist eine Quecksilberhochdrucklampe mit einer variablen Leistungsaufnahme von 1000 bis 20000 Watt h. Es können aber auch andere Standard-Hg-Lampen eingesetzt werden, wenn sie eine entsprechende Leistung im härtungsrelevanten UV-Bereich (250 bis 400 nm, vorzugsweise jedoch im Bereich von 360 bis 380 nm) abgeben.The uncured film on the surface of the substrate should immediately after spinning with the help of a suitable type of radiation such as UV or Electron beams are cured, but preferably by ultraviolet radiation; expedient at room temperature up to about 45 ° Celsius. Suitable UV radiation sources are, for example, unpulsed radiation sources. Pulsed radiation sources are not used here in the practice of UV radiation curing. In principle, electron radiation (EB) can be used for curing radiation-crosslinkable coating materials, but in practice EB curing devices have proven to be too large or too slow in terms of process time. The radiation power of the UV lamps used in the system used is variable from 1000 to 20,000 watts, preferably approx. 1600 to 2200 watts (for CD, CD-R, CD-RW and DVD). The UV lamp used (manufacturer: Singulus; type: 200 BTZ / DF) is a high-pressure mercury lamp with a variable power consumption from 1000 to 20000 watt h. However, other standard mercury lamps can also be used if they deliver a corresponding output in the curing-relevant UV range (250 to 400 nm, but preferably in the range from 360 to 380 nm).
Die bei diesem Härtungsverfahren sonst übliche Verwendung einer Inertgasatmosphäre, wie einer Stickstoffatmosphäre, ist bei diesen Verfahren nicht erforderlich.The otherwise customary use of an inert gas atmosphere, such as a nitrogen atmosphere, in this hardening process is not necessary in these processes.
Die Dicke der resultierenden gehärteten Beschichtung sollte bevorzugt maximal 100 Mikron betragen, um eine ausreichende Durchhärtung zu gewährleisten. Höhere Schichtdicken können durch Schrumpf bei der Durchhärtung zur Verformung (dishing) der optischen Datenträger führen, so dass diese nicht mehr lesbar bzw. beschreibbar sind. Bevorzugte Schichtdicken liegen in einem Bereich zwischen 100 und 1 Mikron. Besonders bevorzugte Schichtdicken liegen in einem Bereich zwischen 10 und 3 Mikron.The thickness of the resulting hardened coating should preferably be at most 100 microns in order to ensure adequate hardening. Higher layer thicknesses can lead to deformation (dishing) of the optical data carriers due to shrinkage during hardening, so that they can no longer be read or written. Preferred layer thicknesses are in a range between 100 and 1 micron. Particularly preferred layer thicknesses are in a range between 10 and 3 microns.
Das erfindungsgemäß verwendete Uberzugsmittel stellt im allgemeinen die äußere Schicht der Schreibe- und Leseseite, d.h. die Seite des beschichteten optischen Datenträgers dar, die der Laserstrahl durchdringt,. Sie kann aber auch sowohl zur Beschichtung der Schreibe- und Leseseite als auch zur Beschichtung der gegenüberliegenden Seite verwendet werden.The coating agent used according to the invention generally represents the outer layer of the writing and reading side, ie the side of the coated side optical data carrier, which the laser beam penetrates ,. However, it can also be used both for coating the writing and reading side and for coating the opposite side.
Die erfindungsgemäß hergestellten Beschichtungen bieten eine Reihe von Vorteilen gegenüber dem Stand der Technik.The coatings produced according to the invention offer a number of advantages over the prior art.
Sie haben eine besonders gute Adhäsion zu ihren Substraten, insbesondere zu Polycarbonat, insbesondere nach Alterung durch den Klimatest für CD, DVD und DV-R.They have a particularly good adhesion to their substrates, in particular to polycarbonate, especially after aging through the climate test for CD, DVD and DV-R.
Die erfindungsgemäß hergestellten Beschichtungen besitzen weiterhin gegenüber den im Stand der Technik verwendeten Beschichtungen eine verbesserte Härte und Kratzfestigkeit.The coatings produced according to the invention also have improved hardness and scratch resistance compared to the coatings used in the prior art.
Außerdem verursachen die erfindungsgemäß hergestellten Beschichtungen bei den CD bzw. DVD entweder kein „electronic noise" oder keine zusätzlichen Fehler, die sich auf die Auslesegenauigkeit oder die Beschreibbarkeit negativ auswirken können.In addition, the coatings produced according to the invention in the case of the CD or DVD either cause no “electronic noise” or no additional errors which can have a negative effect on the reading accuracy or the writeability.
Die nachfolgenden Beispiele sollen die Erfindung erläutern.The following examples are intended to explain the invention.
In den Beispielen wurden die folgenden Testverfahren angewendet:The following test procedures were used in the examples:
1. Klimatest1. Climate test
Im Klimatest werden die beschichteten CD oder DVD unter bestimmten künstlich eingestellten klimatischen Bedingungen gelagert (Temperatur: 70°Celsius; relative Luftfeuchtigkeit: 50%; Lagerzeit: 96 Stunden; In einer verschärften Variante diese Tests werden die CD bzw. DVD unter anderen Bedingungen gelagert: Temperatur: 80° Celsus; relative Luftfeuchtigkeit: 95%, Lagerzeit: 96 Stunden; in einer weiter verschärften Variante dieses Tests werden die CD bzw. DVD unter anderen Bedingungen gelagert: Temperatur: 70° Celsius; relative Luftfeuchtigkeit: 90 %; Lagerzeit: 500 Stunden). Nach Beendigung der jeweiligen Lagerzeit unter den jeweils genannten Bedingungen beläßt man die CD bzw. DVD in einem Normklima für 24 Stunden und mißt anschließend die Abweichung von der Planarität. Ferner wird der Zustand der Beschichtung mit dem Auge begutachtet. Es dürfen keine Stellen mit Ablösungen der Beschichtung sichtbar sein.In the climate test, the coated CD or DVD is stored under certain artificially set climatic conditions (temperature: 70 ° Celsius; relative humidity: 50%; storage time: 96 hours; in a more stringent variant of these tests, the CD or DVD is stored under other conditions: Temperature: 80 ° Celsus; relative humidity: 95%, storage time: 96 hours; in a further tightened variant of this test the CD or DVD are stored under different conditions: temperature: 70 ° Celsius; relative humidity: 90%; Storage time: 500 hours). After the end of the respective storage period under the conditions mentioned in each case, the CD or DVD is left in a standard atmosphere for 24 hours and the deviation from the planarity is then measured. The condition of the coating is also examined by eye. No spots with peeling of the coating may be visible.
Zusätzlich wird durch den Gitterschnitt-Test die Haftung der Beschichtung vor und nach Durchführung des Klimatests überprüft. Der genannten Gitterschnitt- Test wird durchgeführt, indem man mit Hilfe eines Mehrfachmessers parallele Einschnitte in das CD/DVD-Material einbringt. Danach wird die Scheibe um 90 ° gedreht und die Operation wiederholt. Dadurch wird ein Gitterschnittmuster mit 1 mm2 Mustern auf der Beschichtung erzeugt. Mit einem Klebeband z.B. des Typs 3M Scotch 710 wird der Gitterschnitt kurz bedeckt und das Band daraufhin abgezogen.In addition, the cross-cut test checks the adhesion of the coating before and after the climatic test. The above-mentioned cross-cut test is carried out by making parallel incisions in the CD / DVD material with the aid of a multiple knife. The disc is then rotated 90 ° and the operation repeated. This creates a cross-hatch pattern with 1 mm 2 patterns on the coating. The cross cut is briefly covered with an adhesive tape, for example of the type 3M Scotch 710, and the tape is then pulled off.
Eine Probe besteht den Gitterschnitt-Test nicht, wenn eines der erzeugten Quadrate durch das Klebeband vom Substrat abgelöst wird. Dieser Versuch wird bei jeder Probe dreimal wiederholt.A sample does not pass the cross-cut test if one of the squares produced is detached from the substrate by the adhesive tape. This experiment is repeated three times for each sample.
2. Kratzfestigkeit2. Scratch resistance
Die Kratzfestigkeit wird nach der Methode der Bleistifthärte und nach der „TaberThe scratch resistance is determined using the pencil hardness method and the “Taber
Abrader" Methode bestimmt.Abrader "method determined.
Bei der Methode nach der Bleistifthärte werden handelsübliche Bleistiftminen von 2 mm Durchmesser auf feinem Korundpapier zweiseitig so angeschliffen, daß eine Schneide entsteht. Diese Schneide wird mit der Hand auf die Beschichtung aufgesetzt und vorwärtsgeschoben. Wenn die verwendete Bleistiftmine härter als die zu untersuchende Beschichtung ist, entsteht eine Einkerbung auf der Oberfläche der Beschichtung; ist die Bleistiftmine weicher als das zu untersuchende Substrat, hinterläßt die Mine keine Einkerbung (Kratzer). Diejenige Bleistifthärte gilt als Härte der Beschichtung, die noch keine Verkratzung der Beschichtungsoberfläche erzeugen konnte. Der Versuch wird jeweils dreimal pro Probe wiederholt.In the pencil hardness method, commercially available pencil leads with a diameter of 2 mm are ground on two sides on fine corundum paper so that a cutting edge is created. This cutting edge is placed on the coating by hand and pushed forward. If the pencil lead used is harder than the coating to be examined, a notch is formed on the surface of the coating; if the pencil lead is softer than the substrate to be examined, the lead leaves no notch (scratches). The pencil hardness is the hardness of the coating, which is not yet Could scratch the coating surface. The experiment is repeated three times per sample.
Der Taber Abrader Test verwendet runde Scheiben, die in der Mitte mit einem Loch versehen sind. Der Taber Abrader ist mit CS-1 OF Rädern ausgestattet, die alle 500 Cyclen neu konditioniert werden, indem man sie für 15 Cyclen auf einer S-111 -Scheibe laufen läßt. Die dabei verwendeten Gewichte betragen 500 g. Bei jeder beschichteten Scheibe wird an 4 Stellen der zukünftigen Abrasion die Trübung mit einem GARDNER Trübungsmessgerät gemessen. Die Probe wird über eine bestimmte Zyklenzahl abradiert und von anhaftenden Partikel gereinigt. Die Trübungsdifferenz wird aus dem nach gleichem Vorgehen ermittelten Trübungswert abzüglich der Anfangstrübung als Delta Haze ermittelt. Jede Messung wird jeweils an 5 Proben durchgeführt.The Taber Abrader Test uses round disks with a hole in the middle. The Taber Abrader is equipped with CS-1 OF wheels that are reconditioned every 500 cycles by running them on an S-111 disc for 15 cycles. The weights used are 500 g. For each coated pane, the turbidity is measured at 4 points of future abrasion using a GARDNER turbidity meter. The sample is abraded over a certain number of cycles and cleaned of adhering particles. The turbidity difference is determined from the turbidity value determined using the same procedure minus the initial turbidity as delta haze. Each measurement is carried out on 5 samples.
Beispiel 1example 1
Eine Mischung aus 50 Teilen t-Butanol, 16.6 Teilen Naicoag 1034A, ein Produkt der Nalco Company, Oak Brook, Illinois und 1 Teil gamma- Methacryloxypropyltrimethoxysilan (MAPTMS) wurde während 5 Minuten zum Rückfluß erhitzt. Nach Abkühlung auf Raumtemperatur wurden 13.2 Teile einer 1 :1 Mischung Hexandioldiacrylat und Trimethylolpropantriacrylat zugegeben. Das Lösungsmittel wurde anschließend unter reduziertem Druck abdestilliert. Nachdem etwa die Hälfte des Lösungsmittels abdestilliert war, wurden zusätzliche 30 Teile t-Butanol zugegeben. Das gesamte Lösungsmittel sowie Wasser wurde abdestilliert. Man erhielt eine klare Lösung. Zu 100 Teilen dieser Lösung wurden 1.5 Teile alpha,alpha-Diethoxyacetophenon zugesetzt.A mixture of 50 parts t-butanol, 16.6 parts Naicoag 1034A, a product of the Nalco Company, Oak Brook, Illinois and 1 part gamma methacryloxypropyltrimethoxysilane (MAPTMS) was heated to reflux for 5 minutes. After cooling to room temperature, 13.2 parts of a 1: 1 mixture of hexanediol diacrylate and trimethylolpropane triacrylate were added. The solvent was then distilled off under reduced pressure. After about half of the solvent was distilled off, an additional 30 parts of t-butanol were added. All of the solvent and water were distilled off. A clear solution was obtained. 1.5 parts of alpha, alpha-diethoxyacetophenone were added to 100 parts of this solution.
Das so erhaltene UV-härtbare Beschichtungsmittel wurde in einer automatischen Beschichtungsanlage der Fa. STEAG-Hamatech, Type DVD- R2500 in der Weise auf CD-R Scheiben, die aus eigener Produktion stammen aufgetragen, gecoated und während 2 Sekunden bei 2200 Watt/h Leistungsaufnahme der UV-Lampe gehärtet. Die Eigenschaften der erhaltenen Beschichtung sind Tabelle 1 gezeigt.The UV-curable coating agent obtained in this way was coated in an automatic coating system from STEAG-Hamatech, type DVD-R2500, on CD-R disks which come from its own production, coated and for 2 seconds at 2200 watt / h power consumption the UV lamp hardened. The properties of the coating obtained are shown in Table 1.
Beispiel 2Example 2
Eine Mischung von 52 g Naicoag 1034A (kolloidales Silicasol) und 10 g gamma-Methacryloxypropyltrimethoxysilan, gelöst in 80 g Isobutanol und 80 g Isopropanol wurde während 30 Minuten zum Rückfluß erhitzt. Nach dem Abkühlen auf Raumtemperatur wurde ein Tropfen einer 50 %-igen Natriumhydroxidlösung zugesetzt. Unter vermindertem Druck wurde das Lösungsmittel entfernt. Das dickflüssige Harz wurde in 3.2 g Diethylenglycoldiacrylat, 3.2 g Trimethylolpropantriacrylat und 4 g N-Vinyl- pyrrolidon aufgenommen. Nach dem Verdampfen der Lösungsmittel und des Wassers gab man als Photoinitiator 2,1 g Benzophenon und 2,1 g Methyldiethanolamin pro 100 g des erhaltenen Reaktionsgemisches zu. Dieses Beschichtungsmittel wurde in einer automatischen Beschichtungsanlage der Fa. STEAG-Hamatech, Type DVD-R2500 in der Weise auf eine CD-RW aufgetragen, gecoated und gehärtet, wie in Beispiel 1 angegeben.A mixture of 52 g Naicoag 1034A (colloidal silica sol) and 10 g gamma-methacryloxypropyltrimethoxysilane, dissolved in 80 g isobutanol and 80 g isopropanol, was heated to reflux for 30 minutes. After cooling to room temperature, a drop of a 50% sodium hydroxide solution was added. The solvent was removed under reduced pressure. The viscous resin was taken up in 3.2 g of diethylene glycol diacrylate, 3.2 g of trimethylolpropane triacrylate and 4 g of N-vinylpyrrolidone. After evaporation of the solvents and water, 2.1 g of benzophenone and 2.1 g of methyldiethanolamine were added as 100% of the reaction mixture obtained as photoinitiator. This coating composition was applied to a CD-RW in an automatic coating system from STEAG-Hamatech, type DVD-R2500, in the manner, coated and hardened, as indicated in Example 1.
Die Eigenschaften der erhaltenen Beschichtung sind Tabelle 1 gezeigt.The properties of the coating obtained are shown in Table 1.
Beispiel 3 (VerqleichsbeispiePExample 3 (Comparative Example
Zum Vergleich wurde ein kratzfester Lack aus dem Markt eingesetzt, der als besonders geeignet für die Lackierung von transparenten thermoplastischen Kunststoffen herausgestellt wird. Dieser Lack ist unter der Bezeichnung UVT 200 erhältlich (Hersteller: Red Spot and Varnish Co., Evansville, USA).For comparison, a scratch-resistant paint from the market was used, which is shown to be particularly suitable for painting transparent thermoplastic materials. This varnish is available under the name UVT 200 (manufacturer: Red Spot and Varnish Co., Evansville, USA).
Die Aufbringung auf dem Substrat erfolgte unter den gleichen Bedingungen wie bei der Applikation der erfindungsgemäßen Lacke. Das Abschleudern im Spincoater erfolgte bei 3000 U/min für 2 sec. Hierbei wurde eine Schichtdicke von 8.5 Mikron (μm) erhalten.The application to the substrate was carried out under the same conditions as when the lacquers according to the invention were applied. The spin coater was spun off at 3000 rpm for 2 seconds. A layer thickness of 8.5 microns (μm) was obtained.
Die Eigenschaften der erhaltenen Beschichtung sind Tabelle 1 gezeigt. Beispiel 4 (VergleichsbeispieOThe properties of the coating obtained are shown in Table 1. Example 4 (comparative example
Zum Vergleich wurde ein speziell für die CD-Beschichtung empfohlener Lack (Type: Daicure Clear SD-715, Hersteller: Dainippon Ink & Chemicals, Inc., Japan) auf CD-R in der im Beispiel 3 dargestellten Weise aufgetragen, Nach der Härtung wurde eine Schichtdicke von 5 Mikron (μm) gemessen.For comparison, a varnish specially recommended for CD coating (type: Daicure Clear SD-715, manufacturer: Dainippon Ink & Chemicals, Inc., Japan) was applied to CD-R in the manner shown in Example 3. After curing, measured a layer thickness of 5 microns (μm).
In der folgenden Tabelle 1 sind die mechanischen Daten der erhaltenenen Beschichtungen gegenübergestellt. Tabelle 1The mechanical data of the coatings obtained are compared in Table 1 below. Table 1
In Tabelle 2 sind die elektrischen Eigenschaften und die Klimabeständigkeit der beschichteten Substrate dargestellt. Table 2 shows the electrical properties and the climate resistance of the coated substrates.
Tabelle 2Table 2
BLER = Block Error Rate; Änderung gegenüber ungebeschichteten Produkt; Korrektureinheiten / sec, die für eine Lesekorrektur erforderlich sind. BLER wird als Rate der aufgetretenen Fehler pro Sekunde angegeben. Die Spezifikationsgrenze liegt bei 220 Fehlern pro Sekunde, wobei für CD-ROM eine Spezifikation von 50 Fehlern pro Sekunde als maximalem Durchschnittwert und 100 Fehlern pro Sekunde als maximalem Spitzenwert zu empfehlen ist. BLER ist insofern von entscheidender Bedeutung, als die Anzahl der auftretenden Fehler so gering wie möglich zu halten ist, um die Datenintegrität zu gewährleisten. Radial Noise(RN) = gemessene Spurveränderung gemäß ISO/IEC 10 149, hat innerhalb einer Bandbreite von 500 bis 2500 Hz einen Grenzwert von 30 Nanometern. RN tritt auf, wenn die Spur beschädigt ist. Bei hohen RN-Spitzen kann die Servosteuerung Spuren überspringen. Ein hohes durchschnittliches RN-Niveau ist ein Indiz für schlecht definierte Pits.BLER = Block Error Rate; Change from uncoated product; Correction units / sec required for reading correction. BLER is given as the rate of errors per second. The specification limit is 220 errors per second, whereby a specification of 50 errors per second as the maximum average value and 100 errors per second as the maximum peak value is recommended for CD-ROM. BLER is critical in that the number of errors that occur should be kept as low as possible to ensure data integrity. Radial Noise (RN) = measured track change according to ISO / IEC 10 149, has a limit of 30 nanometers within a bandwidth of 500 to 2500 Hz. RN occurs when the track is damaged. At high RN peaks, the servo control can skip tracks. A high average RN level is an indication of poorly defined pits.
Deviation (DEV) = in Winkelgrad (°) gemessene (Höhen)Abweichung von der Ebene aus Sicht der metallisierten Oberseite. DEV wird an 10 verschiedenen Durchmessern, verteilt über die Diskoberfläche gemessen. Er ergibt sich aus dem Winkel zwischen Scheibenmittelpunkt und der von der Ebene abweichenden Fläche der Scheibe Die Spezifikation für die DEV erlaubt im Randbereich sowohl für bespielte wie unbespielte CD-R eine Höhenabweichung zur Ebene von +/-0.5 mm. Zu hohe Werte für die Deviation verursachen Probleme bei der Fokussierung und damit den Verlust des HF- Signals.Deviation (DEV) = deviation (height) measured in angular degrees (°) from the plane from the view of the metallized top. DEV is measured on 10 different diameters, distributed over the disk surface. It results from the angle between the center of the disc and the surface of the disc that deviates from the plane. The specification for the DEV allows a height deviation of +/- 0.5 mm to the plane for both recorded and unrecorded CD-Rs. Excessive values for the deviation cause problems with the focusing and thus the loss of the RF signal.
Obwohl dass Uberzugsmittel gem. Vergleichsversuch in einer größeren Dicke aufgetragen wurde, zeigt es eine deutliche geringere Härte und einen stärkeren Schrumpf der zum Verbiegen des optischen Datenträgers führt. Although the coating agent according to Comparative experiment was applied in a greater thickness, it shows a significantly lower hardness and a greater shrinkage which leads to the bending of the optical data carrier.

Claims

Patentansprüche claims
1. Optische Datenspeicher, dadurch gekennzeichnet, daß sie mit einer Beschichtung, versehen sind, die durch Strahlungshärtung eines strahlungshärtbaren Überzugsmittels, dass mindestens ein kolloidales1. Optical data storage, characterized in that they are provided with a coating, by radiation curing a radiation-curable coating agent that at least one colloidal
Metalloxid, mindestens ein Hydrolyseprodukt mindestens eines Alkoxysilylacrylates, mindestens ein Acrylat-Monomer sowie gegebenenfalls einen UV-Photoinitiator umfaßt, erhalten wird.Metal oxide, at least one hydrolysis product of at least one alkoxysilylacrylate, at least one acrylate monomer and optionally a UV photoinitiator is obtained.
2. Optische Datenspeicher nach Anspruch 1 , worin das strahlungshärtbare2. Optical data storage device according to claim 1, wherein the radiation-curable
Uberzugsmittel ein UV-härtbares Uberzugsmittel ist, das mindestens einen UV-Photoinitiator umfaßt.Coating agent is a UV-curable coating agent which comprises at least one UV photoinitiator.
3. Optische Datenspeicher nach Anspruch 1 oder 2, worin das UV- härtbares Uberzugsmittel3. Optical data storage device according to claim 1 or 2, wherein the UV-curable coating agent
(A) 1 bis 60 Gew.-% mindestens eines kolloidalen Metalloxids, (B) 0,1 bis 50 Gew.-% mindestens eines Hydrolyseproduktes eines Alkoxysilylacrylates, (C)25 bis 90 Gew.-% mindestens eines Acrylat-Monomers, und(A) 1 to 60% by weight of at least one colloidal metal oxide, (B) 0.1 to 50% by weight of at least one hydrolysis product of an alkoxysilyl acrylate, (C) 25 to 90% by weight of at least one acrylate monomer, and
(D)0,01 bis 15 Gew.-% mindestens eines UV-Photoinitiators,(D) 0.01 to 15% by weight of at least one UV photoinitiator,
jeweils bezogen auf die Gesamtmenge der Zusammensetzung enthält.each based on the total amount of the composition contains.
4. Optische Datenträger nach einem der Ansprüche 1 bis 3, bei denen es sich um optische Datenträger auf Basis von Polycarbonaten handelt.4. Optical data carrier according to one of claims 1 to 3, which are optical data carriers based on polycarbonates.
5. Optische Datenträger nach einem der Ansprüche 1 bis 4, bei denen es sich um CD, DVD oder DVD-R auf Basis von Polycarbonaten handelt. 5. Optical data carrier according to one of claims 1 to 4, which is CD, DVD or DVD-R based on polycarbonates.
6. Verfahren zur Herstellung von optischen Datenträgen nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das strahlungshärtbare Uberzugsmittel auf das Substrat aufgebracht, durch ein Schleuderverfahren auf die gewünschte Dicke eingestelllt und anschließend gehärtet wird.6. A method for producing optical data carriers according to one of claims 1 to 5, characterized in that the radiation-curable coating agent is applied to the substrate, adjusted to the desired thickness by a centrifugal process and then cured.
7. Verwendung eines strahlungshärtbaren Überzugsmittels, dass mindestens ein kolloidales Metalloxid, mindestens ein Hydrolyseprodukt mindestens eines Alkoxysilylacrylates, mindestens ein Acrylat-Monomer sowie gegebenenfalls mindestens einen Photoinitiator umfaßt, zur7. Use of a radiation-curable coating composition which comprises at least one colloidal metal oxide, at least one hydrolysis product of at least one alkoxysilylacrylate, at least one acrylate monomer and, if appropriate, at least one photoinitiator
Beschichtung von optischen Datenträgern. Coating of optical data carriers.
EP02801907A 2001-10-24 2002-10-22 Scratch-resistant coating method for optical storage media Withdrawn EP1446455A2 (en)

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DE10151853A DE10151853C1 (en) 2001-10-24 2001-10-24 Optical data storage medium, preferably polycarbonate compact disc or digital versatile disc, comprises a radiation-cured acrylate coating containing colloidal metal oxide and hydrolyzed alkoxysilyl acrylate
DE10151853 2001-10-24
PCT/EP2002/011790 WO2003035773A2 (en) 2001-10-24 2002-10-22 Scratch-resistant coating method for optical storage media

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6972143B2 (en) 2003-10-27 2005-12-06 Kyle Baldwin Protective U.V. curable cover layer for optical media
DE102005020511A1 (en) 2005-04-29 2006-11-09 Basf Ag Composite element, in particular window pane
DE102006016642A1 (en) * 2006-04-08 2007-10-18 Bayer Materialscience Ag UV-curing protective layer for thermoplastic substrates
KR20090019317A (en) * 2007-08-20 2009-02-25 엘지전자 주식회사 A film for electric home appliance and a ome appliance using the film
JP5525152B2 (en) * 2007-10-01 2014-06-18 アトミクス株式会社 UV-curable coating composition, method for producing the same, and resin-coated article coated therewith
CN104530461B (en) * 2011-01-28 2018-05-18 大日本印刷株式会社 Decoration sheet and the decorated resin molded article formed using it
WO2012101820A1 (en) 2011-01-28 2012-08-02 大日本印刷株式会社 Decorative sheet, and decorative resin-molded article employing same
JP5747626B2 (en) * 2011-03-30 2015-07-15 大日本印刷株式会社 Decorative sheet and decorative resin molded product using the same
US8691915B2 (en) 2012-04-23 2014-04-08 Sabic Innovative Plastics Ip B.V. Copolymers and polymer blends having improved refractive indices
DE102017101978B4 (en) 2017-02-01 2023-02-02 Fachhochschule Kiel Transparent anti-scratch coating with antifouling properties and method of making the same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4198465A (en) * 1978-11-01 1980-04-15 General Electric Company Photocurable acrylic coated polycarbonate articles
US4455205A (en) * 1981-06-01 1984-06-19 General Electric Company UV Curable polysiloxane from colloidal silica, methacryloyl silane, diacrylate, resorcinol monobenzoate and photoinitiator
US4491508A (en) * 1981-06-01 1985-01-01 General Electric Company Method of preparing curable coating composition from alcohol, colloidal silica, silylacrylate and multiacrylate monomer
US5176943A (en) * 1991-07-09 1993-01-05 Minnesota Mining And Manufacturing Company Optical recording medium with antistatic hard coating
DE69213647T2 (en) * 1991-10-24 1997-02-06 Tosoh Corp Protective covering material
US5318850A (en) * 1991-11-27 1994-06-07 General Electric Company UV curable abrasion-resistant coatings with improved weatherability
US5662988A (en) * 1993-01-22 1997-09-02 Sharp Kabushiki Kaisha Magneto-optical recording medium
JP3486709B2 (en) * 1996-06-21 2004-01-13 株式会社リコー Optical recording medium
TW376517B (en) * 1997-08-15 1999-12-11 Ricoh Kk Optical recording medium and recording and reproducing method using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03035773A2 *

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CN1575324A (en) 2005-02-02
CA2464376A1 (en) 2003-05-01
WO2003035773A3 (en) 2003-12-31
JP2005506649A (en) 2005-03-03
CN1292030C (en) 2006-12-27
DE10151853C1 (en) 2003-03-20
RU2004115756A (en) 2005-10-27
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MXPA04003810A (en) 2005-04-08

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